JP2001200291A - Solid agent for toilet cleaning - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid agent for toilet cleaning excellent in stainproof and bacteria-removing effects. SOLUTION: The solid agent for toilet cleaning comprises a fluorine- containing amphoteric substance and, incorporated therewith, at least one bactericide selected from the group consisting of a cationic bactericide, a phenolic bactericide, a carbanilide-based bactericide, a pyridine-based bactericide and an amine-based bactericide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid toilet cleaning agent excellent in antifouling and disinfecting effects.

[0002]

2. Description of the Related Art Conventionally, as solid toilet cleaning agents, those containing a surfactant such as an anionic surfactant or a cationic surfactant, an enzyme such as protease or lipase, and a chelating agent are known.

[0003]

However, these solids for toilet cleaning do not have sufficient antifouling and disinfecting effects, and there is room for improvement. In view of such a situation, an object of the present invention is to provide a toilet cleaning solid which is more excellent in antifouling and sterilization effects than conventional ones.

[0004]

Means for Solving the Problems As a result of diligent studies, the present inventors have found that the above-mentioned object can be satisfied by the following toilet-cleaning solid preparation, and have accomplished the present invention. (1) A fluorine-based amphipathic substance and a cationic fungicide, a phenol-based fungicide, a carbanilide-based fungicide, a pyridine-based fungicide and at least one fungicide selected from the group consisting of an amine-based fungicide were blended. A solid preparation for toilet cleaning, characterized by that: (2) The solid for toilet cleaning according to the above (1), wherein the disinfectant is a cationic disinfectant. (3) The fungicide is benzalkonium chloride, (1)-above
The solid preparation for toilet washing according to any one of (2).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The fluorine-based amphiphilic substance used for the solid preparation for toilet cleaning of the present invention is a substance having a property of being compatible with both polar and non-polar solvents and having a fluorine atom in the molecule. As the substance, a substance having a surface active action is suitable, and an anion type, a nonion type,
Cationic and amphoteric types are also included. Among these, nonionic or anionic types are preferable, and examples thereof include fluorinated alkyl POE (polyoxyethylene) esters, fluorinated alkyl hydrophilic group-containing oligomers, and fluorinated alkyl ester addition polymers. Further more preferably a fluorinated alkyl ester addition polymers Among these, the Examples of the perfluoroalkyl group (C _n F _{2n + 1)} can be exemplified _{C 6 F 13 ~C 10 F 21} . In the solid composition for toilet flushing of the present invention, 0.01 to 50% by weight, preferably 0.01 to 10% by weight of the above-mentioned fluorine-based amphiphilic substance can be blended.

[0006] The fungicides (antibacterial agents and disinfectants) used in the present invention include phenol fungicides such as triclosan, carbanilide fungicides such as trichlorocarbanilide, pyridine fungicides such as zinc pyrithione, and cetyl chloride. Examples include cationic fungicides such as pyridinium and benzalkonium chloride, and amine fungicides such as trialkyltriamine. Examples of the cationic fungicide include cetylpyridinium chloride, benzalkonium chloride and the like.
Grade ammonium salts are preferred, and benzalkonium chloride having an alkyl group of 12 to 16 is particularly preferred in consideration of stability in the preparation and sterilization efficacy. Benzalkonium chloride can be formulated stably against light, does not react with commonly used pigments, does not emit heavy metals (zinc, silver, etc.), and is resistant to septic tank bacteria. It has the advantage of not having any adverse effects. In the solid composition for toilet washing of the present invention, the above-mentioned bactericide can be blended in an amount of 0.01 to 50% by weight, preferably 0.01 to 10% by weight.

In the present invention, various components such as general surfactants, fragrances and dyes known in the art can be blended as long as the effects of the invention are not hindered. Specific examples are shown below. Examples of the surfactant include anionic types such as, for example, higher fatty acids such as myristic acid, stearic acid, palmitic acid, behenic acid, and oleic acid; potassium, sodium, monoethanolamine, diethanolamine, triethanolamine, and aminomethylpropanolamine acid. And the like; the above-mentioned alkali salts of ether carboxylic acids; higher alkyl sulfonates, and the like.

As a nonionic type, for example, POE
POE branched alkyl ethers such as octyldodecyl alcohol and POE-2-decyltetradecyl alcohol;
POE alkyl ethers such as POE oleyl alcohol ether, POE behenyl alcohol ether, POE stearyl alcohol ether and POE cetyl alcohol ether; sorbitan esters such as sorbitan monooleate, sorbitan monoisostearate and sorbitan monolaurate; POE sorbitan monooleate and POE
POE sorbitan esters such as E sorbitan monoisostearate and POE sorbitan monolaurate; glycerin fatty acid esters such as glyceryl monooleate, glyceryl monostearate and glyceryl monomyristate; POE glyceryl monooleate, POE glyceryl monostearate and POE glyceryl POE glycerin fatty acid esters such as monomyristate; POE dihydrocholesterol ester, POE hydrogenated castor oil, POE
POE hardened castor oil fatty acid esters such as hardened castor oil isostearate; POE nonylphenyl ether, PO
POE alkyl phenyl ether such as E-octyl phenyl ether; glyceryl ether such as ethylene glycol / propylene glycol block polymer, glyceryl isostearyl ether, glyceryl myristyl ether; POE glyceryl isostearyl ether;
POE glyceryl ethers such as E-glyceryl myristyl ether; polyglycerin fatty acid esters such as diglyceryl monostearate, decaglyceryl decastearate, decaglycerylpentane isostearate, decaglyceryl decaisostearate, and diglycerin diisostearate. Can be

The cation type includes, for example, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, dimyristyldimethylammonium chloride, stearylbenzyldimethylammonium chloride, dimyristyldimethylammonium methylsulfate and the like.

The amphoteric types include, for example, betaine lauryldimethylaminoacetate, betaine stearyldimethylaminoacetate, 2-alkyl-N-carboxymethyl-
N-hydroxyethyl imidazolinium betaine and the like. Examples of the amino acid type include sodium laurylaminopropionate.

These surfactants are contained in the composition in an amount of from 1 to 9%.
9% by weight, preferably 70 to 85% by weight can be added.

Examples of the flavor include essential oils extracted from lemon, orange, bergamot, grapefruit, lavender, rosemary, jasmine, rose, peppermint, eucalyptus, etc .; limonene, linalool, linalool acetate, borneol, citral, citronellal, menthol, Fragrances such as cineole are mentioned. These can be used alone or in combination,
1 to 30% by weight, preferably 5 to 20% by weight in the composition
Can be blended.

As the dye, a water-soluble legal dye is preferable. For example, Red No. 2, Red No. 3, Red No. 102, Red No. 104 (1), Red No. 105 (1), Red No. 106
No. 4, Yellow No. 4, Yellow No. 5, Blue No. 1, Blue No. 2, Green No. 3
No. Red 201, Red 205, Red 213, Red 214, Red 219, Red 227, Red 230 (1), Red 230 (2), Red 231 and Red 232, Orange No. 207, Yellow No. 202 (2), Yellow No. 203, Green No. 205, Blue No. 202, Blue No. 203
No., Blue No. 205, Brown No. 201, Red No. 401, Red No. 205, Red No. 503, Red No. 504, Red No. 506
No. 402, Yellow No. 402, Yellow No. 403 (1), Yellow No. 406, Yellow No. 407, Green No. 401,
Green No. 402, Purple No. 401, Black No. 401 and the like. These can be used alone or in combination to obtain a desired color tone, and can be incorporated in the composition in an amount of 1 to 20% by weight, preferably 5 to 10% by weight.

Further, according to the purpose, an acidic component, a pH adjuster, an enzyme, a chelating agent and the like may be added. Examples of the acidic component include an organic acid such as oxalic acid; an inorganic acid such as sulfamic acid; an acid salt such as ammonium bifluoride; and a phosphate such as metaphosphate and orthophosphate.

Examples of the pH adjuster include sodium bicarbonate, sodium carbonate, calcium hydroxide, sodium silicate, sodium tartrate, tartaric acid, sodium citrate, citric acid, acetic acid, sodium acetate, sodium gluconate and the like. . Examples of the enzyme include protease, lipase, amylase, pectinase, cellulase, lysozyme and the like. Examples of the chelating agent include ethylenediaminetetraacetic acid (EDTA),
Nitrilotriacetic acid (NTA), sodium gluconate, and the like.

In addition, specific gravity adjusters such as inorganic salts, antifoaming agents such as silicone oil, peroxides such as sodium percarbonate, potassium percarbonate and sodium perborate may be added.

The solid preparation for toilet cleaning of the present invention comprises a cube,
The shape may be a rectangular parallelepiped, a cylinder, a disk, a polygon, or the like. When used in a flush toilet water storage tank, it is preferable that at least one surface is flat so as to be easily attached to and fixed to the bottom of the tank. The solid agent may also be in the form of animals such as dolphins or plants such as leaves and flowers.

Further, the solid agent having the above-mentioned form may be wrapped in a water-soluble packaging material.
Cellulose derivatives such as methylcellulose, pidroxypropylcellulose and carboxymethylcellulose; starch derivatives such as soluble starch and starch glycol derivatives; natural polysaccharides such as pectin, carrageenan, guar gum, xanthan gum and the like; sodium polyacrylate, polyvinyl alcohol, polyethylene glycol and the like Synthetic thickening gelling agents are included. In addition to the above-mentioned usage forms, the solidifying agent of the present invention may be a container (for example, plastic, metal, ceramic, or a combination of these) installed inside or outside a flush toilet water storage tank. (A plastic hand washing unit installation container, etc.).

[0019]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

(Test Formulation) 60% by weight of a nonionic surfactant (POE / POP block polymer, POE alkyl ether, POE alkyl ester), 5% by weight of a dye (Blue No. 1), 0.1% by weight Fluorinated amphiphile (fluorinated alkyl addition polymer of C ₆ F _{13 to} C ₁₀ F ₂₁ ), 100% by weight of 1% by weight of one of various fungicides shown in Table 1, plus a fragrance and an inorganic salt % Toilet preparations (5 cm × 5 cm × 1.5 cm) were prepared.

(Sterilization Efficacy Test) Actual Use Concentration (20 pp
m), 0.1 ml of the test bacterium (Staphylococcus auresus) was added to 10 ml of the aqueous solution of each fungicide-containing preparation prepared in
It was left at room temperature for hours. The aqueous solution was inoculated into the SDCLP medium using a micro planter of Sakuma Seisakusho Co., Ltd.
After culturing at 1 ° C. for 1 day, the degree of bacterial growth was confirmed. Table 1 shows the results. In Table 1, .largecircle. Indicates a preparation having a disinfecting effect, and X indicates a preparation having no disinfecting effect.

[0022]

Table 1 Formulation No. Fungicide name Type Result 1. Triclosan phenol 〇2. 2. Trichlorocarbanitrite 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. 3. Symbolic Principle 系 4. Cetyl peridinium chloride cation type (quaternary ammonium salt) ５5. Hensadkonium chloride (C = 14) Cationic (quaternary ammonium salt) ６6. N-bis (3-aminofuropropyl) todecylamine amine-based 系 7. AGZ (trade name, made by Toa Gosei Co.) metal (silver) salt _{× [(Ag x H y Na} z Zr 2 (PO 4) 3; (x + y + z = 1)] 8. bi Osaito 981 (trade name , Manufactured by Taisho Technos) Organic nitrogen halogen compound × 9. Alkasite RT-D (trade name, manufactured by Osaka Kasei) Organic nitrogen compound × 10. Quercerin monocaprate Quercerin fatty acid ester type ×

Among the preparations which were confirmed to be effective in the above-mentioned sterilization efficacy test, the preparations of Nos. 1 to 5 in Table 1 were tested for sustained solubility, confirmation of the preparation color, and photostability as follows.

A flushing device (1)
Time interval, running water 3L, flushing period: 32
), The duration, dissolution period, dissolution state and shape change were confirmed. (Confirmation of formulation color) The color tone of the above-mentioned five formulations was visually confirmed, and the color of the liquid when dissolved in water was confirmed. (Light stability) The above five preparations were blister-packed and irradiated with ultraviolet rays continuously for 36 hours using a sun tester to visually confirm the state of the preparations.

The results are shown in Table 2. Table 2
In Table 1, those with excellent solubility, formulation color and light stability were indicated by 〇, and those with poor solubility, by ×.

[0026]

[Table 2] Formulation Flusink ゛ Color tone Light stability. No. 1 32 days 〇 〇 〇 No. 233 days 〇 〇 〇 No. 3 32 days 〇 〇 〇 No. 4 32 days 〇 〇 △ * No. 5 32 days 〇 〇 〇 No fungicide 32 days 〇 〇 〇

As described above, there was no problem in the preparation of the solid preparation for toilet flushing of the present invention. (When cetylpyridinium chloride of formulation No. 4 was used as a bactericide, the formulation was slightly discolored when irradiated with light, but this was not a problem.)

(Anti-fouling effect under actual use conditions) Among the ones which were confirmed to be effective in the above-mentioned disinfection efficacy test, No. 1 to No. 1 in Table 1
5 were evaluated for antifouling effects in actual use. 90 g of the test preparation is put in the tank of the toilet bowl,
Water was run continuously at time intervals and used for 4 months. The condition of the dirt in the toilet after 4 months can be determined by using a combination of a bactericide (bactericide) and a fluorine-based amphipathic substance, a combination of only a fluorine-based amphipathic substance, or both. The following evaluation criteria were used for comparative evaluations of the case where no water was added and the case where only water was supplied. ◎ High antifouling effect 〇 Antifouling effect △ Some effect × No effect The evaluation results are shown in Table 3.

[0029]

[Table 3]

(Consideration of the results) The addition of the fluorine-based amphipathic substance and the specific bactericide resulted in less adhesion of dirt than the fluorine-based amphipathic substance alone and not added. As described above, by mixing the fluorine-based amphiphilic substance and the specific bactericide, the effect of preventing contamination by synergistic action was recognized.

[0031]

The solid preparation for toilet cleaning of the present invention contains a fluorine-based amphipathic substance and a specific disinfectant, and removes and prevents dirt adhering to the toilet bowl or the toilet storage tank. Excellent soiling and sanitizing effects. And the effect becomes more remarkable by using a fluorine amphiphilic substance and a cationic fungicide, especially benzalkonium chloride.

Claims (3)

[Claims] 1. A fluorinated amphiphile, a cationic bactericide, a phenolic bactericide, a carbanilide bactericide,
A toilet cleaning solid composition comprising at least one bactericide selected from the group consisting of a pyridine bactericide and an amine bactericide. 2. The solid preparation for toilet cleaning according to claim 1, wherein the fungicide is a cationic fungicide. 3. The fungicide is benzalkonium chloride.
The solid for toilet cleaning according to any one of claims 1 to 2.