JP2013043988A - Urinary calculus removing agent - Google Patents

Abstract

The present invention provides an urinary stone removal agent that is harmless to the human body and is environmentally friendly.
A urolith removal agent containing a protease and a marine humic substance extract is provided. Protease has a function of dissolving protein that functions as a binder of urine stone, and marine humic substance extract has a function of activating the protein hydrolyzing reaction of protease containing various kinds of mineral components. . Such a marine humic substance extract contains magnesium, calcium, manganese, copper, iron, zinc, aluminum, and sodium, and promotes a protein hydrolysis reaction of protease.
[Selection] Figure 1

Description

  The present invention relates to a urine stone removing agent that is harmless to the human body and is environmentally friendly.

  In public toilets such as stations and parks, an unpleasant odor is generated, which may cause discomfort during use. Moreover, since calcium in urine becomes calcite of sparingly soluble calcium and adheres to the toilet bowl, causing odor and clogging, the removal work is periodically performed.

  In the work of removing urine stones, conventionally, work of dissolving urine stones using a powerful drug such as hydrochloric acid or organic acid has been performed. Since powerful drugs are used, wearing urine stones requires wearing masks, protective glasses, and gloves, and there is a problem that the working environment deteriorates in a hot environment in summer. In addition, if powerful medicine is used, powerful medicine may flow into wastewater treatment facilities such as septic tanks connected to flush toilets, resulting in functional failure of wastewater treatment facilities such as septic tanks that utilize the purification action of microorganisms. There is also the problem of being.

Therefore, development of a urinary stone removing agent that does not use a powerful drug has been performed. For example, Patent Document 1 discloses a detergent composition in which an acidic protease and a cationic surfactant are combined.
JP 2005-194296 A

However, the cleaning composition disclosed in Patent Document 1 needs to contain an acid that may be harmful to the human body in order to be acidic. Cationic surfactants are dangerous components that can cause blindness when they enter the eye. Moreover, the surfactant may cause water pollution of the river.
This invention is made | formed in view of the said subject, and it aims at providing the urine stone removal agent harmless to a human body and friendly to an environment.

  In order to achieve the above object, the present invention firstly provides a urolith remover characterized by containing a protease and a marine humic substance extract.

  Protease has the function of hydrolyzing the protein that functions as a binder of urine and dissolves urine, and the marine humic substance extract contains many kinds of mineral components and activates the protein hydrolysis reaction of protease. Has the function of Therefore, the urolith remover of the present invention can effectively remove urolith. In addition, both protease and marine humic substance extract are harmless to the human body, and there is no risk of environmental degradation.

Secondly, the present invention provides a urolith remover characterized in that the first urolith remover is an aqueous solution.
By using the urinary stone removing agent in the aqueous solution, the urinary stone removing work can be facilitated.

  Third, in the first or second urolith remover, the marine humic substance extract contains magnesium, calcium, manganese, copper, iron, zinc, aluminum, and sodium. A urolith remover is provided.

  It is considered that the hydrolysis reaction of protease protein is promoted by the marine humic substance extract containing various mineral components.

  Fourthly, the present invention provides the urolith remover characterized in that, in the first to third urolith removers, the protease has activity under neutrality.

  Alkaline proteases and acidic proteases need to add components that make the aqueous solution alkaline or acidic, but neutral proteases do not require the addition of components that are harmful to the human body.

  The urinary stone removing agent of the present invention can effectively remove urinary stones while using environmentally friendly components that are harmless to the human body.

It is the photograph which image | photographed the adhesion state of the urine stone of the toilet bowl which actually administered the urolith remover of this invention with the fiberscope, (1) Photograph before administration, (2) Photograph for one week after administration, (3) It is a photograph 3 weeks after administration.

Hereinafter, although the embodiment of the urolith removal agent of the present invention is described, the present invention is not limited to the following embodiment.
The urolith removal agent of the present invention is characterized by containing a protease and a marine humic substance extract.

  Protease (Protease, EC 3.4 group) is a peptide (generally less than 100 residues, relatively low molecular weight) or protein (generally more than 100 residues, relatively high molecular weight) in which amino acids are linked in a chain by peptide bonds. It is an enzyme that hydrolyzes peptide bonds and is a proteolytic enzyme.

  Representative types of protease include serine protease, thiol protease, metalloprotease, and aspartic protease (also called acidic protease). Representative examples of serine proteases include trypsin, Bacillus subtilis origin, Streptomyces genus and Aspergillus genus alkaline protease. Representative examples of thiol protease include papain. Representative examples of metalloproteases include Bacillus subtilis-derived, Streptomyces genus and Aspergillus genus neutral protease.

  The protease includes alkaline protease having an activity, acidic protease having acid activity, and neutral protease having neutral activity, and any protease can be used in the present invention. It is preferable to use a neutral protease that is not necessary.

  Examples of neutral protease include neutral protease derived from Aspergillus, papain contained in papaya, bromelain contained in pineapple, and the like. Available from Amano Enzyme Inc., Tokyo Kasei Kogyo Co., Ltd. Further, papaya and pineapple non-heated fruit juice, concentrated fruit juice, or powdered fruit juice may be used. Two or more proteases may be used in combination.

  Marine humic substances are extracted from marine humic soil, which is produced by repeated decomposition and fermentation of plants, seafood and algae that have been killed tens of millions of years ago and accumulated deep in the seabed. Extracted. Containing components are mainly humic acid, various amino acids such as alanine and glycine, and calcium, potassium, magnesium, zinc, manganese, sodium, silicon, iron, lanthanum, strontium, aluminum, chromium, cobalt, copper, phosphorus It contains mineral components such as selenium, and has a pH of about 2.8. Marine humic substance extracts are commercially available for drinking, for example, and are safe aqueous solutions. Moreover, since it originally existed on the surface of the earth, there is no fear of polluting the environment. An example of actual measurement data of the mineral component content is shown in Table 1 described later.

  Urolith that adheres firmly to the toilet bowl is a complex composed of an inorganic salt such as a calcium phosphate in urine that is hardly soluble calcium phosphate and an organic substance such as protein.

  It is known that uric stones can be removed by hydrolyzing proteins and degrading proteins that function as binders for uroliths. The present invention has been made by finding that a marine humic substance extract can promote the hydrolysis action of such protease. Due to the fact that the function is exerted with a very small amount of the marine humic substance extract, various mineral components in the marine humic substance extract serve to catalytically promote the hydrolysis action of the protease. It is presumed that

  The urine stone removing agent of the present invention contains a protease and a marine humic substance extract, and is supplied in a granular or powder form, for example, in which a marine humic substance extract is mixed with a granular or powdery protease. can do. However, from the viewpoint of workability, it will generally be supplied in the form of an aqueous solution.

  When supplied as an aqueous solution, the amount of protease is in the range of 0.0001 mg to 100 g / liter, preferably in the range of 0.0005 mg to 70 g / liter, particularly preferably in the range of 0.001 mg to 10 g / liter. If the blending amount is too small, urine stone removal will be insufficient, while if too large, the urine stone removal effect will not be as high as the blending amount, which may be economically disadvantageous.

  The blending amount of the marine humic substance extract is in the range of 0.1 ml to 100 ml, preferably in the range of 0.2 ml to 50 ml, particularly preferably in the range of 0.3 ml to 30 ml, per liter. For example, when 1 ml of marine humic substance extract is diluted in 1 liter of water, the mineral components shown in Table 1 are mixed in an amount of less than 1 ppm and are extremely small. It is a new finding of the present inventor that the hydrolysis reaction of protease can be promoted with such a small amount. If the blending amount of the marine humic substance extract is too small, the hydrolysis reaction promoting effect of the protease may not be expressed. On the other hand, if the blending amount is too large, the protease hydrolysis reaction will not improve as much as the blending amount, which is uneconomical. It may become.

  When the urolith remover of the present invention is used as an aqueous solution, the pH of the aqueous solution is neutral, for example, in the range of 5.8 to 8.6, which is the same as the standard of tap water, so that the tap water can be used without using the pH adjuster. It is effective as a urinary stone remover just by adding protease and marine humic substance extract to water.

  In addition to protease and marine humic substance extract, for example, surfactant, preservative, antioxidant, pH adjuster, fragrance, pigment, antibacterial agent, etc. are added to the urolith remover of the present invention. can do.

  The method of using the urolith remover of the present invention is dissolved in water so as to have the above-mentioned blending amount in the case of a granular or powder form, for example, about 0.5 to 1 liter per toilet, or What is necessary is just to make it supply every day or every other day using the means to drop gradually.

  Thereby, the ammonia odor of a toilet bowl decreases gradually. In addition, it has been observed that urine stones adhering to toilet pipes and the like increase in volume from a hard state to become inflated and gradually peel off. If the toilet bowl is washed under high pressure in such a state, urine stones are easily removed. Therefore, the urolith removal agent of the present invention can remove urolith alone or may be used as a pretreatment for high-pressure washing.

1. Experiments using artificial uroliths Various types of urolith removal agents were prepared, and the urolith removal effect was measured using artificial uroliths.

(1) Preparation of urolith remover
Example 1
The pineapple enzyme was mixed with tap water at a rate of 1 μg / ml and the marine humic substance extract at 0.001 ml / ml.
Example 2
Commercial protease (aspergillus-derived neutral protease, Tokyo Kasei, Lot. FGG01, prepared to 20 mg / ml) 1 μg / ml, marine humic substance extract 0.001 ml / ml was mixed with tap water.
Comparative Example 1
Only tap water was used.
Comparative Example 2
The marine humic substance extract was mixed with tap water at a rate of 0.001 ml / ml.
Comparative Example 3
Pineapple enzyme was mixed with tap water at a rate of 1 μg / ml.
Comparative Example 4
The commercially available protease was mixed with tap water at a rate of 1 μg / ml.

Table 1 shows analysis values of the mineral components of the used marine humic substance extract.

(2) Preparation of artificial urolith Casein (Merck, Hammarsten Type) 0.1 g, calcium phosphate (hydroxyapatite, Wako Pure Chemicals, for column chromatography, high flow rate type) 0.5 g, uric acid (Wako Pure Chemicals, special grade) 0 0.1 g of urea (GE Healthcare Bio-Sciences, ALF Grade) 0.2 g was dispersed in 50 ml of pure water. 1.0 ml of this dispersion was spread on a 20 mm square slide glass and dried and solidified in a blow dryer at 60 ° C. for 24 hours to obtain an artificial urine stone. Due to the adhesion of artificial urine stone, the slide glass became cloudy glass.

(3) Cleaning test 30 ml of urine stone removing agent was dispensed into a 50 ml sample tube, and artificial urine stone prepared on a slide glass was immersed at 37 ° C. for 24 hours. Thereafter, the slide glass was taken out, thoroughly rinsed with pure water, and dried in a blow dryer at 60 ° C. for 1 hour. Five artificial urine stones were used for one type of urine stone removing agent.

(4) Evaluation of cleaning performance of urolith remover The transmittance at 600 nm of the slide glass before and after washing with the urolith remover was measured with a spectrophotometer (Hitachi, U-2000A).
The cleaning rate was calculated from the measured transmittance according to the following formula.
Washing rate (%) = (transmittance after cleaning (%) − transmittance before cleaning (%) / (100−transmittance before cleaning (%)) × 100
The transmittance was calculated for each of the five artificial urine stones, the maximum value and the minimum value were excluded, and the remaining three average values were used as the cleaning rate. Values that were 50% or more higher than the remaining three average values were deleted from the average values as abnormal values. The results are shown in Table 2.

  It is recognized that there is almost no cleaning effect only with tap water and the marine humic substance extract. Although the cleaning liquid containing only the pineapple enzyme showed a slightly higher cleaning rate than tap water alone, it was considerably lower than the commercially available protease.

  Example 1 in which a marine humic substance extract is blended with a pineapple enzyme and Example 2 in which a marine humic substance extract is blended with a commercially available protease are higher than Comparative Examples 3 and 4 in which an enzyme is blended alone. It has a washing rate, and it is recognized that the marine humic substance extract promotes the proteolytic action of the enzyme.

2. Experiment using real urine stone (1) Preparation of urine stone remover
Example 3
The same pineapple enzyme as before was mixed with tap water at a rate of 0.004 ml / ml and the same marine humic substance extract as before.
Example 4
The same commercial protease as before was mixed with tap water at a rate of 1 μg / ml and the above marine humic substance extract at 0.004 ml / ml.
Comparative Example 5
Only tap water was used.
Comparative Example 6
The pineapple enzyme was mixed with tap water at a rate of 4 μg / ml.
Comparative Example 7
The commercially available protease was mixed with tap water at a rate of 1 μg / ml.
(2) Properties of real urine stone Granules collected from a toilet in a factory that has been in operation for 30 years, and its water content was 53.8%.

(3) Cleaning test 2.9 g of wet urine stone (corresponding to about 1.35 g in dry weight) and 30 ml of urine stone removing agent were added to a 50 ml sample tube and immersed at 28 ° C. and 30 rpm. After 3 hours, 6 hours, 1 day, 2 days, 3 days, 4 days, and 7 days after the start of soaking, 0.5 ml of each liquid was collected, filtered with 0.75 ml of 5% trichloroacetic acid, Proteolytic activity was evaluated by measuring the absorbance of the filtrate at 280 nm. Each sample had n = 5. As a blank for absorbance measurement, a filtrate obtained by adding 0.75 ml of trichloroacetic acid to 0.5 ml of pure water and filtering was used. This measurement is based on the finding that the amount of amino acid produced by the hydrolysis reaction of protein protease after denaturing the remaining protein with trichloroacetic acid is proportional to the absorbance. That is, in this experiment, the amount of proteolysis is indirectly measured from the amino acid produced.
When the sample was collected from the immersed sample, the actual urine stone was observed, but no change was observed.
In any sample, the absorbance rapidly increased with the passage of time, and it was also observed in Comparative Example 5 containing no protease. Therefore, this was the elution of amino acids and low molecular peptides originally present in actual urine stones. It is thought to be due to.
After 4 days, the absorbance of each sample decreased rapidly. This is thought to be due to the decrease in absorbance due to the influence of the propagation of bacteria that feed on amino acids and peptides.
For this reason, the absorbance after 2 days immersion, which had the least influence of the propagation of various bacteria and the progress of protein degradation, was used as an index of proteolytic activity. The results are shown in Table 3.

  In the case of the pineapple enzyme alone, the proteolytic activity is slightly higher than that of the tap water alone, whereas in the case of the commercially available protease, the proteolytic activity is lower than that of the tap water. The combination of the pineapple enzyme and the marine humic substance extract is slightly more proteolytic than the pineapple enzyme alone, and the combination of the commercial protease and the marine humic substance extract is clearly more proteolytic than the commercial protease alone. It is recognized that the activity is high.

  The pineapple enzyme has a clearly higher proteolytic activity than the commercially available protease because the amount of the protease in the pineapple enzyme is increased to about 4 times that in the experiment using artificial urine stones to approximate the amount of the commercially available protease. It is thought that it is because.

3. Field test (1) Preparation of urinary stone remover 3 g / 1000 ml of pineapple enzyme and 1 ml / 1000 ml of marine humic substance extract containing mineral components shown in Table 1 were blended. Hereinafter, the prepared cleaning liquid is referred to as a field cleaning liquid.

(2) Verification of deodorizing effect of toilets 2-1) Implementation at Sakai Station on Yokohama Subway From October 14 to November 18, 2009, once a day, 1 liter of field cleaning solution is used every other day in the toilet bowl. Administered.
The ammonia concentration decreased from the initial 0.15 ppm to 0.02 ppm. This corresponds to a reduction rate of 86.7%.

2-2) Implementation at JR Sakai Station 1 liter of field washing solution was administered to the toilet once a day from March 8 to 19, 2010 for 8 days.
The ammonia concentration decreased from the initial 0.15 ppm to 0.05 ppm. This corresponds to a reduction rate of 67.3%.

(3) Implementation at Yokohama Subway Sakai Station From May 12 to June 12, 2009, 1 liter of field washing solution was administered once a day to the toilet every 14 days for a total of 14 times. The urine stones in the vicinity of the joint between the urinal trap and the water pipe were photographed with a fiberscope.
FIG. 1 shows (1) a photograph before administration of a field cleaning solution, (2) a photograph of one week after administration of the field cleaning solution, and (3) a photograph of three weeks after administration of the field cleaning solution.
It is recognized that the urinary stones increase in volume and peel off.

The urine stone removing agent of the present invention can be used in the cleaning industry for removing urine stones attached to a toilet.

In order to achieve the above object, the present invention first provides a urolith remover characterized by containing a neutral and active protease and a marine humic substance extract.

Protease has the function of hydrolyzing the protein that functions as a binder of urine and dissolves urine, and the marine humic substance extract contains many kinds of mineral components and activates the protein hydrolysis reaction of protease. Has the function of Therefore, the urolith remover of the present invention can effectively remove urolith. In addition, both protease and marine humic substance extract are harmless to the human body, and there is no risk of environmental degradation. Alkaline proteases and acidic proteases need to add components that make the aqueous solution alkaline or acidic, but neutral proteases do not require the addition of components that are harmful to the human body.

Claims (4)

  A urolith removal agent comprising a protease and a marine humic substance extract.   2. The urolith remover according to claim 1, which is an aqueous solution.   The urolith removal agent according to claim 1 or 2, wherein the marine humic substance extract contains magnesium, calcium, manganese, copper, iron, zinc, aluminum, and sodium.   The urolith removal agent according to any one of claims 1 to 3, wherein the protease is neutral and active.

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