JP3356711B2 - Solid detergent for flush toilet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid cleaning agent for flush toilets, and more particularly to a flush toilet having uniform solubility (slow solubility) which is not affected by water temperature and which can be uniformly flushed many times throughout the year. Solid detergent for cleaning.

[0002]

2. Description of the Related Art Conventional slowly soluble solid detergents for flush toilets include polyoxyethylene polyoxypropylene alkyl ether and its derivatives, polyoxyethylene alkyl ether, polyethylene glycol and its derivatives,
Those using a non-ionic surfactant such as alkanolamide as a main base material and those using an anionic surfactant such as sodium alkylbenzenesulfonate as a main base material are commercially available. However, there is a large difference in the number of times of flush flushing between toilets between hot water (about 25 ° C.) in summer and cold water (about 5 ° C.) in winter, and the cleaning power as designed by the manufacturer cannot be obtained. In particular, in winter, there is a problem that not only the cleaning power is greatly reduced, but also the unmelted residue blocks the drain port of the toilet tank.

To improve this, Japanese Patent Application Laid-Open No. Hei 8-2
No. 83796 discloses a solid detergent for toilets in which the difference in solubility between winter and summer is reduced, which is an excellent, but water-soluble alkaline earth metal salt as a dissolution regulator. Incorporation of an alkali metal salt of a fatty acid as a cleaning component causes a problem of generation of scum, and further improvement has been desired from the viewpoint of biodegradability.

[0004]

Therefore, the present invention is not affected by water temperature, exhibits a uniform slow-dissolving property every flash washing throughout the year, is excellent in biodegradability, and produces scum which causes stains on toilets. The aim is to provide a solid detergent for flush toilets.

[0005]

As a result of intensive studies to achieve the object, at least a predetermined amount of a specific alkali metal salt of a fatty acid, a predetermined amount of a specific aliphatic higher alcohol, and a nonionic interface It has been found that a detergent which can solve the above problem can be obtained by combining a predetermined amount of the activator and a predetermined amount of the alkali metal salt of carboxymethyl cellulose, thereby completing the present invention.

That is, the invention according to claim 1 of the present invention provides at least 3% by weight to 80% by weight of (1) an alkali metal salt of a fatty acid having an alkyl group having 8 to 22 carbon atoms.
And (2) 1% to 30% by weight of the nonionic surfactant
And (3) 3% to 30% by weight of an alkali metal salt of carboxymethyl cellulose, and (4) 1% to 10% by weight of an aliphatic higher alcohol having an alkyl group having 12 to 24 carbon atoms. And a solid cleaning agent for flush toilets.

The alkali metal salt of a fatty acid having an alkyl group having 8 to 22 carbon atoms is not particularly limited, but is preferably a trivalent alkali metal (Na, K, Li, Mg,
Ca, Ba, Al, Zn, Cd, Mn, Pb, etc.) which are generally called metal soaps. However, the metal salt is preferably a monovalent one, and particularly preferably a sodium salt. Specific examples include sodium or potassium tallow fatty acid, sodium or potassium coconut fatty acid, and sodium or potassium pam oil fatty acid.

When the amount of the alkali metal salt of the fatty acid is 3
If the amount is less than 3% by weight, it is not preferable from the viewpoint of moldability. On the other hand, if it exceeds 80% by weight, it is difficult to reduce the difference in solubility of the detergent due to the water temperature in summer and winter. Because it becomes.

The nonionic surfactant used in the present invention is not particularly limited as long as it is a nonionic surfactant, but it may be a so-called conventional polyethylene glycol type or a polyvalent alcohol type. Can be. In this case, the polyethylene glycol type is R (or Ar) -O (C
₂ H ₄ O) _n H ether and R (or Ar) —COO
(C ₂ H ₄ O) _n H ester (where R is an alkyl group and Ar is a phenyl group to which an alkyl group is bonded) and the like.
Glycerin, pentaerythritol, sorbitol,
Examples thereof include esters and amides of polyhydric alcohols such as sorbitan and sucrose.

However, it is preferable that (1) polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid as a monofunctional alkylene oxide adduct, Ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene polyoxyalkylene alkyl ether, polyoxyethylene polyoxyalkylene alkylphenyl ether, polyoxyethylene polyoxyalkylene fatty acid ester, polyoxyethylene poly Oxyalkylenealkylamines, polyoxyethylenepolyoxyalkylenealkylamides, (2) ethylene oxide adducts of polyhydric alcohols as polyfunctional alkylene oxide adducts (for example, polyalkylene Ethylene oxide adduct of polyamine, polyoxyethylene polyoxyalkylene glycol (specifically, polyoxyethylene polyoxypropylene glycol, etc.), ethylenediamine tetrapolyoxyethylene polyoxyalkylene (specifically, ethylenediamine (E.g., tetrapolyoxyethylene polyoxypropylene), polyhydric alcohol ethylene oxide / alkylene oxide adducts (eg, polyalkylene polyamine ethylene oxide / alkylene oxide adducts), (3) polyalkylene glycol fatty acid esters, 4) fatty acid alkanolamides, (5) polyhydric alcohol fatty acid esters, (6) polyoxyethylene polyhydric alcohol fatty acid esters, (7) polyoxyethylene polyoxyalkylene polyhydric alcohol fatty acid esters, It is preferable to use those species or of two or more. In this case,
As the alkylene oxide which is a monomer of polyoxyalkylene, propylene oxide, butylene oxide and styrene oxide are used, and as the polyhydric alcohol, alkylene glycol (EG, PG, PEG, PP) is used.
G), glycerin, sorbitol, sorbitan, polyglycerin, pentaerythritol, and sucrose are preferably used.

When the blending amount of the nonionic surfactant used in the present invention is from 1% by weight to 30% by weight, if it is less than 1% by weight, it is difficult to reduce the difference in solubility of the detergent depending on the water temperature in summer and winter. On the other hand, if it exceeds 30% by weight, it is not preferable in terms of moldability. Preferably, the content is 3 to 15% by weight.

The carboxymethyl cellulose used in the present invention
The alkali metal salt of sulfuric acid is not particularly limited, and examples thereof include sodium and potassium salts of carboxymethylcellulose. However, from the viewpoint of versatility, it is preferable to use a sodium salt. When the amount of the alkali metal salt is set to 3% by weight to 30% by weight, if it is less than 3% by weight, the function of wrapping and protecting the detergent is weak, and the dissolving rate of the detergent may be too fast. If the content is more than 10% by weight, it may swell significantly in water, causing a problem of blocking the drain port of the tank, or the dissolution rate of the detergent may be too slow, resulting in insufficient washing power.

The aliphatic higher alcohol having an alkyl group having 12 to 24 carbon atoms used in the present invention is not particularly limited, and examples thereof include those obtained by reducing fats and oils. Therefore, from the viewpoint of versatility, it is preferable to use those having 14 to 20 carbon atoms. If the amount of the aliphatic higher alcohol is set to 1% by weight to 10% by weight, if it is less than 1% by weight, it will be difficult to delay the dissolution of the detergent, and it will not be possible to sufficiently achieve the purpose of gradually dissolving. On the other hand, if it exceeds 10% by weight, the retarding effect becomes too large, the dissolving speed becomes slow, and the detergency at every flash cleaning becomes insufficient.

In the present invention, a hydrophobic fragrance (eg, terpineol, linalool, citronellol, citronellol) which is liquid at 20 ° C. is added to add or improve an aroma function.
, Limonene, lemongrass oil, lavender oil and the like or a mixture of two or more thereof) may be contained in an amount of 0.5% by weight to 15% by weight. Further, a coloring matter, a bulking agent (a water-soluble inorganic salt such as sodium sulfate, sodium carbonate, sodium hydrogen carbonate, etc.), a chelating agent, an enzyme, a deodorant, a water repellent and the like may be appropriately blended.

With this arrangement, the solubility of the detergent in water is adjusted by the alkali metal salt of carboxymethyl cellulose, the higher aliphatic alcohol having an alkyl group having 6 to 22 carbon atoms, and the nonionic surfactant. Combined with the action and the action of homogenizing the solubility in cold and hot water, the solid detergent for flush toilet in-tank according to the present invention exhibits a uniform slow-dissolving property every flash washing throughout the year and has a naturally derived soap structure. Since an alkali metal salt of a fatty acid having an alkyl group having 8 to 22 carbon atoms is used, it is excellent in biodegradability, and there is no need to use the above-mentioned conventional water-soluble alkaline earth metal salt as a dissolution regulator. There is no scum that causes scum.

According to a third aspect of the present invention, in the first or second aspect, the nonionic surfactant exhibits a higher solubility in cold water than in hot water. It is a solid cleaning agent for flush toilet in tanks. Examples of such nonionic surfactants include polyoxyethylene polyoxyalkylene alkyl ether, polyoxyethylene polyoxyalkylene alkyl phenyl ether, polyoxyethylene polyoxyalkylene fatty acid ester, and polyoxyethylene polyoxyalkylene alkyl. Amine, polyoxyethylene polyoxyalkylene alkylamide, polyoxyethylene polyalkylene glycol (for example, polyoxyethylene polypropylene glycol), ethylenediaminetetrapolyoxyethylenepolyoxyalkylene (for example, ethylenediaminetetrapolyoxyethylenepolyoxy) Propylene, etc.) and ethylene oxide / alkylene oxide adducts of polyhydric alcohols (eg, ethylene oxide of polyalkylene polyamine). Alkylene oxide adducts, etc.)
Etc. are exemplified.

These surfactants are more soluble in cold water than in hot water, and when these surfactants are blended with other blending agents that are more soluble in warm water than in cold water, the solubility adjustment in cold and hot water It is considered that the action proceeds in a more preferable direction (direction of uniform dissolution). Therefore, if such a surfactant is used, uniform solid solubility of the solid detergent for flush toilet in-tank according to the present invention throughout the year can be more reliably achieved.

According to a fourth aspect of the present invention, in the first, second or third aspect, the 1% aqueous solution of the alkali metal salt of carboxymethyl cellulose has a solution viscosity of 3000 cps at 25 ° C. It is a solid cleaning agent for flush toilets, characterized by having a weight of ~ 25,000 cps. When the solution viscosity is 3000 cps to 25000 cps, the dissolution rate of the solid detergent tends to be too high when the solution viscosity is less than 3000 cps, and the swelling of the detergent tends to be too large when the solution viscosity exceeds 25000 cps. The preferred solution viscosity is 3000 cps to 20,000
cps, more preferred solution viscosity is 5000 cps-150
000 cps.

With this configuration, the solubility of the solid detergent is sufficiently adjusted, and the swelling can be reliably prevented. Therefore, this action is combined with the above-mentioned action of a nonionic surfactant or an aliphatic higher alcohol, so that the solid cleaning agent for flush toilets according to the present invention can more reliably achieve a uniform slow solubility throughout the year. it can.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below, but the present invention is not limited to the flush toilet in-tank cleaning agent shown in this embodiment.

The solid detergent for flush toilets according to the embodiment of the present invention comprises (1) at least 10% by weight to 70% by weight of a sodium salt of a fatty acid having an alkyl group having 12 to 20 carbon atoms.
% By weight, and (2) polyoxyethylene alkyl ether,
Polyoxyethylene polyoxypropylene alkyl ether
3 to 15% by weight of a nonionic surfactant of an ether type such as ter, an ester type such as a sorbitan fatty acid ester, a propylene glycol fatty acid ester, or an amide type such as a fatty acid alkanolamide; ) 1% aqueous solution 2
5% to 25% by weight of a sodium salt of carboxymethyl cellulose having a solution viscosity at 5 ° C. of 5,000 to 15,000 cps, and (4) 2% by weight of a higher aliphatic alcohol having an alkyl group having 12 to 20 carbon atoms. % To 8% by weight, a mixture of 3% to 10% by weight of fragrance and sodium sulfate, and a mixture adjusted to a total amount of 100% by weight, kneaded by a conventional method, put into a mold, and pressurized to a predetermined pressure. It can be manufactured by press molding.

The solid detergent produced as described above is
If used in a flush toilet ro-tank, the solid detergent dissolves at an average rate of 2 g / day during the period of use (however, the flush toilet ro-tank has a water storage capacity of 9 liters M).
(TOTOOS-721B manufactured by Totoki Kikai Co., Ltd. is used, and the number of flashes is set to 24 times a day.) Slow solubility of less than or equal, and almost uniform solubility (washing) in hot water in summer and cold water in winter Sex) is secured. In addition, since a sodium salt of a fatty acid having an alkyl group having 14 to 20 carbon atoms, which is easily biodegradable, is used, the biodegradability is excellent, and in addition to the conventional water-soluble alkaline earth metal, aliphatic Since the high-grade alcohol is used, scum which causes stains on the toilet does not occur. The flush toilet cleaner of the present invention can be suitably used particularly for in-tank use.

[0023]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 As shown in Table 1, 10% by weight of sodium tallow fatty acid as an alkali metal salt of fatty acid, 5% by weight of polyoxyethylene polyoxypropylene glycol as a nonionic surfactant and 5% by weight of coconut oil monoethanolamide, 3% by weight of stearyl alcohol as an aliphatic higher alcohol, and sodium salt of carboxymethyl cellulose (viscosity of 10,000 cp)
s; 25 ° C., 1% aqueous solution), 10% by weight, 5% by weight of green floral blended flavor, 3% by weight of pigment (Blue No. 1), and 59% by weight of sodium sulfate as a bulking agent. The raw materials in weight% are blended with a Hensyl mixer (manufactured by Mitsui Miike Co., Ltd.). Next, this mixed raw material was kneaded with a KRC kneader (manufactured by Kurimoto Ironworks Co., Ltd.), and 60 g of the kneaded product was put into a tableting mold and 100 kg / kg.
Press molding was performed under a pressure of cm ² to prepare a cylindrical cleaning agent.

(Examples 2 to 8) In the same manner as in Example 1, a raw material in which the respective components were blended at the blending ratios shown in Table 1 was prepared.
By mixing and kneading, 60 g of the kneaded material was molded to obtain each cleaning agent having the same shape as in Example 1.

(Comparative Examples 1 to 4) In the same manner as in Example 1, a raw material in which the respective components were mixed at the mixing ratios shown in Table 2 was prepared.
By mixing and kneading, 60 g of the kneaded material was molded to obtain each cleaning agent having the same shape as in Example 1. Comparative Example 1 contains the alkali metal salt of the fatty acid used in the present invention, Comparative Example 2 contains the nonionic surfactant used in the present invention, and Comparative Examples 3 and 4 contain the aliphatic higher alcohol used in the present invention. Not blended. In Comparative Example 4, conventional magnesium sulfate was blended as a dissolution regulator.

(Evaluation Method of Cleaning Agent) The solubility of the solid cleaning agent in water and the generation of scum were evaluated as follows. The results are shown in Tables 1 and 2, with the former being “the number of uses (the number of flashes)” and the latter being “the occurrence of scum”.

Solubility of the solid detergent in water;
8. The solid cleaning agents of Comparative Examples 1 to 4 are respectively installed at the bottom of a low-tank (9 liters of water, TOTO S-721B manufactured by Tohoku Kiki Co., Ltd.) of a household flush toilet,
The water temperature in the low tank and the inflow water were maintained at 25 ° C. (set as summer water temperature) or 5 ° C. (set as winter water temperature), and each was flushed once an hour. The number of flushes until the detergent was exhausted was used as the number of uses, and the number of uses was used as an evaluation of the solubility of the solid detergent in hot and cold water.

Occurrence of scum: The drainage caused by the flash in the above-mentioned solubility test was visually observed, and the presence or absence of floating of the scum was examined. Those with floating scum were evaluated as “Yes”, and those with no floating scum were evaluated as “No”.

The solution viscosity of the sodium salt of carboxymethyl cellulose was measured using a B-type viscometer under the following conditions. Concentration: 1% aqueous solution (liquid temperature 25 ° C), rotor used; N
O. 4, its rotation speed; 30 rotations / minute.

[0031]

[Table 1]

As shown in Table 1, each of the cleaning agents of the examples used more than 720 times, and the difference in the number of times of use between hot water in summer and cold water in winter was the largest in Example 8.
48 times, the minimum being 0 and no difference is observed. By the way, this kind of cleaning agent is evaluated as follows.
Assuming that the device can be used for about a month and that it is used once an hour, it is desirable that the number of uses be about 720 times (or more). The solid detergent according to the present embodiment makes the difference in solubility between cold and hot water in winter and summer very small, and ensures no scum, while ensuring the detergency of each flash of the detergent having such slow solubility. I have.

[0033]

[Table 2]

In Comparative Examples 1 and 3, as shown in Table 2, the case where the nonionic surfactant or the alkali metal salt of carboxymethyl cellulose was not blended, the difference in the number of uses between the hot water and the cold water was small. Not only does it exceed 100 times, but the maximum number of uses is 672 times, 3 times, respectively.
Comparative Example 2 is a case where no aliphatic higher alcohol is blended. The difference in the number of uses is as small as 24 times, but the maximum number of uses is also as small as 504 times. In Comparative Example 4, the number of times of use was as large as 720 times at 25 ° C., and the difference in the number of times of use was 72 times. Thus, the difference in solubility was achieved to some extent, but the generation of scum could not be prevented.

[0035]

As described above, according to the detergent of the present invention, an alkali metal salt of carboxymethyl cellulose, an aliphatic higher alcohol having an alkyl group having 12 to 24 carbon atoms, and a nonionic interface The combination of the activator with the action of adjusting the dissolution of the solid detergent in water and the effect of dissolving and homogenizing it in cold and hot water, the solid detergent for flush toilets according to the present invention exhibits a slow solubility that meets the needs of consumers. At the same time, it shows uniform solubility (detergency) every flash cleaning throughout the year.
Further, since an alkali metal salt of a fatty acid having an alkyl group having 8 to 22 carbon atoms, which is a naturally occurring soap structure, is used, it is excellent in biodegradability, and a conventional water-soluble alkaline earth metal salt is used as a dissolution regulator. Since there is no need to use it, there is no scum that would cause toilet contamination.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) C11D 10/04 C11D 3/20 C11D 3/382 C11D 17/00

Claims (4)

(57) [Claims] (1) at least 3% by weight to 80% by weight of an alkali metal salt of a fatty acid having an alkyl group having 8 to 22 carbon atoms;
(2) 1% to 30% by weight of the nonionic surfactant, (3) 3% to 30% by weight of the alkali metal salt of carboxymethyl cellulose, and (4) 12 carbon atoms. ~ 24
1% by weight to 1% by weight of an aliphatic higher alcohol having an alkyl group
0% by weight of a solid detergent for flush toilets. 2. The method according to claim 1, wherein the nonionic surfactant is (1) a polyoxyethylene alkyl ether, a polyoxyethylene alkylphenyl ether, a polyoxyethylene fatty acid ester, or a polyoxyethylene alkyl ether as a monofunctional alkylene oxide adduct. Ethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene polyoxyalkylene alkyl ether, polyoxyethylene polyoxyalkylene alkylphenyl ether, polyoxyethylene polyoxyalkylene fatty acid ester,
Polyoxyethylene polyoxyalkylenealkylamine, polyoxyethylene polyoxyalkylenealkylamide, (2) polyoxyalkylene oxide adduct, polyhydric alcohol ethyleneoxyside adduct, polyhydric alcohol ethylene oxide. Alkylene oxide adduct, (3) polyalkylene glycol fatty acid ester, (4) fatty acid alkanolamide, (5) polyhydric alcohol fatty acid ester, (6) polyoxyethylene polyhydric alcohol fatty acid ester, ( 7) The solid cleaning agent for flush toilets according to claim 1, which is one or more of polyoxyethylene polyoxyalkylene polyhydric alcohol fatty acid esters. 3. The solid detergent for flush toilets according to claim 1, wherein the nonionic surfactant has higher solubility in cold water than in hot water. 4. A 1% aqueous solution of the alkali metal salt of carboxymethyl cellulose has a solution viscosity of 3000 at 25 ° C.
The solid cleaning agent for flush toilets according to claim 1, wherein the solid cleaning agent is cps to 25000 cps.