JPH02147699A - Aromatic urinary calculus preventive - Google Patents

Abstract

PURPOSE:To obtain the title preventive which is freed from a problem of decomposition of a perfume, can mask a bad odor and can prevent urinary calculus from depositing on a urinal or the like by molding a mixture of a specified solid acid with a perfume. CONSTITUTION:At least 20wt.% at least one solid acid (A) selected from among normally solid organic carboxylic acids, cyanuric acid, metaphosphoric acid and boric acid is mixed with 0.5-10wt.% perfume (B), 20-80wt.% base (C) selected from a sublimable material (a) (e.g. p-dichlorobenzene), a water-soluble material (b) (e.g. polyethylene glycol) and a mixture (c) prepared by mixing component (a) with component (b) in a weight ratio of 4/6<=1/b<=9/1 is optionally mixed with a dissolution rate modifier, a surfactant, etc., (D), and the mixture is molded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a urinary stone preventive agent, and more specifically, an aromatic urinary stone preventive agent which is a urinary stone preventive agent whose main component is a solid acid and a fragrance added thereto. Regarding.

The aromatic urinary stone inhibitor of the present invention is used in various types of flushing toilets or non-flushing toilets to prevent urinary stones from adhering to the toilet bowl.

[Conventional technology]

Toilet bowls, especially men's urinals, and the drain pipes from the toilets are covered with scale, a mixture of calcium-based compounds and organic matter produced by the decomposition of urine, so-called urinary stones, which obstruct the flow of urine and washing water. In severe cases, it may block the drain pipe. Furthermore, organic matter in urine and urinary stones is putrefied and decomposed by bacteria, producing a foul odor.

To mask the bad odor emitted from toilet bowls using fragrances and other fragrances, air fresheners such as molded products of paradichlorobenzene and molded products of paradichlorobenzene containing fragrance are commercially available (product name/fragrance). ball, beauty salon
On the other hand, in order to prevent these urinary stones from adhering to toilet bowls and drain pipes, the applicant has developed an anti-scaling agent for toilet drain pipes that contains a solid acid as an active ingredient to prevent the formation of urinary stones. (Refer to Japanese Patent Application Laid-Open No. 62-038299), an anti-urinary stone agent to be placed in a men's urinal made of a sublimable substance containing sulfamic acid as an active ingredient and a water-soluble permeable substance as a base material. was aged.

In addition, detergent ingredients such as surfactants and ion sequestering agents, fragrances,
Disclosed is an aromatic cleaning agent for urinals, which is made of a mixture of aromatic substances such as paradichlorhenzene, disinfectants, etc., and is formed using a water-soluble substance such as polyethylene glycol as a base material, and is used mainly by being placed in men's urinals. (Special Public Interest Publication 1977-30)
No. 706, JP-A No. 57-16866868668 Problems to be solved by the invention] The air fresheners cited above cannot be expected to have any effect on preventing urinary stones from adhering to toilet bowls, and are In toilets that are used by many people, the effectiveness of masking bad odors generated from the toilets is insufficient. On the other hand, although aromatic cleaners have been shown to have the effect of preventing urinary stones from adhering to the toilet bowl and masking bad odors, their effectiveness in preventing urinary stones from adhering to the drain pipe from the toilet bowl is insufficient, and those containing disinfectants are not effective. , disinfectants have an effect on the septic tank, and for those containing ion sequestering agents, in order to completely prevent urinary stones from adhering to the toilet bowl, it is necessary to use an expensive ion sequestering agent at 063 to 1 TItf% of the urine. ? 8 It is not contradictory at all because it has to be understood.

In contrast, the drainage pipe scale inhibitor proposed by the present applicant not only has an extremely excellent effect of preventing urinary stones from adhering to toilet bowls and drain pipes, but also contains a solid acid containing dissolved ammonia produced by the decomposition of urine. Because it reacts with water to produce a water-soluble ammonium salt, it also has an extremely good deodorizing effect. However, even if ammonia odor can be removed, Wav
Removal or masking of A odor is still insufficient.

As a result of adding various fragrances to the composition of the commercially available urinary stone inhibitor for the purpose of masking organic odor, most of the fragrances, except for certain fragrances, are decomposed by solid acids and lose their effectiveness completely, or It produced an unpleasant odor which was contrary to the purpose.

An object of the present invention is to provide an aromatic urinary stone inhibitor that is sufficiently effective in preventing urinary stones from adhering to toilet bowls and drain pipes, and has an excellent odor masking effect.

c. Means to Solve the Problem] As a result of intensive research to achieve the above object, the present inventors have found that organic carboxylic acid, metaphosphoric acid, and/or solid organic carboxylic acid at room temperature.
It has also been discovered that by using boric acid and fragrance in combination, the decomposition of the fragrance can be prevented and the effect of masking bad odors can be obtained, as well as the effect of preventing urinary stones from adhering to toilet bowls etc. can be sufficiently obtained, and the present invention has been made. completed.

The present invention provides an aromatic urine product comprising a molded article containing at least one solid acid selected from the group consisting of organic carboxylic acids, cyanuric acid, metaphosphoric acid, and boric acid, which are solid at room temperature, and a fragrance. It is an anti-stone agent.

In the present invention, organic carboxylic acids that are solid at room temperature can be monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, vitrocarboxylic acids, a$l as long as they are solid at room temperature and water-soluble.
Any anhydride may be used, such as adipic acid, succinic acid, citric acid, tartaric acid, oxalic acid, dl-malic acid, maleic acid, benzoic acid, 0-phthalic acid, terephthalic acid, isophthalic acid, gallic acid, hydroxyacetic acid. , salicylic acid,
Brassylic acid, nitrotriacetic acid, hydrocinnamic acid, maleic anhydride, phthalic anhydride, etc. and mixtures of two or more thereof can be used.

On the other hand, inorganic solid acidic substances such as sulfamic acid, potassium hydrogen sulfate, and sodium hydrogen sulfate, sulfonic acids such as para-toluenesulfonic acid and benzenesulfonic acid, and chlorinated cyanuric acids with oxidizing properties, such as trichloroisocyanuric acid and dichloroisocyanuric acid, Nuric acids etc. cannot be used for the purposes of the present invention.

The fragrance may be any fragrance as long as it masks toilet odors and gives the user a good impression, and natural fragrances, synthetic fragrances, mixed fragrances, and the like can be used without particular restrictions.

Aromatic urinary stone prevention agent of the present invention (hereinafter simply referred to as "agent")
is a molded product obtained by molding the mixture of the solid acid and fragrance into an arbitrary dosage form, and it can be used in toilets, especially in the flushing water and/or urine flow path of men's urinals, in the low tank for flushing water, and in toilet bowls. It is used by directly putting it into a trap or storing it in a specific container.

There are no particular restrictions on these dosage forms, and depending on the usage, they may be granular, granular, spherical, cylindrical, disc-shaped, perforated disc-shaped (doughnut-shaped) [ )-shaped, half-doughnut-shaped, or cubic. Any dosage form can be selected, such as cylindrical, conical, pyramidal, animal or plant shapes, etc. 2. Especially when dispensing directly into the urinal, spherical or perforated disks that have good contact with the flushing water can be used. Shapes like U-shaped, U-shaped, and half-doughnut shapes are preferably explored.

The main rule is that the molded product may be made of only the solid acid and fragrance, but usually the solid acid contains 20% by weight or more and no fragrance.
．． It is a molded article containing 5 to 10 weight percent of weight material, 20 to 80 weight percent of weight material, and various additives.

The base material is used to stably hold the fragrance in the agent when forming the agent, and to improve its moldability. It is used as a regulator of the rate of acid dissolution and the release rate of fragrances from.

As these base materials, sublimable base materials, water-soluble base materials, and mixture bases thereof can be used, and are selected depending on the usage B.

As the water-soluble base material, water-soluble polymers that are solid at room temperature, such as bases used in ordinary pharmaceutical preparations such as polyethylene glycol and volip-11 pyrene glycol, various surfactants, ion sequestering agents, etc., and mixtures thereof. is used. Moreover, the above-mentioned fragrance, which is a component as a main ingredient, can also be included in the water-soluble base material if it is compatible with the water-soluble base material.

On the other hand, as a sublimable base material, 0.05 to 5
Slightly water-soluble substances having a vapor pressure of about mmHg, such as bala-dichlorobenzene, naphthalene, camphor, etc., and mixtures thereof can be used, and para-dichlorobenzene is preferably used because it does not interfere with the odor of 1ffi regular fragrances and is easily available. be done.

In the case of agents that are applied to areas where flushing water and/or liquid is constantly present, such as in toilet traps, only water-soluble substrates are preferably used as substrates.

On the other hand, when applied to a wave channel where washing water and/or urine flows intermittently, such as inside a men's urinal or a low tank, only a sublimable base material or a mixed base material is used, and the latter is particularly preferred. be done.

When using a mixed base material, the mixing ratio of the sublimable base material (A) and the water-soluble base material (B) is 4/6≦A/B≦9 on a weight basis.
/1, preferably 515≦A/B≦8/2.

Various additives such as dissolution rate regulators, surfactants, deodorants, colorants, corrosion inhibitors, bactericidal agents, ion sequestrants, etc. can be added as desired.

The main rules are to form a powder mixture of each of the above components into tablets, to extrude and compression mold, to mold the powder mixture by heating and melting it and casting it, to form granules by extrusion and granulation, and through a fluidizing device. It can be manufactured by molding by a known method such as a method of granulating it using etc.

[For production]

The aromatic urinary stone preventive agent of the present invention is characterized by being composed of a molded article containing a specific solid acid and a fragrance, as described above.

In the present invention, the selected solid acid not only has a sufficient effect of preventing urinary stone from adhering to the toilet bowl or its drain pipe, but also has a 0.01N aqueous solution at 20°C or a 2N
The concentration of saturated aqueous solution at 0°C is 0.0 I IJ! Since the solid acid is a weak acid with a saturated aqueous solution having a pH of 2.2 or more, the solid acid has a low reactivity with the perfume, and the perfume is dissipated without deterioration, thereby masking the bad odor.

On the other hand, inorganic acidic substances and organic sulfonic acids, etc., exhibit strong acidity with a pH of less than 2.2 in a 0.01N aqueous solution at 20°C, so they react with fragrances and change their quality.
Fragrance dissipation is reduced and, in some cases, malodors are generated. Furthermore, oxidizing acids such as chlorinated isocyanuric acid have even stronger reactivity with fragrances.

On the other hand, the base material not only improves the moldability during the production of the agent, but also adjusts the dissolution rate of the solid acid and the diffusion rate of the fragrance during its use, and prevents swelling and deformation of the agent.

In particular, for agents installed or installed in channels where cleaning water and/or urine flows intermittently, by using a mixed base material, it is possible to use a water-soluble base together with the water-soluble base material when the cleaning water etc. comes into contact with the agent. As the solid acid is eluted into the washing water, etc., a sublimable base layer is formed on the surface of the agent, and the excess solid acid is dissolved into the washing water, etc.
On the other hand, in the case of non-contact, as the sublimable base material sublimes, a water-soluble base material layer is formed on the surface of the agent, and excessive dispersion of the fragrance and the sublimable base material is prevented. As a result, by using the basic rules, it is possible to prevent urinary stones from adhering to toilet bowls, etc. over a long period of time.
The F effect and the masking effect of the bad odor generated from them are sustained.

Explain in detail.

However, the scope of the present invention is not limited in any way by the following examples.

In addition, in the following examples, "part j" and "%J" are based on weight unless otherwise specified.

+l+ Effect of various solid acids on fragrances Mixed fragrances of citrus type, osmanthus type, and rose type and 1/1 orange oil (natural fragrance) are added to various solid acid powders.
% added, mixed and kept at a temperature of 40°C for 3 months,
The presence or absence of deterioration of the fragrance was determined by a sensory test.

The test results are 0, 0! of solid acid at 20°C. In the case of normal aqueous solutions or solid acids whose saturated solubility is less than 0.01 normal, the pH values of the saturated aqueous solutions are shown in Table 1.

〔Example〕

The present invention has been demonstrated through Examples and Comparative Examples, and as shown in Table 1, in the mixed system of the solid acid and perfume selected in the present invention, no deterioration of the perfume is observed.
In mixed systems of inorganic acidic substances or organic sulfonic acids and perfumes, deterioration of the perfume is observed in all systems.

(2) Production of aromatic urinary stone inhibitor (al sample/l-1 30 parts of paradichlorobenzene and average molecular weight fJt6.
A slurry was prepared by mixing and heating and melting 20 parts of OOO polyethylene glycol, and then adding and mixing 50 parts of adipic acid, 2 parts of an osmanthus-based controlled fragrance, and 1 part of an alkylthiourea-based corrosion inhibitor.

This slurry was poured into a mold and cooled to a diameter of 4Qmm.
Aromatic rough stone inhibitor consisting of a disc-shaped molded body weighing 50 g:
Sample A-1 was manufactured.

fbl Sample A-2 30 parts of Balajichlorobenzene and 1 tlo of average molecule,
50 parts of succinic acid was mixed and heated to melt 20 parts of ethylene oxide-propylene oxide copolymer.
A slurry was prepared by adding and mixing 5 parts of orange-based controlled fragrance and 1 part of alkylthiourea-based corrosion inhibitor.

This slurry was poured into a mold and cooled to a diameter of 4Qmm.
An aromatic urinary stone inhibitor consisting of a disk-shaped molded body weighing 50 g:
Sample A-2 was produced.

(C1 Sample A-3 Added a homogeneous mixture consisting of 60 parts of benzoic acid pulverized product, 40 parts of amber #, 2 parts of a powdered fragrance obtained by impregnating fine silica gel powder with 50% rose-based adjusted fragrance t↓, and 1 part of calcium stearate. An aromatic urinary stone inhibitor: Sample A-3 was produced by pressure molding and consisting of a disk-shaped molded body with a diameter of 40 mm and a weight of 150 g.

+dl Sample A-4 3 parts of a 10% aqueous solution of polyvinylpyrrolidone in a mixture with 100 parts of fumaric acid and 1 part of a triazole corrosion inhibitor.
After adding 0 part of the mixture and kneading it using a Ni-Goo, it was granulated using an extrusion granulator and dried to prepare granules with an average diameter of 1.5 mm. Next, a homogeneous mixture consisting of 104 parts of the above-prepared granules, 4 parts of a powdered fragrance made by impregnating fine silica gel powder with 50% orange oil, and 1 part of calcium stearate was pressure-molded to form a disk shape with a diameter of 40 mm and a weight of 50 g. An aromatic urinary stone inhibitor consisting of a molded body: Sample A-4 was produced.

(el Sample A-5 35 parts of Balajichlorobenzene, average fractional yield 1o, o o
15 parts of polyethylene glycol of o, average molecular weight ffi
10. Mix 10 parts of OOO ethylene oxide-propylene oxide copolymer and add 2! ! A slurry was prepared by adding and mixing 10 parts of a citrus-based controlled fragrance, 40 parts of citric acid powder, and 1 part of an alkylthiourea-based corrosion inhibitor to the melt.

This slurry was poured into a mold and cooled to form a mold with a diameter of 40 mm.
An aromatic urinary stone inhibitor: Sample A-5 consisting of a spherical molded body weighing 145 g was produced.

ff+ Sample A-6 20 parts of a 10% aqueous solution of polyvinylpyrrolidone was added to a mixture of 100 parts of isophthalic acid and 1 part of a triazole corrosion inhibitor, and treated in the same manner as Sample A-4 to obtain an average diameter of 1
．． Granules of 5 mm were prepared.

In addition, 70 parts of polyethylene glycol with an average molecular weight of 1t20,000 is heated and melted, 30 parts of osmanthus-based adjusted fragrance are added and mixed therein, and the mixture is cooled to solidify and pulverized.
~2 mm granules were prepared.

A homogeneous mixture consisting of 90 parts of isophthalic acid granules, 10 parts of fragrance granules, and 1 part of calcium stearate prepared above was pressure-molded to form a cylindrical molded body with a diameter of 30 mm and a weight of 20 g: an aromatic urinary stone inhibitor: Sample A -6 was manufactured.

(a Sample A-7 25 parts of paradichlorobenzene, 10 parts of polyethylene glycol with an average molecular weight M6.000, and 10 parts of the above-mentioned ethylene oxide-propylene oxide copolymer were mixed and heated to melt, and 2 parts of osmanthus-based modified fragrance and adipic acid were mixed and heated.) 60 parts and 1 part of a triazole corrosion inhibitor were added and mixed to prepare a slurry.

The obtained slurry was poured into a mold, cooled and solidified to produce an aromatic urinary stone inhibitor: Sample A-7 consisting of a doughnut-shaped molded body with an outer diameter of 110 mm and an inner diameter of 70 mm.

(11) Sample A-8 30 parts of paradichlorobenzene, average molecular weight l.

000 polyethylene glycol 10 parts, average molecular end 2
0,000 parts of polyethylene glycol and 10 parts of utylene oxide dobrobylene oxide copolymer were mixed and heated to melt, and in this mixture were added 2 parts of peach-based modified fragrance, 50 parts of adipic acid, 0 parts of di-milled apple, and alkylthio. 0.5 parts of a urea-based corrosion inhibitor and 0.5 parts of a triazole-based corrosion inhibitor were added and mixed to prepare a slurry.

The obtained slurry was injected into a mold, cooled and solidified to produce an aromatic urinary stone prevention cutting sample A8 consisting of a semi-doughnut-shaped molded body with an outer diameter of 140 mm and an inner diameter of 110 mm.

(1) Comparative samples CA-1~CA 4 samples A-1~
Comparative sample CA-, in which only the fragrance component was removed from the composition of A-4.
1-CA-4 were produced in the same manner as Samples A-1 to 8-4, respectively.

fil Comparative Sample CA-5 Comparative Sample CI! was prepared in the same manner as Sample A-2 except that 50 parts of sulfamic acid was used in place of the succinic acid in Sample A-2. −
5 was manufactured.

(kl Comparative sample CA-6 Powder fragrance 4 made by impregnating 100 parts of paradichlorobenzene and 50% osmanthus-based adjusted fragrance into fine silica gel powder)
Comparative sample CA-6 was produced by pressure molding the iQ compound with the above-mentioned parts to produce a disc-shaped molded body having a diameter of 40 m + u and a weight of 140 g.

fil Comparative Sample CA-7 Comparative Sample CA-7 was a commercially available hand-washing low-tank aromatic cleaning agent (citrus scent) consisting of a surfactant, fragrance, and colorant.

(3) Urine stone adhesion prevention test-1 In 16 men's urinals with approximately the same number of users,
Three urinals and a 12e wash water tank are connected by piping,
The trap section of each urinal, which was set to be cleaned at 1.5 hour intervals, was cleaned using hydrochloric acid containing TIA anti-corrosion agent to remove attached urinary stones.

Inside each urinal trap, the diameter is 35mm and the length is 70mm.
Aromatic urinary stone inhibitor produced in the above item (2): Sample A-
-1-A-4 and comparative sample C^1-CA-6 were housed in a perforated plastic container and placed at the trap entrance. In addition, sample A7 was placed in a donut-shaped container.
Sample A-5 was placed on the urinal tray without being placed in the container, and three samples A-6 were placed in the trap.

In addition, a control area was a toilet where no medication was installed.

The toilet was used as usual, and the presence or absence of a bad odor was determined by a sensory test. Furthermore, after 3 months had elapsed, the cylinders made of stainless steel wire mesh were collected, and after drying, the cylinders were measured and the amount of snow adhering to urinary stones was calculated.

The average amount of urinary stones deposited and the average number of drug effective days for the three toilet bowls are shown in Table 2, along with the composition on each side.

In addition, the following abbreviations were used in Table 2.

〔component〕

ADPA: Adipic acid, 5CCA: BEZA succinic acid
;benzoic acid, FMRA: 7? /L/acid CTRA: citric acid, IPLA: isophthalic acid DLM
A4dl-malic acid 5UPA: Sulfamic acid PF-1: Osmanthus-based adjusted fragrance PF-2 Orange-based adjusted fragrance PF-3: Rose-based adjusted fragrance impregnated powder fragrance PF-4 Orange oil-impregnated powder fragrance PF-5 Rainbow truss-based fragrance PF-6: Rose-based controlled fragrance PDCB: Paradichlorobenzene PEG1: Polyethylene glycol (Mn=1,0
00) PEG6: polyethylene glycol (Mn-6,
000) PEG2: polyethylene glycol (Mn=2
0.000) EGPG: Ethylene oxide propylene oxide copolymer (Mn=10000) PVPD
: Vorivinylpyrrolidone ATUA : Alkylthiourea corrosion inhibitor TRAZ:
) Lyazole corrosion inhibitor 37Mg Magnesium nistearate 5TCa Calcium nistearate [sQ judgment] O: No foul odor Δ: Slightly foul odor ×: Strong foul odor As shown in Table 2, system containing no solid acid In (see Comparative Examples 2 to 6), although a slight odor masking effect was observed, the effective number of days was small, and no urinary stone adhesion prevention effect was observed. In addition, in the system excluding fragrance (see Comparative Examples 2-1 to 2-4) and the system using sulfamic acid as the solid acid (Comparative Example 2-5),
Although the effect of preventing urinary stone adhesion is similar to that of the Examples, the effect of masking bad odor is insufficient, and in particular, in Comparative Example 2-5, generation of abnormal odor due to deterioration of fragrance is observed.

In contrast, the product of the present invention is excellent in both the effect of preventing urinary stone adhesion and the effect of masking bad odor.

(4) Urine stone adhesion prevention test-2 Toilet bowls in 8 locations in general households with a low tank equipped with hand washing facilities (number of users: 2 adults, 2 children) were tested in the above-mentioned (3)
2 samples A-1 of the aromatic urinary stone inhibitor produced in the above section (2) were washed in the same manner as in section ) and placed in the hand washing section of the low tank.
, A-4, A-5 and comparative samples CA-1, C^-4, and C^-7 were placed in containers. In addition, three samples A-6 were housed in a container made of stainless wire mesh, and the containers were immersed in a low tank.

In addition, a toilet under the same conditions as above without any medicine installed was used as a control area.

When the remaining amount of the agent decreased to 20% or less of the initial amount, the container and the container were replaced with a new agent and used for two months, and the state of adhesion of dirt to the toilet bowl and the occurrence of bad odor were observed.

The test results are shown in Table 3.

In addition, in Table 3, the following abbreviations were used.

[Judgment of foul odor] [Judgment of dirt] O: No foul odor No foul odor observed Δ: Slight foul odor Slight foul odor observed ×: Strong foul odor
Not only is it excellent in the Table 3 effect against heavy dirt, but it is also extremely effective in masking bad odors.

The present invention provides an aromatic urinary stone inhibitor that is extremely effective in preventing urinary stones and stains from adhering to toilet bowls and in masking bad odors in toilets, and has extremely great public health and industrial significance.

Patent applicant (430) Representative of Nippon Soda Co., Ltd.
People (7125) Yoshimi Yokoyama (96)
48) Yutaka Tokai As shown in Table 3, the aromatic urinary stone inhibitor of the present invention is
Even when used in a low tank, it has excellent urinary stone prevention effects and bad odor masking effects, similar to item (3) above.

[Effects of the Invention] As shown in the above examples, the aromatic urinary stone preventive agent of the present invention is applicable to the amended procedure for preventing urinary stones from adhering to toilet bowls and drain pipes, dated March 17, 1999.

Claims (2)

[Claims] (1) An aromatic urinary stone characterized by being composed of a molded article containing at least one solid acid selected from the group consisting of organic carboxylic acids, cyanuric acid, metaphosphoric acid, and boric acid, which are solid at room temperature, and a fragrance. inhibitor (2) In claim (1), the base material of the molded article is a sublimable base material, a water-soluble base material, or a mixed base material of a sublimable base material and a water-soluble base material. Aromatic urinary stone inhibitor