JPH1180799A - Detergent for toilet and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent for toilet that has excellent solidification and corruption resistance and shows high microbicidal action and easy removal of urinary calculus on the toilet. SOLUTION: A microbicidal agent as butyl p-hydroxybenzoate and/or 2- bromo-2-nitropropane-1,3-diol and a surfactant are stirred with heat and they are selected so that they are compatible with each other and the compatible solution may solidify at room temperature. In addition, a combination that the solidified product does not melt, even when it is heated up to 40 deg.C is selected from the above-selected combinations. The selected microbicidal agent and the surfactant are mixed with a solid acid, heated, stirred and the resultant mixture is solidified by cooling to produce the toilet cleaning detergent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hard-to-disintegrate solid toilet cleaner having an excellent action for sterilizing toilet drain pipes and controlling urinary stones.

[0002]

2. Description of the Related Art Paradichlorobenzene, which has the property of being sublimable and being insoluble in water, has been known to be used together with solid acids as a base for cleaning insects for toilets in addition to insecticides for clothing. (Japanese Patent Laid-Open No. 55-88766)
JP, JP-A-8-206688, French Patent No. 1
No. 501248, British Patent 879733, etc.).

[0003] As the toilet cleaner containing no paradichlorobenzene, for example, the following are known. Known is a slowly dissolving base for a solid cleaning agent for flush toilets containing a urethane compound obtained by reacting a polyoxyalkylene compound with an aliphatic monoisocyanate compound, which is directly poured into a toilet water tank. (JP-A-8-67898).

[0004] As a base, at least one of bactericide P-hydroxyhydroxybenzoate, methacetide acetoacetate, anilide acetoacetate or orthotoluide acetoacetate (Group 1) and 2-bromo-2 which is also a bactericide Toilet cleaners containing nitro-1,3 propanediol (Group 2) are known (Japanese Unexamined Patent Publication No.
-304604).

[0005] A solid molded body composed of sulfamic acid having a specific particle size and a sucrose fatty acid ester having the property of a polyhydric alcohol-based nonionic surfactant is used as a toilet scale remover (Japanese Patent Application Laid-Open No. Hei 7-26300). A solid molded product comprising a water-soluble organic binder such as sulfamic acid and stearic acid monoglyceride having a specific particle size and a nonionic surfactant is used as a scale remover for toilet (Japanese Patent Laid-Open No. 7 (1995)).
No.-48598) is known.

[0006] There is known a solid detergent for flush toilets of the type which is directly poured into a toilet water tank containing polyoxyethylene fatty acid monoethanolamine as an active ingredient (Japanese Patent Application Laid-Open No. 8-67898).

A stable color tone independent of water temperature, in which a monoester type nonionic surfactant comprising behenic acid or behenic acid and stearic acid to which 50 to 120 moles of ethylene oxide has been added is blended. There is known a solid composition for washing flush toilets containing a dye which can be obtained (JP-A-8-81695).

One or more organic acids having a low melting point and low solubility in water selected from the group consisting of maleic anhydride, chloroacetic acid, cis-cinnamic acid and crotonic acid;
There is known a solid deodorant for male urinals containing succinic acid and / or fumaric acid having appropriate solubility in water (JP-A-9-28777).

[0009]

Problems to be Solved by the Invention Paradichlorobenzene has been frequently used as a base for toilet cleaners due to its properties such as sublimability and water insolubility. The use of paradichlorobenzene-containing products is being avoided in public and railway related organizations. Therefore, it is necessary to develop a base that can be used as a substitute for p-dichlorobenzene in toilet cleaners and the like, which used p-dichlorobenzene as the base in the past. No toilet cleaner excellent in disintegration and excellent in bactericidal action and urinary stone controlling action has been known.

[0010] An object of the present invention is to provide a toilet cleaner which is excellent in solidifying property and hardly disintegrating property and excellent in sterilizing action and urinary stone controlling action.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, screened for a surfactant that is compatible with a bactericide and has a solidifying ability at room temperature after compatibility. The present invention has been completed based on the finding that the use of such a method can provide a toilet cleaner excellent in solidification and hard-to-disintegrate.

That is, the present invention relates to butyl parahydroxybenzoate, 2-bromo-2-nitropropane-1,3-
One or more fungicides selected from diols and the like, particularly preferably a fungicide containing butyl parahydroxybenzoate and 2-bromo-2-nitropropane-1,3-diol; A surfactant which is compatible and has a solidifying ability at room temperature and which is compatible with the bactericide, and one selected from sulfamic acid, succinic acid, adipic acid, etc.
The present invention relates to a toilet cleaner containing one or more kinds of solid acids and not melting even when the solid molded body is heated to 40 ° C.

The present invention also provides a fungicide and a surfactant which are heated and agitated to select a combination of a fungicide and a surfactant which have compatibility and have a solidifying ability at room temperature. Among the combinations, further selected a combination that does not melt even if the solidified product of the fungicide and the surfactant is heated to 40 ° C.
The present invention relates to a method for producing a toilet cleaner, which comprises adding a solid acid to the selected bactericide and surfactant and cooling and solidifying a mixture obtained by heating and stirring.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION As a bactericide in the present invention,
Examples thereof include butyl parahydroxybenzoate and 2-bromo-2-nitropropane-1,3-diol.

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 glyceryl monostearate, polyoxyethylene oleyl ether, molecular weight 10
Surfactants such as nonionic surfactants composed of a copolymer of polyethylene glycol, propylene oxide and ethylene oxide having a molecular weight of 00 to 20000.

In the present invention, the surfactant having compatibility with the germicide and having a solidifying ability at room temperature, which is compatible with the germicide, can be used in a compatibility test, a solidification test, and a heat-forming maintainability described later. Can be selected by testing.

In order to carry out these tests, first, a mixture of a bactericide and a surfactant as a candidate was prepared in an arbitrary ratio, and the compatibility, solidification, and warming maintenance properties were determined for each item. The experiment is performed in the order of a compatibility test, a solidification test, and a warm forming maintenance test. By further adding a solid acid to the composition having cleared all the test items, the toilet cleaner of the present invention can be obtained. In addition, for the compounds that did not clear all the tests, a compound was prepared by changing the mixing ratio of the fungicide and the candidate surfactant, and the experiment was repeated for each of the above test items to select the compound. You can also.

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, and the mixture is stirred while being heated to 80 to 85 ° C. in a water bath. After melting, it can be taken out of the water bath and allowed to cool. After cooling, it can be carried out by observing whether 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 “OK”, and if not, the compatibility is determined to be “impossible”.

In the solidification test, a predetermined amount of a surfactant is weighed into a glass sample bottle, a predetermined amount of a bactericide is put therein, and the mixture is stirred while being heated to 80 to 85 ° C. in a water bath. After melting, remove from the water bath and allow to cool. After cooling, the disinfectant and the candidate surfactant are in a substantially uniform mixed state. For the melt determined to be compatible for 24 hours, It can be carried out by observing the state of solidification after standing. If it is solidified, it is determined that the solidification property is “OK”, and if it is not solidified or is in a semi-solidified state, it is determined that the solidification property is “impossible”.

In the above-mentioned warming molding retention test, the solidification test result of which is “OK” is heated at 40 ° C. for 3 hours.
It can be carried out by observing the state of moldability and melting. Then, when the shape is maintained and not melted, it is determined that the warm forming maintainability is “possible”, and otherwise, it is determined that the warm forming maintainability is “impossible”.

Next, a solid acid was further added to the composition in which the compatibility test, the solidification test, and the warming maintenance test were all cleared, and the warming maintenance test and the next disintegration test were performed again. I do. The warming maintenance test can be performed in the same manner as described above except that a solid acid is added. The preparation of a molded product for a collapse test is performed, for example, as follows. A predetermined amount of solid acid is weighed in a polycup in advance, mixed well, and placed in a thermostat at 60 ° C. and warmed for 1 hour or more.
Separately, a predetermined amount of a surfactant is weighed into a polycup, then a predetermined amount of a bactericide is weighed, and the mixture is heated and mixed and melted at 80 to 85 ° C. in a water bath. The solid acid-containing composition, which has been warmed for one hour or longer, is put into the mixed melt, mixed well and stirred until uniform, and then left to cool. After cooling and solidifying, take out from the polycup to obtain a molded product for a collapse test.

In the disintegration test, the mass of the molded product for disintegration test prepared above was weighed and placed in a plastic container. Then, water was almost completely filled into the container, and the container was left at 25 ° C. for 3 days. Take out of the container, wipe off the water, weigh,
It can be carried out by determining the decay 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, by the following equation. Initial mass (g)-Mass after 3 days (g) / Initial mass (g) x
100

As the solid acid in the present invention, any acid can be used as long as it is a solid at ordinary temperature. Examples thereof include sulfamic acid, adipic acid, and succinic acid, and sulfamic acid is preferred.

[0024] The toilet detergent of the present invention is obtained by heating and stirring a disinfectant comprising butyl parahydroxybenzoate and / or 2-bromo-2-nitropropane-1,3-diol and a surfactant. A combination of a disinfectant and a surfactant having a solubility and a compatible substance capable of solidifying at room temperature is selected, and a solidified product of the disinfectant and the surfactant is heated to 40 ° C from the selected combination. A combination that does not melt even when heated is further selected, a solid acid such as sulfamic acid is added to the selected fungicide and surfactant, and the mixture obtained by heating and stirring at 40 to 90 ° C. is cooled and solidified. It can be manufactured by doing. In the manufacture of a toilet cleaner, in addition to the above-mentioned bactericide, surfactant, and solid acid, a corrosion inhibitor, a pigment, a fragrance, and the like can be added and blended as necessary.

[0025]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1: Use of butyl parahydroxybenzoate as a fungicide (test items and test order) A blend of 12 g of butyl parahydroxybenzoate and 8 g of various surfactants (formulation ratio 6: 4) was prepared. For each item of compatibility, solidification, and warm forming maintainability, conduct an experiment in the order of compatibility test, solidification test, and warm forming maintainability test. To make a molded product containing
The following disintegration / dissolution test was performed.

(Compatibility test) The surfactant at room temperature solid was previously melted, and the surfactant at room temperature liquid was 30
A predetermined amount is weighed and placed in a ml glass sample bottle, and a predetermined amount of butyl parahydroxybenzoate is placed therein, stirred while being heated to 80 to 85 ° C. in a water bath, melted, taken out of the water bath and allowed to cool. I do. After cooling, if the butyl parahydroxybenzoate and the candidate surfactant are in a nearly uniform mixed state, they are compatible.
If not, the compatibility was determined as “impossible”.

Since butyl parahydroxybenzoate showed compatibility with most of the surfactants tested, a solidification test was carried out. Diethanol laurate ("Tohoru N-230X" manufactured by Toho Chemical Co., Ltd.) was used. "), Polyethylene glycol distearate (" Pegnol PD ")
S-60A "), polyoxyethylene lauryl ether (" Pegnol L-20S "), polyoxyethylene oleyl ether (" Pegnol O-16A "," Pegnol O-20 "," Pegnol O-24 "), Polyethylene glycol monostearate ("Pegnol 14-S"), polyoxyethylene cetyl ether ("Pegnol C-18"), a non-surfactant composed of propylene oxide and ethylene oxide copolymer ("Pepol B-" 308 "," Pepol B-188 ") and the like, the solidification was determined to be impossible.

Next, ethylene glycol distearate (the same as “Pegnol ED”) was determined to be solidifiable.
S "), sorbitan monopalmitate (" Sorbon S "
-40 "), sorbitan monostearate (" Sorbone S-60 "), lipophilic surfactants such as glyceryl monostearate (" Sorbone MG-100 ") and butyl parahydroxybenzoate At 40 ° C
When a warming maintenance test was carried out by heating for 3 hours and observing the molten state, most of the solidification properties were determined to be acceptable, and most of them were also determined to be acceptable in the warm molding retention test.

Next, succinic acid, adipic acid, succinic acid, adipic acid,
Sulfamic acid was added and blended to prepare a solid molded body, which was heated at 40 ° C. for 3 hours. Observation of the moldability and molten state revealed that ethylene glycol distearate (the same “Pegnol EDS”), monopalmitic acid Sorbitan (Sorbone S-40), sorbitan monostearate (Sorbone S-60), lipophilic glyceryl monostearate (Sorbone MG-100), etc., can be subjected to a heated molding retention test. Was determined.

Thus, succinic acid, adipic acid,
Each of the solid molded bodies contains sulfamic acid,
The toilet cleaner of the present invention which does not melt even when heated to 0 ° C. was obtained. In addition, when the disintegration test was performed on the toilet detergent of the present invention, which did not melt even when the solid molded body was heated to 40 ° C., excellent results were obtained.

Example 2: As fungicides, butyl parahydroxybenzoate and 2-bromo-2-nitropropane-1,
Use of 3-diol The same procedure as in Example 1 was carried out except that an equivalent mixture of butyl parahydroxybenzoate and 2-bromo-2-nitropropane-1,3-diol was used as a bactericide. The result was obtained. As the bactericide, butyl parahydroxybenzoate and 2-bromo-2-nitropropane-
Toilet cleaner comprising 1,3-diol and solid acid,
In addition to the extremely excellent bactericidal effect and the urinary stone preventing effect, it also had the property that the bactericidal effect was maintained.

[0032]

According to the present invention, it is possible to obtain a toilet cleaner which is excellent in solidifying properties and hardly disintegrating, and is excellent in bactericidal action and urinary stone controlling action.

Claims (4)

[Claims] 1. A solid molded product comprising a bactericide, a surfactant having compatibility with the bactericide and having a solidifying ability at room temperature, and a solid acid. At 40 ° C
A toilet cleaner characterized in that it does not melt even when heated. 2. A fungicide comprising butyl parahydroxybenzoate and / or 2-bromo-2-nitropropane-
2. The composition according to claim 1, further comprising 1,3-diol.
The toilet cleaner according to the above. 3. The toilet cleaner according to claim 1, wherein the solid acid comprises one or more solid acids selected from sulfamic acid, succinic acid, and adipic acid. . 4. A disinfectant and a surfactant are heated and stirred to select a combination of a disinfectant and a surfactant having a compatibility and a solidification ability of a compatible substance at room temperature. From among them, further select a combination that does not melt even if the solidified product of the disinfectant and the surfactant is heated to 40 ° C., and a solid acid is added to the selected disinfectant and the surfactant, and A method for producing a toilet cleaner, comprising cooling and solidifying a mixture obtained by stirring.