JPH11228433A - Antibacterial agent imparted with deodorizing ability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject antibacterial agent effective, in particular, against food positioning bacteria such as pathogenic Escherichia coil O-157 and Legionella bacterial, by including phytonicide and organic matter bearing tropolone skeleton. SOLUTION: This antibacterial agent contains, as active ingredients, (A) pref. 0.3-30 wt.% of phytoncide (e.g. an extract prepared by extracting about 180 kinds of organic compounds using each unique squeezing equipment and vacuum dry distillation column from 35 kinds of plants with the main stocks including Cryptomeria japonica, white cedar (Hinoki), Abies firma, Urtica thumbergia, Cinnamomum camphora, Pins Thunbergii, Pinus densiflora, Picea jezoensis, persimmon, Sasa albo-marginata, Artemisia princeps, tea, Betula tauschii, perilla frutescens crispa, aloe, Zanthoxylum piperitum and Gynostemma pentaphyllum, followed by blending the resultant respective extracts), and (B pref. 0.1-2 wt.% of organic substance(s) bearing tropolone skeleton (e.g. hinokitiol, β-dolabrin), and pref. further, (C) 0.5-10 wt.% of an emulsifier and (D 0.5-5 wt.% of organic acid(s). It is preferable that this antibacterial agent is made to a gel-like material by the further addition of a gelatinizer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an antibacterial agent having a deodorant property, comprising a plant-derived component as its active ingredient.

[0002]

2. Description of the Related Art Generally, a plant deodorant is obtained by extracting organic compounds from leaves, stems, etc. of a plant by a squeezing method, vacuum distillation, or the like, and mixing the organic compounds extracted from several types of plants. It has high safety because it contains plant-derived components as active ingredients. However, antibacterial properties are not generally imparted to such deodorants, and deodorant antibacterial agents having both antibacterial properties and deodorant properties are desired.

[0003] In recent years, food poisoning due to food poisoning bacteria has occurred in various places at any time due to the spread of heating equipment in cooking facilities and the like. In particular, pathogenic Escherichia coli O157 is a source of infection. Identification is also a difficult and major social problem. In addition, circulating warm water baths (so-called 24-hour baths), which purify and circulate hot water in bathtubs, have become widespread, but since hot water at around 40 ° C is always stored, various germs are easy to propagate, especially for pneumonia. It has been pointed out that the causative Legionella bacterium is easy to propagate, which is a problem.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an antibacterial agent having a deodorant property, comprising a plant-derived component as its active ingredient. In particular, it is to provide an effective antibacterial agent against food poisoning bacteria such as pathogenic Escherichia coli O157 and Legionella bacteria.

[0005]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies and found that phytoncide, which has plant extracts extracted from many plants as active ingredients and has deodorant properties, The present inventors have found that by combining an organic substance having a tropolone skeleton such as hinokitiol and β-drabulin, which are considered to have an antibacterial effect, a high deodorizing effect and a high antibacterial effect can be obtained, and the present invention has been completed. That is, the antibacterial agent imparted with the deodorant of the present invention,
Phytoncide and an organic substance having a tropolone skeleton.

In Russian, phytoncide refers to an aromatic substance (essential oil component) having a bactericidal action that is released together with oxygen when trees and grasses undergo carbon assimilation. Phytoncide has a deodorizing effect and deodorizes odors by neutralizing and canceling. It is preferable that an emulsifier is further contained in addition to the phytontide and the organic substance having a tropolone skeleton. As the organic substance having the tropolone skeleton, hinokitiol and β-drabrin are preferable. It is preferable to add a gelling agent to form a gel.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. As an example of phytoncide in the present invention, cedar, cypress, fir tree, nettle, camphor, black pine, red pine, spruce pine, persimmon, kuma bamboo, mugwort, tea, birch, perilla, aloe, sansho, amacha zuru, etc. Approximately 180 kinds of organic compounds are extracted from 35 kinds of plants by a unique squeezing device and vacuum distillation apparatus, and there is an extracted extract in which these are blended. Such an extract is water-soluble and has a high deodorizing effect.

Examples of the organic substance having a tropolone skeleton include hinokitiol (also known as β-thyaprisin), β-drabrin, and derivatives thereof. Hinokitiol is an oil-soluble crystalline substance and has strong antibacterial properties. Hinokitiol may be either a natural product or a synthetic product. Natural products are found in Aomori Hiba oil, Taiwan Hinoki oil, Western Red Cedar oil and others. Natural products contain the same amount of hinokitiol as well as β-Drabulin, which has the same antibacterial properties as hinokitiol. Therefore, natural products are more advantageous in cost than synthetic products.

Since phytontide is water-soluble and hinokitiol as an organic substance having a tropolone skeleton is oil-soluble, an emulsifier (surfactant) is added to uniformly mix them. Such an emulsifier is not particularly limited as long as both can be uniformly mixed and emulsified, such as castor oil. Further, when an organic acid, an organic acid salt or an organic acid ester is added, the emulsifiability is increased. Examples of such organic acids include citric acid, sodium citrate, triethyl citrate and the like. Water is used as the solvent, but alcohol can also be added because hinokitiol has alcohol solubility. The water used here is preferably ion-exchanged water that does not contain impurities such as chlorine and minerals.

The mixing ratio of the above components varies depending on the type of components used, but when at least one of hinokitiol and β-drabrin is used as the organic substance having a tropolone skeleton, phytontide 0.3 to 30% by weight, hinokitiol or β-Drabrin 0.1 to 2% by weight, emulsifier 0.5 to 10% by weight, organic acids 0.5 to 5% by weight, and the remaining solvent is used. If the amount of phytoncide is too small, the deodorizing effect becomes insufficient, and if it is too large, the cost increases. If the amount of hinokitiol is too small, a sufficient antibacterial effect cannot be obtained, and if it is too large, the cost increases. If the amount of the emulsifier or the organic acid is too small, the emulsification becomes insufficient and hinokitiol or β-drabulin is crystallized and precipitated. On the other hand, if the amount is too large, the emulsifier and the like become cloudy and the amount of the precipitate increases.

As a form of use, it can be used as an aqueous solution (liquid substance). However, for use in a refrigerator, in a car, indoors, etc., it is preferable to put it in a container as a gel substance to volatilize the active ingredient. It is convenient. For use in a so-called 24-hour bath, a liquid substance can be added to and mixed with bath water, but a gel-like substance packed in a container can also be used by installing it in an air intake of a circulating warm bath. it can.
To obtain a gel, a water-absorbing resin may be added as a gelling agent. Phytontide, hinokitiol or β
-The active ingredient such as dravulin has volatility, and by making it into a gel, the surface area is increased to promote the volatilization of the active ingredient, thereby enhancing the deodorizing effect and the antibacterial effect. When left in the air as a gel, the water in the water-absorbent resin evaporates. At this time, the water evaporates with the active ingredient adsorbed on the surface of the resin.

When used as a gel, the water-absorbent resin is blended in an amount of about 4 to 15% by weight based on the whole gel. If the compounding ratio is too small, the surface area becomes insufficient and the volatility of the active ingredient deteriorates, and if it is too large, the volatility improves, but the bulk specific gravity decreases and a large container must be used to contain the same amount of the active ingredient. Have to be.

[0013]

The present invention will be described more specifically with reference to the following examples. These examples do not limit the scope of the claims. In these examples, phytoncide manufactured by Tokai Kosan Co., Ltd. (trade name “Smernark”) was used as phytoncide, and hinokitiol manufactured by Ogawa Koran Co., Ltd. (trade name “hinokitiol”) was used as hinokitiol. This hinokitiol does not contain β-Drabulin. In addition, "Smernak"
Liquid, specific gravity 1.0037, oil content 0.2%, organic acid 0.
37%, surfactant equivalent 1.38%, free alkali 0
%. “Hinokitiol” is a crystal, a crystalline powder or a lump, having a melting point of 48 to 52 ° C., a loss on drying of 0.5% or less, a content of 98.0 to 105.0%, a heavy metal content (as Pb) of 20 ppm or less, and an arsenic content. It is 2 ppm or less (as As ₂ O ₃ ).

[Antimicrobial Effect Test] The antimicrobial effect of each of "Smernark" alone, catechin alone, "hinokitiol" alone, and a mixed solution of "Smernark" and "hinokitiol" was tested.

EXPERIMENTAL EXAMPLE 1 A solution of "Smernark" having a predetermined concentration was used as a test solution, and a bacterial solution of Escherichia coli (serotype O157: H7) was inoculated into the test solution, and allowed to act at room temperature. Were examined for the presence of surviving bacteria.

Escherichia coli as a test bacterium, serotype O157: H
7. Vero toxin non-producing strain (Escherichia coli ATCC 4388
8) was used. When preparing the bacterial solution, use an NA medium (normal agar medium (manufactured by Eiken Chemical Co., Ltd.)) at 37 ± 1 ° C.
The cells pre-cultured for 24 hours were inoculated again into the NA medium, and 37 ±
The cells were cultured at 1 ° C. for 16 to 20 hours, and the cells thus obtained were uniformly dispersed in physiological saline to prepare a bacterial solution so that the number of cells per ml was about 10 ⁸ . As a test solution,
Specimen (“Smernark”) undiluted solution, 10
5, 2.5% (V / V) solutions were prepared and used as test liquids. Then, 10 ml of the test solution was inoculated with 1 ml of the bacterial solution and allowed to act at room temperature. After 0.5, 1, 3, and 6 hours, one loopful of the loop was added to an NB medium (normal broth containing 0.2% meat extract ( Inoculation and culture (2 days at 37 ° C)
Then, the presence or absence of growth was confirmed. Table 1 shows the results. The sign “+” in the table indicates that there is growth, and the sign “−” indicates that there is no growth.

[0017]

[Table 1]

Experimental Example 2 Catechin was used as a sample, and catechin was purified with purified water.
The test was performed in the same manner as in Experimental Example 1 except that 0, 0.5, and 0.1% (W / V) solutions were prepared and used as test solutions. Table 2 shows the results.
Shown in The sign “+” in the table indicates that there is growth.

[0019]

[Table 2]

EXPERIMENTAL EXAMPLE 3 "Hinokitiol" was used as a sample, and "hinokitiol" was dissolved in a 5% (V / V) ethanol solution at 1.0 and 0.1%.
Tests were conducted in the same manner as in Experimental Example 1 except that 1, 0.01 and 0% (W / V) solutions were prepared and used as test solutions. Table 3 shows the results. However, 0% test solution is only ethanol solution,
This is to prove that there is no antibacterial effect. The sign “+” in the table indicates that there is growth, and the sign “−” indicates that there is no growth.

[0021]

[Table 3]

Experimental Example 4 A test solution was prepared by adding about 1% of "hinokitiol" to a 2.5% (V / V) solution of "Smernarch", and the test solution was inoculated with bacterial solutions of various bacteria. And the presence of surviving bacteria in the test solution was examined over time.

Test bacteria (1) Escherichia coli, serotype O15
7: H7, non-verotoxin-producing strain (Escherichia coli ATCC
43888), (2) Escherichia coli IFO 397
2), (3) Staphylococcus aureus I
FO 12732), (4) Salmonella enteritid
is IFO 3313), (5) Vibrio parahaem
olyticus IFO 12711) was used.

When preparing a bacterial solution, E. coli (O15
7: H7), Escherichia coli, Staphylococcus aureus and Salmonella were cultured on NA medium (normal agar medium (manufactured by Eiken Chemical Co., Ltd.)) at 37 ± 1 ° C. for 16 to 24 hours.
The NA medium was inoculated again and cultured at 37 ± 1 ° C. for 16 to 20 hours. The cells thus obtained were uniformly dispersed in physiological saline, and the number of cells per ml was about 10 ^8. The liquid was adjusted. For Vibrio parahaemolyticus, 3% NaC
l NA medium (NA medium supplemented with 3% sodium chloride)
At 37 ± 1 ° C. for 16-24 hours at 3% N
Inoculate the aCl-added NA medium again at 37 ± 1 ° C, 16-2
After culturing for 0 hour, the cells thus obtained were uniformly dispersed in a 3% sodium chloride solution, so that the number of cells per ml was about 1
Was prepared cell suspension such that 0 ^8. The test solution is
To 80 ml of a 2.5% (V / V) solution of Smernak,
4m of 20% (W / V) ethanol solution of "hinokitiol"
Obtained by adding l.

Then, 10 ml of the test solution was inoculated with 1 ml of the bacterial solution, allowed to act at room temperature, and after 30 minutes, 1, 3 and 6 hours, one loopful of NB medium (normal broth containing 0.2% meat extract) was added. (Manufactured by Eiken Chemical Co., Ltd.)
C. for 2 days) to check for growth. For Vibrio parahaemolyticus, an NB medium supplemented with 3% NaCl (NB medium supplemented with 3% sodium chloride) was used instead of the NB medium. Table 4 shows the results. The symbol "-" in the table indicates that there is no growth.

[0026]

[Table 4]

Experimental Example 5 A mixture of "Smernarch" and "hinokitiol", wherein the amount of "hinokitiol" was 0.75%, 0.5%
% And 0.25%, respectively, as test liquid 1), test liquid 2) and test liquid 3). These test liquids were inoculated with a bacterial solution and allowed to act at room temperature. The presence or absence of bacterial growth was observed over time.

As test bacteria, (1) Escherichia
coli IFO 3972), (2) Staphylococ
cus aureus IFO 12732). When preparing the bacterial solution, first, the cells are pre-cultured in an NA medium (normal agar medium (manufactured by Eiken Chemical Co., Ltd.)) at 37 ± 1 ° C. for 16 to 24 hours, and then inoculated into the NA medium again. Then, the cells were cultured at 37 ± 1 ° C. for 16 to 20 hours. Subsequently, the bacterial cells thus obtained were uniformly dispersed in physiological saline, and the bacterial solution was adjusted so that the number of bacteria per ml was about 10 ⁸ . In addition, test solutions 1), 2),
3) is a 2.5% (V / V) "Smernark" solution 8
It was obtained by adding an appropriate amount of ethanol containing 20% (W / V) of "hinokitiol" to 0 ml.

Then, 1 ml of the bacterial solution prepared as described above was inoculated into 10 ml of each of the test solutions 1), 2) and 3) and allowed to act at room temperature. 10, 30, 60 and 180 minutes later, one platinum loop was weighed and NB medium (meat extract 0.
Ordinary bouillon with 2% added (Eiken Chemical Co., Ltd.))
Was inoculated and cultured (cultured at 37 ° C. for 2 days), and the presence or absence of growth was observed. Table 5 shows the results. The symbol "-" in the table indicates that there is no growth.

[0030]

[Table 5]

As can be seen from the above experimental results, the use of "Smelnarck" alone against Escherichia coli (O157: H7) has an antibacterial effect in a stock solution, but no effect upon dilution. Catechin has no antibacterial effect. "Hinokitiol" has an antibacterial effect. In a mixture of "Smernarch" and "hinokitiol", E. coli (O157: H
7) A stronger antibacterial effect is observed against other bacteria (Escherichia coli, Staphylococcus aureus, Salmonella, Vibrio parahaemolyticus). In addition, in the case where "Smernarch" and "hinokitiol" are mixed, the antibacterial effect is recognized when the amount of "hinokitiol" is 0.25% or more.

[Production of gel-like material ] Gel-like material 1) 2.5% by weight of "Smernarch", 1.0% by weight of "hinokitiol", 5% by weight of unmodified alcohol (ethanol), polyoxyethylene-cured castor as emulsifier 2.0% by weight of oil (manufactured by Nippon Surfactant Industry Co., Ltd., trade name NIKKOL HCO-50) and polyoxyethylene hydrogenated castor oil (manufactured by Japan Surfactant Industry Co., Ltd., trade name: NIKKOL HCO-60)
2.0% by weight, citric acid 0.3% by weight, sodium citrate 0.2% by weight, water-absorbent resin (manufactured by Kuraray, trade name: KI gel 201K) 4.0% by weight, and the remaining ion-exchanged water "Hinokitiol" was dissolved in undenatured alcohol, and "hinokitiol", "Smernark" and other components dissolved in alcohol were dissolved in ion-exchanged water and uniformly mixed. Next, a water-absorbent resin was added to and mixed with this mixture to obtain a pale yellow translucent gel-like substance 1).

Gel 2) A pale yellow translucent gel treated in the same manner as described in 1) except that the mixing ratio of unmodified alcohol (ethanol) was 20.0% by weight. Compound 2) was obtained. The gel-like substance 1) and the gel-like substance 2) have an alcohol odor because they contain alcohol, but when left for 2 to 3 days, the alcohol volatilizes and the alcohol odor disappears.

Gel 3) 2.5% by weight of "Smernarch", 1.0% by weight of "hinokitiol", 3.0% by weight of triethyl citrate, polyoxyethylene hydrogenated castor oil (manufactured by Nippon Surfactant Industries, Ltd.) as an emulsifier 1.0% by weight of water-absorbent resin (manufactured by Kuraray, trade name: KI gel 201K)
4.0% by weight, with the balance being ion-exchanged water, "hinokitiol", triethyl citrate, NI
KKOL HCO-50 was mixed, and a part of ion-exchanged water was added thereto, followed by emulsification with a mixer. Next, a water-absorbent resin was added to and mixed with this mixture to obtain a pale yellow translucent gel 3). This gel 3) was substantially odorless.

Gel-like substance 4) Triethyl citrate, polyoxyethylene hydrogenated castor oil (manufactured by Nippon Surfactant Industry Co., Ltd., trade name NIKKOL HCO-50) and water-absorbing resin (manufactured by Kuraray, trade name KI Gel 201)
Except that the compounding ratio of K) was set to 7.0% by weight, 2.0% by weight, and 7.0% by weight, respectively, gel-like material 4) was treated in the same manner as described above for gel-like material 3). Obtained.

[Antibacterial effect test 1 of gel-like substance] A gel-like substance 3) was used as a specimen 1), and a gel-like substance 2) was used as a specimen 2).
As shown in FIG. 1, a gel material (specimen) 10 is packed in a container 11 and a plate medium 12 coated with bacterial solutions of various bacteria.
Into a sealed container (about 2.7 liters)
After culturing at 10 ° C. and 35 ° C. in No. 3, the viable cell count was measured.

As the test bacteria, those used in Experimental Example 4 and Legionella (Legionella pneumophila GIFU 913) were used.
4) was used. When preparing a bacterial solution, E. coli (O15
7: H7), Escherichia coli, Staphylococcus aureus and Salmonella were cultured on NA medium (normal agar medium (manufactured by Eiken Chemical Co., Ltd.)) at 37 ± 1 ° C. for 16 to 24 hours.
The NA medium was inoculated again and cultured at 37 ± 1 ° C. for 16 to 20 hours. The cells thus obtained were uniformly dispersed in a phosphate buffer so that the number of cells per ml was about 10 ^3. A bacterial solution was prepared. For Vibrio parahaemolyticus, 3% Na
The cells pre-cultured at 37 ± 1 ° C. for 16 to 24 hours in a Cl-added NA medium (NA medium containing 3% sodium chloride) were used.
% NaCl-supplemented NA medium and inoculated again at 37 ± 1 ° C, 16
After culturing for about 20 hours, the cells thus obtained were uniformly dispersed in a 3% sodium chloride solution, and the number of cells was adjusted so that the number of cells per ml was about 10 ³ . For Legionella, 37 ± 1 on B-CYEα agar medium (Polymedia)
The cells pre-cultured at 16 ° C. for 16 to 24 hours are again inoculated on a B-CYEα agar medium and cultured at 37 ± 1 ° C. for 16 to 20 hours, and the obtained cells are uniformly dispersed in a phosphate buffer. The number of bacteria was adjusted so that the number of bacteria per ml was about 10 ³ .

For Escherichia coli (O157: H7), Escherichia coli, Staphylococcus aureus and Salmonella, 0.1 ml of the bacterial solution was spread on an SA plate medium (standard agar medium, manufactured by Eiken Chemical Co., Ltd.) 12 10 and placed in a closed container 13 and cultured at 10 ° C. for 7 days and at 35 ° C. for 2 days, and the viable cell count was measured. For Vibrio parahaemolyticus, an SA plate medium supplemented with 3% NaCl (SA medium supplemented with 3% sodium chloride) was used instead of the SA plate medium. For Legionella, 0.1 ml of the bacterial solution was smeared on B-CYEα agar medium 12, placed in a closed container 13 together with sample 10, cultured at 10 ° C. for 7 days and at 35 ° C. for 5 days, and the number of viable bacteria was measured. Also,
Those cultured without the specimen 10 (control) were also tested. Table 6 shows the results. In Table 6, the symbol "-"
Indicates that the cells did not grow.

[0039]

[Table 6]

From the results shown in Table 6, it can be seen that even when the antibacterial agent of the present invention is made into a gel, the active ingredient volatilized from the gel has a high antibacterial effect on various bacteria. In addition, about Staphylococcus aureus, Vibrio parahaemolyticus, and Legionella, it turns out that a microbial cell does not grow at 10 degreeC, and is weak to low temperature.

[Test of antibacterial effect of gel-like substance 2] Using the above-mentioned gel-like substance 4) as a sample, an antibacterial effect test on various bacteria in a refrigerator (about 294 liters) was performed.

As test bacteria (1) Enterohemorrhagic Escherichia coli O1
57, VT-2 producing strain (Escherichia coli IID 959),
(2) Escherichia coli IFO 3972, (3)
Staphylococcus aureus IFO 1273
2), (4) Salmonella Typhimurium IFO
12529), (5) Vibrio parahaemolytic
us IFO 12711).

About enterohemorrhagic Escherichia coli, Escherichia coli, Staphylococcus aureus and Salmonella, after culturing in an SCD medium for 18 hours, and uniformly dispersing in a phosphate buffer, the number of bacteria per ml becomes about 10 ^4. Was prepared as described above. For Vibrio parahaemolyticus, 3% NaCl
SCD medium supplemented (SCD medium supplemented with 3% sodium chloride)
After culturing for 18 hours, the cells were uniformly dispersed in a 3% NaCl-added phosphate buffer to obtain a cell suspension prepared so that the number of cells per ml was about 10 ⁴ .

0.1 ml of the bacterial solution prepared as described above is smeared on an agar medium for a sensitive disk (manufactured by Nissui Pharmaceutical Co., Ltd.), and the sample (gel-like substance 4) has been placed for 24 hours. It was placed in a refrigerator (about 294 liters, 10 ° C.). Then, the presence or absence of growth of each test strain in this refrigerator was 1,
Observations were made after 3, 6, 24 hours and one week. As a control, the presence or absence of growth of each test strain in a refrigerator (about 294 liters, 10 ° C.) containing no sample was also observed. Table 7 shows the results. The sign “+” in the table indicates that there is growth, and the sign “−” indicates that there is no growth.

[0045]

[Table 7]

As shown in Table 7, in the control, growth was observed in all the test strains after 24 hours or 1 week, whereas when the sample was added,
No growth was observed in any of the test bacteria. From these results, it can be seen that when the gel of the antibacterial agent having the deodorizing property of the present invention is placed in a refrigerator, it has an antibacterial effect against various bacteria.

[Test 3 for Antibacterial Effect of Gel-like Material] As shown in FIG. 2, about 200 liters of hot water 16 of about 40 ° C. was stored in a bathtub 15 and a circulating hot bath apparatus 17 was installed.
The circulating warm bath apparatus 17 was operated so as to keep the temperature around 0 ° C., and the antibacterial effect of the gel-like substance 3) 28 on Legionella was tested. For comparison, blank tests were also performed when ozone was applied, when chlorine was added to the bath water 16, and when blank water was used. Here, the addition amount of ozone is 0.05
Approximately 0.1 g / hour, and continuously operated for 8 hours. Chlorine was added so that the initial concentration of chlorine in the bath water 16 became 1.5 ppm. During the test, the ambient temperature of the chamber was about 50 ° C.

As shown in FIG. 3, the circulating warm bath apparatus 17 sucks bath water 16 from a suction nozzle 19 by a pump 18, removes large debris such as hair and lint by a hair catcher 20, and removes scale by a cartridge filter 21. The foreign matter is prevented from being mixed into the pump 18 by suction, and the bath water sucked up by the pump 18 is sent to the filter media 22a and 22b while pressurizing. Organic substances and various germs are adsorbed and removed by the filter media 22 a and 22 b, and heated and maintained by the heater 23, and are discharged from the discharge nozzle 24 into the bath 15. Reference numeral 25 denotes an ozone generator which can connect the ozone generated from the ozone generator 25 to the discharge nozzle 24 via an air tube 26 and discharge the ozone from the discharge nozzle 24. The ozone generator 25 was operated to apply ozone (otherwise, the ozone generator 25 was not operated). Then, the gel-like substance 3) 2 is inserted into the air intake port 27 of the ozone generator 25.
8 was connected, and the vaporized antibacterial agent was discharged from the discharge nozzle 24. In this case, the ozone generator 25 is not operated, and only the air is discharged from the discharge nozzle 24.
It was sent to. In FIG. 3, reference numeral 30 denotes a suction hose, reference numeral 31 denotes a discharge hose, and reference numeral 32 denotes a check valve. Table 8 shows the test results.

[0049]

[Table 8]

As can be seen from the results in Table 8, the antibacterial effect can be recognized by the ozone treatment after continuous treatment for about 8 hours. However, if the treatment is not continued for a long period of several hours or more, a sufficient antibacterial effect can be obtained. I can't. In the case of adding chlorine, a high antibacterial effect is recognized, but the allowable amount recognized by the Ministry of Health and Welfare (1.
0 ppm) or less, and the residual chlorine concentration decreases with the passage of time. However, it is not preferable because the residual chlorine odor (calcium odor) remains. In contrast, in the case of the gel-like material of the present invention, after 4 hours, the number of bacteria was 1000 CFU / 10
It becomes 0 ml or less, and a sufficient antibacterial effect is recognized. At the same time, it has a deodorizing effect, so that bath water and indoor deodorizing can be preferably performed.

[Test for Deodorizing Effect of Gel-like Material] A predetermined amount of the above-mentioned gel-like material 1) 180 g (sample 1)) and gel-like material 2) 170 g (sample 2)) were placed in a container having a diameter of 72 mm and a height of 55 mm. Stuffing,
With the upper part of the container opened, it was installed in various places to test the deodorizing effect. Table 9 shows the results.

[0052]

[Table 9]

From the results shown in Table 9, it can be seen that the deodorizing effect is good at any equipment location. In addition, when installed in a refrigerator, freshness of fresh food such as vegetables placed in the refrigerator is 20 to 4 times higher than when no gel-like material is installed.
It was held for about 0% longer. This is probably because the antibacterial effect was exhibited.

[Analytical Test for Content of Heavy Metals, Poisons, etc.] Liquid substances obtained by treating in the same manner as described in 3) above except that no gelling agent was added, heavy metals, toxic substances, etc. Content analysis test. Table 10 shows the results.
From the results in Table 10, it can be seen that no heavy metals and no toxic substances were detected from the antibacterial agent of the present invention.

[0055]

[Table 10] [Acute oral toxicity test in mice] OECD Chemical Toxicity Test Guideline (1987) using the same liquid substance as used in the above [Analytical Test for Content of Heavy Metals, Toxins, etc.]
In accordance with, an acute oral toxicity test (limit test) in mice was performed at the Japan Food Research Laboratories. As test animals, 4-week-old ICR male and female mice were purchased from Japan SLC Co., Ltd., and preliminarily reared for about one week to confirm that there was no abnormality in health, and then used in the test. Five test animals were housed in polycarbonate cages, each being housed in a breeding room set at a room temperature of 23 ± 2 ° C. and an illumination time of 12 hours / day. Feed (mouse / rat solid feed (Lab MR Stock, manufactured by Nihon Nosan Kogyo Co., Ltd.)) and drinking water (tap water) were allowed to be taken freely.

The test and control groups each used 10 males and 10 females, and the test animals were fasted for about 4 hours before administration. After measuring the body weight, in the test group both males and females were 20 ml / k
Specimens were administered a single oral gavage using a gastric probe at a dose of g. The control group received 0.6 ml of purified water for males and 0.5 ml for females in the same manner. The observation period was 14 days, and the administration was performed frequently on the administration day and once a day from the next day. Body weight was measured every week after administration, and comparison between groups was performed at a significance level of 5% by t-test. All animals were necropsied at the end of the study period.

As a result of the above test, no deaths were observed during the observation period for both males and females. As a clinical symptom, in the test group, a decrease in locomotor activity was observed in all cases from a few minutes after administration in both males and females, writhing reaction and abnormal body posture (prone position) were observed in 2 males and 1 female. Was. In addition, staggered walking was also observed in four males and four females. The agony reaction was 30 minutes after administration,
Other symptoms generally recovered after 5 hours, and 1 hour after administration.
No abnormalities were seen after the day. In the control group, no abnormality was observed throughout the observation period. Table 11 shows the results of measurement of body weight at 1 week and 2 weeks after administration as body weight change. The body weight was represented by a mean value ± standard deviation (unit: g). The number of animals is shown in parentheses. This weight measurement showed no difference in weight gain between the test group and the control group in both sexes.
Necropsy findings showed no major organ abnormalities in each group in both sexes at necropsy after the observation period.

According to the OECD Guidelines for Chemical Toxicity Test (1987), when the specimen is a liquid, the dose is 2 m / 100 g of body weight.
l (20ml / kg) should not be exceeded,
In this study, there were no deaths at the highest dose that could be administered, and no abnormalities were seen at necropsy. Therefore, it was confirmed that the lethal dose of a single oral administration of the sample to mice was 20 ml / kg or more for both males and females.

[0059]

[Table 11]

[Primary skin irritation test in rabbits] A liquid substance obtained by treating in the same manner as described in 3) except that no gelling agent was added was used as a sample, and OECD
A primary skin irritation test using rabbits was performed at the Japan Food Research Laboratories in accordance with the Chemical Toxicity Test Guideline (1987).

A Japanese white male rabbit was purchased from Kitayama Labes Co., Ltd. and preliminarily bred for at least one week to confirm that there was no abnormality in health. Rabbits
The animals were bred individually in FRP cages in a breeding room set at 22 ± 2 ° C. and an illumination time of 12 hours / day. Rabbit solid feed (CR-3, manufactured by Nippon Clara Co., Ltd.) was supplied as a feed, and tap water was freely taken.

The test used three rabbits. Twenty-four hours before the test, the coat of the back of the trunk of each rabbit was shaved, and after measuring the weight, four test sites of about 2 cm × 3 cm were provided for each rabbit. Two of the test sites were scratched (injured) in the polylayer so as not to reach the dermis, and the other two test sites were untreated (intact). Then, about 2 specimens each having 0.5 ml applied to one of the injured and intact test sites were applied.
A gauze patch of cm × 3 cm was applied and fixed with a bandage. Furthermore, the gauze patch was fixed with surgical tape so that the skin was in good contact with the skin. The remaining test sites served as controls.

The exposure time of the gauze patch was 4 hours.
After the gauze patch was removed, the surface of the test section was wiped with 70% ethanol, and observed at 1, 24, 48, and 72 hours thereafter to evaluate the degree of skin reaction. When evaluating the degree of the skin reaction, it was scored according to the evaluation criteria shown in Table 12. Furthermore, the primary irritation index (PII) was determined by calculating the average of all rabbits obtained by dividing the score values at 1, 24 and 48 hours and dividing by 6 to obtain an average value for all rabbits. The observation was continued after 72 hours, if necessary. Table 13 shows the scoring results for the skin reaction evaluation.

[0064]

[Table 12]

[0065]

[Table 13]

As can be seen from the results in Table 13, no skin reaction was observed for edema. With regard to erythema and crust, very mild erythema or clear erythema was observed at one hour after the removal of the gauze patch at all test sites where the gauze patch was applied. However, in one case (rabbit 1 in Table 13), it disappeared after 24 hours, and in another case (rabbit 3), it disappeared after 48 hours. As for the remaining one case (rabbit 2),
In the intact test site, it has been reduced after 24 hours,
At the injured test site, the skin reaction was limited to the abraded area. In addition, the value of the primary irritability index (PII) was 0.7. OECD Chemical Toxicity Test Guidelines (198
According to 7), this value falls into the category of "weak stimulant"
The specimen used in this test is evaluated as having low irritation.

[Eye irritation test in rabbits] The same liquid substance used in the above-mentioned "Primary skin irritation test in rabbits" was used as a sample, and in accordance with the OECD Guidelines for Chemical Toxicity Test (1987), The irritation test was performed at the Japan Food Research Laboratories.

A Japanese white male rabbit was purchased from Kitayama Labes Co., Ltd., and was bred for one week or more to confirm that there was no abnormality in health. In addition, within 24 hours before the start of the test, both eyes were examined to confirm that there was no abnormality. Rabbits were individually housed in FRP cages in a breeding room set at 22 ± 2 ° C. and an illumination time of 12 hours / day.
Bred. Rabbit solid feed (CR-3, manufactured by Nippon Clara Co., Ltd.) was supplied as a feed, and tap water was freely taken.

[0069] Three rabbits were used in the test. After measuring the weight of each rabbit, the sample is 50% with deionized water.
0.1 ml of the test solution diluted to (V / V) was instilled into the conjunctival sac of one eye, and the upper and lower eyelids were gently held for about 1 second. In order to use the other eye as a control, the same amount of ion-exchanged water alone was applied. 1, 24, 48 after instillation
After 72 hours, the cornea, iris and conjunctiva were observed using a slit lamp (× 10, manufactured by Kowa Co., Ltd.),
The degree of the eye irritation response was evaluated. When evaluating the degree of the eye irritant reaction, scoring was performed according to the evaluation criteria shown in Table 14, and a score was obtained. The total score was calculated for each rabbit for each elapsed time, and the average total score of three rabbits was calculated. Table 15 shows the results.

[0070]

[Table 14]

[0071]

[Table 15]

When one hour has elapsed since the sample was instilled, 2 hours
Examples (rabbits 1 and 3 in Table 15) showed conjunctival redness (scoring 1) and edema (scoring 1), and two cases (rabbits 1 and 2) showed secretions (scoring 1-2). . The secretions were tear liquid or white solid containing the specimen. At the elapse of 24 hours, the stimulus response disappeared in two cases (rabbits 2 and 3). In the remaining one case (rabbit 1), redness of the conjunctiva (scoring 2), edema (scoring 2), and tear secretion (scoring 3) were observed. However, when 72 hours had elapsed, the stimulus response disappeared even in this one case. No irritation was observed in any of the control eyes at any time. As can be seen from the results in Table 15, the highest average total score was 4.7 (after 1 and 24 hours). O
According to the ECD Chemical Toxicity Test Guidelines (1987), this value falls under the category of "irritant".

[Mutagenicity Test] A mutagenicity test was conducted at the Japan Food Research Laboratories, using the same liquid as that used in the above [Primary skin irritation test in rabbits]. The test method was based on Ministry of Labor Notification No. 77 (September 1, 1988). In other words, the bacteria were cultured on a plate medium to which the sample was added, the number of colonies that appeared due to reversion was counted, and the number was compared with a negative control and a positive control to determine the presence or absence of mutagenicity of the sample. .

As test bacteria, (1) Salmonella typhimurium TA 100 (2) Salmonella typhimurium TA 98 (3) Salmonella typhimurium TA 1535 (4) Salmonella typhimurium TA 1537 (5) Escherichia coli (WP2 uvrA) was used.

The amount of sample added was 156, 313, 62 per plate.
5, 1250, 2500 and 5000 μg. For each,
Culture was performed under both metabolic activation and metabolic deactivation conditions. In the metabolic activation condition, the activator S9 (manufactured by Kikkoman Corporation, inducer phenobarbital, 5,6-
S9 solution containing benzoflavone) was added to the plate medium. Under metabolic inactivation conditions, 0.1 M Na-phosphate buffer (ph7.4) was added instead. The composition of the S9 solution is as follows.

Composition of S9 solution (per 1 ml) S9 0.1 ml MgCl 8 μmol KCl 33 μmol G-6-P 5 μmol NADPH 4 μmol NADH 4 μmol Na-phosphate buffer (ph7.4) 100 μmol

In the case of the negative control, the culture was performed without adding any sample. In the positive control, a mutagen was added instead of the sample. Table 16 shows the types and amounts of the mutagenic substances for each test bacterium.

[0078]

[Table 16]

The procedure for culturing the test bacteria is described below. First, in a sterilized test tube, a test solution containing a predetermined amount of a sample is added.
1 ml or predetermined amount of mutagen (positive control), S9
Solution (under metabolic activation conditions) or 0.1 M Na-
0.5 ml of a phosphate buffer (ph7.4) (under metabolic deactivation conditions) and 0.1 ml of a suitably prepared bacterial solution are sequentially added. Next, after shaking for 20 minutes in a thermostat set at 37 ° C., 2 ml of top agar (0.6% “Bacto agar” (manufactured by Difco), 0.5% NaCl) is added. The top agar contains 1/10 volume of 0.5 mM L-histidine-0.5 mM D-biotin solution for Salmonella and 0.5 mM L-tryptophan solution for Escherichia coli. Subsequently, the cells are uniformly spread on a minimum agar glucose plate medium (Crimedia AM-N medium, manufactured by Oriental Yeast Co., Ltd.) and cultured in a thermostat set at 37 ° C. for 48 hours.

This test was performed in duplicate. When counting colonies, an automatic colony counter (manufactured by Yoshikawa Kogyo Co., Ltd.) was used as needed. Table 17 shows the average number of colonies per plate. In addition, as a sterility test, the test solution,
Only the S9 solution and the top agar were added, and the cells were cultured for 48 hours in a thermostat set at 37 ° C., and the presence or absence of colonies was observed.

[0081]

[Table 17]

No colonies were observed in the sterility test. As shown in Table 17, even when the sample was added to the medium and cultured, the number of colonies was not much different from that of the negative control. On the other hand, the number of colonies was clearly smaller as compared with the positive control. That is, even when the sample was added to the medium and cultured, no colonies appeared due to reversion were observed. From this, it is determined that the antibacterial agent of the present invention has no mutagenic properties.

[0083]

As described above, according to the antibacterial agent imparted with deodorizing properties of the present invention, a plant-derived component is used as its active ingredient, so that it is highly safe and has both deodorizing properties and antibacterial effects. be able to. Further, by making the antibacterial agent imparted with deodorant properties of the present invention a gel, it is possible to promote the volatilization of the active ingredient and enhance the deodorant and antibacterial effects. Especially,
High antibacterial effects are also obtained against food poisoning bacteria such as pathogenic Escherichia coli O157 and Legionella bacteria.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of a method for testing an antibacterial effect of a gel.

FIG. 2 is an explanatory diagram of a method for testing an antibacterial effect in a bathtub.

FIG. 3 is an explanatory view of a circulating warm bath apparatus.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Gel-like thing (sample) 11 Container 12 Plate medium 13 Closed container 15 Bath 16 Hot water 17 Circulating warm bath device 18 Pump 19 Suction nozzle 20 Hair catcher 21 Cartridge filter 22a, 22b Filter material 23 Heater 24 Discharge nozzle 25 Ozone generator 26 Air Tube 27 air intake 28 gel-like material 29 container 30 suction hose 31 discharge hose 32 check valve

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁶ Identification code FI A61L 9/01 A61L 9/01 R

Claims (8)

[Claims] 1. An antibacterial agent having deodorant properties, comprising phytontide and an organic substance having a tropolone skeleton. 2. The deodorizing antibacterial agent according to claim 1, further comprising an emulsifier in addition to the phytontide and the organic substance having the tropolone skeleton. 3. The deodorizing antibacterial agent according to claim 2, further comprising an organic acid in addition to the phytontide, the organic substance having a tropolone skeleton, and the emulsifier. 4. The antibacterial agent having a deodorant property according to claim 1, wherein the organic substance having a tropolone skeleton is at least one of hinokitiol and β-drabrin. 5. The organic substance having a tropolone skeleton is at least one of hinokitiol and β-drabrin,
The mixing ratio of the phytontide, hinokitiol or β-drabulin, the emulsifier, and the organic acid is 0.3 to 30% by weight, 0.1 to 2% by weight, 0.5 to 10% by weight, respectively, based on the total weight. The antibacterial agent provided with deodorant according to claim 3, which is in the range of 0.5 to 5% by weight. 6. The antibacterial agent having a deodorant property according to claim 1, wherein a gelling agent is further added to form a gel. 7. The gelling agent according to claim 6, wherein the gelling agent is a water-absorbing resin.
An antibacterial agent imparted with the deodorant property described in 1. 8. The antibacterial agent having deodorant properties according to claim 7, wherein the mixing ratio of the water-absorbing resin is in the range of 4 to 15% by weight based on the total weight.