JPS6115101B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a composition for coloring a cleaning liquid, and more particularly, to a composition for coloring a cleaning liquid for coloring, for example, flushing water of a flush toilet. BACKGROUND ART Conventionally, for example, in ordinary flush toilets in households and buildings, blue-colored flushing water or sterilizing water has generally been used to give a visually clean and refreshing feeling after use. Especially when it is necessary to use limited amount of washing water repeatedly, such as in vehicles, aircraft, ships, etc.
Blue-colored cleaning water is mainly used to sterilize and disinfect, as well as to hide the unpleasant color of human urine and give a sense of cleanliness. However, many of the colorants conventionally used to color wash water blue usually do not remove the color at all, even after the wash water has been used and goes through its final treatment step, depending on the treatment method used. Because the color is not removed or is only incompletely decolorized, it is discharged as colored wastewater and causes secondary pollution. In other words, blue coloring agents such as methylene blue and threne blue are conventionally used to color washing water, but these can be used in neutral or alkaline conditions due to excess chlorine, hypochlorite aqueous solution, etc. Even if chlorine treatment is performed using a chlorine-based decolorizing agent, the color will not be completely or incompletely decolored, so the washed water should be treated with ordinary household purification treatment or with ordinary sewage treatment such as air aeration, activated sludge treatment, etc. Of course,
After these normal treatments, decolorization is extremely difficult even with high-grade chlorine treatment such as chlorine sterilization when discharging into rivers, etc. Therefore, it is currently not possible to easily and completely decolorize the human waste after processing it. There is a strong demand for the development of cleaning liquid colorants that can The inventors of the present invention have considered the above-mentioned problems and have conducted extensive research. As a result, certain indigo-based sulfonate colored compounds or similar colored compounds have been found to be effective against extremely low concentrations of chlorine-based processing agents, and even more commonly. The inventors have discovered that the color can be easily and completely decolored by microbial treatment, leading to the completion of the present invention. Therefore, an object of the present invention is to provide a cleaning liquid coloring composition that can be easily and completely decolored after being used for cleaning toilet bowls, etc. treatment with agents,
Another object of the present invention is to provide a cleaning liquid coloring composition that can be easily decolored by ordinary microbial treatment. The cleaning liquid coloring composition according to the present invention has the general formula: (However, A and B each independently represent a carbonyl group and Y or Z with a 1,2-phenylene group,
An aromatic group selected from the group consisting of 1,2-naphthylene group, 2,3-naphthylene group and 1,8-naphthylene group, Y and Z each independently represent -NH- and -S- A group selected from the group consisting of -SO ₃ M is a group of an alkali metal sulfonic acid salt on A and/or B, m is a number from 1 to 4, and A and B are substituents other than the above -SO ₃ M. It may have. ) at least one colorant represented by
or as well as A general formula selected from the group (where A is a carbonyl group and Y is a 1,2-phenylene group, a 1,2-
Naphthylene group, 2,3-naphthylene group and 1,8
- Aromatic group bonded in a form selected from the group consisting of naphthylene groups, Y is a group selected from the group consisting of -NH- and -S-, -SO ₃ M is an alkali sulfonate on the aromatic nucleus in the molecule In the metal salt group, X is a halogen atom, m is a number from 1 to 4, and n is an integer of 1 or 2, and the aromatic nucleus may have a substituent other than -SO ₃ M. ), and may contain other ingredients such as a bactericide, a PH regulator, a fragrance, a surfactant, a chelating agent, etc., and can be used as an aqueous solution or It is used after being shaped into a solid material such as powder, granules, or pellets together with appropriate excipients and, if desired, fillers. In the present invention, the structure of the indigo colorant molecule represented by the general formula () may be symmetrical or asymmetrical, but the structure of the indigo colorant molecule represented by the general formula () to
The aromatic nucleus in the molecule (through parentheses) must have 1 to 4 groups of alkali metal sulfonic acid salts, and examples of the alkali metal include potassium and sodium. From the viewpoint of production and use of colorants, sodium is often preferred. Further, the aromatic nucleus in the molecule may have a substituent other than the -SO ₃ M group. That is, carbon number 1-3
In addition to lower alkyl groups and lower alkoxy groups, especially methyl and methoxy groups, amino groups, hydroxyl groups,
It may have 1 to 3 of one or more types of halogen atoms such as chlorine and bromine as substituents. Regarding the introduction of the group of the alkali metal sulfonic acid salt in general formulas () to (), the sulfonic acid group may be introduced into the intermediate during the production of the colorant, and the sulfonic acid group may be introduced into the intermediate having the same skeleton as the colorant. A sulfonic acid group may be introduced by sulfonating the base dye. Furthermore, m does not necessarily have to be an integer, and m is a parent dye having the same skeleton but a different number of −SO ₃ M
Mixtures of colorants having groups may also be suitably used in the present invention. Some of the colorants represented by the above general formula used in the present invention are new compounds. Depending on its structure, the coloring agent represented by the above general formula exhibits a wide range of colors from red to blue to green when dissolved in water. In the present invention, a reddish-blue to greenish-blue coloring agent is usually used in order to give a visually clean and refreshing feeling to the washing water. For other reasons, if necessary, a red or green coloring agent may be used in combination. These colorants can also be used alone if desired. Next, preferred examples of the colorant used in the present invention will be shown. In the colorant composition according to the present invention, the concentration of the colorant represented by the above general formula in the washing water is 0.0015 to
It is used in a range of 0.03% (% indicates weight %; the same applies hereinafter), preferably in the range of 0.003 to 0.015%, depending on the visual effect to give the desired cleanliness and the effect of hiding human waste. Its usage is determined. The coloring agents represented by the above general formulas that are preferably used in the present invention are relatively easily produced or industrially and economically available, such as C.1.No.73015. It is also used as a food coloring and is highly safe for the human body. Moreover, these colorants are chlorine-based decolorizers,
For example, since it is easily and completely decolored by chlorine gas or an aqueous hypochlorite solution, the colorant composition according to the present invention containing the colorant represented by the general formula above, including the colorant exemplified above, can be used in washing water. Not only does it give a clean and refreshing feeling by coloring it, but it also hides the unpleasant color of human waste, and if washed wastewater is treated with a small amount of the above-mentioned chlorine-based treatment agent after the human waste has been treated, it can be immediately and completely decolorized. It is something that Furthermore, these colorants are not only treated with the above-mentioned chlorine-based treatment agents, but also microbial treatment that is carried out in normal sewage treatment, rather than physical decolorization due to adsorption, aggregation, etc. It is chemically decomposed and completely decolored. The above-mentioned treatment using microorganisms includes treatment using activated sludge method, sprinkled bed method, etc. using aerobic bacteria in the presence of oxygen, and treatment using anaerobic digestion tank method using anaerobic bacteria. Examples include Zooglaea bacteria and Sphaerotails bacteria, and examples of anaerobic bacteria include Pseudomonas bacteria and Methanobacteria. Therefore, if wash water colored with the above colorant or wash water colored with a colorant composition containing the above colorant is treated with the above chlorine decolorizer and/or microorganisms, it will be possible to treat human waste and sewage. There is no possibility that colored wastewater will flow out afterwards. In order to color the cleaning water with the colorant according to the present invention, the colorant represented by the general formula described above may be directly added to the cleaning water and dissolved, or together with this colorant, a sterilizer, a disinfectant, an interface A cleaning composition containing an activator, a chelating agent, a perfume, etc. may be added to the cleaning water and dissolved in the form of an aqueous solution or a shaped solid such as a powder or pellet. When the colorant composition of the present invention is used as an aqueous solution, a certain amount is mixed into the washing water manually or automatically at the time of use, such as when washing a toilet bowl. In the case of circulating toilet cleaning, etc., the colorant composition of the present invention is made into a powder form, or formed into water-soluble pellets using an excipient, and immersed in a washing water tank in advance to dissolve a predetermined amount. Sometimes it is convenient to use it in this way. The germicidal disinfectant that can be contained in the colorant composition of the present invention is not particularly limited as long as it does not destroy the colorant, but quaternary ammonium salts include benzyltrimethylammonium chloride, dodecyltrimethylammonium chloride, dodecyldimethylbenzyl Ammonium chloride, dodecylpyridinium chloride, dichlorobenzylmethyldodecyl ammonium chloride, Aerosol
M, i.e. Examples include octylphenoxyethoxyethyldimethylbenzyl ammonium chloride, and organic sulfur fungicides such as tetramethylthiuram, sodium methylthiocarbamate,
Ammonium methylthiocarbamate, N-(p
-phenol)dimethylthiocarbamate, 1,
2-benziisothiazolone, methylenebisthiocyanate, etc., and organic nitrogen disinfectants such as sodium azide, N-(p-phenol)trichloroalkyl cyanide, nitrofuran, halogenacetamide, 1,3-dinonylbenzimidazolium bromide , 1-(2-hydroxyethyl)-1
-benzyl-2-tridecylimidazolium, tris(hydroxymethyl)nitromethane, 1-N
-piperazino-2-nitropropylbenzene,
Examples include 2,6-bisdimethylaminomethylcyclohexanone. In addition, amphoteric fungicides such as dodecyldi(aminoethyl)glycine, β-alkylaminopropionate, dodecyldimethylbetaine, dodecylmethylbenzylbetaine, cetyldimethylbetaine, pentachlorophenol, trichlorophenol, o-benzyl-p-chloro Examples include chlorine-based disinfectants such as phenol and 2,2'-thiobis(4,6-dichlorophenol), and organotin-based disinfectants such as tributyltin oxide. These sterilizing disinfectants are used alone or as a mixture of two or more, and some of these sterilizing disinfectants have stronger sterilizing power on the acidic or alkaline side. The type and concentration of the agent are advantageously selected, and if necessary, for example, soda ash, tetrasodium pyrophosphate, sodium tripolyphosphate, acetic acid, sodium acetate, citric acid, sodium citrate, tartaric acid, sodium tartrate, sodium silicate, etc. PH regulators such as calcium hydroxide and sodium hydrogen carbonate are used together. Furthermore, various fragrances or deodorants can be used to prevent deodorization or impart fragrance during cleaning. For example, anisaldehyde, ethyl acetoacetate, anisole, anethole, amyl cinnamic aldehyde, methyl anthranilate, methyl benzoate, geranyl formate, cinnamic alcohol, cinnamaldehyde, terpinyl acetate, butylcyclohexyl acetate, benzyl acetate, methyl salicylate, citronellol, terpineol. , β. Examples include phenylethyl alcohol, benzyl alcohol, methylacetophenone, menthol, etc., and of course prepared fragrances can also be used. Examples of surfactants include sodium salts and potassium salts of various fatty acids, sodium alkylbenzenesulfonates, higher alcohol sulfate ester salts, α-
Examples include olefin sulfonate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene glycol fatty acid ester, propylene glycol fatty acid ester, and the like. If desired, the wash water or colorant composition may contain a chelating agent in the present invention. Examples of the chelating agent include sodium tripolyphosphate, sodium hexametaphosphate, EDTA, nitrilotriacetic acid, aminomethylene phosphonate, methylene phosphonic acid, and phosphonocarboxylate. Next, according to the present invention, excipients for shaping the cleaning composition into an appropriate shape include CMC,
Examples include CMS, PEG, PPG, PVA, and mixtures thereof, and excipients may contain fillers or extenders in addition to the above-mentioned bactericides, surfactants, fragrances, PH regulators, and chelating agents. can be used. Examples of the filler include sodium sulfate, potassium sulfate, ammonium sulfate, and urea. Taking the case of using PEG as an excipient as an example, PEG having a degree of polymerization of preferably about 6,000 to 20,000 is heated and melted, and according to the present invention, a coloring agent, a bactericidal agent, and further, if necessary, are added to the melted PEG. Fillers, surfactants, fragrances, etc. are added, thoroughly stirred to obtain a uniform composition, and then cooled, solidified, and molded. still,
When using a liquid flavor, for example, a water-soluble solid, such as a eutectic solidified product of the flavor and PEG or alkylphenol with polyethylene oxide, etc., is formed in advance, and this is used at the time of shaping. Good too. Synthesis examples of the colorant used in the present invention are shown below. In addition, in the following, all parts indicate parts by weight. Synthesis Example 1 (Synthesis of Colorant (1)) 10 parts of Indigo (Mitsui Toatsu Chemical Co., Ltd.) was dissolved in 180 parts of concentrated sulfuric acid and stirred at room temperature for about 1 hour.
When a drop of this reaction product was dropped into a test tube containing hot water at 70°C, it turned purple. The reaction product was cooled by pouring it into water, and the precipitate was separated. The cake thus obtained was dissolved in a small amount of hot water, neutralized with sodium carbonate and cooled. The precipitate was separated, washed with a small amount of water, and then dried to obtain 12 parts of colorant (1). This colorant gave a blue color when dissolved in water.
When this colorant was purified and subjected to elemental analysis, the analytical value of sulfur was 8.9% (theoretical value 8.79%). Synthesis Example 2 (Synthesis of the colorant (2)) 5-sulfophenylglycine-2-carboxylic acid
10 parts and 30 parts of sodium hydroxide powder were mixed, heated to a temperature of 220 to 230°C for 3 hours while blocking air, and then cooled. The obtained melt was crushed and dissolved in 300 parts of an aqueous solution containing 40 parts of ammonium chloride. Air was blown into the solution to oxidize the product and precipitate the colorant (2). The yield after removal and drying was 5 parts. This colorant (2) dissolved in water and exhibited a greenish-blue color. The elemental analysis value of sulfur in colorant (2) purified from boiling water is 13.6% (theoretical value 13.73).
%). Synthesis Example 3 (Synthesis of the colorant (3)) 10 parts of Indigo (Mitsui Toatsu Chemical Co., Ltd.) was dissolved in 180 parts of concentrated sulfuric acid, stirred for 2 hours while heating in a water bath, and then poured into water. Almost neutralized with sodium carbonate. Remove the precipitate, dry it, and add the colorant (3)
I got 7 copies. This colorant (3) was dissolved in water and exhibited a blue color. In addition, elemental analysis of the colorant (3) purified with boiling water showed that sulfur was 13.80%. Synthesis Example 4 (Synthesis of the colorant (6)) 10 parts of 4,4'-dichloroindigo was dissolved in 180% 100% sulfuric acid.
colorant (6) in the same manner as in Synthesis Example 3.
Got 5.5 copies. This colorant (6) exhibited color when dissolved in water. In addition, the elemental analysis value of sulfur was 12.2% (theoretical value 11.98%). Synthesis Example 5 (Synthesis of Colorant (9)) While cooling, add 10 parts of 5,5'-dibromoindigo to 200 parts of 5% oleum and dissolve.
5 parts of colorant (9) was obtained in the same manner as above. This coloring agent (9) exhibited color when dissolved in water. In addition, the elemental analysis value of sulfur was 10.38% (theoretical value 10.25%). Synthesis Example 6 (Synthesis of the colorant (11)) While cooling on ice, add 5, 6,
10 parts of 5',6'-dibenzothioindigo was added and dissolved, and the mixture was reacted at 100°C. Thereafter, the same treatment as in Synthesis Example 3 was carried out to obtain 10 parts of colorant (11). This colorant (11)
When dissolved in water, it took on a greenish-gray color. Elemental analysis reveals 23.15% sulfur and approximately 2.5 sodium sulfonate bases per molecule of colorant (11). Synthesis Example 7 (Synthesis of the colorant (15)) 2,5-dichloro-7-methoxy-4-methyl-3-pseudoindone and 4-chloro-1-
Naphthol was condensed in chlorobenzene according to a conventional method to obtain CIVat Blue 8 (CI73800).
10 parts of this dye was dissolved in 180 parts of 20% oleum,
The same treatment as in Synthesis Example 3 was carried out to obtain 12 parts of colorant (15). This colorant (15) exhibits a blue color when dissolved in water, and the elemental analysis value of sulfur is 6.65% (theoretical value
6.55%). Synthesis Example 8 (Synthesis of the colorant (16)) 10 parts of 5-hydroxy-7-sulfo-2-naphthylglycine was dissolved in 60 parts of concentrated sulfuric acid at 100°C.
After heating to ℃ to carry out the cyclization reaction, cooling,
It was placed in ice water. After washing the precipitate with ice water and neutralizing the cake-like material with sodium carbonate, it was once dissolved in hot water and cooled again. The precipitate was separated, washed with water, and dried to obtain 15 parts of colorant (16). This colorant (16) was dissolved in water to give a green color, and elemental analysis of sulfur in the product purified several times from water was 10.62% (theoretical value 10.70%). Examples are given below to explain the present invention in more detail, but the present invention is of course not limited to these. Example 1 (Production of detergent composition) 5 parts of water were added to 88 parts of PEG (degree of polymerization 6000) and melted by heating, and 4 parts of the colorant (2) and 5 parts of perfume were added and dissolved and dispersed. This was placed in a cylindrical glass bottle, cooled and solidified to produce a solid detergent composition according to the present invention. This is used for household flush toilets.
It was immersed in a 20 capacity washing water tank to obtain green-blue washing water. Similarly, the colorant (10) 5 parts, (11) 6.5 parts,
A solid detergent composition was obtained using 6.5 parts of (13) or 7 parts of (16), respectively. All of these gave blue to blue-green washing water when immersed in the washing water tank in the same manner as described above. Example 2 (Production of cleaning composition) Benzyltrimethylammonium chloride 20
50 parts of EDTA, 10 parts of sodium phosphate, 100 parts of sodium sulfate, 5 parts of fragrance, 5 parts of nonionic surfactant, and 10 parts of the colorant (2) above were mixed to form a powder, which was wrapped in PVA film. , a cleaning composition to be immersed in circulating cleaning water. Example 3 (Production of cleaning composition) 60 parts of PEG (degree of polymerization 6000), 20 parts of urea, 5 parts of benzyltrimethylammonium chloride, 5 parts of anhydrous sodium acetate, 3 parts of sodium phosphate, 0.5 parts of the above colorant (6) 1 part, 5 parts of perfume, and 7 parts of water were treated in the same manner as in Example 1 to obtain a solid cleaning composition. When this was immersed in a washing water tank, it provided blue germicidal washing water. Example 4 (Production of cleaning composition) Benzyltrimethylammonium chloride 12
50 parts of urea, 5 parts of sodium phosphate, 3 parts of fragrance
3 parts of the colorant (10), 0.3 parts of the colorant (12) and 10 parts of PEG (degree of polymerization 10000) were mixed and melted,
After cooling and solidifying, it was crushed to obtain a powdered cleaning composition. For example, this water is dissolved in approximately 30% water to provide cleaning water, which is circulated and used. Example 5 (Decolorization test) Using various colorants, cleaning compositions were manufactured according to the following formulations, and each was dissolved in water for 10 minutes.
of washing water was obtained. Benzyltrimethylammonium chloride
18.6g Urea 35.7g Sodium phosphate 15.0g Fragrance 5.0g PEG (degree of polymerization 10000) 7.0g Colorant Postscript First, in the above formulation, the cleaning composition containing 2.5g of colorant (10) was used for the above cleaning. After taking 100 c.c. of water, adding 100 c.c. of human urine and leaving it to stand, a decolorization test with a 0.05% sodium hypochlorite aqueous solution was performed. Completely bleached. Note that the concentration of hypochlorite in this case corresponds to 39.4 ppm. On the other hand, in the above formulation, when 1.0 g of methylene blue (CI52015) is used as the colorant, 250 c.c. of 0.05% sodium hypochlorite aqueous solution is used.
Even when added, the colorant was not bleached. Acid Brilliant Blue AF (C.
I.42080), Kayaras Supra Blue FFR6 (C.
The same result was obtained when a detergent composition containing 1.0 g of each of I.51320) was used. In addition, in the case of a cleaning composition containing 1.0g of Nichiron Piure Blue 7G, add 300% of 0.05% sodium hypochlorite aqueous solution.
Even with the addition of cc, the colorant was not bleached. Example 6 (Decolorization test) In Example 5, the colorant (3) was used as the colorant.
Dissolve the detergent composition containing 2.5g in water to give 0.25g.
%, 0.15%, 0.075%, 0.025% and 0.0125%, respectively. The test was based on JIS K0102. Next, add 400ml of washing water of each concentration above to 1
Activated sludge (obtained from Sakai City Sewage Treatment Plant, MLSS8600g/ml,
Add 200ml of COD2400g/ml), add standard substances glucose and glutamic acid, and calculate BOD to 6100.
Samples were prepared so that Immediately after preparation, 1 day, 2 days, and 7 days later, the contents were collected from each beaker, and after centrifugation and filtration, the absorbance of the filtrate was measured at the maximum absorption wavelength of 615 mμ of the colorant (3) using water as a control liquid. The decolorization of the colorant by activated sludge was tested by measuring the rate. As shown in the table below, when the detergent composition concentration was 0.025%, the color was removed after only 2 days.

[Table] However, for comparison, when cleaning water containing 1.0 g of Nichiron Piure Blue 7G as a coloring agent was tested in the same manner as above, activated sludge bacteria were detected even when the cleaning composition concentration was 0.0125%. No decolorization of the colorant itself was observed.

Claims (1)

[Claims] 1. General formula (However, A and B each independently represent a carbonyl group and Y or Z with a 1,2-phenylene group,
An aromatic group selected from the group consisting of 1,2-naphthylene group, 2,3-naphthylene group and 1,8.naphthylene group, Y and Z each independently represent -NH- and -S- _-SO3M is a group of sulfonic acid alkali metal salt on A and/or B, m is a number from 1 to 4, and A and B are substituents other than _-SO3M . It may have. ) A cleaning liquid coloring composition comprising at least one colorant represented by: 2. The composition for coloring a cleaning liquid according to claim 1, which contains one or more additives selected from the group consisting of a disinfectant, a PH regulator, a fragrance, a surfactant, and a chelating agent. thing. 3. The composition for coloring a cleaning liquid according to claim 1 or 2, characterized in that it is shaped by an excipient. 4 A general formula selected from the group consisting of (where A is a carbonyl group and Y is a 1,2-
Phenylene group, 1,2-naphthylene group, 2,3-
An aromatic group bonded in a form selected from the group consisting of a naphthylene group and a 1,8-naphthylene group, Y is -
a group selected from the group consisting of NH- and -S-, -
SO ₃ M is a sulfonic acid alkali metal salt group on the aromatic nucleus in the molecule, X is a halogen atom, m is a number from 1 to 4, and n is an integer of 1 or 2, and the aromatic nucleus is -
It may have a substituent other than SO ³ M. ) A composition for coloring a cleaning liquid, characterized by containing at least one colorant represented by: 5. The cleaning liquid coloring according to claim 4, which contains one or more additives selected from the group consisting of disinfectants, PH regulators, fragrances, surfactants, and chelating agents. Composition for use. 6. The composition for coloring a cleaning liquid according to claim 5 or 6, characterized in that it is shaped by an excipient.