JPS61197696A - Two-agent type flash toilet bowl cleanser composition - 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 [Field of Industrial Application] The present invention relates to a two-component flush toilet bowl cleaner composition, more specifically, a two-component flush toilet bowl cleaner composition having excellent stain removal and stain prevention effects. The present invention relates to cleaning compositions.

[Conventional technology]

Conventionally, cleaning compositions containing surfactants, solvents, abrasives, etc., in combination with acidic detergents containing hydrochloric acid as the main ingredient and alkaline detergents such as sodium hydroxide have been commonly used to clean flush toilets, etc. .

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, due to the safety concerns such as skin irritation, sufficient care must be taken when using the method, and the use of toilet brushes is labor-intensive.

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 Seal Auto Cleaner) installed in the water storage tank of the flush toilet or inside the toilet bowl. prevent,
Cleaning compositions that clean and maintain cleanliness have come into use. There are liquid types and solid types of this cleaning agent, but these usually have surfactants, fragrances, and pigments as basic ingredients, and if necessary, solidifying agents, disinfectants, and deodorizers. The cleaning and antifouling effects of toilet bowl cleaners and the like are very poor, and most of them are no more than toilet air fresheners that emit colorants and fragrances into the flushing water. And as a result,
Even in toilets that use conventional flushing AutoClean-9, it is rare for the inner surface of the toilet bowl to show yellowing or for a ring of dirt to form on the water seal. Therefore, even when such a cleaning agent composition is used, it is necessary to use a conventional cleaning agent and clean the toilet bowl with a brush. [Problem to be solved by the invention] There has been a desire for a cleaning agent composition for a flush autocleaner that can advantageously clean and remove dirt adhering to a toilet bowl and also has the effect of preventing dirt from adhering to the toilet bowl.

[Means for solving problems]

When a flush toilet is used continuously for a long period of time, colored dirt accumulates on the inner surface of the toilet and on the water reservoir surface, especially on the water seal. organic excreta, microorganisms or their metabolites, etc.

Therefore, the present inventor conducted research on the properties of contamination and the contamination mechanism, as well as research on methods for removing and preventing contamination based on the results.
ld) Effective water-soluble organic substances and insoluble inorganic substances are used in a specific ratio, and these ingredients are combined with bleaching agent 7, which is concerned about a decrease in stability when coexisting with other ingredients, separated into two agents. The inventors have discovered that the above problems can be solved by doing so, and have completed the present invention.

That is, the present invention provides a mucilage agent, which is a composition containing a stimulant, and the following:
0% by weight (b) A two-part type flush toilet bowl cleaner consisting of a B agent containing 1 to 95% by weight of an insoluble inorganic substance and having a weight ratio of (a) / (b) = 0.01-1. The first invention relates to a composition, and the second invention relates to a two-component flush toilet bowl cleaner composition, in which the B agent of this composition further contains 1 to 50% by weight of a surfactant. It is.

In the detergent composition of the present invention, the bleaching agent is
Chlorine type 3! An oxygen-based bleach is used. Examples of chlorine bleaches include hypochloric acid, dichloroisocyanuric acid, trichloroincyanuric acid, alkali metal or alkaline earth metal salts thereof, or alkali metal salts of chlorous acid. More specifically, sodium hypochlorite, potassium hypochlorite, lithium hypochlorite,
Calcium hypochlorite, hypochlorite dihydrate, -basic calcium hypochlorite, potassium dichloroisocyanurate, sodium trichloroisocyanurate, potassium trichloroisocyanurate, sodium trichlor 4
Examples include socyanurate. Among these, hypochlorite is particularly preferred.

Also, I! 12 Thread coloring agents include the following (a)-(l): (1) Organic peroxides that generate hydrogen peroxide in aqueous solution, and inorganic hydrogen peroxide adducts. , sodium carbonate) 13 um hydrogen peroxide adduct (sodium percarbonate), sodium trilyphosphate hydrogen peroxide adduct, 1-1 um pyrophosphate hydrogen peroxide adduct, urea hydrogen peroxide adduct, or 4N
Examples include a, So, -2H20, -N&C1, and the like.

There are also inorganic peroxides such as sodium perborate hydrate, sodium perborate tetrahydrate, sodium peroxide, and calcium peroxide. Among these, particularly preferred are sodium carbonate hydrogen peroxide adduct, sodium perborate hydrate, and sodium perborate tetrahydrate.

(2) Persulfate &) Monopersulfate Sodium monopersulfate, potassium monopersulfate, ammonium monopersulfate, etc. are included, and among these, potassium monopersulfate is the most preferred. Generally, potassium monopersulfate is Kl (So
S: Kuso4: is commercially available in the form of a double salt of 2SO4=2:l:l (theoretical effective oxygen concentration 5.2%).
:Commercially available product approx. 4.5%), b) Zopersulfates Sodium zopersulfate, Potassium zopersulfate, Ammonium zopersulfate, etc. ■Organic peracids Organic peracids include peracetic acid, perpropionic acid, perbutyric acid, Monoperacids of aliphatic carboxylic acids such as percaprylic acid and perlauric acid, phosphoric acid, glutaric acid, azogic acid,
Azelazonic acid, 1.9-nonanedicarboxylic acid, 1.10
-Decanicarpic acid, 1.11-hendecanezocalg
Monoperacids of aliphatic zocarboxylic acids such as phosphoric acid, 1,12-dodecanedicarboxylic acid, etc., or zoperacids, perbenzoic acids,
Monoperphthalic acid, zoperphthalic acid, monoperterephthalic acid, zoperterephthalic acid, 9-chlorperbenzoic acid,
monoaromatic carboxylic acids such as, and percarboxylic acid,
Alternatively, alkali metal salts, alkaline earth metal salts, etc. of these organic peracids are exemplified. Among these, monoperphthalic acid, zoperphthalic acid, dodecanedicarboxylic acid, and alkali metal salts or alkaline earth metal salts thereof are preferred.

Among these bleaching agents, chlorine bleach contains 40=
+00% by weight (hereinafter expressed as %) 1 to 60 in terms of available chlorine amount
It is preferable to mix so that the effective chlorine amount is 1%.
If it is less than 60%, sufficient cleaning power will not be obtained, and if it exceeds 60%, there is concern that it will affect the offshore tank and it will be dangerous to handle it at home. Further, the oxygen bleach is preferably blended so that the effective oxygen concentration is 0.2% or more. These bleaching agents can be used alone or in combinations of more than 200 million.

Moreover, an activator can be blended into Part A together with an oxygen bleach. Examples of the activator include nitrile compounds such as γ-cetonitrile and phthalonitrile; 0-acetylated compounds such as glucose pentaacetate and triacetin; N-acylated compounds such as tetraacetylethylenecyamine and tetraacetyl glycoluril; phthalic anhydride;
Examples include acid anhydrides such as phosphoric anhydride. These activators can be used alone or in combination of two or more.

When the activator is used in combination with an oxygen bleach, the oxygen bleach is 20-95%, especially 30-90%, and the activator is 5-7%.
It is preferable to mix the oxygen bleach to 0%, particularly 10 to 50%, and the weight ratio of the oxygen bleach to the activator to be O.l -10.

Part A can be in various forms such as liquid, solid, paste, powder, and granules, and powders, granules, and solid cakes are particularly preferred.

In the B agent of the detergent composition of the present invention, the water-soluble organic substance having a threshold effect of component (a) is a water-soluble organic substance having the function of suppressing the growth of crystal nuclei of inorganic substances such as calcium phosphate. Lycarzenic acid polymer, amino?
Examples include licarmenic acid, hydroxylicarmenic acid, polyaminophosphonic acid and salts thereof.

? For example, is Recarvone a polymer? Reacrylha,? Rimethacrylic acid? Limaleic acid? Examples include lyacetal carboxylic acid, acrylic acid-methacrylic acid copolymer, acrylic acid-maleic anhydride copolymer, and methacrylic acid-maledic anhydride copolymer, among which the average molecular weight is 1.
00 to 1500 is preferred. Examples of the aminocarzenic acid include ethylenecyaminetetraacetic acid and nitrilotriacetic acid. Examples of the hydroxypolycarboxylic acid include citric acid, malic acid, tartaric acid, and gluconic acid. Examples of polyaminophosphonic acids include ethylenecyaminetetramethylenephosphonic acid, hexamethylenecyaminetetramethylenephosphonic acid,
Examples include zoethylenetriaminebentamethylenephosphonic acid and aminotrimethylenephosphonic acid. These compounds can be used in acid form or as alkali metal, alkaline earth metal, ammonium or amine salts. Among these water-soluble organic substances, hydroxypolycarmenates, particularly citrates, particularly sodium citrate, are preferred.

These water bathing organic substances having a threshold effect may be either liquid or solid, but solid ones are particularly preferred, and these can be used alone or in combinations of 211 or more. The threshold effect of suppressing the growth of crystal nuclei of inorganic substances such as calcium phosphate by such water-soluble organic substances is expressed at O.lppm or more, but if the concentration becomes too high, salting out occurs and the opposite effect is exhibited. Therefore, the water-soluble organic substance in the present invention has a concentration of O, 1 at the time of action.
li#I to be ~60 ppm! It is necessary to do this, and for that purpose, the amount of the three drugs should be adjusted to 0.1 to 60%.
It is preferable to

In addition, as the insoluble inorganic substance that is the (b) component of agent B,
Examples include anhydrous silicic acid, alumina, and water-insoluble sulfates, carbonates, phosphates, silicates, and the like. Examples of water-insoluble sulfates include calcium sulfate and barium sulfate; examples of carbonates include calcium carbonate; and examples of phosphates include calcium phosphate, calcium hydrogen phosphate, and calcium dihydrogen phosphate. Examples of the silicates include sodium aluminosilicate, -S, -1-, -γ-luminosilicate potassium, aluminum aluminosilicate, calcium silicate, and the like. Among these, silicic anhydride and silicates are particularly preferred. Further, these insoluble inorganic substances are preferably in the form of fluid and powder, and can be used alone or in combination of two or more. The insoluble inorganic substance is blended in the B agent in an amount of 1 to 95%, preferably 1 to 70%.

Furthermore, the surfactant blended into agent B in the second invention may be any of anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants;
Among these, anionic surfactants and nonionic surfactants are preferred.

Examples of anionic surfactants include alkylbenzene sulfonates, alkyl sulfate ester salts, γ-alkylethoxy sulfur ester salts, olefin sulfonates, alkanesulfonates, fatty acid salts, alkyl ethoxycarboxylate salts, and α-sulfo fatty acids. salt, α-sulfo fatty acid ester salt,
Alkenyl succinates, phosphate ester salts, etc.; nonionic surfactants include ethylene oxide and delobylene oxide block co-? Rimmer? Lioxyethylene alkyl ether,? Lyoxyethylene alkylphenol ether,? Lioxypropylene alkyl ether,? Liethylene glycol? Examples include liderovirene glycol, higher fatty acid alkanolamide, higher fatty acid glycol ester, and sucrose fatty acid ester. Among the anionic surfactants, alkyl ethoxy sulfate salts are used, and what about nonionic surfactants?
Lioxyethylene higher alcohol ether is preferred.

These surfactants can be used alone or in combination of two or more, and the amount thereof is 1 to 50%, preferably 2 to 25% in the B agent. are liquid, solid, paste,
Although it can be in various forms such as powder and granules, it is preferably powder, granules, or solid cake in consideration of storage stability, workability during use, etc., and particularly preferred is solid cake.

When using Form B as a solid and gradually dissolving the composition by pouring or immersing it into water sealed in a flush toilet or water in a low tank, it is a technical issue how to control the dissolution. This is an important topic. As a result of extensive research on this point, we found that (1) the presence of water-soluble organic substances in Agent B promotes the dissolution of water-soluble organic substances, and they disappear in just a few weeks; (2) the presence of water-soluble organic substances in Agent B; It was found that the blending ratio of insoluble inorganic substances greatly affects solubility. Therefore, for at least 1 month, preferably from 3 to
In order to obtain a composition that can quantitatively control the dissolution of water-soluble organic substances for 4 months, it is preferable to form and prepare agent B using only insoluble inorganic substances without containing water-soluble inorganic substances. Also,
The blending ratio of component (a) and component (b) in agent B is (a)/(b)=0. It is necessary to keep the value within the range of 01 to 5.

In addition to the above-mentioned essential ingredients, the ingredients and/or B agent of the two-component flush toilet cleanser composition of the present invention include rust preventives, preservatives, fragrances, solvents, and colorants to the extent that the effects are not impaired. Additives that are commonly added to detergents, such as fillers and bulking agents, can be added. It is preferable to incorporate rust preventive agents, fragrances, and coloring agents into Part B. In addition, the weight ratio of human drug and B drug is (A drug)/(
B agent) = O, preferably from 1 to 10.0, particularly preferably from 0.2 to 5.0.

The method for producing the detergent composition of the present invention is not particularly limited, but for example, in the case of a solid cake, the above-mentioned raw materials for Part A or Part B are uniformly mixed and extruded using a screw extruder. Cut the extruded bar to an appropriate length. The thus-obtained mucilage and B agent are stored in separate containers or wrapped in film until use. The two-component flush toilet bowl cleaner composition of the present invention can It is used by filling a container capable of dispensing a certain amount and setting the container in a water seal or low tank of a toilet bowl, or by putting the cleaning composition of the present invention itself into a water seal or low tank. It is preferable to set the discharge container in the low tank rather than the water seal part, and it is preferable to provide an air tortoise so that the human agent and B agent are completely separated in the container and do not elute into the low tank until they are discharged by flushing. When the detergent composition of the present invention itself is added, the mucilage agent and agent B can be added at the same time. The mucilage agent and B agent of the cleaning composition of the present invention are usually used in a weight of 5 to 150 f.

〔Effect of the invention〕

The two-component flush toilet bowl cleaner composition of the present invention is constructed as described above, and has not only a stain removal effect but also an excellent antifouling effect.

〔Example〕

Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples. In addition, each test in Examples was conducted by the following method.

(a) Preparation of model soil Select a piece of white ceramic as a test piece, attach it to the toilet bowl of a flush toilet, and apply paper stain as usual. After one month of use, the test piece was taken out, and after drying, those that fell within a predetermined range as measured by a reflective wheel were used as model stains and samples for cleanliness testing.

(-) Cleaning power test method (a) An aqueous solution prepared by dispersing and dissolving each composition of human agent 1001q and B agent 100119 in 2 tK of tap water is placed in a beaker, and a test sample of the model stain prepared in advance is applied to the beaker. Soak and leave at room temperature while stirring with a stirrer. 24
After a period of time, the test piece was taken out and dried, the reflectance was measured, and the cleanliness rate was calculated using the following formula.

0-RA D: fW Cleaning rate % 11 Lo2 Reflectance of unused test piece (J) A = Reflectance of test piece with model dirt % RB = Reflectance of test piece after cleaning ■ (j) Clean Force test method (2) A test piece with a model stain is attached to the toilet bowl of a flush toilet, and a specified amount of mucus agent and agent B of each composition is added to 100 m of tap water and left to stand at room temperature to prepare a dead water solution. The supernatant liquid was discharged 5 times per flush using a metering system, and tap water was replenished for 5 days after each discharge. After 3 months of use in this way, the test piece was taken out, dried, and the reflectance was measured.
I) The cleanliness rate was calculated.

(av) Cleaning power test method (3) The cleaning of the flush toilet was discontinued for 3 months, and the cleaning power of each composition against accumulated dirt (% KIJ ring part and water seal part dirt) was investigated. Regarding the composition of the present invention, after discharging the aqueous solution for three months as in the cleaning power test (2),
For comparison products, after cleaning according to the specified usage instructions, visually judge the cleanliness of the toilet bowl surface.
Yosho evaluated it. The evaluation criteria are as follows.

O: Almost no dirt Δ: Partial dirt left Quantify the supernatant liquid of an aqueous solution prepared by adding a predetermined amount of the gum agent and agent B to 100% tap water and allowing it to stand at room temperature. 5f11 for every flash on the card! After discharge, tap water was refilled for 5 d. After using it in this way for 3 months, take out the test piece, dry it and measure the reflectance.
The antifouling rate was calculated using the following formula.

Ro Rc SR: Antifouling rate (to) ~: Reflectance of the test piece after being cleaned for 3 months A TLc = Reflectance of the test piece after being left uncleaned for 3 months R8 = Also has the same meaning as above. For comparison products, after washing 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 gear was taken out, dried, and its reflectance was measured, and the paper stain resistance was calculated using the following formula.

RO-R.

SR: Antifouling Ro: Reflection of test piece cleaned with comparison product Honsuzu Ro: Reflection after 3 months of use of test piece cleaned with comparison product before use! s (to) RF: Reflectance % of untreated test piece after 3 months of use (vi) Workability evaluation/? The products of the present invention and the comparative product were actually used by Nell IO, and the ease of workability was investigated after 3 months. The criteria for judgment are as follows.

O: Cleaning work is easy Δ: Cleaning work is somewhat difficult and poor
The cleaning power against model stains was measured based on ItC.

The results are shown in Table-1.

Margin below J Product name Toyo Builder (Toyo 1 Datsuri Zeolite) Hata 2 Product name Tokusil NR (Tokuyama Soda Formation) Pot 3 Product name Florai) R (Tokuyama Soda Formation) Fist 4 Highly Sarashi Powder (6
0%) Example 2 Regarding the compositions shown in Table 2, the cleansing group and antifouling group were measured based on the cleaning power test method (2) and the stain-proofing power test method, respectively.

The results are shown in Table-2.

Margins below: Product name Toyobuilder (zeolite manufactured by Toyo Soda) 2 Product name Tokusil NR (manufactured by Tokuyama Soda) 113 Product name Fluorai) R (manufactured by Tokuyama Soda) ◆ 4 High-grade Sarashi powder (
60%) Example 3 Using the cleaning agent composition of the present invention and the comparative product shown in Table 3,
The cleaning power against model stains was measured using the cleaning power test method (2), and the cleaning power against toilet stains was measured using the cleaning power test method (3). Comparative products were evaluated according to the specified usage instructions: N119 and Yo20 were cleaned using a toilet brush, and Nn21 was evaluated by placing the container in a low tank. Ta. Table 3 shows the results.
Shown below.

Margin below: 1 Product name Tokuseal NR (manufactured by Tokuyama Soda) Geki 2 Product name
Fluorai) R (manufactured by Tokuyama Soda) Sai 3 Product name Toyobuilder (zeolite manufactured by Toyo Soda) Kasa 4 High-grade Sarashi powder (60%) The cleaning composition of the present invention has excellent effects in both cleaning power and antifouling power. Not only does it keep the toilet bowl of a flush toilet clean, but it has also been found to have extremely good workability.

- 10,000, Comparative products 19 and N120 had to be cleaned using a toilet brush, etc., and although they had some temporary cleaning power, they had no antifouling power at all and required a lot of effort to clean. eAlso, the comparison product Nn21, which was aimed at simplicity, did not have any cleanliness or antifouling functions, and required cleaning work with other comparison products, so no satisfactory comparison product was found.

Example 4 Regarding the compositions shown in Table 4, the cleaning power against model stains was measured based on the cleaning power test method (a). The results are shown in Table 4.

The following is a blank space.Product name: TOYOBUILDER (zeolite manufactured by Toyo Soda) 1.Product name TOKUSHIEL NR (manufactured by Tokuyama Soda) ◆3.Product name
Fluorite 8 (manufactured by Tokuyama Ichida)'Example 5! ! Regarding the composition shown in -5, the cleanliness rate and antifouling rate were measured based on the cleaning power test method (2) and the antifouling power test method, respectively. The results are shown in Table-5.

1 product name with blank space below Toyobuilder (zeolite made by Toyo Soda) +12 product name Tokusil NR (Tokuyama Sodabu) Ken 3 product name Fluorite R (Tokuyama Soda layer) 114 monopersulfate potassium double salt (manufactured by Dune) Example 6 Using the cleaning agent composition of the present invention and comparative products shown in Table 6,
The cleaning power against model stains was measured using the cleaning power test method (2), and the cleaning power against toilet stains was measured using the cleaning power test method (3). and investigated workability. As for comparative products, according to the specified usage instructions, N119 and M20 were cleaned by applying the standard usage amount to a toilet brush, and I'4121 was evaluated by placing the container in a four-tank. The results are shown in Table-6.

The following margin is ml.Product name: Tokusil NR (manufactured by Tokuyama Ichida) Product name: Fluorite R (manufactured by Tokuyama Soda) ◆3-Monopersulfate potassium double salt (manufactured by Dune) The composition of the present invention has cleaning and antifouling properties. In all cases, it was found that the method not only exhibited excellent effects and kept flush toilet bowls clean, but also was extremely easy to work with. On the other hand, comparison products 11 & 119 and floor 20 had to be cleaned using a toilet brush, and although they had temporary cleaning power, they had no antifouling power at all.
The comparison product t1kL21, which was designed for simplicity, required a great deal of labor to perform the work.The comparison product, t1kL21, had no cleanliness and antifouling functions, and it required cleaning work with other comparison products.
No satisfactory comparison products were found.

Claims (1)

[Claims] 1. Part A, which is a composition containing a bleaching agent, and the following (a)
and (b), (a) a water-soluble organic substance having a threshold effect.
0.1 to 60% by weight (b) Two agents consisting of B agent containing 1 to 95% by weight of an insoluble inorganic substance and having a weight ratio of (a)/(b) = 0.01 to 5.0 Cleaner composition for type flush toilets. 2. Claim 1, wherein the water-soluble organic substance having a threshold effect is selected from the group consisting of polycarboxylic acid polymers, aminopolycarboxylic acids, hydroxypolycarboxylic acids, polyaminophosphonic acids, and salts thereof. The two-component flush toilet bowl cleaner composition described above. 3. Part A, which is a composition containing a bleaching agent, and the following (a)
, (b) and (c), (a) Water-soluble organic substance with threshold effect
Contains 0.1 to 60% by weight (b) insoluble inorganic substance 1 to 95% by weight (c) surfactant 1 to 50% by weight, the weight ratio of which is (a)/(b) = 0.01 to 5 A two-component flush toilet bowl cleaner composition comprising Agent B.