JP2003128908A - Gradually water-soluble solid composition and deodorizing agent for toilet utilizing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gradually water-soluble solid composition not containing a surfactant, having safety and scarcely causing environmental contamination, a solid composition capable of stably and gradually dissolving an active ingredient of the composition and additives as necessary contained therein and a readily usable and safe deodorizing agent for toilet capable of stably retaining the effect for a long period without polluting the environment. SOLUTION: This solid composition comprises the active ingredient contained in accordance with the intended use and a necessary additive and can gradually dissolve the active ingredients and the additive in water. In the solid composition, isopropyltrioxane and para-oxybenzoic acid ester as dissolution regulators are formulated in a polyethylene glycol which is solid at ordinary temperature. This deodorizing agent for toilet which is gradually soluble in water is obtained by formulating the solid composition with a microorganism and fumaric acid as active ingredients.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a solid composition in which active ingredients and additives contained therein are gradually dissolved in water, and a toilet deodorant using the same. More specifically, the present invention is, for example, a deodorant for flush urinals and drains, a deodorant and slime remover for kitchen drainage drains, a bactericide for drainage purifiers, an insecticide, a tree nutrient and a water-soluble fertilizer, A solid composition slowly soluble in water suitable for holding substances such as pesticides and the like, which is necessary to gradually dissolve the contained active ingredients into water for a desired period of time, and washing with it The present invention relates to a toilet deodorant installed and used near the urinal of a urinal.

[0002]

2. Description of the Related Art In order to maintain a desired effect of a medicinal active ingredient for a certain period, a technique of adjusting the dissolution rate of a compounding base material and gradually dissolving it in water has been widely used. For example, a solid composition that solidifies in a state of containing an active ingredient and an additive suitable for the purpose of use and dissolves when contacted with water to dissolve the active ingredient and the additive contained in water is mentioned. To be This solid composition is used as a base material for carrying a deodorant component of a deodorant installed in a urinal, for example.

Conventionally, many solid compositions of this type generally use polyethylene glycol as a molding base material, and are not suitable for applications in which they are gradually dissolved in water for a long time to sustain. For the purpose of improving water resistance, water-insoluble lipids and petroleum waxes are added as a dissolution rate adjusting component together with a large amount of a surfactant to be solidified. For example, a deodorant base material in which a water-insoluble stearic acid and a water-soluble prolonic nonionic surfactant or polyethylene glycol are mixed is common. However, in this deodorant base material, there is a problem that it is difficult to adjust the dissolution rate and disappears in a short time, or conversely, stearic acid becomes flaky and remains unclean, giving a dirty impression. In order to solve this, a prolonic nonionic surfactant 5 to 20 wt%, polyethylene glycol 20 to 70 wt%, stearic acid 2 to 8 wt% and isopropyl trioxane 20 to 70 wt% have been proposed. (Japanese Patent Laid-Open No. 7-323078).
This base material contains sublimable isopropyltrioxane as a water-insoluble substance in order to reduce the blending amount of stearic acid which causes flaky residue.

Further, as a toilet deodorant which continues to release and elute components excluding a bad odor generated in a flush urinal using such a solid composition for a long period of time, conventionally, a bactericide or a fragrance is used. It is common to use a drug to which is added, or a masking agent that disguises a foul odor with only a strong fragrance. In particular,
Conventional deodorizers for flush urinals that carry an active ingredient for decomposing urinary stones and neutralizing ammonia and gradually dissolve in water contain a dangerous acidic substance such as sulfamic acid as an active ingredient. Is common.

[0005]

However, in any case, since a large amount of the surfactant is used, there are many problems to the environment such as polluting the drainage and causing foaming. Also, the duration of dissolution time is as short as about one week,
There is a problem that none of the ingredients can be gradually dissolved in water stably over a long period of 1 to 2 months.

Furthermore, there is no toilet deodorant which is easy to use, safe and environmentally friendly, whichever physical, chemical or sensory deodorant method is used, and the duration of its effect is also long. It is short and has the drawback that it can maintain its effect only at the moment of use or for about a week.

Further, as disclosed in JP-A-7-323078, isopropyltrioxane is useful for adjusting the water dissolution rate of the deodorizing base material, but it is not dissolved in solid polyethylene glycol and is separated. As a result of an experiment conducted by the present inventors, it was found that there is a problem that it occurs.

An object of the present invention is to provide a solid composition which does not contain a surfactant and is safe and slowly soluble in water, which hardly causes environmental pollution. Another object of the present invention is to provide a solid composition capable of stabilizing an active ingredient as well as additives contained as needed for a long period of time and gradually dissolving it in water. Another object of the present invention is to provide a toilet deodorant that is easy to use, safe, and has a stable effect for a long period of time without polluting the environment.

[0009]

In order to achieve the above object, the present inventors have conducted various studies and experiments with the purpose of not using a surfactant that deteriorates the environment.
It was discovered that paraoxybenzoic acid ester is effective for solving the problem that isopropyltrioxane does not dissolve in solid polyethylene glycol and separates. That is, it was discovered that by using paraoxybenzoic acid ester as a medium, isopropyltrioxane, which is useful for adjusting the water dissolution rate, and solid polyethylene glycol become a uniform viscous liquid without separation. Then, add an active ingredient according to the purpose of use and an additive according to need to the liquid, mix and heat / fill /
It was confirmed that by solidifying etc., a molded product suitable for the purpose could be obtained without using a surfactant.

The present invention is based on such knowledge, and contains an active ingredient and an additive which meet the needs according to the purpose of use, and the active ingredient and the additive which are gradually dissolved in water are contained in water. In the solid composition to be dissolved, isopropyltrioxane and paraoxybenzoic acid ester as a dissolution modifier are added to polyethylene glycol which is solid at room temperature. In this case, by the action of paraoxybenzoic acid ester and isopropyltrioxane, the strength of the polyethylene glycol molded product that is easily soluble in water is increased and the solubility in water is adjusted, and the content is maintained for a long time without using a surfactant. The active ingredient etc. can be gradually dissolved in water. And
These polyethylene glycols, paraoxybenzoic acid esters, and isopropyltrioxane do not cause the polluting property as seen in surfactants even when dissolved in water. Here, as the dissolution modifier, the compounding amount of isopropyltrioxane is preferably 2 to 20% by weight and the compounding amount of paraoxybenzoic acid ester is preferably 2 to 20% by weight, and the compounding amount of isopropyltrioxane is 5 to 10% by weight. % And the amount of paraoxybenzoic acid ester mixed is 3 to 7
When it is represented by weight%, it exhibits the most suitable physical properties as a solid composition containing an active ingredient according to the purpose of use and an additive according to need, especially for use as a base material of a deodorant for flush urinals.

Further, the inventors of the present invention have conducted various studies and experiments to solve the problems of the conventional deodorants for urinals, and as a result, have focused on microorganisms (slow-acting). Microorganisms are environmentally friendly and safe, and have a great deodorizing effect and a long duration. From this point, it is most suitable as the main ingredient of the deodorant. However, since it has a problem that it is inferior in immediate effect to the chemical deodorant component, it is not suitable as a deodorant for urinals as it is. Therefore, we considered a combination of a microorganism that is slow-acting but has a high ability to decompose organic substances and safety, and an organic acid that has a fast-acting effect. Normally, when an organic acid is used, the pH becomes acidic, so the microorganism is added. It is not possible. However, when a fumaric acid is combined with a microorganism that forms spores even at a temperature at which polyethylene glycol is melted and has a high ability to decompose organic substances and acid resistance, the microorganism is killed in a solid composition based on polyethylene glycol. It was discovered that fumaric acid, which can be encapsulated without being used and has an immediate effect on use, softens urinary stones that have adhered to the toilet or drainage route and facilitates the invasion of microorganisms into the softened urinary stones. I arrived. From this, it was also confirmed that it has the property of promoting the decomposition action and deodorizing action by microorganisms, and it was found to be very suitable as an organic acid to be added to the deodorant of the present invention.

The toilet water deodorant according to the present invention, which is slowly soluble in water, is based on the above findings, and has the above-mentioned claim 1.
Microorganisms and fumaric acid are added to the solid composition according to any one of 1 to 3 as active ingredients. Here, as the microorganism, for example, it is preferable to use a useful microorganism derived from soil called Bacillus subtilis. As the dissolution modifier, it is preferable that the blending amount of isopropyltrioxane is 2 to 20% by weight and the blending amount of paraoxybenzoic acid ester is 2 to 20% by weight, and the blending amount of isopropyltrioxane is 5 to 10% by weight and paraoxybenzoic acid. When the compounding amount of benzoic acid ester is 3 to 7% by weight, the physical properties most suitable for use as a base material of the deodorant for flush urinal are shown.

Soil-derived useful microorganisms called Bacillus subtilis have a degrading effect on oils and fats and a deodorizing effect on bad odors. Therefore, a formulation of this is a source of bad odors such as scales attached to drains of kitchens and drains. Widely used as the main agent of deodorant against. This microorganism is 65-70 ° C
It does not spores and die even at high temperatures, it does not die even if the base polyethylene glycol is mixed by heating and liquefied and solidified, and because it has acid resistance, it is used in combination with fumaric acid. Will never be deactivated. Therefore, fumaric acid, which has a low solubility in water, is gradually dissolved every time when it is discharged to neutralize ammonia and amine odors to deodorize it and soften the urinary stone adhered to the pipe, etc. Microbes invade the inside and multiply to continuously decompose urinary stones, which are the source of malodor, and strongly prevent the generation of malodor.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION A solid composition slowly soluble in water and a toilet deodorant for urinals using the same according to the present invention will be described in detail below.

The solid composition of the present invention contains polyethylene glycol, paraoxybenzoic acid ester and isopropyltrioxane in common so that the solid composition gradually dissolves in water over a long period of time without using a surfactant. The active ingredient and the like are dissolved. Therefore, if an active ingredient and an additive suitable for the purpose of use are contained, the active ingredient and the additive contained by gradually dissolving in water when placed in an environment in contact with water for a long period of time are included. It can be stably melted. Here, as the dissolution modifier, the compounding amount of isopropyltrioxane is preferably 2 to 20% by weight and the compounding amount of paraoxybenzoic acid ester is preferably 2 to 20% by weight, and the compounding amount of isopropyltrioxane is 5 to 10% by weight. % And the amount of paraoxybenzoic acid ester to be 3 to 7% by weight, as a solid composition containing an active ingredient according to the purpose of use and an additive according to need, particularly as a deodorant for flush urinals. It exhibits the most suitable physical properties for use as a base material. In addition, if a microorganism such as Bacillus subtilis useful soil-derived microorganism and fumaric acid are blended as an active ingredient in the solid composition, a toilet deodorant that is slowly soluble in water can be formed.

Polyethylene glycol, which is one of the essential components of the solid composition, is solid at room temperature and is suitable as a base material for mixing and molding powdery active ingredients.
It is a safe substance that is often used in pharmaceuticals and cosmetics, as well as having convenient moldability that it melts well in water and liquefies at about 65 ° C when heated, and solidifies when mixed with other drugs.

Isopropyltrioxane (chemical formula 1)
Was originally developed as a substitute for paradichlorobenzene, which is environmentally problematic and has been pointed out to be carcinogenic. It is suitable for use as a fragrance by compression-molding or melting and solidifying with a fragrance. It has high stability and safety, but it has not been used so far because it is expensive. In the present invention, this isopropyltrioxane is used as an agent for increasing the strength of the molded product and controlling the solubility in water. The amount of isopropyltrioxane added to the solid composition is, for example, 2 to 20% by weight, preferably 5 to 1%.
Although it is in the range of 0% by weight, if the amount is small, the solid composition dissolves in water quickly, and if it is large, it becomes insoluble and becomes long-lasting. It is a thing. Further, by using isopropyltrioxane, swelling in water of the solid composition, which tends to occur when a surfactant is used, does not occur at all, and the solid composition does not crack even during long-term use and is uniform from the outside. Melt

[Chemical 1]

As described above, isopropyltrioxane is useful for controlling and extending the dissolution time of a solid composition, but has a problem that it is not dissolved in solid polyethylene glycol and is separated. Therefore, in the present invention, paraoxybenzoic acid ester is used as a mixing aid (dissolution aid). By sharing the paraoxybenzoic acid ester, the isopropyltrioxane and the solid polyethylene glycol become a uniform viscous liquid without separation. If the paraoxybenzoic acid ester is not shared, isopropyltrioxane and polyethylene glycol will be separated immediately even if heated and mixed, and fumaric acid and other components will be forcibly mixed to cool and solidify to obtain a solid. However, it is not possible to commercialize it in water, as it will become rough after a few days.

Paraoxybenzoic acid esters include propyl compounds, isopropyl compounds, butyl compounds, isobutyl compounds and the like, depending on the substituents of the ester. Of these, methyl compounds and ethyl compounds are not limited to specific substances. Since they are separated, they are not suitable for the present invention. An example of a substance suitable for the present invention is butyl paraoxybenzoate (chemical formula 2), which is non-sticky. Butyl paraoxybenzoate is a safe substance that is listed in the Japanese Pharmacopoeia and official compendials such as the standards for cosmetic raw materials and is widely used as a preservative in cosmetics and pharmaceuticals.

[Chemical 2]

Further, since the paraoxybenzoic acid ester has an antibacterial action against various fungi, it can be expected to more effectively suppress the generation of malodor due to the propagation of various fungi. Furthermore, there is an advantage that even if it coexists with the microorganism (Bacillus subtilis) used for the toilet deodorant for urinals according to the present invention, it has no adverse effect. According to the experiment conducted for reference, 10 ⁶ viable bacteria were contained per 1 gram of the toilet deodorant for urinals containing 5 to 10% by weight of butyl paraoxybenzoate and 0.5 to 1.0% by weight of Bacillus subtilis preparation. It was confirmed that it was maintained. In this way, the use of paraoxybenzoic acid ester is not only a mixing aid, but also has an antibacterial effect, and can be shared with spore-forming microorganisms such as Bacillus subtilis, and has the great advantage of further increasing the deodorizing effect. is there. The amount of paraoxybenzoic acid ester added to the solid composition is, for example, 2 to 20% by weight, preferably 2 to 10% by weight, more preferably 3 to 7% by weight, as a range in which a stable molded product is obtained. . In addition, there is no precedent that paraoxybenzoic acid ester was shared with a spore-forming microorganism (Bacillus subtilis), and there was no precedent that it was used for the purpose of a solubilizing agent.

Further, as a microorganism contained as one of the active ingredients for producing a toilet deodorant, it is preferable to use a useful soil-derived microorganism called Bacillus subtilis. This microorganism does not die by forming spores even at a high temperature of 65 to 70 ° C. Therefore, even when it is mixed with the polyethylene glycol base material in a liquefied state by heating, it does not die and can be cooled and solidified thereafter. In addition, since it has acid resistance, it is not deactivated when used in combination with fumaric acid. Further, it has a strong effect of decomposing organic substances, and as a result, it has an effect of eliminating the source of bad odor.

Microorganisms are generally safe and have a wide range of applications and can be expected to have a continuous effect on deodorizing bad odors, but since they are inferior in immediate effect to chemical deodorant components, they are commercialized individually. However, there is a drawback that it is difficult to confirm the effect. Therefore, it is decided to use fumaric acid, which has an immediate effect that can immediately neutralize the odors of ammonia and amines to make them odorless. The amount used in the toilet deodorant according to the present invention is, for example, about 5% by weight as a formulation.

Fumaric acid (Chemical formula 3) is one of the organic solid acids malic acid, citric acid and others which are frequently used for deodorants and acidulants for foods. Unlike other organic acids, it has a low solubility in water, so it gradually dissolves,
When compounded in a molding agent, it has the advantage of longevity. If the toilet deodorant according to the present invention contains, for example, about 40% by weight of fumaric acid powder of 300 mesh pass, a stable molded product can be obtained.

[Chemical 3]

As a result of the experiments conducted by the present inventors, it was confirmed that fumaric acid softens the scale adhered to the toilet or drainage route. From this, it was also confirmed that it has the property of promoting the decomposition action and deodorizing action by microorganisms, and it was found that it is very suitable as an organic acid to be added to the deodorant of the present invention.

Example 1 As a specific example of the present invention, a deodorant for a men's toilet bowl using the solid composition of the present invention was experimentally produced and its effect was confirmed. That is, polyethylene glycol, isopropyltrioxane, and butyl paraoxybenzoate were mixed and dissolved by heating at about 65 ° C. to form a viscous translucent and uniform liquid, in which fumaric acid and the prepared microorganism Bacillus subtilis BN-1001 were prepared. Was mixed, a rust preventive agent and other necessary components were added, and a uniform cloudy suspended content was poured into a mold and cooled to solidify to produce. The appearance of the toilet deodorant thus obtained is white and extremely hard, and it can be used as it is or as a deodorant by placing it in a suitable container and placing it on the perforated plate of the men's toilet or in the drainage route. A. Solubility test Test period: April 2 to May 21, 2001 Test place: World Bio Laboratory (Asakusabashi, Taito-ku, Tokyo) Test method: Sample 1 shown in Table 1 in a water tank with an internal capacity of 20 liters And 60 grams of each of Sample 2 is placed. A mechanism that automatically injects 5 liters of water at a time into this aquarium and discharges the same amount of water is provided 10 times per hour and 4 times a day.
Repeat the operation 0 times. Drain water and leave empty at night. This operation was repeated every day and the amount of reduction after 30 days and 50 days was measured. The water temperature was 12 to 16 ° C.

[Table 1] Test Results As shown in Table 2, Sample 1 was dissolved for 30 days and Sample 2 was dissolved by 80% for 50 days, and the results were small, and the expected results were obtained.

[Table 2] B. Deodorant effect The deodorant effect of the present invention was confirmed by measuring the deodorant effect in two stages of a laboratory test and a field test. Tests are in Table 1
The sample 2 shown in FIG.

(1) Laboratory test (confirmation of immediate effect of deodorizing fumaric acid) Measurement date: June 20, 2001 Place of implementation: World Bio Laboratory (Asakusabashi, Taito-ku, Tokyo) Test sample: Table 1 Sample 2 Measurement method and result: (a) 100 ml of an ammonia solution having an odor intensity of 5 (corresponding to 50 ppm) is placed in a 200 ml beaker. When 0.5 g of the powder of the agent is added to this, the strength immediately becomes 0 (no odor). (B) Similarly, a trimethylamine solution with an odor intensity of 5 (3 pp
(corresponding to m), the odor intensity immediately becomes 0 (no odor).

(2) Field test (synergistic deodorizing effect of fumaric acid and microorganisms) Date of measurement: April 2 to May 21, 2001 Place of implementation: Men's toilet in the Takanawa Takanawa Kaikan, Minato-ku, Tokyo Test sample: Sample 2 shown in Table 1 Measurement method: A test is performed using two men's flush toilets that are in use without cleaning for one month. One 60 g of this drug was set under the bowl of the toilet bowl, and nothing was placed on one of the toilet bowls for comparison. An inspection hole will be provided in the middle of the drain pipe near the trap.
In this condition, use the toilet every day and do not clean it until the end of the test. After 30 days and 50 days from the start of the test, the agent is taken out and weighed, and at the same time, the occurrence of a bad odor in the drainage route, the condition of the adhered matter, discoloration, etc. are observed. The results are shown in Table 3. From this test, the long-term deodorizing effect of the deodorant of the present invention could be confirmed.

[Table 3]

The above-described embodiment is an example of a preferred embodiment of the present invention, but the present invention is not limited to this, and various modifications can be made without departing from the gist of the present invention. For example, although the solid composition of the present invention was mainly described in the examples as being applied as a toilet deodorant, it is not particularly limited thereto, and for example, a deodorant for drainage pipes, kitchen drainage pipes, etc. Deodorant and slime remover, waste water purifier, bactericide, insecticide, tree nutrient, water-soluble fertilizer, pesticides, etc. need to be gradually dissolved in water for the desired period of time. Needless to say, it can be applied to all of. It is useful for household, agricultural, and industrial use, depending on the use that requires slow solubility in water. By properly selecting the compounding active ingredient and the necessary additives, it can be used as a solid composition for various purposes.

[0028]

EFFECTS OF THE INVENTION As is clear from the above description, the solid molded article of the present invention can be, for example, about 1 month or 2 months even if the surfactant is not used, as is clear from the experiment shown in Table 2. The contained components can be gradually dissolved in water over a long period of time. Then, this period can be easily adjusted by adjusting the blending amounts of isopropyltrioxane and paraoxybenzoic acid ester.

In addition, since the solid composition of the present invention uses isopropyltrioxane and paraoxybenzoic acid ester as a base material polyethylene glycol dissolution rate modifier without using a surfactant, There is no concern about the pollution of the wastewater due to the above, nor is there any foaming in the wastewater, and the added isopropyltrioxane or the like as a dissolution modifier becomes fine particles that flow into the running water and do not adhere to the inner wall or the drainage route. That is, it does not remain as a residue and does not dissolve at a concentration enough to contaminate it, so it does not have the contaminating property found in surfactants. Further, according to the solid molded product of the present invention, it does not collapse or swell even during long-term use in water.

Further, according to the toilet deodorant of the present invention, fumaric acid, which has a low solubility in water, is gradually dissolved at every discharge of water to immediately neutralize ammonia and amine odors to deodorize them and fix them to pipes and the like. The urinary stones are softened, and microorganisms penetrate into the softened urinary stones to proliferate and continuously decompose the urinary stones that are the source of malodor. Therefore, due to the synergistic effect of fumaric acid and the microorganisms, Table 2 and Table 2 As shown in 3, the deodorant effect is obtained by gradually dissolving in water over a long period of 1 to 2 months as compared with the conventional toilet deodorant for urinals. Moreover, since the deodorant of the present invention does not use a surfactant and contains only safe ingredients and microorganisms, it is easy to use and safe, and the efficacy is stable for a long period of time without polluting the environment. Hold it.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/159 C08K 5/159 (72) Inventor Tadashi Baba 4-70-1 Narashinodai, Funabashi City, Chiba Prefecture F-term (reference) 4C080 AA03 BB02 CC13 HH01 JJ03 KK08 LL03 MM14 MM33 NN12 NN15 NN27 4J002 AD002 CH021 EF078 EH127 EL116 FD206 FD207 GD02

Claims (4)

[Claims] 1. A solid composition containing an active ingredient according to the purpose of use and an additive according to need, which is gradually dissolved in water to dissolve the active ingredient and the additive, and is a solid at room temperature. 2. A solid composition slowly soluble in water, characterized in that it comprises propylene trioxane and para-oxybenzoic acid ester as a dissolution modifier, mixed with the polyethylene glycol. 2. The amount of isopropyltrioxane as the dissolution modifier is 2 to 20% by weight and the amount of paraoxybenzoic acid ester is 2 to 20% by weight, which is sustained in water according to claim 1. Soluble solid composition. 3. The water as set forth in claim 1, wherein the amount of isopropyltrioxane as the dissolution modifier is 5 to 10% by weight and the amount of paraoxybenzoic acid ester is 3 to 7% by weight. Soluble solid composition. 4. A toilet water deodorant that is slowly soluble in water, characterized in that a microorganism and fumaric acid are added to the solid composition according to any one of claims 1 to 3 as active ingredients.