JPH09132797A - Mildew stain detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition with no generation of toxic chlorine, safely usable even at closed sites, having no adverse effects on human health and the environment, and extremely high in mildew-removing effect, comprising a specific compound and a complex composed of a metal and a multi-site ligand. SOLUTION: This mildew stain detergent composition comprises (A) at least one compound selected from hydrogen peroxide, alkali metal carbonate hydrogen peroxide adducts (pref. sodium carbonate hydrogen peroxide adduct) and perborates (pref. sodium perborate) and (B) a complex composed of (i) a metal selected from group 3 to group 12 metals and (ii) a multi-site ligand [e.g. 2,6-bis(oxazolyl)pyridine-dichloromanganese(II) complex], and pref. furthermore, (C) a surfactant. It is preferable that the content of the component A be 0.0001-20wt.% in terms of the total concentration of the active oxygen in the composition and the content of the component B 0.01-1000wt.ppm in the composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel mold and stain cleaning agent.

[0002]

2. Description of the Related Art Tile surfaces in bathrooms, tile joints and ceilings, sinks in kitchens, triangular corners, and other places where there is a lot of contact with moisture or humidity, and indoor floorboards, tatami mats, furniture, etc. However, black mold develops in places with relatively high humidity. When cleaning stains caused by these black molds, it is difficult to remove the mold stains even if a detergent or cleanser containing a surfactant as a main component is used. Usually, a fungicide cleaner containing hypochlorite as a main component is used to remove these fungal stains. However, although hypochlorite is stable at room temperature in an aqueous solution containing a high concentration of caustic soda, it decomposes when the concentration of caustic soda becomes low or the temperature rises, and toxic chlorine gas is generated. Also,
Even if the alkaline detergent is mistakenly mixed with the acidic detergent, the hypochlorite is decomposed by the neutralization reaction to generate chlorine gas. In fact, it is well known that accidents due to the generation of chlorine gas have been reported during the use of hypochlorite type mildew cleaning agents. Furthermore, the mildew stain cleaning agent containing hypochlorite as a main component has a strong chlorine-based odor, which makes it resistant to use in a small room such as a bathroom.

Therefore, in recent years, a non-chlorine anti-mold stain cleaning agent has been investigated. For example, in Japanese Patent Laid-Open No. 60-1299,
A fungicide containing an inorganic peroxide together with hydrogen peroxysulfate is disclosed, and JP-A-60-233.
No. 200 discloses a fungicide containing an inorganic chloride and a magnesium compound or a copper compound together with hydrogen peroxysulfate. However, hydrogen peroxysulfate is not practical because it has a risk of igniting by violently reacting with a combustible substance, and various uses of hydrogen peroxide compounds, which are milder oxidants, have been studied.

For example, JP-A-59-164400 discloses that a mildly acidic liquid detergent containing hydrogen peroxide, a certain organic acid, a certain surfactant and water is effective for mold removal. In addition, organic polymers such as vinyl-based synthetic polymers (JP-A-61-158907), amorphous silica (JP-A-61-1549496), carbon number 8-18
Anhydrous saturated fatty acid (JP-A-62-1795), and a water-soluble or water-dispersible acrylonitrile homopolymer or a copolymer of acrylonitrile and one or more monomers copolymerizable with acrylonitrile (JP-A-62-1945). No. 72798) and a peroxide such as hydrogen peroxide are disclosed. in this way,
Some anti-mildew detergents containing peroxides and various additives have been investigated, but none of them have sufficient anti-mildew removal effect and have not yet been put to practical use.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a mildew stain cleaner which does not generate toxic chlorine gas and is therefore highly safe and highly effective.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve these objects, the present inventors have found that hydrogen peroxide,
At least one compound selected from the group consisting of hydrogen peroxide adducts of alkali metal carbonates and perborate salts,
A composition containing a complex of a metal and a polydentate ligand selected from the group consisting of Groups 3 to 12 of the Periodic Table is very effective for removing stains on mold. Found
The present invention has been completed.

That is, the present invention comprises (a) at least one compound selected from the group consisting of hydrogen peroxide, hydrogen peroxide adducts of alkali metal carbonates and perborate, and (b) a periodic table. The present invention provides a mold and stain cleaning composition comprising a complex of a metal selected from the group consisting of Groups 3 to 12 and a polydentate ligand.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION (a) At least one compound selected from the group consisting of (a) hydrogen peroxide, a hydrogen peroxide adduct of an alkali metal carbonate and a perborate, which is one of the main components in the present invention, is , Each may be used alone, or may be used in combination. Specifically, in addition to hydrogen peroxide, examples of hydrogen peroxide adducts of alkali metal carbonates include sodium carbonate hydrogen peroxide adducts and potassium carbonate hydrogen peroxide adducts. Examples include sodium perborate, sodium perborate monohydrate, sodium perborate tetrahydrate, and the like.

At least one compound selected from the group consisting of (a) hydrogen peroxide, hydrogen peroxide adducts of alkali metal carbonates, and perborate can be used as it is as a pure product. It is preferably used as a solution of a solvent such as alcohol or alcohol, and particularly preferably used as an aqueous solution. Further, at least one compound selected from the group consisting of (a) hydrogen peroxide, hydrogen peroxide adduct of alkali metal carbonate and perborate (hereinafter
It is abbreviated as component (a). Is preferably added so that the total concentration of available oxygen contained in the composition is 0.0001 to 20% by weight, and more preferably 0.001 to 20% by weight.
It is in the range of 1 to 10% by weight.

The other main component in the present invention
(b) A complex of a metal selected from the group consisting of Groups 3 to 12 of the periodic table and a polydentate ligand (hereinafter abbreviated as component (b)) is, for example, cerium, titanium or vanadium. , Niobium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, cobalt, rhodium, nickel,
A complex of a metal and a polydentate ligand selected from the group consisting of palladium, copper, silver, and zinc, and preferably cerium, titanium, vanadium, manganese, rhenium,
Iron, ruthenium, cobalt, nickel, and a complex of a metal and a polydentate ligand selected from the group consisting of copper, more preferably, a metal selected from the group consisting of cerium, titanium, rhenium and ruthenium. It is a complex with a polydentate ligand. The polydentate ligand has two or more heteroatoms selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur, and forms a complex by coordinating with a metal through at least two of the heteroatoms. It is an organic compound that can be produced, for example, G.WILKINSON ed. "COMPREHENSIVECOORDINATION CHEMI
Among the ligands exemplified in STRY, Volume 2 "(published by PERGAMON PRESS), those which meet the above-mentioned conditions. Preferred polydentate ligands are from the group consisting of nitrogen, phosphorus, oxygen and sulfur. An organic compound having two or more selected hetero atoms, capable of forming a complex by coordinating with a metal through at least two of the hetero atoms, and at least one hetero atom coordinating with the metal being a nitrogen atom Is.

Specifically, for example, 1,4,7-trimethyldiethylenetriamine, 1,1,4,7,7-pentamethyldiethylenetriamine, 1,1,5,9,9-pentamethyldipropylenetriamine, N- (2-aminoethyl) -1,3-propanediamine, 3,3'-diamino-N-methyldipropylamine, 1,1,4,7,
10,10-hexamethyltriethylenetetramine,
N, N'-bis (2-aminoethyl) -1,3-propanediamine, pentaethylenehexamine, or 3,
Polyalkylene polyamines such as 3′-iminobispropylamine, 1,4,7-triazacyclononane, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,5. 9-triazacyclododecane,
1,5,9-trimethyl-1,5,9-triazacyclododecane, 1,4,8,11-tetraazacyclotetradecane, 1,4,8,11-tetramethyl-1,4
8,11-tetraazacyclotetradecane, 1,4
8,12-Tetraazacyclopentadecane, 1,4
7,10-Tetraazacyclododecane, 1,4,7,1
0,13,16-hexamethyl-1,4,7,10,1
3,16-hexaazacyclooctadecane, or 1,
Cyclic polyamines such as 4,8,12-tetraazacyclopentadecane, 2-aminoethanol, 2-dimethylaminoethanol, 1-amino-2-propanol, diethanolamine, serinol, or 2- (2
-Aminoethylamino) -ethanol and other amino alcohols such as glycine, alanine, iminodiacetic acid,
An amino acid or peptide compound such as N, N-dimethylglycine, proline or glycylglycine,
Dimethylglyoxime, 1,2-cyclohexanedionedioxime, alpha-furyldioxime, 3-phenylimino-2-butanone oxime, 3- (2-aminoethylimino) -2-butanone oxime or 3- (2-
Oximes such as pyridylethylimino) -2-butanone oxime, N-salicylidenecyclohexylamine, N, N′-disalicylideneethylenediamine, N,
N '-(1,2-ethanediylidene) biscyclohexylamine, glyoxalbis (2-hydroxyanil), N, N'-bis (salicylidene) ethylenediamine, or N, N'-bis (salicylidene) -1,3-
A Schiff base compound such as propanediamine, or 2,2′-dipyridyl, 1,10-phenanthroline,
Aromatic polyamines such as 8-hydroxyquinoline, 2- (2-piperidinoethyl) -pyridine, 2- (2-methylaminoethyl) -pyridine, hydrotris (1-pyrazolyl) borate, or 2,6-bis (oxazolyl) pyridine Kind of things.

The metal and the polydentate ligand are 1: 0.2 to 1: 3 (molar ratio), preferably 1: 0.3 to 1:
It forms a complex at a ratio of 2.0 (molar ratio), and may have other monodentate ligands, counter ions, and the like as long as the polydentate ligand is bound to the metal within this range. These complexes may be polynuclear complexes of two or more kinds of metals, complexes having two or more kinds of polydentate ligands, and a plurality of complexes may be mixed and used. As these complexes, for example,
The Chemical Society of Japan, "Experimental Chemistry Course, 4th Edition", Volume 17, 2
The complex etc. which are described in pages 17-407 and 477-512 are mentioned. These complexes are preferably prepared separately and isolated and used as a single product or a mixture, but those prepared in a solution such as an aqueous solution may be used as they are without isolation.

These complexes have a metal atom concentration of
Usually, 0.01 to 1000 ppm by weight, preferably 0.1 to 100 ppm by weight, is added to the composition. In the mold stain cleaner of the present invention, it is preferable to contain a surfactant in order to retain the cleaner composition on the mold stain surface for a long time and more effectively exhibit the mold stain removing effect. As the surfactant, an anionic surfactant,
Nonionic, cationic or zwitterionic surfactants can be used.

Examples of the anionic surfactant include higher fatty acid salts having 10 to 22 carbon atoms, alkylbenzene sulfonates having 10 to 22 carbon atoms, sulfuric acid ester salts of higher alcohols having 10 to 22 carbon atoms, and 10 carbon atoms.
To C22 alkyl ether sulfate, C10 to C22 α-olefin sulfonate, C10 to C22 alkane sulfonate, and the like.
Examples of the salt include sodium, potassium, ammonium or substituted ammonium salt and the like.

Examples of the nonionic surfactant include higher alcohols having 8 to 24 carbon atoms and 8 to 2 carbon atoms.
4 fatty acids, polyethylene glycol or polypropylene glycol with a degree of polymerization of 3 to 100 and 10 carbon atoms
Ether with alcohol of 22 to 22 or degree of polymerization 3
Examples thereof include esters of polyethylene glycol or polypropylene glycol of 1 to 100 and carboxylic acid of 10 to 22 carbon atoms.

These surfactants are usually used in the composition.
The content is 0% by weight or less, preferably 0.1 to 5% by weight. In addition to the above-mentioned components, various additives may be appropriately added to the mold and stain cleaning agent of the present invention, if necessary. Examples of these additives include buffers for adjusting pH, organic and inorganic builders for further enhancing the effect of removing mold and stains, chelating agents and antioxidants for improving the stability of aqueous hydrogen peroxide solution. In addition to thickeners and hydrotropes for increasing the viscosity of the composition and making it easier to use, abrasives, penetrants, water-soluble solvents, solubilizers, pigments, dyes, fragrances and the like can be mentioned. Further, in order to stabilize the complex and further enhance the mold cleaning effect, the same polydentate ligand used in the complex can be further added. Furthermore, an activator which has been publicly known in the art for an oxygen-based mold stain remover can be used in combination.

Examples of the buffering agent include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal silicates such as sodium silicate, and sodium sulfate. Alkali metal sulfate, alkali metal bicarbonate such as sodium bicarbonate, alkali metal pyrophosphate such as sodium pyrophosphate, alkali metal tripolyphosphate such as sodium tripolyphosphate, ammonium hydroxide, ammonium carbonate, ammonium silicate, ammonium sulfate Alternatively, an inorganic ammonium salt such as ammonium bicarbonate may be used. These buffers are added to the p of the detergent composition.
It is compounded so as to adjust H to 4 to 13, and usually 20% by weight or less, preferably 10% by weight or less in the composition.

Examples of the builder include sodium sulfate, sodium silicate, sodium tripolyphosphate, sodium ethylenediaminetetraacetate, sodium nitrilotriacetate and the like. Other examples include phosphate,
Examples thereof include polyacrylic acid salts, polycarboxylic acid salts, zeolites and the like. These builders have 50
It is mixed in an amount of not more than 30% by weight, preferably not more than 30% by weight.

Examples of the chelating agent include phosphoric acid compounds such as phytic acid or alkali metal salts thereof, ethane-1,1-diphosphonic acid and ethane-1-hydroxy-.
1,1-diphosphonic acid or ethanehydroxy-1,
Phosphonic acids such as 1,2-triphosphonic acid or alkali metal salts thereof, phosphonocarboxylic acids such as 2-phosphonobutane-1,2-dicarboxylic acid or 1-phosphonobutane-2,3,4-tricarboxylic acid or alkalis thereof Examples thereof include metal salts, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, and alkali metal salts thereof. These chelating agents are incorporated in the composition in an amount of 5% by weight or less, preferably 1% by weight or less.

Examples of antioxidants include phenacetin, butylated hydroxyanisole (BHA), and 2,6-ditertiarybutyl-4-methylphenol (BHT). These antioxidants are
5% by weight or less, preferably 1% by weight or less is blended in the composition.

Examples of the thickener include polyacrylic acid salts, acrylic acid-maleic acid copolymers, carboxymethylcellulose derivatives, synthetic polymers such as methylcellulose or hydroxymethylcellulose, natural polymers such as xanthan gum, guar gum or kerzan, or Examples thereof include water-swelling clay minerals such as montmorillonite and veegum. These thickeners are usually added to the composition in an amount of 30% by weight or less, preferably 20% by weight or less.

Examples of the hydrotrope agent include diols having 2 to 6 carbon atoms such as ethylene glycol or propylene glycol, alkenyl succinic acid having 6 to 18 carbon atoms or an alkali metal salt thereof, ortho or paratoluene sulfonate, or Examples thereof include alkali metal salts thereof, ortho or para-xylene sulfonic acid, alkali metal salts thereof and the like. These hydrotropes are usually incorporated in the composition in an amount of 30% by weight or less, preferably 20% by weight or less.

Examples of the water-soluble solvent include monohydric alcohols such as methanol, ethanol or propanol, dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol or butylene glycol, trihydric alcohols such as glycerin, or ethylene glycol monomethyl ether. Alternatively, mono- or diethers of dihydric or trihydric alcohols such as diethylene glycol monomethyl ether can be used. These water-soluble solvents are added to the composition in an amount of 60% by weight or less, preferably 20% by weight or less.

Examples of the solubilizer include sodium paratoluene sulfonate, sodium xylene sulfonate, urea and the like. These solubilizers are incorporated in the composition in an amount of 10% by weight or less, preferably 5% by weight or less. Further conventionally known activators include nitriles such as acetonitrile or phthalonitrile, O-acetylated products such as glucose pentaacetate or acetoxybenzene sulfonate, N, N, N ', N'-tetraacetylethylenediamine or N, Examples thereof include N-acylated products such as N-diacetylaniline, and acid anhydrides such as phthalic anhydride or succinic anhydride. These activators are incorporated in the composition in an amount of 30% by weight or less, preferably 20% by weight or less.

In using the mold stain cleaning composition of the present invention, when the component (a) is used as a solution such as an aqueous solution, in order to sufficiently exert the cleaning effect, the solution of the component (a) is solid or solid. It is preferable that after the component (b) of the solution is blended, it is immediately brought into contact with the mold stain surface. Or
It is also possible to bring the component (a) and the component (b) of the solution into contact with the mold-fouling surface individually and to exert the effect while mixing them directly on the mold-fouling surface. Further, when the component (a) is used as a solid, the component (b) of the solution can be blended and then immediately contacted with the mold surface, or the solid component (b) can be blended in advance. Alternatively, a solvent such as water may be added thereto to adjust the concentration, and then the surface may be immediately brought into contact with the mold stain surface. Among these, it is preferable to separately enclose the component (a) and the component (b), mix them, and immediately bring them into contact with the mold surface, and the most preferable use method is to incorporate a surfactant. Was
The solid solution or the component (b) of the solution is blended with the aqueous solution of the component (a), and this is immediately brought into contact with the mold stain surface. When blending additives, etc., beforehand (a) component or (b)
It is preferable to mix the above components with each other, but it is also possible to mix three or more of them at the same time and to immediately bring them into contact with the mold stain surface. As a method for bringing the mold stain cleaning agent into contact with the mold stain surface, a spraying method using a spray container or a coating method can be applied.

[0026]

The present invention will be described in more detail with reference to the following examples. <Production of model black mold / urethane carrier> A foamed urethane carrier (5 mm cube) was attached to Aspergil Niger.
glucose peptone medium 10 with spores of
It was dipped in ml and cultured for 2 weeks under the conditions of a temperature of 25 ° C. and a humidity of 90% or more to prepare a urethane carrier on which black mold spores were formed.

Example 1 One model black mold / urethane carrier was inserted into a 20 ml test tube, and a commercially available 31.0% by weight hydrogen peroxide aqueous solution (manufactured by Mitsubishi Gas Chemical Co., Inc.) was added to the ion-exchanged water. An aqueous solution (pH = 4.8) diluted with 6.0% to 5.0% by weight.
0 gram was added, and 50 weight pp of 2,6-bis (oxazolyl) pyridine-dichloro-manganese (II) complex was further added.
5.0 g of an aqueous solution was added, and the mixture was left for 2 hours. The compounding amount of the composition evaluated as the mildew stain cleaner is 3.0% by weight of hydrogen peroxide and 25 ppm by weight of manganese complex. After standing for 2 hours, the urethane carrier was taken out with tweezers and washed thoroughly with ion-exchanged water. As a result, almost no black mold was adhered to the urethane carrier, and mold stains were almost completely removed. Table 1 shows the results. The judgment standard of the mold stain removal effect was visually evaluated according to the following. Judgment Criteria A The mold stains were almost completely removed. B A little mold stain was removed. C Almost no mildew cleaning effect.

Comparative Example 1 Evaluation of mold stain cleaning ability was carried out in the same manner as in Example 1 except that the manganese complex used in Example 1 was not used. The amount of the composition evaluated as a mildew stain cleaner is 3.0% by weight of hydrogen peroxide. After leaving for 2 hours, the urethane carrier was taken out with tweezers and thoroughly washed with ion-exchanged water. There was almost no change in the properties and amount of black mold attached to the urethane carrier, and no mold stain cleaning effect was observed. .

Comparative Example 2 Evaluation of mold stain cleaning ability was conducted in the same manner as in Example 1 except that the hydrogen peroxide used in Example 1 was not used. The compounding amount of the composition evaluated as a mildew stain cleaner is 25 ppm by weight of the manganese complex. After leaving for 2 hours, the urethane carrier was taken out with tweezers and washed thoroughly with ion-exchanged water. The properties and amount of black mold attached to the urethane carrier did not change at all, and no mold stain cleaning effect was observed. .

Comparative Example 3 The mold stain cleaning ability was evaluated in the same manner as in Example 1 except that manganese chloride was used instead of the manganese complex used in Example 1. The compounding amount of the composition evaluated as a mildew stain cleaner is 3.0% by weight of hydrogen peroxide and 25 ppm by weight of manganese chloride. After leaving for 2 hours, the urethane carrier was taken out with tweezers and washed thoroughly with ion-exchanged water. The black mold attached to the urethane carrier was slightly lighter in color, but it did not change much before the test. No dirt cleaning effect was observed.

Example 2 According to Angew.Chem.Int.Ed.Engl., 24, p5 (1985), a binuclear copper complex [LCu (μ-O) (μ-H ₂ O) CuL] (Cl
O ₄ ) ₂ , where L is 1,4,7-trimethyl-1,4
7-triazacyclononane was synthesized.

A 20 ml test tube was charged with 1.0 g of sodium percarbonate and 0.5 g of sodium dodecylbenzenesulfonate, and ion-exchanged water was added to dilute to 5 g. An appropriate amount of 50 wt% sodium hydroxide aqueous solution was added to this solution to adjust the pH to 11.0. One black mold / urethane carrier was inserted therein, and then the above-synthesized binuclear copper complex was added to a 50 wt ppm aqueous solution of 5.0.
Added gram. The content of the composition evaluated as a mildew stain cleaner is 10.0% by weight of sodium percarbonate, 5.0% by weight of sodium dodecylbenzenesulfonate, and 25 ppm by weight of dinuclear copper complex. After standing for 2 hours, the urethane carrier was taken out with tweezers and washed thoroughly with ion-exchanged water. As a result, almost no black mold was adhered to the urethane carrier, and mold stains were almost completely removed.

Comparative Example 4 The mold stain cleaning ability was evaluated in the same manner as in Example 2 except that the binuclear copper complex used in Example 2 was not used. The compounding amount of the composition evaluated as a mildew stain cleaning agent is 10.0% by weight of sodium percarbonate and 5.0% by weight of sodium dodecylbenzenesulfonate. After leaving for 2 hours, the urethane carrier was taken out with tweezers and thoroughly washed with ion-exchanged water. There was almost no change in the properties and amount of black mold attached to the urethane carrier, and no mold stain cleaning effect was observed. .

Comparative Example 5 The mold stain cleaning ability was evaluated in the same manner as in Example 2 except that copper sulfate was used instead of the binuclear copper complex used in Example 2. The amount of the composition evaluated as a mildew stain cleaner was 10.0% by weight of sodium percarbonate, 5.0% by weight of sodium dodecylbenzenesulfonate, and 25 ppm by weight of copper sulfate. After leaving for 2 hours, the urethane carrier was taken out with tweezers and washed thoroughly with ion-exchanged water. The color of the black mold adhering to the urethane carrier became light, and some cleaning effect was observed, but it was notable No significant effect was seen. As described above, Examples 1 and 2
The results of Comparative Examples 1 to 5 are summarized in Table 1.

Example 3 JR Hartman, et.al., J. Am. Chem. Soc., 109, p7387-7396
(1987), binuclear iron complex [LFe (μ-O) (μ-O
COCH ₃ ) ₂ FeL] (PF ₆ ) ₂ , where L is 1, 4,
7-trimethyl-1,4,7-triazacyclononane,
Was synthesized. In a 20 milliliter test tube, 1.6 grams of 31% by weight hydrogen peroxide, 0.8 grams of polyoxyethylene (20) stearyl ether, and ethanol of 0.
8 g was charged, and ion-exchanged water was added to dilute to 5 g. An appropriate amount of 50 wt% sodium hydroxide aqueous solution was added to this solution to adjust the pH to 11.0. One black mold / urethane carrier was inserted therein, and then 5.0 g of a 100 wt ppm aqueous solution of the binuclear iron complex synthesized above was added. The amount of the composition evaluated as a mildew stain cleaner is
Hydrogen peroxide 5.0% by weight, polyoxyethylene (20)
The amount is 8.0% by weight of stearyl ether, 8.0% by weight of ethanol, and 50 ppm by weight of a dinuclear iron complex. After standing for 2 hours, the urethane carrier was taken out with tweezers and washed thoroughly with ion-exchanged water. As a result, almost no black mold was adhered to the urethane carrier, and mold stains were almost completely removed.

Comparative Example 6 The mold stain cleaning ability was evaluated in the same manner as in Example 3 except that the binuclear iron complex used in Example 3 was not used. The amount of the composition evaluated as a mold and stain cleaning agent was 5.0% by weight of hydrogen peroxide and polyoxyethylene (2
0) Stearyl ether is 8.0% by weight, and ethanol is 8.0% by weight. After leaving for 2 hours, the urethane carrier was taken out with tweezers and thoroughly washed with ion-exchanged water. There was almost no change in the properties and amount of black mold attached to the urethane carrier, and no mold stain cleaning effect was observed. .

Examples 4-10 Instead of the binuclear iron complex used in Example 3, Table 2
Evaluation of mold stain cleaning ability was performed in exactly the same manner as in Example 3 except that the complex shown in Table 1 was used in the blending amount shown in Table 2. The results are shown in Table 2 together with the results of Example 3 and Comparative example 6.

Example 11 In a 100 ml Erlenmeyer flask, cuprous acetate / 1
2.1 g (10.6 mmol) of the hydrate, 2.1 g (11.9 mmol) of pentamethyldiethylenetriamine and 40 ml of ethyl alcohol were charged. While stirring at room temperature, 7.11 g (42.4 mmol) of sodium hexafluorophosphate was added little by little, and a blue precipitate was formed. This was filtered with suction using a membrane filter, and a small amount of it was filtered. After washing with ethyl alcohol, it was dried under reduced pressure at 50 ° C.
3.63 grams of a blue solid was obtained.

Example 3 except that this synthesized copper complex was used in place of the binuclear iron complex used in Example 3.
Evaluation of mold cleaning ability was performed in the same manner as
The black mold on the urethane carrier was almost completely removed.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

EFFECT OF THE INVENTION The mildew stain cleaner composition of the present invention has no influence on the body and the environment, which is found in conventional hypochlorous acid type mildew stain cleaners, and does not generate chlorine gas. But it can be used safely. Moreover, the effect of removing mold stains is extremely high.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takuji Takagi 1190, Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (12)

[Claims] 1. At least one compound selected from the group consisting of (a) hydrogen peroxide, hydrogen peroxide adducts of alkali metal carbonates, and perborate, and (b) Group 3 to 3 of the periodic table. A mold and stain cleaner composition comprising a complex of a metal selected from the group consisting of Group 12 and a polydentate ligand. 2. The mold and stain cleaning composition according to claim 1, further comprising a surfactant. 3. The mold stain cleaning composition according to claim 1, wherein the hydrogen peroxide adduct of alkali metal carbonate is sodium carbonate hydrogen peroxide adduct or potassium carbonate hydrogen peroxide adduct. 4. The mold stain cleaning composition according to claim 1 or 2, wherein the perborate salt is sodium perborate, sodium perborate monohydrate or sodium perborate tetrahydrate. 5. The metal selected from the group consisting of Groups 3 to 12 of the periodic table is cerium, titanium, vanadium, niobium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, cobalt, rhodium, nickel. The mold stain cleaning composition according to any one of claims 1 to 4, which is a metal selected from the group consisting of palladium, copper, silver, and zinc. 6. A metal selected from the group consisting of Groups 3 to 12 of the periodic table is cerium, titanium, vanadium, manganese, rhenium, iron, ruthenium, cobalt,
The mold stain cleaning composition according to any one of claims 1 to 4, which is a metal selected from the group consisting of nickel and copper. 7. A metal selected from the group consisting of Groups 3 to 12 of the periodic table is cerium, titanium, rhenium,
The mold stain cleaning composition according to any one of claims 1 to 4, which is a metal selected from the group consisting of and ruthenium. 8. A complex in which the polydentate ligand has two or more heteroatoms selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur, and coordinates with a metal through at least two of the heteroatoms. The mold stain cleaning composition according to any one of claims 1 to 7, which is an organic compound capable of forming a stain. 9. A complex in which the polydentate ligand has two or more heteroatoms selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur, and coordinates with a metal through at least two of the heteroatoms. The mold stain cleaning composition according to any one of claims 1 to 7, which is an organic compound in which at least one heteroatom capable of forming a hydrogen atom and coordinating with a metal is a nitrogen atom. 10. The polydentate ligand is polyalkylene polyamines, cyclic polyamines, amino alcohols, amino acid or peptide compounds, oximes, Schiff base compounds, or aromatic polyamines. The mold stain cleaning composition according to any one of claims. 11. An effective oxygen content of a composition containing at least one compound selected from the group consisting of (a) hydrogen peroxide, hydrogen peroxide adducts of alkali metal carbonates, and perborate. Total concentration of 0.0001 to 2
0% by weight, and (b) the content of the complex of a metal and a polydentate ligand selected from the group consisting of Groups 3 to 12 of the periodic table is 0.01 to 1000 in the composition. The mold stain cleaning composition according to any one of claims 1 to 10, which has a weight ppm. 12. The method according to claim 1, wherein at least one compound selected from the group consisting of hydrogen peroxide, hydrogen peroxide adducts of alkali metal carbonates and perborate is an aqueous solution of the compound. The mold stain cleaner composition described.