JP2010018576A - COSMETIC COMPOSITION CONTAINING POLY-gamma-L-GLUTAMIC ACID-CROSSLINKED MATERIAL - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cosmetic and a skin preparation for external use, blended with an antibacterial agent, without having a problem in safety issues such as skin irritation, etc., and further equipped simultaneously with extensibility, moist feeling and hardly having roughness. <P>SOLUTION: This cosmetic composition containing a poly-γ-L-glutamic acid-crosslinked material and the anti-bacterial agent is provided by reducing the irritation of the anti-bacterial agent, and also can equip the extensibility, moist feeling and hardly having roughness simultaneously. The antibacterial agent may be an organic antibacterial agent or an inorganic antibacterial agent. The cosmetic composition can be utilized as a cosmetic, quasi-drug, medical supply, hygienic material or medicine. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a cosmetic composition comprising a poly-γ-L-glutamic acid cross-linked product as an active ingredient, and is particularly used for cosmetics, quasi-drugs, medical products, hygiene products, and pharmaceuticals.

In cosmetics, benzoic acid and its salts, isopropylmethylphenol, paraoxybenzoic acid ester (paraben), phenoxyethanol, undecylenic acid and its salts, chloride to prevent deterioration due to contamination with bacteria, molds, etc. during manufacture and use Antibacterial agents such as benzethonium and alkyltrimethylammonium chloride have been used. However, these antibacterial agents are irritating to the skin. In addition, with the recent increase in the safety orientation of consumers, cosmetics that are less allergic and less irritating than conventional and are hypoallergenic and hypoallergenic are desired.

On the other hand, biopolymers produced by microorganisms are promising, and among them, attention is focused on the potential of a group of biopolymers called polyamino acids composed of amino acids by condensation polymerization. Three types of polyamino acids have been identified so far: poly-γ-glutamic acid (hereinafter sometimes referred to as “PGA”), poly-ε-lysine and cyanophysin.

PGA, one of these polyamino acid groups, is a polyamino acid in which the α-amino group and γ-carboxyl group of glutamic acid are amide-bonded. known. As an attractive function of PGA, it is known that it has both biodegradability and high water absorption. By using these functions, various cosmetics, medical products, foods, and the like described above can be used. It is expected to be used in fields and applications.

PGAs for various uses have already been commercialized. Currently, commercially available PGAs are chemically heterogeneous γ-DL-polyglutamic acids in which D-glutamic acid and L-glutamic acid are irregularly bound ( Hereinafter, it may be expressed as “DL-PGA”). In more detail, DL-PGA currently commercialized is produced from Bacillus natto and its related bacteria, and the sequences of D-glutamic acid and L-glutamic acid, and the content ratio thereof, It varies from culture to culture. In general, the structural characteristics of polyamino acids (optical activity and type of constituent amino acids, molecular size, binding mode, etc.) strongly influence their functions. Therefore, these DL-PGAs have different properties for each production lot. It is difficult to stably produce a DL-PGA having a desired quality.

On the other hand, bacteria producing homopoly-γ-glutamic acid have also been reported. For example, Bacillus anthracis has been reported to produce poly-γ-D-glutamic acid (hereinafter sometimes referred to as D-PGA) consisting only of D-glutamic acid (Non-patent Document 1, Non-Patent Document 1, Patent Document 2, Non-Patent Document 3). However, since this bacterium is a bacterium having a strong pathogenicity, it is inappropriate as an industrial PGA-producing bacterium, and the molecular weight of D-PGA produced is small. Further, it has been reported that the alkalophilic bacterium Bacillus halodurans produces poly-γ-L-glutamic acid (hereinafter sometimes referred to as L-PGA) consisting only of L-glutamic acid, which is reported in Non-patent Document 3). However, L-PGA produced by this bacterium has an extremely small molecular weight, and is insufficient to obtain practical performance.

On the other hand, it has been reported that a halophilic archaeon, Naturalba aegyptica, produces L-PGA having a molecular weight of about 100,000 to 1,000,000 as a high-molecular-weight homopoly-γ-glutamic acid-producing bacterium. However, since this bacterium has a molecular weight as small as about 100,000 under liquid culture conditions and hardly produces L-PGA, there is a problem as an industrially produced bacterium (Non-patent Document 4, Patent Document 1).

In addition to the above, examples of organisms that produce L-PGA include hydra and the like, but hydra also has a problem that its molecular weight is extremely small. (Non Patent Literature 3)

As a result of intensive studies, the present inventors have made it possible to prepare a large amount of L-PGA with uniform optical purity and high molecular weight by liquid culture. More specifically, L-PGA having a number average molecular weight of 1.3 million or more and uniform optical purity is obtained with a high productivity of 4.99 g or more per liter of culture solution (Patent Document 2).

Further, a method for cross-linking L-PGA, a cross-linked L-PGA (Patent Document 3), and an external preparation for skin (Patent Document 4) comprising at least one of L-PGA and L-PGA cross-linked body There is a report.

Although it is such a situation, it was not reported that the irritation | stimulation with respect to skin could be reduced by using L-PGA crosslinked body together with an antibacterial agent, without impairing the antibacterial effect.

Special Table 2002-517204 JP 2007-314434 A JP 2008-120910 A JP 2008-120725 A Handy, W. E., and H.N.Rydon, Biochem J., 40, 297-309 (1946) Makino, S., I. Uchida, N. Terakado, C. Sasakawa, and M. Yoshikawa, J. Bacteriaol., 171, 722-730 (1989) Biology and Chemistry Vol.40, No.4, p212-214 (2002) Hezayen, F. F., B. H. A. Rehm, B. J. Tindall and A. Steinbuchel, Int. J. Syst. E., 51, 1133-1142 (2001)

Conventionally, cosmetics are prevented from being deteriorated by contamination with bacteria, molds, etc. during manufacture and use, benzoic acid and its salt, isopropylmethylphenol, paraoxybenzoic acid ester (paraben), phenoxyethanol, undecylenic acid and its salt Antibacterial agents such as benzethonium chloride and alkyltrimethylammonium chloride have been used. However, these antibacterial agents are irritating to the skin. In addition, with the recent increase in the safety orientation of consumers, cosmetics that are less allergic and less irritating than conventional and are hypoallergenic and hypoallergenic are desired.

The object of the present invention is to provide an L-PGA cross-linked product and / or a salt thereof and an antibacterial agent which have improved the above-mentioned problems, have no problem in safety such as skin irritation, and further have a feeling of spreading, moist feeling, and difficulty in sticking The object is to provide a blended cosmetic and a skin external preparation. Furthermore, the objective of this invention is providing the cosmetics, a quasi-drug, a medical article, a hygiene article, and a pharmaceutical containing the said cosmetics and a skin external preparation.

As a result of diligent efforts to achieve the above object, the present inventors have found that it is effective to blend an L-PGA crosslinked product in a skin external preparation containing an antibacterial agent.

Furthermore, as a result of intensive research efforts for the topical skin preparation containing the antibacterial agent, the inventors of the present invention have sought to obtain a topical skin preparation that has little irritation, and has a feeling of spreading, moist feeling, and difficulty in bulking. Together with the L-PGA cross-linked product, it was found that the stimulation of the antibacterial agent can be reduced, and that it can be combined with a feeling of spreading, moist feeling and difficulty in bulking, and the present invention has been completed.

That is, the present invention includes the following inventions (1) to (3).
(1) A cosmetic composition comprising a crosslinked poly-γ-L-glutamic acid and an antibacterial agent.
(2) The cosmetic composition according to claim 1, wherein the antibacterial agent is an organic antibacterial agent and / or an inorganic antibacterial agent.
(3) The cosmetic composition according to any one of 1 to 2, which is used as a cosmetic, a quasi-drug, a medical product, a hygiene product, or a pharmaceutical product.

The cosmetic composition containing the L-PGA cross-linked product of the present invention and an antibacterial agent is a cosmetic, quasi-drug, medical product, hygiene product, pharmaceutical product that is less irritating and has a combination of softness, moist feeling, and bulkiness. Can be provided. In particular, according to the present invention, a skin external preparation with less irritation can be provided in an external preparation for skin containing an antibacterial agent. Moreover, since the poly-γ-L-glutamic acid crosslinked product is a biologically derived natural polymer, it is excellent in safety, and the cosmetic composition of the present invention can sufficiently withstand long-term use. Furthermore, since the L-PGA cross-linked product can be obtained by irradiating L-PGA with γ-rays, mass production is easy, and L-PGA as a raw material can be produced at low cost from microorganisms, so that the production cost is also low. .

The cosmetic composition of the present invention contains an L-PGA crosslinked product and an antibacterial agent as essential components.

The “L-PGA cross-linked product” of the present invention is a product obtained by cross-linking L-PGA, which is a homopolymer consisting only of L-glutamic acid, by γ-rays. The structure of L-PGA is a structure represented by the formula (I), and the hydrogen of αCOOH may be hydrogen or another metal counter ion. For example, there is no need to limit the general materials such as sodium, potassium, magnesium, manganese, calcium, zinc and iron. Of these, sodium is preferred.

The “molecular weight” of the present invention refers to the number average molecular weight (Mn) calculated in terms of the molecular weight of the pullulan standard substance.

The L-PGA crosslinked product of the present invention can be obtained by an existing method. For example, L-PGA is obtained by the method described in Patent Document 2 (Japanese Patent Laid-Open No. 2007-314434), and γ-rays are obtained by the method described in Patent Document 3 (Japanese Patent Laid-Open No. 2008-120910). It can be obtained by crosslinking. Hereinafter, as an example, a method for producing a crosslinked L-PGA with reference to Patent Documents 2 and 3 will be described, but the present invention is not limited thereto.

For example, the National Institute of Advanced Industrial Science and Technology (NIST) Patent Biological Depositary Center includes the Nationalba aegyptica 0830-82 strain (trusted organization: National Institute of Advanced Industrial Science and Technology Patent Biological Depositary). April 4, 2006, accession number: FERM BP-20872), Natrialba aegyptica 0830-243 strain (trusted organization name: National Institute of Advanced Industrial Science and Technology, Patent Biological Depositary Center), accession date: Heisei 18 April 4, 2000, accession number: FERM BP-20873), or Natrialba aegyptica 0831-264 strain (trusted organization name: National Institute of Advanced Industrial Science and Technology, Patent Organism Depositary) Deposit date: April 4, 2006, Deposit number: FERM BP-20874) When using the strain deposited to obtain poly-γ-L-glutamic acid, L-PGA can be obtained by liquid culture. . Alternatively, the microorganism can be mutated by the method described in Patent Document 2 (Japanese Patent Application Laid-Open No. 2007-314434), and a microorganism capable of producing L-PGA by liquid culture can be produced to produce L-PGA. Moreover, it is also possible to produce L-PGA by solid-phase culture of Natalba aegyptica by a conventional method.

In the case of liquid culture, it is desirable to carry out under aerobic conditions such as shaking culture and aeration stirring culture. The culture temperature at that time is 30 to 50 ° C, preferably 35 to 45 ° C. The pH of the medium can be adjusted with sodium hydroxide, potassium hydroxide, ammonia, hydrochloric acid, sulfuric acid, or an aqueous solution thereof, but is not limited as long as the pH can be adjusted. It is desirable to culture at a culture pH of 5.0 to 9.0, preferably at a pH of 6.0 to 8.5. In addition, the culture period is usually about 2 to 7 days. Further, it is desirable to culture at a NaCl concentration of 10 to 30%, preferably 15 to 25% during culture. Further, it is desirable to culture at a yeast extract concentration of 0.1 to 10%, preferably 0.5 to 5.0%. Also in the case of solid culture, the culture temperature is 30 to 50 ° C., preferably 35 to 45 ° C., and the pH during the culture is 5.0 to 9.0, preferably pH 6.0, in the case of liquid culture and application. -8.5, NaCl concentration during culture is 10-30%, preferably 15-25%, Yeast Extract concentration is 0.1-10%, preferably 0.5-5%. When cultured in this manner, L-PGA accumulates mainly outside the cells and is contained in the aforementioned culture. Although not specifically limited, PGA production liquid medium-1 (22.5% NaCl, 2% MgSO ₄ .7H ₂ O, 0.2% KCl, 3% Trisodium Citrate, 1% Yeast Extract, 0.75% Casamino acid ) May be used, and the amount of each additive may be appropriately adjusted according to the strain.

  As a method for quantifying L-PGA in a culture solution, precipitation is performed from a sample containing L-PGA using copper sulfate or ethanol, and the weight of the precipitate is measured and total nitrogen is measured by the Kijderder method. (M. Bovarnick, J. Biol. Chem., 145, 415, 1942), a method for measuring the amount of glutamic acid after hydrolysis of hydrochloric acid (RD Housewright, CB Thorne, J. Biol. Chem., 145, 415, 1942). Bacteriol., 60, 89, 1950) and a colorimetric method using quantitative binding with a basic dye (M. Bovarnick et al., J. Biol. Chem., 207, 593). Page, 1954) is known, but a colorimetric method utilizing quantitative binding with a basic dye is preferred.

  Examples of basic dyes include crystal violet, aniline blue, safranino, methylene blue, methyl violet, toluine nebula, congo red, azocarmine, thionine, and hematoxylin, with safranino being preferred.

  In order to separate and collect L-PGA from this culture, the above-mentioned known methods such as precipitation using copper sulfate or ethanol may be used. As an example, for example, the culture solution is centrifuged to remove the cells. Subsequently, after adding and diluting 3 times the amount of water to the obtained supernatant, the pH is adjusted to 3.0. After pH adjustment, the mixture was stirred at room temperature for 5 hours. Thereafter, 3 times the amount of ethanol was added, and L-PGA was recovered as a precipitate. The precipitate is dissolved in 0.1 mM Tris-HCl buffer (pH 8.0), and low-molecular substances are removed by dialysis. After dialysis, the resulting solution may be treated with DNase or RNase for nucleic acid removal, and then with proteinase treatment for protein removal. After the proteinase treatment, the low molecular weight substance may be removed by dialysis. After dialysis, dry L-PGA may be obtained by freeze drying or the like. Moreover, although refinement | purification using an anion exchange resin can be performed if necessary, it can refine | purify on general conditions.

Although the molecular weight of L-PGA used for this invention is not specifically limited, Preferably it is 500,000 or more, More preferably, it is 800,000 or more, More preferably, it is 1 million or more, Especially preferably, it is 1.3 million or more.

The upper limit value of the molecular weight of L-PGA is not particularly limited, but according to the above-described L-PGA production method, for example, L-PGA having 6 million or 15 million at the maximum can be obtained.

Since this L-PGA is produced by archaea and has a peculiar odor reduced compared to DL-PGA produced by Bacillus natto, cosmetics, quasi-drugs, medical products, hygiene products or pharmaceuticals The quality will not be impaired even if it is used for any purpose.

[Method for producing L-PGA crosslinked product of the present invention]
The L-PGA crosslinked product of the present invention can be obtained by an existing method. Hereinafter, as an example, a method for producing an L-PGA crosslinked body with reference to JP-A-2008-120910 will be described, but the present invention is not limited thereto.

  The manufacturing method of L-PGA crosslinked body should just include the bridge | crosslinking process which bridge | crosslinks the molecules of L-PGA. By cross-linking L-PGA consisting only of L-glutamic acid and having uniform optical activity as a raw material, the properties of the L-PGA cross-linked product are uniform. Therefore, it is possible to stably produce an L-PGA crosslinked product having a desired quality.

L-PGA may be subjected to a crosslinking reaction after dissolving in a solvent to prepare a solution of L-PGA. The solvent for dissolving L-PGA is not limited as long as L-PGA can be dissolved, and examples thereof include water, alcohol, acetone, methyl acetate, and ethyl acetate. Water, methyl alcohol, and ethyl alcohol are preferable, and water is more preferable. The concentration of L-PGA when dissolved in these solvents is not particularly limited, but is preferably 1% by weight to 10% by weight, more preferably 2% by weight to 8% by weight. Particularly preferably, it is 2% by weight or more and 7% by weight or less. The pH of the L-PGA solution is not particularly limited, but is preferably pH 1.0 or higher and 14.0 or lower, more preferably pH 2.0 or higher and 13.0 or lower.

When a cross-linking reaction is performed on the L-PGA solution, a cross-linked product of L-PGA is formed in the solution, and the L-PGA cross-linked product swells containing the solvent, whereby a hydrogel is obtained. This is one of the aspects of the hydrogel according to the present invention described later. Furthermore, L-PGA crosslinked body which does not contain the said solvent component can be obtained by removing the solvent component by freeze-drying the said hydrogel. The hydrogel according to the present invention will be described later.

  According to the above-mentioned method for producing a crosslinked L-PGA, L-PGA can be obtained, for example, at a gelation rate of 50% to 100%, particularly 70% to 100% in the crosslinking reaction described above.

 In the present specification, the “gelation rate” intends the percentage of the weight of L-PGA formed by a crosslinking reaction with respect to the weight of L-PGA used as a raw material. In other words, the “gelation rate” represents the yield of the obtained L-PGA crosslinked body and thus the hydrogel with respect to the L-PGA used as a raw material. Specifically, the value obtained by dividing the dry weight of the hydrogel obtained by the crosslinking reaction by the dry weight of L-PGA subjected to the crosslinking reaction is calculated by multiplying by 100.

 The method for the crosslinking reaction of L-PGA is not limited as long as L-PGA molecules can be crosslinked with each other, and may be performed by a conventionally known method. For example, a cross-linking agent may be used and radiation may be used, but it is preferable to use radiation. If radiation is used, an operation for removing the crosslinking agent is not required after the crosslinking reaction, and a highly pure L-PGA crosslinked product can be produced.

  The radiation that can be used in the method for producing an L-PGA crosslinked body is not particularly limited, and α rays, β rays, γ rays, electron beams, neutron rays, X rays, and the like may be used. Among these, γ rays are preferable. The γ rays may be generated using a conventionally known method and apparatus such as an irradiation apparatus using cobalt 60 as a radiation source.

 Further, the radiation dose to the L-PGA is preferably 0.5 kGy or more and 20 kGy or less, more preferably 2 kGy or more and 10 kGy or less, and particularly preferably 3 kGy or more and 7 kGy or less. What is necessary is just to set suitably according to the use etc. of a body. In general, a hard hydrogel can be obtained if the irradiation dose is large, and a soft hydrogel can be obtained if the irradiation dose is small. For example, when the irradiation dose is set to 1 kGy and 3 kGy, a highly fluid hydrogel that naturally spreads in the horizontal direction even when placed on a flat plate can be obtained. When the irradiation dose is 5 kGy or 7 kGy, the hydrogel is horizontal even when placed on a flat plate. A hydrogel with low fluidity that can be left stationary without spreading in the direction is obtained.

 Moreover, when using a radiation for the bridge | crosslinking of L-PGA, what is necessary is just to put the solution of L-PGA in a radiation transparent container. The radiation transmissive container is not particularly limited, and for example, a glass container such as a glass vial can be used.

 After putting the L-PGA solution in the radiation transmissive container, radiation may be applied as it is, but it is preferable to bubble the solution beforehand using nitrogen. By removing oxygen contained in the solution, inhibition of the crosslinking reaction can be prevented.

 In addition, when using a crosslinking agent for crosslinking of L-PGA, a conventionally known crosslinking agent such as an epoxy compound, a polysaccharide containing a carboxylic acid group and / or a carboxylate group, an amino acid, etc. may be used, and is particularly limited. is not. For example, the epoxy compound includes glycerin triglycidyl ether, di-glycerin polyglycidyl ether, poly-glycerin polyglycidyl ether, polyoxyethylene sorbitol polyglycidyl ether, and the polysaccharide includes glucose, fructose, galactose, and glucuronic acid. Mixtures, mixtures of rhamnose, glucose, galactose, and glucuronic acid, and polycarboxylic acids based on hyaluronic acid, amino acids include polyaspartic acid, polylysine, aspartic acid, lysine, arginine, and mixtures thereof It is done. These may be used singly or may be used in combination of two or more.

  The L-PGA used in the above-mentioned method for producing a crosslinked L-PGA is not limited as long as L-PGA molecules can be crosslinked with each other. However, as described above, L-PGA having a large average molecular weight is used. PGA is preferable.

 Moreover, L-PGA used for the manufacturing method of the above-mentioned L-PGA crosslinked body may be in the state of a salt, for example, sodium salt, potassium salt, magnesium salt, calcium salt etc. can be used. Of these, sodium salts are preferred.

  As the L-PGA used in the above-described method for producing a crosslinked L-PGA, L-PGA obtained by various conventionally known methods may be used. For example, L-PGA obtained by using a microorganism that produces L-PGA. -PGA may be used.

What is necessary is just to add the addition amount of the L-PGA crosslinked body in a cosmetic composition in the range which does not impair the effect | action which L-PGA crosslinked body has, Usually 0.001-50 mass% is preferable, 0.01-30 mass % Is more preferable, 0.1 to 10% by mass is further preferable, and 0.5 to 5% by mass is particularly preferable.

The cosmetic composition of the present invention contains an antibacterial agent in addition to the above L-PGA crosslinked product. The antibacterial agent may be an organic antibacterial agent and / or an inorganic antibacterial agent.

Antibacterial agents include alum extract, halocarban, chlorophenesine, lysozyme chloride, alkyldiaminoethylglycine hydrochloride, isopropylmethylphenol, thymol, hexachlorophene, berberine, thioxolone, salicylic acid and their derivatives, benzoic acid, sodium benzoate , Paraoxybenzoic acid ester, parachlormetacresol, benzalkonium chloride, phenoxyethanol, isopropylmethylphenol, carboxylic acid, sorbic acid, potassium sorbate, hexachlorophene, chlorhexidine chloride, trichlorocarbanilide, photosensitizer, bis (2-pyridylthio) -1-oxide) zinc, thianthol, hinokitiol, triclosan, trichlorohydroxydiphenyl ether, chlorhexidine gluconate, Bruno butoxyethanol, resorcinol, azulene, salicylic acid, zinc pyrithione, sodium mononitroguayacol, fennel extract, pepper extract, cetylpyridinium chloride, etc. benzethonium chloride and undecylenic acid derivatives.

These antibacterial agents can be used alone or in combination of two or more.

 The blending amount of the antibacterial agent used in the present invention is not particularly limited, but is preferably 0.001% by weight or more and 10% by weight or less, and preferably 0.01% by weight or more and 8% or less, based on the total amount of the composition in the present invention. % By weight or less is preferable, more preferably 0.05% by weight or more and 5% by weight or less.

The form of the cosmetic composition containing the L-PGA crosslinked product is not particularly limited. Therefore, it may take any state such as solid, liquid, paste, jelly, and powder.

The cosmetic composition containing the L-PGA cross-linked product of the present invention has an excellent moisturizing effect, thickening action and hair improving action, and can impart appropriate moisture to the skin surface to keep it firm and shiny. It has been confirmed.

For example, a cosmetic composition containing the L-PGA crosslinked product of the present invention can be used as a cosmetic. Cosmetics include cosmetic soap, shampoo, facial cleanser, rinse, eye cream, eye shadow, cream / milky lotion, lotion, perfume, funny, cosmetic oil, hair cosmetics, hair dye, paste perfume, powder, pack, cleansing cream , Shaving cream, shaving lotion, tanning oil, sunscreen oil, tanning lotion, sunscreen lotion, tanning cream, sunscreen cream, foundation, powdered perfume, blusher, mascara, eyebrow, nail cream, beautiful nail enamel, beautiful nails Examples include enamel remover, hair wash, bath cosmetic, lipstick, lip balm, eyeliner, toothpaste, deodorant, eau de cologne, hair nourishing agent, and hair restorer. The cosmetic composition containing the crosslinked poly-γ-L-glutamic acid of the present invention can also be used as an ointment or a poultice.

The cosmetic composition containing the L-PGA crosslinked product of the present invention can be used in combination with quasi-drugs, medical supplies, hygiene products, and pharmaceuticals in addition to cosmetics.

When the cosmetic composition containing the cross-linked poly L-PGA of the present invention is implemented in the form of a quasi-drug, medical product, hygiene product, or pharmaceutical product, the dosage form is not limited and ampules, capsules, powders, granules Pills, tablets, solids, liquids, gels, bubbles, emulsions, creams, ointments, sheets, mousses, bathing agents, and the like.

As quasi-drugs, medical supplies, hygiene products, and pharmaceuticals, for example, internal and external pharmaceutical preparations, skin lotions, emulsions, creams, ointments, lotions, oils, packs, and other basic cosmetics, facial cleansers and skin cleansers, Hair cosmetics such as shampoo, rinse, hair treatment, hair cream, pomade, hair spray, hair conditioner, permanent agent, hair nick, hair dye, hair growth and hair restorer, foundation, white powder, funny, lipstick, blusher, eye shadow, Makeup cosmetics such as eyeliner, mascara, eyebrows, eyelashes, cosmetics for finishing such as nail care, perfumes, bath preparations, toothpastes, mouth fresheners, gargles, liquid odors and deodorants, Sanitary goods, sanitary cotton, wet tissue and the like. The cosmetic composition containing the L-PGA crosslinked product of the present invention can also be used as an ointment or a poultice.

The cosmetic composition containing the L-PGA cross-linked product of the present invention is suitably applied to humans, but may be applied to animals other than humans as long as each effect can be expected. it can.

  The cosmetic composition containing the L-PGA cross-linked product of the present invention contains ingredients and additives used in quasi-drugs, medical products, hygiene products, and pharmaceuticals as long as the effects of the present invention are not impaired as necessary. An agent can be used in combination.

For example, as the surfactant, anionic surfactant (carboxylate, sulfonate, sulfate ester salt, phosphate ester salt), cationic surfactant (amine salt, quaternary ammonium salt), amphoteric surfactant ( Carboxylic acid type amphoteric surfactant, sulfate ester type amphoteric surfactant, sulfonic acid type amphoteric surfactant, phosphate ester type amphoteric surfactant), nonionic surfactant (ether type nonionic surfactant, ether ester) Type nonionic surfactant, ester type nonionic surfactant, block polymer type nonionic surfactant, nitrogen-containing type nonionic surfactant), other surfactants (natural surfactants, protein hydrolysates) Derivatives, polymer surfactants, surfactants containing titanium and silicon, fluorocarbon surfactants, and the like.

Nonionic surfactants include, for example, sorbitan fatty acid esters (for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate). Glycerol, penta-2-ethylhexyl diglycerol sorbitan, tetra-2-ethylhexyl diglycerol sorbitan, etc.); glycerin polyglycerin fatty acids (eg mono cottonseed oil fatty acid glycerin, monoerucic acid glycerin, sesquioleate glycerin, glyceryl monostearate) , Α, α′-oleic acid pyroglutamate glycerin, monostearate glycerin malate, etc.); propylene glycol fatty acid esters (for example, monos Propylene glycol tea acrylate, etc.); hardened castor oil derivative; glycerin alkyl ether and the like.

Examples of the POE-based hydrophilic nonionic surfactant include POE-sorbitan fatty acid esters (for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate). POE sorbite fatty acid esters (eg, POE-sorbite monolaurate, POE-sorbite monooleate, POE-sorbite pentaoleate, POE-sorbite monostearate, etc.); POE-glycerin fatty acid esters (eg, POE-glycerol monostearate, POE-glycerin monoisostearate, POE-monooleate such as POE-glycerol triisostearate, etc.); POE-fatty acid esters (for example, POE-distearate) POE-alkyl ethers (for example, POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether), POE-monodiolate, ethylene glycol distearate, etc. POE-cholestanol ether, etc.); Pluronic type (for example, Pluronic, etc.); POE • POP-alkyl ethers (for example, POE • POP-cetyl ether, POE • POP-2-decyltetradecyl ether, POE • POP−) Monobutyl ether, POE / POP-hydrogenated lanolin, POE / POP-glycerin ether, etc.); tetra-POE / tetra-POP-ethylenediamine condensates (for example, Tetronic, etc.); POE-castor oil-cured castor Oil derivatives (eg POE-castor oil, POE-hardened castor oil, POE-hardened castor oil monoisostearate, POE-hardened castor oil triisostearate, POE-hardened castor oil monopyroglutamic acid monoisostearic acid diester, POE -Hardened castor oil maleic acid, etc.); POE-beeswax lanolin derivatives (eg POE-sorbite beeswax etc.); alkanolamides (eg coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide etc.); POE- Examples thereof include propylene glycol fatty acid ester; POE-alkylamine; POE-fatty acid amide; sucrose fatty acid ester; alkylethoxydimethylamine oxide; trioleyl phosphate.

Examples of the lower alcohol include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol, lauryl alcohol, cetanol, stearyl alcohol, oleyl alcohol and the like.

Examples of the polyhydric alcohol include divalent alcohols (for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, Pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, octylene glycol, etc.); trivalent alcohol (eg, glycerin, trimethylolpropane, etc.); tetravalent alcohol (eg, 1, 2, 6) Pentaerythritol such as hexanetriol, etc .; pentavalent alcohol (eg, xylitol, etc.); hexavalent alcohol (eg, sorbitol, mannitol, etc.); polyhydric alcohol polymer (eg, diethylene glycol, dipropylene glycol, Tylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin, etc.); divalent alcohol alkyl ethers (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol) Monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol Dibutyl Dihydric alcohol alkyl ethers (for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol) Monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol Dibutyl alcohol ether ester (for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diazebate, ethylene glycol disuccine) Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc.); glycerin monoalkyl ether (example) Sugar alcohol (eg, sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, amylolytic sugar, maltose, xylitol, starch decomposition) Sugar-reduced alcohol, etc.); glycolide; tetrahydrofurfuryl alcohol; POE-tetrahydrofurfuryl alcohol; POP-butyl ether; POP / POE-butyl ether; tripolyoxypropylene glycerin ether; POP-glycerin ether; POP · POE-pentane erythritol ether, polyglycerin and the like.
Examples of the higher alcohol include lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, jojoba alcohol, lanolin alcohol, batyl alcohol, 2-decyltetrathececinol, cholesterol, phytosterol, and isostearyl. Alcohol etc. are mentioned.
Examples of other alcohols include natural alcohols such as cholesterol and phytosterol, and synthetic alcohols such as 2-hexyldecanol, isostearyl alcohol, and 2-octyldodecanol.

Oils include avocado oil, olive oil, sesame oil, camellia oil, evening primrose oil, turtle oil, macadamian nut oil, corn oil, mink oil, rapeseed oil, egg yolk oil, persic oil, wheat germ oil, sasanca oil, castor oil , Linseed oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, kiri oil, jojoba oil, cacao butter, palm oil, horse oil, palm oil, palm kernel oil , Beef tallow, sheep fat, lard, lanolin, whale wax, beeswax, carnauba wax, molasses, candelilla wax, squalane, etc. and its hardened oil, mineral oils such as liquid paraffin, petrolatum, synthesis of glycerin tripalmitate, etc. Triglycerin is mentioned.

Examples of fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, 12-hydroxystearic acid, undecylenic acid, tall oil, lanolin fatty acid and other natural fatty acids, isononanoic acid, caproic acid, 2- Synthetic fatty acids such as ethyl butanoic acid, isopentanoic acid, 2-methylpentanoic acid, 2-ethylhexanoic acid and isopentanoic acid are exemplified. Examples of other higher fatty acids include linoleic acid, linolenic acid, isostearic acid, eicosapentaenoic acid, and docosahexaenoic acid.

For example, esters include isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, oleyl oleate, decyl oleate, octyldodecyl myristate, hexyl decyl dimethyloctanoate, cetyl lactate, lactic acid Myristyl, diethyl phthalate, dibutyl phthalate, lanolin acetate, ethylene glycol monostearate, propylene glycol monostearate, propylene glycol dioleate, cetyl octanoate, octyldodecyl myristate, isopropyl myristate, myristyl myristate, isopropyl palmitate , Butyl stearate, dimethyloctanoic acid, and the like.
Examples of silicone include chain polysiloxanes such as dimethylpolysiloxane and methylphenylpolysiloxane, cyclic polysiloxanes such as decamethylcyclopolysiloxane, and three-dimensional network structures such as silicone resins.

Examples of waxes include beeswax, carnauba wax, whale wax, lanolin, liquid lanolin, reduced lanolin, hard lanolin, candelilla wax, montan wax, shellac wax, and the like.

Examples of mineral oils include liquid paraffin, petrolatum, paraffin, ozokelide, ceresin, microcristan wax, polyethylene powder, squalene, squalane, and pristane.

For example, examples of the metal soap include aluminum stearate, magnesium stearate, zinc stearate, calcium stearate, zinc palmitate, magnesium myristate, zinc laurate, and zinc undecylate.

For example, gum and water-soluble polymer compounds include gum arabic, benzoin gum, danmar gum, guaiac oil, Irish moss, Karaya gum, tragacanth gum, carob gum, quinseed, agar, casein, dextrin, gelatin, pectin, starch, carrageenan, Carboxyalkylchitin, chitosan, hydroxyalkylchitin, low molecular chitosan, chitosan salt, sulfated chitin, phosphorylated chitin, alginic acid and its salt, hyaluronic acid and its salt, chondroitin sulfate, heparin, ethylcellulose, methylcellulose, carboxymethylcellulose, carboxyethylcellulose , Sodium carboxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, nitrocellulose, crystalline cellulose Scan, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, polyvinyl methacrylate, polyacrylic acid salts, polyalkylene oxide or crosslinked polymer thereof such as polyethylene oxide or polypropylene oxide, carboxyvinyl polymers, such as polyethyleneimine.

For example, as vitamins, retinol, retinal (vitamin A1), dehydroretinal (vitamin A2), carotene, lycopene (provitamin A), vitamin B group, thiamine hydrochloride, thiamine sulfate (vitamin B1) ), Riboflavin (vitamin B2), pyridoxine (vitamin B6), cyanocobalamin (vitamin B12), folic acid, nicotinic acids, pantothenic acids, biotins, choline, inositols, vitamin C, ascorbic acid and its derivatives, vitamin D In the group, ergocalciferol (vitamin D2), cholecalciferol (vitamin D3), dihydrotachysterol, in vitamin E group, tocopherol and its derivatives, ubiquinones, in vitamin K group, phytonadione (vita) Emissions K1), menaquinone (vitamin K2), menadione (vitamin K3), and the like menadiol (vitamin K4).

For example, amino acids include valine, leucine, isoleucine, threonine, methionine, phenylalanine, tryptophan, lysine, glycine, alanine, asparagine, glutamine, serine, cysteine, cystine, tyrosine, proline, hydroxyproline, aspartic acid, glutamic acid, hydroxylysine , Arginine, ornithine, histidine, and the like, and sulfates, phosphates, nitrates, citrates, and amino acid derivatives such as pyrrolidone carboxylic acid.

For example, extracts or extracts of animals or plants and herbal medicines include Asenyaku (Asenyaku), Ashitaba, Acerola, Altea, Arnica, Avocado, Achacha (Amacha), Aloe, Aloe Vera, Nettle, Ginkgo (Ginkgo leaf, Ginkgo), Fennel (cage), turmeric (red gold), usba saishin (spicy), Japanese apricot (salmon plum), Japanese white beetle, walrus, green rose (fruit), hikikoshi (life-extending grass), Japanese oak (yellow cocoon), Koganebana (Ogon), Yamazakura ( Cherry bark), yellowfin, yellow orchid, ginseng, carrot, helicopter, licorice, holland garashi, orange, himehagi (distant), eel-brush (summer hay), tsurugokudami (what head-knot), enju (槐花）, mugwort (guy leaf), scallops (莪 朮), kudu (kazune), kanoko Cormorant (Valgarine), Chamomile, Kikarasuuri (Gorne), Kawamomogi (Golden Chrysanthemum), Licorice (licorice), Japanese licorice (Cavity Winter Flower, Cicada Winter Leaves), Japanese Strawberry, Kiwi Fruit, Japanese Clover (Kikkyo), Chrysanthemum (Chrysanthemum Flower) ), Catalpa (fruit), Citrus genus fruit (fruit), Tachibana (tachibana skin), cucumber, Udo or Shishido (living, solitary), apricots, wolfberry (bone crust, coconut, coconut leaves) , Clara, bittersweet, Kumazasa, grapefruit fruit, Nikkei, Keikei, Ebisugusa, Maruba morning glory or morning glory (Ken bull), safflower (Safflower), Gobaishi (penta), Confrey , Copaiba, gardenia, gentian, honoki (shoku), hinata taikozu (cow knee), goshuyu (burdock), burdock, butterfly Ngomushi (Gomiko), Rice, Rice bran, Wheat, Mishima Saiko (Saiko), Saffron, Savonso, Hawthorn (Yamazako), Salamander (Samurai), Salvia, Sancynin carrot (Ginseng ginseng), Shiitake mushroom (Shiitake), Jiou (jihuang), Shikunshi (Mr. Kimiko), Murasaki (Shine), Perilla (Shiso leaf, Shiso), Oyster (柿蒂), Peonies (glaze), Psyllium (car forerunner, car front grass), Ginger (ginger), Shobu (Japanese cypress), Japanese horned potato (Sadako), Shimotsuke, Shiraba, Honeysuckle (Gin and silver flowers, Shinobu), Ivy, Achillea millefolium, Elderberry, Azuki (Red Azuki), Elderberry (Bone), Zeniaoi, Senkyu ), Assembly (this drug), mulberry (mulberry white skin, mulberry leaf), jujube (daegu), soybean, taranoki, chiketsu carrot (bamboo ginseng) ), Hanasuge (knowing mother), Waremokkou (earth), Dokudami (10 medicines), Fuyumushinatsusatake (Cycium cordyceps), chili pepper, physalis (Torone), Tachikakuso, Ryokucha (green tea), kocha (tea), clove (Clove), mandarin orange (Chen bark), camellia, camellia, capsicum (panju), crested sardine (Tochigi), red bellflower, daidai (orange peel), bituminous (ground), corn (southern fur), tochu (Tochu) , 杜 中葉), tomato, Nanten (Southern fruit), garlic (large sun), barley (malt), hakusen (white birch), janohi (barley winter), parsley, batata, mint (light load), hamamelis, rose , Loquat leaves, pine pods, grapes or their leaves, loofah, bodaiju, buttons (peony skin), hops, maikai , Matsuba, Maronie, Mannenrou, Mukuroji, Melissa, Merirot, Bokeh (Kiso), Palms, Peach (Peachin, Peach), Hiogi (Garden-dried), Binroju (Mellow wax), Swordfish (Mothera), Cornflower, Yukinoshita Grass), bayberry (Yellow Plum), Yashabushi (Yakuin), pearl barley (Yokuinin), mugwort, sagebrush, lavender, apple fruit, garlic mushroom (reishi), lemon fruit, forsythia (lily), forsythia, genus , Hashiridokoro (roth root), chicken tosaka, cattle / human placenta extract, pig / cow stomach, duodenum, or intestinal extract or its degradation product, water-soluble collagen, water-soluble collagen derivative, collagen hydrolyzate, Elastin, elastin hydrolyzate, water-soluble elastin derivative, silk protein, sill Protein hydrolyzate, and the like cow blood cell protein hydrolyzate.

Examples of microbial culture metabolites include yeast extract, zinc-containing yeast extract, germanium-containing yeast extract, selenium-containing yeast extract, magnesium-containing yeast extract, rice fermentation extract, Euglena extract, and lactic acid fermented milk powder. .

For example, examples of the α-hydroxy acid include glycolic acid, citric acid, malic acid, tartaric acid, and lactic acid.

For example, inorganic pigments include anhydrous silicic acid, magnesium silicate, talc, kaolin, bentonite, mica, titanium mica, bismuth oxychloride, zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, calcium carbonate, magnesium carbonate, yellow oxide Examples include iron, bengara, black iron oxide, gunjo, chromium oxide, chromium hydroxide, carbon black, and calamine.

For example, astringents include lactic acid, tartaric acid, succinic acid, citric acid, allantoin, zinc chloride, zinc sulfate, zinc oxide, calamine, zinc p-phenolsulfonate, potassium aluminum sulfate, resorcin, ferric chloride, tannic acid Etc.

Examples of the bactericidal / disinfectant include acrinol, sulfur, benzalkonium chloride, benzethonium chloride, methyl rosaniline chloride, cresol, calcium gluconate, chlorhexidine gluconate, sulfamine, mercurochrome, lactoferrin or a hydrolyzate thereof.

For example, selenium disulfide, alkylisoquinolinium bromide, zinc pyrithione, biphenamine, thianthol, castari tincture, ginger tincture, pepper tincture, quinine hydrochloride, strong ammonia water, potassium bromate, sodium bromate And thioglycolic acid.

For example, as perfumes, natural animal perfumes such as musk, civet, castorium, ambergris, anise essential oil, angelica essential oil, Iran essential oil, Iris essential oil, fennel essential oil, orange essential oil, cananga essential oil, caraway essential oil, cardamom essential oil, guayakwood essential oil , Cumin essential oil, black letter essential oil, cinnamon essential oil, cinnamon essential oil, geranium essential oil, copaiba balsam essential oil, coriandel essential oil, perilla essential oil, cedarwood essential oil, citronella essential oil, jasmine essential oil, gingergrass essential oil, cedar essential oil, spearmint essential oil, western peppermint essential oil , Otsuka perfume essential oil, tuberose essential oil, clove essential oil, orange flower essential oil, winter green essential oil, trout balsam essential oil, buttery essential oil, rose essential oil, palmarosa essential oil, persimmon essential oil, hiba essential oil, sandalwood essential oil, petitgren essential oil, bay essential oil, vetiva essential oil, bell Vegetable fragrances such as Mott essential oil, Peruvian balsam essential oil, Boad Rose essential oil, melamine essential oil, mandarin essential oil, eucalyptus essential oil, lime essential oil, lavender essential oil, linaloe essential oil, lemongrass essential oil, lemon essential oil, rosemary essential oil, Japanese seed mint essential oil, Other synthetic fragrances can be mentioned.

For example, as a dye / colorant, a red cabbage dye, a red rice dye, an akane dye, an anato dye, an squid dye, a turmeric dye, an enju dye, a krill dye, an amber dye, a caramel, a gold, a silver, a gardenia dye, a corn dye, Examples include onion pigment, tamarind pigment, spirulina pigment, buckwheat whole plant pigment, cherry pigment, laver pigment, hibiscus pigment, grape juice pigment, marigold pigment, purple potato pigment, purple yam pigment, lac pigment and rutin.

Examples of sweeteners include sugar, sweet tea, fructose, arabinose, galactose, xylose, mannose, maltose, honey, glucose, miraculin, monelin and the like.

For example, examples of the nutrient fortifier include shell calcined calcium, cyanocolabamine, yeast, wheat germ, soybean germ, egg yolk powder, hemicellulose, heme iron and the like.

Other ingredients and additives that can be blended into the cosmetic composition containing the crosslinked L-PGA of the present invention include hormones, sequestering agents, pH adjusters, chelating agents, antiseptic and antibacterial agents , Fresheners, stabilizers, emulsifiers, animal / plant proteins and their degradation products, animal / plant polysaccharides and their degradation products, animal / plant glycoproteins and their degradation products, blood flow promoters, anti-inflammatory agents / Antiallergic agents, cell activators, keratolytic agents, wound treatment agents, foaming agents, thickeners, oral preparations, deodorizing / deodorizing agents, bittering agents, seasonings, enzymes and the like.

The cosmetic composition containing the L-PGA crosslinked product of the present invention can be widely used when a moisturizing effect, a thickening effect, a hair improving effect and the like are required. The amount to be used is determined within a range in which the desired moisturizing effect, thickening effect, hair improving effect and the like are sufficiently exhibited.

Of course, the cosmetic composition of the present invention can be used as a cosmetic composition or a cosmetic because of the above-mentioned effects. In addition, the quasi-drug composition, the medical product composition, and the hygiene product composition are used. Products, pharmaceutical compositions, functional food compositions, quasi-drugs, medical supplies, hygiene products, pharmaceutical products, and premixed products.

The following examples further illustrate the present invention in detail but are not to be construed to limit the scope thereof.

Example 1
(1) Production of L-PGA
Natalba aegyptica 0831-264 strain (Accession number :) obtained on the basis of Patent Document 2 (Japanese Patent Laid-Open No. 2007-314434) and deposited at the National Institute of Advanced Industrial Science and Technology Patent Biological Depositary Center A single colony of FERM BP-20874) was scraped with a platinum loop, and 3 ml of PGA production liquid medium-1 (22.5% NaCl, 2.0% MgSO ₄ .7H ₂ O, 0.2% KCl, 3 0% Trisodium Citrate, 1.0% Yeast Extract, 0.75% Cassino acid) / 18 ml test tube × 5 cells, and cultured at 37 ° C. and 300 rpm for 3 days. 0.5 ml of the obtained culture solution was inoculated into 50 ml of PGA production liquid medium-1 / 500 ml Sakaguchi flask × 10 and cultured at 37 ° C. for 5 days. The obtained culture broth was centrifuged to remove the cells. Subsequently, the obtained supernatant was diluted with 3 times the amount of water, and then the pH was adjusted to 3.0. After pH adjustment, the mixture was stirred at room temperature for 5 hours. Thereafter, 3 times the amount of ethanol was added and centrifuged, and poly-γ-L-glutamic acid was recovered as a precipitate. The precipitate was dissolved in 0.1 mM Tris-HCl buffer (pH 8.0) and dialyzed to remove low molecular weight substances. After dialysis, the resulting solution was added to 1 mM MgCl ₂ , 10 U / ml DNase I (TaKaRa), 20 μg / ml RNase I (NIPPON GENE) for incubation for 2 hours at 37 ° C. did. Subsequently, 3 U / ml Proteinase K (manufactured by TaKaRa) treatment was incubated at 37 ° C. for 5 hours for protein removal. After Proteinase K treatment, dialyzed against MilliQ water to remove low molecular weight substances. After dialysis, poly-γ-L-glutamic acid was adsorbed onto an anion exchange resin, Q Sepharose Fast Flow (manufactured by Amersham Biosciences), and after washing, eluted with 1M NaCl. The resulting solution was dialyzed against MilliQ water, and the solution after dialysis was freeze-dried to obtain poly-γ-L-glutamic acid / Na salt.
The H-NMR spectrum (500 MHz) of the obtained poly-γ-L-glutamic acid was measured using heavy water, and confirmed to be poly-γ-L-glutamic acid.

(2) GPC analysis and IR analysis of Na salt The average molecular weight of the obtained poly-γ-L-glutamic acid / Na salt was measured by GPC analysis. IR analysis was also performed.
As a result of GPC analysis, it was confirmed that Mw = 7,522,000, Mn = 3,704,000, and Mw / Mn = 2.031 (in pullulan conversion).
The GPC analysis conditions are as follows.
Apparatus: HCl-8220GPC (manufactured by Tosoh Corporation)
Column: TSGel α-M (manufactured by Tosoh Corporation)
Flow rate: 0.6 ml / min
Eluent: 0.15M NaCl aqueous solution Column temperature: 40 ° C
Injection volume: 10 μl
Detector: It was shown that it was Na salt from the result of the differential refractometer IR analysis.

(Example 2) Production of L-PGA cross-linked product A 5 wt% aqueous solution of L-PGA · Na salt obtained in Example 1 was prepared, and the obtained 5 wt% L-PGA · Na salt aqueous solution was used with nitrogen. After 3 minutes of bubbling, 2 ml of each was dispensed into 10 ml sample bottles with lids and the lids were closed.

 Next, 2 ml of a 5% by weight aqueous solution of L-PGA / Na salt bubbled with nitrogen for 3 minutes was put in the sample bottle closed and γ-rays were emitted using a γ-ray irradiator with cobalt 60 as the radiation source. Irradiated. Irradiation dose was 5 kGy. The product obtained after γ-ray irradiation was taken out of the sample bottle, excess water was drained with an 80-mesh wire mesh, and freeze-dried to obtain L-PGA crosslinked powder. The excess water contains uncrosslinked L-PGA, and the main purpose of draining is to remove uncrosslinked L-PGA.

Next, the obtained L-PGA cross-linked powder was placed in a sufficient amount of water for the L-PGA cross-linked powder to swell and allowed to stand for 1 week. After leaving still, uncrosslinked L-PGA was removed by filtering with an 80 mesh wire mesh, and hydrogel was obtained.

(Example 3) Manufacture of essence (1) Manufacture of essence containing antibacterial agent and L-PGA cross-linked body A essence having the composition shown below was produced by a conventional method. As the L-PGA crosslinked product, the L-PGA crosslinked product described in Example 2 was used.
(Composition) (wt%)
Oil phase component: stearic acid 3.0
Squalane 5.0
Olive oil 5.0
Poly-γ-L-glutamic acid crosslinked product 2.0
Emulsifier: POE sorbitan monolaurate 5.0
Sorbitan monostearate 5.0
Alkali: Triethanolamine 1.0
Antibacterial agent: zinc undecylenate 4.0
Aqueous phase component: propylene glycol 5.0
Total amount of purified water is 100

(2) Manufacture of serum containing antibacterial agent (comparative example)
As a control (comparative example), a serum containing no L-PGA crosslinked product was also produced.
(Composition) (wt%)
Oil phase component: stearic acid 3.0
Squalane 5.0
Olive oil 5.0
Emulsifier: POE sorbitan monolaurate 5.0
Sorbitan monostearate 5.0
Alkali: Triethanolamine 1.0
Antibacterial agent: zinc undecylenate 4.0
Aqueous phase component: propylene glycol 5.0
Total amount of purified water is 100

(Example 4) Evaluation of serum (1) Evaluation of serum (control) (Comparative example)
Using the cosmetic liquid of the comparative example, five panelists evaluated the spread, lack of tingling, moist feeling, and difficulty in sticking when using this, and judged according to the following criteria.
The results are shown in Table 1.
Judgment criteria:
A: 4 or more out of 5 evaluated as good.
A: 3 out of 5 people evaluated it as good.
(Triangle | delta): Two persons evaluated that 5 persons were favorable.
X: 1 or less out of 5 evaluated as good.

(2) Evaluation of serum (L-PGA cross-linked product)
Using the serum of the composition shown in Example 3, five panelists evaluated the spread, no tingling, moist feeling, and difficulty in sticking when used, and determined according to the following criteria: did. The results are shown in Table 2. In any case, the inclusion of the L-PGA cross-linked product makes the spread and moist feeling good, eliminates the tingling sensation as an index of irritation, and improves the difficulty of bulking as an index of antibacterial effect. Rated as good.
Judgment criteria:
A: 4 or more out of 5 evaluated as good.
A: 3 out of 5 people evaluated it as good.
(Triangle | delta): Two persons evaluated that 5 persons were favorable.
X: 1 or less out of 5 evaluated as good.

A cosmetic composition comprising the crosslinked poly-γ-L-glutamic acid of the present invention and an antibacterial agent, and having a problem of safety such as skin irritation, and also has a feeling of spreading, moist feeling, and being hard to be crushed, Quasi-drugs, medical supplies, hygiene products, and pharmaceuticals can be provided. Furthermore, since the raw material cost is low, mass production is possible, and it can sufficiently withstand long-term use, it is expected to contribute greatly to the industry.

Claims (3)

  A cosmetic composition comprising a poly-γ-L-glutamic acid crosslinked product and an antibacterial agent.   The cosmetic composition according to claim 1, wherein the antibacterial agent is an organic antibacterial agent and / or an inorganic antibacterial agent.   The cosmetic composition according to any one of claims 1 to 2, wherein the cosmetic composition is used as a cosmetic, a quasi-drug, a medical product, a hygiene product, or a pharmaceutical product.