JP7335067B2 - Antifungal agent composition and antifungal method - Google Patents

Description

TECHNICAL FIELD The present invention relates to an antifungal agent composition, and further to a wet sheet agent holding the antifungal agent composition and an antifungal method using the wet sheet agent.

In living environments, mold contamination tends to be a problem in wet places with a lot of moisture such as bathrooms and washrooms. Such places are frequently exposed to water due to condensation, running water, and the like, and fungal contamination (proliferation of fungi) progresses quickly using this abundant moisture.

Such mold contamination causes unbearable discomfort to consumers, and may also cause health hazards such as allergies. There has been a demand for a method capable of efficiently suppressing the growth of mold in such places called wet areas.
However, since most of the components used to prevent the growth of mold in such living environments are soluble in water, it has been difficult to maintain the anti-mold effect in places that are easily exposed to water.

On the other hand, by using a lipophilic antifungal agent, it is possible to retain the antifungal agent on the surface to be treated. Since there is concern about the influence on the member (member to be treated), the member to be treated and the treatment method are limited, and it has not been possible to use it easily in general households.

On the other hand, it has been reported that lipophilic antifungal agents can be easily used even in ordinary households by emulsification. For example, in Patent Document 1, an antifungal agent is added to an aqueous penetrating anti-absorption agent obtained by aqueous emulsification of a water-repellent alkylalkoxysilane in the presence of a nonionic emulsifier and an anionic emulsifier. Mold treatment materials have been proposed. Patent Document 2 proposes that an antifungal agent and a spreading agent made of modified silicone are dissolved in water to obtain an antifungal agent by emulsification. A siloxane, octamethylcyclotetrasiloxane has been used, neither of which is an amphiphilic silicone.

As antifungal components, phenolic antifungal agents (phenolic antifungal agents) such as isopropylmethylphenol are known. These have very high efficacy and safety as they are also used in cosmetics. In addition, compared to other ingredients, it is relatively easy to formulate as an aqueous solution. Therefore, it is ideal as an antifungal component for general household use.

JP-A-11-158418 JP 2017-160136 A

However, when the treated surface is exposed to water, the phenolic antifungal agent tends to flow away with the water, and there is a problem that the antifungal effect on the treated surface does not last long.
Further, when the surface to be treated is treated with the antifungal agent composition, uneven treatment of the lipophilic surface with the antifungal agent composition may occur. It is presumed that this is due to the low affinity between the antifungal agent composition or the antifungal agent and the surface to be treated. Furthermore, due to this low affinity, the antifungal agent composition does not penetrate into fine scratches, making it difficult to exert antifungal effects on the inside of such scratches.

Therefore, the present invention provides an antifungal agent composition containing a phenolic antifungal agent, which is excellent in water resistance (sustainability) and has excellent resistance to fine scratches while maintaining the excellent antifungal effect of the phenolic antifungal agent. To provide an anti-mold agent composition which permeates into the inside of a mold, exerts an anti-mold effect, and reduces uneven treatment.

As a result of extensive studies, the inventors of the present invention have found that when an amphiphilic silicone is blended into an antifungal agent composition, the affinity between the antifungal agent composition and the surface to be treated increases, and an excellent antifungal effect is maintained. In addition, the inventors have found that the water resistance (sustainability) of the antifungal agent composition and the ability to penetrate into fine wounds can be enhanced, and that uneven treatment can be reduced, leading to the completion of the present invention.

That is, the present invention is characterized by the following (1) to (5).
(1) An antifungal composition comprising an amphiphilic silicone and a phenolic antifungal agent.
(2) The antifungal agent composition according to (1) above, wherein the amphiphilic silicone is at least one of phenyl-modified silicone and polyether-modified silicone.
(3) The antifungal agent composition according to (1) or (2) above, which further contains a lower alcohol.
(4) A wet sheet agent holding the antifungal agent composition according to any one of the above (1) to (3).
(5) An antifungal method using an antifungal preparation,
An antifungal method, wherein the antifungal formulation is the wet sheet agent according to (4) above, and antifungal treatment is applied to the surface to be treated by wiping the surface to be treated with the wet sheet agent.

By applying an antifungal treatment to the surface to be treated using the antifungal agent composition according to the present invention, an excellent antifungal effect can be obtained evenly over the entire treated surface, including fine scratches, over a long period of time. can demonstrate.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail.
<Antifungal agent composition>
The antifungal agent composition according to the present invention comprises an amphiphilic silicone and a phenolic antifungal agent.

A phenolic antifungal agent has a very high antifungal effect and safety, and is relatively easy to formulate as an aqueous solution as compared with other ingredients.
Phenolic antifungal agents specifically include 4-isopropyl-3-methylphenol (cLogP = 3.093), ethylparaben (cLogP = 2.091), methylparaben (cLogP = 1.656), and propylparaben. (cLogP = 2.556, metacresol (cLogP = 1.998), o,p-cresol (cLogP = 1.997), o-phenylphenol sodium (cLogP = 3.364), chlorophene (cLogP = 4. 022), p-chlorometaxylenol (cLogP = 2.926), p-chlorometacresol (cLogP = 2.61), thymol (cLogP = 3.093), etc. Here, cLogP is a hydrophobic index. The value of cLogP is preferably about 1.5 to 4, and 4-isopropyl-3-methylphenol is particularly preferable from the viewpoint of antifungal effect.

The content of the phenolic antifungal agent is not particularly limited as long as the antifungal effect can be obtained, but is preferably 0.0001 w/w% or more, more preferably 0.01 w/w% or more, from the viewpoint of exhibiting the antifungal effect more. . Moreover, from the point of being able to mix stably, 5.0 w/w% or less is preferable, and 1.0 w/w% or less is more preferable.

The antifungal agent composition according to the present invention can be used in combination with the above phenolic antifungal agent, and other antifungal agents can also be used. Other antifungal agents such as cetylpyridinium salt, sodium pyrithione, cetyltrimethylammonium bromide, etc. are preferably used because they are water-soluble.

Amphiphilic silicones are silicones that have a hydrophobic portion and a hydrophilic portion.
When the amphiphilic silicone has a hydrophobic portion, the affinity between the hydrophobic (lipophilic) surface to be treated and the antifungal agent composition is increased. Therefore, even if the antifungal agent composition on the treated surface is exposed to water, it is less likely to flow away and more likely to remain, so that the antifungal effect is maintained.
Furthermore, if the antifungal agent composition is hydrophilic, the treatment unevenness is observed due to the low affinity with the lipophilic surface to be treated, but the hydrophobic part of the amphiphilic silicone Affinity with the surface to be treated increases, and the uneven treatment can be reduced. The effect of reducing unevenness in treatment can be exhibited more remarkably when the antifungal agent composition contains a lower alcohol.
In addition, since the affinity between the surface to be treated and the antifungal agent composition is increased, the antifungal agent composition can infiltrate even into fine scratches due to capillary action or the like. It becomes possible to bring about an antifungal effect up to.

On the other hand, when the antifungal agent composition is applied to the surface to be treated, the presence of a large amount of the hydrophilic portion of the amphiphilic silicone on the outside (surface side) causes oily stains that cause mold growth (food for mold). By making it difficult to adsorb, it is possible to exhibit a higher antifungal effect.
Furthermore, since the surface of fungal spores is generally hydrophobic, the effect of preventing the adhesion of fungal spores can be expected by making the outside (surface side) of the antifungal agent composition hydrophilic.

Amphiphilic silicones are not particularly limited as long as they are silicones having a hydrophobic portion and a hydrophilic portion, and examples thereof include phenyl-modified silicones, polyether-modified silicones, polyglucoside-modified silicones, and the like. It is preferable to use at least one of phenyl-modified silicone and polyether-modified silicone because it provides a more excellent water resistance (durability) of the antifungal effect.

Phenyl-modified silicone refers to a silicone in which the methyl group of polydimethylsiloxane is replaced with a phenyl group and an oxyethylene group or an oxypropylene group. BELSIL (registered trademark) PF200 manufactured by Wacker Silicone Co., Ltd.) and the like.

Polyether-modified silicone refers to a silicone in which the methyl group of polydimethylsiloxane is substituted with an oxyethylene group or an oxypropylene group. registered trademark) DMC6031), bisPEG-15 methyl ether dimethicone (manufactured by the same company, BELSIL (registered trademark) DMC6038), PEG/PPG-20/20 copolymer, PEG/PPG-20/20 dimethicone (manufactured by the same company, BELSIL (registered trademark) ) OW1500) and the like.

The amphiphilic silicone content is not particularly limited as long as the above effects can be obtained, and varies depending on the type. w % or more is more preferable. From the viewpoint of affinity for treated surfaces and stains such as mold, it is preferably 5.0 w/w% or less, more preferably 1.0 w/w% or less.

Water and/or a water-soluble solvent is used as a solvent or dispersion medium in the antifungal agent composition. Examples of water-soluble solvents include lower alcohols, glycols such as propylene glycol, and glycol ethers such as propylene glycol monomethyl ether. Among them, it is preferable to contain a lower alcohol from the viewpoint of increasing the solubility of the phenolic antifungal agent and the oily component among the optional components described later.
Ethanol and isopropyl alcohol are more preferred as lower alcohols.

When a lower alcohol is contained in the antifungal agent composition, the lower alcohol is preferred because of its structure, it increases the solubility of the hydrophobic antifungal agent contained in the antifungal agent composition and enhances the stability of the system. . On the other hand, if a lower alcohol is used in a high concentration, it may affect the chemical resistance of the treated surface and degrease the oil on the skin of the hands, which may cause rough skin.

The content of the lower alcohol is preferably 0.5 w/w% or more, more preferably 1.0 w/w% or more, from the point of solubility. From the viewpoint of chemical resistance and prevention of degreasing, the content is preferably 15 w/w% or less, more preferably 10 w/w% or less.

The antifungal agent composition may contain optional components contained in general antifungal agent compositions as long as the effects of the present invention are exhibited.
Examples of optional components that can be used include surfactants, deodorants, fragrances, pH adjusters, rust preventives, stabilizers, pigments, and the like.

Nonionic surfactants and anionic surfactants can be used as surfactants, and among them, nonionic surfactants are preferred. Examples of nonionic surfactants include POE (polyoxyethylene) alkyl ethers and POE hydrogenated castor oils, among which POE alkyl ethers are preferred from the viewpoint of solubilization and stable dispersion of the composition.

The content of the surfactant is preferably 0.1 w/w% or more, more preferably 0.5 w/w% or more, from the viewpoint of solubilization and stable dispersion. In addition, it is preferably 3.0 w/w% or less, more preferably 1.0 w/w% or less, because of the effect on the functionality of the amphiphilic silicone.

Examples of deodorants include lauryl methacrylate, geranyl chlorinate, catechin, polyphenol, charcoal and the like.

Examples of perfumes include natural perfumes extracted from various plants and animals, synthetic perfumes chemically synthesized, and compounded perfumes made by mixing many of these perfume ingredients.
Perfumes are described in various literature, eg, "Perfume and Flavor Materials of Natural Origin", Steffen Arctander, Allured Pub. Co. (1960), "Encyclopedia of Aroma", edited by Japan Perfume Association, Asakura Shoten (1989), "Flower oils and Floral Compounds In Perfumery", Danute Pajaujis Anonis, Allured Pub. Co. (1993), "Perfume and Flavor Chemicals (aroma chemicals)", Vols. I and II, Steffen Arctander, Allured Pub. Co. (1994), "Fundamental Knowledge of Perfume and Perfume", edited by Mototaka Nakajima, Sangyo Tosho (1995), "Synthetic Perfume Chemistry and Product Knowledge", Genichi Indo, Kagaku Kogyo Nippousha (1996), "Encyclopedia of Fragrances"Encyclopedia", edited by Mitsukatsu Yatagai, Maruzen (2005) can be used. each incorporated herein by reference. Specific representative examples of perfumes are listed below, but the present invention is not limited to these.

Examples of natural fragrances include natural essential oils such as orange oil, lemon oil, lavender oil, lavandin oil, bergamot oil, patchouli oil, cedarwood oil, and peppermint oil.
Synthetic perfumes include hydrocarbon terpenes such as α-pinene, β-pinene, limonene, p-cymene, terpinolene, α-terpinene, γ-terpinene, α-phellandrene, myrcene, camphene, and ocimene; heptanal, octanal , decanal, benzaldehyde, salicylic aldehyde, phenylacetaldehyde, citronellal, hydroxycitronellal, hydrotropic aldehyde, ligustral, citral, α-hexylcinnamic aldehyde, α-amylcinnamic aldehyde, lyrial, cyclamenaldehyde, lyral, heliotropine , anisaldehyde, helional, vanillin, ethyl vanillin and other aldehydes; ethyl formate, methyl acetate, ethyl acetate, methyl propionate, methyl isobutyrate, ethyl isobutyrate, ethyl butyrate, propyl butyrate, isobutyl acetate , isobutyl isobutyrate, isobutyl butyrate, isobutyl isovalerate, ethyl-2-methyl valerate, isoamyl acetate, terpinyl acetate, isoamyl propionate, amyl propionate, amyl isobutyrate, amyl butyrate, amyl isovalerate, allyl hexanoate, ethyl acetoacetate, ethyl heptylate, heptyl acetate, methyl benzoate, ethyl benzoate, ethyl octylate, styraryl acetate, benzyl acetate, nonyl acetate, bornyl acetate, linalyl acetate, ortho -ter-butyl cyclohexyl acetate, linalyl benzoate, benzyl benzoate, triethyl citrate, ethyl cinnamate, methyl salicylate, hexyl salicylate, hexyl acetate, hexyl butyrate, menthyl acetate, terpinyl acetate, anisyl acetate, phenyl ethyl iso Esters and lactones such as butyrate, methyl jasmonate, methyl dihydrojasmonate, ethylene brassylate, γ-undecalactone, γ-nonyllactone, cyclopentadecanolide, coumarin; anisole, p-cresyl methyl ether, Ethers such as dimethylhydroquinone, methyl eugenol, β-naphthol methyl ether, β-naphthol ethyl ether, anethole, diphenyl oxide, rose oxide, galaxolide, ambrox; isopropyl alcohol, cis-3-hexenol, heptanol, 2-octanol, Alcohols such as dimetol, dihydromyrcenol, linalool, benzyl alcohol, citronellol, geraniol, nerol, terpineol, tetrahydrogeraniol, l-menthol, cedrol, santalol, anise alcohol, phenylethyl alcohol, hexanol; diacetyl, menthone, isomenthone, thiomenthone, acetophenone, α- or β-damascone, α- or β-damascenone, α-, β- or γ-ionone, α-, β- or γ-methylionone, methyl-β-naphthyl ketone, benzophenone, tentalome , acetylcedrene, α- or β-isomethylionone, α-, β- or γ-ylone, maltol, ethyl maltol, cis-jasmone, dihydrojasmone, l-carvone, dihydrocarvone, ketones such as methyl amyl ketone, camphor , 1,8-cineol, allyl amyl glycolate, isopulegol, ligustral, allylcaproate and the like. These perfumes may be used singly or in any combination of two or more to be used as a blended perfume. Furthermore, the perfume can be used as a mixture (perfume composition) containing perfume ingredients, solvents, perfume stabilizers and the like.

Examples of pH adjusters include citric acid, phosphoric acid and salts thereof.
Rust inhibitors include, for example, 1,2,3-benzotriazole and dicyclohexylammonium nitrite.
Examples of stabilizers include dibutylhydroxytoluene, butylhydroxyanisole, tocopherol, ascorbic acid and salts thereof.

The form of the antifungal preparation containing the antifungal agent composition according to the present invention is not particularly limited, such as a wet sheet, a spray, an aerosol, etc., but the amount of application is easy to control, and the surface to be treated can be wiped off after treatment. A wet sheet agent is preferable because it is not necessary to separately perform the above.
Methods for holding the antifungal agent composition in the wet sheet agent include dripping, coating, immersion, and the like.

(Anti-mildew method)
The present invention also relates to an antifungal method, which comprises applying the antifungal agent composition to a surface to be treated. That is, the surface to be treated is subjected to an antifungal treatment using an antifungal preparation containing the antifungal agent composition. For example, it is preferable to apply antifungal treatment to the surface to be treated by wiping the surface to be treated with a wet sheet agent holding the antifungal agent composition.
At this time, by including amphiphilic silicone in the antifungal agent composition, it is possible to apply antifungal treatment even to the inside of fine scratches without uneven treatment, and to maintain excellent antifungal effects evenly over a long period of time. It is possible to perform.

The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

(Test Examples 1 to 6)
According to the sample formulation shown in Table 1, isopropylmethylphenol (IPMP), ethanol, and silicones were mixed at room temperature. Isopropylmethylphenol (IPMP) and silicones were added to ethanol and mixed at about 300 rpm for 3 minutes, then water was added and the mixture was further stirred for 3 minutes to obtain an antifungal agent composition. As silicones, phenyl-modified silicone or polyether-modified silicone, which are amphipathic silicones, or alkylaralkyl-modified silicone, which is hydrophobic silicone, or a mixture of dimethiconol and dimethicone (dimethiconol + dimethicone) was used.

(Test Example 7)
Isopropylmethylphenol (IPMP) and phenyl-modified silicone were mixed at room temperature. After mixing isopropylmethylphenol (IPMP) and phenyl-modified silicone at about 300 rpm for 3 minutes, water was added and the mixture was further stirred for 3 minutes to obtain an antifungal agent composition.

(Test Examples 8 and 9)
An antifungal composition was obtained in the same manner as in Test Example 2, except that thymol or p-chlorometaxylenol was used instead of isopropylmethylphenol (IPMP).

Here, Test Examples 2 to 4 and 7 to 9 are examples, and Test Examples 1, 5 and 6 are comparative examples.

(Water resistance (sustainability) evaluation)
400 μL of the antifungal agent composition was dropped in the center of a 5×5 cm FRP (fiber reinforced plastic) plate and spread over the entire plate with the tip of a micropipetter. After the test piece was dried, the surface of the test piece was washed by pouring 10 mL of ion-exchanged water over the test piece with a graduated pipette while tilting the test piece at about 45°. After air-drying the test pieces, 50 μL of spore fluid (Cladosporium cladosporioides NBRC6348, hereinafter referred to as “C.c.”) was applied to 6 drops (2 columns×3 rows). It was stored for 7 days under conditions of 99% RH and 25° C., and the water resistance (durability) of the antifungal effect was evaluated from the degree of coloration of the droplets.
In addition, C.I. c. A spore solution was prepared in a potato dextrose broth (PDB) at a concentration of 1/10. c. was added to a potato dextrose agar (PDA) slant medium, and a platinum loop was used to remove C. c. Spores were scraped off and prepared. This stock solution was diluted to an appropriate concentration of approximately 1.0×10 ⁵ to 1.0×10 ⁶ CFU/mL for testing. A series of operations were all performed in a safety cabinet.

Evaluation criteria for water resistance (durability) are as follows.
0: Spores grow and all droplets are darkly colored.
1: Some droplets have grown spores and are partially colored.
2: Growth of spores is observed, and some droplets are colored, but the degree is light.
3: No coloring is observed in any of the droplets.

(Evaluation of permeability to fine scratches)
A test piece was prepared by making nine parallel scratches on the surface of a 5×5 cm FRP plate with a router. This test piece was coated with C.I. c. 400 μL of the spore liquid stock solution (approximately 1.0×10 ⁷ to 1.0×10 ⁸ CFU/mL) was added dropwise, covered with a film, and allowed to stand for 20 minutes to spread the spore liquid uniformly on the surface of the test piece. unfolded.
A 10×10 cm non-woven fabric was impregnated with an antifungal agent composition in an amount 2.5 times the weight of the sheet, and a wet sheet was placed on a weight of 7×5.5 cm and weighing 150 g. A wiping operation (antifungal treatment) was performed by winding and reciprocating the surface of the previously obtained test piece 5 times at a speed of 1 reciprocation/second.
After standing for 10 minutes, the test piece was placed in 10 mL of a lecithin/polysorbate 80/glucose/peptone (GPLP) liquid medium and the surface was rubbed to elute the spores into the medium. The eluted material was spread on a potato dextrose agar (PDA) plate medium, cultured at 25° C. for 3 days, and the number of colonies was counted to compare the sterilization efficacy.
A series of operations were all performed in a safety cabinet.

For the evaluation of permeability to fine wounds, the sterilization rate was calculated from the number of viable bacteria using the following formula. c. Evaluation of efficacy against spores was performed. CFU in the formula means colony forming units.
A control group was prepared by impregnating 2.5 times the amount of ion-exchanged water.
Sterilization rate (%) = [{control group (CFU / test piece) - treatment group (CFU / test piece)} / control group (CFU / test piece)] × 100

(Evaluation of uneven processing)
Using a pipetter, 500 μL of the antifungal agent composition was dropped onto the center of a 5×5 cm FRP plate, and air-dried to obtain a test piece.
On the surface of the test piece, the C.I. c. The same concentration of spore liquid as the spore liquid was sprayed evenly. After that, the test piece was placed in a tapper and allowed to stand at 99% RH and 25°C for 7 days. After 7 days, the diameter of the part where the fungal growth was suppressed by treating the antifungal composition on the surface of the test piece (the part that is not colored black) (if it is not circular, the average of the longest and shortest parts) value) was measured, and processing unevenness was evaluated from the diameter.

The evaluation criteria for processing unevenness are as follows. The average value of the diameter is the average value when the above evaluation is performed on three test pieces.
1: Average diameter less than 1 cm 2: Average diameter 1 cm or more and less than 2 cm 3: Average diameter 2 cm or more and less than 3 cm 4: Average diameter 3 cm or more and less than 4 cm 5: Average diameter 4 cm that's all

Table 1 shows the evaluation results of each antifungal agent composition.

From the above results, the antifungal agent composition according to the present invention has little treatment unevenness, has an antifungal effect on the inside of fine scratches, and has an excellent antifungal effect evenly on the treated surface. can be exhibited, and the effect can be exhibited continuously.

Claims (4)

An antifungal composition comprising an amphiphilic silicone and a phenolic antifungal agent,
The amphipathic silicone is a silicone having a hydrophobic portion and a hydrophilic portion, and is a phenyl-modified silicone and polydimethylsiloxane in which methyl groups of polydimethylsiloxane are substituted with phenyl groups and oxyethylene groups or oxypropylene groups. At least one of a polyether-modified silicone in which the methyl group of siloxane is substituted with an oxyethylene group or an oxypropylene group,
The antifungal composition, wherein the phenolic antifungal agent is at least one selected from the group consisting of 4-isopropyl-3-methylphenol , p -chlorometaxylenol, and thymol. The antifungal agent composition according to claim 1 , further comprising a lower alcohol. A wet sheet agent holding the antifungal agent composition according to claim 1 or 2 . An antifungal method using an antifungal preparation,
4. An antifungal method, wherein the antifungal agent is the wet sheet agent according to claim 3 , and antifungal treatment is applied to the surface to be treated by wiping the surface to be treated with the wet sheet agent.
However, the surface of human skin is excluded from the surface to be treated.