JP3992332B2 - Toilet cleaner and method for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a hardly disintegrable solid toilet cleaner having an action excellent in sterilizing toilet drain pipes and the like and controlling urine stones.
[0002]
[Prior art]
Conventionally, paradichlorobenzene, which has sublimation properties and is insoluble in water, is known to be used together with a solid acid as a base material for toilet cleaners, in addition to pesticides for clothing (Japanese Patent Application Laid-Open (JP-A)). No. 55-88766, JP-A-8-206688, French Patent No. 1501248, British Patent No. 877733, etc.).
[0003]
Moreover, the following are known as a toilet cleaner which does not contain paradichlorobenzene, for example. A slow-dissolving base is known for a solid detergent for flush toilets that contains a urethane compound obtained by reacting a polyoxyalkylene compound and an aliphatic monoisocyanate compound and that is directly fed into a toilet reservoir. (JP-A-8-67898).
[0004]
One or more of butyl P-hydroxybenzoate, metaxylide acetoacetate, anilide acetoacetate or orthotoluidide acetoacetate (Group 1) as a base and 2-bromo-2nitro-1 which is also a fungicide , 3 propanediol (Group 2) is known (Japanese Unexamined Patent Publication No. 7-304604).
[0005]
A solid molded article comprising a sucrose fatty acid ester having properties of a specific particle size sulfamic acid and a polyhydric alcohol nonionic surfactant is used as a toilet scale remover (Japanese Patent Laid-Open No. 7-26300), or a specific particle size It is known that a solid molded article comprising a water-soluble organic binder such as sulfamic acid and stearic acid monoglyceride and a nonionic surfactant is used as a toilet scale remover (JP-A-7-48598). .
[0006]
There is known a solid detergent for flush toilets of the type that is directly charged into a toilet water tank containing polyoxyethylene fatty acid monoethanolamine as an active ingredient (Japanese Patent Laid-Open No. 8-67898).
[0007]
A stable color tone can be obtained without depending on the water temperature, in which a monoester type nonionic surfactant composed of behenic acid or behenic acid and stearic acid added with 50 to 120 moles of ethylene oxide is added. A solid composition for washing toilets containing a pigment is known (JP-A-8-81695).
[0008]
An organic acid having low melting point and low solubility in water selected from the group consisting of maleic anhydride, chloroacetic acid, cis-cinnamic acid and crotonic acid and moderate solubility in water A solid deodorant for male urinals containing succinic acid and / or fumaric acid is known (Japanese Patent Laid-Open No. 9-28777).
[0009]
[Problems to be Solved by the Invention]
Paradichlorobenzene has been used extensively as a base for toilet cleaners because of its properties such as sublimation and water insolubility, but in recent years its use has become a problem in the emission standards and the Ministry of Labor Sanitation Guidelines. In public institutions and railway-related institutions, the use of paradichlorobenzene-containing products is being avoided. Therefore, it is necessary to develop a base that can be used as a substitute for paradichlorobenzene in toilet cleaners that previously used paradichlorobenzene as the base. However, solidification and difficulty in place of paradichlorobenzene are required. No toilet cleaner has been known which is excellent in disintegration and excellent in bactericidal action and urine stone control action.
[0010]
The subject of this invention is providing the detergent for toilets which was excellent in the solidification property and hardly disintegrating property, and was excellent in the bactericidal action and the urine stone control action.
[0011]
[Means for Solving the Problems]
As a result of diligent research to solve the above problems, the present inventors have adopted a method of screening for a surfactant having compatibility with a bactericide and having a solidification ability at room temperature after the solution. And based on the knowledge that the detergent for toilets excellent in difficulty disintegration can be found, it came to complete this invention.
[0012]
That is, the present invention
(1) (a) a bactericidal agent containing butyl parahydroxybenzoate and / or 2-bromo-2-nitropropane-1,3-diol , ( b ) the bactericidal agent having compatibility with the bactericidal agent A solid molded product containing ethylene glycol distearate, sorbitan monopalmitate, sorbitan monostearate or oleophilic glyceryl monostearate, and (c) a solid acid, which has a solidifying ability at room temperature. A toilet cleaner, which does not melt even when heated to 40 ° C;
(2) The present invention relates to the toilet cleaner according to (1) above, which contains one or more solid acids selected from sulfamic acid, succinic acid, and adipic acid as the solid acid .
[0013]
The present invention also provides
(3) A bactericide and a surfactant containing butyl parahydroxybenzoate and / or 2-bromo-2-nitropropane-1,3-diol are heated and stirred to have compatibility and a compatible product Choose a combination of a bactericidal agent and a surfactant that has a solidifying ability at room temperature, and select a combination that does not melt even if the solidified product of the bactericidal agent and the surfactant is heated to 40 ° C. from the selected combination. further selection, on the said selected fungicides surfactant solid acid added above, characterized in that the mixture obtained by heating and stirring to cool and solidify (1) of the toilet cleaning agent according It relates to a manufacturing method.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the bactericidal agent in the present invention include butyl parahydroxybenzoate, 2-bromo-2-nitropropane-1,3-diol, and the like.
[0015]
As the surfactant in the present invention, any of nonionic surfactants, amphoteric surfactants, cationic surfactants, anionic surfactants and the like can be used, but nonionic surfactants are preferred. As the surfactant used in the present invention, for example, ethylene glycol distearate, sorbitan monopalmitate, sorbitan monostearate, lipophilic glycerol monostearate, and polyethylene glycol or Ranaru nonionic molecular weight 1,000 to 20,000 Mention may be made of surfactants.
[0016]
In the present invention, a surfactant having compatibility with a bactericide and having a solidification ability at room temperature with a compatible product with the bactericide is selected by a compatibility test, a solidification test, and a heating molding maintenance test described later. can do.
[0017]
In order to carry out these tests, first, a blend of an arbitrary ratio of a bactericidal agent and a candidate surfactant is prepared, and a compatibility test is performed for each of the items of compatibility, solidification property, and warm molding maintenance property. The experiment is performed in the order of the solidification test and the warming mold maintenance test. The toilet cleaner of the present invention can be obtained by further adding a solid acid to a formulation that has cleared all the test items. In addition, for the formulations that could not clear all the tests, prepared by changing the blending ratio of the bactericide and the candidate surfactant, and selecting again by conducting an experiment for each of the above test items. You can also
[0018]
In the compatibility test, a predetermined amount of a surfactant is weighed into a glass sample bottle, a predetermined amount of a bactericide is put therein, stirred while heating to 80 to 85 ° C. in a water bath, and melted. It can be carried out by taking out from the water bath and allowing to cool, and after cooling, observing whether or not the disinfectant and the candidate surfactant are in a substantially uniform mixed state. If the disinfectant and the candidate surfactant are in a substantially uniform mixed state, the compatibility is determined to be “good”, and if not, the compatibility is determined to be “impossible”.
[0019]
In the solidification test, a predetermined amount of surfactant is weighed in a glass sample bottle, a predetermined amount of bactericidal agent is put therein, stirred while heating to 80 to 85 ° C. in a water bath, and melted. Take out the product from the water bath and let it cool. After standing to cool, the disinfectant and the candidate surfactant are in a nearly uniform mixed state. It can be carried out by observing the solidified state. Then, when solidified, the solidification property is “possible”, and when not solidified or semi-solidified, the solidification property is “impossible”.
[0020]
The warm molding maintainability test can be carried out by heating at 40 ° C. for 3 hours and observing the moldability / melting state for those having a solidification test result of “OK”. And when the shape is maintained and it is not melted, it is determined that the warm-molding maintainability is “possible”, and otherwise, the warm-molding maintainability is “impossible”.
[0021]
Next, a solid acid is further added to the blend that has cleared all of the items of the compatibility test, the solidification test, and the warming molding maintenance test, and the warming molding maintenance test and the next disintegration test are performed again. The warming molding maintainability test can be performed in the same manner as described above except that a solid acid is added. Moreover, preparation of the molded article for a disintegration test is performed as follows, for example. A predetermined amount of solid acid is weighed in a polycup in advance and mixed well, and then placed in a 60 ° C. incubator and kept warm for 1 hour or more. Separately, a predetermined amount of surfactant is weighed in a polycup, and then a predetermined amount of bactericidal agent is weighed and stirred and heated to 80 to 85 ° C. in a water bath to mix and melt. The solid acid-containing composition that has been warmed for 1 hour or longer is put into the mixed melt, and the mixture is thoroughly mixed and stirred until uniform, and then allowed to cool. After cooling and solidifying, it is taken out from the polycup and made into a molded article for a disintegration test.
[0022]
In the disintegration test, the weight of the molded product for the disintegration test prepared above was weighed, put into a plastic container, and then filled with water until it was almost full. It can be carried out by wiping off the water, measuring the mass, and determining the disintegration rate. The disintegration rate (%) is obtained by dividing the difference between the mass (g) of the molded product before the start of the test and the mass (g) after 3 days by the mass (g) of the molded product before the start of the test and multiplying by 100. That is, it is obtained by the following equation.
Initial mass (g) —mass after 3 days (g) / initial mass (g) × 100
[0023]
As the solid acid in the present invention, any acid can be used as long as it is solid at room temperature, and sulfamic acid, adipic acid, succinic acid and the like can be exemplified, but sulfamic acid is preferable.
[0024]
The toilet cleaner of the present invention has a compatibility by heating and stirring a bactericide composed of butyl parahydroxybenzoate and / or 2-bromo-2-nitropropane-1,3-diol, etc. and a surfactant. In addition, a combination of a bactericidal agent and a surfactant having a solidifying ability at room temperature is selected, and the solidified product of the bactericidal agent and the surfactant is heated to 40 ° C. from the selected combination. A combination that does not melt even further is selected, a solid acid such as sulfamic acid is added to the selected bactericidal agent and surfactant, and the mixture obtained by heating and stirring to 40 to 90 ° C. is cooled and solidified. Can be manufactured by. In the production of the toilet cleaner, in addition to the above bactericides, surfactants, and solid acids, corrosion inhibitors, pigments, fragrances, and the like can be added and blended as necessary.
[0025]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not restrict | limited at all by these Examples.
Example 1: Use of butyl parahydroxybenzoate as a bactericidal agent (test items and test order) Prepare a blend of 12 g of butyl parahydroxybenzoate and 8 g of various surfactants (blending ratio 6: 4), For each of the compatibility, solidification, and warming mold maintainability items, an experiment was conducted in the order of the compatibility test, solidification test, and warming mold maintainability test. Was made, and the following disintegration / dissolution tests were conducted.
[0026]
(Compatibility test)
The normal temperature solid surfactant is melted in advance, and the normal temperature liquid surfactant is directly weighed into a 30 ml glass sample bottle, and a predetermined amount of butyl parahydroxybenzoate is put in this, and 80% in a water bath. Stir while heating to ˜85 ° C. After melting, remove from water bath and allow to cool. After allowing to cool, the compatibility was determined as “Yes” when the butyl parahydroxybenzoate and the candidate surfactant were in a substantially uniform mixed state, and the compatibility was determined as “No” when not.
[0027]
Since butyl parahydroxybenzoate was compatible with most of the tested surfactants, a solidification test was performed next. Diethanol laurate (“Tohoru N-230X” manufactured by Toho Chemical Co., Ltd.) Polyethylene glycol distearate (same “Pegnol PDS-60A”), polyoxyethylene lauryl ether (same “Pegnol L-20S”), polyoxyethylene oleyl ether (same “Pegnol O-16A”, “Pegnol O-20”, “Pegnol O-24”), polyethylene glycol monostearate (“Pegnol 14-S”), polyoxyethylene cetyl ether (“Pegnol C-18”), non-interface consisting of propylene oxide and ethylene oxide copolymer Activator ("Pepol B-308", "Pepo Solidifying is judged impossible in Le B-188 ") and the like.
[0028]
Next, ethylene glycol distearate ("Pegnol EDS"), sorbitan monopalmitate ("Sorbon S-40"), sorbitan monostearate ("Sorbon S-60"), which were determined to be solidified. ), A combination of a surfactant such as lipophilic glyceryl monostearate (the same “Sorbon MG-100”) and butyl parahydroxybenzoate is heated at 40 ° C. for 3 hours to observe the molten state When the molding maintainability test was performed, most of the solidification properties that were determined to be acceptable were also determined to be acceptable in the warming molding sustainability test.
[0029]
Next, succinic acid, adipic acid, and sulfamic acid were added and blended as solid acids to the surfactant and butyl parahydroxybenzoate, which were determined to be acceptable in the warming molding maintenance test. Was prepared, heated at 40 ° C. for 3 hours, and observed for moldability / melting state, ethylene glycol distearate (Pegnol EDS), sorbitan monopalmitate (Sorbon S-40), In the case of sorbitan monostearate (“Sorbone S-60”), lipophilic glyceryl monostearate (“Sorbon MG-100”) and the like, it was determined that a warming molding maintenance test was possible.
[0030]
In this way, the toilet cleaner of the present invention containing succinic acid, adipic acid, and sulfamic acid, which did not melt even when the solid molded body was heated to 40 ° C., was obtained. Moreover, when the disintegration test was done about the detergent for toilets of this invention which the solid molding does not melt even if it heats to 40 degreeC, the outstanding result was obtained.
[0031]
Example 2: Use of butyl parahydroxybenzoate and 2-bromo-2-nitropropane-1,3-diol as fungicides Butyl parahydroxybenzoate and 2-bromo-2-nitropropane-1,3 as fungicides -When the same procedure as in Example 1 was performed except that an equal amount of diol was used, almost the same result was obtained. As this disinfectant, a toilet cleaner composed of butyl parahydroxybenzoate, 2-bromo-2-nitropropane-1,3-diol and a solid acid has an excellent disinfectant effect and urine stone preventive effect, as well as a disinfectant. It also had the characteristic that the effect lasted.
[0032]
【The invention's effect】
According to the present invention, it is possible to obtain a toilet cleaner that is excellent in solidification and hardly disintegrating, and excellent in bactericidal action and urine stone control action.

Claims (3)

(A) a disinfectant containing butyl parahydroxybenzoate and / or 2-bromo-2-nitropropane-1,3-diol ,
(B) ethylene glycol distearate, sorbitan monopalmitate, sorbitan monostearate or lipophilic glyceryl monostearate, which is compatible with the fungicide and has a solidifying ability at room temperature. ,as well as
(C) A toilet cleaner, which contains a solid acid and does not melt even when the solid molded body is heated to 40 ° C. The toilet cleaner according to claim 1, comprising one or more solid acids selected from sulfamic acid, succinic acid, and adipic acid as the solid acid. A bactericide containing butyl parahydroxybenzoate and / or 2-bromo-2-nitropropane-1,3-diol and a surfactant are heated and stirred to have compatibility and the compatible solidifies at room temperature. A combination of a fungicide and a surfactant having a function is selected, and a combination that does not melt even when the solidified product of the bactericide and the surfactant is heated to 40 ° C is further selected from the selected combinations. The method for producing a toilet cleaner according to claim 1 , wherein a solid acid is added to the selected bactericide and surfactant, and the mixture obtained by heating and stirring is cooled and solidified.