JPS61159496A - Fungicidal composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel mold remover, and more particularly to a mold remover characterized by containing peroxide and amorphous silica.

[Conventional technology and problems]

Black stains on bathroom ceilings, tile joints, plastic walls, and triangular corners in the kitchen cannot be removed with cleansers or active agents alone, so currently, spray mold removers that use hypochlorite are available. It is covered with cloth. Also,
Even in the patents published so far, most of the mold removal agents use hypochlorite or the like. The reason for this is that peroxides such as hydrogen peroxide, organic peracids, and inorganic peracids have weak mold removal power and cannot completely remove mold. On the other hand, mold removers using hypochlorite have excellent performance, but are highly dangerous to the eyes and skin, and spray-type ones are especially unsuitable for removing mold from ceilings and the like.

Furthermore, it has a strong chlorine odor, making it difficult to use it in small bathrooms.

[Means for solving problems]

Therefore, the inventors of the present invention have conducted intensive research to improve the effects of peroxide, and have found that by combining peroxide and amorphous silica, an effect that cannot be achieved with peroxide alone can be achieved. Heading The invention has been completed.

That is, the present invention uses peroxide and the chemical formula msiO2-nH2O.
(m is an integer of 1 or more, n is an integer of 0 or more).

Peroxides used in the present invention include hydrogen peroxide, inorganic and organic peroxides that produce hydrogen peroxide in aqueous solution, or a combination thereof with an activator, peroxymonosulfate, and peroxysulfate. Salts, organic peracids and their salts, etc. can be used.

The amount of peroxide is 0.5 to 95% (% is weight %, the same applies hereinafter), preferably 5 to 90%, particularly preferably 30 to 90%.
%.

To give more specific examples, examples of peroxides that generate hydrogen peroxide in an aqueous solution include organic and inorganic hydrogen peroxide adducts such as sodium carbonate hydrogen peroxide adduct, sodium tripolyphosphate hydrogen peroxide adduct, and pyrroline. acid) + Jium hydrogen peroxide adduct, urea hydrogen peroxide adduct, or 4
Examples include NazSOa, 2H20□, and NaCl.

Further, there are inorganic peroxides such as sodium perborate hydrate, sodium perborate tetrahydrate, sodium peroxide, and calcium peroxide. Among these, particularly preferred are sodium carbonate hydrogen peroxide adduct, sodium perborate hydrate, and sodium perborate tetrahydrate.

Further, as the activator used in combination with these, hydrogen peroxide or a compound that reacts with peroxide in an aqueous solution to produce an organic peracid or a bleaching active species can be used. Activators used in the present invention include nitriles such as acetonitrile, malononitrile, phthalonitrile, benzoyliminodiacetonitrile, glucose pentaacetate, octaacetyl sucrose,
Triacetin, sorbitol hexaacetate, acetoxybenzenesulfonate, or 0-acetylated products such as triacetyl cyanuric acid, methyl chloroformate, N
,N.

N'' Nl-tetraacetylethylenediamine or tetraacetylglycolyluril, N-benzoylimidazole, di-N-acetyldimethylglyoxime, 1-
N-acylated products such as phenyl-3-acetylhydantoin, N,N-diacetylaniline, N-acetyldiglykolimide, diacetylmethylene diformamide, and phthalic anhydride, succinic anhydride, benzoic anhydride, glutaric anhydride , acid anhydrides such as alkyl sulfuric anhydrides, anhydrides of carboxylic and organic sulfonic acids, sulfonyloximes such as di(methanesulfonyl)dimethylglyoxime, acylated phosphates such as di-ethylbenzoyl phosphate, Examples include phenylsulfonate ester, organic phosphoric acid azide such as diphenylphosphinic azide, disulfone such as diphenyldisulfone, N-sulfonylimidazole, cyanamide, halogenated triazine, and the like. These activators can be used alone or in combination of two or more.

The amount of peroxide of this type is between 0.5 and 95%, preferably 5%.
-90%, particularly preferably 30-90%.

In addition, when using an activator together, the amount is 0.1 to 70%.
, preferably 1 to 50%.

The peroxymonosulfate used in the composition containing peroxymonosulfate or peroxydisulfate in the present invention includes sodium peroxysulfate, sodium peroxysulfate,
Potassium sulfate, peroxy-ammonium sulfate, etc. are available, and among these, potassium peroxy-sulfate is the most preferred. Generally, potassium peroxy-sulfate is KHSO5
:KHSO4:KHSO4=2:1:1 commercially available in the form of a double salt (theoretical effective oxygen concentration 5.2%:
commercially available product (approximately 4.3%). Examples of the peroxydisulfate include sodium peroxydisulfate, potassium peroxydisulfate, ammonium peroxydisulfate, and the like, and among these, sodium peroxydisulfate and ammonium peroxydisulfate are most preferred.

The amount of peroxide of this type is between 1 and 95%, preferably between 5 and 9%.
0%, particularly preferably 30-90%.

The organic peroxide used in the organic peroxide-containing composition in the present invention is particularly preferably an organic peracid, or an alkali metal salt or alkaline earth metal salt of an organic peracid. Examples of organic peracids include monoperacids of aliphatic carboxylic acids such as peracetic acid, perpropionic acid, perbutyric acid, percaprylic acid, and perlauric acid, succinic acid, glutaric acid, adipic acid, azelaic acid, 1.9 - Monoperacids of aliphatic dicarboxylic acids such as nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-hendecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, etc., or diperacids, perbenzoic acids, mono- Perphthalic acid, diperphthalic acid, monoperterephthalic acid,
Examples include mono- and dicarboxylic acids of aromatic carboxylic acids such as diperterephthalic acid and parachloroperbenzoic acid, or alkali metal salts and alkaline earth metal salts of organic peracids thereof. Among these, perphthalic acid and its salts, heptanoperacid or diperacid of dodecanedicarboxylic acid and its salts are preferred, and monoperphthalic acid magnesium salt is particularly preferred.

The amount of peroxide of this type is between 5 and 95%, preferably between 10 and 95%.
90%, particularly preferably 30-90%.

Next, amorphous silica, which is the second component of the composition of the present invention, will be explained. Generally, there are two main types of substances called "silica" and represented by the chemical formula 5i02. One is naturally occurring "crystalline silica," which has a certain crystal structure like quartz, and the other is called hydrated silicon, wet silica, synthetic silicic acid, etc., and has a 5i-0 network. It is an “amorphous” or “amorphous” silica that has no fixed crystalline structure. In the present invention, a dry method,
Any synthetic amorphous silica or natural amorphous silica produced by the airgel method, wet method, etc. can be used, but dry method is preferable, and preferably the specific surface area by BET method is 10 to 700 (m"). /g) with an average particle size of 30
Less than μ is better. Furthermore, primary particles may aggregate to form secondary particles, but these may also be used in the present invention without any problem. The blending amount is 0.1 to 50%, preferably 0.5
~30%.

The effect of the mold removal composition of the present invention can be further enhanced by adding a buffer for adjusting the pH.

These buffers include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, ammonium hydroxide, amine derivatives such as mono-, di-, and triethanolamine, and alkali metal hydroxides such as sodium carbonate and potassium carbonate. Carbonates, ammonium carbonates, etc., alkali metal orthophosphates such as sodium orthophosphate, potassium orthophosphate, orthophosphates such as ammonium orthophosphate, alkali metal silicates such as sodium silicate, potassium silicate, silicic acids such as ammonium silicate. Salt etc. can be used.

The pH buffer may be used in an amount that adjusts the pH to provide the optimum effect depending on the type of peroxide used.

Furthermore, if necessary, alkali metals such as sodium chloride, potassium chloride, lithium chloride, ammonium chloride, sodium bromide, potassium bromide, lithium bromide, ammonium bromide, or ammonium halides, sodium sulfate, potassium sulfate, lithium sulfate. or alkali metal bicarbonates such as ammonium sulfate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, ammonium bicarbonate, alkali pyrophosphates such as sodium pyrophosphate, potassium pyrophosphate, lithium pyrophosphate. Metal salts, alkali metal salts of tripolyphosphate such as ammonium pyrophosphate, sodium tripolyphosphate, potassium tripolyphosphate, lithium tripolyphosphate, alkali metal condensed phosphates such as ammonium tripolyphosphate, or ammonium salts can be used.

An activator such as an anionic activator, a nonionic activator, a cationic activator, or a zwitterion activator can be added to the composition of the present invention, if necessary.

Examples of anionic activators include sulfate ester salts of higher alcohols having 10 to 22 carbon atoms, carboxylic acid salts having 10 to 22 carbon atoms, α-olefin sulfonates having 10 to 22 carbon atoms, and alkyl groups having 10 to 22 carbon atoms. alkylbenzene sulfonate, sodium alkyl sulfosuccinate, paraffin sulfonate with 10 to 22 carbon atoms, sulfuric ester of ethylene oxide adduct (number of moles added: 1 to 100) of higher alcohol with 10 to 22 carbon atoms, 8 carbon atoms Examples include sulfuric esters of alkylphenol/polyethylene glycol ether having ~22 alkyl groups.

Examples of nonionic activators include higher alcohols with linear or branched chains having 10 to 22 carbon atoms, polyethylene glycol ether (degree of polymerization: 3 to 100), and ethylene glycol ether having 1 carbon number.
Poly of 0 to 22 carboxylic acids (degree of polymerization: 3 to 100)
Ethylene glycol ester, alkylphenol poly with an alkyl group having 8 to 22 carbon atoms (degree of polymerization: 3 to
100) Examples include ethylene glycol ether.

If necessary, p-) Solubilizing agents such as sodium luenesulfonate, sodium xylene sulfonate, urea, polymers such as carboxymethyl cellulose, polyvinylpyrrolidone, polyethylene glycol, aluminum silicates such as montmorillonite, seviolite, attapulgite, etc. Abrasives such as magnesium silicate, calcium carbonate, silicon dioxide, pigments, dyes, fragrances, etc. can be added.

When using the mold remover composition of the present invention, the effective oxygen concentration may be 0.1% or more, preferably 0.
．． 2% or more, concentration 0.5-50%, preferably 1
It is preferable to add the composition to water to form a solution, slurry, or paste so that the concentration is ~30%, and immediately sprinkle or spray it on the target surface (within 1 hour, preferably within 30 minutes). In particular, it is desirable to apply it in the form of a slurry or paste because the liquid does not scatter as in spraying.

To give a more specific example, a composition containing hydrogen peroxide or an organic or inorganic peroxide that generates hydrogen peroxide in an aqueous solution has an effective oxygen concentration of 0.1%.
-10%, preferably 0.2%-6%, and pH is 8-13, preferably 9-11.

The composition containing peroxymonosulfate or peroxydisulfate in the present invention has an organic oxygen concentration of 0.1% to 1.5%, preferably 0.2% to 1.0%. (The pH is preferably 5 to 13, more preferably 6 to 11.)

When using a composition containing an organic peroxide in the present invention, it is preferable that the effective oxygen content is 0.2% to 3%, and the pH is 5 to 11, more preferably 6. ~10
Good.

The concentration of amorphous silica during use is 0.1 to 30%,
The content is preferably 0.5 to 20%.

〔Effect of the invention〕

The mold remover made from the composition of the present invention has no peculiar chlorine odor (
Also, even if it accidentally mixes with acidic cleaning agents, there is no risk of generating chlorine gas (it can be used with confidence).

〔Example〕

The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

Mold removal rate: The mold removal rate is based on Talatusborium herbalum (Cla.
dosporium herbarum).・3
0℃.

A clay plate cultured for 7 days was used as a model plate, and the reflectance was measured before and after treatment.

(Calculation formula) % formula % RO is the reflectance of the unglazed plate before mold inoculation R5 is the reflectance of the mold plate before treatment R- is the reflectance measurement of the mold plate after treatment Model name Manufactured by Nippon Denshoku Industries Co., Ltd. NDR-101DP Color Difference Meter Example 1 The liquid compositions obtained by adjusting the formulations shown in Table 1 were sprayed or applied onto mold plates, and the mold removal rate was measured after 15 minutes. All pH values are Nap)! I adjusted it to 8.0. The results are shown in Table 1.

Table 1 (t ml H-48; mo/supercap) L4R-7 Gnesium 6HzO (Interox m*2
il; Specific surface area (200m”/g), particle size (12μ
) (Japan Aerosil...*3R4 Rance (the whole I
Example 2 A liquid composition obtained by adjusting the formulation shown in Table 2 was sprayed or applied onto a mold plate, and the mold removal rate was measured after 15 minutes. The pH was adjusted with NaOH in all cases. The results are shown in Table 2.

Table 2 CtD * 0XONE, peroxy-potassium sulfate double salt (Du Pont; tk) Example 3 A liquid composition obtained by adjusting the formulation shown in Table 3 was sprayed or applied on actual mold stains, After 15 minutes,
The mold removal ability was sensory evaluated.

When the compositions of Comparative Examples 7 and 8 were used, the actual mold stains were severe and some mold remained, but when any of the compositions of Inventions 7 to 10 were used, mold was removed and good mold was obtained. The results were obtained.

Claims (1)

[Scope of Claims] 1. A mold removal composition characterized by containing peroxide and amorphous silica represented by the chemical formula mSiO_2·nH_2O (m is an integer of 1 or more, n is an integer of 0 or more) . 2. The mold remover composition according to claim 1, wherein the peroxide content is 0.5 to 95% by weight, and the amorphous silica content is 0.1 to 50% by weight. 3. The peroxide is hydrogen peroxide, sodium carbonate hydrogen peroxide adduct, sodium perborate, peroxymonosulfate,
Claim 1 or 2 is one or more selected from the group consisting of peroxydisulfate, perphthalic acid and its salts, monoperacid or diperacid of dodecanedicarboxylic acid and its salts. The mold-killing agent composition according to item 2. 4 A patent claim in which the amorphous silica is one or more synthetic amorphous silicas with a specific surface area of 10 to 700 (m^2/g) according to the BET method and an average particle size of 30 μ or less The mold remover composition according to scope 1 or 2. 5 When using a mold remover composition containing peroxide and amorphous silica represented by the chemical formula mSiO_2・nH_2O (m is an integer of 1 or more, n is an integer of 0 or more), water is added to form a solution or slurry. or paste-like liquid composition and pear;
A mold removal method characterized by immediately applying or spraying this on the target surface.