JP2000247802A - Solid remover of mildew - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid remover of mildew, capable of exhibiting excellent effect on removing mold in a small quantity consumed, excellent in water washing property and storage stability, and not causing liquid spill even when external pressure is exerted on the remover. SOLUTION: This remover comprises 0.5-2 wt.% alkali metal salt of hypochlorous acid in terms of effective chlorine concentration, 0.5-5 wt.% hydroxide of an alkali metal, 0.3-20 wt.% alkali metal salt of at least one kind of aliphatic carboxylic acids, 0.2-5 wt.% polyacrylic acid-based thickener and 70-95 wt.% water as essential effective ingredients.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of directly acting on an attached mold (mold) generated on the surface of various members indoors and outdoors to kill it and bleach the working surface. And a mold remover capable of providing a clean surface again. The solid mold remover of the present invention can be constituted with a small amount of components, is excellent in water washability and storage stability, and bleeds out liquid components (water and the like) contained even when an external pressure such as a pressing force is applied. Does not leak or leak.

[0002]

2. Description of the Related Art Conventionally, various types of fungicides have been widely used to remove molds generated on surfaces of various members indoors and outdoors. In particular, since a large amount of mold is generated on constantly wet parts such as bathrooms, kitchens, and lavatories, for example, on wall surfaces (particularly at joints between tiles), many mold removers for bathrooms, kitchens, and lavatories are commercially available. Have been. Specifically, such commercially available fungicides are usually provided in the form of a combination of a strong alkali such as sodium hydroxide and a strong oxidizing agent such as hypochlorite, The form is usually a liquid contained in a container, and can be applied to a mold removing portion by impregnating a liquid-absorbing material such as a cloth or a sponge, and when the container is a spray container, the liquid Can be applied by spraying an appropriate amount of the mold onto the mold removing site.

In the case of using an appropriate amount of liquid by impregnating it with another liquid-absorbing material as in the former case, it is troublesome in that the appropriate amount must be measured each time.
In addition, there is a trouble such as a need to wear vinyl gloves to protect hands when handling the liquid. Also,
When the liquid is sprayed from the spray container as in the latter case, it is possible to avoid the unnecessary spraying of the liquid not only to the target mold removal area but also to the surrounding area which should not be sprayed. Can not. Therefore, such a liquid spraying method is not only economically disadvantageous, but also when used in a small bathroom, kitchen, washroom, etc., the concentration of the spray particles of the fungicide floating in the air becomes high, Workers may feel uncomfortable due to the peculiar pungent odor, cause accidents due to inhalation of spray particles by workers, or adhere to scattered spray particles on the skin.
It may cause skin irritation.

[0004] As a solution to the above-mentioned problems, a paint-type mold remover equipped with a felt-like applicator has been proposed. Since the mold remover can be used by including a liquid mold remover in the applicator, the inconveniences described above can be avoided, and in particular, accidents caused by spray particles can be prevented or It is worth noting that it can be reduced. However, when a mold removing agent is included in the applicator, it is difficult to prevent excess liquid from dripping out of the applicator. The occurrence of dripping means that the fungicide is used in excess, and can be economically lost, and as long as the fungicide is liquid, it can be used in combination with an acidic detergent. The danger of the generation of chlorine gas due to is considered sufficiently.

[0005] Oxygen bleaching agents, especially mold removers containing hydrogen peroxide as a main component, reduce the danger of chlorine gas generation when used in combination with an acidic cleaning agent. In this type of fungicide, since the hydrogen peroxide is alkaline and unstable, the fungicide itself becomes weakly acidic and may not be effective enough to kill a large amount of mold. That is, when a mold removing agent containing an oxygen-based bleach as a main component is used, it is necessary to frequently perform a mold removing operation. In addition, although a lactic acid-based fungicide containing no bleaching component is also known, in the case of such a fungicide, the mold coloring when the mold is killed remains as it is, It is hard to say that the cleaning effect is sufficient.

It is desirable that the fungicide is applied to a mold removing site, used, and then easily and cleanly removed by washing with water. It is desirable that inconveniences such as change do not occur, and therefore, it can be stored stably for a long time. Further, when a solid mold remover is applied with an external pressure such as a pressing force, the liquid component (eg, water) contained in the solid mold remover often leaks out or leaks. It is desirable to eliminate this.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the prior art and to directly act on mold to kill it and bleach the working surface. Is a mold removing agent that can provide a clean surface again, is safe and easy to use, can exhibit a mold removing effect without waste and reliably, and is excellent in water washability and storage stability, and Another object of the present invention is to provide an improved mold removing agent which does not leak or leak liquid components contained therein even when an external pressure such as a pressing force is applied.

Another object of the present invention is to provide a fungicide having the desired fungicidal effect by combining various components in the past, but to achieve this by using fewer components. It is in.

[0009]

According to the present invention, the above object is achieved by converting the following components: available chlorine concentration to 0.5.
Alkali metal hypochlorous acid in an amount of 0.5 to 5%
% Alkali metal hydroxide, 0.3-20% alkali metal salt of at least one aliphatic carboxylic acid,
0.2-5% of a polyacrylic acid-based thickener, and 70-9
This can be achieved by a solid mold remover characterized by containing 5% of water as an essential active ingredient.

[0010]

Next, the present invention will be described with reference to preferred embodiments. The present inventors have renewed the recognition that the problem of the conventional technology as described above is that the fungicide is used as a liquid, and if the fungicide can be used as a solid, it is expected that We gained the knowledge that many advantages that did not come out could be led, and as a result of trying to solidify various active ingredients, we used oxidized bleach as an active ingredient,
A solid mold remover characterized by using a gelling agent to solidify the bleaching agent has been completed.

The solid mold remover is preferably composed of a base, an oxidized bleach, a gelling agent, a surfactant, a humectant, a thickener and water, wherein the bleach is preferably used. Is at least one compound selected from the group consisting of hypohalous acid, an alkali metal salt or an alkaline earth metal salt of a halogen acid or a halogen acid, and the gelling agent preferably has 10 to 10 carbon atoms. It is at least one compound selected from the group consisting of an alkali metal salt or an ammonium salt of an aliphatic carboxylic acid and 1,2-hydroxystearic acid.

Although this solid mold remover is safer and easier to use than conventional mold removers, and can exert a mold removing effect without waste, the present inventors have found that a more excellent solid mold remover can be obtained. He continued his intensive research to develop a stripping agent. In particular, with regard to the water washability, it can be easily removed only by water wash, and it is advantageous to wash the water by spraying lukewarm water on the mold removing part and paying attention to the amount of gelling agent and thickener etc. However, it was not possible to assure better water washability. Similarly, regarding the storage stability, no attempt has been made to more specifically attempt to improve the storage stability.

The present inventors have now constructed a solid mold remover consisting of an oxidized bleach, a base, a solidifying agent, a thickener and water, and at this time, as effective components thereof, an effective chlorine concentration 0.5 to 2% of an alkali metal salt of hypochlorous acid (as an oxidized bleach) in an amount of 0.5 to 5%
Alkali metal hydroxide (as a base or strong alkali), 0.3 to 20% of an alkali metal salt of at least one aliphatic carboxylic acid (as a solidifying agent);
2-5% polyacrylic acid thickener, and 70-95%
It was found that by using water, the intended purpose could be achieved.

In the practice of the present invention, the oxidized bleach as an active ingredient is an alkali metal salt of hypochlorous acid, such as a sodium salt or a potassium salt, and more preferably, sodium hypochlorite or hypochlorous acid. And potassium chlorate. By using such a specific bleaching compound, the fungicide of the present invention embodied an excellent oxidizing action, thereby killing the mold and, at the same time, being darkened by the mold and contaminated with other colors. The site can be bleached on the principle of so-called dye bleaching.

Among the bleaching compounds described above,
In particular, sodium hypochlorite and potassium hypochlorite can be advantageously used, and these compounds may be used alone or in combination. The amount of the alkali metal hypochlorous acid used is in the range of 0.5 to 2% in terms of the effective chlorine concentration. Therefore, the amount of the effective chlorine in the fungicide is 0.1%. It is necessary to adjust the amount of the alkali metal salt of hypochlorous acid so as to fall within the range of 5 to 2%.
In fact, when the amount of available chlorine derived from such hypochlorite is less than 0.5%, the bleaching effect of mold becomes insufficient, and conversely, the amount of available chlorine increases to 2%. If it exceeds, sufficient hardness cannot be imparted to the obtained mold removing agent despite the use of the solidifying agent.

In the mold removing agent of the present invention, it is essential to use a hydroxide of an alkali metal as a base. Alkali metal hydroxides that can be used here are
Sodium hydroxide or potassium hydroxide, and these hydroxides may be used alone or in combination. When such a base compound is blended in the fungicide of the present invention, it can mainly exhibit the function of inhibiting the growth of mold, and in addition,
An oxidized bleaching agent, that is, a function of suppressing the decomposition of an alkali metal salt of hypochlorous acid can also be exerted. Therefore, in the present invention, when adding a base to the fungicide, it is preferable to adjust the amount of the base added so that the final pH value of the fungicide is greater than 11, preferably 12 or more. It is more preferable to adjust to.

By the way, from the viewpoint of mold growth inhibition,
It is desired that the final pH value of the fungicide be greater than 11, or less than 2. This is because although mold is generally considered to be suitable for cell activity near pH = 5-6, it inhabits many parts of the naturally occurring substrate in a wide range of pH = 3-10, especially This is because mold can easily grow in a wider pH range such as pH = 2 to 11 under an environment of high temperature (30 ° C. or higher) and high humidity (80% RH or higher). Also, from the viewpoint of decomposition of metal hypochlorite used as a bleaching agent,
That is, since these compounds are more active in the decomposition reaction near neutrality, the pH is generally at least higher than 11.
Value, more preferably a pH value of 12 or more,
It is preferable to adjust the amount of the base added.

The amount of the alkali metal hydroxide as the base is in the range of 0.5 to 5%. If the compounding amount of this compound is less than 0.5%, the function of inhibiting the growth of mold as described above will not be sufficiently exhibited, and conversely, even if it exceeds 5%, the obtained function will notably increase. Can not expect. In the mold removing agent of the present invention, at least one alkali metal salt of an aliphatic carboxylic acid is used as a solidifying agent in order to solidify an aqueous solution containing an active ingredient, that is, a precursor of a solid mold removing agent. . This type of solidifying agent can be uniformly dissolved in an aqueous solution containing the active ingredient by being heated to an elevated temperature of 60 to 100 ° C., and can form a hydrated solid by subsequent cooling. is there.

The alkali metal salt of an aliphatic carboxylic acid which can be used is further described. The aliphatic carboxylic acid used herein is preferably an aliphatic carboxylic acid having 10 to 18 carbon atoms, more preferably, for example, stearic acid. ,
Palmitic acid, myristic acid, lauric acid, etc.
The alkali metal used to form such a carboxylic acid salt is preferably sodium, potassium or the like.

In the practice of the present invention, a suitable solidifying agent can be formed by arbitrarily combining the carboxylic acid and the alkali metal as described above, and the alkali metal salt of the carboxylic acid can be used as a solidifying agent. May be used alone or as a mixture. In particular, a single or mixture of myristate and laurate can be advantageously used as a solidifying agent,
If necessary, a stearate or a palmitate can be further added to such a salt. In addition,
Stearate alone tends to be difficult to heat and melt, but this can be solved by using another carboxylate in combination, and a carboxylate suitable for such purpose is For example, myristate and laurate.

The amount of the solidifying agent in the mold remover is
It is necessary to be in the range of 0.3 to 20%, more preferably in the range of 0.5 to 10%, and most preferably in the range of 1.0 to 8%. When the amount of the solidifying agent is less than 0.3%, the solid state of the mold removing agent cannot be sufficiently maintained, and for example, when used in a stick-shaped container, it is difficult to draw it out of the container. become. Conversely, if the amount of the solidifying agent increases to exceed 20%, the mold removing agent becomes too hard, and when used, a sufficient amount of the mold removing agent may be applied to a predetermined site. It is no longer possible and the application operation has to be carried out repeatedly in order to apply the active ingredient in a predetermined amount.

In the mold remover of the present invention, polyacrylic acid or a derivative thereof is used as a thickener. When polyacrylic acid and its derivatives (hereinafter also referred to as "polyacrylic acid-based thickener") are included in the mold remover of the present invention, when an external pressure such as pressing force is applied, the mold remover will It can help prevent or at least reduce the bleeding or leakage of liquid components. In addition, as an additional function, the polyacrylic acid-based thickener does not promote the decomposition reaction of the hypochlorous acid-based bleach used as the main component, and can be easily washed with water after use. It is possible. Although polyacrylic acid and its derivatives may be advantageously used as thickeners in the practice of the present invention, a wide range is preferred, but preferably about 1,000,000
000 or more, more preferably about 2,000
It has a molecular weight in the range of from 000 to about 5,000,000. This is because the desired function as described above is sufficiently exhibited at such a high molecular weight.

The amount of the polyacrylic acid thickener in the fungicide must be in the range of 0.2 to 5%, and more preferably in the range of 0.5 to 3%. When the amount of the thickener is less than 0.2%, when an external pressure is applied to the mold removing agent, a liquid component (here,
Seepage or leakage of “content liquid”). Conversely, if the amount of the thickening agent is increased to exceed 5%, the composition becomes too viscous to dissolve the components used.

By the way, although there are many types of general-purpose thickeners, when they are used in the fungicide of the present invention, they cannot exhibit the effect equivalent to that of the polyacrylic acid-based thickener. For example, natural polysaccharide-based thickeners such as starch derivatives, cellulose derivatives, sodium alginate, and gums cause the decomposition reaction of hypochlorous acid-based bleaching agents and decrease the stability of the fungicide. Can not. In addition, inorganic thickeners such as synthetic mica and synthetic smectite cannot be advantageously used because they are less washable and removable than polyacrylic acid thickeners.

In the mold-removing agent of the present invention, water is essential for the purpose of, for example, penetration of the drug, but the amount of water added is usually a balanced amount. The mold remover of the present invention can be prepared by arbitrarily blending the above components. Preferably, a mold remover precursor is prepared by blending all components except for the solidifying agent in an arbitrary order, and then a predetermined amount of the solidifying agent is blended with this precursor, and after heating and dissolving, It can be prepared in a mold. A solid mold remover having a desired shape is obtained.

The fungicide of the present invention is provided in a solid state, and is more preferably provided in the form of a stick, crayon, or rectangular box. For example,
It is preferable that the stick-shaped mold remover is housed in a container so that it can be gradually fed out at the time of use. The stick may have the shape of a small cylinder or a small prism, and is preferably a small cylinder in consideration of ease of feeding out of the container. When the stick is a small cylinder, its size is 10 to 50 mm from the viewpoint of handleability.
And preferably 50 to 150 mm in length,
However, a diameter smaller than 10 mm may be employed, if necessary, in order to be able to be used in a thin, streak-shaped mold removing portion.

The fungicide of the present invention can be applied to fungicide in the same manner as a conventional fungicide, but in an easier way. For example, when removing mold generated on the wall surface of the bathroom, a required amount of the mold removing agent is drawn out from the stick-shaped container, and the mold removing agent is rubbed into the joints of the tiles on the wall surface. The application of the mildew remover is usually sufficient only once or twice a few times, and may be further applied as needed. The coating thickness of the mold removing agent is sufficient even if the mold removing agent is in contact with the mold. After the application of the mold remover is completed, the mold is left as it is so that the action on the mold proceeds sufficiently. The standing time is sufficient for a short time, and is usually several minutes to several tens of minutes, depending on the portion to be coated. The progress of the mold removing effect can be easily visually confirmed by the disappearance of the mold color, that is, the disappearance of the mold pigment. After the color of the mold disappears,
The mold removing agent attached to the wall is removed by washing.
The mold removing agent of the present invention can be easily and cleanly removed only by washing with water such as spraying tap water. If necessary, rinsing can be performed more quickly by spraying lukewarm water from a shower or the like onto the mold removing portion. Subsequent drying can be performed by leaving,
If necessary, operations such as blowing hot air may be combined.

[0028]

The present invention will be described in more detail with reference to the following examples. The compounds used for the preparation of the fungicide in the following examples are each commercially available, and are represented by the following abbreviations for simplification of the description.

Abbreviations such as the source of the compound name Abbreviations such as sodium hypochlorite reagent grade, effective chlorine concentration = 5.0% I sodium hydroxide reagent grade IIa potassium hydroxide reagent grade IIb sodium laurate reagent grade IIIa sodium myristate reagent grade IIIb Sodium palmitate Reagent grade IIIc Sodium stearate Reagent grade IIId Potassium myristate Reagent grade IIIe Polyacrylic acid-based thickener "ARON A20-P" manufactured by Toa Gosei Co., Ltd. IVa Polyacrylic acid-based thickener "Carbopol" manufactured by BFGoodrich 1342 "IVb Synthetic Mica" SWN "V manufactured by Corp Chemical V Guar Gum" Monat Gum GS "manufactured by Dainippon Pharmaceutical Co., Ltd. VI Sodium alginate Reagent grade VII Water VIII Also, the amount of these compounds described in the following table is
Unless otherwise specified, it means% by weight. Example 1 The following compounds were mixed in the amounts indicated, as described in Table 1 below.

Sodium hypochlorite (effective chlorine concentration = 5%) 25.0% by weight Sodium hydroxide 1.0% by weight Sodium myristate 5.0% by weight Polyacrylic acid-based thickener, manufactured by Toa Gosei Co., Ltd. ARON A20-P "0.5% by weight Water 68.5% by weight First, sodium hydroxide and water were put in a glass container (a commercially available mayonnaise bottle was washed) and mixed, and then, while continuing stirring, The polyacrylic acid-based thickener was gradually added and uniformly dissolved. A solution of sodium hypochlorite was poured into the resulting solution, mixed uniformly, and then sodium myristate was added. The resulting blend is 70-90
Heated to ° C. After the entire amount of sodium myristate used as a solidifying agent was completely dissolved, the obtained viscous solution was filled into an elliptic cylindrical plastic container having a long inner diameter of 46 mm, a shorter inner diameter of 26 mm and a depth of 70 mm, and allowed to reach room temperature. Cool.
Stick-shaped solid mold remover (effective chlorine concentration = 1.2
5%).

The obtained fungicide was applied thinly to the joints where mold had propagated on the tile surface in the bathroom, and left for 5 minutes. After application of the mold remover, the color of the mold gradually decreased, and after 5 minutes, it became almost colorless. Subsequently, when tap water from a shower was sprayed on the spot where the mold removing agent was applied, it could be quickly and completely washed and removed without leaving the mold removing agent and its slippage. Example 2 The procedure described in Example 1 was repeated, but in this example, as shown in Table 1 below, the following compounds were mixed in the amounts described.

Sodium hypochlorite (effective chlorine concentration = 5%) 25.0% by weight Sodium hydroxide 1.0% by weight Sodium myristate 5.0% by weight Polyacrylic acid-based thickener, “Carbo” manufactured by BFGoodrich Paul 1342 "1.0% by weight Water 68.0% by weight The obtained stick-shaped solid mold remover (effective chlorine concentration = 1.25%) is thinly applied to the joints on the tile surface in the bathroom where mold has grown. And left for 5 minutes. After application of the mold remover, the color of the mold gradually decreased, and after 5 minutes, it became almost colorless. Subsequently, when tap water from a shower was sprayed on the spot where the mold removing agent was applied, it could be quickly and completely washed and removed without leaving the mold removing agent and its slippage. Example 3 The procedure described in Example 1 above was repeated, but in this example, as shown in Table 1 below, the following compounds were mixed in the amounts described.

Sodium hypochlorite (effective chlorine concentration = 5%) 25.0% by weight Potassium hydroxide 1.0% by weight Sodium myristate 5.0% by weight Polyacrylic acid-based thickener, manufactured by Toa Gosei Co., Ltd. ARON A20-P "0.5% by weight Water 68.5% by weight The obtained solid mold remover (effective chlorine concentration = 1.25%) is applied to the joints where mold on the tile surface in the bathroom has grown. Apply lightly and leave for 5 minutes. After application of the mold remover, the color of the mold gradually decreased, and after 5 minutes, it became almost colorless. Subsequently, when tap water from a shower was sprayed on the spot where the mold removing agent was applied, it could be quickly and completely washed and removed without leaving the mold removing agent and its slippage. Example 4 The procedure described in Example 1 was repeated, but in this example, as shown in Table 1 below, the following compounds were mixed in the amounts described.

Sodium hypochlorite (effective chlorine concentration = 5%) 25.0% by weight Potassium hydroxide 1.0% by weight Potassium myristate 5.0% by weight Polyacrylic acid-based thickener, manufactured by Toa Gosei Co., Ltd. ARON A20-P "0.5% by weight Water 68.5% by weight The obtained solid mold remover (effective chlorine concentration = 1.25%) is applied to the joints where mold on the tile surface in the bathroom has grown. Apply lightly and leave for 5 minutes. After application of the mold remover, the color of the mold gradually decreased, and after 5 minutes, it became almost colorless. Subsequently, when tap water from a shower was sprayed on the spot where the mold removing agent was applied, it could be quickly and completely washed and removed without leaving the mold removing agent and its slippage. Comparative Examples 1 to 3 The procedure described in Example 1 was repeated. In this example, as described in Table 1 below, the following thickening agents were used instead of the polyacrylic acid-based thickening agents. Such a general-purpose thickener compound was used.

Comparative Example 1 Synthetic mica, “SWN” manufactured by Coop Chemical Co., Ltd. Comparative Example 2 Guar gum, “Monat gum GS” manufactured by Dainippon Pharmaceutical Co., Ltd. Comparative Example 3 Reagent grade sodium alginate The tile on the inner side was lightly applied to a joint where mold had propagated, and left for 5 minutes. After application of the mold remover, the color of the mold gradually decreased, but the degree of fading was slower than in Examples 1 to 4. It became almost colorless after about 10 to 20 minutes. Subsequently, tap water from the shower was repeatedly sprayed on the application area of the mold removing agent, but a large amount of tap water and washing time were required to completely wash and remove the mold removing agent and its slip. .

[0036]

[Table 1]

[Evaluation Test 1] In order to evaluate the storage stability of the stick-shaped solid fungicide prepared in Examples 1 to 4 and Comparative Examples 1 to 3, sodium hypochlorite in each fungicide was used. The change of the content due to heating was measured. Preliminary test Each test fungicide was placed in an oven at 88 ° C,
After heating for at least 12 hours (H) as described in Table 2 below, the amount of residual sodium hypochlorite was determined by iodine thiosulfuric acid titration. The second below
The residual ratio (%) as shown in the table was confirmed. This test was performed to evaluate the storage stability of the test fungicides (Examples 1 to 4 and Comparative Example 1) in which the residual sodium hypochlorite was confirmed in the preliminary test before this test .

The content (initial concentration,%) of sodium hypochlorite in a new test mold remover was measured by iodine thiosulfuric acid titration. Then, each test mold remover was added to 5
It was placed in a 0 ° C. oven and kept warm for 20 days.
Thereafter, the content of sodium hypochlorite in the test mold remover was measured by iodine thiosulfuric acid titration in the same manner as in the measurement of the initial concentration, and the residual ratio of sodium hypochlorite (% ) Was calculated. The obtained evaluation results are shown in Table 2 below.

[0039]

[Table 2]

As can be understood from the results shown in Table 2 above, the fungicide according to the present invention (Examples 1 to 4, using a polyacrylic acid thickener) and the conventional fungicide (comparative) Example 1, using synthetic mica as a thickener) provides satisfactory storage stability. However, when guar gum (Comparative Example 2) or sodium alginate (Comparative Example 3) is used as a thickener, Obviously only poor storage stability can be obtained. Examples 5 and 6 The procedure described in Example 1 was repeated, but in this example, as shown in Table 3 below, the amount of the polyacrylic acid-based thickener was changed as described. In Table 3 below, the blending examples of Examples 1, 3 and 4 are also described for reference.

The obtained stick-shaped solid mold remover was applied thinly to the joint where mold had grown on the tile surface in the bathroom, and left for 5 minutes. After application of the mold remover, the color of the mold gradually decreased, and after 5 minutes, it became almost colorless. Subsequently, when tap water from a shower was sprayed on the spot where the mold removing agent was applied, it could be quickly and completely washed and removed without leaving the mold removing agent and its slippage. Comparative Examples 4 and 5 The procedure described in Example 1 was repeated. In this example, as shown in Table 3 below, no thickener was used (Comparative Example 4), or polyacrylic acid was used. Instead of a system thickener,
Synthetic mica was used in the amounts indicated (Comparative Example 5). In Table 3 below, the formulation of Comparative Example 1 is also described for reference.

[0042]

[Table 3]

[Evaluation Test 2] The sticky mold removers prepared in Examples 1, 3 to 6 and Comparative Examples 1, 4 and 5 were washed with water and prevented from oozing out (the content of the liquid under external pressure was reduced). To prevent bleeding)
Each fungicide was tested according to the following procedure. Rinse test Prepare 63 white tiles (24mm x 24mm)
It was stuck tightly to a 45 mm x 190 mm substrate panel and the joints between the tiles were filled with Portland cement. Each mold removing agent was applied to the surface of the obtained tile panel in four strokes, and subsequently, washed with water. Washing was carried out by spraying 200 ml of tap water from the nozzle of the washing bottle onto the tile surface each time, and rinsing the fungicide with a water stream. After completion of the washing, a test solution containing 0.5% potassium iodide and 0.5% starch is sprayed on the tile surface to check the residual state of the fungicide, and the purple color is visually observed. It was observed and evaluated in five steps according to the criteria described in Table 4-1 below.

The washing test was repeated according to the criteria shown in Table 4-1 below until a score of "2" was obtained. That is,
Washing with tap water is repeated, the score is recorded each time, the obtained score is multiplied by the biased weight shown in Table 4-2 below, and the total is summed up. It was scored.

[0045]

[Table 4]

The test results (total score) as shown in Table 5 below were obtained. In addition, it is understood that the relationship between the quality of the water-washing property and the total score of the water-washing test indicates that the lower the total score, the better the water-washing property. [Squeezed juice test] In order to evaluate the bleeding-prevention property, which is a property of preventing bleeding of the content liquid due to external pressure, the amount of the liquid component (squeezed juice) that was squeezed was measured by applying external pressure simulated. . Stick-shaped solid mold remover (Long outer diameter 46
mm, a short outer diameter of 26 mm and a length of 70 mm) were cut at a thickness of about 5 mm to prepare test pieces. First, the weight of the specimen before the test was measured and recorded. Next, the test piece was divided at the center part to obtain two semi-elliptical test pieces. These test pieces were placed on the center of a separately prepared polypropylene plate (50 mm x 80 mm, hereinafter referred to as "PP plate"), taking care not to protrude from the end of the PP plate. Placed, lightly pressed and stuck. Next, the PP plate with the test piece was placed on a stainless steel shallow plate such that the test piece was sandwiched between the shallow plate and the PP plate. Further, the shallow dish was placed on a test tube vibrator, and after a 2 kg weight was placed on the PP plate, the plate was vibrated for 1 minute while applying a load. As a result of applying vibration while applying a load, the content liquid (liquid component of the fungicide) contained therein was squeezed out of the test piece. After taking out only the test piece from the shallow dish, the weight of the test piece was measured again, and the weight of the squeezed liquid component (squeezed juice) was calculated and recorded.

The evaluation results as shown in Table 5 below were obtained. In addition, the numerical value described in the column of the squeezed juice test in this table is the ratio (% by weight) of the squeezed liquid component that can be measured by such a test. The relationship between the quality of the bleeding prevention and the ratio of the squeezed liquid component (% by weight), the lower the ratio of the liquid component,
It will be understood that the bleeding prevention property is more excellent.

[0048]

[Table 5]

As can be seen from the results shown in Table 5 above, the fungicide according to the present invention (Example 1, Example 3 to Example 6, using a polyacrylic acid-based thickener in different amounts) and The conventional mold removers (Comparative Examples 1, 4 and 5; no thickener was used or synthetic mica was used as a thickener in a different blending amount) were remarkable in terms of both water-washing properties and anti-bleeding properties. There are differences in the effects. In addition, in the case of a conventional mold removing agent, it is better not to incorporate synthetic mica as a thickening agent, so that excellent washing properties can be obtained. Examples 7 to 17 The procedure described in Example 1 was repeated, but in this example, the type and amount of the solidifying agent were changed as described in Table 6 below. In Table 6 below, the formulation example of Example 1 is also described for reference.

[0050]

[Table 6]

The obtained stick-shaped solid mold removing agent was thinly applied to a joint where mold had propagated on the tile surface in the bathroom, and allowed to stand for 5 minutes. After application of the mold remover, the color of the mold gradually decreased, and after 5 minutes, it became almost colorless. Subsequently, when tap water from a shower was sprayed on the spot where the mold removing agent was applied, it could be quickly and completely washed and removed without leaving the mold removing agent and its slippage. In addition, since it was observed that the amount of application to the joint fluctuated due to the mold remover used, to evaluate the dependence of the amount of application on the amount of the solidifying agent,
The following evaluation test was performed. [Evaluation Test 3] The dependency of the amount of the stick-shaped solid mold remover prepared in Examples 1 and 7 to 17 on the amount of the solidifying agent was evaluated according to the following procedure. Measurement of Application Amount Copy paper (plain paper) was prepared and its weight was measured. Next, a predetermined area (254 mm
× 178 mm) with each of the mold removers in four strokes. The same application operation was repeated five times for each mold remover. Immediately after application of the mold remover, the copy paper was weighed again before the mold remover had not dried. The amount of the mold remover applied (g / 0.0451 m ² ) was determined from the change in the weight of the copy paper before and after the application, and plotted in FIG.

As described above, a satisfactory mold removing effect was obtained with any of the mold removing agents.
Considering the measurement results in FIG. 1, when the amount of the solidifying agent is relatively small (for example, when sodium laurate or sodium myristate is blended in an amount of 0.5%), the amount Variations tend to occur, so some care may need to be taken in the application operation.
As can be understood from the plot of FIG. 1, the mold removing agent containing the solidifying agent in an amount of 1.0% or more can be applied with a smaller application amount variation. Examples 18 to 22 The procedure described in Example 1 was repeated, but in this example, as shown in Table 7 below, the amount of sodium hypochlorite used as the bleach was changed.

The obtained stick-shaped solid mold removing agent was lightly applied to a joint where mold had propagated on the tile surface in the bathroom, and allowed to stand for 5 minutes. After application of the mold remover, the color of the mold gradually decreased, and after 5 minutes, the mold became almost colorless. Subsequently, when tap water from a shower was sprayed on the area where the mold removing agent was applied, it was quickly and completely washed and removed without leaving the mold removing agent and its slippage. [Evaluation Test 4] In order to evaluate the storage stability of the stick-shaped solid fungicides prepared in Examples 18 to 22, accelerated deterioration tests of each fungicide were performed according to the following procedure. Accelerated Deterioration Test The content of sodium hypochlorite in each test fungicide was measured by iodine thiosulfuric acid titration. Next, each of the test fungicides was placed in an oven at 50 ° C.
It was kept warm for 0 days. Then, the sodium hypochlorite content (effective chlorine concentration) of the test mold remover was measured by iodine thiosulfuric acid titration in the same manner as the initial concentration measurement, and sodium hypochlorite was compared with the initial concentration. Was calculated. The obtained evaluation results are shown in Table 7 below.

[0054]

[Table 7]

As can be seen from the results shown in Table 7 above, in the case of the fungicide according to the present invention, the decomposition problem is small if the initial concentration of available chlorine is at least 2%. Also, from the consideration of the effects of the prior application of the present invention described by the present inventors referring to the constituent requirements, the effective chlorine concentration is effective when the concentration is 0.5% or more.
The content of sodium hypochlorite in the fungicide of the present invention is preferably in the range of 0.5 to 2%, expressed as an effective chlorine concentration.

[0056]

As described above, when the solid mold remover of the present invention is used, the active ingredient directly acts on mold and kills it, and the active surface is bleached again. A clean surface can be provided, and a mold removing operation and a cleaning operation can be performed safely, easily, without waste and reliably.

Further, the solid mold removing agent of the present invention is excellent in water-washing properties, and can be easily dissolved and removed only by simple water washing after use. In addition, since this solid mold removing agent has excellent storage stability, even if it is stored for a long period of time, it does not cause deterioration or the like, and its mold removing effect can be stably maintained. Further, the solid mold remover of the present invention is prepared by blending a small amount of components as described above, but the effect is remarkably superior to the conventional mold remover.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the amount of a mold remover applied and the amount of a solidifying agent.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A01N 59/08 A01N 59/08 A C11D 9/08 C11D 9/08 9/50 9/50 (72) Invention Person Toshihiro Funabiki 3-8-8 Minamihashimoto, Sagamihara City, Kanagawa Prefecture F-term in Sumitomo 3M Limited (reference) 4H003 AB03 BA02 DA08 DB01 EA21 EA25 EB30 EB41 EB46 ED02 EE08 FA34 4H011 AA03 BA01 BA02 BA04 BB18 BC06 BC18 BC19 DA01 DA01 DA01 DH02

Claims (4)

[Claims] 1. The following components: an alkali metal salt of hypochlorous acid in an amount of 0.5 to 2% in terms of an effective chlorine concentration; an alkali metal hydroxide of 0.5 to 5%; 3-20% of an alkali metal salt of at least one aliphatic carboxylic acid, 0.2-5% of a polyacrylic thickener, and 70-9
A mold remover comprising 5% water as an essential active ingredient. 2. The solid mold remover according to claim 1, wherein the alkali metal hydroxide is sodium hydroxide, potassium hydroxide or a mixture thereof. 3. The solid mold removing agent according to claim 1, wherein the aliphatic carboxylic acid is stearic acid, palmitic acid, myristic acid or lauric acid. 4. The solid mold removing agent according to claim 1, wherein the agent has a stick shape and is contained in a container so that it can be gradually fed out during use.