JP6650276B2 - Antibacterial pigment and antibacterial composition - Google Patents

Description

  The present invention relates to an antibacterial pigment and an antibacterial composition exhibiting an excellent antibacterial effect on inflammatory causative bacteria of the skin.

  Staphylococcus aureus is known to have pathogenicity, and that bacteria attached to the hands adhere to food and proliferate, causing food poisoning by eating the food. Staphylococcus aureus is also present on normal skin, and when the skin is dry or rough, and especially on inflamed sites such as on the skin or wounds of patients with atopic dermatitis. It is known that atopic dermatitis and inflammatory response are exacerbated by toxins and antigens produced by Staphylococcus aureus. Furthermore, the toxin produced by Staphylococcus aureus promotes the proliferation of epidermal cells and may cause the formation and deterioration of skin dryness and rough skin.

  It has been desired to develop a highly safe antibacterial / bactericidal agent that prevents the growth of Staphylococcus aureus, and α-D-glycopyranosylglycerol (see Patent Document 1) and certain fatty acids exhibit excellent effects. Has recently become clear (see Patent Document 2). In particular, among fatty acids, branched saturated fatty acids having 10 to 18 carbon atoms, 6-hexadecenoic acid, palmitoleic acid, linoleic acid, etc. show a proliferative effect on Staphylococcus epidermidis present on the surface of healthy skin, and disinfect against Staphylococcus aureus. It is known to exhibit growth inhibition (see Patent Document 3). In addition, the calcium salt of palmitoleic acid is excellent in immediate bactericidal effect and persistence, and further exhibits selective bactericidal properties not only on Staphylococcus aureus but also on acne bacteria (Propionibacterium acnes). It is expected to be applied to materials (see Patent Document 4).

  However, in makeup cosmetics, formulation has not been studied so much because of effects on the skin and difficulty in formulating. Many women who are worried about skin whose barrier function has weakened due to atopic dermatitis, etc., are sensitive to irritation and show resistance to applying makeup. Therefore, something that protects the skin reliably from external stimuli such as bacteria while making up and that effectively leads the skin to a healthy state is necessary, but it has not been proposed yet. .

JP 2004-331577 A JP 2006-232860 A JP 2001-172176 A JP 2014-172848 A

  The present invention has been made in view of the above circumstances, has excellent adhesiveness (persistence) to the skin, exhibits high antibacterial properties against Staphylococcus aureus and acne bacteria, and can be easily applied to cosmetics and the like. It is an object of the present invention to provide an antibacterial pigment that can be blended, and to further provide an antibacterial composition containing the antibacterial pigment.

  In order to achieve the above object, the present inventors have conducted intensive studies and found that by supporting palmitoleic acid, a fatty acid bactericide, on the surface of pigment powder, high antibacterial properties against Staphylococcus aureus and Acne bacteria were achieved. The antibacterial pigments shown in the drawings were obtained, and it was found that the same antibacterial effect can be obtained even with a composition containing the antibacterial pigments, thereby completing the present invention.

  In short, the antibacterial pigment according to the first invention is characterized in that palmitoleic acid or a metal salt thereof having antibacterial activity against Staphylococcus aureus and Acne is carried on the surface of the pigment powder.

  Next, the antibacterial composition according to the second invention contains the antibacterial pigment according to the first invention.

  According to the antibacterial pigment of the present invention, palmitoleic acid or a metal salt thereof having antibacterial properties against Staphylococcus aureus and Acne is carried on the surface of the pigment powder, so that adhesion to skin (persistence) is improved. It is excellent and shows high antibacterial properties against Staphylococcus aureus and Acne bacteria, and can be blended into cosmetics and the like without difficulty. Since the antibacterial pigment has improved adhesion to the skin, the antibacterial composition containing the antibacterial pigment has a long-lasting antibacterial effect.

  Next, specific embodiments of the antibacterial pigment and the antibacterial composition according to the present invention will be described.

  As a treatment method for obtaining the antibacterial pigment of the present invention, palmitoleic acid is dissolved or dispersed in an appropriate organic solvent, and the mixture is stirred and mixed with a desired pigment powder, and then the organic solvent is removed. Thus, a pigment in which palmitoleic acid is supported on the surface of the pigment powder can be obtained.

  The origin of the palmitoleic acid in the present invention is not particularly limited, and may be natural or synthetic, and may be a metal salt of these palmitoleic acids. Examples of the metal salt of palmitoleic acid include a calcium salt, a sodium salt, a potassium salt, a magnesium salt, and an aluminum salt. Among them, a calcium salt can be preferably exemplified. These metal salts of palmitoleic acid may be used alone or in combination of two or more.

  Examples of the organic solvent used herein include alcohols such as ethanol, isopropyl alcohol and isobutanol, hydrocarbon organic solvents such as toluene, n-hexane and cyclohexane, and polar organic solvents such as acetone, ethyl acetate and butyl acetate. And the like.

  Further, as the mixing and dispersing method, an appropriate method can be selected according to the concentration and viscosity of the solvent, and preferable examples thereof include Disper, Henschel mixer, Loedige mixer, kneader, V-type mixer, and roll mill. A method using a mixer such as a bead mill or a twin-screw kneader, or a method such as spray drying in which an aqueous solution and a pigment are sprayed into heated air to remove water at a stroke can be selected. In the case of performing pulverization, a normal pulverizer such as a hammer mill, a ball mill, a side mill, and a jet mill can be used, and the same quality can be obtained with any pulverizer. Not something.

  The amount of palmitoleic acid adhering to or covering the pigment powder surface is not particularly limited, but is 0.1% by mass or more in order to exhibit the desired antibacterial effect and to obtain excellent adhesion and water resistance. The content is desirably 30% by mass or less. If the coating amount is less than 0.1% by mass, the antibacterial effect and the sustainability are not sufficient, and if it exceeds 30% by mass, the feel becomes very poor, and it is not suitable for cosmetics.

  In the present invention, at the time of surface treatment, other conventionally known surface treatment agents may be used for simultaneous or multiple surface treatment. Examples of conventionally known surface treatments include, for example, fluorine compound treatment (perfluoroalkylphosphate treatment, perfluoroalkylsilane treatment, perfluoropolyether treatment, fluorosilicone treatment, fluorinated silicone resin treatment, etc.), silicone treatment ( Methyl hydrogen polysiloxane treatment, dimethyl polysiloxane treatment, vapor phase tetramethyltetrahydrogen cyclotetrasiloxane treatment, etc.), silicone resin treatment (trimethylsiloxysilicic acid treatment, etc.), pendant treatment (gas chain silicone treatment followed by alkyl chain Method, silane coupling agent treatment, titanium coupling agent treatment, aluminum coupling agent treatment, silane treatment (alkylated silane or alkylated silazane treatment, etc.), oil treatment, polyacrylic Treatment, metal soap treatment (such as stearate or myristate treated), hydrogenated lecithin treated, acrylic resin treatment, may be mentioned a metal oxide treatment, also may be used by combining a plurality of these processes.

  As the pigment coated with palmitoleic acid, conventionally known pigments can be used, and the shape (spherical shape, rod shape, needle shape, plate shape, irregular shape, scale shape, spindle shape, etc.) and particle size (fume Irrespective of the shape, fine particles, pigment grade, etc.) and the particle structure (porous, non-porous, etc.). For example, inorganic powder, organic powder, colored pigment, pearl pigment, metal powder pigment and the like can be mentioned.

  Specifically, examples of the inorganic powder include titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, and cellulite. Site, muscovite, synthetic mica, phlogopite, rhombic mica, biotite, lithia mica, silicic acid, silicic anhydride, aluminum silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, barium silicate, silicate Strontium, metal tungstate, hydroxyapatite, vermiculite, heidilite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, dibasic calcium phosphate, alumina, aluminum hydroxide, boron nitride, boron nitride, silicon nitride Mosquitoes, and the like.

  Further, as the organic powder, for example, polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, polytetrafluoroethylene powder, polymethyl methacrylate powder, cellulose, silk Powder, nylon powder, 12 nylon, 6 nylon, acrylic powder, acrylic elastomer, styrene / acrylic acid copolymer, divinylbenzene / styrene copolymer, vinyl resin, urea resin, phenol resin, fluororesin, silicon resin, acrylic resin Melamine resin, epoxy resin, polycarbonate resin, microcrystalline fiber powder, starch powder, lauroyl lysine, and the like.

  Further, as the colored pigments, for example, inorganic red pigments of iron oxide, iron hydroxide, iron titanate, inorganic brown pigments such as γ-iron oxide, yellow iron oxide, inorganic yellow pigments such as loess, black iron oxide , Inorganic black pigments such as manganese violet and cobalt violet, inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide, and cobalt titanate; inorganic blue pigments such as navy blue and ultramarine blue; and fine particles. Fine particle powders such as titanium oxide, fine particle cerium oxide, and fine particle zinc oxide, those obtained by laked tar dyes, those obtained by laked natural dyes, and synthetic resin powders obtained by compounding these powders. .

  Examples of the pearl pigment include titanium oxide-coated mica, titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish scale foil, and titanium oxide-coated colored mica.

  Examples of the metal powder pigments include powders selected from aluminum powder, copper powder, stainless powder, and the like.

  The antibacterial effect of the antibacterial pigment in the present invention has been confirmed by the following method. As a test method, an antibacterial test based on JIS L1902-2008 (Antibacterial test method and antibacterial effect of textile products) 9 qualitative test (halo method) was used. The test powder is placed in the center of the agar medium coated with the bacteria, and the medium is left at 32.5 to 37 ° C. for 24 hours. In a situation where the bacteria have propagated on the medium, the bacteria do not propagate around the test powder. The presence or absence of a zone of inhibition (halo) was confirmed, and the antibacterial effect was evaluated. When performed using the antibacterial pigment of the present invention, since a zone of inhibition in which bacteria do not propagate around the antibacterial pigment is formed, the cosmetic composition containing the antibacterial pigment of the present invention has a high cosmetic composition. Can maintain antimicrobial properties.

  Next, the antibacterial composition according to the present invention will be described. The composition of the present invention can obtain an antibacterial effect against Staphylococcus aureus and Acne by mixing a pigment powder (antibacterial pigment) having a surface treated with palmitoleic acid. As the dosage form, it can be used for skin care products such as creams, emulsions, lotions, makeup products such as foundations and lipsticks, ultraviolet protection products, hair products, antiperspirant products and the like. The blending amount is not particularly limited, but can be blended in the range of 0.1 to 99% by mass, more preferably 1 to 80% by mass, based on the mass of the composition.

  Further, the antimicrobial composition of the present invention includes components usually used in cosmetics and quasi-drugs, for example, powders, surfactants, oils, gelling agents, polymers, cosmetic ingredients, humectants, pigments , Preservatives, fragrances and the like can be used as long as the effects of the present invention are not impaired.

  As the form of the antibacterial composition of the present invention, any dosage form such as powder, emulsion, cream, stick, solid, spray, and multi-layer separation type may be used, but powder is more preferable. It is.

  Next, the present invention will be described more specifically based on examples and comparative examples of the antibacterial pigment according to the present invention and the antibacterial composition containing the antibacterial pigment, but the present invention is limited to the following examples. It is not something to be done. In addition, all% in an Example means a mass%.

(Example 1)
100 g of sericite was put into a mixer, and a solution of 5.0 g of palmitoleic acid (trade name: cis-9-hexadecenoic acid, manufactured by Tokyo Chemical Industry Co., Ltd.) in 5.0 g of isopropyl alcohol was dropped and mixed. Mixed well with sericite. Thereafter, the powder was taken out of the mixer, vacuum-dried at 80 ° C. for 8 hours, and pulverized to obtain sericite treated with palmitoleic acid at 5%. In the same process, spherical cellulose powder (trade name: CELLULOBEADS D-10, manufactured by Daito Kasei Kogyo Co., Ltd.) was subjected to the same surface coating treatment to obtain respective samples.

(Example 2)
In the same manner as the 5% -treated pigment prepared in Example 1, a sample of sericite treated with palmitoleic acid at 10% and a spherical cellulose powder were obtained.

(Comparative Example 1)
1000 g of water was put into a 3 L beaker equipped with a stirrer, 5.0 g of stearic acid (trade name: LUNAC S-90V, manufactured by Kao Corporation) and sodium hydroxide were added, and the mixture was heated. 100 g was added and sufficiently stirred and dispersed. Further, 1.8 g of magnesium chloride hexahydrate was added and mixed, neutralized with an acid solution, washed with water and filtered. The solid content was dried until the water content became 1% or less, and pulverized to obtain sericite treated with 5% of magnesium stearate. In the same process, spherical cellulose powder (trade name: CELLULOBEADS D-10, manufactured by Daito Kasei Kogyo Co., Ltd.) was subjected to the same surface coating treatment to obtain respective samples.

  Here, the surface-treated powder (antibacterial pigment) of palmitoleic acid according to the present example was tested for its antibacterial effect on microorganisms.

<Antibacterial: Staphylococcus aureus>
The antibacterial property was evaluated based on JIS L1902-2008 (Antibacterial property test method and antibacterial effect of textile products) 9 qualitative test (Halo method). The test bacterium is adjusted to 1.0 × 10 ⁸ cfu / mL with a normal broth medium, and the 10-fold diluted bacterial solution is spread on an SCD agar medium, and 0.2 g of the test powder is placed at the center. And cultured for 24 hours at 32.5 ℃, it was observed deter band (halo). A sample having a stop band around the sample was marked as +, and a sample without a stop band was marked as-.

<Antibacterial: Acne bacteria>
The antibacterial property was evaluated based on JIS L1902-2008 (Antibacterial property test method and antibacterial effect of textile products) 9 qualitative test (Halo method). The test bacteria were pre-cultured on a GAM agar medium, and those pre-cultured on a GAM broth medium were diluted to 1.7 × 10 ⁷ cfu / mL. Smear onto GAM agar medium, and place in the center thereof a test powder to which a small amount of purified water has been added. 48 hours anaerobic culture at 37 ℃, was observed deter band (halo). A sample having a stop band around the sample was marked as +, and a sample without a stop band was marked as-.
Table 1 shows the cellulite treated with palmitoleic acid of Examples 1 and 2, the spherical cellulose powder, the sericite treated with 5% magnesium stearate of Comparative Example 1, and the spherical cellulose powder treated with 5% magnesium stearate with respect to each bacterial species. The results of antibacterial effect were shown.

  The 5% palmitoleic acid-treated sericite and spherical cellulose powder of Example 1 exhibited antibacterial properties against Staphylococcus aureus and Acne bacteria. In Example 2 in which the treatment amount was increased to 10%, the antibacterial activity against those bacteria was more remarkably exhibited. The sericite and spherical cellulose powder of Comparative Example 1 did not have an antibacterial effect on all bacteria.

  Next, examples of the antibacterial composition of the present invention will be described.

表２に示す全成分をブレンダーミキサーで混合した後、粉砕機を通して粉砕し、ふるいにかけて実施例３の抗菌性組成物を得た。 (Example 3: Loose powder using palmitoleic acid surface-treated pigment)

After mixing all the components shown in Table 2 with a blender mixer, the mixture was pulverized through a pulverizer and sieved to obtain the antibacterial composition of Example 3.

  Here, the antibacterial composition according to Example 3 was tested for its bactericidal effect on microorganisms. The test method was performed in the same manner as the palmitoleic acid-treated powder according to Examples 1 and 2, and the type of the bacterium was Staphylococcus aureus. The result was shown in Table 3 as + when there was a stop band (halo) around the sample, and-when there was no band.

  Loose powder containing 10% of palmitoleic acid-treated sericite and spherical cellulose powder of Example 3 exhibited antibacterial activity against Staphylococcus aureus.

The antibacterial pigment of the present invention has selective bactericidal properties, can be suitably used in cosmetics and quasi-drugs, and has great industrial applicability.

Claims (4)

  An antibacterial pigment comprising palmitoleic acid or a metal salt thereof having antibacterial activity against Staphylococcus aureus and / or acne bacteria, supported on the surface of the pigment powder.   2. The antibacterial pigment according to claim 1, wherein an amount of the palmitoleic acid or a metal salt thereof attached to or coated on the surface of the pigment powder is 0.1% by mass or more and 30% by mass or less. An antibacterial composition comprising the antibacterial pigment according to claim 1 . The antibacterial composition according to claim 3 , which is configured in a powder form.