JPH0482959A - Bleaching composition - Google Patents

Abstract

PURPOSE:To provide the subject bleaching composition containing hydrogen peroxide, a substance releasing halogens in water and an organophosphorus compound, having a wide antibacterial spectrum and effective for bleaching and sterilizing fibers and tablewares, etc. CONSTITUTION:A composition containing (A) hydrogen peroxide, (B) an electro lyte type inorganic or organic halide such as sodium chloride, ammonium chlo ride, benzalkonium chloride or pyridinium cetyl chloride releasing halogens in water in an amount of 0.01-10mol, preferably 0.1-5mol based on 1mol (A) and (C) an organphosphonic acid such as a phosphonic acid (salt) or a polyaminophosphonic acid in an amount of 0.002-1wt.%, preferably 0.01-10wt.% in terms of PO4 base based on the total amount of the composition. In bleaching and sterilization, this composition acts effectively by using a diluted solution having about 100-20000ppm concentration on active oxygen concentration base.

Description

[Detailed Description of the Invention] [Industrial Application Field] The product of the present invention is suitably used for bleaching and removing mold from clothing, textiles, pulp, and kitchen utensils, especially for bleaching and sterilizing kitchen utensils such as dish towels and tableware. , peroxide-based bleach compositions with a broad antibacterial spectrum.

[Conventional technology]

Conventionally, chlorine bleach, which has been commonly used as a liquid bleach, is cheap, has a strong bleaching blade, and has a wide antibacterial spectrum from Durham-positive bacteria to Durham-negative bacteria, but it discolors the pigments of colored and patterned clothing. It has the disadvantage of causing discoloration, and in recent years, it has also caused social problems such as chlorine gas being generated when mixed with acidic cleaning agents and causing fatal accidents.

On the other hand, oxygen bleach is superior in that it is safe for colored and patterned clothing and does not generate problems with chlorine gas, but it also exhibits excellent sterilizing power against Durham-negative bacteria such as E. coli. However, it has the disadvantage that it does not have sufficient bactericidal activity against Durham-positive bacteria such as Staphylococcus aureus.

On the other hand, Japanese Patent Publication No. Sho 61-59360 discloses a cleaning agent for automatic blood analyzers that combines specific amounts of sodium chloride, a buffer, a surfactant, and a peroxide. The mechanism of action of this cleaning agent is that peroxide reacts with peroxidase in hemoglobin, resulting in oxygen gas (
0□) is generated, and this molecular oxygen gas physically removes dirt. Additionally, oxygen gas is said to have a bactericidal effect, but the problem is that molecular oxygen gas is only effective against certain anaerobic bacteria and does not work effectively against all bacteria. be. Also, in this cleaning agent, sodium chloride is used to adjust the osmotic pressure and impedance of the liquid to be equivalent to that of a diluted blood liquid.

On the other hand, Japanese Patent Publication No. 61-16317 discloses that by combining a specific amount of an organic peracid (including a combination of an organic peracid precursor and a persalt) and a water-soluble iodide salt, dyes can be removed during cleaning. Although techniques have been disclosed to reduce the metastasis of
If an organic peracid is used, there is a problem in that an effect superior to the sterilizing and bleaching effect of the organic peracid cannot be obtained.

[Problems to be Solved by the Invention] Therefore, an object of the present invention is to provide a liquid oxygen bleach composition having a broad antibacterial spectrum ranging from Durum-positive bacteria to Durum-negative bacteria.

[Means to solve the problem]

The present invention is based on the knowledge that when hydrogen peroxide is combined with a compound capable of releasing halogen ions in water and an organic phosphorus compound, a bactericidal effect can be exerted on not only Gram-negative bacteria but also Durham-positive bacteria. It was done.

That is, the present invention provides a liquid bleach composition characterized by containing (A) hydrogen peroxide, (B) a substance that releases halogen ions in water, and (C) an organic phosphorus compound.

Hydrogen peroxide, which is the component (A) of the present invention, is produced by various production methods such as electrolytic method and autoxidation method, and its concentration is 30%.
~60% JIS standard products are commercially available. Furthermore, in recent years, 30% hydrogen peroxide, which contains almost no impurities, has been commercially available for use in the electronic industry (for cleaning electronic parts, etc.). In the present invention, there is no particular problem in using any of these, and when used in the present invention, it is diluted so that the concentration of hydrogen peroxide in the product is about 0.1 to 10%.

Furthermore, when actually carrying out bleaching and sterilization treatment in the kitchen, etc., it is effective to dilute the bleach stock solution so that the effective oxygen concentration is approximately 100 to 20,000 ppm.

Examples of the component (B) of the present invention, which releases halogen ions in water, include inorganic and organic electrolyte-type halogen compounds. Specifically, inorganic compounds include sodium chloride, potassium chloride, aluminum chloride,
These are various halides such as ammonium chloride and hydrochloric acid, and halogens include chlorine, bromine, and iodine. Therefore, compounds such as potassium bromide and potassium iodide can also be used. Examples of organic halides include quaternary ammonium salt type compounds such as dihardened beef tallow dimethylammonium chloride and alkyltrimethylammonium chloride, and methyl-1-oleylamide ethyl-2
- Compounds such as imidazolinium salts such as olelimidazolinium chloride, amine hydrochlorides such as dodecylamine hydrochloride, and halides of cationic polymers such as MERQ [IAT 100]. Further, compounds having bactericidal properties such as benzalkonium chloride and cetylpyridinium chloride are more preferable since they can further enhance the bactericidal properties. Among these, inorganic salts such as sodium chloride are particularly preferred from the viewpoint of cost, but ammonium salts such as ammonium chloride and organic halides are preferred from consideration of stability (precipitation property) at low temperatures. In addition, the blending amount of component (B) is per mole of hydrogen peroxide of component (A>),
It is about 0.01 mol to 10 mol, preferably 0.1 mol.
~5 moles.

Examples of the organic phosphorus compound of component (C) of the present invention include sodium alkyl phosphate, POE (p-10) sodium alkyl ether phosphate, tri(lower 2) alkyl ether phosphoric acid, monoalkyl phosphate ester, and phytic acid. Organic phosphoric acid (Estenope salt) compounds such as 2-
Examples include phosphonic acids (salts) such as phosphono-1,24-tricarboxylic acid and 1-hydroxyethane-1.1-diphosphonic acid. The term "alkyl group" as used herein is a general term for saturated, unsaturated, or branched alkyl groups having an average carbon number of 8 to 20117. Furthermore, the following - general formula (
Examples include polyaminophosphonic acids represented by compounds represented by I) to (I).

N (CH2P 03 H2) 3
(I)(H2O2P CH2)2N(CH2)-N
(CH2PO3H2)2(I[) (H203PCH2)2N(CH2),,N(CH2)
. N(CH2P○3H2)2CH2PO,H2 (I[I) (in the formula, m=2-6, n=1-2) Among these, phosphonic acid (salt)'F! Preferred are polyaminophosphonic acids. The blending amount of component (C) is PO, converted to 0.
Approximately 0.002 to 1% is necessary, preferably 0.01 to 1%.
It is 1%.

The pH of the liquid bleach of the present invention is 7 or less, preferably 6 or less, particularly preferably 5 or less, and the lower the pH, the more stable it is.

To adjust the pH, you can use inorganic acids such as sulfuric acid and phosphoric acid, organic acids such as toluenesulfonic acid and benzenesulfonic acid, or add chelating agents and anionic surfactants (described later) in acid form, or hydroxylated accordingly) I
It is best to adjust using a caustic alkali such as Jium or potassium hydroxide.

In the present invention, the above components (A) to (C) are essential, but
Furthermore, various compounds can be contained. For example, phosphoric acid, barbyric acid, uric acid, acetanilide, oxyquinoline, zenacetin, ethylenediaminetetraacetate, diethylenetriaminepentaacetate, hydroxyethyliminodiacetate, etc., which are known as hydrogen peroxide stabilizers, are representative. Inorganic phosphorus compounds represented by aminopolycarboxylic acids, tripolyphosphates, pyrophosphates, OL-α-tocopherol, gallic acid derivatives,
Butylated hydroxyanisole (BHA), 2,6-tert-butyl-4-methylphenol (BHT)
etc. can be added. The amount of these stabilizers added depends on the concentration of hydrogen peroxide, but it is usually about 0 to 5%, preferably 0.01 to 3%.

The liquid bleach of the present invention may contain various known additives in addition to the above-mentioned hydrogen peroxide stabilizer. Among these, relatively important ones include surfactants for increasing penetration power and cleaning power. As the surfactant, nonionic surfactants are particularly preferred. Examples of nonionic surfactants include carbon atoms of about 8 to 24
These are alkylene oxide adducts of higher alcohols, fatty acids, fatty acid amides, fatty acid amines, and alkylphenols. As the alkylene oxide, ethylene oxide, propylene oxide, and butylene oxide are used. Specifically, POE lauryl: L −f )beP
OE C12--Secondary alkyl ether, POE hexyl decyl ether, POE nonylphenyl ether, POE stearyl ether, POE glyceryl monostearate, POE isostearyl ether, POE
) Lyncholpropane, POE hydrogenated castor oil, POE
cured castor monolaurate OE sorbitan monoole), POE glyceryl triisostearate, PO
E nostearate, POE monostearate, POE stearylamine, lauroyl jetanolamide, PO
E stearylamide, POEPOPC+2-14 secondary alkyl ether, etc. In addition, POE represents polyoxyethylene and POP represents polyoxypropylene.

In addition to nonionic surfactants, alkylbenzene sulfonates, olefin sulfonates, polyoxyethylene (p=0.5-8) alkyl ether sulfates, alkyl (alkenyl) sulfates, saturated or unsaturated fatty acid salts, and Anionic surfactants such as α-sulfo fatty acid salts or esters, cationic surfactants such as benzalkonium chloride, dialkyldimethylammonium chloride, alkyltrimethylammonium chloride, amphoteric surfactants such as alkylamidocarboxybetaine, alkyldimethylamine oxides, etc. These include semi-polar surfactants and fluorocarbon surfactants. The term "alkyl group" or "acyl group" as used herein is a general term for a saturated, unsaturated, or branched alkyl group or acyl group having an average carbon number of 8 to 20. The amount of surfactant added is usually about 0 to 20%, preferably 0.1 to 10%.

A hydrotrope may be added for the purpose of stabilizing the liquid at low temperatures and improving freeze-recovery properties or preventing liquid separation at high temperatures. Such hydrotropes generally include short-chain alkylbenzene sulfonates such as toluene sulfonate and xylene sulfonate, ethanol, ethylene glycol, propylene glycol, hexylene glycol, and glycerin. Representative alcohols and polyhydric alcohols, and the general formula % Formula % R is an alkyl group having 1 to 6 carbon atoms R' is hydrogen, or a methyl group R' is hydrogen, or an alkyl group having 1 to 6 carbon atoms, m and n is an alkylene glycol ether represented by a number from 0 to 6, or the like.

The hydrotrope can be blended in an amount of about 0 to 30%, but as mentioned above, blending in too much will impair the stability of hydrogen peroxide, so blending a large amount is not preferable. Preferably, it is blended in an amount of 0 to 30%.

It may contain substances known as discoloration and fading inhibitors. Such substances include amino acids and amino acid salts such as glycine, alanine, curtamic acid, phenylalanine, histidine, lysine, tyrosine, and methionine, and amino or imide compounds such as iminodiacetic acid and hydroxyiminodiacetic acid. It is a copolymer of acrylonitrile having a quaternary ammonium group and one or more copolymerizable monomers.

Although optical isomers exist in amino acids, optical isomers do not affect the effects of the present invention. Therefore, it is also possible to use chemically synthesized amino acids.

As optical brighteners to increase the bleaching effect on white fibers, Tinopal CBS [: Ciba-Geigy], Tinopal SWN [Ciba-Geigy] Yacolor Index optical brightener 28, Optical brighteners such as 40, 61.71, etc. may be added in an amount of 0 to 5%.

A thickener can be added in an amount of 0 to 20% for the purpose of increasing the viscosity of the composition and improving its usability.

In general, synthetic polymers such as polyacrylates, acrylic acid maleic acid copolymers, carboxymethyl cellulose derivatives, methyl cellulose, and hydroxymethyl cellulose, natural polymers such as xanthan gum, guar gum, and kelsan, and water-swellable clay minerals such as montmorillonite and vegum etc. Also, JP-A-1-31960
It is also possible to impart viscoelastic rheological properties by combining an amphoteric surfactant and an anionic surfactant as described in Publication No. 0.

In addition, the present invention further includes appropriate amounts (approximately 0 to about 2% each) of various trace additives such as colorants such as dyes and pigments, fragrances, silicones, disinfectants, ultraviolet absorbers, and inorganic electrolytes. I can do it. In addition, as the dye, an acidic dye having hydrogen peroxide resistance in an acidic solution is particularly preferable.

Additionally, compounds such as organic peracids can be used to enhance the bleaching effect. Examples of such organic peracids include dodecane diperacid and monoperphthalic acid, and these organic peracids are preferably added after being adjusted to an aqueous dispersion system by a known method.

Further, in order to enhance the bleaching effect, a known activator for hydrogen peroxide may be used. Such activators include N-acyl, ○-, which reacts with hydrogen peroxide to produce an organic peracid.
Acyl-type peracid precursors, JP-A-63-270800, JP-A-63-10700, JP-A-1-929
N that generates singlet oxygen as an oxygen active species described in Publication No. 8 and Japanese Unexamined Patent Publication No. 1-245099, etc.
-Halohindered amine compounds and the like are known. Specific compounds include tetraacetylglycoluril, pentaacetylglucose, tetraacetylethylenediamine, sodium nonanoyloxybenzenesulfotetraate, etc. as organic peracid formation activators, and - as oxygen generation activators. , 1-chloro-4-hydroxy-2゜2.6.6-titramethylpiperidine, 1-chloro-4-CN-acetyl-N-methylamino]2.2,
6.6-titramethylpiperidine, sodium p-toluenesulfone chloroamide, and the like. The amount of these activators to be added is preferably about 0.02 to 1 mole per 1 mole of hydrogen peroxide, which is the main component used.

As for the blending method, since direct addition of these compounds impairs the stability of hydrogen peroxide, it is preferable to melt and disperse them in a compound such as a fatty acid, for example. In some cases, the bleach may be a two-component type (a two-component type, in which a hydrogen peroxide solution and an activator are placed in separate containers) which are stored in separate containers.

The mechanism of action of the invention is estimated as follows. That is,
Literature (Kanofsky J, Ro, Wright
J., MilesRichardson G.B.
, Tauber, 8, J., , J., Biol, C.
hem,.

252, p. 4803-4810 (1980)), it is said that one of the reactions of peroxidase distributed in living organisms is the reaction of hydrogen peroxide with halogen ions to produce hypohalogen ions. There is. In other words, the hydrogen peroxide of component (A>) and the halogen ion derived from component (B) are taken into the microbial body, and the corresponding hypohalogen ions are generated by the action of peroxidase, and this hypohalogen ion is effective. It is thought that the hypohalogen ions produced by this reaction may further react with hydrogen peroxide to produce singlet oxygen, or react with superoxide to form hydroxyl radicals. It is also believed that the bactericidal action progresses effectively due to these oxygen active species.Therefore, since component (B) forms a hypohalogen cycle, its presence in the reaction system in small amounts is sufficient; It is thought that even a small amount is effective.

Furthermore, if the organic phosphorus compound of component (C) is present, these compounds act as a stabilizer for the hypohalogen produced, causing the hypohalogen to rapidly react and change into other substances. It is presumed that the bactericidal effect is further improved because of the suppression of sterilization.

〔Effect of the invention〕

The bleach composition of this product has a wide antibacterial spectrum, so it exhibits an excellent sterilizing effect against not only Durum-negative bacteria but also Durum-positive bacteria, so it can be used especially in kitchen areas such as dish towels, cutting boards, and triangular corners. It can be used extremely effectively as a bleaching agent for surrounding areas. Of course, it can also be used as a clothing bleach or mold remover.

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

〔Example〕

Example 1 The composition shown in Table 1 was prepared using 31% ultra-pure hydrogen peroxide ELM manufactured and sold by Mitsubishi Gas Chemical Co., Ltd. for the electronic industry. Incidentally, the ultrapure hydrogen peroxide used here does not substantially contain any stabilizer or the like. Immediately before adjusting the whole to 100%, the pH was adjusted to 10.5 using a 1N hydroxide standard solution.

The following preserved bacterial strains were used for bactericidal evaluation.

Staphylococcus aureus: 5taphylococcus au
reusATC: C6538 Escherichia coli: ε5cherichia coli ATCC
The above test bacteria cultured in 8739TSA medium at 37°C for 24 hours was added to sterilized ion exchange water as lO'CF[I/
A test bacterial solution was prepared by suspending the bacteria to give a total weight of 1.3 g. This test bacterial solution 1- was inoculated into 100 bottles of the bleach solution shown in Table 1.

Therefore, the bacterial concentration in this bleach solution is 107 CF [17
g. The bleach solution inoculated with this bacterium was left to inoculate at 25°C for 2 hours, and then added to 5CDLPB medium for 10 to 1000
1 ml of the diluted solution was placed in a sterilized petri dish, and 18 ml of 5CDLPA medium was poured into it. After the medium was gently stirred and solidified, it was cultured at 37° C. for 48 hours, and then the number of bacteria was measured. The number of bacteria in the diluted culture dish was converted into the concentration of bacteria (CFU/g) in the bleach solution before dilution, and the bactericidal properties were evaluated according to the following criteria.

Bactericidal evaluation X: Initial bacterial count 107 (CPU/g) → 106 ~ after 2 hours
10'(CF[I/g)△; initial bacterial count 107 (CFU
/g) - 10'-106 (CFII/g) O after 2 hours;
Initial bacterial count 107 (CFU/g>-102-10 after 2 hours)
'(CF[J/g)◎; Initial bacterial count 107 (CF[1/g)
g) → 102 (CF [I/g) or less after 2 hours] The evaluation results of bactericidal properties are shown in Table 1.

As can be seen from Table 1, the composition of the present invention exhibits good bactericidal effects against not only Durham-negative E. coli but also Durham-positive Staphylococcus aureus.

Example 2 Compositions were prepared with various types and concentrations of components, and bactericidal properties were evaluated. The bactericidal properties were evaluated using bleached dish towels that had been used in a home kitchen for two days and were evenly soiled. This dish towel 3
After being stored for 1 day at 7°C and 85% R11, approximately 1.7
The test cloth was cut into cm pieces. 5 test cloths (
Place the test cloth (area of 15 clTI) into a sterilized 30 m vial and add diluted bleaching solution (dilution rate is stated separately) = 1 m
1 was added dropwise to completely wet the test cloth. Store at 37°C for 2 hours, add 20ml of sterile physiological saline, and mix at 30°C.
The cells were shaken 30 times at centimeters to extract the bacteria. 1 d of the extract solution was prepared in the same manner as in Example 1 (10 times to 10,000 times as needed if necessary).
The number of general viable bacteria was measured using a double diluted solution (culture) and converted to the number of general viable bacteria per 100c++f dish towel.

The results are shown in Table-2.

As can be seen from Table 2, all of the products of the present invention have a good bactericidal effect against common viable bacteria.

Example 3 A two-component container was prepared by fixing two 125 ml polyethylene unit cleaning bottles made by NALGEN with the nozzle tip and the container side. This two-liquid type container was filled with 100 d each of liquids (1) and (2) having the following compositions.

■Liquid sodium bicarbonate 2.0 Sodium hydroxide 1.2 Garbage from the triangular corner of the kitchen Approximately 2
00 g, two bolts were squeezed at the same time to discharge both liquids at the same time and in approximately the same amount (approximately 20 ml each, approximately 40 g in total), and sprinkled on garbage. Store this garbage at room temperature (
It was left for half a day at about 27°C. In the products that were not sprinkled with the product of the present invention, a putrid odor due to the action of microorganisms was observed, but
The rotten odor of the food sprinkled with the product of the present invention was unbearable.

■Liquid ■ Potassium chloride 5.0 (%) , β4

Claims (1)

[Claims] (A) hydrogen peroxide, (B) a substance that releases halogen ions in water, and (C)
A liquid bleach composition containing an organophosphorus compound.