JP4157990B2 - Scale formation inhibitor, method for producing the same, and solid excipient - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a solid drug used for preventing the formation of a scale mainly composed of calcium on the surface of a substrate in contact with urine drainage, a method for producing the same, and a solid excipient.
In particular, the solid drug of the present invention is a drug shaped into a solid by heating and melting, and is useful for preventing the generation of scale on the inner surface of a toilet urinal water pipe.
[0002]
[Prior art]
As the scale generated on the inner surface of the drainage pipe accumulates, the water distribution pipe becomes clogged. In particular, since the removal of the scale generated in the toilet water pipe is troublesome, the generation of such a scale is prevented in advance.
According to research on the scale generation of toilet water pipes, especially urinal water pipes, the enzyme acts on urea in the water pipes remaining in the drain pipes to decompose urea, and this decomposition produces ammonia. It has been elucidated that the residual wastewater becomes alkaline and the dissolved calcium content in the urine is finally deposited as a scale. And the method of preventing the production | generation of this scale by dissolving an acidic substance in waste water and maintaining this waste water acidic from the vicinity of neutrality is already known, and there are also many proposals regarding the improvement.
[0003]
British Patent No. 877733 contains a solid acid such as sulfamic acid, sodium hydrogen sulfate, citric acid, tartaric acid, a chlorine releasing agent such as chloramine T, a surfactant such as coconut fatty acid diethanolamide, and a binder such as paradichlorobenzene. A toilet block obtained by pressure molding the composition is described. In this specification, among the solid acids, sulfamic acid is soluble in its calcium salt, magnesium salt, iron salt, etc., and therefore has the dual effect of preventing scale formation and slowly removing old scale. The point which is convenient is pointed out and the example which uses this block suspended in a toilet bowl is disclosed.
[0004]
Japanese Patent Publication No. 55-14115 discloses a main blending amount of mono- or diethanolamide of a long chain fatty acid having a water solubility of about 0.01 to 0.5% at 20 ° C., for example, 20 ° C. 1 to 100% of a surfactant having a water solubility of, for example, 50 mol ethoxylated beef tallow alcohol, and a water softener such as ethylenediaminetetraacetic acid or polyphosphate as an optional component. A toilet cleaner mass that can be used is described. And this gazette explains that when this detergent mass is immersed and used in the water tank of a washroom, this detergent mass gradually releases the detergent component into water.
[0005]
Japanese Laid-Open Patent Publication No. 62-38299 discloses a toilet drain pipe comprising a molded body containing a readily soluble solid acid such as sulfamic acid and a water-soluble base material of 20 to 80% by weight, for example, a surfactant such as polyethylene glycol. Scale inhibitors are described. In addition to this readily soluble solid acid, this publication contains a slow-soluble solid acid having a saturated solubility of 0.2 to 20 g, such as succinic acid, in 100 g of water at 20 ° C. In addition to the above-mentioned easily soluble solid acid, in addition to the above-described readily soluble solid acid, the molded body is used in the toilet drainage pipe entrance, the toilet wall surface and the bottom washing water flow path, the faucet of the hand-washing part low tank, etc. In a toilet trap part, a drain pipe, and a washing water pipe, a molded body containing 20% by weight or more of a hardly soluble solid acid having a saturation solubility of 0.001 to 0.2 g in 100 g of water, for example, isophthalic acid. In addition, an example in which it is installed in a washing water storage tank or the like and used in a submerged state is disclosed.
[0006]
As a base material which is formed into a solid by heating and melting, mono- or diethanolamide of a long-chain fatty acid, polyethylene glycol or the like as a water-soluble surfactant, and paradichlorobenzene, naphthalene or the like as a sublimation substance has been used.
Japanese Patent Application Laid-Open No. 63-205400 describes an example of a molded article of a scale remover by pressure molding of a mixture of 50 parts by weight of sulfamic acid, 50 parts by weight of benzoic acid and 2 parts by weight of a corrosion inhibitor. Yes.
[0007]
[Problems to be solved by the invention]
In the block described in the above-mentioned British Patent No. 877733, paradichlorobenzene in the block sublimated while not in contact with the washing water acts as a fragrance, and sulfamic acid is formed on the block surface by the sublimation. The exposed sulfamic acid elutes in the wash water when it is exposed and then comes into contact with the wash water, which is efficient for maintaining the block shape and supplying acid to the drainage. When used in a submerged state, this block is not effective in preventing scale formation because water-insoluble paradichlorobenzene covers the surface of the block and prevents elution of the solid acid inside the block into water.
[0008]
The above Japanese Patent Publication No. 55-14115 does not disclose an example of a detergent mass containing an acid. The molded article described in JP-A-62-38299 is liable to swell, soften, or generate cracks in water, and it is difficult to proceed the supply of acid into wastewater that occurs during practical use as designed. The pressure molding of the mixture of sulfamic acid and benzoic acid described in JP-A-63-205400 is prone to cracking in water, and the supply of acid to wastewater that occurs in practical use is also as designed. It is difficult to progress.
[0009]
The present invention provides an improved scale formation inhibitor, particularly a shape stability that does not cause swelling, softening, cracking, etc. when used in water, and elutes a preferred amount of acid in the water in contact with it, An object of the present invention is to provide a solid scale formation inhibitor exhibiting durability, a production method characterized by melt molding thereof, and a solid excipient for melt molding thereof.
[0010]
[Means for Solving the Problems]
The solid scale inhibitor of the present invention contains a solid acid that passes through a 12 mesh sieve but does not pass through a 250 mesh sieve, a benzoic acid-based eutectic mixture as a solid excipient, and water at 20 ° C. It has the ability to elute 5-50 g of the solid acid into the water per hour per 1000 cm ^{2 of} the surface area in contact with the water.
[0011]
And the manufacturing method of the solid scale inhibitor forms 100 parts by weight of a solid acid having a particle size that passes through a 12-mesh sieve but not through a 250-mesh sieve, and forms a eutectic mixture of benzoic acid and benzoic acid. And 5 to 1000 parts by weight of a mixture composed of an organic compound.
The dissolution rate of the solid acid was as follows: a disk-shaped molded article having a weight of about 50 g, a diameter of 4.5 cm and a thickness of 2.5 cm was immersed in 500 ml of pure water having a temperature of 20 ° C. for 1 hour in a beaker. Calculated by filtering the beaker contents at this point and measuring the amount of the solid acid in the filtrate.
[0012]
And the solid excipient | filler for melt molding is a mixture which consists of an organic compound which forms a benzoic acid and benzoic acid type eutectic mixture which has a melting start point of 100 degrees C or less.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the solid acid used in the present invention include various solid acids from those having a high solubility in water to those having a low solubility, such as sulfamic acid, fumaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, Succinic acid, maleic acid, maleic anhydride, boric acid, methylene succinic acid, benzoic acid, salicylic acid, isocyanuric acid, tartaric acid, malic acid, citric acid, glutaric acid, oxalic acid, ascorbic acid, nicotinic acid, aspartic acid, p- Examples include toluenesulfonic acid, gallic acid, hydroxyacetic acid, hydrocinnamic acid, DL-2-pyrrolidone-5-carboxylic acid, sodium hydrogen sulfate, glycolic acid, aluminum sulfate and the like. As this solid acid, those having a solubility of 0.2 to 80% by weight with respect to 100 g of water at 20 ° C. are preferable, and sulfamic acid, benzoic acid, malic acid, citric acid, oxalic acid, sodium hydrogen sulfate, tartaric acid, Succinic acid and the like are preferred. In particular, sulfamic acid is preferable. A solid acid having a relatively high water solubility can be mixed and used.
[0014]
The solid acid has a large particle size that does not pass through a 12-mesh sieve but passes through a 9-mesh sieve, and a small particle size that passes through a 250-mesh sieve but does not pass through a 350-mesh sieve. However, it is preferable to have a particle size that passes through a 12-mesh sieve but does not pass through a 250-mesh sieve. If necessary, the solid acid having such a particle size can be obtained by subjecting the obtained solid acid to operations such as pulverization and sieving. When a solid acid having such a large particle size that does not pass through a 9-mesh sieve is used in the preparation of the solid drug of the present invention, the resulting solid drug is not smooth when consumed by contact with water. It is easy to expose and is not preferable. If a solid acid having a particle size smaller than 250 mesh, particularly smaller than 350 mesh, is used for the preparation of the solid drug, it tends to be powdered in the molding process, making the molding operation difficult.
[0015]
Examples of organic compounds forming a benzoic acid and benzoic acid-based eutectic mixture in solid excipients include acetanilide, acetoacetanilide, o-acetotoluizide, m-acetotoluidide, p-acetoluridide, acetoanthranilic acid, o-acetaniside, m- Acetanisidide, p-acetanisidide, acetamide, p-ethoxyacetanilide, o-phenylphenol, m-phenylphenol, p-phenylphenol and the like can be mentioned.
[0016]
Moreover, as an organic compound which forms a benzoic acid system eutectic mixture, what has a solubility of 0.01 to 0.6 weight% with respect to 20 degreeC water is more preferable, As an example, an acetanilide, an acetoacetanilide, Examples include p-acetoluidide, acetoanthranilic acid, o-acetaniside, m-acetaniside, p-acetoaniside, p-ethoxyacetanilide and the like.
[0017]
The composition of the mixture composed of benzoic acid and the organic compound forming the benzoic acid-based eutectic mixture is more preferably a eutectic composition resulting from the organic compound forming the benzoic acid and the benzoic acid-based eutectic mixture, but sublimation of benzoic acid. It may be a composition that is heated and melted at 100 ° C. or less at which the start of slag starts, and may deviate from the eutectic point composition.
The solid drug of the present invention is produced from a melt of 100 parts by weight of the solid acid having the above particle size and 5 to 1000 parts by weight, preferably 10 to 900 parts by weight of the solid excipient. A drug containing a solid excipient in an amount of more than 1000 parts by weight with respect to 100 parts by weight of the solid acid cannot sufficiently lower the pH of water in contact therewith, and the scale formation preventing effect is not sufficient. . On the other hand, those containing less than 5 parts of solid excipient with respect to 100 parts by weight of solid acid have a large effect of preventing scale formation but cannot be melt-molded.
[0018]
In addition, benzoic acid has a function of a solid acid and a solid excipient here. Therefore, when the solid acid is benzoic acid, 100 parts by weight of benzoic acid and 2.5 to 83 parts by weight, preferably 5 to 81 parts by weight of the organic compound forming the benzoic acid-based eutectic mixture are melt-molded. A solid drug is built.
In addition to the solid acid and the organic compound forming the benzoic acid-based eutectic mixture of benzoic acid and benzoic acid as the solid excipient, the solid drug contains a small amount of various conventionally used additives as desired. be able to. Examples of these additives include binders, lubricants, bactericides, antifungal agents, corrosion inhibitors, chelating agents, dissolution preparation agents, dyes, fragrances, and the like. It is preferred to make a solid drug from a mixture of desired additives. In particular, a solid drug having a prepared dissolution rate can be obtained by adding a dissolution preparation agent.
[0019]
As a method for producing a solid drug, a solid acid of the above ratio, a eutectic mixture raw material and a desired additive are uniformly mixed, and the eutectic mixture can be maintained in a molten state in a kneading extruder, for example, 60 A method may be mentioned in which a fluid mixture obtained by kneading at -100 ° C is poured into a mold and cooled.
[0020]
【Example】
As a solid acid, granular sulfamic acid as an industrial product was pulverized with a hammer mill and then sieved to prepare sulfamic acid having a particle size that passes through a 12-mesh sieve but does not pass through a 250-mesh sieve.
As the benzoic acid-based eutectic mixture as a solid excipient, acetanilide and p-acetoanisidide were prepared as organic compounds forming benzoic acid and a benzoic acid-based eutectic mixture. As a water-soluble surfactant, a copolymer of propylene oxide and ethylene oxide having a molecular weight of 20,000 and a nonionic surfactant of polyoxyethylene nonylphenol ether were prepared. Paradichlorobenzene was prepared as a volatile substance.
[0021]
In the following Examples 1-2 and Comparative Examples 1-3, according to the prescription, after charging into a beaker and melting a solid excipient using a predetermined thermostatic bath, uniformly mixed by stirring, The molded body could be prepared by cooling and solidifying. These compacts removed from the beaker had a weight of about 50 g, a diameter of 4.5 cm and a thickness of 2.5 cm, and a surface area of about 40 cm ² .
[0022]
Example 1
Prescription parts by weight
Sulfamic acid 100
Benzoic acid 33.3
Acetanilide 33.3
According to this formulation, all the components were melted and mixed at about 90 ° C., and then cooled and solidified at room temperature to obtain a molded body.
[0023]
Example 2
Prescription parts by weight
Sulfamic acid 100
Benzoic acid 33.3
p-Acetanisidide 33.3
A molded body was obtained in the same manner as in Example 1.
[0024]
Comparative Example 1
Prescription parts by weight
Sulfamic acid 100
Paradichlorobenzene 33.3
Nonionic surfactant 33.3
In addition, as a nonionic surfactant, a copolymer of propylene oxide and ethylene oxide having a molecular weight of 20,000 was used.
[0025]
According to this formulation, all the components were heated and melted and mixed at about 75 ° C., and cooled and solidified at room temperature to obtain a molded body.
Comparative Example 2
Prescription parts by weight
Sulfamic acid 100
Nonionic surfactant 66.6
In addition, as a nonionic surfactant, a copolymer of propylene oxide and ethylene oxide having a molecular weight of 20,000 was used.
[0026]
A molded body was obtained in the same manner as in Comparative Example 1.
Comparative Example 3
Prescription parts by weight
Sulfamic acid 100
Nonionic surfactant 66.6
In addition, polyoxyethylene nonylphenol ether was used as a nonionic surfactant.
A molded body was obtained in the same manner as in Comparative Example 1.
[0027]
Comparative Example 4
Prescription parts by weight
Sulfamic acid 100
Benzoic acid 66.6
In order to obtain a molded body by heating and melting, it was heated to a melting point of 122 ° C. of benzoic acid. At that time, benzoic acid sublimated, and the desired molded article could not be obtained.
[0028]
Evaluation test 1
Using the molded bodies obtained in Examples 1 and 2 and Comparative Examples 1 to 3, each agent was immersed in water at 20 ° C. in a beaker, and the shape of the inhibitor in the beaker at the time when 5 days passed, When the presence or absence of changes such as swelling or disintegration was observed, the results shown in Table 1 were obtained.
[0029]
[Table 1]
Table 1
Molded body Shape of molded body Example 1 No change Example 2 No change Comparative example 1 No change Comparative example 2 Swelling
Comparative Example 3 Swelling
Table 1 shows that when the molded article of the present invention is immersed in water, neither swelling nor collapse occurs, but the molded articles of Comparative Examples 2 and 3 cause swelling.
[0030]
Evaluation test 2
Using the molded bodies obtained in Examples 1-2 and Comparative Examples 1-3, the elution rate of sulfamic acid was measured. The elution rate of sulfamic acid was obtained by immersing the whole surface in 500 ml of pure water at 20 ° C. for 1 hour in a beaker, and taking out the molded body in the beaker at this point, and filtering the contents in the beaker. About the filtrate, it calculated | required by measuring the quantity of the sulfamic acid in the said filtrate with the quantitative analysis method by sodium nitrite prescribed | regulated to JISK-8588. Table 2 lists these measurement results. In the same table, the elution amount of sulfamic acid is a value [g / (1000 cm ² · h)] converted per 1000 cm ² of the surface area of the molded product per hour.
[0031]
[Table 2]
Table 2
Molded body Elution amount of sulfamic acid Shape of molded body Example 1 11.7 g No change Example 2 11.7 g No change Comparative Example 1 7.8 g No change Comparative Example 2 95.7 g Swelling
Comparative Example 3 98.4 g swelling
The results of Table 2 show that the molded products of the examples of the present invention exhibited a preferable acid dissolution rate without causing a shape change when immersed in water, whereas the inhibitors of Comparative Examples 2 and 3 swelled. The acid elution rate is too fast. Further, Comparative Example 1 does not cause a molding change and shows a preferable acid dissolution rate.
[0032]
【The invention's effect】
Sulfamic acid has a high water solubility of 17.6% by weight in water at 20 ° C. and it is quite difficult to supply over a long period of time. However, the fact that the molded article of the present invention containing sulfamic acid exhibits an elution rate of sulfamic acid adjusted to 5 to 50 g / (1000 cm ² · h) indicates that the benzoic acid-based eutectic mixture shown above is water and It is considered that the surface of the molded body that comes into contact covers the surface of the sulfamic acid particles having an adjusted particle size, so that the elution rate of sulfamic acid is controlled and the swelling and softening of the molded body are controlled. The scale formation inhibitor of the present invention does not swell, soften or collapse when immersed in water, and gradually dissolves over a long period of time while releasing a solid acid in water at a preferred acid elution rate. Even in a method of using the scale formation inhibitor in contact with flush toilet water where the wash water flows intermittently, this scale formation inhibitor gradually dissolves in the wash water without causing a shape change, and its medicinal effect is prolonged. Persist across.
[0033]
A solid excipient having a melting start point of 100 ° C. or lower, characterized by a mixture composed of benzoic acid and an organic compound forming a benzoic acid-based eutectic mixture of the present invention, is used for washing, sterilizing, deodorizing and the like. By appropriately selecting the necessary components, it is useful as a solid excipient for solid medicines such as toilets, kitchens, bathroom sinks, septic tanks, and pools as well as toilets for male toilets.

Claims (3)

100 parts by weight of a solid acid having a particle size that passes through a 12-mesh sieve but not through a 250-mesh sieve, and 5 to 1000 parts by weight of a mixture comprising an organic compound forming a benzoic acid and benzoic acid-based eutectic mixture A solid scale formation inhibitor that elutes 5 to 50 g of the solid acid into the water per 1000 cm ^{2 of} the surface area that comes into contact with the water at 20 ° C. 100 parts by weight of a solid acid having a particle size that passes through a 12-mesh sieve but not through a 250-mesh sieve, and 5 to 1000 parts by weight of a mixture comprising an organic compound forming a benzoic acid and benzoic acid-based eutectic mixture Of a solid scale formation inhibitor that elutes 5-50 g of the solid acid into the water per hour per 1000 cm ^{2 of} the surface area that comes into contact with the water at 20 ° C. Method. Acetanilide, acetoacetanilide, p-acetoluidide, acetoform which forms a benzoic acid eutectic mixture with 100 parts by weight as benzoic acid and has a solubility of 0.01 to 0.6% by weight in water at 20 ° C Solid scale formation characterized by a mixture comprising 5 to 81 parts by weight as one organic compound selected from the group consisting of anthranilic acid, o-acetaniside, m-acetaniside, p-acetaniside and p-ethoxyacetanilide Solid excipient for melt molding for inhibitors .