JPS5949280B2 - Solid deodorant cleaner for flush toilets - Google Patents

Description

[Detailed Description of the Invention] The present invention relates to polyethylene glycol (hereinafter abbreviated as PEG)
The present invention relates to a solid deodorizing cleaning agent for flush toilets which has a derivative of as a main component, and it relates to a solid deodorizing cleaning agent that can be used by being put into the water tank of a flushing toilet without using a container.

Various types of deodorant cleaning agents for flush toilets are known, including those that are used in containers. These are mainly composed of compounds with high solubility in water such as PEG and urea.
A container suspended in a water storage tank is a concentrated aqueous solution, and the deodorizing cleaning component usually diffuses into the water in the water storage tank along with the concentrated aqueous solution of the main component. In this method, it is time-consuming to attach and remove the container, and this often stains hands, clothes, and the area around the water tank. Moreover, since a container with a complicated shape is used, it becomes expensive. On the other hand, a method in which the solid deodorant cleaning agent is poured into a water tank without using a container is easier to handle, saves resources, and is less expensive because no container is used.

However, in this case, the deodorizing cleaning component acts only in the amount released into the water, so the following performance is required.

(1) The dissolution rate is appropriate and an effective amount of deodorant cleaning ingredients are released over a long period of time.

(2) Emit an effective amount of deodorizing cleaning ingredients even when flushing toilets are used continuously.

In addition, the deodorizing cleaning ingredient should not be released in excess even after long periods of non-use. (3) Retain its shape underwater.

(4) The entire solid substance dissolves in water and disappears as the deodorizing cleaning component is consumed.

The inventors of the present invention have conducted extensive research in order to produce a solid deodorizing detergent for flush toilets that combines these extremely difficult-to-achieve performances required without the use of a container.As a result, (a) the following general formula The compound represented by (g) and the following general formula (
11) The compound represented by (g)/(j=100/0
Mixture 25-8 consisting of a ratio of ~10/90 (weight ratio)
5% by weight, borax 5-40% by weight, (c) deodorizing ingredient 5
~20% by weight, and (iv) 5% by weight or more of the cleaning component, preferably 5 to 20% by weight, thereby achieving both the above performances (1) to (4) without the need for a container. It has been found that a solid deodorant cleaning agent for flush toilets can be obtained.

(However, m and n are the same or different, and 50 to 50
The present invention is based on this finding. R1, R2 and R3 are the same or different and are an alkylaryl group, an aryl group, an alkyl group, an alkenyl group or a fatty acid ester residue. The compounds represented by the general formula or general formula (11) used in the present invention are as follows. The degrees of polymerization m and n are the same or different and are 50 to 500. When m and n are less than 50, shape retention in water becomes poor and lumps or concentrated liquid may flow, resulting in a shortened shelf life. Furthermore, as m and n become smaller, it becomes difficult to dissolve in water, and agglomerates lacking active ingredients will remain in the water tank. On the other hand, M
, n exceeds 500, processing becomes difficult as high temperatures are required for processing. Preferable M and n are 50 to 250, particularly preferably in the range of 100 to 200. Rl, R2 and R3 in the above general formula are the same or different and are an alkylaryl group, an aryl group, an alkyl group, an alkenyl group or a fatty acid ester residue. Preferred alkylaryl groups include octylphenyl and nonylphenyl groups; aryl groups include phenyl; and alkyl groups preferably have 8 to 22 carbon atoms, including octyl, lauryl, cetyl, stearyl, and decyl groups. Alkenyl groups include oleyl groups, fatty acid ester residues include lauric acid ester residues, palmitic acid ester residues, stearic acid ester residues, oleic acid ester residues, linoleic acid ester residues, and erucic acid ester residues. Examples thereof include a group, a bristanoic acid ester residue, and the like. A mixture of the compound represented by the general formula (1) and the compound represented by the general formula () can be prepared by reacting the hydroxyl group of PEG with alcohol or acid to obtain
) can also be obtained by adjusting the amount of alcohol or acid when synthesizing the compound.

The ratio of the compound represented by general formula (1) to the compound represented by general formula (n) is usually the ratio of the compound represented by general formula (1) to the compound represented by general formula (1). Compound represented by formula ()=1
00/0 to 10/90 (weight ratio), preferably 75/25 to 25/75.

Among the compounds represented by general formula (g) or 01),
Preferred are higher fatty acid esters, particularly stearic acid esters. Although these compounds dissolve in water, the rate of dissolution is low, and a solid deodorant cleaning agent using them as a main component gradually dissolves in a water tank and releases the deodorizing cleaning component. Deodorizing ingredients include menthol, gunfur, naphthalene, paradichlorobenzene, mixed fragrances, and other substances that eliminate bad odors with fragrance, or zorpic acid, dehydroacetic acid, glycolic acid, malic acid, glyoxal, zinc chloride, and wood vinegar components. Substances such as these are used to eliminate bad odors by reacting with malodorous components. In addition, cleaning ingredients include surfactants with detergency of about HLB12 to 16, such as monononyl phenyl ether of PEG, ethylene glycol-propylene glycol protox copolymer, etc., and metal ion scavengers such as ethylenediaminetetraacetic acid. is used.

Further, when borax is contained in an amount of 5 to 40% by weight, the shape retention in water increases, and the material gradually dissolves from the surface while maintaining a certain shape until the end.

Borax in this case is not particularly limited, but it is preferable to use a commonly available decahydrate. Furthermore, in order to clearly determine the effective period of use as a deodorant cleaning agent, a coloring agent that is eluted at the same time as the deodorizing cleaning component is added.

Acidic dyes or direct dyes are preferred as the coloring agent, and green, blue, and navy blue dyes can give a sense of sterilization to running water. Preferred dyes include Foot Blue, Turkish Blue Direct Blue, and the like. As other components, fillers, thickeners, dissolution rate regulators, solubilizers used when oily aroma components are separated in water, bactericides, etc. are preferably used in an amount of 0 to 65% by weight.

Bulking agents are primarily water-soluble substances such as urea, melamine, acetanilide, glucose, magnesium chloride, and sodium phosphate.

Thickeners include high molecular weight PEGl polyvinyl methyl ether, polyvinylpyrrolidone, and the like. As the dissolution rate regulator, surfactants having an HLB of 1 to 6 can be suitably used, such as esters of mono- or polyhydric higher fatty acids such as ethylene glycol, propylene glycol, glycerin, sorbitol, and polyglycerin. Preferred dissolution rate modifiers include glycerin monostearate, triglycerin tristearate, and the like. ．． The solubilizer is a surfactant with an HLBl of about 3 to 16. The solid deodorant cleaning agent of the present invention is generally produced as follows.

(1) Place each ingredient in a container and heat while stirring until it becomes liquid.
In this state, thoroughly mix each component. The mixing temperature varies depending on the type and composition ratio of the components, but is preferably 70 to 100°C. (2) The mixed liquid is filled into a cup using a dispenser or the like, and when it is cooled, it solidifies at 40 to 90°C to obtain a solid deodorizing cleaning agent. Cover with film until ready to use. When a polypropylene cup is used, the solid deodorant cleaning agent can be easily removed from the cup.
3. When using, peel off the lid of the cup, remove the solid deodorizing detergent from the cup, and drop it into the water tank. The solid deodorizing cleaning agent No. 309 maintains its deodorizing cleaning effect for 20 to 40 days in ordinary household toilets.

3 Next, the present invention will be specifically explained with reference to Examples. The above ingredients were heated and placed in a container equipped with a stirring device, and the temperature was raised to 90°C.

The melt was mixed well and the mixture was filled into polypropylene cylindrical cups. When allowed to cool to room temperature, it solidified at about 50°C. The above ingredients were heated and placed in a container equipped with a stirring device, and the temperature was raised to 80°C. The melt was thoroughly mixed, and the mixture was filled into a cylindrical cup made of polypropylene 7. When allowed to cool to room temperature, it solidified at about 45°C. The above ingredients were heated and placed in a container equipped with a stirring device, and the temperature was raised to 90°C. The melt was mixed well and the mixture was filled into polypropylene cylindrical cups. When allowed to cool to room temperature, it solidified at about 50°C. Example 2 PEG (n=150-180) and stearic acid were mixed and heated to react, and when the degree of esterification reached approximately 1.5, the reaction was stopped to obtain a mixture.

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The above components were heated to 95° C. and a solid was obtained in the same manner as in Comparative Example 1.

Heat the above ingredients and put them in a container equipped with a stirring device.8
The temperature was raised to 0°C.

The melt was mixed well and the mixture was filled into polypropylene cylindrical cups. Upon cooling to room temperature, it solidified at about 45°C. The above ingredients were heated and placed in a container equipped with a stirring device, and the temperature was raised to 90°C. The melt was mixed well and the mixture was filled into polypropylene cylindrical cups. When allowed to cool to room temperature, it solidified at about 50°C. Comparative Example 3 PEG of Comparative Example 1
number average molecular weight 20 instead of monohigher fatty acid ester
A solid substance was obtained in the same manner except that ,000 PEG was used.

Example 5 The following experiment was conducted using the solids obtained in Examples 1 to 5 and Comparative Examples 1 to 3 (cylindrical solids with a diameter of 16 RR and a weight of 5 f!).

(1) Flowing water test A siphon was attached to a cylindrical container with a diameter of 1001 gft so that water could be continuously poured from above.

A solid substance was placed at the bottom, and 51 ml of water was forcibly replaced at a rate of once every 40 seconds, and the shape of the solid substance after 1 hour and the weight after drying were examined. (2) Still water test diameter 110w1
The solid material was placed at the bottom of a beaker, and water was added thereto.

After 1 hour and 24 hours of standing at 25°C, the depth of the blue color of the water was measured using a colorimeter at a wavelength of 62011 gt.

(3) Stirring test After the static water test, replace the water and 15 x 701I! The mixture was stirred using a 1 ton rectangular blade at 60 rpm for 5 minutes and 2 hours.

The depth of the blue color of the water was examined in the same manner as the static water test above.
In addition, the shape and weight of the solids were examined. (4) Validity period test A cylindrical solid object with a diameter of 30 mm and a weight of 30 f1 was placed in 20 locations in the water tank of a household flush toilet to examine its shelf life.

The average number of uses per day is 20 times, and the maximum amount of water per time is 12 times.
11 average was about 71, and the water temperature was 10-20°C.

Moreover, after one week, the diameter of the bottom surface of the cylindrical solid was measured.
The above results are shown in Table 1. As shown in Table 1, when the solid deodorizing detergent for flush toilets of the present invention is placed in water, it releases the active ingredient in a short time, and its concentration does not become extremely high even if it is left for a long time.

In addition, it has good shape retention in water and gradually dissolves from the surface, so it can be seen that it has a sufficient shelf life without using a container. Further, it can be seen that the solid deodorant cleaning agent for flush toilets of the present invention has excellent shape retention even when submerged in water for a long time, based on the rate of change in the diameter of the bottom surface of the cylindrical solid after one week.

Claims (1)

[Claims] 1 (a) A compound represented by the following general formula (I) and a compound represented by the following general formula (II) are (I)/(II)
= 25 to 85% by weight of a mixture consisting of a ratio of 100/0 to 10/90 (weight ratio), (b) 5 to 40% by weight of borax,
(3) A solid deodorant cleaning agent for flush toilets comprising 5 to 20% by weight of a deodorizing component and (d) 5% by weight or more of a cleaning component. (I) H-O■CH_2CH_2-O■__mR^1(
II) R^2-O■CH_2CH_2-O■_nR^3(
However, m and n are the same or different integers of 50 to 500, and R^1, R^2, and R^3 are the same or different and are an alkylaryl group, an aryl group, an alkyl group, an alkenyl group, or a fatty acid ester residue. ).