JPH07509275A - Sanitary cleaning methods and sanitary cleaners - 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

[Detailed description of the invention] Sanitary cleaning method and sanitary cleaner - The present invention provides a sanitary cleaner (cleaning agent'). I. an amount of at least about 0.5 g/kg of microbial activity-inhibiting organic material; of lime-soluble water-soluble acid and at least 10 mg of kite per kg of sanitary cleaner. The microbial activity-promoting organic substance resistant to lime-soluble water-soluble acids and diluted or blown After lashing, any other additive that promotes the action of microorganisms to decompose organic matter in the water Sanitary cleaning (washing) with liquid or solid sanitary cleaners containing additives. and a sanitary cleaner for carrying out the method.

The above-mentioned prior art is disclosed in the international patent application PCT/E P90101718. This patent application describes, for example, hygiene in toilet bowls (toilet bowls). In the first stage of action of fresh cleaners, the desired inhibitory effect on microbial action is achieved on the one hand. on the other hand, the microflora in the wastewater (in the second activity stage) This shows the advantage of not disturbing the decomposition efficiency of plant-based microorganisms. Therefore, regarding this point , is effective only in the prior art, and this effectiveness extends to the second stage of activity. So (yonari).

This cleaner is available in tablet form and primarily works to remove limescale residues. , citric acid can be used as a lime solvent.

In the sanitary cleaner described in PCT='E P90101718, preferably 1 In particular, they have been found to be more effective in the second stage. U.S. Patent No. 4.01.3 ．． In the prior art described in No. 579 and East German Patent No. 241.747, such No suggestions are made regarding desirable improvements. )<National Patent No.-1.0+3.57 Item 9 applies to cleaning agents that forcibly contain furocarboxylic acids or their derivatives. states. These cleaning agents remove γη substances adhering to the object. U.S. Patent No. 4. 013.579 In the bow, P CT, / E P90101718 beginning (second The simultaneous use of microbial-promoting substances and microbial-promoting substances as described is prohibited. and l: dual function as achieved by the method of ft-terminus; However, it is not the case that JI levonic acid or their derivatives play a role. U.S. Patent No. 4,0 13.579+kouU) [Furancarphonic acid or A group of compounds of their derivatives (as opposed to those previously used in the prior art) It replaces oxalic acid. On the contrary, FCA does not exhibit relatively high toxicity. It is considered easier and safer to handle. In any case, FCA is also still highly toxic. The present invention described below is characterized by intended to avoid the use of such toxic agents in sanitary cleaners. This is what I did. Mixing these is the process of microorganisms in the second activity stage mentioned above. The inhibition of activity is removed and the toxicity of the FCA present prevents the growth of the desired microorganisms. means excluded or at least undesirably reduced. East Germany Pat. Information on chemicals for cleaning and disinfecting flush water tanks and bees. It is stated that Improving the decomposition of organic substances in wastewater by microbial bacteria There is no hint that compounds with relatively high complex dust content may further contaminate the wastewater, e.g. Fatty alcohols, ethylene-propylene copolymers and alkylphenols Polyglycolethane is used.

The purpose of the present invention is to prevent microbial activity in the first stage of activity in the toilet bee. While maintaining the desired suppression, the microflow of the wastewater (of the ffi2 active stage) further improvements to the prior art mentioned at the beginning, so as to further improve the decomposition activity of the It is in.

The above purpose is to promote microorganisms using the formula (1) R, R2H-Co-NR3R4 as a seed material. (Here, R3-R1 exists separately in an open chain or cyclic form, hydrogen, 1 to 4 carbon atoms) lower alkyl group having atomic atoms, cycloalkyl group having 3 to 6 carbon atoms aryl group, phenyl group or naphthyl residue, containing 7 to 18 carbon atoms an aralkyl group having 7 to 18 carbon atoms or an aralkyl group having 7 to 18 carbon atoms or 2 a heterocyclic group having ~5 carbon atoms and having O, S or N) This is achieved by the present invention, which is a cleaner.

The following urea derivatives are also included within the scope of the above formula (1).

R,R2H-Co-■　,■-co-■ and R,N-Co-NR2\~-1no In formula (1), each residue R1, R2, R3 and R, is hydrogen. Of course, each basic compound is commercially available or easily manufactured. This is because. Within the scope of the invention, as set out in the above definition of the invention. Substitutes are particularly suitable. As a lower alkyl group having 1 to 4 carbon atoms is a species of methyl group, ethyl group, n-propyl group, l-propyl group and butyl group. It is thought that each of them includes a sexual body. cycloalkyl having 3 to 6 carbon atoms In particular, cyclopropyl, cyclobutyl, cyclopentyl and and cyclohexyl groups, as aralkyl groups having 7 to 18 carbon atoms. have 7 to 18 carbon atoms, especially benzyl and phenethyl groups. Alkylaryl groups include in particular tolyl groups, having 2 to 5 carbon atoms. In particular, the heterocyclic group containing at least one oxygen or sulfur or There are some that have 1 or 1 atoms. Suitable examples include oxirane, tetrahydro Mention may be made of the radicals of furan, dioxane and bilane. Basically Compounds of formula (1) may be treated with their salts or other precursors which can increase their solubility. It can be used in any condition. In some cases, the sanitary cleaner according to the invention simply increase the desired solubility. Therefore, we set the free compound of formula (1) or compounds that can exhibit efficacy only in aqueous media can be used. Ru.

The following description of the foot may be made, for example, by a compound of formula (1), or a suitable derivative or It always refers to those parts of a compound.

In addition to the above compounds of formula (1), international patent application PCT/E P90101718 Other (organic substances promoting microbial activity) known from Other known organic substances that promote microbial activity and inhibit microbial activity. A quality has a common predetermined property. Therefore especially in urea and urea derivatives As such, these materials are within the scope of this invention and are subject to normal temperature and pH levels. The organic acids or their salts can be added to a sufficient amount in the container.

As organic substances that suppress microbial activity, especially acidic organic substances or their salts or There are suitable derivatives, and ether oils. As a substance that suppresses microbial activity Natural organic substances are preferred. The above acidic organic substances include aromatic, aliphatic, Alicyclic and/or heterocyclic carboxylic acids or their salts, especially alkali salts or or alkaline earth salts, or suitable derivatives thereof. Furthermore, microbial activity Acidic organic substances that exhibit a preferable inhibitory effect include those that have sufficient water solubility. Must. In a given case, the carboxylic acid itself has little water solubility However, some of these salts are sufficiently water-soluble and suitable. especially Suitable aliphatic carboxylic acids include, in particular, lower carboxylic acids having 1 to 7 carbon atoms. For example, formic acid, acetic acid, propionic acid, caproic acid, malonic acid, oxalic acid only. 6 to 12 carbon atoms, if it can be used as a suitable water-soluble salt. There are various fatty acids such as sorbic acid and undecylenic acid. 13 or more carbon sources Fatty acids with f- are not themselves water soluble, and none of their multiple salts are water soluble. , gamma juice does not satisfy the following conditions, so it is generally not suitable. Considered as a lower fatty acid However, acetic acid is not recommended due to its unpleasant odor. Suitability of the above carboxylic acids Examples of suitable derivatives include hydroxy acids such as glycolic acid, tartaric acid and citric acid. as well as oxoacids, such as acetoacetic acid and propic acid. Sufficient water solubility aromatic carboxylic acids such as benzoic acid, salicylic acid and other phenolic acids. Also particularly effective are carboxylic acids.

Ether oils are also particularly effective. Tyno is a microbicidal ether oil. Ura, Citrus Ura, Eucalyptus oil, Clove oil, Hanahanoka oil, Rosemary oil, Cinnamo oil, camphor oil, camphor oil, j1 leaf oil, and fennel oil. be. Among these, thyme oil is particularly preferred. Instead of these, the contents contained within It is also possible to use active substances. Microbial activity inhibitors contained in ether oil Examples include thymol, carvaclove, terpineol, cineole, and feline. There is a ncorn. Ether oil is water-insoluble, especially for water-insoluble vitamins. along with suitable emulsifiers or solubilizers that are not harmful to the environment, such as microbial inhibitors. Can be used in sanitary cleaners.

Almost all surfactants can be used as solubilizers for the above substance groups. Can be done. The most suitable solubilizer for aqueous systems is selected according to the HLB system and tested Therefore, each ether oil must be found separately. 12-18 Ren Solubilizers with HLB values within the range are particularly suitable for ethereal oils.

Solubilizers, especially as described in Range's Chemical Lexicon, 8th Edition, Volume 3, Page 2399 should be selected. Basically, the following surfactants, which can be divided into groups, are preferred. Yes. For example, aliphatic alkyl sulfonates as anionic surfactants, e.g. For example, Na-lauryl ether sulfate, a cationic surfactant with a tetravalent ammonium compounds such as dodecyldimethylammonium chloride, betaine derivatives, such as fatty acid amidoprobyl dimethylamino acid-resistant betaine, non-ionogen emulsifiers or solution intermediates, fruit acid esters of monodiglycerides, e.g. Citric acid ester, polyoxynylene 1-ren glycerol fatty acid ester, e.g. For example, a polyoxyethylene glycerol monolayer containing 30 moles of ethylene oxide There is a rate.

Examples of organic acids that suppress microbial activity include formic acid, acetic acid, propylic acid, benzoic acid, and benzoic acid. , simple derivatives of Q aromatic acid, sorbic acid, as well as their suitable water-soluble salts, e.g. Particular preference is given to thoriated and phosphate salts. Lime-soluble organic acids, e.g. Phosphoric acids are generally effective in inhibiting microbial activity in suitable sanitary cleaners. An organic acid is y (in a given case, an organic acid can dissolve lime on the one hand, and It has the effect of suppressing microbial activity. Generally such substances have special calcareous action. At the same time as using acids, especially 1 such organic compounds that highly inhibit radiobiological activity. It is difficult to use it.

The sanitary cleaner according to the present invention contains sanitary cleaners, whether in powder, granular or liquid form. An amount of at least about 0.5g per kg of cleaner, preferably 1k of sanitary cleaner 05 to 150 g per gram, especially 1 to 80 g per 1 kg of sanitary cleaner. amount, more preferably about 2 to 7 g per kg of sanitary cleaner. Three substances are present.

The concentration of microorganism-inhibiting organic substances in the first action stage is determined by their concentration and the washroom to be cleaned. The concentration in the chamber is at least about the minimum inhibitory concentration (MHK), and this minimum inhibitory concentration (Ml It is preferable to adjust the amount so that it does not exceed about 200 times that of (K). 1st stage The concentration of microbially inhibiting organic substances during floor activity should be at least about the minimum inhibitory concentration. It is particularly preferred that the amount be doubled, which does not exceed about 50 times, especially about 30 times.

Within the scope of the present invention, in addition to the abovementioned compounds of formula (I) as microbial promoters, amino acids as well as noic and/or orotic acids or their suitable salts or derivatives. Vitamins can also be used. The above derivatization results in the desired microbial promotion effect. ``r! It must not have any adverse effects. Preferred amino acids include , alanine, arginine, asparagine, aspartic acid, citrulline, cysteine cine, cystine, glutamine, glutamic acid, glycine, histidine, hydroxy Cyproline, isoleucine, leucine, lysine, methionine, ornithine, fe Nealalanine, florine, serine, threonine, tryptophan, tyrosine and valine. Particularly suitable vitamins, including provitamins, include L-as Corbic acid, salts of ascorbic acid, especially Ca salts, L-ascobilbramitate, (10)-biotin, B-carotene, cholecalciferol, dianocobalamin, Dihydrofolic acid, dehydroascorbic acid, ergocalciferol, folic acid, hydride Loxincobalamin, niacinamide, nicotinic acid (niacin), D-pan tenol, D-pantothenic acid, pyridoxal, pyridoxal-5-phosph ate, pyridoxyamine, pyridoxamine-5°-phosphate, pyridoxyamine Syn, pyridoxyphosphate, riboflavin, riboflavin-5゛-phosphate Phate, rutin, rutin acid especially rutin sulfate, tetrahydrofolic acid, thia thiamine nitrate, thiamine phosphoric ester, thiamine pyro Phosphate, 6-tocopherol, δ-tocopherol, α-tocopherol acetate, α-tocopherolquinone, α-tocopheryl phosphate α-tocopheryl succinate, vitamin A acetate, vitamin A alde water, vitamin A alcohol, vitamin A acid, vitamin B4 (adenine), vitamin A 1 for tamin, 4 for vitamin, vitamin P and vitamin U (methionine S-methionine) (tylsulfonium chloride). Vitamins have acid or alkaline groups. If so, it is generally possible to use their appropriate salts.

The present invention enables sanitary equipment to be used without disturbing the decomposition of organic substances by microorganisms in wastewater. This allows for sanitary cleaning. Such apparently contradictory properties are In the first stage of action, for example, when the toilet bowl is in use, The sanitary cream according to the present invention is It is obtained by introducing the above-mentioned microbial inhibitor or microbicide into the container.

The term "minimum inhibitory concentration" is a well-known technical term. 1st stage microorganism-promoting organic material in the product at the concentration or amount after normal dilution of the medium. An example of a product that exerts a growth-promoting effect on microorganisms that invade wastewater upon introduction. For example, using the sanitary cleaner according to the invention, which can be in powder, granular or liquid form, This can be diluted with a small amount of water, for example in a toilet bowl. Hygiene agent is small They exhibit bioinhibitory or microbicidal effects, whereas microbial promoters do not act initially. There remains no. Flush the water into the toilet bowl after the action of the sanitary cleaner Since the concentration of microorganism-inhibiting organic substances is lower than the MKH value after will no longer work. On the other hand, microorganism-promoting organic substances can be flushed or significantly + Promotes the activity of microorganisms in wastewater that decompose organic substances even after dilution. These substances are distributed in the concentration within the sanitary cleaner according to the present invention. organic substances accelerate, or at least disturb, the biological purification of wastewater. do not have.

Microbial promotion as a compound of formula (I) in a sanitary cleaner according to the invention The amount of matter is not critical. Which minimum concentration should be used in each case? Need to test if it should. As a quantitative minimum value, sanitary cleaner 1 About 10mg of dragon per kg, especially about 10mg to 5 per kg of sanitary cleaner Sanitary cleaner 1k in the range 0g, especially compound (1) and/or (II) A value of about 1 g to 15 g per gram is considered.

Other microorganisms which can be incorporated in addition to the above-mentioned microorganism-promoting organic substances as compounds of formula CI) The standard guideline for promoting organic substances is a minimum of 10 mg/kg , especially about 10 to 1000 mg/kg. As another microorganism-promoting organic substance The above-mentioned substances, preferably amino acids, vitamins, orotic acid and p-aminoamines , Q8 acids are believed to be preferred. Approximately 2mg biotin, approximately 20mg nicotine amide, about 10 mg thiamine, about 10 mg p-aminobenzoic acid, about 5 mg pantothenic acid, approximately 50 mg pyridoxamine, approximately 2 mg cyanocarbalamin ( A mixture of vitamin B12) and about 10 mg of orotic acid is practical; Preferably, the mixture is present in 1 kg of sanitary cleaner. the above substance When used as a mixture qualitatively and quantitatively with respect to each environment, the desired microorganisms To optimize the action of the promoting organic substances, choose the same.

The sanitary cleaner according to the invention may contain, for example, a coloring agent, a biological foaming agent, etc. Other known additives can be incorporated. The foaming agent used is especially water-soluble wheythane. presence of water-soluble protein substances with associated biopromoting effects, such as proteins; is known. The preferred concentration of water-soluble protein material is approximately 1 kg of powdered sanitary cream. about 2 to 30 g for liquid sanitary cleaner or about 10,100 O.

Most preferably about 5-10 g. Naturally, the present invention does not apply to other conventionally known substances. This does not preclude the addition of additives, and these additives should be kept as close to the environment as possible. The choice must be made keeping in mind the preservation of advantages such as adaptability.

A special advantage of the present invention is that the respiratory activity of microflora in urban wastewater can be As shown in the examples, this can be surprisingly improved. follow The reason for this is that the sanitary cleaner according to the present invention can significantly reduce environmental pollution. , whose bactericidal action is a degradable natural substance, that is, a natural substance lime-soluble water-soluble microorganisms as acidic acids, microbially inhibiting organic substances and compounds according to formula (I), urea. This is because it originates from promoting organic substances. Therefore, the sanitary cleaner according to the present invention are particularly environmentally friendly, meet the conditions imposed on the environment, and are This significantly satisfies the demands of environmentally conscious consumers. Therefore, this Since the cleaner can be used in many areas, all areas of sanitary cleaning, e.g. toilet bowls, urinals, bathtubs, bidets, basins, and showers. It can be used in This list of possible uses is not exclusive.

Next, the present invention will be further explained with reference to three composition examples.

Example 1. (Ratio described in Water-based product/PCT/EP 90101718 Comparative example) Citric acid 175g Sodium hydroxide 22g Formic acid 10ml Sodium benzoate 2g Phosphorus sorbate 2g Mixture of vitamins and amino acids (see below) 0.5g thickener (xanthine) 5 g Soluble whey protein 10g Water was added to the above mixture to bring the temperature to 10,100O.

A mixture of vitamins and amino acids was combined as follows. i.e. 2mg bio Chin, 20 mg nicotinamide, 10 mg thiamine, and 10 mg p- aminobenzoic acid, 5 mg of pantothenic acid, 50 mg of pyridoxamine, 2 Combined with mg of dianocobalamin (vitamin old 2) and 10mg of orotic acid. .

Example 2. (This invention) Citric acid 175g Sodium hydroxide 1 unit 22g Formic acid 10ml Sodium Rest Acid 2g Thinner (xanthine) 5g Soluble whey protein 10g Water was added to this mixture to make it 10,100O.

Examples 3 and 4. (This invention) The composition of Example 2 is different in that the amount of j4 atoms is changed. In Example 3, 2g In Example 4, the dish weighed 5 g.

Comparative experiment example.

Reliable effects of the sanitary cleaners of Examples 1 to 4 on microflora in wastewater The effect was tested. The above sanitary cleaners can promote microflora, but what do you think? Also, in order to easily check whether it can be easily decomposed, The respiratory activity of black flora was measured. Products of Examples 1 to 4 with 3 different concentrations To this, fresh water was added. After 24 hours, measure the carbon dioxide produced. Ta.

The dry matter content and pH of the product were determined.

Test results Product pH and dry matter Product pH value Dry matter (%) The products vary somewhat in terms of pH value and dry matter content.

The following figure 1 shows the variation in the respiratory activity of the microflora.

(Microflora in wastewater depending on the composition of sanitary cleaners in water and their concentration) respiratory activity) The above comparison values are due to the addition of urea, which reduces respiratory activity compared to the comparison product (1). This shows that there has been a marked increase in Growth essentials for sanitary cleaner No. 4 By adding 5g of urea as an element, respiration is average compared to comparison product (1). It increased to 135%. Therefore, as a result of adding the amount of urea shown in the diagram, The effectiveness of Loflora has increased significantly.

Claims (10)

[Claims] 1. Sanitary cleaner - inhibits microbial activity in an amount of at least about 0.5 g/kg organic substances, normal lime-soluble water-soluble acids and sanitary cleaners - at least 1 kg and an amount of 10 mg of the lime-soluble water-soluble acid-resistant microbial activity-promoting organic substance. , after dilution or brushing, promotes the action of microorganisms that decompose organic substances in the water. Sanitary cleaning by liquid or solid sanitary cleaners containing any additives A method of manufacturing, wherein the sanitary cleaner is a microorganism-promoting organic substance having the formula ( 1) R1R2N-CO-NR3R4 (here, R1 to R4 are open-chain or cyclic) hydrogen, lower alkyl groups having 1 to 4 carbon atoms, 3 to 6 carbon atoms; cycloalkyl group, phenyl group, or naphthyl residue-like aryl group having an elementary atom aralkyl group having 7 to 18 carbon atoms, aralkyl group having 7 to 18 carbon atoms or an alkylaryl group having 2 to 5 carbon atoms and having O, S or N a heterocyclic group). 2. Said residues R1, R2, R3 and R4 are hydrogen and the compound of formula (I) 2. A method according to claim 1, characterized in that it is pure. 3. The concentration of the microorganism-promoting compound of formula (I) in the sanitary cleaner The amount should be about 10 mg to 50 g, especially about 1 g to 15 g per 1 kg. The method according to claim 1 or 2, characterized in that: 4. For optimal effectiveness, sanitary cleaners are supplemented with amino acids, orotic acids or add other microbial promoters in the form of their salts and/or vitamins. Method according to at least one of the preceding claims, characterized in that: 5. The amount of the sanitary cleaner is about 1 to 150 g per 1 kg of this sanitary cleaner. , especially in an amount of about 1 to 80 g of a microbially inhibiting organic substance, and also a sanitary cleaner - per 1 kg. lime-soluble water in an amount of at least 10 mg, especially in an amount of 100 to 1000 mg. The above-mentioned claim is characterized in that it contains a microorganism-promoting organic substance that is resistant to soluble acids. The method described in at least one of the claims. 6. Sanitary cleaners - concentrations of at least about 0.5 g per kg, especially sanitary cleaners. Bioinhibiting organic substances and sanitary cleaners in an amount of about 1 to 150 g per kg of in the form of a compound of formula (I) in an amount of at least 10 mg per kg, in particular up to 50 g. containing microorganism-promoting organic substances that are resistant to lime-soluble and water-soluble acids. Sanitary cleaner specifically for carrying out the method according to at least one of the claims. Nah. 7. further comprising a microbial-promoting water-soluble protein as a foam carrier. , The sanitary cleaner according to claim 6. 8. Characterized by containing about 2 to 30 g of water-soluble protein material per kg The sanitary cleaner according to claim 7. 9. The water-soluble protein substance is water-soluble whey protein. The sanitary cleaner according to claim 7 or 8. 10. Lime-soluble water-soluble acids, microbial-inhibiting organic substances and/or microbial-promoting organic substances At least one of claims 6 to 9, wherein the substance is a natural substance. Sanitary cleaners listed in.