JP4099305B2 - Toilet washing solid agent - Google Patents

Description

【００２３】
前記の除菌効力試験で効果が認められたもののうち、表１の No.１〜５の製剤について、持続溶解性、製剤色の確認、光安定性を下記のとおり試験した。
【００２４】
上記の５つの製剤をフラッシング装置（１時間インターバル、流水３Ｌ、フラッシング期間：３２日）にかけ、持続時間、溶解期間、溶解状態と形状の変化を確認した。
（製剤色の確認）
前記の５つの製剤の色調を目視で確認、及び水に溶解させたときの液色を確認した。
（光安定性）
前記の５つの製剤をブリスター包装し、サンテスターを用い、連続３６時間紫外線の照射を行い製剤の状態を目視で確認した。
【００２５】
それらの結果は表２のとおりである。表２において、溶解性、製剤色、光安定性の優れたものを〇で示し、劣るものを×で示した。
【００２６】
【表２】

【００２７】
以上のとおり、本発明のトイレ洗浄用固形剤は製剤上の問題は認められなかった。(製剤No.4の塩化セチルピリジニウムを殺菌剤とした場合には、光を照射すると製剤に若干、変色があったが、特に問題にはならない程度であった。)
【００２８】
（実使用条件での防汚効果）
前記の除菌効力試験で効果が認められたもののうち、表１の No.１〜５の製剤について、実使用での防汚効果について評価を行った。
便器のタンク内に供試製剤９０ｇを投入し、２時間インターバルで連続的に流水を行い、４ケ月間使用した。４ケ月後の便器内の汚れの状態を、殺菌剤（除菌剤）とフッ素系両親媒性物質を配合しているもの、フッ素系両親媒性物質のみを配合しているもの、両者のいずれも配合しないもの、及び水のみを流水したものについて下記の評価基準で比較評価を行った。
◎ 高い防汚効果あり
〇 防汚効果あり
△ 若干効果あり
× 効果なし
評価結果を表３に示す。
【００２９】
【表３】

【００３０】
（結果の考察）
フッ素系両親媒性物質及び特定の殺菌剤を添加することにより、フッ素系両親媒性物質のみ及び添加していないものに比べ汚れの付着が少なかった。このように、フッ素系両親媒性物質及び特定の殺菌剤を配合することにより、相乗的な働きで汚れを防止する効果が認められた。
【００３１】
【発明の効果】
本発明のトイレ洗浄用固形剤は、フッ素系両親媒性物質及び特定の殺菌剤を配合したものであり、トイレ便器内やトイレ貯水タンク内に付着した汚垢の除去及び防汚効果、そして除菌効果に優れる。そして、フッ素系両親媒性物質とカチオン系殺菌剤、特に塩化ベンザルコニウムを用いることによりその効果はさらに顕著になる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a solid agent for toilet cleaning having excellent antifouling and sterilizing effects.
[0002]
[Prior art]
Conventionally, as a toilet cleaning solid agent, a combination of a surfactant such as an anionic surfactant and a cationic surfactant, an enzyme such as protease and lipase, and a chelating agent is known.
[0003]
[Problems to be solved by the invention]
However, these toilet washing solid preparations have not enough antifouling and sterilizing 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 agent that is superior in antifouling and sterilizing effects as compared with conventional ones.
[0004]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that the above-described problems can be satisfied by the antifouling and disinfecting solid agent of the flush toilet toilet described below, and have reached the present invention.
(1) 0.01 to 10% by weight of fluorinated alkyl (C ₆ F _{13 to} C ₁₀ F ₂₁ ) ester addition polymer as an active ingredient, 0.01% of benzalkonium chloride (alkyl group 12 to 16) 10% by weight is mixed and put into a flush toilet storage tank or stored in a storage body installed inside or outside the flush toilet storage tank, and the antifouling effect inside the toilet under running water is obtained. Solid agent for antifouling and disinfection of flush toilets .
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The fluorine-based amphiphilic substance used in the toilet cleaning solid agent of the present invention is a substance having a fluorine atom in the molecule having a property that is compatible with both polar and nonpolar solvents, and has a surface-active effect as the substance. Suitable are those having an anion type, nonionic type, cationic type and amphoteric type.
Among these, nonionic type or anion type are preferable, and examples thereof include fluorinated alkyl POE (polyoxyethylene) ester, fluorinated alkyl hydrophilic group-containing oligomer, and fluorinated alkyl ester addition polymer.
Of these, a fluorinated alkyl ester addition polymer is more preferable, and examples of the perfluoroalkyl group (C _n F _{2n + 1} ) include C ₆ F _{13 to} C ₁₀ F ₂₁ .
In the toilet cleaning solid composition of the present invention, the above-mentioned fluorine-based amphiphile can be blended in an amount of 0.01 to 50% by weight, preferably 0.01 to 10% by weight.
[0006]
As the bactericides (antibacterial agents and disinfectants) used in the present invention, phenolic bactericides such as triclosan, carbanilide bactericides such as trichlorocarbanilide, pyridine bactericides such as zinc pyrithione, cetylpyridinium chloride, chloride Examples include cationic fungicides such as benzalkonium and amine fungicides such as trialkyltriamine. As the cationic bactericidal agent, quaternary ammonium salts exemplified by cetylpyridinium chloride, benzalkonium chloride and the like are preferable, and in consideration of stability and disinfection efficacy in the preparation, chlorides having an alkyl group of 12 to 16 are particularly preferable. Benzalkonium is preferred. Benzalkonium chloride can be formulated to be stable to light, does not react with commonly used pigments, does not discharge heavy metals (zinc, silver, etc.), There is an advantage of not having an adverse effect.
In the toilet cleaning solid composition of the present invention, the above bactericidal agent can be blended in an amount of 0.01 to 50% by weight, preferably 0.01 to 10% by weight.
[0007]
Moreover, in this invention, unless the effect of invention is prevented, various components, such as a well-known general surfactant in the said field | area, a fragrance | flavor, a pigment | dye, can be mix | blended. Specific examples are shown below.
As surfactants, anionic types include, for example, higher fatty acids such as myristic acid, stearic acid, palmitic acid, behenic acid, oleic acid; potassium, sodium, monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanolamic acid The above-mentioned alkali salts of ether carboxylic acids; higher alkyl sulfonates, and the like.
[0008]
Nonionic types include, for example, POE branched alkyl ethers such as POE 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, sorbitan monolaurate; POE sorbitan esters such as POE sorbitan monooleate, POE sorbitan monoisostearate, POE sorbitan monolaurate; glyceryl monooleate, glyceryl monostearate Glycerin fatty acid esters such as rate and glyceryl monomyristate; POE glyceryl monoole POE glyceryl fatty acid esters such as POE glyceryl monostearate and POE glyceryl monomyristate; POE hydrogenated castor oil fatty acid esters such as POE dihydrocholesterol ester, POE hydrogenated castor oil, POE hydrogenated castor oil isostearate; POE nonyl phenyl ether; POE alkyl phenyl ethers such as POE octyl phenyl ether; ethylene glycol / propylene glycol block polymers, glyceryl ethers such as glyceryl isostearyl ether and glyceryl myristyl ether; POE glyceryl ethers such as POE glyceryl isostearyl ether and POE glyceryl myristyl ether; diglyceryl Monostearate, decaglyceryl decastearate, decaglyceryl pentane Stearate, decaglyceryl Le big Seo stearate, include polyglycerol fatty acid esters such as diglycerol diisostearate.
[0009]
Examples of the cation type include stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dimyristyl dimethyl ammonium chloride, stearyl benzyl dimethyl ammonium chloride, dimyristyl dimethyl ammonium methyl sulfate, and the like.
[0010]
Examples of the amphoteric type include lauryldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, and the like.
Examples of amino acid types include sodium laurylaminopropionate.
[0011]
These surfactants can be blended in the composition in an amount of 1 to 99% by weight, preferably 70 to 85% by weight.
[0012]
Examples of flavors include essential oils extracted from lemon, orange, bergamot, grapefruit, lavender, rosemary, jasmine, rose, peppermint, eucalyptus, etc .; limonene, linalool, linalool acetate, borneol, citral, citronellal, menthol, cineole A fragrance is mentioned.
These can be used alone or in combination, and can be incorporated in the composition in an amount of 1 to 30% by weight, preferably 5 to 20% by weight.
[0013]
The dye is preferably a water-soluble legal dye. For example, Red No. 2, Red No. 3, Red No. 102, Red No. 104 (1), Red No. 105 (1), Red No. 106, Yellow No. 4, Yellow No. 5, Blue No. 1, Blue No. 2, Green No. 3, Red No. 201, Red No. 205, Red No. 213, Red No. 214, Red No. 219, Red No. 227, Red No. 230 (1), Red No. 230 (2), Red 231, Red 232, Orange 207, Yellow 202 (2), Yellow 203, Green 205, Blue 202, Blue 203, Blue 205, Brown 201, Red 401, Red 205, Red 503, Red 504, Red 506, Orange 402, Yellow 402, Yellow 403 (1), Yellow 406, Yellow 407, Green 401, Green 402 , Purple 401, black 401 And the like.
These can be used alone or in combination as a desired color tone, and can be blended in the composition in an amount of 1 to 20% by weight, preferably 5 to 10% by weight.
[0014]
Furthermore, an acidic component, a pH adjuster, an enzyme, a chelating agent, etc. may be blended depending on the purpose.
Examples of the acidic component include organic acids such as oxalic acid: inorganic acids such as sulfamic acid: acidic salts such as ammonium bifluoride: phosphates such as metaphosphate and orthophosphate.
[0015]
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.
[0016]
In addition to this, a specific gravity regulator such as inorganic salts, an antifoaming agent such as silicone oil, a peroxide such as sodium percarbonate, potassium percarbonate, sodium perborate, etc. may be blended.
[0017]
The solid agent for toilet cleaning of the present invention can be in the shape of a cube, a rectangular parallelepiped, a cylinder, a disk, a polygon or the like. When used by being put into a flush toilet water storage tank, it is preferable that at least one surface is a flat surface so that it can be easily attached and fixed to the bottom of the tank.
In addition to this, the form of the solid agent may be in the form of animals such as dolphins and plants such as leaves and flowers.
[0018]
Further, the solid agent having the above-mentioned form may be wrapped with a water-soluble packaging material. Examples of such packaging materials include cellulose derivatives such as methyl cellulose, pyroxypropyl cellulose, carboxymethyl cellulose; soluble starch, starch glycol derivatives. Starch derivatives such as pectin, carrageenan, natural polysaccharides such as guar gum, xanthan gum; and synthetic thickening gelling agents such as sodium polyacrylate, polyvinyl alcohol, and polyethylene glycol.
In addition to the above usage forms, the solid agent of the present invention can be used for a storage body (for example, plastic, metal, ceramics, or a combination thereof) installed inside or outside the flush toilet storage tank. It can also be used by being housed in a plastic hand-washing section installation container.
[0019]
【Example】
EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
[0020]
(Test prescription)
60% by weight of nonionic surfactant (POE / POP block polymer, POE alkyl ether, POE alkyl ester), 5% by weight of dye (Blue No. 1), 0.1% by weight of fluorinated amphiphile (C ₆ F _{13 to} C ₁₀ F ₂₁ fluorinated alkyl addition polymer) Toilet cleaning preparation (100% by weight) by adding 1% by weight of one of the various bactericides shown in Table 1 and fragrances and inorganic salts ( Each of 5 cm × 5 cm × 1.5 cm) was prepared.
[0021]
(Bacteria elimination test)
0.1 ml of a test bacterium (Staphylococcus auresus) was added to 10 ml of each bactericide-containing preparation aqueous solution adjusted to the actual use concentration (20 ppm), and left at room temperature for 24 hours. The aqueous solution was inoculated into SDCLP medium using a Sakuma Seisakusho microplanter and cultured at 36 ° C. for 1 day, and then the degree of growth of the bacteria was confirmed. The results are shown in Table 1. In Table 1, ○ indicates a preparation having a sterilizing effect, and × indicates a preparation having no sterilizing effect.
[0022]
[Table 1]

[0023]
Among those whose effects were confirmed in the sterilization efficacy test, the preparations Nos. 1 to 5 in Table 1 were tested for continuous solubility, preparation color confirmation, and photostability as follows.
[0024]
The above five preparations were subjected to a flushing device (1 hour interval, running water 3 L, flushing period: 32 days), and the changes in duration, dissolution period, dissolution state and shape were confirmed.
(Confirmation of formulation color)
The color tone of the five preparations was visually confirmed, and the liquid color when dissolved in water was confirmed.
(Light stability)
The above five preparations were blister-packed and irradiated with ultraviolet rays for 36 hours using a sun tester to visually check the state of the preparation.
[0025]
The results are shown in Table 2. In Table 2, those excellent in solubility, preparation color and light stability are indicated by 〇, and those inferior are indicated by ×.
[0026]
[Table 2]

[0027]
As described above, the formulation for the toilet cleaning solid preparation of the present invention was not recognized. (When preparation No. 4 cetylpyridinium chloride was used as a disinfectant, the preparation was slightly discolored when irradiated with light, but it was not a problem.)
[0028]
(Anti-fouling effect under actual use conditions)
Among those whose effects were recognized in the sterilization efficacy test, the antifouling effect in actual use was evaluated for the preparations Nos. 1 to 5 in Table 1.
90 g of the test preparation was placed in the toilet tank, and water was continuously run at 2-hour intervals, and used for 4 months. After 4 months, the condition of the soil in the toilet bowl is either mixed with bactericide (disinfectant) and fluorinated amphiphile, or only fluorinated amphiphile. Comparative evaluation was carried out according to the following evaluation criteria for those not blended and those in which only water was run.
◎ High antifouling effect 〇 Antifouling effect △ Some effect × No effect Evaluation results are shown in Table 3.
[0029]
[Table 3]

[0030]
(Consideration of results)
By adding the fluorinated amphiphile and the specific bactericidal agent, the adhesion of dirt was less than that of the fluorinated amphiphile alone or not added. Thus, the effect which prevents a stain | pollution | contamination by a synergistic action was recognized by mix | blending a fluorine-type amphiphile and a specific disinfectant.
[0031]
【The invention's effect】
The toilet cleaning solid preparation of the present invention contains a fluorine-based amphiphile and a specific disinfectant, and removes and removes dirt adhered to the toilet bowl and toilet water tank. Excellent bacteria effect. And the effect becomes further remarkable by using a fluorinated amphiphile and a cationic fungicide, especially benzalkonium chloride.

Claims (1)

As active ingredients, 0.01 to 10% by weight of a fluorinated alkyl (C ₆ F _{13 to} C ₁₀ F ₂₁ ) ester addition polymer, and 0.01 to 10% by weight of benzalkonium chloride (alkyl group 12 to 16). Flushing toilet, which can be mixed into a flush toilet storage tank or stored in a storage body installed inside or outside the flush toilet storage tank to obtain an antifouling effect inside the toilet under running water Solid agent for antifouling and disinfecting toilet bowls .