JP2001342496A - Fungicidal detergent composition for hard surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fungicidal detergent composition for a hard surface exhibiting high fungicidal and detergent effects on sporulating bacteria and molds. SOLUTION: This fungicidal detergent composition for the hard surface comprises one or more kinds selected from a hypochlorite and hypochlorous acid (A), one or more kinds selected from an amphoteric surfactant and a cationic surfactant (B) and a pH controlling agent (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a germicidal detergent composition for hard surfaces suitable for germicidal cleaning of hard surfaces such as plastics, metals, glass and tiles.

[0002]

[Prior Art] Food manufacturing plants, pharmaceutical manufacturing plants, hospitals,
Many facilities require a sanitary environment, such as nursing homes, kitchens and toilets. In these cases, in order to maintain a sanitary environment, frequent sterilization treatment of floors, walls, etc. and used equipment is indispensable.

For the sterilization and cleaning of these hard surfaces, liquid or powdered detergents, disinfectants, and disinfectants containing a surfactant or a disinfectant are mainly used. When a sterilization washing step is incorporated into an industrial manufacturing process, steps such as supply, mixing, and application (application, spraying, etc.) of the active ingredient are often automated.

[0004]

However, the conventional germicidal detergent for hard surfaces has a low germicidal effect on spores and molds which are difficult to sterilize, and provides a sufficient germicidal cleaning effect. Required a very high temperature and a long time treatment.

[0005]

According to the present invention, at least one kind selected from hypochlorite and hypochlorous acid (A) and at least one kind selected from amphoteric surfactants and cationic surfactants are provided. The present invention relates to a germicidal detergent composition for hard surfaces containing (B) and a pH adjuster (C).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As the hypochlorite of the component (A), alkali metal hypochlorites such as potassium hypochlorite and sodium hypochlorite, calcium hypochlorite, and hypochlorite Alkaline earth metal hypochlorites such as magnesium oxychloride and the like, and alkali metal hypochlorites are preferable,
Particularly, sodium hypochlorite is preferable. The component (A)
The effective chlorine concentration of the composition is preferably 1 to 5000 pp
m, more preferably 10 to 1000 ppm, even more preferably 50 to 500 ppm.

Examples of the amphoteric surfactant of the component (B) include amine oxides such as alkyldimethylamine oxide, betaines such as alkyldimethylamino fatty acid betaine and alkylcarboxymethylhydroxyethyl imidazolium betaine. Above all, carbon number 8-1
Alkyl dimethylamine oxide having an alkyl group of 8 is preferred. Examples of the cationic surfactant of the component (B) include a primary amine salt, a secondary amine salt, a tertiary amine salt, and a quaternary ammonium salt. Is particularly preferred. As the quaternary ammonium salt, at least one of the four substituents is an alkyl or alkenyl group having 8 to 28 carbon atoms in total, and the remainder is a benzyl group, an alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 5 carbon atoms. And a compound which is a group selected from a hydroxyalkyl group. An alkyl or alkenyl group having a total of 8 to 28 carbon atoms may be an alkoxyl group,
The composition of the present invention which may be substituted with an alkenyloxy group, an alkanoylamino group, an alkenoylamino group, an alkanoyloxy group or an alkenoyloxy group comprises the component (B) in an amount of 1 ppm to 5% by weight,
Further, the content is preferably 5 ppm to 1% by weight, particularly preferably 10 to 5000 ppm.

In the composition of the present invention, the weight ratio of the components (A) and (B) is (A) /
(B) = 10/1 to 1/10, more preferably 5/1 to 1/5, particularly preferably 5/1 to 1/10
It is 1/2.

Examples of the pH adjuster (C) include an alkali metal hydroxide, an alkaline earth metal hydroxide, an inorganic acid or a salt thereof, an organic acid or a salt thereof, and the like. Alkali metal hydroxides, alkaline earth metal hydroxides,
Examples include sodium hydroxide, potassium hydroxide, calcium hydroxide and the like. Inorganic acids or salts thereof include hydrochloric acid, sulfuric acid, sodium sulfate, sodium nitrate, sodium chloride, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, magnesium sulfate, magnesium nitrate, magnesium chloride, magnesium carbonate, phosphoric acid Trisodium, tripotassium phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium polyphosphate and the like can be mentioned. As the organic acid or a salt thereof, malonic acid,
Saturated dibasic acids such as succinic acid, glutaric acid, adipic acid and sebacic acid or salts thereof, and unsaturated dibasic acids such as fumaric acid and maleic acid or salts thereof are exemplified. Preferably a saturated dibasic acid or a salt thereof, more preferably 3 to 10 carbon atoms
And particularly preferred is succinic acid or a salt thereof.

The composition of the present invention has a pH (20 ° C.) of 3 to 8, more preferably 5 to 8, especially 5 to 7, from the viewpoint of improving bactericidal activity.
It is preferred that The component (C) is preferably used in such an amount that the pH falls within this range.

Further, the composition of the present invention can contain an anionic surfactant (D) for improving the permeability to soil. Examples of the anionic surfactant (D) include higher fatty acid salts, higher alcohol sulfates, higher alcohol sulfonates, sulfated fatty acid salts, sulfonated fatty acid salts, phosphate ester salts, fatty acid ester sulfate salts, and fatty acid esters. Sulfonate esters of esters, sulfates of higher alcohol ethers, sulfonates of higher alcohol ethers, acetates substituted with higher alcohol ethers, condensates of fatty acids and amino acids, alkylolated sulfates of fatty acid amides, fatty acids Alkylated sulfonates of amides, sulfosuccinates,
Alkyl benzene sulfonate, alkyl phenol sulfonate, alkyl naphthalene sulfonate, alkyl benzimidazole sulfonate, amide ether carboxylic acid or salt thereof, ether carboxylic acid or salt thereof,
N-acyl-N-methyltaurine or a salt thereof, amide ether sulfate or a salt thereof, N-acylglutamic acid or a salt thereof, N-amidoethyl-N-hydroxyethylacetic acid or a salt thereof, acyloxyethanesulfonic acid or a salt thereof,
N-acyl-β-alanine or a salt thereof, N-acyl-N
-Carboxyethyltaurine or a salt thereof, N-acyl-
Examples include N-carboxyethylglycine or a salt thereof, and alkyl or alkenylaminocarbonylmethyl sulfate or a salt thereof. The compounding amount of the anionic surfactant (D) is 1 ppm to 5% by weight, more preferably 10 ppm to
0.5% by weight, especially 50 to 500 ppm, is preferred.

The composition of the present invention is also suitable for a system using an automatic spray device and a spray gun. Further, foam washing and sterilization by adding a foaming agent is also possible.

[0013]

Industrial Applicability According to the present invention, a hard hard material which exhibits excellent detergency against hard surfaces and which exhibits excellent bactericidal activity against spores and mold even at a lower temperature and for a shorter time than ordinary operations. A germicidal cleaning composition for surfaces is obtained.

[0014]

EXAMPLES Examples 1 to 5 and Comparative Examples 1 to 3 The following tests were carried out using compositions having the components shown in Table 1. Table 1 shows the results. The effective chlorine concentration in Table 1 is measured according to JIS K-0101 “Iodine method”.

Each composition is prepared by mixing a predetermined amount of an aqueous solution of sodium hypochlorite (effective chlorine concentration: 60,000 ppm) with the component (B) or the component (D) to an ion concentration of twice the final compounding concentration. It was obtained by mixing equal amounts of a mixture diluted with exchanged water and a mixture of succinic acid diluted with ion-exchanged water to twice the final compounding concentration.

(1) Detergency After preparing each model stain of oil stain and protein stain,
The detergency of each was evaluated by the improved method of Rinatsu test. In each test, a test aqueous solution obtained by diluting the composition shown in Table 1 so as to have the effective chlorine concentration shown in Table 1 was used.

(1-1) Detergency of oil stains 20 g of fat and oil, 0.25 g of monoolein, and 0.1 g of oil red obtained by mixing beef tallow and soybean oil at a volume ratio of 1: 1 are dissolved in 60 ml of chloroform to prepare an oil stain liquid. I do. A set of six clean slide glasses is used, and the mass of each is measured up to 1 mg. The slide glass is immersed in an oil stain liquid at 25 ± 1 ° C. one by one to a position of about 55 mm for about 2 seconds, and after taking out the oil stain, the slide glass is taken out. A pool of oil stains adhering to the lower portion of the slide glass is sucked off using a cloth such as clean gauze or filter paper, and the oil stains are made uniform, air-dried at 25 ± 1 ° C., and the mass is measured. The model stained glass piece is used for the test within 1 hour or more and 2 hours or less. At this time, the amount of oil stain adhesion per six model stain glass pieces is set to 0.140 ± 0.010 g.

Six sets of the model stained glass pieces were placed at 25 ° C. ±
Wash at 2 ° C. for 5 minutes using a Lynatsu improved washing machine, and rinse with ion-exchanged water at 25 ± 2 ° C. for 30 seconds. The rinsed glass pieces are air-dried all day and night. The evaluation of the cleaning power is calculated from the weight of the model stained glass pieces before and after cleaning. That is, the weight difference between before and after washing is determined, and the washing rate (%) is calculated by the following equation. Washing rate (%) = (weight before washing−weight after washing) / amount of stains × 100 The washing rate was determined for each of the six glass pieces, and the average of the washing rates of the four pieces excluding the maximum value and the minimum value was determined. The value was taken as the cleaning rate of the composition.

(1-2) Detergency of protein stain 20 g of skim milk powder is diluted and dissolved in ion-exchanged water at 60 ° C. to make a total of 100 g, which is used as a protein stain liquid. 25 ° C ±
A clean slide glass is immersed in a protein stain solution at 1 ° C. one by one to a position of about 55 mm for about 2 seconds, and after the protein stain is attached, it is taken out. The accumulation of protein stains attached to the lower part of the slide glass is absorbed using a cloth such as clean gauze or filter paper, and the attachment of the protein stains is made uniform,
Air dry at 25 ± 1 ° C. This is repeated once again, and after one-sided dirt is completely removed, it is air-dried and denatured at 110 ° C. for 1 hour to obtain a test piece. This test piece is used for the test within 12 hours to 24 hours. The test piece is washed at 25 ° C. ± 2 ° C. for 5 minutes using a Lynatsu improved washing machine, and rinsed with ion exchanged water at 25 ± 2 ° C. for 30 seconds. After rinsing, 3 at 70 ° C
After drying for 0 minutes and coloring with a 1% by weight solution of erythrosine, the coloring area (S ₁ ) was measured by photographic judgment, and the initial area (before washing) was determined.
The washing rate (%) is calculated by the following equation from the protein stain area (S ₀ ). Cleaning rate (%) = (S ₀ −S ₁ ) / S ₀ × 100 The cleaning rate was determined for each of the six glass pieces, and the average value of the cleaning rates of the four pieces excluding the maximum value and the minimum value was calculated. The washing rate of the object was taken.

(2) Bactericidal activity (2-1) Spore killing test Bacillus subtilis ATCC663 which is a spore-forming bacterium
The bacteria pre-cultured in 3) on SCD agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.) were scraped with a platinum loop and suspended in 1 ml of sterilized water.
After heat treatment at 5 ° C. for 30 minutes, the mixture was centrifuged and washed twice and used for the test (10 ⁵ cells / ml).

0.1 ml of this spore bacterium solution for test is taken, and the composition comprising the components shown in Table 1 is inoculated into 10 ml of a test aqueous solution (temperature: 25 ° C.) diluted with sterilized ion-exchanged water.
Acted for 3 minutes at room temperature. Apply the bacterial contact solution within 10 seconds.
0 μl was collected and inoculated into a micro Petri dish (96-Cell Wells, CORNING) containing 0.2 ml of SCDLP medium for post-culture (containing 3.3% of sodium thiosulfate). Three
After culturing at 0 ° C. for 48 hours, the growth of the bacterium is visually observed, and whether or not the bacterium is growing on a micro Petri dish is observed. Sterilizing effective chlorine concentration) was determined. The effective chlorine concentration is measured according to JIS K-0101 “Iodine method”.

(2-2) Fungicidal test Mold (fungi, Aspergillus niger IFO634) was used as a test bacterium.
1) was cultured at 25 ° C. for 7 days using a PDA medium.
After the obtained cells were homogenized using a glass ball method, foreign substances were removed with sterile gauze to obtain a bacterial solution (about 10 ⁵ cell / m 2).
l). 0.1 ml of this bacterial solution was taken, and the composition comprising the components shown in Table 1 was inoculated into 10 ml of an aqueous solution (temperature: 25 ° C.) diluted with sterilized ion-exchanged water, and allowed to act at room temperature for 3 minutes. Collect 0.1 ml within 10 seconds and post-culture PD
A medium (containing 3.3% sodium thiosulfate) was inoculated. Incubate at 25 ° C for 7 hours, observe the growth of the bacteria with the naked eye,
Evaluation was performed in the same manner as described above.

[0023]

[Table 1]

(1): The value in parentheses indicates the effective chlorine concentration (the same applies hereinafter). (2): Amphitol 20N (manufactured by Kao Corporation, effective component 3)
5%) so that the concentration of the active ingredient became the value in Table 1. (3): Sanizole C (manufactured by Kao Corporation, effective content 50%)
The concentration of the effective component was adjusted to the value shown in Table 1 by using. (4): Emar 20C (manufactured by Kao Corporation, effective component 25)
%), The concentration of the active ingredient was adjusted to the value shown in Table 1. (5): Using Emulgen 106 (manufactured by Kao Corporation), the effective component concentration was adjusted to the value shown in Table 1.

Example 6, Comparative Example 4 Of the so-called electrolytic oxidized water obtained by the diaphragm method, hypochlorous acid water (pH (25 ° C.) 2.7, effective chlorine concentration 50 ppm) generated on the anode side was used. The pH was adjusted to 11 with an aqueous 0.1 mol / L sodium hydroxide solution to obtain a composition of Comparative Example 4 in Table 2. In addition, the above hypochlorous acid solution is
After adjusting the pH to 5 with an aqueous sol / L disodium succinate solution, the mixture was added so that the concentration of lauryl dimethylamine oxide (the same as in Example 1) became 25 ppm to obtain the composition of Example 6 in Table 2. A bactericidal power test was performed using them in the same manner as in Example 1;
Certain cases were marked "x". Table 2 shows the results.

[0026]

[Table 2]

Examples 7 to 11 and Comparative Examples 5 to 8 The following tests were carried out using compositions having the components shown in Table 3. Table 3 shows the results.

Each composition was prepared by mixing a predetermined amount of an aqueous solution of sodium hypochlorite (effective chlorine concentration: 60,000 ppm) with the component (B) and / or the component (D), which was twice the final compounding concentration. And succinic acid diluted to twice the final blending concentration with ion-exchanged water in equal amounts.

In each test, the composition shown in Table 3 was used.
A test aqueous solution diluted to have the effective chlorine concentration shown in Table 3 was used. The effective chlorine concentration in Table 3 is based on JIS K-
0101 "Iodine method". The components in Table 3 are the same as those in Table 1.

(I) Detergency 20 g of fat mixed with beef tallow and soybean oil at a volume ratio of 1: 1, 0.25 g of monoolein and 0.1 g of oil red are dissolved in 60 ml of chloroform to prepare an oil stain liquid. 6 clean glass slides (76 mm x 26 mm x 1 mm)
One set is used, and each mass is measured up to 1 mg. The slide glass is immersed in an oil stain liquid at 25 ± 1 ° C. one by one to a position of about 55 mm for about 2 seconds, and after taking out the oil stain, the slide glass is taken out. The pool of oil stains adhering to the lower part of the slide glass is sucked up using a cloth such as clean gauze or filter paper, and the oil stains are uniformly attached to the slide glass at 25 ± 1 ° C.
Air-dry with and measure the mass. The model stained glass piece is used for the test within 1 hour or more and 2 hours or less. On this occasion,
The amount of oil stain adhering to six pieces of model stained glass pieces was 0.
It should be 140 ± 0.010 g.

In a 300 ml beaker, place the test aqueous solution 300
ml (25 ° C.), a silicon hose having an air stone attached to the tip is immersed in the test aqueous solution, and air is sent by an air pump (flow rate: 1.5 liter / min) to generate foam. The overflowed foam is brought into contact with a piece of model stained glass one by one for 5 minutes, and rinsed with ion-exchanged water at 25 ± 2 ° C. for 30 seconds. The rinsed glass pieces are air-dried all day and night. The evaluation of the cleaning power is calculated from the weight of the model stained glass pieces before and after cleaning. That is, the weight difference between before and after washing is determined, and the washing rate (%) is calculated by the following equation.

Washing rate (%) = (weight before washing−weight after washing) / amount of stain × 100 The washing rate was determined for each of the six glass pieces, and the four washing pieces excluding the maximum and minimum values were washed. The average value of the ratio was defined as the cleaning ratio of the composition.

(II) Bactericidal activity Bacillus subtilis ATCC663 which is a spore-forming bacterium
The bacteria pre-cultured in 3) on SCD agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.) were scraped with a platinum loop and suspended in 1 ml of sterilized water.
After heat treatment at 5 ° C. for 30 minutes, the mixture was centrifuged and washed twice and used for the test (10 ⁵ cells / ml). 0.5 ml of this test spore bacterium solution was uniformly inoculated on one model soiled glass piece prepared in the same manner as in the above (1), and then air-dried to obtain a sterilization test glass piece.

The glass piece for sterilization test was brought into contact with the foam of the test aqueous solution generated in the same manner as in the above (I) for 5 minutes and immediately rinsed with sterile water. Before the glass piece surface dries,
A predetermined area (20 mm × 20 mm) of the glass piece was wiped off with a sterile cotton swab, and the cotton swab was immersed in 1 ml of sterilized water to suspend the deposit. 25 μl of the suspension was used for SCDL for post-culture.
0.2 ml of P medium (containing 3.3% sodium thiosulfate)
Micro Petri dish (Corning, 96-Cell Well)
s). After culturing at 30 ° C. for 48 hours, the growth of the bacteria was observed with the naked eye. Table 3 shows the results.

[0035]

[Table 3]

Example 12, Comparative Example 9 Of the so-called electrolytic oxidized water obtained by the diaphragm method, hypochlorous acid water (pH (25 ° C.) 2.7, effective chlorine concentration 50 ppm) generated on the anode side was used. PH was adjusted to 11 with an aqueous 0.1 mol / L sodium hydroxide solution, and polyoxyethylene lauryl ether (the same as in Comparative Examples 7 and 8) was added so as to have a concentration of 200 ppm.
Was obtained. Further, the above-described hypochlorous acid solution was added to 1 mo
After adjusting the pH to 5 with a 1 / L aqueous solution of disodium succinate, lauryl dimethylamine oxide (same as in Example 7) was added so as to have a concentration of 200 ppm to obtain a composition of Example 12 in Table 2. Using them, Examples 7 to
A test for bactericidal activity was performed in the same manner as in No. 11. Table 4 shows the results.

However, in this example, the contact time between the foam and the glass piece for the sterilization test was 10 minutes, and the temperature of the test aqueous solution for foam formation was 50 ° C.

[0038]

[Table 4]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 3/20 C11D 3/20 (72) Inventor Tetsuya Okano 1334 Minato 1334 Minato, Wakayama-shi, Wakayama Pref. (72) Inventor Toshikazu Higashi 1334 Minato, Wakayama City, Wakayama Prefecture, 1334 Kao Corporation Research Institute DA09 DA12 EB07 ED02 EE08 FA28 FA34 4H011 AA02 AA03 BA01 BA05 BB18 BC04 BC06 BC07 BC18 DA13 DG16

Claims (5)

[Claims] 1. A pH adjuster comprising at least one kind selected from hypochlorite and hypochlorous acid (A), at least one kind selected from amphoteric surfactants and cationic surfactants (B), and a pH adjuster And (C) a germicidal detergent composition for hard surfaces. 2. The germicidal detergent composition for hard surfaces according to claim 1, wherein the effective chlorine concentration is 1 to 5000 ppm. 3. The germicidal detergent composition for hard surfaces according to claim 1, wherein the pH adjuster (C) is at least one selected from organic acids and salts thereof. 4. The germicidal detergent composition for hard surfaces according to claim 1, further comprising an anionic surfactant (D). 5. The germicidal detergent composition for hard surfaces according to claim 1, which comprises an amine oxide as the component (B).