JP5076591B2 - Urine stone adhesion inhibitor - Google Patents

Description

  The present invention relates to a urolith adhesion inhibitor.

  Urolith is a scale mainly composed of calcium in urine, and is known to adhere to and generate in toilets and drainage systems of toilets and block drain pipes. Furthermore, urine stone contains organic substances such as urine, and there is a problem that malodors are generated when microorganisms decompose the organic substances.

  As a method for removing such urine stones, there are known a method of dissolving and removing with a strong inorganic acid such as hydrochloric acid, and a method using a solid molded body obtained by molding a sulfamic acid powder and a sucrose fatty acid ester powder (Patent Document 1). ing. However, since these methods use strong acid, there are problems such as corrosion of equipment and piping, danger during operation, and the like. Furthermore, it is very difficult to completely remove urine stones once adhered. Therefore, it is important to prevent adhesion of urine stones.

  For the purpose of preventing adhesion of urine stone, a readily water-soluble solid preparation or liquid preparation containing a detergent such as a surfactant is used. In the case of a liquid preparation, the equipment becomes complicated and a stable supply cannot be performed, and therefore a solid preparation is preferably used. Solid preparations have the advantage that a certain amount of detergent is supplied stably for each flush with simple equipment. For example, Patent Document 2 discloses a solid composition for washing toilets which contains a nonionic surfactant and a pigment that are solid at room temperature. Patent Document 3 contains 0.1 to 80% by weight of a chlorine-based disinfectant, 0.1 to 80% by weight of a solid acid, and 0.01 to 80% by weight of a surfactant. Solid disinfectant cleaners with a 2 to 12 are disclosed. Patent Document 4 discloses an inorganic peroxide of 5 to 90% by weight, a cationic fungicide of 0.1 to 30% by weight, a water-soluble carbonate, phosphate, sulfate, silicate, or hydroxide. Solid disinfecting detergents containing ˜95 wt% and water soluble surfactants 0.5 to 30 wt% are disclosed.

  However, these solid compositions or solid sterilizing detergents have detergent and antibacterial properties, but control the rate of dissolution of the surfactant in water and maintain the solidity of the solid formulation (shape retention). There is a problem in terms of sex. For example, when the surfactant elution amount is small, a sufficient urine stone prevention effect cannot be obtained, while when the surfactant elution amount is large, there is a problem that the cleaning effect cannot be obtained in a short period of time. . Furthermore, when the shape retention is insufficient, the solid preparation easily disintegrates, and sufficient cleaning effect and antibacterial effect are not exhibited. In addition, the surface of the solid preparation melts and collapses, and there is a problem that the inlet or the inner pipe of the water supply / drainage pipe is blocked.

  For this reason, in solid preparations, control of the elution amount of detergent and improvement of shape retention have been studied. Patent Document 5 discloses a solid detergent using isopropyltrioxane as a dissolution regulator and blending a deodorant, polyethylene glycol that is solid at room temperature, and paraoxybenzoic acid ester.

  Patent Document 6 includes 5 to 80% by weight of an alkali metal salt of a fatty acid having 8 to 22 carbon atoms, 1 to 35% by weight of a nonionic surfactant having a melting point of 45 ° C. or higher, and an alkali metal salt of carboxymethyl cellulose 1 to 35. Disclosed is an on-tank solid cleaning agent for toilets comprising 0% to 25% by weight of a hydrophobic substance that is liquid at 20 ° C. and 0 to 80% by weight of a water-soluble inorganic or organic filler. It is disclosed that this composition makes the dissolution rate less susceptible to water temperature.

  Patent Document 7 discloses a solid detergent that dissolves slowly in water and is characterized by comprising polyethylene glycol that is solid at room temperature, and stearyl alcohol as a dissolution regulator, and that does not contain a surfactant. Yes.

However, these dissolution regulators or solid detergents having a dissolution rate adjusted by the blending ratio of the surfactants are insufficient, although the dissolution rate can be adjusted to some extent. Furthermore, the shape retention is insufficient. Thus, it is difficult to control the dissolution rate to obtain an excellent cleaning effect and to have shape retention.
JP-A-7-26300 JP-A-8-81695 JP-A-11-148098 JP 11-124597 A JP 2003-128908 A JP-A-11-92796 JP 2004-166844 A

  An object of the present invention is to provide an agent for preventing adhesion of urine stone that has an appropriate solubility, is excellent in the effect of preventing adhesion of urine stone, and has good shape retention.

  In order to solve the above-mentioned problems, the present inventors have intensively studied a solid urolith adhesion inhibitor. As a result, behenic acid (a), benzalkonium chloride (b), polyethylene glycol (c), and ethylene oxide are obtained. And a block copolymer (d) of propylene oxide with a specific ratio and a specific dissolution rate so as to have an appropriate solubility and to prevent adhesion of urine stones. The present invention was completed by finding that a urine stone adhesion preventing agent having an excellent prevention effect (cleaning effect) and good shape retention was obtained.

The urolith adhesion inhibitor of the present invention comprises 5 to 20% by mass of behenic acid (a), 15 to 30% by mass of benzalkonium chloride (b), 35 to 55% by mass of polyethylene glycol (c), and ethylene oxide. 10 to 35% by mass of a block copolymer (d) of styrene and propylene oxide, and the total amount of (a), (b), (c) and (d) is 100% by mass. And the dissolution rate in the solubility test is 10 to 35%,
The polyethylene glycol (c) is represented by the following general formula (1):
HO— (CH ₂ CH ₂ O) _n —H (1)
(Wherein n represents an average degree of polymerization and is 90 to 700), and the block copolymer (d) of ethylene oxide and propylene oxide has the following general formula (2):
_{HO (CH 2 CH 2 O)} x (CH (CH 3) CH 2 O) y (CH 2 CH 2 O) z H (2)
(Wherein, x, y, and z represent the average number of added moles, x + z is 1 to 300, and y is 5 to 90).

  The urinary stone adhesion preventive agent of the present invention has moderate solubility, is excellent in cleaning effect (particularly urinary stone adhesion preventive effect), and has good shape retention. In other words, since this urine stone adhesion inhibitor has moderate solubility, it can stably supply a cleaning agent in a certain number of flashes, and can maintain an excellent cleaning effect for a long period of time. Therefore, the surface of the urine stone adhesion preventing agent is less likely to melt and collapse, and there is little risk of clogging the inlet or the inner tube of the water supply / drainage pipe.

  The behenic acid (a) used in the present invention imparts moderate solubility to the obtained urolith adhesion inhibitor, and also prevents good melting and imparts good shape retention. When fatty acids other than behenic acid, such as stearic acid or lauric acid, are used, the solubility of the resulting urolith adhesion inhibitor becomes too high, so that detergents (benzalkonium chloride (b) and polyethylene glycol (c) )) Is eluted in a short period of time, and an excellent cleaning effect cannot be maintained for a long period of time. Furthermore, melting and collapse are also likely to occur.

  Content of behenic acid (a) in the urine stone adhesion preventing agent of the present invention is 5 to 20% by mass. When the content of behenic acid (a) is less than 5% by mass, the shape retention of the obtained urine stone adhesion preventing agent is deteriorated. When the content of behenic acid (a) exceeds 20% by mass, the obtained urolith adhesion inhibitor is difficult to dissolve, so that the cleaning agent is not sufficiently eluted and the cleaning property is deteriorated. The content of behenic acid (a) is set according to the water temperature used. For example, when the water temperature is high as in summer, it is preferable to set a large amount of behenic acid (a) within the above range, and when the water temperature is low as in winter, set the amount of behenic acid (a) small. Is preferred.

  Benzalkonium chloride (b) used in the present invention prevents the adhesion of so-called dirt such as urine stone and scale by coating the surface of the toilet bowl with a cationic membrane. Furthermore, it functions effectively as an antibacterial agent. From the viewpoint of preparing a solid urolith adhesion inhibitor, benzalkonium chloride (b) is preferably used in a solid form such as powder, solid, or flake.

  The content of benzalkonium chloride (b) in the uric stone adhesion inhibitor of the present invention is 15 to 30% by mass. When the amount of benzalkonium chloride is less than 15% by mass, the dirt adhesion preventing effect (urine stone adhesion preventing effect) cannot be sufficiently obtained. Furthermore, it is insufficient from the viewpoint of obtaining antibacterial properties. When it exceeds 30 mass%, the effect corresponding to the addition amount is not acquired.

The polyethylene glycol (c) used in the present invention has the following general formula (1):
HO— (CH ₂ CH ₂ O) _n —H (1)
(In the formula, n represents an average degree of polymerization and is 90 to 700). This polyethylene glycol (c) mainly functions as a cleaning agent and cleans urine and other dirt.

  In the said General formula (1), n shows an average degree of polymerization and is 90-700. When the value of n is less than 90, the dissolution rate of the obtained urine stone adhesive becomes too high, so that the cleaning agent is eluted in a short period of time. When the value of n exceeds 700, the shape retention property of the obtained urine stone adhesion preventing agent is good, but polyethylene glycol is difficult to elute. Furthermore, when the urine stone adhesion inhibitor is melted and prepared, the melt viscosity of polyethylene glycol is increased, which may reduce productivity and yield.

  The content of polyethylene glycol (c) in the urine stone adhesion preventing agent of the present invention is 35 to 55% by mass from the viewpoint of obtaining an excellent cleaning effect.

The block copolymer (d) of ethylene oxide and propylene oxide used in the present invention (hereinafter sometimes simply referred to as a block copolymer (d)) has the following general formula (2):
_{HO (CH 2 CH 2 O)} x (CH (CH 3) CH 2 O) y (CH 2 CH 2 O) z H (2)
(Wherein, x, y, and z represent the average number of added moles, x + z is 1 to 300, and y is 5 to 90). This block copolymer (d) is contained mainly for the purpose of adjusting the solubility of the detergent, particularly polyethylene glycol (c). The block copolymer (d) can be liquid or solid depending on the average number of moles added. The solid block copolymer (d) is particularly preferably used from the viewpoint of appropriately eluting the cleaning agent in the urine stone adhesion preventing agent and the shape retention of the obtained urine stone adhesion preventing agent.

  In the said General formula (2), x, y, and z show average addition mole number, x + z is 1-300, y is 5-90, Preferably it is 20-70. When x + z exceeds 300, the shape retention of the obtained urine stone adhesion preventing agent becomes insufficient, and when immersed in water, it tends to swell and melt. On the other hand, when y is less than 5, the solubility of the obtained urolith adhesion inhibitor becomes too high, so that the cleaning agent is eluted in a short period of time, and an excellent cleaning effect cannot be maintained for a long period of time. In addition, shape retention is insufficient and melting and collapse are likely to occur. When y exceeds 90, the shape retention property of the obtained urolith adhesion inhibitor becomes insufficient.

  Content of the block copolymer (d) in the urine stone adhesion preventing agent of this invention is 10-35 mass%. When the block copolymer (d) exceeds 35% by mass, the shape retention of the obtained urolith adhesion inhibitor becomes insufficient, and when immersed in water, it tends to melt and collapse due to swelling. The content of the block copolymer (d) is set according to the average addition mole number y of propylene oxide groups of the block copolymer, the water temperature used, and the like. For example, when the average added mole number y is small, or when the water temperature is high as in summer, it is preferable to reduce the amount of the block copolymer (d) within the above range. When the average added mole number y is large, or when the water temperature is low as in winter, it is preferable to increase the amount of the block copolymer (d) within the above range.

  The urinary stone adhesion preventive agent of the present invention contains the behenic acid (a), the benzalkonium chloride (b), the polyethylene glycol (c), and the block copolymer (d) in the above proportions, and It is contained so that the total amount of (a), (b), (c) and (d) is 100% by mass. If each component is out of the above range, the resulting urolith adhesion preventive agent will not have adequate solubility, so the cleaning agent will not be stably supplied after a certain number of flushes, and an excellent cleaning effect will be achieved over a long period of time. It cannot be maintained. Furthermore, the shape retention is insufficient, and melting and collapse are likely to occur.

The urine stone adhesion preventing agent of the present invention has a dissolution rate in a dissolution test of 10 to 35%. In the present specification, the “dissolution rate” is a dissolution amount (%) when a 20 mm × 40 mm × 15 mm test piece (urine stone adhesion preventing agent) is immersed in water at 25 ° C. for 24 hours. Specifically, when the mass of the urine stone adhesion preventing agent before being immersed in water is A, and the mass of the urine stone adhesion preventing agent remaining after being immersed in water at 25 ° C. for 24 hours is B, the following formula:
Dissolution rate (%) = (1−B / A) × 100
It is represented by When the dissolution rate is less than 10%, the obtained urine stone adhesion inhibitor is difficult to dissolve and the cleaning agent is not sufficiently eluted, so that a sufficient cleaning effect cannot be obtained. When it exceeds 35%, the detergent is eluted in a short period due to excessive dissolution, and an excellent cleaning effect cannot be maintained for a long period. Furthermore, there arises a problem that the inlet of the water supply / drainage pipe or the internal pipe is blocked by melting and collapsing.

  The urinary stone adhesion preventive agent of the present invention is prepared, for example, by heating and melting and mixing predetermined amounts of components (a) to (d) at 80 to 90 ° C. and then allowing to cool to room temperature. In the preparation, it is preferable to consider the variation in solubility due to the water temperature. For example, when the water temperature is high as in summer, the content of behenic acid (a) is set high, and the dissolution rate of the obtained urine stone adhesion inhibitor is adjusted to be low within a range of 10 to 35%. On the other hand, when the water temperature is low as in winter, for example, the content of behenic acid (a) is set low, and the resulting dissolution rate of the urine stone adhesion inhibitor is adjusted to be high within a range of 10 to 35%. To do.

  The urine stone adhesion preventive agent of the present invention is an additive usually used by those skilled in the art for the urine stone adhesion preventive agent within a range not impairing the effects of the present invention, such as a deodorant, a colorant, a metal sequestering agent, a bulking agent, etc. Can be used in combination. These additives can be appropriately added, for example, at the time of preparing the urolith adhesion agent.

  Since the urine stone adhesion preventive agent of the present invention has an appropriate solubility, it can stably supply a cleaning agent in a flash of a predetermined number of times or more, and can maintain an excellent cleaning effect for a long period of time. Furthermore, since the shape retention is good, the surface of the urine stone adhesion preventing agent is unlikely to melt and collapse, and there is little possibility of clogging the inlet or the inner pipe of the water supply / drainage pipe. The urine stone adhesion preventing agent of the present invention is installed and used in a flush toilet.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples. In the examples,% means mass%.

(Example 1: Preparation and evaluation of urinary stone inhibitor)
Weigh out behenic acid (a), benzalkonium chloride (b), polyethylene glycol (c), and block copolymer (d) of ethylene oxide and propylene oxide in a predetermined amount shown in Table 1 into a stainless steel container, After being melted with stirring in a water bath at about 90 ° C., it was poured into a paper container (20 mm × 40 mm square column) and allowed to cool at room temperature to solidify. This solid was cut into a size of 20 mm × 40 mm × 15 mm to obtain a test molded body.

  The solubility of this molded article for test was evaluated by the following test method. Furthermore, the molded object for a test was installed in the automatic washing apparatus of the men's urinal made from TOTO, and the following methods evaluated the urine stone adhesion prevention effect (washing effect) and shape retention. The results are shown in Table 1.

(1) Solubility test First, after measuring the mass of the molding for a test, it put into a 100 mL beaker. Let this mass be A. Further, 60 mL of purified water (25 ° C.) was added to immerse the molded article for test, and left still for 24 hours. Thereafter, the test molded body was taken out, placed on Kim Towel (manufactured by Crecia Co., Ltd.), and allowed to stand for 2 hours, and then the mass was measured. Let this mass be B. Using the obtained masses A and B, the dissolution rate was determined from the following equation.
Dissolution rate (%) = (1−B / A) × 100

(2) Urine stone adhesion prevention effect (cleaning effect)
The condition of the urinal after 2 months of installation in a male urinal was visually evaluated according to the following criteria.

(Evaluation criteria)
Dirt is inconspicuous ... ○
Slightly dirty ... △
Obviously dirty ... ×

(3) Shape retention The deformation of the molded article one month after installation in a male urinal was visually evaluated according to the following criteria.

(Evaluation criteria)
The molded body is not deformed ...
The molded body is slightly deformed ... △
The molded body is clearly deformed. ×

(Examples 2-9)
Examples except that behenic acid (a), benzalkonium chloride (b), polyethylene glycol (c), and block copolymer (d) of ethylene oxide and propylene oxide were used in predetermined amounts shown in Table 1. In the same manner as in No. 1, a test molded body was prepared and evaluated for (1) solubility, (2) urine stone adhesion prevention effect (cleaning effect), and (3) shape retention. The results are shown in Table 1.

(Comparative Examples 1-5)
A fatty acid (at least one of behenic acid (a), stearic acid, and lauric acid), benzalkonium chloride (b), polyethylene glycol (c), and a block copolymer (d) of ethylene oxide and propylene oxide; Except having been used in the predetermined amount shown in 1, a test molded body was prepared in the same manner as in Example 1, and (1) solubility, (2) urine stone adhesion preventing effect (cleaning effect), and (3 ) The shape retention was evaluated. The results are shown in Table 2.

  From the results in Table 1, all of the test molded bodies of Examples 1 to 9 had moderate solubility, excellent cleaning effect, and good shape retention.

  On the other hand, it turns out that the molded object for a test of Comparative Examples 1-5 does not satisfy | fill the range of this invention, but the performance as a urolith adhesion prevention agent is not fully acquired. That is, in Comparative Example 1, since stearic acid was used instead of behenic acid (a), the dissolution rate was high and the shape retention was insufficient. In Comparative Example 2, since a mixture of behenic acid and stearic acid was used instead of behenic acid (a), the dissolution rate was high and the shape retention was insufficient. In Comparative Example 3, since lauric acid was used instead of behenic acid (a), the dissolution rate was very high. Therefore, since the cleaning agent was eluted in a short period of time, the cleaning effect was insufficient. Furthermore, the shape retention was insufficient. In Comparative Example 4, since the content of behenic acid (a) was high and the content of polyethylene glycol was low, the dissolution rate was low. Therefore, the cleaning agent was not sufficiently eluted and the cleaning effect was insufficient. And in the comparative example 5, since behenic acid (a) was not contained, the dissolution rate was very high. Therefore, since the cleaning agent was eluted in a short period of time, the cleaning effect was insufficient. Furthermore, the shape retention was insufficient.

  ADVANTAGE OF THE INVENTION According to this invention, the urine stone adhesion prevention agent which has moderate solubility, is excellent in a cleaning effect (especially urine stone adhesion prevention effect), and has a good shape retention property is provided. Therefore, this urine stone adhesion preventive agent can supply the cleaning agent stably after a certain number of flushes, and the surface of the urine stone adhesion preventive agent is less likely to melt and collapse. There is little risk of blocking. The urine stone adhesion preventing agent of the present invention is installed and used in a flush toilet or the like.

Claims (1)

5 to 20% by mass of behenic acid (a), 15 to 30% by mass of benzalkonium chloride (b), 35 to 55% by mass of polyethylene glycol (c), and a block copolymer of ethylene oxide and propylene oxide ( d) is contained in an amount of 10 to 35% by mass, and the total amount of (a), (b), (c) and (d) is 100% by mass, and dissolution in the solubility test shown below A urinary stone adhesion preventive agent having a rate of 10 to 35%,
The polyethylene glycol (c) is represented by the following general formula (1):
HO— (CH ₂ CH ₂ O) _n —H (1)
(Wherein n represents an average degree of polymerization and is 90 to 700), and the block copolymer (d) of ethylene oxide and propylene oxide has the following general formula (2):
_{HO (CH 2 CH 2 O)} x (CH (CH 3) CH 2 O) y (CH 2 CH 2 O) z H (2)
(Wherein, x, y, and z represent the average number of added moles, x + z is 1 to 300, and y is 5 to 90).
Urine stone adhesion inhibitor.
[Solubility test]
The sample is weighed into a stainless steel container, melted with stirring in a water bath at about 90 ° C., poured into a paper container (20 mm × 40 mm square column), allowed to cool at room temperature and solidified. This solid material is cut into a size of 20 mm × 40 mm × 15 mm to obtain a test molded body.
After measuring the mass of the test compact, it was placed in a 100 mL beaker. Let this mass be A. Further, 60 mL of purified water (25 ° C.) is added to immerse the molded article for testing, and left to stand for 24 hours. Thereafter, the test molded body is taken out, placed on Kim Towel (manufactured by Crecia Co., Ltd.), and left for another 2 hours, and then the mass is measured. Let this mass be B. Using the obtained masses A and B, the dissolution rate is determined from the following equation.
Dissolution rate (%) = (1−B / A) × 100