WO2013057805A1

WO2013057805A1 - Protectant against urinary calculi

Info

Publication number: WO2013057805A1
Application number: PCT/JP2011/074044
Authority: WO
Inventors: 繁齋藤; 高田　秀夫; 賢一関原
Original assignee: 日本曹達株式会社
Priority date: 2011-10-19
Filing date: 2011-10-19
Publication date: 2013-04-25
Also published as: KR101591614B1; KR20140063822A; CN103889908A; HK1195546A1; CN103889908B

Abstract

The present invention relates to: a tableted molding comprising a solid acid that acts as the main component, a porous adsorbent, an oily volatile substance that is adsorbed on the porous adsorbent, and a powdered base material; and a protectant against urinary calculi for use in a toilet drain pipe, which comprises the tableted molding.

Description

Urine stone inhibitor

The present invention relates to a tableting molded product containing a solid acid as a main component and containing an oily volatile substance by tableting and a uric stone inhibitor comprising the tableting molded product. The urinary stone preventive agent of the present invention can be applied to various flush toilets or men's toilets without flush facilities.

Toilet drain pipes, especially men's toilet drain pipes, scales called urine stones, to which a mixture of calcium-based compounds and organic substances produced by urine decomposition adheres, generate urine and wash water flow. When it gets worse, in severe cases, the drain pipe is blocked and the toilet becomes unusable. In addition, organic substances in urine stone rot by bacteria and generate bad odor. The bad smell of men's toilets is a mixed odor of bad smell caused by organic decay and ammonia generated by decomposition of urine.

Conventionally, as a method for preventing the scale of a toilet drain pipe, a method of injecting a drug into the wash water pipe and a method of putting a spherically shaped drug into a toilet of a men's toilet have been put into practical use. Various drugs containing surfactants, bactericides, and fragrances have been proposed as drugs used in these methods.

For example, Patent Document 1 discloses a deodorant cleaning agent for a flush toilet, which is obtained by melt-mixing a surfactant, an ion sequestering agent, a fragrance, and the like together with polyethylene glycol or polypropylene glycol and an aromatic substance, and injection molding. Describes a washing antifouling fragrance formed by cooling and solidifying a mixed melt composed of additives such as polyethylene glycol which is solid at room temperature, a poorly water-soluble fragrance, a nonionic surfactant and a fragrance. Yes. Furthermore, as a method for controlling the scale once fixed to the toilet drain pipe, a method of dissolving the scale using an inorganic strong acid such as hydrochloric acid, or a method of removing the toilet and removing the scale mechanically is employed.

However, none of the above methods have sufficient anti-sticking effect on the scales of toilet water pipes, or even if they have anti-sticking effects, they are expensive, difficult to work, and have an adverse effect on the septic tank. There was a problem such as.
Therefore, the present applicant has developed a urinary stone inhibitor composed of a molded product containing a solid acid as an active ingredient (Patent Document 3).
Thereafter, the present applicant has also proposed a urine stone inhibitor containing a solid acid as a main component and containing a fragrance or the like (Patent Document 4), but in the case of containing a volatile substance such as a fragrance or an insecticide. However, it was difficult to produce a molded body of a urolith inhibitor that can withstand long-term use.

Japanese Patent Publication No. 45-30706 Japanese Unexamined Patent Publication No. 57-168668 Japanese Patent Publication No. Sho 62-38299 Japanese Laid-Open Patent Publication No. 2-147699

The present invention has been made in view of such circumstances, and has an object to provide a urinary stone inhibitor that has a sustained release property of a volatile substance such as a fragrance over a long period of time and is difficult to disintegrate. To do.

As a result of intensive studies to solve the above problems, the inventors of the present invention used a kneaded product obtained by kneading an oily volatile perfume with a porous adsorbent and further kneading the kneaded raw material with a powdered base. It has been found that, by forming a tablet, it can form a stable aromatic urolithic inhibitor with a sustained release of a fragrance over a long period of time. Has been found to have a similar effect, and the present invention has been completed.

That is, the present invention relates to the following (1) to (6).
(1) a solid acid as a main component;
Porous adsorbent;
An oil-based volatile substance adsorbed on the porous adsorbent; and a tableted molded article containing a powdered base.
(2) The tableting molded article according to (1), wherein the oily volatile substance is a fragrance, a repellent, an insect repellent, a deodorant or a deodorant.
(3) The tableting molded product according to (1) or (2), wherein the powdered base is a polysaccharide.
(4) The tableting molded product according to any one of (1) to (3), wherein the powdered base is a gum.
(5) The tableting molding according to any one of (1) to (4), wherein the porous adsorbent to which the oily volatile substance is adsorbed contains particles dispersed in the powdered base. body.

(6) A urinary stone inhibitor for a toilet water distribution pipe comprising the tableting molded product according to any one of (1) to (5).

According to the present invention, an oily volatile fragrance can be contained without oozing out on the tablet surface, and a tablet having stability capable of withstanding use can be obtained without disintegrating for a long period of time.
The present invention can also be applied to bactericides and insect repellents other than fragrances as long as they are oily volatile substances.

(Urinestone inhibitor)
The urolith inhibitor of the present invention comprises a tableted molded article containing a solid acid as an active ingredient and containing a porous adsorbent, a powdered base and an oily volatile substance.
Below, each component is demonstrated.

(Solid acid)
In the present invention, solid acid is an acidic substance that is solid at room temperature, and does not react with calcium ions to form a salt having a solubility in water in the range of pH 5 to 8.5 of 0.001 g / 100 g (water) or less. If it is a thing, there will be no restriction | limiting in particular. For example, water-soluble acidic salts such as sodium hydrogen sulfate, potassium hydrogen sulfate, and ammonium hydrogen sulfate, water-soluble salts of strong acid and weak base such as ammonium chloride and ammonium sulfate, boric acid, sulfamic acid and the like can be mentioned. Room temperature solids such as succinic acid, citric acid, maleic acid, isophthalic acid, tartaric acid, hydroxyacetic acid, P-toluenesulfonic acid, fumaric acid, adipic acid, salicylic acid, pracidylic acid, hydrocinnamic acid, maleic anhydride, benzoic acid, etc. These acidic substances can be used alone or as a mixture of two or more.
The content of the solid acid in the tableting product is usually 50 to 95% by mass, preferably 75 to 95% by mass.

(Oil volatile substance)
In the present invention, the oily volatile substance means a substance containing a poorly water-soluble volatile component, and in addition to a fragrance, a repellent or insect repellent, a deodorant or deodorant, an insecticide, a pesticide and the like can be used. .
The fragrance is not particularly limited as long as it masks the odor of the toilet and the urine stone inhibitor component, and makes the user feel good, and natural fragrances, synthetic fragrances, blended fragrances and the like can be used. . For example, natural flavors include mastic oil, parsley oil, anise oil, eucalyptus oil, winter green oil, cassia oil, menthol oil, spearmint oil, peppermint oil, lemon oil, coriander oil, orange oil, mandarin oil, lime oil, Lavender oil, laurel oil, chamomile oil, cardamom oil, caraway oil, bay oil, lemongrass oil, pine needle oil, neroli oil, rose oil, jasmine oil, Iris concrete, absolute peppermint, absolute rose, orange flower, citrus oil , Mixed fruit oil, strawberry oil, cinnamon oil, clove oil, grape oil and the like.

Synthetic fragrances include carvone, anethole, methyl salicylate, cinnamic aldehyde, linalool, linalyl acetate, limonene, menthone, menthyl acetate, pinene, octyl aldehyde, citral, pregon, carbyl acetate, anisaldehyde, ethyl acetate, ethyl butyrate Rate, allylcyclohexanepropionate, methylanthranilate, ethylmethylanthranilate, vanillin, undecalactone, hexanal, ethinone alcohol, propyl alcohol, butanol, isoamyl alcohol, hexenol, dimethylsulfide, cycloten, furfural, trimethyl Examples include pyrazine, ethyl lactate, and ethyl thioacetate.

Synthetic and / or natural flavors include strawberry flavor, apple flavor, banana flavor, pineapple flavor, grape flavor, mango flavor, tropical fruit flavor, butter flavor, milk flavor, yogurt flavor, fruit mix flavor, herb Examples include mint flavor.

Moreover, the following are mentioned as a repellent or insect repellent, a deodorizer or deodorant, an insecticide, an agrochemical, etc.
Examples of repellents or insect repellents include capsaicin, peppermint oil, eucalyptus, cypress, cypress, menthol oil, allyl isothiocyanate, methyl salicylate, ethyl salicylate, vanillylamide nonyl and the like.
Examples of the deodorizer or deodorizer include phthalate esters, phosphate esters, vegetable oil extracts, and terpene deodorizers.

Pesticides include fenitrothion, methyl parathion, parathion, diazinone, warfarin, alachlor, pyrethrin, cycloheximide, cetoxidim, trifiumizole and the like.
Insecticides include permethrin, pyrethroid compounds, fipronil and the like.
The content of the volatile substance in the tableting product is usually 0.1 to 5.0% by mass, preferably 1.0 to 2.0% by mass.

(Porous adsorbent)
In the present invention, the porous adsorbent is used for the purpose of adsorbing and holding the oily volatile substance described above and further providing sustained release. The porous adsorbent is not particularly limited as long as it is a fine particle having small pores or minute voids, but has an average primary particle size of 1.0 to 120 μm and a porosity of 1.0 to 2.0 mL / g. Those are preferred.
Examples of the fine particles include organic and inorganic fine particles. Examples of the organic fine particles include porous cellulose and porous cellulose derivatives.
Examples of the inorganic fine particles include calcium silicate, silicon dioxide, hydrous silicon dioxide; silicic acids such as light anhydrous silicic acid, magnesium silicate, magnesium aluminate metasilicate; zeolite and the like. Fluorite R (Tokuyama) for calcium silicate, Silicia (Fuji Silysia), Carplex (Yoshio Shionogi) for hydrous silicon dioxide, AEROSIL (Nippon Aerosil), magnesium aluminate metasilicate for light anhydrous silicic acid Neusilin (Fuji Chemical Co., Ltd.) is commercially available and can be easily obtained.
The content of the porous adsorbent in the tableting product is usually 0.1 to 5% by mass, preferably 0.1 to 1% by mass, and more preferably 0.2 to 0.7% by mass.

(Powdered base)
In the present invention, as the powdered base, those usually used as an excipient for oily substances can be used, and they are used as an adsorbent for the porous adsorbent. As the powdered base, polysaccharides are preferable, and gums such as gum arabic, sun tan gum, tragacanth gum, gellan gum, locust bean gum, tamarind seed gum, carrageenan, agar, LM pectin, HM pectin and the like can be mentioned.
The polysaccharide used for the powdered base is preferably a polysaccharide mainly containing a polysaccharide having a molecular weight of 1000 or more, more preferably 30,000 to 300,000.
The content of the powdered base in the tableting molded body is usually 0.1 to 45% by mass, preferably 1 to 15% by mass.
The ratio of the porous adsorbent to the powdered base is 1 to 450 parts by weight, preferably 5 to 450 parts by weight, more preferably 10 to 10 parts by weight of the powdered base with respect to 1 part by weight of the porous adsorbent. 100 parts by mass.

(Other additives)
In addition to the above-mentioned additives, the urinary stone inhibitor for toilet drain pipes of the present invention is a dissolution rate adjusting agent, a surfactant, a coloring agent such as a pigment, a corrosion inhibitor, a bactericidal agent, an ion sequestering agent, a binder, a slippery agent. Sap agents and the like can be added.

(Manufacturing method)
The production method of the urolith inhibitor of the present invention is particularly limited as long as it can be contained without causing oily volatile substances to bleed out, and can be used for a long time without being disintegrated. However, (A) an oily volatile substance is kneaded with a porous adsorbent to produce a kneaded raw material, and then (B) a step of kneading the kneaded raw material with a powdered base, (C) a solid acid It is preferable to mix the other ingredients such as and tableting.
The step (A) is a step of adsorbing the oily volatile substance to the porous adsorbent and can be kneaded by a known method. The kneading time is not particularly limited, but is usually 1 to 20 minutes. The kneading temperature is not particularly limited, but is usually 10 to 30 ° C.
Step (B) is a step of kneading the kneaded product obtained in step (A) with a powdered base material, and can be kneaded by a known method. The kneading time is not particularly limited, but is usually 1 to 20 minutes. The kneading temperature is not particularly limited, but is usually 10 to 30 ° C.
Step (C) is a step in which the kneaded product obtained in step (B) is mixed with other components and tableted by a known method.
The urinary stone inhibitor of the present invention can be tableted into any shape, for example, a spherical shape, a cylindrical shape, a perforated cylindrical shape, a disc shape, a cubic shape, a conical shape, a pyramid shape, an animal and plant shape.

In the above production method of the present invention, in the step (A), when a powdered base is used in place of the porous substance, or when the steps (A) and (B) are performed at the same time, tableting that exhibits the effects of the present invention is achieved. It is difficult to obtain a molded product.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by the following examples.
The meanings of the abbreviations are as follows.
HPC: Hydroxypropylcellulose St-Ca: Calcium stearate Further, in the examples, the manufacturer names of the raw materials used are as follows.
HPC-SL: Nippon Soda Co., Ltd. DK Ester F20W: Daiichi Kogyo Seiyaku Co., Ltd. Chromophthal Blue: Ciba Specialty Chemicals Co., Ltd. Arabic gum: Wako Pure Chemical Industries, Ltd. (reagent)
Silicia (registered trademark): manufactured by Fuji Silysia Chemical Co., Ltd. Neusilin (registered trademark): manufactured by Fuji Chemical Industry Co., Ltd. Zeolite: manufactured by Nitto Flour Industry Co., Ltd. α gel (registered trademark): manufactured by Alpha Japan Co., Ltd. GREEN APPLE AF-17735 , -18046: ORANGE AF-18047 manufactured by Iwata Fragrance Co., Ltd. CLEAN DEW AF-18048 manufactured by Iwata Fragrance Co., Ltd. PERFUME 17823 manufactured by Iwata Fragrance Co., Ltd. 17737: Made by Kamata Fragrance Co., Ltd.
[Example]

(Manufacture of urine stone inhibitor)
Liquid fragrance and Cylicia (registered trademark) (amorphous silicon dioxide manufactured by Fuji Silysia) were mixed in the ratio shown in Table 1, and kneaded in a mortar for 5 minutes. Further, a predetermined amount of gum arabic was added and kneaded in a mortar for 10 minutes. To this kneaded product, other additives are added to obtain a uniform mixture, and a urinary stone inhibitor 1 to 12 of the present invention having a diameter of 40 mm and a thickness of 25 mm is obtained using a tableting machine (UD100 / 90 manufactured by Masina Co., Ltd.). Manufactured.

(Evaluation test)
The urinary stone inhibitors 1 to 12 in the present invention were subjected to evaluation tests on the following items. The results are shown in Table 2.
(I) Bulk powder test After mixing the bulk powder, the presence or absence of dampness and stickiness was confirmed. A sample without dampness or stickiness was marked with ◯, a sample with slight moisture was marked with △, and a sample with little was marked with ×.
(II) Tableting property test (II-1) Tableting property The presence or absence of tableting troubles such as capping and cracking when the drug was tableted with a tableting machine was confirmed. Those with excellent tableting properties were indicated with ◯, those with slightly inferiority were indicated with Δ, and those with poor tabletability were indicated with ×.
(II-2) Flowability of bulk powder We confirmed how the bulk powder fell from the bulk powder hopper to the mortar. A sample having excellent fluidity was marked with ◯, a sample with slightly poor fluid was marked with Δ, and a sample with poor fluidity was marked with ×.
(II-3) Dust adherence to bulk powder It was confirmed whether or not the mold was stuck to the bulk powder. A sample with no adhesion was marked with ◯, a sample with slight adhesion was marked with Δ, and a sample with little adhesion was marked with ×.
(III) Abuse Test The drug was placed in an aluminum lami zip, placed in a thermostatic bath at 60 ° C. and stored for 7 days, and alteration / discoloration was confirmed. A sample with no alteration or the like was marked with ◯, a sample with slight alteration was marked with Δ, and a sample with poor quality was marked with ×.
(IV) Disintegration test 1 L of tap water was put into a 1 L polycup, and 1 tablet of urine stone inhibitor was submerged in it and allowed to stand for 3 days, and cracking / disintegration of the drug was confirmed. The thing which does not have a crack etc. was set as (circle), and a certain thing was set as x.
(V) Fragrance effect The urine stone inhibitor of the present invention was put in a cassette (plastic container) in a drain pipe of a boy's urinal for 1 month, and the presence or absence of fragrance was confirmed by a sensory test. Those with a strong fragrance were marked with ◎, those with a fragrance felt with ○, and those with no fragrance felt with ×.

[Comparative example]
[Comparative Example 1] When no adsorbent (porous adsorbent and powdered base) is contained (manufacture of uric stone inhibitor)
Powder fragrance or liquid fragrance and other additives were put in a plastic bag at a ratio shown in Table 3 and mixed for 1 minute. From the uniform mixture, cylindrical urine stone inhibitors 13 to 28 having a diameter of 40 mm and a thickness of 25 mm were produced by a tableting machine. Further, a uric stone inhibitor containing no fragrance was produced in the same manner as composition 29.

(Evaluation test)
An evaluation test was performed in the same manner as in the examples. The results are shown in Table 4.
As is apparent from Table 4, the powdered fragrance was easy to be tableted, but no fragrance was obtained, and the liquid fragrance was fragrant, but it was difficult to form a tablet.

[Comparative Example 2] When one of the porous adsorbent and the powdered base as the adsorbent is not used (production of uric stone inhibitor)
Liquid fragrances and other additives were placed in a plastic bag at the ratio shown in Table 5 and mixed for 1 minute. From the uniform mixture, columnar urolith inhibitors 30 to 41 having a diameter of 40 mm and a thickness of 25 mm were produced by a tableting machine.

(Evaluation test)
An evaluation test was performed in the same manner as in the examples. The results are shown in Table 6.
As is apparent from Table 6, in the case where either one of the porous adsorbent as an adsorbent or the powdered base was not used, a tablet having both fragrance and stability could not be obtained.

[Comparative Example 3] When the order of addition of the porous adsorbent, which is an adsorbent, and the powdered base is reversed from that in the example (production of urinary stone inhibitor)
Liquid fragrance and gum arabic were placed in a plastic bag at the ratio shown in Table 7 and mixed for 1 minute. Further, other additives were added to obtain a uniform mixture, and columnar urinary stone inhibitors 42 to 50 having a diameter of 40 mm and a thickness of 25 mm were produced by a tableting machine.

(Evaluation test)
An evaluation test was performed in the same manner as in the examples. The results are shown in Table 8.
As is clear from Table 8, only in the addition order of the porous adsorbent and the powdered base was a deterioration in the tabletability test, and the fragrance was inferior to the examples.

Claims

Solid acid as the main component;
Porous adsorbent;
An oil-based volatile substance adsorbed on the porous adsorbent; and a tableted molded article containing a powdered base.
The tableting molded article according to claim 1, wherein the oily volatile substance is a fragrance, repellent, insect repellent, deodorant or deodorant.
The tableting molded product according to claim 1 or 2, wherein the powdered base is a polysaccharide.
The tableting molded product according to any one of claims 1 to 3, wherein the powdered base is a gum.
The tableting molded article according to any one of claims 1 to 4, comprising particles formed by dispersing the porous adsorbent adsorbing the oily volatile substance in the powdered base.
A urinary stone inhibitor for a toilet water pipe comprising the tableting molded product according to any one of claims 1 to 5.