JPS63205400A - Urolith removing agent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a toilet cleaning agent, and more particularly, to a scale mainly composed of calcium-based compounds that adheres to toilets, especially the drain pipes of men's toilets. , relates to a so-called urinary stone remover.

[Conventional technology]

Urinary stones, mainly composed of calcium-based compounds, that adhere to the drain pipes of toilets, especially men's restrooms, impair the flow of urine, and in extreme cases, block the drain pipes, making the toilet unusable. Furthermore, the organic matter contained in the urinary stone is putrefied and decomposed by bacteria, and when mixed with ammonia generated by the decomposition of the urine, a foul odor is generated.

Conventionally, urinary stones have been removed by removing the toilet bowl and removing them mechanically, or by dissolving and removing them using a mineral acid such as concentrated hydrochloric acid containing a corrosion inhibitor.

JP-A-56-118499 discloses a solid urinary stone remover with an adjusted dissolution rate, which is formed from a mixture of condensed phosphoric acid or a salt thereof and a metal salt. , proposed a molded product containing a solid acid as an active ingredient as an inhibitor of urinary stone formation, JP-A-61-246.
No. 281 and Japanese Patent Application No. 61-095648).

[Problem that the invention seeks to solve]

Mechanical methods of removing urinary stones, which have traditionally been used for toilet maintenance, not only risk damaging the toilet bowl and drain pipes, but also make it difficult to remove urinary stones from traps with complex shapes. Even if the flow of wastewater can be restored, the foul odor remains. In addition, in the method of dissolving and removing urinary stones using mineral acids, mineral acids are harmful substances, so sufficient knowledge and caution are required when using them (mineral acids and urinary stones). Because the urinary stones react rapidly, the peeled urinary stones may clog the drain pipe and worsen the drainage flow, and the scum and foul-smelling gas generated by the dissolution of the urinary stones may flow back into the toilet bowl. Therefore, these methods are currently carried out by some specialized contractors with special knowledge and experience, and the toilet cannot be used for a time while the work is being carried out.

Therefore, these tasks must be performed during limited hours such as at night or on holidays, making the tasks even more difficult.

On the other hand, the solid removal agent disclosed in the above-cited Japanese Patent Application Laid-open No. 118499/1984 is placed in a toilet bowl, dissolves condensed phosphoric acid or its salt in urine or washing water, and chelates condensed phosphate ions. Its composition is to chelate calcium ions and dissolve and remove urinary stones.However, urinary stones that have already adhered to the drain pipe are treated with calcium apatite (Cas), which is a compound of phosphoric acid and calcium.
(po4) 30tl) and calcium carbonate (CaCO:+
), it is difficult to dissolve and remove it due to the chelating effect of condensed phosphate ions. In addition, an aqueous solution of condensed phosphoric acid is quite acidic, so although it is possible to temporarily dissolve urinary stones, it reacts with calcium ions to produce salts that are poorly soluble in water. On the contrary, poorly soluble substances precipitate on the surface of the urinary stone and inhibit the dissolution of the urinary stone. Furthermore, once dissolved, urinary stones re-deposit in the depths of drain pipes and septic tanks where the pH increases, forming even stronger scales.

In addition, the urinary stone prevention agent proposed and put into practical use by the present inventors suppresses the rate of elution of solid acid into the washing water and/or urine to a level that prevents the formation of urinary stones. Although it is extremely effective in preventing formation and malodor generation, it is hardly effective in dissolving and removing urinary stones adhering to drain pipes and the like.

The present invention aims to provide an easy-to-handle solid urinary stone remover that does not block drain pipes or generate scum or bad odor, and can remove urinary stones without using the toilet normally.
That purpose.

[Means for solving problems]

As a result of intensive research to achieve the above object, the present inventors have found that urinary stones are dissolved in an acidic solution with a pH of 3.5 or less, and that when the amount of acidic substances in the acidic solution is below a certain concentration, The present invention was completed based on the discovery that it can be dissolved and removed without clogging drain pipes or producing scum or bad odor.

The present invention comprises a molded article containing an acidic substance in which H of a 1% by weight aqueous solution (however, a 20°C saturated aqueous solution if the concentration of the 20°C saturated aqueous solution is less than 1% by weight) is 3 or less, The urinary stone remover is characterized in that the elution rate of acidic substances into water from the molded body is 0.5 to 300 g/hour.

The urinary stone remover of the present invention can be applied to places where it comes into continuous or intermittent contact with flush water and/or urine in men's restrooms, such as inside the flush water tank, inside the toilet bowl, inside the trap, inside the drain pipe, etc. Depending on the situation, one or more of them may be placed and used in a specific container or without.

In the present invention, the acidic substance reacts with calcium ions and has a solubility of 0.1 g/10 in an aqueous solution with a pH of 5 to 9.
It is a compound that does not produce 0g (water) or less of a reaction product and can be handled as a solid or substantially solid at room temperature. For example, as an acidic substance that is solid at room temperature, sodium hydrogen sulfate,
Water-soluble inorganic acid salts such as potassium hydrogen sulfate and ammonium hydrogen sulfate, succinic acid, maleic acid, tartaric acid, dβ-
Examples include organic acids such as malic acid, hydroxyacetic acid U, p-1-luenesulfonic acid, adipic acid, salicylic acid, fumaric acid, ditrilotriacetic acid, and benzoic acid, acid anhydrides such as maleic anhydride, and sulfamic acid. It will be done. In addition, as an acidic substance that can be treated as a substantially solid, it can be mixed with an aqueous water glass solution, gelled by adding water-soluble polymers such as gelatin, supported on porous materials such as clay minerals and activated carbon 2-foam plastic, and encapsulated. Hydrochloric acid solidified by

Examples include mineral acids such as sulfuric acid and organic acids such as acetic acid.

Preferably, the aforementioned acidic substances that are solid at room temperature are used, more preferably sodium hydrogen sulfate, potassium hydrogen sulfate, succinic acid, maleic acid, benzoic acid, sulfamic acid, and the like.

The urinary stone remover of the present invention may contain one of the above acidic substances or a mixture of two or more of them, or a mixture of these with various additives, in the form of a sphere, a disc, a cylinder, a cube, It is molded into any shape such as a rectangular parallelepiped, does not disintegrate rapidly on contact with water, and has a concentration of 0.5 to 300% of the acidic substance.
It is a molded body that dissolves into the contact water at a dissolution rate of g/h.

The rate of elution of the acidic substance from the molded body into the contact water depends on the manner of use as a urinary stone remover.For example, when stored in a specific container and used, Also, when using multiple units at the same time,
Use several of them at the same time using method A below (when using the urinary stone remover by soaking it in standing water in a trap, drain pipe, etc.)
Or, it is a value measured by method B (when used intermittently in contact with flushing water and/or urine, such as when placed in a toilet bowl, or when used by being installed in a flushing water tank).

A: Take 500 ml of distilled water in a cylindrical container with a diameter of 10 cm, immerse the required number of molded bodies in this water according to the usage mode, maintain the water temperature at 20'C ± 2°C, and leave it for 1 hour. , The amount of acidic substance (g) calculated from the measured value by measuring the concentration of acidic substance in the aqueous solution after removing the remaining molded body and disintegrated insoluble components.

B: Install the required number of molded bodies in the urinal or high tank of a men's urinal with a high tank type wash water storage tank (manufactured by Toto Kiki, U-23 type) according to the usage mode, and then remove from the high tank. , 20'C ± 2°C, 20'C with 4p wash water.
The acidic substance concentration in the acidic substance aqueous solution 12p for 1 hour flowing out from the trap part outlet is measured,
The amount of acidic substance (g) calculated from the measured value.

However, in both methods A and B, if the acidic substance is completely eluted in less than 1 hour, the elution rate is calculated by proportional calculation from the total elution time.

Various additives for urinary stone removers include, for example, binders and lubricants required during molding, dissolution rate regulators, corrosion inhibitors, colorants, surfactants, fragrances, deodorants, bactericidal agents, and organic substances. Examples include degrading enzymes, chelating agents, and the like. As these additives, those that do not react with calcium ions to produce poorly soluble substances are used.

The binder is added for the purpose of imparting moldability to the acidic substance and shape retention of the molded article when it comes into contact with water. As a binder, water-soluble inorganic or organic substances that are solid at room temperature, such as boric acid, calcium chloride, ammonium chloride, polyethylene glycol that is solid at room temperature, nonionic surfactants, 1,6-hexanediol, etc. , water glass,
Gelling agents such as gelatin, clay minerals, etc. are used.

Additionally, porous materials such as activated carbon and foamed plastic that have already been formed also function as binders.

A lubricant is added for the purpose of improving workability during molding, particularly during tablet molding. As the lubricant, for example, fine powder of calcium stearate, magnesium stearate, talc, etc. is used.

The dissolution rate regulator is added for the purpose of adjusting the dissolution rate of the acidic substance in the molded body into the contact water. As the dissolution rate regulator, poorly water-soluble substances such as higher fatty acids, higher alcohols, nonionic surfactants, and the above-mentioned lubricants are used.

Corrosion inhibitors are added for the purpose of preventing corrosion of metal parts of drain pipes, and include various known corrosion inhibitors for preventing acid corrosion, such as cationic surfactants having amino groups, alkylthioureas, etc. is preferably used.

The surfactant is added for the purpose of permeating acidic substances into the urinary stones and dispersing organic substances insoluble in the acids in the urinary stones into the washing water. As the surfactant, nonionic surfactants and cationic surfactants that do not react with acidic substances are preferably used.

Deodorants and fragrances are added for the purpose of deodorizing and masking bad odors. Further, the coloring agent is added for the purpose of detecting the remaining amount of the active ingredient in the molded product and masking the coloring of the molded product due to urine or the like.

The disinfectant is added for the purpose of sterilizing the inside of the toilet bowl, the trap, the drain pipe, etc., and at the same time preventing the generation of bad odors due to decay of organic matter contained in urinary stones. As a disinfectant,
Cationic surfactants that do not react with acidic substances can be preferably used, and the amount added is within a range that does not affect bacteria in the septic tank.

Further, the chelating agent is added for the purpose of assisting the dissolution of urinary stones by an acidic substance, and an acidic chelating agent such as nitrilotriacetic acid is preferably used.

There is no particular restriction on the method for producing the molded body, and any method such as pressure molding, injection molding of heated melt, kneading molding, etc. can be adopted. In addition, there are products made by adding a gelling agent to a liquid acidic substance and molding them, products made by adsorbing a liquid acidic substance to a porous material and molding them, and products made by adsorbing and supporting a liquid acidic substance on a molded porous material. Moldings of acidic substances whose elution rate is controlled within the above range are included in molded articles of acidic substances.

The urinary stone remover of the present invention is used by being installed in any water flow path of a men's toilet, for example, in the flush water tank, in the urinal, in the trap, in the drain pipe, etc. In this state of use, the acidic substances in the urinary stone remover are eluted into the urine or washing water, and as a result, the pH is maintained at 3.5 or less.
Urine stones attached to the toilet bowl or trap are gradually dissolved and removed.

For example, the urinary stone remover is immersed in a washing water tank, trap, etc., and it is stored in a container that does not obstruct the flow of washing water in a toilet bowl, drain pipe, etc. Furthermore, it can also be used by simply throwing it into the toilet bowl.

The composition, shape, size, etc. of the urinary stone remover are selected depending on its usage form.

[For production]

The urinary stone remover of the present invention is a molded body of an acidic substance in which the pH of a 1% aqueous solution or a saturated aqueous solution at 20°C is 0 to 3, and the elution rate of the acidic substance from this molded body is 0 under the above-mentioned conditions. It is characterized by being controlled at .5 to 300 g/hour.

Urine stones attached to toilet bowls, traps, drain pipes, etc. can be dissolved by adjusting the pH of the water and/or urine that come into contact with them to 3.5 or less, preferably 3.0 or less. However, if the concentration of acidic substances in the water and/or urine that comes into contact with the urinary stones becomes excessive and the pi of the water and/or urine reaches zero, the urinary stones will rapidly dissolve and peel off from the drain pipe. On the other hand, if the concentration of acidic substances in the water and/or urine that comes into contact with urinary stones is too low, it may be difficult to maintain the pH below 3.5, causing scum and bad odor to flow back into the toilet bowl. The dissolution rate of the stone becomes slow, making it impractical.

Therefore, the acidic substances used are limited to those whose 1% aqueous solution or saturated aqueous solution at 20°C has a pH of 3 or less, and the rate of elution from the molded body is 0.
By limiting the amount to 5 to 300 g/hour, the dissolution rate of urinary stones can be kept within a practically acceptable range.

The preferred rate of elution of acidic substances from the urinary stone remover varies depending on the manner in which the urinary stone remover is used. For example, as mentioned above, in a type that is used by being immersed in accumulated water in a trap or drain pipe, the concentration of acidic substances tends to increase, so the elution rate of acidic substances measured by method A above is 1 to 100 g.
/ hours is preferred. On the other hand, for types that are used in the toilet bowl or in the running water path and come into intermittent contact with flush water and/or urine, and types that are installed and used in the flush water tank, the elution rate measured by method B is 5. ~200
It is preferable to set it as g/hour.

The elution rate of acidic substances from the urinary stone remover can be controlled by the selection of the acidic substance and additives used, especially the type and content of the dissolution rate modifier, the dosage form (size and surface area), and the molding method. can.

In particular, types that use deliquescent substances such as calcium chloride as a binder and are used intermittently in contact with flushing water and/or urine absorb moisture from the atmosphere even when the toilet is not in use. Acidic substances are entrained in the deliquescence of the binder and flow into the trap, thereby effectively removing the urinary stones.

Furthermore, since the solution of the urinary stone remover is an acidic solution as described above, there is a risk that metal parts such as drain pipes will be corroded. Therefore, it is preferable to add a corrosion inhibitor as a component, and especially in the case of the immersion type, the addition of a corrosion inhibitor is essential.

Furthermore, since the urinary stone remover of the present invention is a molded body,
Unlike conventional liquid urinary stone removers, urinary stones can be removed without using the toilet normally.

〔Example〕

The present invention will be explained in more detail with reference to Examples and Comparative Examples.

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

(1) Manufacture of urinary stone remover +81 Sample (A-1) A mixture of 100 parts by weight of succinic acid (1% aqueous solution pH 2,66) and 2 parts by weight of a corrosion inhibitor was press-molded, and a diameter of 3
0mm, thickness 3Qmm, weight 30g molded object (A-1)
I got it.

(bl Sample (A-2) 50 parts by weight of sulfamic acid (1% aqueous solution pH 1,52), boric acid (1% aqueous solution pH 4,60) as a binder 5
Pressure molding a mixture of 0 parts by weight, 1 part by weight of calcium stearate as a lubricant and 1 part by weight of a corrosion inhibitor,
A molded body with a diameter of 30 mm, a thickness of 25 mm, and a weight of 30 g (A
-2) was obtained.

(C1 sample (A-3) 50 parts by weight of sulfamic acid (mentioned above), benzoic acid (20°
A mixture of 50 parts by weight of C saturated aqueous solution (pH 2.88) and 2 parts by weight of a corrosion inhibitor was pressure molded to obtain a molded article (A-3) having a diameter of 30 mm, a thickness of 37 mm, and a weight of 40 g.

(dl Sample (A-4) Molecular weight 6.00 as a dissolution rate regulator. In a heated and melted mixture of 40 parts by weight of OOO polyethylene glycol and 10 parts by weight of valmitic acid, 50 parts of pulverized sulfamic acid (described above) was added. A slurry in which parts by weight and 1 part by weight of a corrosion inhibitor were added and mixed was poured into a polyethylene container, cooled and solidified, and molded to obtain a molded product (A-4) with a diameter of 33 mm, a thickness of 87 mm, and a weight of 100 g. Ta.

(e) Sample (A-5) 70 parts by weight of sulfamic acid (listed above), succinic acid (listed above)
A mixture of 30 parts by weight and 2 parts by weight of the corrosion inhibitor was pressure molded to obtain a prismatic molded article (A, -5) measuring 30 mm x 30 mm x 90 mm and weighing 120 g.

(fl Sample (A-6) Maleic acid (1% aqueous solution pH 1,83) was pressure molded,
A molded body with a diameter of 40 mm, a thickness of 35 mm, and a weight of 70 g (A
-6) was obtained.

fgl Sample (A-7) A mixture of 60 parts by weight of sulfamic acid (above), 40 parts by weight of calcium chloride as a binder, and 1 part by weight of a corrosion inhibitor was pressure-molded, and the product had a diameter of 45 mm, a thickness of 38 mm, and a weight of 90 g. A molded article (A-7) was obtained.

(hl Sample (,6,-8) 60 parts by weight of pulverized sulfamic acid (mentioned above) in a heated melt of 40 parts by weight of ethylene oxide/propylene oxide block copolymer (nonionic surfactant), corrosion 1 part by weight of inhibitor, 1 part by weight of fragrance, and 0 parts of coloring agent.
．． The slurry mixed with 01 parts by weight was poured into a metal mold, cooled and solidified, and molded into a mold with a diameter of 45 mm and a weight of 70 mm.
A spherical shaped body (A-8) of g was obtained.

(11 samples (A-9) 60 parts by weight of sulfamic acid (described above), succinic acid (described above)
A mixture of 40 parts by weight and 3 parts by weight of corrosion inhibitor was pressure molded to a diameter of 45. A molded body having a diameter of 35 mm, a thickness of 35 mm, and a weight of 90 g was obtained. Ten pieces of this molded body were stored in a polyethylene container having ten pores each having a diameter of 1 mm on the bottom, side, and top lid, and was used as a sample (A-9).

01 Sample (A-10> 700 g of 20% hydrochloric acid (1% aqueous hydrogen chloride solution pH 0.57) containing 2% by weight of corrosion inhibitor was adsorbed onto a cubic hydrophilic urethane foam with sides of 90 mm.This adsorption The molded body was stored in a plastic performance type container, and a sample (A-1
0).

(kl Sample (A=11) Granular sodium hydrogen sulfate monohydrate (
A sample (A-11) was prepared by storing 100 g of a mixture of 100 parts by weight of a 1% aqueous sodium hydrogen sulfate solution (pH 1.74) and 2 parts by weight of a corrosion inhibitor.

(1) Comparative sample (CA-1) Comparative sample (CA-1) is a molded product having a diameter of 30 mm, a thickness of 3 Q mm, and a weight of N 30 g obtained by pressure molding boric acid (1% aqueous solution pH 4,60). And so.

(ml Comparative sample (CA-2) 20 parts by weight of sulfamic acid (above), isophthalic acid as a dissolution rate regulator (1% aqueous solution pH 3,42) 80
Comparative sample (CA-2) was a molded article having a diameter of 30 mm, a thickness of 27 mm, and a weight of 30 g, which was obtained by pressure molding a mixture of parts by weight and 2 parts by weight of a corrosion inhibitor. This molded article had an acidic substance dissolution rate of 0.22 g/hour as measured by method A.

tnl Comparative sample (CA-3) A sample with a diameter of 3Q mm and a thickness of 26 mm obtained by pressure molding sodium tripolyphosphate described in the literature cited as the prior art.
A comparative sample (CA-3) was a molded product having a diameter of 30 g and a weight of 30 g. 1% water of sl-lium tripolyphosphate? Yong? (9,
The pH of the solution was 9.25.

(0) Comparative Sample (CA-4) A commercially available liquid urinary stone remover containing 20% by weight of hydrogen chloride (described above) and 1% of a corrosion inhibitor was used as a comparative sample (CA-4).

(pi Comparative Sample (CA-5) A commercially available powdered urinary stone remover containing 35% of sulfamic acid (described above) was used as a comparative sample (CA-5).

(2) Urine stone removal test The trap part of the self-cleaning men's toilet in which urinary stones were removed using a liquid urinary stone remover was made of stainless steel wire mesh with a diameter of 2 mm.
Attach a cylindrical test piece with a diameter of 0 mm and a length of 30 mm.
By adjusting the amount of washing water, 10 g of urinary stone was attached to the test piece. During this time, urinary stones also adhered to the trap and the inner surface of the drain pipe.

The amount of water used to flush this toilet is 4J! Set the cleaning interval every 20 minutes and every 2 hours, place the required number of each sample prepared in the previous section and the comparison sample in the designated place, and remove the urinary stones in the sample while using it normally unless trouble occurs. All removed components were eluted.

After all of the urinary stone removal components in the sample were eluted, the state of adhesion of urinary stones in the trap was visually observed, and the weight of the test piece was measured to calculate the urinary stone removal rate.

We also observed the occurrence of blockages, scum, and bad odors in the drain pipes during use.

Urine stone removal components in the samples prepared in the above (1) and comparative samples, number of each sample used, amount of active ingredient in all samples used, pH of 1% aqueous solution or 20 ° C saturated aqueous solution of drug
Table 1 shows the elution rate of the active ingredient into water measured by method A or method B.

Further, Table 2 shows the installation location of the sample, the total elution time of the active ingredient in the sample, the dissolution rate of urinary stones adhering to the test piece, and the results of each visual observation.

In addition, in Table 2, each visual observation result was expressed according to the following criteria.

○ △ × Drainage pipe blockage No blockage Flow deterioration Closed Backflow of base scum No backflow A small amount of backflow Backflow generates a large odor
No bad odor Slightly bad odor Large bad odor [Effects of the invention] As shown in the examples above, in the system (example) using the specific acidic substance of the present invention and the sample in which the elution rate of the acidic substance was adjusted, Urine stones can be removed without using the toilet under normal conditions without causing problems such as blockage of the drain pipe, backflow of scum, and bad smells.

On the other hand, 1% water, which is an acidic substance? In the system where the pH of the 8 liquid exceeds 3 (Comparative Example 1), the system in which the elution rate of acidic substances is slow (Comparative Example 2), and the system using sodium tripolyphosphate disclosed in the prior art (Comparative Example 2), Almost no urinary stone removal effect was observed, and in the systems using liquid or powdered acidic substances (Comparative Examples 4 and 5), the dissolution rate of urinary stones was too fast, causing urinary stones to peel off and form drain pipes. Using the toilet significantly reduces the effectiveness of urinary stone removal in a short period of time, as it causes blockage and backflow of scum and bad smells, and acidic substances are flushed out in a short period of time due to the flushing water. do.

That is, the pH of a 1% aqueous solution or a 20°C saturated solution
It is clear that it is effective to use an acidic substance with a value of 3 or less and to control the elution rate of the acidic substance.

In the example, a men's restroom with an automatic flushing device was used, but similar results can be obtained in men's restrooms with a manual flushing device, men's restrooms without a cleaning device, and unisex toilets with a cleaning device. .

The present invention provides a urinary stone remover that is easy to use, causes no trouble, and can remove urinary stones without using the toilet normally. , the industrial significance is extremely large.

Claims (2)

[Claims] (1) 1% by weight aqueous solution (However, if the concentration of the 20°C saturated aqueous solution is less than 1% by weight, use the 20°C saturated aqueous solution)
consisting of a molded body containing an acidic substance whose pH is 3 or less, and the elution rate of the acidic substance from the molded body into water is 0.5.
A urinary stone remover characterized in that the amount is ~300g/hour (2) Acidic substances include sodium hydrogen sulfate, potassium hydrogen sulfate, ammonium hydrogen sulfate, succinic acid, maleic acid, tartaric acid, dl-malic acid, hydroxyacetic acid, p-toluenesulfonic acid, adipic acid, salicylic acid, fumaric acid, and nitrile acid. The urinary stone remover according to claim (1), which is one or more selected from the group consisting of acetic acid, benzoic acid, maleic anhydride, and sulfamic acid.