JPH08311496A - Mold stain cleaning composition - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a mildew stain cleaner composition which has no effects on the body and the environment, can be used safely without generation of chlorine gas, and is extremely effective. [Structure] A mold stain cleaning composition comprising (a) hydrogen peroxide and / or an inorganic peroxide and (b) a polyhydroxycarboxylic acid.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel mold 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 occurs in places with relatively high humidity. When cleaning such stains caused by black mold, 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 mold stain cleaning agent containing hypochlorite as a main component is used to remove these mold 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, if the alkaline detergent is mistakenly mixed with the acidic detergent, the hypochlorite is decomposed by the neutralization reaction and chlorine gas is generated. In fact, it is well known that accidents due to the generation of chlorine gas have been reported during the use of hypochlorite-based mold stain cleaners. Furthermore, since the mold stain cleaning agent containing hypochlorite as a main component has a strong chlorine-based odor, it is resistant to use in a small room such as a bathroom.

For this reason, non-chlorine mold stain cleaning agents have recently been investigated. For example, Japanese Examined Patent Publication No. 63-40478 discloses that a weakly acidic liquid detergent containing hydrogen peroxide, a certain organic acid, a certain surfactant and water is effective for mold removal. In addition, Japanese Patent Publication No. 5731
No. 7, discloses a fungicide containing an inorganic peroxide together with a hydrogen peroxysulfate. In addition, organic polymers such as vinyl-based synthetic polymers (JP-A-61-1)
58907), amorphous silica (Japanese Patent Publication No. 6-3559)
8), anhydrous saturated fatty acids having 8 to 18 carbon atoms (Japanese Patent Laid-Open No. 62-62-62).
1795), and a water-soluble or water-dispersible acrylonitrile homopolymer or a copolymer of acrylonitrile and one or more monomers copolymerizable with acrylonitrile (Japanese Patent Publication No. 6-99720), and peroxide such as hydrogen peroxide. And a mold stain cleaning agent containing the same are disclosed. As described above, some mold stain cleaning agents containing a peroxide and various additives have been investigated, but none of them have sufficient mold stain removing effect and have not yet been put to practical use. .

[0004]

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

[0005]

Means for Solving the Problems As a result of intensive studies to achieve these objects, the present inventors have found that a composition containing hydrogen peroxide and / or an inorganic peroxide and polyhydroxycarboxylic acid. They have found that the product is very effective for mold stain removal, and have completed the present invention.

That is, the present invention provides (a) hydrogen peroxide and / or
Another object of the present invention is to provide a mold stain cleaner composition comprising an inorganic peroxide and (b) a polyhydroxycarboxylic acid.

As the hydrogen peroxide and / or the inorganic peroxide (a) which is one of the main components in the present invention, hydrogen peroxide or the inorganic peroxide may be used alone or in combination thereof. May be. As the hydrogen peroxide in the present invention, pure hydrogen peroxide can be used, but stability is a problem, so it is preferable to use it as a solution of a solvent such as water or alcohol.

Examples of the inorganic peroxide in the present invention include hydrogen peroxide adducts of carbonates such as sodium carbonate hydrogen peroxide adducts or potassium carbonate hydrogen peroxide adducts, sodium tripolyphosphate hydrogen peroxide adducts, and the like. Hydrogen peroxide adduct of tripolyphosphate, hydrogen peroxide adduct of pyrophosphate such as sodium pyrophosphate hydrogen peroxide, sodium perborate, sodium perborate monohydrate or sodium perborate tetrahydrate Perborate such as hydrate,
Peroxymonosulfate such as potassium peroxymonosulfate (composite salt of 2 moles of potassium peroxysulfate and 1 mole of potassium hydrogensulfate and 1 mole of potassium sulfate), or metal peroxide such as sodium peroxide or calcium peroxide Among these, sodium carbonate hydrogen peroxide adduct, sodium perborate monohydrate or sodium perborate tetrahydrate is preferable. Usually, only one type of these inorganic peroxides is blended, but it is also possible to blend two or more types in combination. The inorganic peroxide can be used as a solid as it is, but is preferably used as an aqueous solution.

Hydrogen peroxide and / or inorganic peroxide is contained in the composition at a total concentration of available oxygen of 0.0
The amount is 001 to 20% by weight, preferably 0.001 to 10% by weight.

Examples of the polyhydroxycarboxylic acid in the present invention include glycolic acid, lactic acid, 3-hydroxypropanoic acid, 2-hydroxybutanoic acid, 3-hydroxybutanoic acid, 4
-Hydroxybutanoic acid, 2-hydroxypentanoic acid, 3-hydroxypentanoic acid, 4-hydroxypentanoic acid, 5
-Hydroxypentanoic acid, 2-hydroxyhexanoic acid, 3-hydroxyhexanoic acid, 4-hydroxyhexanoic acid,
5-hydroxyhexanoic acid, 6-hydroxyhexanoic acid, 2-hydroxyheptanoic acid, 2-hydroxyoctanoic acid, 3-hydroxyvaleric acid, 2-hydroxy-2-methylpropanoic acid Carbon number such as 2-hydroxy-2-methylbutanoic acid, 2-hydroxy-2-ethylbutanoic acid, or 2-hydroxy-2-methylpentanoic acid.
To a polymer of 20 aliphatic hydroxycarboxylic acids, a copolymer thereof or a mixture of these polymers,
Preferably, polylactic acid, polyglycolic acid, poly-3-hydroxybutyric acid, poly-4-hydroxybutyric acid, poly-3-hydroxyvaleric acid, or a mixture or copolymer thereof,
More preferably, it is polyglycolic acid, polylactic acid, or a mixture thereof. As these polyhydroxycarboxylic acids, those having a polymerization degree of 2 to 10,000 are usually used.

The polyhydroxycarboxylic acid is incorporated in the composition in an amount of 0.01 to 95% by weight, preferably 0.01 to 50% by weight. In the mold stain cleaning agent of the present invention, it is preferable to contain a surfactant in order to retain the cleaning 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, a nonionic surfactant, a cationic surfactant or a zwitterionic surfactant 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, if necessary, various additives conventionally used conventionally may be appropriately added to the mold stain cleaning agent of the present invention within a range not impairing the object of the present invention. it can.

Examples of these additives include a buffer for adjusting the pH, organic and inorganic builders for further enhancing the mold stain removing effect, a chelating agent for improving the stability of the hydrogen peroxide aqueous solution, and In addition to antioxidants, thickeners and hydrotropes for increasing the viscosity of the composition and making it easier to use, it may also contain abrasives, penetrants, water-soluble solvents, solubilizers, pigments, dyes, perfumes, etc. it can.
Further, an activator which has been conventionally known in the oxygen-based mold stain removing agent 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 or potassium carbonate, alkali metal silicates such as sodium silicate, alkali metal sulfates such as sodium sulfate, alkali metal bicarbonates such as sodium bicarbonate, alkali metal pyrophosphates such as sodium pyrophosphate Examples thereof include salts, alkali metal salts of tripolyphosphate such as sodium tripolyphosphate, and inorganic ammonium salts such as ammonium hydroxide, ammonium carbonate, ammonium silicate, ammonium sulfate or ammonium bicarbonate. These buffers are blended so as to adjust the pH of the detergent composition to 4 to 13, and usually 20% by weight or less, preferably 10% by weight in the composition.
It is blended below.

Examples of the builder include sodium sulfate, sodium silicate, sodium tripolyphosphate, sodium ethylenediaminetetraacetate, sodium nitrilotriacetate and the like. Other examples include phosphates, polyacrylates and polycarboxylic acid salts. Alternatively, zeolite or the like can be used. These builders are incorporated in the composition in an amount of 50% by weight or less, preferably 30% by weight or less.

Examples of the chelating agent include phosphoric acid compounds such as phytic acid or alkali metal salts thereof, ethane-1,1-diphosphonic acid, 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 alkali metal salts thereof, ortho or paratoluene sulfonates, 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 may be mentioned. 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. Alternatively, an N-acylated compound such as N, N-diacetylaniline, or an acid anhydride such as phthalic anhydride or succinic anhydride can be used. 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 stain surface separately, and to exert the effect while directly mixing on the mold stain surface. When the component (a) is used as a solid,
After blending the component (b) of the solution, it is possible to bring it into contact with the mold stain surface immediately, or the solid component (b) is blended in advance, and a solvent such as water is added to this to obtain the concentration. It is also possible to bring the mold surface into contact immediately after the preparation.
The most preferred method of use is to add a solid or a solution (b) component to an aqueous solution of a component (a) containing a surfactant, and immediately bring this into contact with the mold stain surface.
As a method of bringing these mold stain cleaning agents into contact with the mold stain surface, not only a method of spraying using a spray container but also a method of application can be applied.

[0027]

The present invention will be described in more detail with reference to the following examples. <Preparation of model black mold / urethane carrier> A urethane foam carrier (5 mm cube) was used as an Aspergillus niger (Asperg
ill usniger) spores added glucose peptone medium 1
Immerse in 0 ml and under the conditions of temperature 25 ℃ and humidity 90% or more, 2
A urethane carrier in which black mold spores were formed by culturing for a week was prepared. <Test method for evaluation of mold stain cleaning ability> Composition 10 shown in Table 1
The model black mold / urethane carrier was dipped in milliliters, and the degree of black mold removal after standing at room temperature for 3 hours was visually evaluated by the following criteria.

[0028]

[Table 1]

In Example 1 and Comparative Example 1, no pH adjustment was performed, but in Examples 2 and 3, sodium hydroxide was used to adjust to a predetermined pH. The results are shown in Table 1. As is clear from the results, the effect of removing mold stain was extremely high as compared with the case where the detergent containing polyhydroxycarboxylic acid was not added. Judgment Criteria A Almost all mold stains were removed. B Mild stains were removed. C Almost no mold stain cleaning effect was obtained.

[0030]

EFFECTS OF THE INVENTION According to the present invention, there is no effect on the body and the environment found in the conventional hypochlorous acid type mildew stain cleaner, and since chlorine gas is not generated, it can be used safely even in a closed place. be able to. Moreover, the effect of removing mold stains is extremely high.

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Claims (5)

[Claims] 1. A mold stain cleaning composition comprising (a) hydrogen peroxide and / or an inorganic peroxide and (b) a polyhydroxycarboxylic acid. 2. The mold stain cleaning composition according to claim 1, wherein the mold stain cleaning composition contains a surfactant. 3. The mold stain cleaning composition according to claim 1 or 2, wherein the inorganic peroxide is sodium carbonate hydrogen peroxide adduct, sodium perborate monohydrate or sodium perborate tetrahydrate. Stuff. 4. The mold stain cleaner composition according to claim 1, 2 or 3, wherein the polyhydroxycarboxylic acid is polyglycolic acid, polylactic acid, or a mixture thereof. 5. The hydrogen peroxide and / or the inorganic peroxide is an aqueous solution of the compound, 1, 2, 3 or 4.
The mold stain cleaning composition described.