JP7111308B2 - High-concentration stabilization method and treatment method for bleaching agents for clothing and building interior and exterior materials - Google Patents

Description

Bleaching is an effective action not only for white clothing but also for removing mold stains from the interior and exterior of buildings, and a large number of products have hitherto appeared on the market. Generally, "oxidizing bleaches" include "chlorine-based" and "oxygen-based" bleaches.
The former "chlorine system" is expected to have an oxidation and decomposition action in addition to the chlorination action of hypochlorous acid (chemical formula HOCl) or the same ion (chemical formula OCl ^- ), and does not react with dyes and pigments. However, it utilizes the property of the material that it hardly reacts with vegetable fiber clothing (cellulose such as cotton and linen) and synthetic fibers such as polyester PET, polypropylene PP, and polyethylene PE.
The latter "oxygen system" is a formulation containing chemical substances such as hydrogen peroxide that does not cause chlorination reaction in order to avoid chlorination (chloramine generation) and decomposition by chlorine-based formulations such as hypochlorous acid. and is mainly used for bleaching animal fiber clothing (wool and silk).

Bleaching can be done without using synthetic chemicals, and in the olden days, outer skin fibers such as paper mulberry and mitsumata for papermaking, natural fibers such as linen and cotton, and textiles were bleached when exposed to snow. Are known. This traditional technique is explained by the mechanism by which ultraviolet rays in the sunlight excite the water molecules in the snow to generate active oxygen, and the pigments in the material also absorb the ultraviolet rays, causing a photochemical reaction and finally decomposing the pigments. . Also, anatase titanium dioxide has attracted attention as a photocatalyst for accelerating oxidation.

The present invention relates to "yellowing stains" derived from lipid residues remaining in the interstices of fabric fibers of white clothing such as underwear and dress shirts mainly composed of cellulose-based natural fibers and polyester fibers, which are fed by indigenous bacteria, and the interior and exterior of buildings. The present invention relates to a high-concentration stabilization preparation method and a bleaching treatment method for a chemical that bleaches any pigment derived from fungal mycelium that has invaded the deep part of the wood.

The human epidermis has sebaceous glands, and sebum regulates the skin and hair. In addition, white clothes such as underwear and shirts do not like "yellow stains". Therefore, at home and in cleaning factories, washing, washing and stain removal are frequently carried out. On the other hand, it has been extremely difficult to bleach the pigment derived from fungal hyphae that has penetrated deep into the interior and exterior materials of buildings. If sebum and fat-soluble components remain in the interstices between the fibers of white clothing or on the surface of the interior and exterior materials, the indigenous bacteria on the surface of the body and the interior and exterior materials will change their properties and stain them with colored stains. This is commonly called "yellow stain" or "colored mold stain". Mold is a type of fungus.

Chemicals known as bleaching agents are generally oxidizing agents, and ozone is known as gas, and hypochlorous acid water, hydrogen peroxide water, and ozone water are known as liquids, and are now widely used. However, although sodium sulfite and the like are known as reducing bleaching agents, their applications are limited compared to oxidizing bleaching agents.
In addition, sodium hypochlorite, which belongs to the above chlorine agents, is ionized in an aqueous solution.
If you want to obtain the desired bleaching power with chlorine water that is substantially 100% hypochlorite ion (OCl ^- ), you need a high concentration of 0.5% (= 5,000 mg / L) or more. It is the actual situation to do. Even if the sodium hypochlorite solution is diluted to 3 to 12% during distribution, if it is 0.5% or more, the hypochlorous acid hydrate will evaporate due to gas-liquid equilibrium, giving off a strong chlorine odor and effective chlorine concentration. naturally declines or "deactivates". These glitches were previously unresolved concerns.
On the other hand, if the oxygen-based hydrogen peroxide solution or the percarbonated water described in Patent Document 1, which adsorbs this, is selected, the desorbed hydrogen peroxide is quickly decomposed and deactivated as unreacted oxygen bubbles. Efficacy such as bleaching is inferior to hypochlorous acid water. Therefore, it has been considered suitable for bleaching animal fibers in laundry operations.

Inactivation of the chlorine agent at pH = 6 or higher is, as described in Patent Document 2, between three molecules of hypochlorous acid ion ( ^OCl- ) generated by a dissociation equilibrium reaction with hypochlorous acid (molecular formula: HOCl). In the long-term research of the inventor of the present application, the oxygen atoms in the two molecules are separated and become chloride ions themselves, and the oxygen atoms are rearranged to the remaining one molecule and chlorate ions (ClO ₃ ^- ) is found to be the main cause. Also, the deactivation at pH=4 or less is mainly due to the diffusion of the hydrated gas outlined by “Cl ₂ .8H ₂ O” into the gas phase. That is, it is not volatilization of dry chlorine gas (Cl ₂ ), which is traumatized as a poison gas. Furthermore, it is also a well-known fact that the hydrated chlorine gas is the identity of the chlorine odor that gives a strong stimulus, and that the diffusion rate rises sharply when the pH becomes 4 or less.

On the other hand, the decrease in concentration of high-concentration monochloramine (chemical formula NH ₂ Cl) is believed to be due to the progress of chlorination to dichloramine (NHCl ₂ ) in equilibrium and irreversible spontaneous decomposition. Therefore, high-concentration stabilization of hypochlorite ions, hypochlorous acid, and monochloramine should be possible by suppressing the above-described disproportionation reaction. That is, if a complex compound that inhibits the proximity of three hypochlorite ions (OCl ⁻ ) in the solution is interposed between the ions, high concentration stabilization can be achieved. However, in the "method for removing colored mold" described in Patent Document 3, on-site preparation was required to obtain high-concentration monochloramine water. can be prepared in advance and stored for a long time.

The inventor of the present application discovered that 2-mercaptopyridine-N-oxide (pyrithione as a tautomer) forms a relatively stable complex with iodine and a solution to the coloring caused by free iodine, and added further components and devices. and invented an antifungal agent described in Patent Document 4. However, in the treatment with the antifungal agent, the application is limited to inhibiting the growth of mold, and until the conidiophores mature and overlap and turn black, that is, it is not possible to quickly decompose and bleach mold stains that have already grown. It was difficult.
The most suitable pretreatment agent for inactivating mycelium that has penetrated deep into the substrate is the monochloramine aqueous solution shown in Patent Document 5, but in terms of bleaching, it takes about a month to determine the efficacy of monochloramine. In short, there was a drawback that the speed was slow.
Although the bleaching power is weak in the above-mentioned pretreatment with a single agent, it is none other than the weakly acidic hypochlorous acid water shown in Patent Document 2 that exhibits its power in combination with the removal of mold that has grown. . The "Method for Removing Colored Mold" in Patent Document 3 is based on this combination effect. However, the upper limit of the concentration of pH-buffering and weakly acidic hypochlorous acid water in Patent Document 3 is 1,000 mg/L = 0.1%, but for the purpose of bleaching, a higher concentration is required after considering the deactivation rate. Hypochlorous acid water can also be put to practical use.

On the other hand, high-concentration monochloramine water exceeding 10 mg/L has difficulty in stabilizing and preserving the high-concentration only by shading, and it has not been distributed as a commercial product. Stabilization of high-concentration monochloramine water is a "chemical substance that can form a complex" that forms physical and chemical bonds such as hydrogen bonds, even if it does not covalently bond with hypochlorous acid, hypochlorite ion, and monochloramine. Searching is the key.
The sensitive group that forms the basis of complex formation is an arrangement structure of nitrogen and oxygen represented by "[identical to]N→O". In addition, the outermost π-orbital electrons are involved in the complex formation of the N-oxide, and similar complex bonds may exist even if the partner other than iodine is chlorine or bromine, which is a homologous halogen element.

However, the addition of a chemical substance that captures or releases active oxygen promotes a chemical reaction with hypochlorite ions, far from preventing deactivation due to complex bond formation. This type of bleaching agent must be stably dissolved in an aqueous solution, and has not been introduced so far due to unsolved problems.

On the other hand, chlorinated isocyanuric acid (isocyanuric chloride) is already known as a chemical substance that forms stronger covalent bonds than complex bonds with hypochlorous acid and hypochlorite ions. The cyanuric acid structure is a six-membered ring in which a nitrogen atom (N) and a carbon atom (C) are alternately bonded. species exist.
However, when the chemical substance in the form of powder or granules is added to water, it easily dissolves and hydrolyzes to dissociate regardless of the number of chlorine substitutions. Hypochlorous acid, hypochlorite ions, and cyanuric acid are produced, and there is some degree of complex bonding between them, although it is difficult to conclude that they are stable complexes. However, since there is no great difference in bactericidal activity between the complex and free chlorine, it is known that the complex bond between the dissociated substances is extremely weak. Therefore, if a reagent species for residual chlorine concentration measurement, such as leuco crystal violet, is selected, it is possible to separate and measure "substantially free residual chlorine that is weakly bound" as "bonded residual chlorine".

Therefore, even if ammonia or an ammonium salt is added to an aqueous solution of chlorinated isocyanuric acid, monochloramine is produced in a pH-controlled manner. Although not as much as the N-oxide formulation example described above, high-concentration monochloramine water in which cyanuric acid coexists also increases in concentration stability and becomes difficult to decompose.

Most of the chlorine-based bleaches are monochloramine (R-NHCl) in which chlorine (Cl) and "R-NH ₂ " in the structure of carbamide such as ammonia, amines, amino acids, urea, etc., are monosubstituted. quickly on the basic side. It is on the acidic side that the rate of disubstitution to form dichloramine (R-NCl ₂ ) increases. In the past, without a good understanding of this general principle, attempts have been made to put the reaction to practical use through trial and error. Therefore, the characteristics of free chlorine and combined chlorine were grasped in detail, and without systematic measures to prevent deactivation, surfactants with low chlorine demand were blindly added and commercialized. be.

Many of the "yellow stains" on clothing mentioned at the beginning of the present application are substances produced by decomposition and denaturation of fatty acid glycerin esters secreted from the body by microorganisms on the body surface. 4-Methyl-3-hexenoic acid, which is said to be the cause of the dry smell, is also a product of this microorganism and has a double bond in its structure. In addition, the above-mentioned fatty acids are not limited to saturated fatty acids and contain unsaturated fatty acids, and various colored substances are produced by the decomposition of microorganisms. That is, if the molecular chains of unsaturated hydrocarbons remain, including the soap scum resulting from the surfactant, the color tends to turn yellow. Furthermore, the double bond of the molecular chain may be oxidized or polymerized. The "yellow stain" is embedded in the fibers and is difficult to remove. As a matter of fact, the conventional washing theory of micelle formation that surrounds with surfactant molecules to increase suspension properties does not apply to removing yellowed stains that have once dried and solidified.

Therefore, the removal and bleaching of "yellow stains", which has been an unsolved problem so far, requires the introduction of a new cleaning concept. That is, in order to weaken the adhesive force between the fibers of the clothing and the colored stains, the concept of first penetrating the adhesive surface deep into the adhesive surface with a chemical that is less susceptible to electrostatic repulsion and has a small molecular weight has become essential. This concept unexpectedly coincided with the concept indispensable for bleaching pigments derived from fungal hyphae embedded deep in building interior and exterior materials. A chemical substance that can be cited as the first example of a new idea is monochloramine, which is a non-dissociating molecule and has the molecular formula of "NH ₂ Cl".

Conventional bleaching agents do not have the concept of generating new or regenerating bleaching chemical substances by causing chemical reactions in the liquid during bleaching treatment. That is, conventionally, the object to be treated is immersed in an aqueous solution formulated to a certain concentration, or the object to be treated is sprayed with a bleaching agent to exert the bleaching power of the dissolved components, and the effect of the bleaching power is It decreased gradually and did not increase during the action.
However, as described in Non-Patent Document 1 and Non-Patent Document 2, if the chlorination of monochloramine proceeds under the condition of pH = 5 to 9 to generate dichloramine (NHCl ₂ ), it naturally decomposes and hypochlorite Regenerate the acid (HOCl). The inventor has established this fact in the treatment of swimming pool water. In conclusion, confirming the regeneration of hypochlorous acid by the increase in free residual chlorine concentration is based on the relationship between the regeneration rate and the consumption rate accompanying the re-reaction, pH = 6.5 to 7.2 and water temperature 15 ° C or less It has been found that the relatively easy and hard-to-identify renaturation reaction occurs over a wider pH range.

In addition, as described in Non-Patent Document 3, monochloramine exhibits a marked effect on exfoliation of slime (biofilm) secreted by microorganisms and mainly composed of polysaccharides, and this knowledge has already been disclosed.
All of these properties can be used for denitrification from water, cyst formation of amoebas, and exfoliation of bacterial flora, and have already been put to practical use. A number of experiments were conducted to arrive at the present invention.

JP-A-49-119933 JP 2014-9227 A JP 2018-16550 A JP 2015-81233 A JP-A-2008-264678

Bernard M. Saunier and Robert E. Selleck, The "Kinetics of Breakpoint Chlorination in continuous Flow Systems"Jour. AWWA, 164-172 (Mar. 1979) Seki Hideyuki, Li Zhengxiong; Proposal for Pool Water Quality Management/Measurement of Monochloramine in Pool Water and Proof of Regeneration of Free Chlorine, Water and Wastewater Vol. 33, Number 5 (1991) Hideyuki Seki, Yutaka Nakao; Practical case report of monochloramine/free chlorine disinfection combined method as a countermeasure against Legionella, Water and Wastewater, Vol. 53, Number 8 (2011) Caroline Nguyen, Carolyn Elfland, MarcEdwards, Impact of advanced water consumption and new copper pipe on rapid chloramine decay and microbial regeneration

First, "yellow stains" derived from lipid residues that are fed by indigenous bacteria remaining in the interstices between fabric fibers of white clothing such as underwear and dress shirts mainly composed of cellulose-based natural fibers and polyester fibers, and the use of building interior and exterior materials. The problem is how to prepare a high-concentration monochloramine that penetrates deep into the “pigment” derived from fungal hyphae and does not readily decompose during penetration. The next problem is how to generate a chemical substance with strong bleaching power, that is, hypochlorous acid, deep inside the object to be bleached.

To solve the first problem, the disproportionation reaction that causes deactivation is caused by adding any complex-forming substance to a chlorine agent aqueous solution in which almost the entire amount is dissociated as hypochlorite ions at high basicity (high pH). Therefore, various experiments were conducted to select an alkylamine oxide. When ammonia (NH ₃ ) or an ammonium salt is added to this, hypochlorite ions and ammonia react under high pH conditions to produce monochloramine at a high concentration. Hence, this becomes the "primary bleaching agent". The added complex-forming substance does not inhibit the chloramine formation reaction, but rather plays a role in stabilizing the structure of the produced monochloramine.

Following treatment with the primary bleach, an aqueous solution of isocyanuric chloride (chlorinated isocyanuric acid) is prepared which acts as a neutralizer to drive the chlorination of monochloramine and accelerate the reaction rate. This becomes the "secondary bleach". The progress of chlorination of monochloramine can be carried out even with an aqueous solution of hypochlorous acid whose pH is adjusted to be weakly acidic. It is also possible to substitute a general-purpose sodium hypochlorite aqueous solution.
The rate of reaction in which chlorination of monochloramine proceeds to form dichloramine is greater at low pH, contrary to monochloramine formation. In addition, all of the decomposition reactions of available chlorine, including the natural decomposition reaction of dichloramine, are acidification reactions, and as the decomposition progresses, the pH of the aqueous bleach solution decreases, further accelerating the decomposition. Therefore, as an initiator for regenerating hypochlorous acid deep inside the object to be bleached, the secondary bleach is preferably weakly acidic.

In other words, the present invention not only functions as a primary bleaching agent with a high concentration of monochloramine at high pH, but also functions as a secondary bleaching agent at low pH by generating and decomposing dichloramine and regenerating hypochlorous acid. It has a remarkable bleaching effect in two steps.

Means for solving the above problems are as follows.
(1) In an aqueous hypochlorite solution with an available chlorine concentration of 2,001 to 20,000 mg/L, 1/4 to 1 mol of alkylamine oxide per 1 mol of available chlorine, and 1 mol of available chlorine Ammonia nitrogen (NH ₃ —N/Cl ₂ =1 to 2 [M/M]≈0.2 to 0.4 [wt./wt.]) equivalent to ~2 moles is added to produce a high concentration of monochloramine. A primary bleaching agent and an aqueous solution characterized by stabilizing a high concentration of the agent by adjusting the pH to 8.0 to 10.4, and immersing the object to be treated in the aqueous solution or immersing the object to be treated in the aqueous solution A bleaching treatment method that sprays toward.
(2) An aqueous solution of isocyanuric acid dichloride or isocyanuric acid trichloride with an available chlorine concentration of 500 to 30,000 mg/L for addition during the bleaching treatment of (1), or pH = 5.0 to 7 immediately before use A secondary bleaching agent characterized by an aqueous hypochlorite solution with an available chlorine concentration of 500 to 30,000 mg/L adjusted to 0.0 and adding said secondary bleaching agent to the primary bleaching solution during treatment as described above (1 A bleaching treatment method comprising immersing the object to be treated following the bleaching treatment of (1), or spraying a secondary bleaching agent onto the object to be treated following the bleaching treatment of (1).

According to the means of (1) above, the "fat-soluble substances" remaining in the interstices between the fibers of white underwear, dress shirts, work socks, etc., mainly composed of natural fibers, polyester fibers, etc., are bleached by oxidizing and decomposing them. became possible. At the same time, due to the complex bonding of alkylamine oxide and monochloramine in the aqueous solution, both odors associated with hypochlorous acid hydrated gas and high chloride gas represented by nitrogen trichloride NCl ₃ , which are likely to be generated during the reaction, are reduced. effect was also obtained.

Regarding the agent (1) above, hypochlorite for preparing an aqueous solution is not limited to sodium salt, and calcium salt and potassium salt can also be used. Examples of alkylamine oxides that are easy to put into practical use include dimethyllauryl (C ₁₂ ) amine oxide, dimethylmyristyl (C ₁₃ ) amine oxide and dimethylstearyl (C ₁₈ ) amine oxide, which are commercially available as surfactants. can also be selected. Additionally, other types of alkylamine oxides that can prevent the conversion of hypochlorite ions to chlorate ions can be used.
In the examples, dimethylmyristyl (C ₁₃ ) amine oxide was chosen because it is readily available.

Regarding the drug of (1) above, ammoniacal nitrogen is at least one of ammonia and ammonium ions. Ammonia water may be used when ammonia is selected. Ammonium salts may be used if the ammonium ion is selected. For example, ammonium chloride, ammonium sulfate, or other salts may be used. Ammonium chloride was used in Examples described later.
Ammonia nitrogen corresponding to 1 to 2 moles of available chlorine is expressed as (NH ₃ —N/Cl ₂ =1 to 2 [M/M]≈0.2 to 0.4 [wt./wt .]).

According to the means (2) above, the effective chlorine of the secondary bleaching agent added to the means (1) above diffuses in the direction of the already permeated primary bleaching agent, thereby chlorinating monochloramine. progresses.
On the other hand, by simply dissolving the powder or granules of isocyanuric acid dichloride in water, the pH of the secondary bleaching agent obtained by means (2) above became 6.3 to 6.7. Further, the pH of the aqueous solution is further lowered with the powder or granules of isocyanuric acid trichloride. Therefore, a neutralization reaction occurs as a result of mixing the primary bleaching agent and the secondary bleaching agent, and the decrease in pH accelerates the formation and decomposition of dichloramine and the regeneration of hypochlorous acid.
Furthermore, the same phenomenon occurs when a hypochlorite aqueous solution with an effective chlorine concentration of 1,000 to 30,000 mg/L adjusted to pH = 5.0 to 7.0 immediately before use is used as a secondary bleaching agent. . In addition, you may mix both aqueous solutions.
The generated dichloramine decomposes spontaneously, regenerates hypochlorous acid deep inside the object to be treated, and releases nitrogen gas (N ₂ ). The regenerated hypochlorous acid is oxidized (oxide generation) by taking away the π-orbital electron, which is one of the double bonds in the structure of the colored substance, and the reaction further proceeds to break the double bond, resulting in a colorless substance. decompose into
In other words, it has become possible to thoroughly decompose and bleach oil-soluble "yellow stains" and fungal mycelium-derived pigments embedded deep in interior and exterior materials by regenerated free chlorine.

In the secondary bleaching agent (2) above, by making isocyanuric acid dichloride or isocyanuric acid trichloride into an aqueous solution, the three substances of hypochlorous acid, hypochlorite ion and cyanuric acid are in dissociation equilibrium. Therefore, there is no need to worry about deactivation due to the generation of chlorate ions.
That is, chlorination of monochloramine progresses to form dichloramine, which causes regeneration of hypochlorous acid and generation of nitrogen bubbles accompanying natural decomposition, and as a result, it has become possible to enhance the bleaching effect. The reaction formula is shown as "2NHCl ₂ +H ₂ O→N ₂ +HOCl+3H ⁺ +3Cl ⁻ ".
Furthermore, the decomposition is an acidification reaction that generates hydrogen ions (H ⁺ ), and as the decomposition progresses, the pH decreases and unreacted hypochlorous acid is generated, leading to a dissociation equilibrium reaction (H ⁺ +OCl ⁻ →HOCl). tilts. Therefore, the bleaching due to the oxidation reaction caused by available chlorine is further accelerated.

On the other hand, if two substances, undissociated monochloramine (molecular formula: NH ₂ Cl) and weakly acidic hypochlorous acid (same as: HOCl), are stabilized at high concentrations and reacted during the bleaching process, At the same time as exhibiting strong sterilization and bleaching power, it can be expected to penetrate into the gaps between various fibers. The molecular diameters of both monochloramine and hypochlorous acid are approximately the same as the molecular diameters of water, and monochloramine, which has weaker reactivity, is more likely to penetrate deep into the gaps between fibers, and can be expected to contribute to the removal of fat-soluble stains.
The main point of the present invention is to regenerate hypochlorous acid, which has a strong bleaching power, in the deep part of the object to be treated. is completely different. It should be noted that the phenomenon of microbubble generation accompanying decomposition/bleaching and denitrification was first discovered by the inventor of the present application and applied to practical use.

With respect to the secondary bleaching agent in (2) above, different dissociation equilibria of aqueous solutions will result in different pH. In the examples, isocyanuric acid dichloride (also known as dichloroisocyanuric acid) was selected to prepare the secondary bleaching agent, considering the difficulty of adjusting the pH to 8.0 to 9.0 and the strength of the odor emitted. Of course, isocyanuric acid trichloride (also known as trichloroisocyanuric acid) can be selected.

Other aspects are as follows.
<1> In an aqueous solution of hypochlorite with an available chlorine concentration of 2,001 to 20,000 mg/L, an alkylamine oxide equivalent to 1/4 to 1 mol per 1 mol of available chlorine, and 1 equivalent to available chlorine Add ammonia nitrogen equivalent to ~2 moles to generate monochloramine and immerse the object to be treated in a primary bleach adjusted to pH = 8.0 to 10.4 or direct the primary bleach to the object to be treated bleaching treatment method.
<2> An aqueous solution of isocyanuric acid dichloride or isocyanuric acid trichloride with an available chlorine concentration of 500 to 30,000 mg/L, or an aqueous solution with an available chlorine concentration of 500 to 30,000 mg/L adjusted to pH = 5.0 to 7.0 The object to be treated after bleaching according to claim 1 is immersed in a chlorite aqueous solution or a secondary bleaching agent obtained by adding at least one of the above aqueous solutions to the primary bleaching agent. A bleaching method, comprising: spraying a bleaching agent onto the object to be treated after bleaching according to <1>.
<3> In an aqueous solution of hypochlorite with an available chlorine concentration of 2,001 to 20,000 mg/L, an alkylamine oxide equivalent to 1/4 to 1 mol per 1 mol of available chlorine, and 1 mol per available chlorine A process for the preparation of a primary bleach, with the addition of ˜2 moles of ammoniacal nitrogen, adjusted to pH=8.0-10.4.
<4> For the primary bleach manufactured in <3>, an aqueous solution of isocyanuric acid dichloride or isocyanuric acid trichloride with an effective chlorine concentration of 500 to 30,000 mg / L, or pH = 5.0 to 7.0 A method for producing a secondary bleaching agent, comprising an adjusted hypochlorite aqueous solution having an available chlorine concentration of 500 to 30,000 mg/L, or adding at least one of the above aqueous solutions to the primary bleaching agent.
<5> A hypochlorite aqueous solution with an available chlorine concentration of 2,001 to 20,000 mg/L;
an alkylamine oxide equivalent to 1/4 to 1 mol per 1 mol of available chlorine;
Ammonia nitrogen equivalent to 1 to 2 moles of available chlorine,
and pH=8.0-10.4.
<6> Contains monochloramine with an available chlorine concentration of 2,001 to 20,000 mg/L, pH = 8.0 to 10.4, and a reduction rate of the available chlorine concentration of monochloramine of 1% / day or less, primary bleach.
<7> An aqueous solution of isocyanuric acid dichloride or isocyanuric acid trichloride with an effective chlorine concentration of 500 to 30,000 mg/L, or an aqueous solution with an effective chlorine concentration of 500 to 30,000 mg/L adjusted to pH = 5.0 to 7.0 A secondary bleaching agent that is an aqueous chlorite solution.
<8> the primary bleaching agent according to <5> or <6>;
An aqueous solution of isocyanuric acid dichloride or isocyanuric acid trichloride with an available chlorine concentration of 500-30,000 mg/L, or hypochlorite with an available chlorine concentration of 500-30,000 mg/L adjusted to pH = 5.0-7.0 an aqueous solution;
A secondary bleaching agent containing
<9> The primary bleaching agent according to <5> or <6>;
An aqueous solution of isocyanuric acid dichloride or isocyanuric acid trichloride with an available chlorine concentration of 500 to 30,000 mg/L, or hypochlorous acid with an available chlorine concentration of 500 to 30,000 mg/L adjusted to pH = 5.0 to 7.0. an aqueous salt solution;
A bleach set, consisting of:

First, "yellow stains" derived from lipid residues that are fed by indigenous bacteria remaining in the interstices between fabric fibers of white clothing such as underwear and dress shirts mainly composed of cellulose-based natural fibers and polyester fibers, and the use of building interior and exterior materials. It is possible to prepare a high-concentration monochloramine that penetrates deep into the “pigment” derived from the fungal mycelium and is difficult to decompose during the penetration. The next effect is the production of a strong bleaching chemical, hypochlorous acid, deep within the bleached object.

It is a figure for demonstrating an example of the structure of the alkylamine oxide which concerns on this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a figure for demonstrating an example of the structure of the chlorinated isocyanuric acid based on this invention. It is a figure for demonstrating that the chlorine concentration of the primary bleaching agent which concerns on this invention is stable. 1 is a photograph for explaining Example 1 of bleaching treatment results according to the present invention. 2 is a photograph for explaining Example 2 of bleaching treatment results according to the present invention. 3 is a photograph for explaining Example 3 of mold stain bleaching according to the present invention.

Hereinafter, the method for preparing and treating bleach according to the embodiment of the present invention will be described with reference to FIGS. 1 to 6. FIG.
Fig. 1 shows the chemical formulas of dimethyllauryl-amine oxide and dimethylmyristyl-amine oxide, and the homologous alkylamine oxide is added to the primary bleaching agent to stabilize the structure of hypochlorite ion and monochloramine. .
FIG. 2 shows the structure of the isocyanuric acid dichloride used in the method (2) above.

FIG. 3 shows the results of measuring the change in effective chlorine concentration over time for each of the low-concentration monochloramine aqueous solution produced and prepared by the general method described in Non-Patent Document 4 and the above-mentioned agent (1) (primary bleaching agent). be. The effective chlorine concentration was measured by a digital display type absorptiometer of the DPD method and the iodine method.
Although the Y axis is scaled logarithmically, the available chlorine concentration can be maintained at around 2,000 mg/L for at least two months after preparation of the drug of the present invention, and there is no need to worry about deactivation during commercial distribution. That is, when comparing the time axis unit and the gradient, about 50 times the stability can be obtained as compared with the conventional method. Of course, if a primary bleaching agent with an effective chlorine concentration of 1,000 mg/L, which is half the concentration, is used, the bleaching speed will decrease accordingly, but it will not be completely unusable. there is no problem. In the primary bleaching agent of the present invention, the decrease in the effective chlorine concentration of monochloramine is very slow. For example, the rate of decrease of the effective chlorine concentration of monochloramine from the initial value (day of production) is preferably 1%/day or less, more preferably 0.5%/day or less, and even more preferably 0.25%/day or less.

The technical idea of the present invention is also reflected in the bleaching agent set consisting of the above (1) primary bleaching agent and the above (2) secondary bleaching agent. For example, when removing stains from the ceiling of a food store as in Example 3, after treatment with the primary bleaching agent, the secondary bleaching agent brought separately was mixed with the primary bleaching agent on the spot. A secondary bleach may be made. Alternatively, you can take out the secondary bleach that you brought separately and spray it on the areas treated with the primary bleach. In any case, the effects of the present invention are exhibited.

[Example 1]
FIG. 4 shows the result of removing stains from an example of a dress shirt with yellow stains remaining on the collar and difficult to wear in the bleaching of white clothing according to Example 1 with the primary bleaching agent and then the secondary bleaching agent.
The pH and components of the primary bleaching agent and secondary bleaching agent are as follows.
<Primary bleach>
<<1>> Effective chlorine concentration: 2,150 mg / L as total residual chlorine
<<2>> Added dimethylmyristylamine oxide concentration: 2,000 mg/L
<<3>> Initial concentration of added ammoniacal nitrogen (NH ₃ —N): 450 mg/L
The produced monochloramine concentration is also 2,150 mg/L as effective chlorine concentration.
<<4>> pH≈10
<Secondary bleach>
<<1>> Effective chlorine concentration: about 2,000 mg/L
<<2>> Ingredients: Aqueous solution of isocyanuric acid dichloride <<3>> pH≈6.7
A dress shirt used as an object to be treated in the practice of the present invention was kept without being worn for a long period of time because the "yellow stain" could not be completely removed even after being taken out to the cleaning company many times.
Comparing the photographs in FIG. 4, it can be seen that the "yellow stain" remaining on the folded collar portion of the shirt was completely bleached without damaging the substrate.

[Example 2]
FIG. 5 shows the result that the white clothing according to Example 2 was bleached in the same manner as in Example 1. FIG. The garment of the example was also stored with the same history as the garment of Example 1.

[Example 3]
In the bleaching of the mold growing on the ceiling of the food store according to Example 3, the result of spraying the secondary bleaching agent following the primary bleaching agent and comparing the ceiling bleaching condition after 1 hour with that before treatment is shown in FIG. is.
In the photograph of FIG. 6, the black mold stains seen in the photograph before bleaching treatment are mainly propagated by "black mold" belonging to Cladosporium (scientific name: Cladosporium). As a result of spraying the secondary bleach after the penetration of the primary bleach, the chlorination of monochloramine and the regeneration of hypochlorous acid accompanying the natural decomposition of dichloramine caused stubborn mold stains without proof of effectiveness through bacterial tests. bleached in no time. And it can be seen that the ceiling surface has been restored to a beautiful state.

According to the present invention, "yellowing stains" derived from lipid residues remaining in the interstices of fabric fibers of white clothing such as underwear and dress shirts mainly composed of cellulose natural fibers and polyester fibers can be removed not only in cleaning factories but also in ordinary homes. Can be bleached. In addition, it can be used to remove mold stains on the interior and exterior of buildings that impair the hygienic appearance and aesthetic appearance, and furniture, fixtures, and decorations that are hydrophobic or have weak water absorption, if bleaching does not cause problems.
Furthermore, it can be applied to remove mold from the ceiling of the bathroom, the dewatering basket of the washing machine, or the outside of the punched metal cylinder of the washing machine, which is hard to reach. can be done. Of course, sterilization, which is one of the original characteristics, is also performed at the same time. In addition, the two chemicals (aqueous solution) used are hypochlorous acid, monochloramine (combined chlorine), cyanuric acid, and general-purpose surfactants that have been proven safe for chlorine disinfection of tap water and swimming pools. Since it is an alkylamine oxide, it has ample potential for use in the restoration of arts and crafts. There is no problem in ensuring the safety of the human body.

Claims (7)

In an aqueous hypochlorite solution with an available chlorine concentration of 2,001 to 20,000 mg/L, 1/4 to 1 mol of alkylamine oxide per 1 mol of available chlorine and 1 to 2 mol of the available chlorine are added. Substantial ammoniacal nitrogen is added to generate monochloramine, and the object to be treated is immersed in a primary bleach adjusted to pH=8.0-10.4 or the primary bleach is sprayed onto the object to be treated. , bleaching treatment method. An aqueous solution of isocyanuric acid dichloride or isocyanuric acid trichloride with an available chlorine concentration of 500 to 30,000 mg/L, or hypochlorous acid with an available chlorine concentration of 500 to 30,000 mg/L adjusted to pH = 5.0 to 7.0. The object to be treated after the bleaching treatment according to claim 1 is immersed in a salt solution or a secondary bleaching agent obtained by adding at least one of the above aqueous solutions to the primary bleaching agent, or the secondary bleaching agent. A bleaching treatment method, which sprays toward the object to be treated after bleaching treatment according to claim 1. In an aqueous hypochlorite solution with an available chlorine concentration of 2,001 to 20,000 mg/L, 1/4 to 1 mol of alkylamine oxide per 1 mol of available chlorine and 1 to 2 mol of the available chlorine are added. A process for the preparation of primary bleaches with the addition of substantial ammoniacal nitrogen and adjusted to pH=8.0-10.4. For the primary bleaching agent produced in claim 3, an aqueous solution of isocyanuric acid dichloride or isocyanuric acid trichloride with an effective chlorine concentration of 500 to 30,000 mg / L, or an effective pH adjusted to 5.0 to 7.0 A method for producing a secondary bleach, comprising an aqueous hypochlorite solution having a chlorine concentration of 500 to 30,000 mg/L, or adding at least one of the above aqueous solutions to the primary bleach. A hypochlorite aqueous solution with an available chlorine concentration of 2,001 to 20,000 mg / L,
an alkylamine oxide equivalent to 1/4 to 1 mol per 1 mol of available chlorine;
Ammonia nitrogen equivalent to 1 to 2 moles of available chlorine,
and pH=8.0-10.4. a primary bleaching agent according to claim 5;
An aqueous solution of isocyanuric acid dichloride or isocyanuric acid trichloride with an available chlorine concentration of 500-30,000 mg/L, or hypochlorite with an available chlorine concentration of 500-30,000 mg/L adjusted to pH = 5.0-7.0 an aqueous solution;
A secondary bleaching agent containing a primary bleaching agent according to claim 5;
An aqueous solution of isocyanuric acid dichloride or isocyanuric acid trichloride with an available chlorine concentration of 500 to 30,000 mg/L, or hypochlorous acid with an available chlorine concentration of 500 to 30,000 mg/L adjusted to pH = 5.0 to 7.0. an aqueous salt solution;
A bleach set, consisting of:

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