JPH0525497A - Bleaching and cleaning of hard surface - Google Patents

Abstract

PURPOSE:To improve the effect of bleaching and cleaning a hard surface by treating the surface with an aqueous solution of a specific organic peroxy acid under specified conditions. CONSTITUTION:A bleaching agent composition comprising H2O2 or a peroxide (e.g. sodium percarbonate) and an organic peroxy acid precursor which reacts with H2O2 to yield an organic peroxy acid of the formula (wherein R<1> is a 1-5C alkyl or alkenyl group that may be substituted; R<2> is a 1-8C alkylene group that may be substituted or a phenylene group that may be substituted by a 1-5C alkyl; A is a 2-4C alkylene group; and (n) is 0-100) (e.g. diester of 3,6-dioxaheptanoic acid with ethylene glycol) is used in two ways. One process comprises bringing a hard surface into contact with an aqueous solution of the bleaching agent composition having a pH of 7.5 or more, allowing the system to stand for 5-30min, reducing the pH of the solution to less than 7.5, allowing the system to stand for 5-60min, and rinsing the surface. Another process comprises allowing an aqueous solution of the bleaching agent composition having a pH of 7.5 or more to stand for 5-30min, reducing the pH to less than 7.5, bringing a hard surface into contact with the resulting solution for 5-6min, and rinsing the surface.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for bleaching and cleaning hard surfaces.

[0002]

[Prior art and its problems] Toilets around the house,
Dirt in bathrooms, bathtubs, drainage pipes, and other places that are difficult to clean cannot be easily removed with ordinary detergents or bleach cleaners whose main purpose is cleaning. To remove these stains, a bleaching action or a foaming action of a composition containing a chlorine-based or oxygen-based bleaching agent as a stain-removing main component is utilized.

Cladospori stains on black ceiling stains in bathroom ceilings, tile joints, plastic walls and triangular corners in the kitchen.
This is caused by the pigment produced by molds such as um, and when the flush toilet is used continuously for a long period of time, colored stains are accumulated on the inner surface of the toilet bowl and the water storage surface, especially the water seal part. Examples include inorganic substances such as calcium phosphate and iron oxide, organic excretion such as crude protein and bile decomposition products, microorganisms and metabolites thereof.

Since it is difficult to remove these stains on the hard surface only with a cleanser or a surfactant, a liquid or spray bleach composition containing a chlorine bleach such as sodium hypochlorite is currently used. ing.

However, the hard surface bleaching agent using sodium hypochlorite is excellent in performance but has a great risk to eyes and skin, and the spray type is not suitable for molds such as ceilings. . In addition, there is a problem that it has a strong chlorine-based odor and is resistant to use in a small bathroom, toilet, etc., and if it is accidentally used with an acidic detergent, it emits toxic gas.

In recent years, a bleaching agent for hard surfaces using such an oxygen-based bleaching agent which has no danger has been investigated. Oxygen-based bleaching agents have the drawback of weaker bleaching power than chlorine-based bleaching agents. Tetraacetyldiamine, tetraacetylglycoluril, pentaerythritol tetraacetate and the like are particularly excellent as the bleaching activator for enhancing the bleaching power of the oxygen-based bleaching agent. However, since these bleach activators generate peracetic acid as a bleaching active species, they have a strong pungent odor and are difficult to put into practical use as a bleaching agent for hard surfaces.

[0007]

Means for Solving the Problems The present inventors have studied bleach activators having no irritating odor, and found that an anhydride of an organic acid having an alkoxy group, an ester or an acid amide exhibits excellent effects, As a result of continuing earnest research to further enhance the bleaching power, it was found that the method of adjusting the pH of the bleaching agent composition containing the bleaching activator and applying it to a hard surface is highly effective, and completes the present invention. Came to.

That is, the present invention relates to (a) hydrogen peroxide or a peroxide which produces hydrogen peroxide in an aqueous solution, and (b) hydrogen peroxide or a peroxide which produces hydrogen peroxide in an aqueous solution. Then, the following general formula (I)

[0009]

[Chemical 3]

[In the formula, R ¹ represents a linear or branched alkyl or alkenyl group having 1 to 5 carbon atoms which may have a substituent, and R ² may have a substituent. Good carbon number 1
8 straight chain or branched chain alkylene group or 1 to 1 carbon atoms
5 represents a phenylene group which may be substituted with a linear or branched alkyl group, n A's are the same or different and each represent an alkylene group having 2 to 4 carbon atoms, and n is 0 to 100 Indicates a number. ] The bleaching composition containing an organic peracid precursor that produces an organic peracid represented by the following (1)
Alternatively, the present invention provides a method for bleaching and cleaning a hard surface, which is characterized in that the method is applied to the hard surface by the method (2). <Method (1)> An aqueous solution of a bleaching agent composition containing components (a) and (b) having a pH of 7.5 or more is brought into contact with a hard surface for 5 to 30
Let stand for 5 minutes, then lower the pH of the aqueous solution on the hard surface to below 7.5 and let stand for another 5-60 minutes, then rinse. <Method (2)> After leaving an aqueous solution of a bleaching agent composition containing components (a) and (b) having a pH of 7.5 or more for 5 to 30 minutes, and then lowering the pH of the aqueous solution to less than 7.5, The aqueous solution is contacted with the hard surface and left for 5-60 minutes, after which it is rinsed.

Among the components (a), peroxides that generate hydrogen peroxide in an aqueous solution include sodium percarbonate, sodium tripolyphosphate / hydrogen peroxide adduct, sodium pyrophosphate / hydrogen peroxide adduct, and urea. -Hydrogen peroxide adduct, 4Na ₂ SO ₄ .NaCl, sodium perborate monohydrate, sodium perborate tetrahydrate, sodium persilicate, sodium peroxide, calcium peroxide and the like are exemplified. Among these, sodium percarbonate, sodium perborate monohydrate and sodium perborate tetrahydrate are particularly preferable.

In the residential bleaching composition of the present invention, the organic peracid represented by the general formula (I) can be used as it is. However, in consideration of storage stability of the organic peracid, it is better to generate the organic peracid at the time of use. That is, hydrogen peroxide or a peroxide (a) that produces hydrogen peroxide in an aqueous solution and an organic peracid precursor (bleach activator) that reacts with hydrogen peroxide to produce the organic peracid are used together. Preferably.

As the organic peracid precursor for producing the above organic peracid (I), the following general formula (II)

[0014]

[Chemical 4]

[Wherein, R ¹ , R ² , A and n have the same meanings as described above. ] An acid anhydride, ester or amide of an organic acid represented by

As the organic acid (II), methoxyacetic acid, 2-
Methoxypropionic acid, p-methoxybenzoic acid, ethoxyacetic acid, 2-ethoxypropionic acid, p-ethoxybenzoic acid, propoxyacetic acid, 2-propoxypropionic acid,
p-propoxybenzoic acid, butoxyacetic acid, 2-butoxypropionic acid, p-butoxybenzoic acid, 2-methoxyethoxyacetic acid, 2-methoxy-1-methylethoxyacetic acid,
2-methoxy-2-methylethoxyacetic acid, 2-ethoxyethoxyacetic acid, 2- (2-ethoxyethoxy) propionic acid, p- (2-ethoxyethoxy) benzoic acid, 2-ethoxy-1-methylethoxyacetic acid, 2- Ethoxy-2-
Methyl ethoxy acetic acid, 2-propoxy ethoxy acetic acid, 2
-Propoxy-1-methylethoxyacetic acid, 2-propoxy-2-methylethoxyacetic acid, 2-butoxyethoxyacetic acid, 2-butoxy-1-methylethoxyacetic acid, 2-butoxy-2-methylethoxyacetic acid, 2- (2- Methoxyethoxy) ethoxyacetic acid, 2- (2-methoxy-1-methylethoxy) ethoxyacetic acid, 2- (2-methoxy-2-)
Methylethoxy) ethoxyacetic acid, 2- (2-ethoxyethoxy) ethoxyacetic acid, 3,6-dioxaheptanoic acid and the like can be mentioned, and these acid anhydrides are used as the organic peracid precursor.

Examples of the organic acid (II) ester include esters of the above organic acid (II) and the following polyhydric alcohols. Examples of the polyhydric alcohol include polyethylene glycols such as ethylene glycol, diethylene glycol and triethylene glycol; alkylene glycols such as trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol and sorbitol; Examples thereof include polyglycerins such as glycerin, diglycerin and triglycerin.

Further, as the acid amide of the organic acid (II),
An acid amide of the above organic acid (II) and the following amines can be mentioned. Examples of amines include ethylamine, isopropylamine, 2-ethylhexylamine, oleylamine, diethylamine, diisopropylamine, diisobutylamine, monoethanolamine, diethanolamine, ethylenediamine, diethylenetriamine, piperidine, morpholine, pyrrole, imidazole and the like.

Of these organic peracid precursors, esters of organic acids (II) with ethylene glycol, diethylene glycol or glycerin or acid amides with ethylenediamine are particularly preferred. R ¹ and R ² in the general formula (II) may have a substituent such as an alkyl group, a methoxy group or an ethoxy group. Further, R ¹ in the general formula (II) has 1 to ¹ carbon atoms.
4, an organic peracid precursor in which R ² is an alkylene group having 1 to 3 carbon atoms or a phenylene group, A is an alkylene group having 2 to 3 carbon atoms, n is 0 to 20, and particularly 1 to 5 is preferable.

Hydrogen peroxide or peroxide (a) is added to the bleaching composition at the time of use in an amount of 1 to 50% by weight so that the effective oxygen concentration is
It is preferable to set it to 0.1 to 3% by weight, particularly 0.2 to 2% by weight. Further, the organic peracid precursor (b) is particularly preferably blended in the bleaching composition at the time of use in an amount of 0.5 to 30% by weight.

The bleaching composition according to the present invention is preferably adjusted to a pH of 8 to 13, particularly 9 to 11.5 in order to enhance the effect, and a buffering agent can be added for this purpose.
As the buffering agent, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; ammonium hydroxide, mono,
Examples thereof include amine derivatives such as di and triethanol; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal silicates such as sodium silicate and potassium silicate; silicates such as ammonium silicate. If necessary, sodium sulfate, potassium sulfate,
Alkali metal sulfates such as lithium sulfate; ammonium sulfates; alkali metal bicarbonates such as sodium bicarbonate, potassium bicarbonate, lithium bicarbonate; ammonium bicarbonate and the like can also be used for improving performance. They are,
It is preferable to add 0 to 30% by weight to the bleaching composition.

The bleaching composition according to the present invention contains a surfactant for the purpose of promoting the penetration of bleaching activated species into soil. Examples of surfactants include alkyl glycosides, polyoxyethylene alkyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethyleneoxypropylene block polymers (Pluronic), fatty acid monoglycerides, and amine oxides. Nonionic surfactants; anionic surfactants such as soaps, alkyl sulfates, alkylbenzene sulfonates, polyoxyethylene alkyl sulfates, sulfosuccinic acid monoesters; mono- or dialkylamines and their polyoxyethylene adducts; mono Alternatively, cationic surfactants such as dilong-chain alkyl quaternary ammonium salts; amphoteric surfactants such as carbobetaine, sulfobetaine, hydroxysulfobetaine and the like. . These are preferably incorporated in the bleaching composition in an amount of 0.5 to 5% by weight.

In the bleaching composition according to the present invention, if necessary, a monohydric alcohol such as methanol, ethanol or propanol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or butylene glycol. , Dihydric alcohols such as hexylene glycol; trihydric alcohols such as glycerin, and the like. Furthermore,
Such as diethylene glycol methyl ether, ethylene glycol methyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monopropyl ether, mono- or diether with a dihydric or trihydric alcohol and a lower monohydric alcohol Solubilizing agents such as water-soluble solvents, sodium p-toluenesulfonate, sodium xylenesulfonate, sodium alkenylsuccinate, urea; penetrants; suspending agents such as clay;
Natural or synthetic polymer thickeners, abrasives, pigments, dyes, fragrances and the like can be added within a range that does not impair the effects of the present invention.

The bleaching agent composition used in the present invention may be used in a single-pack type, but it may be used in the form of hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution and an organic peroxide. Separately pack the acid precursor separately (when hydrogen peroxide is used, it is desirable to also separately pack the alkaline buffer), and mix both immediately before use (add water if necessary). It is preferable to use a solution, slurry or paste which is immediately sprayed or sprayed on the target surface because there is no concern about storage stability. The effective oxygen concentration during use is generally adjusted to 0.1 to 3%, preferably 0.2 to 1%.

The method of bleaching and cleaning the hard surface of the present invention is carried out by applying the bleaching agent composition of the present invention prepared as described above to the hard surface by either of the following two methods. . <Method (1)> 5 to 30 after the aqueous bleaching solution according to the present invention having a pH of 7.5 or more, preferably pH 8 to 13, and particularly preferably pH 9 to 11.5 obtained as described above is brought into contact with a hard surface.
Leave for a minute. Then, an aqueous solution of an acid such as hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid is sprayed or sprayed to remove the aqueous solution on the hard surface.
The bleaching and cleaning effect is improved as compared with the case where the pH is lowered to less than 7.5, the state is left for 5 to 60 minutes in that state, and then the pH is not lowered by rinsing.

<Method (2)> The same aqueous solution of the bleaching agent composition according to the present invention having a pH of 7.5 or more as described above is allowed to stand for 5 to 30 minutes. The pH of the aqueous solution is then lowered to less than 7.5 with an acid as described above, then the aqueous solution is contacted with a hard surface and left for 5-60 minutes, followed by a rinse. Also by this method, an excellent bleaching cleaning effect can be obtained.

[0027]

EXAMPLES Examples of the present invention will be described below.
The invention is not limited to these examples.

Example 1 5% hydrogen peroxide aqueous solution: 45% by weight 3,6-dioxaheptanoic acid / ethylene glycol diester: 5% by weight [potassium carbonate 40% by weight + ethylene glycol monomethyl ether 5% by weight + alkylglycoside] 4% by weight] ... 45% by weight The above solutions 1 to 3 were mixed (pH = 10.5) immediately before use to prepare an aqueous solution of the fungicide composition. Place the model mold plate ^* horizontally and add 40μ of the above aqueous solution of the mold remover composition.
L, dropped for 20 minutes, washed with water, air-dried, and then lightness (L value) using a colorimeter 1001DP manufactured by NEC Corporation.
Was measured. As a result, the L value was 87. Similarly, to the model mold plate, add 40 parts of the above aqueous solution of the mold removing composition.
μL was added dropwise, and the mixture was left for 10 minutes, then an aqueous solution of phosphoric acid was added dropwise to lower the pH to 3.5, left for another 10 minutes, and then rinsed. As a result of measuring the L value in the same manner as described above, it was 92. * Model mold plate Cladoaporium herbaru
m ) inoculated and cultured for 14 days at 30 ° C (ABS
Resin mold) was used as the model mold plate (L value of plastic plate 92.4, L value of model mold plate 60 to 70). Further, the aqueous solution of the mold removal composition was left as it was for 10 minutes, and then an aqueous solution of phosphoric acid was added dropwise, and after lowering the pH of the aqueous solution of the mold removal composition to 3.5, 40 μl of this was added dropwise on the model mold plate. Rinse after leaving for 15 minutes. As a result of measuring the L value in the same manner as above, the L value was 92.

Claims (4)

[Claims] 1. A method of reacting with (a) hydrogen peroxide or a peroxide which produces hydrogen peroxide in an aqueous solution, and (b) hydrogen peroxide or a peroxide which produces hydrogen peroxide in an aqueous solution. Formula (I): [In the formula, R ¹ represents an optionally substituted linear or branched alkyl group or alkenyl group having 1 to 5 carbon atoms,
R ² is a linear or branched alkylene group having 1 to 8 carbon atoms which may have a substituent, or a phenylene group which may be substituted with a linear or branched alkyl group having 1 to 5 carbon atoms. And n A's are the same or different and each represents an alkylene group having 2 to 4 carbon atoms, and n is a number 0 to 100. ] A bleaching cleaning of a hard surface, characterized in that a bleaching composition containing an organic peracid precursor which produces an organic peracid represented by the following (1) or (2) is applied to the hard surface. Method. <Method (1)> An aqueous solution of a bleaching agent composition containing components (a) and (b) having a pH of 7.5 or more is brought into contact with a hard surface for 5 to 30
Let stand for 5 minutes, then lower the pH of the aqueous solution on the hard surface to below 7.5 and let stand for another 5-60 minutes, then rinse. <Method (2)> After leaving the aqueous solution of the bleaching composition having a pH of 7.5 or more containing the components (a) and (b) for 5 to 30 minutes, and then lowering the pH of the aqueous solution to less than 7.5, The aqueous solution is contacted with the hard surface and left for 5-60 minutes, after which it is rinsed. 2. The organic peracid precursor (b) is represented by the following general formula (I
I) [Chemical 2] [In the formula, R ¹ , R ² , A and n have the same meanings as described above. ]
The method for bleaching and cleaning a hard surface according to claim 1, which is an acid anhydride, ester or acid amide of an organic acid represented by: 3. The hard surface according to claim 2, wherein the organic peracid precursor (b) is an ester of an organic acid represented by the general formula (II) with ethylene glycol, diethylene glycol or glycerin, or an acid amide with ethylenediamine. Bleach washing method. 4. R ¹ in the general formula (II) is an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group or phenylene group having 1 to 3 carbon atoms, A is an alkylene group having 2 to 3 carbon atoms, n is 0-20
The method of bleaching and cleaning a hard surface according to claim 2 or 3, wherein