JP2000204397A - Preventing agent for urolith utilizing dissolution rate regulator and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a preventing agent for uroliths capable of carrying out prophylaxis and prevention of adhesion of the uroliths to toilet drainage pipes, etc., for a prescribed period of use regardless of the number of use frequency by using a halogen free dissolution rate regulator substitutable for p- dichlorobenzene as a dissolution rate regulator for a solid acid having preventing effects on the adhesion of the uroliths and to provide a method for producing the preventing agent for the uroliths. SOLUTION: This preventing agent for uroliths is obtained by mixing a nonhalogen-based sublimable substance such as DL-camphor or naphthalene with an organic acid capable of forming a molten mixture with the nonhalogen- based sublimable substance such as a carboxylic acid having phenyl group, e.g. benzoic acid, salicylic acid or cinnamic acid under warming, mixing the resultant molten mixture in a molten state with a solid acid such as adipic acid, succinic acid or sulfamic acid and then molding the prepared mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a urinary stone preventing agent capable of preventing urine stone containing calcium as a main component from adhering to a toilet drain pipe or the like, and a method for producing the same. A melt mixture of a halogen-based sublimable substance and an organic acid such as a carboxylic acid having a phenyl group capable of forming a molten mixture with the non-halogen-based sublimable substance, and a dissolution rate regulator for a solid acid which is an anti-uricic agent And a method for producing the same. The urinary stone inhibitor of the present invention can be applied to various flush toilets or men's toilets without flush facilities.

[0002]

2. Description of the Related Art Conventionally, toilet drain pipes, particularly drain pipes for men's toilets, have a scale called urinary stone to which a mixture of calcium-based compounds and organic substances generated by the decomposition of urine is adhered. It is known that the flow of urine and washing water is deteriorated and, in extreme cases, the drainage pipe is closed, making the toilet unusable. It is also known that the bad smell of the men's toilet is a mixed smell of ammonia generated by decomposition of urine and odor caused by decomposition of organic matter in urine stones by bacteria.

[0003] As an agent for cleaning urine stones in toilet drainage pipes and the like, there has hitherto been used an agent for preventing and preventing urine stones from adhering, but not for removing adhering urine stones. And a urolith control agent which aims to prevent urine stones from sticking and at the same time remove the adhered urine stones. In addition, as a method of applying these urinary stone inhibitors and urine stone controlling agents, a method of dissolving a chemical and injecting it into a washing water pipe, or a method of forming a spherical agent by tableting, injection molding, kneading, or the like is used. A method of putting it in the toilet of a men's toilet has been put to practical use. As these urinary stone inhibitors and urine stone controlling agents, organic acids, Ca chelating agents, bactericides, surfactants,
There have been proposed various ones which appropriately contain a sublimable substance, a corrosion inhibitor, a dye, a fragrance and the like.

For example, Japanese Patent Publication No. 45-30706 discloses a deodorizing method for a flush toilet made by melt-mixing a surfactant, an ion-sequestering agent, a fragrance and the like with polyethylene glycol or polypropylene glycol and an aromatic substance, and casting the mixture. A cleaning agent is described, and JP-A-57-168668 discloses a mixed melt comprising additives such as polyethylene glycol which is solid at ordinary temperature, a sparingly water-soluble aromatic substance, a nonionic surfactant and a fragrance. A cleaning antifouling fragrance molded by cooling and solidifying is described. Also, French Patent No. 15012
No. 48 and British Patent No. 879733,
A cleaning agent consisting of sulfamic acid and paradichlorobenzene is described, but all of these agents prevent urine stones from adhering to the toilet drainpipe. It is also a urolith control agent.

On the other hand, Japanese Patent Application Laid-Open No. 62-38 by the present inventors
Japanese Patent Publication No. 299 discloses a method for preventing scale from sticking to a toilet drainpipe without removing the scale fixed to the toilet drainpipe. A solid acid having a solubility in water of not more than 0.001 g / 100 g (water) and not producing a salt having a solubility of not more than 0.001 as an active ingredient, and a solid acid having a solubility in water at 20 ° C. of 0.001 to 20 g / 100 g and / or Alternatively, a non-sublimable substrate or a molded body containing 20% by weight or more of a sublimable substrate is used, and the pH of urine or a mixed wastewater of urine and washing water is maintained at 5 to 8.5. Has been described. The above-mentioned urinary stone inhibitor using an organic acid as a solid acid has not only the effect of preventing urine stone but also the effect of neutralizing malodor such as ammonia generated.

[0006]

A conventionally known toilet detergent comprising a surfactant, a bactericide and a fragrance is effective in preventing dirt on the wall of a toilet bowl and preventing generation of offensive odor. The effect of preventing stone from sticking is not sufficient, and the flow of fungicide into the septic tank hinders the function of the septic tank bacteria.
There is a problem that the purification capacity of the septic tank is reduced. The use of a cleaning deodorant consisting of a surfactant and a fragrance is also effective in preventing dirt on the toilet bowl wall and preventing generation of offensive odor, but the effect of preventing urine stones from sticking to the toilet drain pipe is further reduced.

[0007] The method of adding an ion-sequestering agent such as a Ca chelating agent to urine or washing water is quite effective in preventing urine stones from sticking. However, in order to completely prevent urine stones from sticking, it is necessary to add an ion-sequestering agent to the urine in an amount of 0.3 to 1% by weight, but the ion-sequestering agent is generally expensive, and this method is widely used. Hateful. Further, in the control of scale by sulfamine as described in the above-mentioned French and British patents, corrosion of drainage pipes and reduction of purification capacity of a septic tank due to low pH pose problems.

On the other hand, a urinary stone inhibitor mainly containing a solid acid such as an organic acid having an effect of preventing urine stones from sticking is an excellent urinary stone inhibitor, but it is necessary to control the dissolution rate of the solid acid. As a dissolution rate controlling agent for such a solid acid, paradiclobenzene has conventionally been used in view of the sublimation rate, melting point, cost and the like. However, recently, this harmful aromatic ring compound such as paradiclobenzene has been regarded as a problem due to its influence on the environment and the like, and has been repelled.

However, other than the halogen-containing aromatic ring compound,
No sublimable substrate having physical properties comparable to paradichlorobenzene in terms of sublimation rate and melting point is known. On the other hand, in the case of a urinary stone inhibitor formed by directly tableting a solid acid powder such as an organic acid without blending a sublimable substance, unlike the case where paradichlorobenzene is used as a dissolution rate regulator, urine and / or Or the frequency of use of washing water and the consumption rate of solid acid due to elution are proportional, so there is an advantage that the acid concentration in urine and washing water is constant each time it is used, but the use period is shortened, for example, for rental products. There was a problem that it could not be applied when it was desired to keep it constant.

The object of the present invention is to use a halogen-free dissolution rate regulator which can be substituted for paradichlorobenzene as a dissolution rate regulator for a solid acid having an effect of preventing urine stones from sticking.
An object of the present invention is to provide a urinary stone inhibitor capable of preventing and preventing urine stones from adhering to a toilet drain pipe or the like during a certain period of use regardless of the frequency of use, and a method for producing the same.

[0011]

Means for Solving the Problems In order to solve the above problems, the present inventors can substitute paradichlorobenzene as a dissolution rate regulator for a solid acid such as an organic acid having an effect of preventing urine from sticking. First, a non-halogen-based sublimable substance was examined. Among these non-halogen sublimable substances, DL-camphor (melting point: 178 ° C.), borneol (melting point: 206 ° C.), adamantane (melting point: 209 to 212 ° C.) having a melting point of more than 100 ° C. can be melted by ordinary operation. It requires special equipment and is not expected to be a substitute for paradichlorobenzene (melting point 54 ° C) in terms of melting point. Further, naphthalene, coumarin, cyclododecane, dimethoxybenzene, triisopropyltrioxane and the like having a melting point of less than 100 ° C. are converted to paradichlorobenzene (vapor pressure: 0.64 mmHg / 20 ° C.).
Because the sublimation rate is slower than that, only the solid acid, which is the active ingredient, is eluted first during use, leaving a phenomenon that only the non-halogen sublimable substance as a dissolution rate regulator remains, and the point of the sublimation rate increases. Predicted that it could not be a substitute for paradichlorobenzene.

However, in order to confirm the above prediction, the present inventors conducted an experiment using a non-halogen sublimable substance.
In the course of the experiment, when a powdered non-halogen sublimable substance and a powdered organic acid such as benzoic acid were mixed and heated, the melting start temperature was low, and a molten mixture was unexpectedly prepared at a low temperature. I found that I could do it. For example, when DL-camphor (melting point 178 ° C.) and benzoic acid (melting point 118 ° C.) powders are mixed and heated in an appropriate ratio, the mixture is heated at a little less than 60 ° C., which is much lower than the melting points of DL-camphor and benzoic acid. Melting has begun. Therefore, various non-halogen-based sublimable substances and an organic acid capable of forming a molten mixture with these non-halogen-based sublimable substances are first screened, and then the melting onset temperature of the organic acid capable of forming a molten mixture is determined. I checked. Table 1 shows the results.

[0013]

[Table 1]

From Table 1, it can be seen that the non-halogen sublimable substances and the screened organic acids have lower melting onset temperatures. Such a finding is different from the case of melting point lowering by a generally known solid-phase melting mixture, and is newly found by the present inventors.
For example, DL-camphor is melted at a high temperature, and a polyoxyethylene polymer-based nonionic surfactant or a block polymer-based nonionic surfactant of polyoxyethylene and polyoxypropylene are dissolved and solidified by cooling,
It melts at 60 ° C to 70 ° C, but just mixing both powders from the beginning does not mean that melting will start at that temperature,
Although the reason is not clear, it has been found that different behaviors occur when the non-halogen sublimable substance and the surfactant are melted and when the non-halogen sublimable substance and the organic acid such as benzoic acid are melted. .

When a molten mixture of a non-halogen sublimable substance and an organic acid such as benzoic acid is used as it is as an uric acid inhibitor, the dissolution rate of the organic acid is so slow that it cannot effectively act as an uric acid inhibitor. all right. However, in the course of various studies in order to make use of the knowledge that the melting onset temperature is lowered, the inventors came up with the idea of using such a molten mixture as a dissolution rate regulator by accident, and newly added the molten mixture as such a dissolution rate regulator as an anti-uricic agent. Produced by mixing and molding a solid acid into the urine. The present inventors have found that this molten mixture functions effectively as a dissolution rate regulator, and have completed the present invention.

That is, according to the present invention, a non-halogen-based sublimable substance and an organic acid capable of forming a molten mixture with the non-halogen-based sublimable substance are heated and mixed, and a solid acid is mixed with the mixture in a molten state. , A method for producing a urinary stone inhibitor characterized by molding, and a non-halogen-based sublimable substance comprising DL
-Camphor, naphthalene, borneol, adamantane, cyclododecane, triisopropyltrioxane,
One or more non-halogen-based sublimable substances selected from dimethoxybenzene and coumarin, a method for producing the above urinary stone inhibitor, and forming a molten mixture with the non-halogen-based sublimable substance Wherein the organic acid that can be produced is a carboxylic acid having a phenyl group, wherein the method for producing an urinary stone inhibitor or the carboxylic acid having a phenyl group is benzoic acid, p-hydroxybenzoic acid, or salicylic acid. , One or more selected from among cinnamic acid, p-toluic acid, m-toluic acid, o-toluic acid, p-anisic acid, m-cresotic acid, o-cresotic acid and DL-mandelic acid Wherein the carboxylic acid having a phenyl group is a carboxylic acid having a phenyl group, and wherein the solid acid is adipic acid, succinic acid, citric acid and sulfamic acid. The production method or molding of the above-mentioned urinary stone inhibitor characterized by being one or more solid acids selected from the group consisting of kneading molding, injection molding or tablet molding. A method for producing the above urinary stone inhibitor, characterized in that:

Further, the present invention provides a urine comprising a non-halogen sublimable substance, a molten mixture of an organic acid capable of forming a molten mixture with the non-halogen sublimable substance, and a solid acid. The stone inhibitor or the non-halogen sublimable substance is one or more non-halogen sublimates selected from DL-camphor, naphthalene, borneol, adamantane, cyclododecane, triisopropyltrioxane, dimethoxybenzene and coumarin. The above-mentioned urinary stone inhibitor, which is characterized by being a non-halogen-based sublimable substance, or an organic acid capable of forming a molten mixture, wherein the carboxylic acid having a phenyl group is a carboxylic acid having a phenyl group. Urinary stone inhibitors and carboxylic acids having a phenyl group are benzoic acid, p-hydroxybenzoic acid, salicylic acid, cinnamic acid, p- Ruiru acid, m- toluic acid, o-
The above urine, which is a carboxylic acid having one or more phenyl groups selected from toluic acid, p-anisic acid, m-cresotic acid, o-cresotic acid and DL-mandelic acid. The present invention relates to the above urinary stone inhibitor, wherein the stone inhibitor or the solid acid is one or more solid acids selected from adipic acid, succinic acid and sulfamic acid.

Further, the present invention provides a method for preventing urine stones from sticking, which comprises using the above-mentioned urinary stone inhibitor, a non-halogen sublimable substance, and a molten mixture with the non-halogen sublimable substance. A dissolution rate regulator for urinary stone inhibitors, comprising a molten mixture with an organic acid that can be
The organic acid capable of forming a molten mixture with a non-halogen-based sublimable substance is a carboxylic acid having a phenyl group.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The urinary stone inhibitor of the present invention comprises a melt mixture of a non-halogen sublimable substance and an organic acid capable of forming a melt mixture with the non-halogen sublimate substance as a dissolution rate regulator. And a molded product containing a solid acid as a main active ingredient. In the present invention, in addition to the completely molten mixture of the non-halogen sublimable substance and the organic acid, for the sake of convenience, a partially unmelted organic acid is contained in the completely molten mixture of both. Included mixtures are also included.

In the present invention, the dissolution rate regulator is used to prevent urine and / or urine from adhering to a toilet drain pipe or the like during a certain period of use regardless of the frequency of use. Or a drug that can adjust the dissolution rate of the urinary stone inhibitor by washing water, using such a dissolution rate control agent, while controlling the sublimation rate and dissolution rate of itself, solid acid and the main active ingredient The dissolution rate of the solid acid in the urinary stone inhibitor can be controlled.

The non-halogen sublimable substance which is a compounding component of the dissolution rate controlling agent of the present invention does not contain a halogen atom, is hardly soluble in water, and has a vapor pressure of 0.03 at room temperature.
Substances having a sublimability of about 5 to 5 mmHg can be exemplified, and specific examples thereof include DL-camphor, borneol, adamantane, dimethoxybenzene, triisoprtrioxane, naphthalene, cyclododecane, and coumarin.

The above-mentioned non-halogen sublimable substances can be used in combination of several kinds at an appropriate ratio according to the purpose, but it is sometimes preferable to use them alone. For example, when naphthalene and DL-camphor are mixed and used, the melting point is lowered to 50 ° C. or lower, and the melting operation is facilitated by the reduction of the melting point. However, a molten mixture of these and an organic acid such as carboxylic acid having a phenyl group is re-used. The urinary stone inhibitor using the solidified dissolution rate controlling agent is, as compared with the case of using naphthalene or DL-camphor alone, similar to the above-described compatible re-solidification of the sublimable substance and the surfactant, the solid acid. The effect of suppressing elution is reduced.

The dissolution rate of the solid acid or dissolution rate regulator, which is a component of the urinary stone inhibitor, largely depends on the sublimation rate of the selected non-halogen sublimable substance.
When a non-halogen sublimable substance having a high sublimation rate such as DL-camphor is mainly used, a product having a high dissolution rate is obtained,
Conversely, when a non-halogen sublimable substance having a low sublimation rate such as coumarin is mainly used, a product having a low dissolution rate and reduced consumption can be obtained.

As the organic acid capable of forming a molten mixture with the non-halogen sublimable substance, which is a compounding component of the dissolution rate regulator of the present invention, a molten mixture with the non-halogen sublimable substance may be formed. Any organic acid can be used, and examples of such organic acids include carboxylic acids having a phenyl group. Examples of the carboxylic acids having a phenyl group include benzoic acid, cinnamic acid, salicylic acid, p Specific examples thereof include -hydroxybenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, p-anisic acid, m-cresotic acid, o-cresotic acid, and DL-mandelic acid. These may be used alone or as a mixture at an appropriate ratio according to the purpose. Among these, it is particularly preferable to use benzoic acid as the main component, because the difference in the consumption rate of the urinary stone inhibitor due to the frequency of use is reduced.

When a molten mixture of an organic acid such as a carboxylic acid having a phenyl group and a non-halogen sublimable substance is used as a dissolution rate regulator, the solid acid contained in the urine and / or washing water in the uremic inhibitor can be reduced. Can be suppressed, and the dissolution rate can be controlled to reduce the difference in consumption rate depending on the frequency of use. For example, depending on the type of organic acid such as a non-halogen sublimable substance and a carboxylic acid containing a phenyl group, the difference in consumption rate is 1.1 to 1.1 even when the frequency of use is doubled.
It can be reduced to 1.9 times. Here, the consumption rate (%) is the weight of the urinary stone inhibitor after use / the weight of the urinary stone inhibitor before use × 10
It is represented by 0.

The mixing ratio of the non-halogen sublimable substance and the organic acid such as carboxylic acid having a phenyl group in the dissolution rate regulator of the present invention may vary depending on the type of non-halogen sublimable substance or organic acid used. However, the content of the non-halogen sublimable substance with respect to the total amount of the non-halogen sublimable substance and the organic acid is 10 to 90% by weight, especially 30 to 90% by weight.
70% by weight is preferred, less than 10% by weight and 90% by weight
When it exceeds, control of the dissolution rate becomes difficult. Further, as described above, the organic acid may be completely melted, or may be used in a ratio in which it is partially unmelted.

The solid acid used as the main active ingredient in the urinary stone inhibitor of the present invention may be a solid acid at room temperature which can prevent urine stones from being fixed when eluted with urine and / or washing water. Any material may be used as long as it does not react with calcium ions to form a salt having a solubility in water of pH 5 to 8.5 having a solubility of 0.001 g / 100 g (water) or less. Specifically, water-soluble acidic salts such as sodium hydrogen sulfate, potassium hydrogen sulfate, and ammonium hydrogen sulfate; water-soluble salts of a strong acid and a weak base such as ammonium chloride and ammonium sulfate; and boric acid, sulfamic acid, succinic acid, and citric acid Room temperature solid organics such as, maleic acid, isophthalic acid, tartaric acid, hydroxyacetic acid, P-toluenesulfonic acid, fumaric acid, adipic acid, salicylic acid, pracidylic acid, hydrocinnamic acid, maleic anhydride, DL-malic acid and benzoic acid Acids can be mentioned. These acidic substances can be used alone or as a mixture of two or more. Among them, sulfamic acid, succinic acid, citric acid and adipic acid are particularly preferable.

In the urinary stone inhibitor of the present invention, in addition to the solid acid and the dissolution rate regulator, a surfactant, a dissolution rate regulator, a corrosion inhibitor, a slime inhibitor, an ion sequestering agent, a coloring agent , A fragrance, a fungicide, a bactericidal / antibacterial agent, and the like can be added according to the purpose. As the surfactant, those capable of facilitating uniform mixing of components such as polyethylene glycol having an average molecular weight of 6000 and a polyoxyethylene polyoxypropylene block polymer surfactant are used. Examples of the dissolution rate adjusting agent for adjusting the dissolution rate include poorly water-soluble substances obtained by heating with other components of the urinary stone inhibitor to obtain a uniform molten mixture, such as fatty acids, higher alcohols, calcium stearate, and stearic acid. Fine powder of a water-repellent substance such as magnesium or talc can be used. Corrosion inhibitors that prevent the corrosion of toilet drainpipes include azole compounds such as benzotriazole,
Cationic surfactants such as alkylthioureas can be used. As a coloring agent, prevention of coloring due to urine or the like of the molded body,
A non-water-soluble or water-soluble coloring agent can be used for the purpose of detecting the remaining amount of the molded body, coloring washing water, and the like. As the fragrance, a fragrance that can mask a bad smell and generate fragrance is used.

As the antifungal agent and the disinfectant / antibacterial agent, a kind that does not affect the septic tank bacterium or an amount in which the influence is negligible is used. Examples of fungicides include methylenebisthiocyanate, 2-methoxycarbonylaminobenzimidazole, 2,3,3-triiodoallyl alcohol, zinc salt of 2-pyridinethiol-1-oxide, 4-chlorophenyl-3-iodopropagyl Formal, 3-iodo-2-propargylbutylcarbamic acid, 3-bromo-
2,3-iodo-2-propenylethyl carbonate,
5-chloro-2-methyl-isothiazolin-3-one,
2,2-dithio-bis- (pyridine-1-oxide), diiodomethyl-p-trisulfone, 2,3
Examples include 5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2-thiocyanomethylthiobenzthiazole, thiabendazole, 1-bromo-3-chloro-5,5-dimethylhydantoin and trichloroisocyanuric acid. Examples of disinfecting and antibacterial agents include methylenebisthiocyanate, 2,3,3-triiodoallyl alcohol, 3-iodo-2-propargylbutylcarbamic acid, and 3-bromo-2,3-iodo-2-propenylethylcarboate. Nate, 5-chloro-2-methyl-isothiazolin-3-one, 2-thiocyanomethylthiobenzthiazole, 2,2-dibromophosphonitroethanol,
2,4,4-trichloro-2-hydroxy-diphenyl ether, 2-bromo-2-nitro-1,3-propanediol, didecyldimethylammonium chloride,
Tetradecyldimethylbenzylammonium chloride, cetylpyridinium chloride, 1-bromo-3-
Chlor-5,5-dimethylhydantoin and trichloroisocyanuric acid can be exemplified.

[0030] The urilithic antioxidant of the present invention is obtained by melting and mixing the above-mentioned non-halogen sublimable substance and an organic acid capable of forming a molten mixture with the non-halogen sublimable substance, and solidifying the molten mixture in a molten state. After uniformly mixing the acid, it can be produced by molding. Melt mixing is preferably performed by heating the mixture of both, but one of them may be heated and dissolved, and the other component may be added thereto to prepare a molten mixture of both.

As the molding method in the method for producing the urinary stone inhibitor of the present invention, there are a casting method in which a homogeneous mixture of the molten mixture and the solid acid is poured into a mold and cooled and solidified, and the molten mixture and the solid acid are mixed. And a tableting method of tableting a granulated product obtained by granulating the molten mixture and a solid acid. Further, the shape of the urinary stone inhibitor of the present invention by molding may be any shape, for example, spherical, cylindrical, perforated cylindrical, disk-shaped, cubic, conical, pyramidal, animal and plant shapes, etc. it can.

The mixing ratio of the dissolution rate regulator and the solid acid as the main active ingredient of the urinary stone inhibitor can be freely selected by setting the frequency of use of the product, setting the period of use, and the like. 20-95% of the total, preferably 40-8
It is preferably set to 0%, and the dissolution rate regulator is set to 5 to 80%, preferably 10 to 60% of the product weight. 5% by weight of dissolution rate regulator
If it is less than 3, when the molded body comes into contact with urine and / or washing water, it tends to lose its shape, and it is difficult to control the dissolution rate. On the other hand, the content of the dissolution rate regulator is 80% by weight.
When the content exceeds the above range, the content of the solid acid, which is an active ingredient, decreases, and the effect of preventing urinary calculus becomes insufficient.

The urinary stone inhibitor of the present invention may be used intermittently with urine and / or urine.
Alternatively, it is preferably installed at a place where it comes into contact with washing water, for example, at the inlet of a drain pipe in a toilet, the washing water flow path on the inner wall surface and bottom of the toilet, under a faucet of a low tank with a hand washing section, in a pipe injection type dissolver, and the like. When the urinary stone inhibitor (molded product) of the present invention is directly or stored in various containers and brought into contact with urine and / or washing water, the solid acid is dissolved in urine and / or washing water, and the solid acid is dissolved in the toilet drain pipe. The pH of the urine or the mixed drainage of the urine and the washing water retained at 5 to 8.5 is maintained at 5 to 8.5. As a result, the urine stone to the toilet drain pipe is removed without removing the urine stone fixed to the toilet drain pipe. Is prevented only from sticking.

[0034]

The present invention will be described in more detail with reference to the following examples, but the technical scope of the present invention is not limited to these examples. Example 1 30 parts by weight of DL-camphor, 11 parts by weight of benzoic acid, and 4 parts by weight of polyethylene glycol having an average molecular weight of 6000 were placed in a polycup, immersed in hot water at 80 ° C., and uniformly dissolved with stirring. Then, succinic acid was mixed well so as to be uniform, poured into a mold, allowed to cool, and solidified and molded. 40 × 40 × 2 molded in this way
A urine-prevention agent of 0 mm was put into a pipe injection type dissolver and used in a flush urinal. The test was performed at 25 ° C in an atmosphere of 10 per day.
The test was carried out under the condition of washing with water at 25 ° C. every 10 minutes and 20 minutes. FIG. 1 shows the relationship between the elapsed days and the consumption rate at that time, and FIG. 2 shows the relationship between the elapsed days and the density. From FIG. 1, even if the frequency of use is twice, the difference in the consumption rate is 1.3 times, and the urinary stone inhibitor of the present invention can be used effectively for 30 days regardless of the frequency of use. We can see that we can do it Further, FIG. 2 shows that the density is almost constant regardless of the frequency of use, and that the dissolution rate of the urinary stone inhibitor of the present invention is adjusted.

Example 2 33 parts by weight of DL-camphor, 10 parts by weight of cinnamic acid, 10 parts by weight of polyoxyethylene poly, instead of 30 parts by weight of DL-camphor, 11 parts by weight of benzoic acid, and 4 parts by weight of polyethylene glycol having an average molecular weight of 6000 Example 1 except that 2 parts by weight of an oxypropylene block polymer surfactant was used.
The test was performed in the same manner as in the above. FIG. 3 shows the relationship between the elapsed days and the consumption rate. FIG. 3 shows that even if the frequency of use is twice, the difference in the consumption rate is 1.5 times, indicating that the urinary stone inhibitor of the present invention can be used effectively for 30 days.

Example 3 15 parts by weight of triisopropyltrioxane, 3 parts by weight of naphthalene, 6 parts by weight of benzoic acid, and 3 parts by weight of a polyoxyethylene polyoxypropylene block polymer surfactant were placed in a polycup and immersed in hot water at 80 ° C. When agitated and uniformly dissolved, add 70 parts by weight of adipic acid, 3 parts by weight of a bactericide / corrosion inhibitor and other components, mix well so that adipic acid becomes uniform, pour into a mold and allow to cool to solidify. Molded. Using this solidified molded product, a test was conducted in the same manner as in Example 1. FIG. 4 shows the relationship between the elapsed days and the consumption rate. FIG. 4 shows that even if the frequency of use is twice, the difference in the consumption rate is 1.3 times, indicating that the urinary stone inhibitor of the present invention can be used effectively for 30 days.

Example 4 35 parts by weight of DL-camphor and 10 parts by weight of cinnamic acid were placed in a polycup, immersed in hot water at 80 ° C., and uniformly dissolved with stirring, and 55 parts by weight of adipic acid were added. Was thoroughly mixed so as to be uniform, poured into a mold, allowed to cool, and solidified and molded. 55φ × 35 molded in this way
The urine stone inhibitor was placed in a male urinal trap cassette, set on the upper portion of the trap, and used. The water used for the water washing was 25 ° C. and the air temperature was 25 ° C. as in Example 1, and the water was washed once every 10 hours and 20 minutes a day. FIG. 5 shows the relationship between the elapsed days and the consumption rate and the pH change of the water in the trap. FIG. 5 shows that the pH was maintained at 7.5 to 8.0, and that the urinary stone inhibitor of the present invention could be used effectively for 30 days.

COMPARATIVE EXAMPLE 1 30 parts by weight of DL-camphor and 15 parts by weight of polyethylene glycol having an average molecular weight of 6000 were placed in a polycup, and
It was immersed in hot water at 0 ° C. and tried to stir until it was uniformly dissolved, but the temperature of the hot water was gradually increased because it did not readily dissolve. Eventually, the boiling water did not dissolve.

Comparative Example 2 30 parts by weight of naphthalene and 15 parts by weight of polyethylene glycol having an average molecular weight of 6000 were placed in a polycup, immersed in hot water at 80 ° C., and uniformly dissolved.
Add parts by weight and mix well. Molded in the same manner as in Example 1,
The test was performed similarly. Those washed with water at 10-minute intervals are 10 days, and those washed with water at 20-minute intervals are only 13 days later, and only succinic acid is extracted and the specific gravity becomes light. . The dissolution test was stopped when it began to float on the water. FIG. 6 shows the relationship between the elapsed days and the consumption rate, and FIG. 7 shows the relationship between the elapsed days and the density. FIG. 7 shows that the dissolution rate of the solid acid cannot be adjusted without using a dissolution rate regulator consisting of a molten mixture of naphthalene and an organic acid capable of forming a molten mixture.

Comparative Example 3 74 parts by weight of benzoic acid, 19 parts by weight of adipic acid, 5 parts by weight of hydroxypropyl cellulose as a binder, 1 part by weight of a benzotriazole-based corrosion inhibitor, an anionic surfactant, and sucrose as a lubricant 0.5 part by weight of each of the fatty acid ester and the fungicide was well mixed. After this mixed powder was molded into a size of 40 × 40 × 20 mm using a tableting machine, a dissolution test was conducted in the same manner as in Example 1. FIG. 8 shows the results. From FIG. 8, it can be seen that the frequency of use and the rate of consumption are almost directly proportional, and the dissolution rate cannot be adjusted due to the frequency of use unless a dissolution rate regulator consisting of a molten mixture with a non-halogen sublimable substance is used. Understand.

[0041]

EFFECTS OF THE INVENTION The urinary stone inhibitor of the present invention can prevent and prevent urine stones from adhering to toilet drainage pipes, etc. during a certain period of use regardless of the frequency of use. For example, it is particularly excellent as a rental product. In addition, the urinary stone inhibitor of the present invention can prevent only urine stones from sticking to the toilet drainage pipe without removing the urine stones sticking to the toilet drainage pipe, so that corrosion of the drainage pipe is extremely small, And it does not adversely affect the septic tank function. Furthermore, the urinary stone inhibitor of the present invention has high safety because it does not use a halogen-containing aromatic ring compound which causes environmental pollution such as paradichlorobenzene as a dissolution rate regulator of a solid acid having an effect of preventing urine stone adhesion. .

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the elapsed days and the consumption rate when the urinary stone inhibitor of Example 1 using DL-camphor and benzoic acid was used.

FIG. 2 is a graph showing the relationship between the number of elapsed days and the density when the urinary stone inhibitor of Example 1 using DL-camphor and benzoic acid is used.

FIG. 3 is a graph showing the relationship between the elapsed days and the consumption rate when the urinary stone inhibitor of Example 2 using DL-camphor and benzoic acid was used.

FIG. 4 is a graph showing the relationship between the elapsed days and the consumption rate when the urinary stone inhibitor of Example 3 using triisopropyltrioxane, naphthalene and benzoic acid was used.

FIG. 5 is a graph showing the relationship between the elapsed days and the consumption rate and the pH change of water in the trap when the urinary stone inhibitor of Example 4 using DL-camphor and cinnamic acid is used.

FIG. 6 is a graph showing the relationship between the elapsed days and the consumption rate when the urinary stone inhibitor of Comparative Example 2 using naphthalene was used.

FIG. 7 is a diagram showing the relationship between the elapsed days and the density when the urinary stone inhibitor of Comparative Example 2 using naphthalene was used.

FIG. 8 is a graph showing the relationship between the elapsed days and the consumption rate when the urinary stone inhibitor of Comparative Example 3 using benzoic acid was used.

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Claims (14)

[Claims] 1. A non-halogen-based sublimable substance and an organic acid capable of forming a molten mixture with the non-halogen-based sublimable substance are heated and mixed, and a solid acid is mixed with the molten mixture and then molded. A method for producing a urinary stone inhibitor. 2. The non-halogen-based sublimable substance is at least one selected from DL-camphor, naphthalene, borneol, adamantane, cyclododecane, triisopropyltrioxane, dimethoxybenzene and coumarin. The method for producing a urinary stone inhibitor according to claim 1, wherein the agent is an anionic substance. 3. The method of claim 1, wherein the organic acid capable of forming a molten mixture with the non-halogen sublimable substance is a carboxylic acid having a phenyl group. Method. 4. The carboxylic acid having a phenyl group is benzoic acid, p-hydroxybenzoic acid, salicylic acid, cinnamic acid, p-toluic acid, m-toluic acid, o-toluic acid, p-anisic acid, m- 4. Urinary stone prevention according to any one of claims 1 to 3, which is a carboxylic acid having one or more phenyl groups selected from cresotic acid, o-cresotic acid and DL-mandelic acid. Method of manufacturing the agent. 5. The solid acid according to claim 1, wherein the solid acid is one or more solid acids selected from adipic acid, succinic acid, citric acid and sulfamic acid.
The method for producing a urinary stone inhibitor according to any one of the above. 6. The molding according to claim 1, wherein the molding is performed by a kneading molding method, an injection molding method or a tablet molding method.
5. The method for producing a urinary stone inhibitor according to any one of the above items 5. 7. An antiurethric agent comprising a non-halogen sublimable substance, a molten mixture of the non-halogen sublimable substance and an organic acid capable of forming a molten mixture, and a solid acid. . 8. The non-halogen sublimation substance is at least one selected from DL-camphor, naphthalene, borneol, adamantane, cyclododecane, triisopropyltrioxane, dimethoxybenzene and coumarin. The urinary stone inhibitor according to claim 7, which is a toxic substance. 9. The urinary stone inhibitor according to claim 7, wherein the organic acid capable of forming a molten mixture with the non-halogen sublimable substance is a carboxylic acid having a phenyl group. 10. The carboxylic acid having a phenyl group is benzoic acid, p-hydroxybenzoic acid, salicylic acid, cinnamic acid, p-toluic acid, m-toluic acid, o-toluic acid, p-anisic acid, m-acid. 10. Urinary stone prevention according to any one of claims 7 to 9, characterized in that it is a carboxylic acid having one or more phenyl groups selected from cresotic acid, o-cresotic acid and DL-mandelic acid. Agent. 11. The urolith according to claim 7, wherein the solid acid is one or more solid acids selected from adipic acid, succinic acid and sulfamic acid. Inhibitor. 12. A dissolution rate controlling agent for an urinary stone inhibitor, comprising a molten mixture of a non-halogen sublimable substance and an organic acid capable of forming a molten mixture with the non-halogen sublimable substance. . 13. The dissolution rate control for an urinary stone inhibitor according to claim 12, wherein the organic acid capable of forming a molten mixture with the non-halogen-based sublimable substance is a carboxylic acid having a phenyl group. Agent. 14. A method for preventing urinary stones from sticking, comprising using the urinary stone inhibitor according to any one of claims 7 to 11.