JPS61197697A - Detergent composition for flash toilet bowl - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a flush toilet bowl cleaning composition, and more particularly to a flush toilet bowl cleaning composition that has excellent stain removal and stain prevention effects.

[Conventional technology]

Conventionally, cleaning compositions containing surfactants, solvents, abrasives, etc., and alkaline cleaners such as hydrochloric acid (IJum), etc., have been widely used for cleaning flush toilets, etc. It had been.

However, although such cleaning compositions may be able to temporarily remove stains, they can hardly be expected to have a stain-preventing effect;
In addition, it has various disadvantages, such as the need to be very careful when using it in terms of safety, such as skin irritation, and the fact that it requires the use of a toilet brush, which requires a lot of effort.

In view of such workability and safety, in recent years, a method has been developed to continuously remove dirt from the toilet by releasing it into the flush water from a flush auto cleaner (toilet bowl auto cleaner) installed in the water tank of the flush toilet or inside the toilet bowl. prevent,
Cleaning compositions that clean and maintain cleanliness have come into use. There are two types of cleaning agent compositions: liquid and solid types, and these usually have surfactants, fragrances, and pigments as basic ingredients, and if necessary, solidifying agents, disinfectants, and deodorizers. The cleaning and antifouling effects on fecal stains are very poor, and most of them are no more than toilet air fresheners that emit colorants and fragrances into the flushing water. . As a result, even in toilets that use conventional flush auto-cleaners, yellowing can be seen on the inner surface of the toilet bowl, and a ring of dirt can form on the water seal. Therefore, even when such a cleaning agent composition is used up, the user is forced to use a conventional cleaning agent and clean the toilet bowl with a brush.

[Problem that the invention seeks to solve]

Therefore, there has been a desire for a cleaning agent composition for a flush autocleaner that can advantageously clean and remove dirt adhering to a flush toilet bowl and also has the effect of preventing dirt from adhering.

[Means for solving problems]

When a flush toilet is used continuously for a long period of time, dirt accumulates on the inside of the toilet and on the water reservoir surface, especially on the water seal. These include organic excreta such as decomposition products, microorganisms or their metabolites, etc.

Therefore, the inventor of the present invention conducted research on the properties of the dirt and the pollution mechanism, and based on the research on dirt removal methods and pollution prevention methods.
If you use a water-soluble substance with ld l effect and bleach,
The inventors have discovered that the above problems can be solved and have completed the present invention.

In other words, the present invention uses 0.1 to 60% by weight of a water-soluble substance having a threshold effect and 0.5 to 8% of a bleaching agent.
The first related to a flush toilet cleaner composition containing 0% by weight
The second invention relates to a flush toilet bowl cleaner composition further containing 1 to 70% by weight of a water-soluble surfactant.
This invention provides the following invention.

The water-soluble substance with a threshold effect used in the present invention is a water-soluble substance that has the function of suppressing the growth of crystal nuclei of inorganic substances such as calcium phosphate.
100 to 1500 polycarboxylic acid polymers, hydroxypolycarboxylic acids, polyaminophosphonic acids, and salts thereof.

Examples of polycarboxylic acid polymers having an average molecular weight of 51,100 to 1,500 include polyacrylic acid, polymethacrylic acid,
Examples include polymaleic acid, polyacetal carboxylic acid, acrylic acid-methacrylic acid copolymer, acrylic acid-maleic anhydride copolymer, methacrylic acid-maleic anhydride copolymer, and the like.

Examples of the hydroxypolycarbo/acid include citric acid,
Examples include malic acid, tartaric acid, and gluconic acid. Examples of the polyaminophosphonic acid include ethylenediaminetetramethidi/phosphonic acid, hexamethylenediaminetetramethine/phosphonic acid, diethylenetriaminepentamethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. These compounds can be used both in acid form and as alkali metal, alkaline earth metal, ammonium or amine salts. Among these water-soluble substances, hydroxypolycarboxylate salts, especially citrate salts, especially sodium citrate, are preferred.

These water-soluble substances having a threshold effect may be either liquid or solid, but solid substances are particularly preferred, and they can be used alone or in combination of two or more. The threshold effect of suppressing the growth of crystal nuclei of inorganic substances such as calcium phosphate due to such water-soluble substances is 0. It is expressed at 1 ppm or more, but if the concentration is too high, salting out may occur and have the opposite effect. Therefore, the water-soluble substance in the present invention has a concentration of 061 to 60p at the time of action.
pm, preferably 0.3 to 30 ppm, and for this purpose, the amount blended in the cleaning agent composition should be adjusted to 0.1 to 60 inches, particularly 0.3 to 30 inches. It is preferable to do so.

In the present invention, a chlorine-based or oxygen-based bleaching agent is used as the bleaching agent. Examples of chlorine bleaches include hypochlorous acid, dichloroisocyanuric acid, trichloroisocyanuric acid, alkali metal or alkaline earth metal salts thereof, or alkali metal salts of sulfuric acid; examples of oxygen bleaches include, for example. Percarbonic acid, perboric acid, persulfuric acid, monoperacid of aliphatic carboxylic acid, mono- or diperacid of aliphatic dicarboxylic acid, mono- or diperacid of aromatic carboxylic acid, or alkali metal or alkaline earth thereof. Examples include metal salts. Among these, hypochlorites, percarbonates, and perphthalates are particularly preferred.

These bleaching agents may be either liquid or solid, but solid ones are particularly preferred, and they can be used alone or in combination of two or more. The antifouling, cleaning and deodorizing effects of bleach are 0.5~
expressed at 80 ppm, preferably 1-70 ppm,
If it exceeds 80 ppm, there is a concern that it may affect septic tanks, etc., so the amount of bleach in the cleaning composition of the present invention should be 0.
5 to 80 inches, particularly 1 to 70 inches is preferred.

Further, the water-soluble surfactant blended in the second invention may be any of anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, but especially anionic surfactants. Ionic and nonionic surfactants are preferred.

Examples of anionic surfactants include alkylbenzene sulfonates, alkyl sulfate ester salts, alkyl ethoxy sulfate ester salts, olefin sulfonates, alkanesulfonate/acid salts, fatty acid salts, alkyl ethoxy7carbo/acid salts, and α-sulfonate salts. Fatty cloth surfactants include ethylene oxide/propylene oxide block copolymer, polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxypropylene alkyl ether, polyethylene glycol, polypropylene glycol, higher fatty acid alkanolamide, higher fatty acid glycol. Examples include esters, sucrose fatty acid esters, and the like. Among the a-ionic surfactants, alkyl ethoxy sulfate salts are preferred, and among the nonionic surfactants, polyoxyethylene higher alcohol ethers are preferred.

These surfactants can be used alone or in combination of two or more, and their amount is 1 to 50% in the detergent composition.
In particular, it is preferable to set the thickness to 2 to 25 inches.

In addition to the above-mentioned essential ingredients, the cleaning composition of the present invention contains alkali metal, alkaline earth metal, and ammonium salts of sulfuric acid, carbonic acid, hydrochloric acid, boric acid, silicic acid, and phosphoric acid, to the extent that the effects are not impaired. Or excipients such as silicic anhydride, fragrances, pigments, bactericides, preservatives, solidifying agents, thickeners, mold release agents, solvents, antifoaming agents,
Surfactants other than those of the present invention can be blended.

The detergent composition of the present invention can be in various forms such as liquid, solid, paste, powder, and powder, but is particularly preferably in the form of a solid cake.

The method for producing the cleaning agent composition of the present invention is not particularly limited, but for example, in the case of a solid cake, the above raw materials are uniformly mixed,
Prepared by extrusion in a screw extruder. The extruded bar is cut into appropriate lengths and filled into containers. Alternatively, the above-mentioned components can be divided into two parts and molded to form a two-component composition.

The cleaning agent composition of the present invention is used by being placed in a discharge container of a flush toilet bowl. In this case, the dispensing container releases a nearly constant composition during flushing with each flush, with a threshold of 0.1 to 60 ppm of water-soluble substances and 0.1 to 60 ppm of bleach, which has a threshold effect in the flush water of the flush toilet. 5-80pp
It is necessary to make it so that m.

〔Example〕

Although the present invention will be congratulated by giving examples to the arrows, the present invention is not limited to these examples. In addition, each test in Examples was conducted by the following method.

(1) Preparation of model stains Select a white ceramic piece as a test piece, attach it to the toilet bowl of a flush toilet, and apply stains as usual. After one month of use, the test piece was taken out, and after drying, those whose reflectance was within a predetermined range were used as model stains and samples for the cleanliness test.

(11) Cleaning power test method (1) Take an aqueous solution prepared by dispersing and dissolving each composition 200rn9 in tap water 2B in a beaker, add a test piece of model soil n prepared in advance to it, and stir with a stirrer. Leave it at room temperature. After 24 hours, the test piece was taken out and dried, the reflectance was measured, and the cleanliness rate was calculated using the following formula.

D: Clean 4 (ch) RO: Reflectance of unused test piece (%) RA: Reflectance of test piece with model dirt (ch) RB: Reflectance of test piece after cleaning (ch) (II+) Cleaning power Test method (
2) Attach a model soiled test piece to the toilet bowl of a flush toilet, and add 80P of each composition to tap water. The supernatant liquid of the aqueous solution prepared by dispersing and dissolving in
The product was discharged. After one month of use in this manner, the test piece was taken out, dried, and the total reflectance was measured, and the cleanliness rate was calculated using equation (I).

(1v) Cleaning power test method (3) Stop flushing the flush toilet for one month, and the accumulated dirt n
The cleaning power of each composition against (% dirt on the ring part and water seal part) was investigated. Regarding the composition of the present invention, the detergency test (
After discharging the aqueous solution for one month in the same manner as in 2), the comparative product was evaluated by visual judgment of the cleanliness of the surface of the trowel and toilet bowl that had been cleaned according to the specified usage method. The evaluation criteria are as follows.

○: Almost no dirt Δ: Partial dirt remains 5 ml of the supernatant liquid of the aqueous solution prepared by dispersing and dissolving it in tap water 22 was discharged for each flush using a metering pump. After one month of use in this manner, the test piece was taken out and dried, the reflectance was measured, and the stain resistance was calculated using the following formula.

SR: Antifouling 4 (chi) REAL Reflectance of test piece after cleaning for 1 month (ch) Rc: Reflectance of test piece after 1 month of non-cleaning 4 (%) RO: Also has the same meaning as above, and comparison After cleaning the test piece according to the specified usage method, attach it to the toilet bowl of a flush toilet, and
After several months of use, the test piece was taken out, dried, and its reflectance was measured, and the stain resistance was calculated using the following formula.

SR, antifouling rate (%) RD, reflectance of the test piece cleaned with the comparison product (chi) RG: reflectance after one month of use of the test piece cleaned with the comparison product before use (ch) RP: not yet Reflection 4 after using the treated test piece for one month (
H) (vl) Workability evaluation panel 10 people were asked to actually use the product of the present invention and the comparison product, and one month later, the ease of workability was investigated. The criteria for judgment are as follows.

○:? 5'C chestnuts are easy to clean Δ: It is somewhat difficult to make washed confectionery. ×: Cleaning work is difficult.

Example 1 Regarding the compositions shown in Table 1, the cleaning power against model stains was measured based on the cleaning power test fl). The results are shown in Table-1.

*1 Molecular weight 6000 *2 Molecule i 500 *3 Ethylenediaminetetramethylenephosphonic acid *4
High quality dry powder (60 pieces) Example 2 The compositions shown in Table 2 were measured based on the cleaning power test method (2) and the antifouling power test method.

The results are shown in Table-2.

1゛j1 Chop Margin Example 3 The cleaning power against this was measured by the cleaning power test method (3), and the stain-proofing power and workability were examined based on the stain-proofing power test method and the workability evaluation method, respectively. The comparison products were evaluated according to the specified usage instructions: 423 and 424 were cleaned by applying the standard usage amount to a toilet brush, and &25 was evaluated by placing the container in a low tank.

The results are shown in Table-3.

Margin Table 3 below: * High-grade cleansing powder (60%) [Effects of the invention] The cleaning agent composition of the present invention exhibits excellent effects in both cleaning power and antifouling power, and keeps flush toilet bowls clean. It was recognized that the method not only maintains a high temperature, but also is extremely easy to work with. On the other hand, the comparative product had to be cleaned using a toilet brush or the like, and although it had some temporary cleaning power, it had no antifouling power and required a great deal of effort. In addition, with respect to the comparative product (Mu25), which was aimed at simplicity, no satisfactory comparative product was found, such as having both cleanliness and antifouling functions, and requiring cleaning work with other comparative products.

that's all

Claims (1)

[Claims] 1. Water-soluble substance having threshold effect 0.1
A cleaning agent composition for flush toilet bowls, characterized in that it contains ~60% by weight and 0.5-80% by weight of a bleaching agent. 2. The flush toilet bowl according to claim 1, wherein the water-soluble substance having a threshold effect is a polycarboxylic acid polymer, hydroxypolycarboxylic acid, polyaminophosphonic acid, or a salt thereof having an average molecular weight of 100 to 1500. Cleaning agent composition. 3. Water-soluble substance with threshold effect 0.1
60% by weight of a flushing toilet bowl, 0.5-80% by weight of a bleaching agent, and 1-70% by weight of a water-soluble surfactant.