JP2013091771A - CATIONIZED β-GLUCAN - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cationized β-glucan that has higher conditioning effect than a conventional cationized polymer and is a cationic polymer derived from a natural polymer.SOLUTION: A cationized β-glucan is obtained by cationizing β-glucans such as a β-1,3-1,6-glucan.

Description

  The present invention relates to a cationized β-glucan that exhibits an excellent effect when blended in cosmetics and the like, and a cosmetic composition containing the cationized β-glucan.

  Cationized polymers (cationic polymers) are used in various applications such as cosmetics, paper, waste liquid treatment, paints, dyes, resin additives, and the like. Among these uses, cosmetics often come into contact with the skin and hair, so that highly safe polymers are often used. Among these polymers, cationic polymers derived from natural polymers are known as polymers with particularly high safety.

  As cationic polymers derived from natural polymers, for example, cationized cellulose, cationized starch, cationized pullulan, cationized guar gum and the like are known, and the thickening, dispersion stability, and shape retention of cosmetics are known. In particular, compositions that are intended to clean the body and hair, such as shampoos, rinses, body soaps, and facial cleansing agents, exert a conditioning effect by adhering to the hair and skin when rinsed. .

  For example, Patent Document 1 discloses a cosmetic for cleaning, which contains a saturated fatty acid ester of silicone, ethylene glycol, xanthan gum, and a cationized polymer. Patent Document 2 includes a specific amphoteric polymer and a cationic polymer such as polydimethylmethylenepiperidinium chloride, cationized cellulose, cationized guar gum, diallyl quaternary ammonium salt / acrylamide copolymer. A cleaning composition is disclosed. Further, Patent Document 3 discloses an N-acyl aspartic acid-based surfactant mainly composed of a specific N-acyl aspartic acid or a salt thereof, and cationized cellulose, cationized guar gum, cationized dextran, cationized hydrolysis. A detergent composition comprising a cationic polymer such as protein, cationized vinyl, and cationic surfactant is disclosed. Patent Document 4 discloses (A) a cationized hyaluronic acid having a quaternary ammonium group-containing group and a cationization degree of 0.15 to 0.6 and / or a salt thereof; (B) An amphoteric surfactant; and (C) a hair cleanser composition containing an anionic surfactant and containing 1 to 5% of the total amount of the component (B) is disclosed. . Further, Patent Document 5 discloses an aqueous liquid detergent composition containing (A) polyoxyethylene alkyl ether sulfate and (B) cationized cellulose.

JP-A-11-228383 JP 2001-064678 A Japanese Patent Laying-Open No. 2005-307019 JP 2010-037228 A JP 2005-162666 A

  However, cationic polymers derived from natural polymers such as cationized cellulose are more conditioned than the synthetic cationic polymers such as homopolymers of dimethyldiallylammonium chloride and copolymers of dimethyldiallylammonium chloride and acrylamide. It has the disadvantage of being inferior in effect. This drawback is not improved even if the addition amount of the cationic polymer is increased, and a cationic polymer derived from a natural polymer having performance equivalent to that of a synthetic cationic polymer has been desired.

  Therefore, the problem to be solved by the present invention is a cationized β-glucan derived from a natural polymer and having a conditioning effect, a moisturizing effect, a thickening property and a coating property higher than those of conventional cationized polymers, and the cationization The object is to provide a cosmetic composition in which β-glucan and a specific cosmetic material are used in combination.

［式中、Ｒ^１〜Ｒ^３は、水素原子又は下記の一般式（５）で表される基を表す。ただし、Ｒ^１〜Ｒ^３のいずれか少なくとも１つは下記の一般式（５）で表される基でなければならない。］
一般式（２）

［式中、Ｒ^４〜Ｒ^６は、水素原子又は下記の一般式（５）で表される基を表す。ただし、Ｒ^４〜Ｒ^６のいずれか少なくとも１つは下記の一般式（５）で表される基でなければならない。］
一般式（３）

［式中、Ｒ^７及びＲ^８は、水素原子又は下記の一般式（５）で表される基を表す。ただし、Ｒ^７及びＲ^８のいずれか少なくとも１つは下記の一般式（５）で表される基でなければならない。］
一般式（４）

［式中、Ｒ^９〜Ｒ^１４は、水素原子又は下記の一般式（５）で表される基を表す。ただし、Ｒ^９〜Ｒ^１４のいずれか少なくとも１つは下記の一般式（５）で表される基でなければならない。］

（式中、Ｒ^１５〜Ｒ^１７は、炭素数１〜３のアルキル基を表し、Ｒ^１８は、炭素数１〜６のアルキレン基又は炭素数２〜６のヒドロキシアルキレン基を表し、Ｘは、ハロゲン原子を表す。） Thus, the present inventors diligently studied, and found that a cationized β-glucan having a specific structure has a high conditioning effect on hair and skin, leading to the present invention.
That is, the present invention is a cationized β-glucan containing any one or more of units represented by the following general formulas (1) to (4):
General formula (1)

[Wherein R ^{1 to} R ³ represent a hydrogen atom or a group represented by the following general formula (5). However, at least one of R ^{1 to} R ³ must be a group represented by the following general formula (5). ]
General formula (2)

[Wherein, R ^{4 to} R ⁶ represent a hydrogen atom or a group represented by the following general formula (5). However, at least one of R ^{4 to} R ⁶ must be a group represented by the following general formula (5). ]
General formula (3)

[Wherein, R ⁷ and R ⁸ represent a hydrogen atom or a group represented by the following general formula (5). However, at least one of R ⁷ and R ⁸ must be a group represented by the following general formula (5). ]
General formula (4)

[Wherein R ^{9 to} R ¹⁴ represent a hydrogen atom or a group represented by the following general formula (5). However, at least one of R ^{9 to} R ¹⁴ must be a group represented by the following general formula (5). ]

(In the formula, R ^{15 to} R ¹⁷ represent an alkyl group having 1 to 3 carbon atoms, R ¹⁸ represents an alkylene group having 1 to 6 carbon atoms or a hydroxyalkylene group having 2 to 6 carbon atoms, and X is Represents a halogen atom.)

  The effect of the present invention is to provide a cationized β-glucan derived from a highly safe natural polymer having an extremely high conditioning effect and antibacterial property, and a cosmetic composition containing the cationized β-glucan. .

Photograph showing results of static electricity generation test for healthy hair Photo showing the result of static electricity generation test on damaged hair Photo showing the results of static electricity generation test of hair treated with cationized β-glucan 1 of Example 1 Photo showing results of static electricity generation test on hair treated with cationized cellulose of Comparative Example 2 Photo showing results of static electricity generation test on hair treated with cationized guar gum of Comparative Example 3 Photo showing the result of static electricity generation test of hair treated with β-glucan of Comparative Example 4

［式中、Ｒ^１〜Ｒ^３は、水素原子又は下記の一般式（５）で表される基を表す。ただし、Ｒ^１〜Ｒ^３のいずれか少なくとも１つは下記の一般式（５）で表される基でなければならない。］
一般式（２）

［式中、Ｒ^４〜Ｒ^６は、水素原子又は下記の一般式（５）で表される基を表す。ただし、Ｒ^４〜Ｒ^６のいずれか少なくとも１つは下記の一般式（５）で表される基でなければならない。］
一般式（３）

［式中、Ｒ^７及びＲ^８は、水素原子又は下記の一般式（５）で表される基を表す。ただし、Ｒ^７及びＲ^８のいずれか少なくとも１つは下記の一般式（５）で表される基でなければならない。］
一般式（４）

［式中、Ｒ^９〜Ｒ^１４は、水素原子又は下記の一般式（５）で表される基を表す。ただし、Ｒ^９〜Ｒ^１４のいずれか少なくとも１つは下記の一般式（５）で表される基でなければならない。］
一般式（５）

（式中、Ｒ^１５〜Ｒ^１７は、炭素数１〜３のアルキル基を表し、Ｒ^１８は、炭素数１〜６のアルキレン基又は炭素数２〜６のヒドロキシアルキレン基を表し、Ｘは、ハロゲン原子を表す。） Glucan is a general term for polysaccharides composed of D-glucose, and is classified into α-glucan having an α-anomeric structure and β-glucan having a β-anomeric structure depending on the configuration of glucose residues. In the present invention, cationized β-glucan refers to a compound in which hydrogen atoms of some hydroxyl groups of β-glucan are substituted with cationic groups.
The cationized β-glucan of the present invention is a cationized β-glucan containing any one or more of units represented by the following general formulas (1) to (4):
General formula (1)

[Wherein R ^{1 to} R ³ represent a hydrogen atom or a group represented by the following general formula (5). However, at least one of R ^{1 to} R ³ must be a group represented by the following general formula (5). ]
General formula (2)

[Wherein, R ^{4 to} R ⁶ represent a hydrogen atom or a group represented by the following general formula (5). However, at least one of R ^{4 to} R ⁶ must be a group represented by the following general formula (5). ]
General formula (3)

[Wherein, R ⁷ and R ⁸ represent a hydrogen atom or a group represented by the following general formula (5). However, at least one of R ⁷ and R ⁸ must be a group represented by the following general formula (5). ]
General formula (4)

[Wherein R ^{9 to} R ¹⁴ represent a hydrogen atom or a group represented by the following general formula (5). However, at least one of R ^{9 to} R ¹⁴ must be a group represented by the following general formula (5). ]
General formula (5)

(In the formula, R ^{15 to} R ¹⁷ represent an alkyl group having 1 to 3 carbon atoms, R ¹⁸ represents an alkylene group having 1 to 6 carbon atoms or a hydroxyalkylene group having 2 to 6 carbon atoms, and X is Represents a halogen atom.)

R ^{1 to} R ^{3 in} the general formula (1), R ^{4 to} R ^{6 in the} general formula (2), R ⁷ and R ^{8 in the} general formula (3), and R ^{9 to} R ¹⁴ in the general formula (4) are hydrogen. This represents an atom or a group represented by the general formula (5). The group represented by the general formula (5) may be located at any position, but since the substitution reaction with the cationic group easily proceeds, the 6th position of the glucose unit, that is, in the case of the general formula (1) In the case of R ¹ and general formula (4), R ⁹ is preferably a group represented by general formula (5). In addition, since the cationized β-glucan of the present invention contains any one or more of the units represented by the general formulas (1) to (4), at least the group represented by the general formula (5) You will have one.

R ^{18 in the} general formula (5) represents an alkylene group having 1 to 6 carbon atoms or a hydroxyalkylene group having 2 to 6 carbon atoms. Examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a tertiary ribylene group, a pentylene group, and a hexylene group. Examples of the hydroxyalkylene group having 2 to 6 carbon atoms include 1-hydroxyethylene group, 2-hydroxyethylene group, 1-hydroxypropylene group, 2-hydroxypropylene group, 3-hydroxypropylene group, hydroxybutylene group, and hydroxypentylene. Examples include a len group and a hydroxyhexylene group. Among these groups, R ¹⁸ is preferably a hydroxyalkylene group having 2 to 6 carbon atoms, more preferably a hydroxypropylene group, and a 2-hydroxypropylene group because the raw material is easily available and can be easily produced. Further preferred.

R < ¹⁵ > -R < ¹⁷ > of General formula (5) represents a C1-C3 alkyl group each independently. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Among these, since the conditioning effect when used as a cosmetic is high, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.

X in the general formula (5) represents a halogen atom, and X ⁻ serves as a counter ion for the cation. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. Among these, a chlorine atom and a bromine atom are preferable, and a chlorine atom is more preferable because it is easily available as a production raw material.

  In the cationized β-glucan of the present invention, the units represented by the general formulas (1) to (4) correspond to the units represented by the following general formulas (1a) to (4a) of the β-glucan, In each of the units represented by the general formulas (1a) to (4a), part or all of the hydrogen atoms of the hydroxyl groups are substituted with groups represented by the general formula (5).

一般式（２ａ）

一般式（３ａ）

一般式（４ａ）

General formula (1a)

General formula (2a)

General formula (3a)

General formula (4a)

  The degree of cationization of the cationized β-glucan of the present invention is preferably 0.1 to 2.0. When the degree of cationization of the cationized β-glucan of the present invention is less than 0.1, a sufficient conditioning effect may not be obtained when blended into a cosmetic composition or the like. Since the cationization reaction requires a long production time and a large amount of cationizing agent, the production is difficult, and the conditioning performance that meets the high degree of cationization cannot be obtained. The degree of cationization of the β-glucan of the present invention is more preferably 0.15 to 1.5, and most preferably 0.2 to 1.0. In the present invention, the degree of cationization means the average value of the number of cationic groups per monosaccharide unit. In the case of the cationized β-glucan of the present invention, the upper limit of the degree of cationization is 3.0. .

  The cationized β-glucan of the present invention can be produced by a method of cationizing β-glucan with a cationizing agent, a method of adding cationized glucose to β-glucan, a method of polymerizing cationized glucose, etc. Since production is easy, it is preferable to produce β-glucan by a method of cationizing with a cationizing agent.

  In the case where the cationized β-glucan of the present invention is produced by a method of cationizing β-glucan with a cationizing agent, the β-glucan is a glucose unit other than the units represented by the general formulas (1a) to (4a). However, β glucan consisting of at least one unit selected from the group consisting of units represented by the general formulas (1a) to (4a) other than the molecular terminals is preferable. As such β-glucan, β-glucan derived from cereals, β-glucan derived from microorganisms, β-glucan derived from basidiomycetes, etc. are known, and extracted from cereals, microorganisms or basidiomycetes containing β-glucan. That's fine. The extraction method of β-glucan is not particularly limited, and it may be extracted by adding an extraction solvent to cereals, microorganisms or basidiomycetes that are raw materials for extraction. As the extraction solvent, water, a salt solution, an aqueous acid solution, an aqueous alkaline solution, an organic solvent, or a mixed solvent of two or more types can be used. Moreover, extraction efficiency can also be improved by using together the enzyme which decomposes | disassembles a cell wall. The extract can be purified by purifying the extract itself in a solid-liquid separation, or a liquid or solid obtained by concentrating β-glucan extracted from the extract by a known method, or purifying the extract by a known method. It can be used in any form, such as liquids and solids that have been raised, in any form, and in any purity. It is also possible to use what is present.

  Among these β-glucans, cationized β-glucan having high water solubility and easy cationization, high conditioning effect on hair and skin, and antibacterial properties can be obtained. Therefore, the β-glucan is represented by the general formula (1a). Β-glucan comprising the unit represented by (4a) and the unit represented by (4a) are preferable, and the molar ratio of the unit represented by (1a) to the unit represented by the general formula (4a) is preferably 1-2. 1.2 to 1.4 is more preferable. A β-glucan composed of only the unit represented by the general formula (1a) is represented by β-1,3-glucan, a unit represented by the general formula (1a) and a β-glucan composed of the unit represented by (4a). Sometimes referred to as β-1,3-1,6-glucan. β-1,3-1,6-glucan can be obtained from black yeast (genus Aureobasidium), for example. In the present invention, a group in which hydrogen atoms of some hydroxyl groups of β-glucan composed of the unit represented by the general formula (1a) and the unit represented by (4a) are represented by the general formula (5). The cationized β-glucan substituted with is sometimes referred to as cationized β-1,3-1,6-glucan.

  When the cationized β-glucan of the present invention is produced by a method of cationizing β-glucan with a cationizing agent, the cationizing agent can react with a cationic group and a hydroxyl group of β-glucan in the molecule. As long as it has two groups with the group and becomes a group represented by the general formula (5) after the reaction, the type is not limited, but since it can be obtained at a low price, the following general formula (6) or (7) A cationizing agent represented by:

［式中、Ｒ^１９は、炭素数１〜４のアルキレン基を表し、Ｒ^１５〜Ｒ^１７及びＸは、一般式（５）と同義である。］

^{Wherein, R 19} represents an alkylene group having 1 to 4 carbon ^atoms, R 15 ^{to R 17} and X are as in formula (5) interchangeably. ]

R ^{19 in the} general formula (6) represents an alkylene group having 1 to 4 carbon atoms. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, an isopropylene group, and an isobutylene group. Among these, a methylene group is preferable because raw materials are easily available. Moreover, R < ¹⁵ > -R < ¹⁷ > and X of General formula (6) are synonymous with General formula (5).

［式中、Ｙはハロゲン原子を表し、Ｒ^１５〜Ｒ^１８及びＸは、一般式（５）と同義である。］

[Wherein, Y represents a halogen atom, and R ^{15 to} R ¹⁸ and X have the same meaning as in general formula (5). ]

Y in the general formula (7) represents a halogen atom. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. Among these, a chlorine atom and a bromine atom are preferable, and a chlorine atom is more preferable because it is easily available as a production raw material. Moreover, R < ¹⁵ > -R < ¹⁸ > and X of General formula (7) are synonymous with General formula (5).

  The cationizing agent represented by the above general formula (6) has an epoxy group as a reactive group that reacts with the hydroxyl group of β-glucan. On the other hand, in the cationizing agent represented by the general formula (7), the halogen atom represented by Y reacts with the hydroxyl group of β-glucan. Although any cationizing agent can be cationized, the cationizing agent represented by the general formula (7) is represented by the general formula (6) with little generation of impurities because a compound containing Y is generated as an impurity. The cationizing agent is preferred.

  The cationization reaction using the cationizing agent may be performed by a known method. For example, when the cationizing agent represented by the general formula (6) is used, water, the cationizing agent, and β-glucan are mixed. The cationization reaction proceeds by adding and mixing an alkali catalyst such as sodium hydroxide or potassium hydroxide as a catalyst. In order to accelerate the reaction, a water-soluble solvent such as methanol, ethanol, isopropanol, acetone, or acetonitrile may be added. In the case of using a water-soluble solvent, the ratio with water is not particularly specified, but water / water-soluble solvent = 1/9 to 9/1 is preferable because the effect of promoting the reaction is high, and water / water-soluble solvent = 2/8 to 7/3 is more preferable. What is necessary is just to set the quantity of the cationizing agent to be used suitably according to the cationization degree of the target cationized β-glucan.

  The form of the cationized β-glucan of the present invention is not particularly limited, and may be any of water, a water-soluble organic solvent, a liquid using water and a water-soluble organic solvent, or a solid from which the solvent is removed. Any solid form may be used, and the liquid cationized β-glucan solvent may be removed to obtain a solid form. In order to further increase the purity, it is preferable to purify liquid cationized β-glucan by dialysis or the like. In the case of a liquid, the concentration may be adjusted so that the cationized β-glucan of the present invention is 0.01 to 50% by mass, preferably 0.1 to 30% by mass.

  Next, the cosmetic composition containing the cationized β-glucan of the present invention will be described. In the present invention, the cosmetic composition containing the cationized β-glucan of the present invention may be referred to as the cosmetic composition of the present invention. The blending amount of the cationized β-glucan of the present invention in the cosmetic composition of the present invention varies depending on the type and use of the cosmetic composition of the present invention, and is not particularly limited. If the effect is not obtained and the amount is too large, the viscosity may be too high to be difficult to use, so 0.001 to 20% by mass is preferable with respect to the total amount of the cosmetic composition. 0.05 to 5 mass% is more preferable, and 0.01 to 1 mass% is most preferable.

  Examples of components other than the cationized β-glucan of the present invention of the cosmetic composition of the present invention include, for example, surfactants, chelating agents, low molecular polyols, plant-derived extracts, zinc compounds, thickeners, oil agents, pigments, Examples include pigments, antibacterial agents, humectants, pH adjusters, antioxidants, ultraviolet absorbers, moisturizers, enzymes, and fragrances.

  Examples of surfactants include anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants. Examples of anionic surfactants include higher fatty acid salts, higher alcohol sulfates, sulfates. Olefin salt, higher alkyl sulfonate, α-olefin sulfonate, sulfated fatty acid salt, sulfonated fatty acid salt, phosphate ester salt, sulfate ester salt of fatty acid ester, glyceride sulfate ester salt, sulfonate salt of fatty acid ester, α-sulfo fatty acid methyl ester salt, polyoxyalkylene alkyl ether sulfate ester salt, polyoxyalkylene alkyl phenyl ether sulfate ester salt, polyoxyalkylene alkyl ether carboxylate salt, acylated peptide, fatty acid alkanolamide or alkylene oxide thereof Sulfuric acid ester salts of idoid adducts, sulfosuccinic acid esters, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkylbenzimidazole sulfonates, polyoxyalkylene sulfosuccinates, N-acyl-N-methyltaurine salts, N- Acyl glutamic acid or a salt thereof, acyloxyethane sulfonate, alkoxyethane sulfonate, N-acyl-β-alanine or a salt thereof, N-acyl-N-carboxyethyl taurine or a salt thereof, N-acyl-N-carboxymethyl Examples thereof include glycine or a salt thereof, acyl lactate, N-acyl sarcosine salt, and alkyl or alkenylaminocarboxymethyl sulfate.

  Nonionic surfactants include, for example, polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether (addition form of ethylene oxide and propylene oxide may be either random or block. ), Polyethylene glycol propylene oxide adduct, polypropylene glycol ethylene oxide adduct, glycerin fatty acid ester or its ethylene oxide adduct, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, alkyl polyglucoside, fatty acid monoethanolamide or its ethylene oxide addition , Fatty acid-N-methylmonoethanolamide or its ethylene oxide adduct, fatty acid dietane Amide or ethylene oxide adducts, sucrose fatty acid esters, alkyl (poly) glycerol ether, polyglycerol fatty acid esters, polyethylene glycol fatty acid esters, fatty acid methyl ester ethoxylates, N- long chain alkyl dimethyl amine oxides, and the like.

  Examples of the cationic surfactant include alkyl (alkenyl) trimethyl ammonium salt, dialkyl (alkenyl) dimethyl ammonium salt, alkyl (alkenyl) quaternary ammonium salt, mono- or dialkyl (alkenyl) containing ether group, ester group or amide group. ) Quaternary ammonium salt, alkyl (alkenyl) pyridinium salt, alkyl (alkenyl) dimethylbenzyl ammonium salt, alkyl (alkenyl) isoquinolinium salt, dialkyl (alkenyl) morphonium salt, polyoxyethylene alkyl (alkenyl) amine, alkyl (alkenyl) amine Examples thereof include salts, polyamine fatty acid derivatives, amyl alcohol fatty acid derivatives, benzalkonium chloride, and benzethonium chloride.

  Examples of the amphoteric surfactant include carboxybetaine, sulfobetaine, phosphobetaine, amide amino acid, imidazolinium betaine surfactant and the like.

  The surfactant may contain one or more of the above. Although the compounding quantity is not specifically limited, Although it changes with kinds of cosmetic composition, 0.01-80 mass% is preferable with respect to cosmetic composition whole quantity, and 0.05-60 mass% is more preferable.

  Examples of chelating agents include aminopolycarboxylic acid chelating agents, aromatic or aliphatic carboxylic acid chelating agents, amino acid chelating agents, ether polycarboxylic acid chelating agents, phosphonic acid chelating agents, phosphoric acid chelating agents, Examples include hydroxycarboxylic acid chelating agents, polymer electrolyte (including oligomer electrolyte) chelating agents, dimethylglyoxime, ascorbic acid, thioglycolic acid, phytic acid, glyoxylic acid, and glyoxalic acid. These chelating agents may be in the free acid form or in the form of a salt such as sodium salt, potassium salt, or ammonium salt. Furthermore, they may be in the form of their ester derivatives which are hydrolysable.

  Examples of the aminopolycarboxylic acid chelating agent include ethylenediaminetetraacetic acid, ethylenediaminediacetic acid, cyclohexanediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N- (2-hydroxyethyl) iminodiacetic acid, diethylenetriaminepentaacetic acid, N- (2 -Hydroxyethyl) ethylenediaminetriacetic acid, glycol etherdiaminetetraacetic acid, glutamic acid diacetic acid, aspartic acid diacetic acid and their salts.

  Examples of aromatic or aliphatic carboxylic acid chelating agents include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, itaconic acid, aconitic acid, pyruvic acid, salicylic acid, Examples include acetylsalicylic acid, hydroxybenzoic acid, aminobenzoic acid (including anthranilic acid), phthalic acid, fumaric acid, trimellitic acid, gallic acid, hexahydrophthalic acid and salts thereof, methyl esters, and ethyl esters.

  Examples of the amino acid chelating agent include glycine, serine, alanine, lysine, cystine, cysteine, ethionine, tyrosine, methionine, and salts and derivatives thereof.

  Examples of the phosphonic acid-based chelating agent include iminodimethylphosphonic acid, alkyldiphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, and salts thereof.

  Examples of the phosphoric acid chelating agent include orthophosphoric acid, pyrophosphoric acid, triphosphoric acid, and polyphosphoric acid.

  Examples of the hydroxycarboxylic acid chelating agent include malic acid, citric acid, glycolic acid, gluconic acid, heptonic acid, tartaric acid, lactic acid, and salts thereof.

  Examples of the polymer electrolyte (including oligomer electrolyte) chelating agent include acrylic acid polymer, maleic anhydride polymer, α-hydroxyacrylic acid polymer, itaconic acid polymer, and two constituent monomers of these polymers. The copolymer which consists of the above and an epoxy succinic acid polymer are mentioned.

  Among these chelating agents, ethylenediaminetetraacetic acid, ethylenediaminediacetic acid, nitrilotriacetic acid, iminodiacetic acid, N- (2-hydroxyethyl) iminodiacetic acid, aspartic acid diacetic acid, succinic acid are highly safe and have a great chelating effect. Acid, salicylic acid, oxalic acid, lactic acid, fumaric acid, citric acid, tartaric acid, 1-hydroxyethane-1,1-diphosphonic acid and salts thereof are preferred.

  A chelating agent may mix | blend said 1 type, or 2 or more types. Although the compounding quantity is not specifically limited, Although it changes with kinds of cosmetic composition, 0.01-30 mass% is preferable with respect to cosmetic composition whole quantity, and 0.05-20 mass% is more preferable.

  The low molecular polyol is a polyol having a molecular weight of 50 to 1000, preferably 50 to 500. For example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3 -Propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3 -Propanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 2-methyl- 1,2-butanediol, 2-methyl-2 3-butanediol, 2-methyl-1,4-butanediol, 3-methyl-1,2-butanediol, 3-methyl-1,3-butanediol, 2-ethyl-1,3-propanediol, 2, 2-dimethyl-1,3-propanediol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 3,3-hexanediol, 2-methyl- 1,3-pentanediol, 2-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 3-methyl-2,3-pentanediol 3-methyl-2,4-pentanediol, 4-methyl-1,2-pentanediol, 2-ethyl-2-methyl-1,3-propanediol, 2,2-di Til-1,3-butanediol, 2,3-dimethyl-1,2-butanediol, 1,2-heptanediol, 1,7-heptanediol, 3,4-heptanediol, 2-propyl-2-methyl -1,3-propanediol, 2-isopropyl-2-methyl-1,3-propanediol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 2-ethyl-1, 3-hexanediol, 2-sec-butyl-2-butyl-1,3-propanediol, 2,2-dimethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2, 2,4-trimethyl-1,3-pentanediol, 1,2-nonanediol, 1,3-nonanediol, 1,9-nonanediol, 3,6-octanediol 2-ethyl-2- (2-methyl) propyl-1,3-propanediol, 2,2,4-trimethyl-1,6-hexanediol, 2,4,4-trimethyl-1,6-hexanediol 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,2-decanediol, 1,10 -Decanediol, 5,6-decanediol, 3,6-dimethyl-3,6-octanediol, 3,7-dimethyl-1,6-octanediol, 3,7-dimethyl-1,7-octanediol, 1,2-undecanediol, 1,4-undecanediol, 1,11-undecanediol, 6-ethyl-3-methyl-1,6-octanediol, 1,2-dodecanediol 1,10-dodecanediol, 1,12-dodecanediol, 2,4-diethyl-1,5-octanediol, 2,8,8-trimethyl-2,7-nonanediol, 1,2-tetradecanediol, 1 , 14-tetradecanediol, 7,8-tetradecanediol, 1,2-pentadecanediol, 1,2-hexadecanediol, 1,16-hexadecanediol, 1,17-heptadecanediol, 1,2-octadecanediol, 1, , 12-octadecanediol, 1,2-eicosanediol, 1,2-docosanediol, saturated diols such as 1,2-tetracosanediol or condensates thereof;

  2-butene-1,4-diol, 3-butene-1,2-diol, 2-methylene-1,3-propanediol, 2-butyne-1,4-diol, 5-hexene-1,2-diol 3-methyl-2-pentene-1,5-diol, 3-methylenepentane-1,5-diol, 1,5-hexadiene-3,4-diol, 7-octene-1,2-diol, 2, 5-dimethyl-3-hexene-2,5-diol, 9-decene-1,2-diol, 2,6-dimethyl-7-octene-2,6-diol, 3,7-dimethyl-7-octene- 1,6-diol, 13-tetradecene-1, 2-diol, 12-hydroxy-9-octadecenol, 2-pentyne-1,4-diol, 3-hexyne-2,5-diol, 4-methyl-2- Pentin , 4-diol, 3-heptin-2,5-diol, 4-methyl-2-pentyne-1,4-diol, 3,4-dimethyl-1-pentyne-3,4-diol, 2,5-dimethyl -3-hexyne-2,5-diol, 5-decyne-4,7-diol, 2,6-dimethyl-7-octyne-2,6-diol, 3,6-dimethyl-4-octyne-3,6 -Diol, 2,3,6,7-tetramethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5,8 , 11-tetramethyl-6-dodecin-5,8-diol, 1,1,4,4-tetraisopropyl-4-octyne-3,6-diol, 5,10-diethyl-7-tetradecine-6,9 -Unsaturated diols such as diols;

  1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cycloheptanediol, 2,3-norbornane Diol, 2,5-norbornanediol, 2,7-norbornanediol, 1,2-cyclooctanediol, 1,4-cyclooctanediol, 1,2-cyclodecanediol, 5-cyclooctene-1,2-diol Alicyclic diols such as 1,5-decalindiol, limonene glycol, 1,2-terpenediol, 4,4′-bicyclohexanediol, 1,2-cyclododecanediol;

  Glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, 2-methyl-1,2,3-propanetriol, 1,2,3-pentanetriol, 1,2,4-pentanetriol 1,3,5-pentanetriol, 2,3,4-pentanetriol, 2-methyl-2,3,4-butanetriol, trimethylolethane, 2,3,4-hexanetriol, 2-ethyl-1 , 2,3-butanetriol, trimethylolpropane, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, triethanolamine, triisopropanolamine, etc. Alcohols;

  Erythritol, pentaerythritol, 1,2,3,4-pentatetrol, 2,3,4,5-hexatetrol, 1,2,4,5-pentanetetrol, 1,3,4,5-hexane Tetrahydric alcohols such as tetrol, diglycerin, sorbitan, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N ′, N′-tetrakis (hydroxyethyl) ethylenediamine;

  Pentavalent alcohols such as adonitol, arabitol, xylitol, triglycerin; hexavalent alcohols such as dipentaerythritol, sorbitol, mannitol, iditol, inositol, dulcitol, talose, allose;

  1-methyl glyceryl ether, 2-methyl glyceryl ether, 1-ethyl glyceryl ether, 2-ethyl glyceryl ether, 1-propyl glyceryl ether, 2-propyl glyceryl ether, 1-isopropyl glyceryl ether, 2-isopropyl glyceryl ether, 1- Butyl glyceryl ether, 2-butyl glyceryl ether, 1-isobutyl glyceryl ether, 2-isobutyl glyceryl ether, 1-pentyl glyceryl ether, 2-pentyl glyceryl ether, 1-hexyl glyceryl ether, 2-hexyl glyceryl ether, 1-heptyl glyceryl Ether, 2-heptyl glyceryl ether, 1-octyl glyceryl ether, 2-octyl glyceryl ether, 1- (2-ethylhexyl) Lyceryl ether, 2- (2-ethylhexyl) glyceryl ether, 1-nonyl glyceryl ether, 2-nonyl glyceryl ether, 1-decyl glyceryl ether, 2-decyl glyceryl ether, 1-undecyl glyceryl ether, 2-undecyl glyceryl Ether, 1-dodecyl glyceryl ether, 2-dodecyl glyceryl ether, 1-tridecyl glyceryl ether, 2-tridecyl glyceryl ether, 1-tetradecyl glyceryl ether, 2-tetradecyl glyceryl ether, 1-hexadecyl glyceryl ether, 2 -Hexadecyl glyceryl ether, 1-octadecyl glyceryl ether, 2-octadecyl glyceryl ether, 1-branched octadecyl glyceryl ether, 2-branched octadecyl glycerin Ryl ether, 1-eicosyl glyceryl ether, 2-eicosyl glyceryl ether, 1-allyl glyceryl ether, 2-allyl glyceryl ether, 1-undecenyl glyceryl ether, 2-undecenyl glyceryl ether, 1-oleyl glyceryl ether, Glycerin monoethers such as 2-oleyl glyceryl ether, 1-phenyl glyceryl ether, 2-phenyl glyceryl ether;

  N-substituted diethanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-isopropyldiethanolamine, N-butyldiethanolamine, N-cyclohexyldiethanolamine, N- (2-ethylhexyl) diethanolamine;

  N-methyldiisopropanolamine, N-ethyldiisopropanolamine, N-propyldiisopropanolamine, N-isopropyldiisopropanolamine, N-butyldiisopropanolamine, N-cyclohexyldiisopropanolamine, N- (2-ethylhexyl) di N-substituted diisopropanolamines such as isopropanolamine;

  3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 3-dipropylamino-1,2-propanediol, 3-diisopropylamino-1,2-propanediol, 3- Examples include N, N-disubstituted-3-amino-1,2-propanediols such as dibutylamino-1,2-propanediol.

  Among these low molecular polyols, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-pentanediol, 3-methyl 1,3-butanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 2-ethyl-1,3-hexanediol, 1,2-nonanediol, 2-butyl- 2-ethyl-1,3-propanediol, 1,2-decanediol, 1,10-decanediol, glycerin, triethanolamine, triisopropanolamine, erythritol, diglycerin, sorbitan, N, N, N ′, N '-Tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N , N′-tetrakis (hydroxyethyl) ethylenediamine, sorbitol, 1-methylglyceryl ether, 1-ethylglyceryl ether, 1-propylglyceryl ether, 1-butylglyceryl ether, 1-octylglyceryl ether, 1- (2-ethylhexyl) Glyceryl ether, 1-decyl glyceryl ether, and 1-allyl glyceryl ether are preferable. Propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,2-octane Diol, glycerin, triethanolamine, diglycerin, sorbitan, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, sorbitol, 1-allylglyceryl Ether are more preferable, and propylene glycol, dipropylene glycol, 1,3-butanediol, 3-methyl-1,3-butanediol, glycerol, sorbitol, 1-glyceryl ether are more preferable.

  A low molecular polyol may mix | blend said 1 type (s) or 2 or more types. Although the compounding quantity is not specifically limited, Although it changes with kinds of cosmetic composition, 0.01-90 mass% is preferable with respect to cosmetic composition whole quantity, and 0.05-70 mass% is more preferable. Some low molecular weight polyols have a moisturizing effect.

  The plant-derived extract is the whole plant or algae or fungi, or specific parts such as flowers, leaves, stems, fruits, bark, roots, seeds, resins, etc. From what is obtained by extracting with a solvent at normal temperature or under heating, it means what is dissolved in water, ethanol, propylene glycol or oil. Alternatively, the extract may be diluted, concentrated or dried. Further, it may be an essential oil obtained by using a steam distillation method, an extraction method, a chromatography method or the like.

  As an extraction solvent for plant-derived extracts, those usually used for extraction of natural product components, such as water; alcohols such as methanol, ethanol, propanol and butanol; polyvalent such as ethylene glycol, propylene glycol, butylene glycol and glycerin Alcohols; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate; ethers such as tetrahydrofuran, diethyl ether and polyethylene glycol; halogenated hydrocarbons such as dichloroethane and chloroform; petroleum ether, n-hexane, Aliphatic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as toluene; pyridines; sodium chloride solution and the like. Water, ethanol, propylene glycol, and butylene glycol are particularly preferable.

Plants that can be used as plant-derived extracts include, for example, arch chalk, almond, eye, Aisenhard thia polystacia, eyebright, blue-green agave, aomoji, acacia concina, acacia senegal, acacia senegal gum, acacia decreens, red clover, Akaharunire, Akayamajiou, Agi, Agrimonia eupatoria, Akebobi, Asagaokakaraksa, thistle, reed, ashitaba, ajugatsu kestanika, azuki, asunaro, asparagus, asparagus sine alice, acerola, asenayaku, asenayakashi, atlas Gaith Suleio Calps, Avenas Trigosa, Avocado, Ama, Amacha, Amacharu, Amadokoro, Amamo, Amiris Balsamifera, American Pikachi, America Shaw, American Shaw, American Carrot, Amomu Aromachiku, Aracasi, Arcana, Arctium Majus, Arctium Minus, Arnica, Arnica Mysonis, Alpinia Officinalum, Alfalfa (aka Muragosago), Aloe Vera, Ansange, Anzu , Angelica, Anti-risbrunellaria, Amperopsis grocedentata, Anmarok, Ikarisou, Izayoi-bara, Japanese knotweed, Italian cypress, Strawberry, Fig, Ichiyakuso, Ginkgo biloba, Itlan, Carob, Ibukitorano, Imosemiru, Nettle, Iranian squirrels , Iris Parida, Iwabenkei, Iwamituba, common bean, fennel, witania somunifera, turmeric, usubasaicin, moray moth, udo, sea urchin memo Ki, Ume, Uyaku, Urarakanzo, Uri, Urbarakutsuka, Urumus davidiana, Uncarriagementa, Unshu mikan, Ages, Eilan Thai, Edelweiss, Ezokogi, Ezosnake Strawberry, Ezosohagi, Echinashi, Echinaceaparida, Enishidae, Ebene , Elemi, Enju, Pea, Empi-biasin, Enmezo, Paramecium, Oren, Great Thistle, Giant Scorpion, Ozodenda, Giant Peanut, Oki Scarlet, Orchis muscara, Orchid, Oak (also known as European oak), Oogurma , Oleander, crape myrtle, giant mandarin orange, barley palm, barley, barley, allspice, casserole, okra, Osileubana, Panax ginseng, Hypericum, Onigashi, Onisarabia, Oni radish, Onis, Opuntia streptacantha, Opuntia tuna, Dutch mustard, Dutch peonies, olives, Origanum herculeochicum, Orthosiphon stamineus, Ormenis mulcauris, Orange , Orobankerapum, Gardenia Tahitensis, Carnation, Khaya Senegalensis, Cacao, Oyster, Cassia, Cashew Nut, Cascara Sagrada, Cassia Alica, Kappa Ficus Albarezi, Cattleya, Canada , Turnip, cattail, chamomile (aka chamomile), scallop, cayupte, carax salmon, oats, oats, carat Ki, Guarana, Gallica Rose, Cauliflower, Karin, Karuna (aka Goryumodoki), Garcinia Cambodia, Carrot, Kawaramugigi (aka Inchinkou), Licorice, Kantachibi, Kistrawberry, Kiwi, Kikarasuuri, Chrysanthemum, Kigeria Africana, Kidachia Aloe, Kidachidakaha Kinanoki, Quinoa, Yellowfin (also known as Awaku), Kibanasushiro, Kibananohachiwame, Millet, Gymnema, Kimokuren, Cassava, Cabbage, Caraway, Cucumber (also known as Cucumber), Kyo-Oh, Gyoryu, Gyorybai, Kiraya, Kiri, Ginkgo Honeysuckle), guar, guava, quince seed, queercas alba, kuinoki, wolfberry, celandine, kudu, camphor, kudamono-keizou, gardenia, bearberry , Kumazasa, Kumahitsura, Anemonefish, Cumin, Clamelli Adriandora, Clara, Granbury, Chrysmarum Michimum, Grindelarobusta, Clintonia Borealis, Burma Solanum, Walnut, Grapefruit, Clematis, Black Pepper, Blackcurrant, Black-eared Currant, Globe, Blackcurrant Kuromiguwa, Mulberry, Caquette, Kay (aka Cinnamon), Geum Urbanum, Geum Rivere, Cape Aloe, Poppy, Geckavidin, Geckoge, Ghetto, Kamiyama Kozolina, Gentian, Gentian Prostrata, Gennoshokko, Kemponasi, Koki, Kokutitan, Kokeitan , Kouhone, Coffee tree, Scaraba, Coccinia indica, Cocktan, Cochlearia officinalis , Cowberry, coconut, gosho strawberry, pepper, white butterfly, cochineal cactus, moth butterfly, moth orchid, white oak, coconut, burdock, sesame, wheat, rice, colander, coriander, coleus, coleus barbatus, gorenshi, koroha, konzlang (Also known as finflower), combretum mcransum, sisal asa, saicin, cyperus esculentus, cypress, saccharum, south rare involcata, saximas button eel, cherry blossom, cherry tree, pomegranate, sugar maple, sugarcane, sugarcane, sasanka, sasafurafuroki , Savonso, salamander, salix nigra, crape myrtle, sanguinaria canadensis, hawthorn, sansikimire, sanchinininji , Sanshuyu, salamander, sunpens, ciateamedurarisu, cyanotis arachnoidea, shea butter tree, shiozakiso, shishinburiumirio, cystrose (also known as labdanum), cystus monsperiensis, cistus suradanfels, perilla, schichenge, Linden, Shibamugi, Gypterix odrata, Siberian fir, Shimaruba, Shimifugadafurika, Shimotsukeso, Potato, Peonies, Jasmine, Janohige, Ganoderma, Shukusha, Juzudama, Gypsophila, Juniperus (Also known as cardamom), shobu, shrimp, birch, silane, log, shirubana indokei, shirubanarupin, shirubanawata, cinchona krisaya, synsepa Mudhurificum, cymbidium, syprocolacesemosa, sweet acacia, watermelon, honeysuckle, scabiosa albensis, horsetail, scutellaria galerlicata, stevia, strobe pine, spiny bamboo, spirulina platensis, spirulina maxima, subehiyu, spell Wheat, Sunflower cherry, Sumilux Aristolochia ehoria, Acacia serrata, Acacia serrata, Ionocera, Atlantic nettle, Psyllium sylvestris, Hypericum perforatum, Pteropia serrata, Pumpkin, Papilio cinerea, Pepper varulis, Prunus serrata Japanese black primrose, primrose, hawthorn, linden, white willow, dandelion, seiyo Horse chestnut, horse chestnut, Atlantic ash, European pear, European cypress, European rowan, Ceylon nyckey, Western elderberry, Carrot box, European squirrel, European yarrow, Hazel, American mint, European holly, American cherry , Mistletoe, yellow strawberry, ceylon nikki, sage, cecropia obtusciphoria, sequoia cedar, cecil oak, sedum purpleum, mallow, senega, geranium, sercidium florum, cereus grandiflorus, celery, senkyu, Sentifolia Rose, Sentipeda Cunninghammy, Senninkoku, Sempukuka, Assembly, Sojutsu, Sohakuhi, Saw Palmetto, Seo Lee, Buckwheat, Solanum lycocarpum, Daiwikyo, Daikon, Daisanchiku, Soybean, Taiso, Daidai, Taitsuogi, Thyme, Hinoki, Takasaburo, Tajikoshio, Tachibana, Tabuno, Tabebia aberanedae, Tamasaki Samurai Damiana, Tarragon, Tanjin, Tamborisa Trichofila, Chigaya, Cha (tea), Chabotodia, Tuberose, Clove, Datura, Chickpea, Chilliatentosa, Tsukushinamerame, Tsuboksa, Tsurugumi, Tsurugukudami, Tsurureshi, Tea Tree, Dios Corea Compositor, Dioscore Avillosa, Dioscorea Mexicana, Teuchigurumi, Tecoma Clearis, Tetsuzainoki, Duke, Dubois Terminaria, tencha, German iris, German spruce, capsicum, capsicum, spruce, pearl millet, capsicum, gerbil, spruce, corn, cornsilk, pearl millet, horsetail, wolfberry, garlic, toshi (also known as mamedaoshi), pepper, tomato, Trigonellafoenum, Tormentilla, Toro-Aoimodoki, Nagabagi-shigishi, Nagii-kada, eggplant, natsuna, jujube, feverfew, jujube jujube, jujube, date palm, nanyo-sangyo, nanbanai, nanbansafuji, ioisumirei , Nigella Sachiba, Nyukoju, Japanese leek, carrot, garlic, Nymphair alba, Japanese pear, Neurose, Neusenhalen, Nojisumire, Chinese Rose, Novorogiku, Pineapple, Hibiscus, Himatsu, Baobab, Bakuhorashia Triodora, Bacmondow, Bacopamonniera, Hagoromogusa, Lotus, Parsley, Patchouli, Hakkakurishi, Baccarius genisteroides, Passiflora arata, pearl barley, honeybee , Vanilla, vanilla tahitensis, hanesenna, papaya, paphiopedilum madiae, haberlea rhodopensis, hamanas, hamamelis, chayote, rose, palyetalia, harienge, harpagophytum, palmarosa, barosma beetulina, van turmeric, buntu , Daisies, toads, bisnagabella, bitter almonds, bitter oranges, hydrastis cananadensis, daisies, chicks Rhinoceros, Binankazura, Pinusheda, Hinoki, Hibamata, Hiragiku, Hipofaerumnoides, Sunflower, Himekouji, Himekora, Himekuri-nichisou, Himena Airkurbaril, Himefuuro, Sandalwood, Hirameo Loquat, Betel Nut, Fafia Paniculata, Fusenka Kazura, Pueraria Mirifica, Ferla Garvaniflua, Fuukidanpopo, Bukuryo, Fusazakisen, Fusagisuri, Fusafujitsugi, Fusanus Spicatus, Petit Gren, Petit Petroleum Orakoides, Bussooge Pterocarp marsium, grape, peach peach, beech, fuyuzansho, fuyubodaiju, fuyumushinatsutake, fragalia tiroensis, Lazil nuts, French cabbage, French lavender, Plantagoa hula, Plantago gossip, Plantagopsilium, Primula shikimensis, Prunes, Prunus africanana, Prunus serotica, Plumeria, Plectrants barbatas, Breccia hyacinthina, Propolis, Bay, Hayflower, hazelnut, pecan, vetiver, loofah, penny royal mint, samurai, safflower, safflower assembly, pepo pumpkin, hera plantain, pelargonium capitatum, helicopterium arealium, helichrymus angsitorium, helichris italikum Peltoholm dasilachis, Peruvian balsam, bergamot, berberis aquiholium, veronica kaficinaris, henna, henruuda, broom Gih, Boushokuboku, Boushunka, Boseka, Horaidaida, Spinach, Hawkweed, Hoonoki, Hokubayofurosou, Bocoa Pau Ascensis, Boswellia Serata, Hosobasenna, Hosobabarengiku, Bodaiju, Button, Hop, Poterium Officinale, Homol , Bold, Ponkan, Macadamia, Magnolia Officinalis, Magnolia Bionge, Magwa, Prunus, Masaki, Madake, Pine, Matsuri, Matecha, Madonna Nari, Majorana, Maria Thistle, Malpigia Grabra, Quince, Maroni, Mango, Mangosteen, Manchuria deer, Mantuea pine, Manjugiku, Mandarin orange, Mandrake, Mishima psycho, Mizuhakka, Mizulemon, Japanese willow, Tsugashiwa, Mitra Carpath Skewer, Mimosa Tenui Flora, Mircaria Dubia, Myrrh (aka Motsuyakuju), Milotanum Flavelifolia, Milobaran, Mukuroji, Murasaki, Murasakikibu, Murasaki Senburi, Murasaki Korenji, Murayako Enji, Mebokoza, Meshimai Sasame Lacta, Melissa (aka Kousuihakka), Melilot, Melosria, Melon, Mentaalbensis, Moukomugi, Mourera fulviachiris, magnolia, moscata rose, moss bean, tsukuyakuju, peach, momotana, yakmoso, cornflower, yashabuk, yachigana, yachiyakuna Yamaguwa, Yamazakura, Yamanomo, Yamamomogi, Yuugao, Eucalyptus, Eupatium Ayapana, Eupatium Leva Jianum Bertoni, Yukinoshita, Yuzu, Yuzoboku, Yucha, Yukkagurauka, Yukkashijigera, Lily, Yotsurukinbai, Yoshokizukiki, Yodogama, European red-bellied grass, European raspberry, European chestnut, European black porcupine, European birch, European beech, European beech Mannengusa, European fir, Artemisia, Artemisia, Lychee (aka Reishi), Lima bean, Lime, Rye, Lilac, Radiata pine, Latania, Peanut, Ranunculus ficusaria, Labandula hybrida, Rahma, lavender, Larix europaea, Lareadei Balikata, Larar Mexicana, Rambutan, Riso, Lisosam calcarum, Lithose agglutinosa, Longan, Liriosumao Bataki, Apple, Rooibos, Lupine, Bucarnos, Lubusviros, Lumpuyan, Borage, Rurihienso, Respeda, Lesedar Teora, Lettuce, Redama, Plestre, Lebanon Sugi, Levischium Officinale, Lemon, Lemongrass, Forsythia, Rose Plants such as wood, rosemary, low bush blueberry, Roman chamomile, laurel (aka laurel), logwood, robusta coffee, wild thyme, wasabi, horseradish, wasabi, cottonweed, cotton bud, walter indica, walmocow;

  Asco Film Nodosum, Aname, Oukimo, Okinawa Mozuku, Gigalchinasterata, Kujermaniela Girata, Sargassum Filipendula, Sargassum Fusifom, Sargassum Muticam, Sfaceraria scoparia, Durvillea Antarcica, Padina Pavonica Himantalia Elongata, Fucus Serats, Pervetian Canarikurata, Macrocystis pirifera, Mitsushi Kombu, Laminaria Ochroika, Laminaria Croustoni, Laminaria Diguitta, Laminaria Hiperborea, Wakame, Asparagopsis Armata, Igis, Kaguibaranori , Catamen giraffe rhinoceros, geridium curchira guineum, saimi, striped primrose, duls, chinolimo, tochaka, porphyridium cruentum, marbatis macronori Lysosamnium cororioides, anaoaosa, chlorella emersoni, chlorella pyrenoidosa, duna riela salina, duna riela daudawil, hiraaonori, spirulina platensis, spirulina maxima, hasrea austria, dereceria sanguinea, picarolobista Algae such as les, haematococcus prubiaris, cyanobacteria, condor crisps, corals, sea whip, red algae;

  Examples include lichens and fungi such as Ebernia furfracea, horned moss, Usnia barbata, Oshagujitake, birch bamboo, shiitake mushroom, nymph mushroom, Japanese pine mushroom, Fuyushinatsutake, birch bamboo shoot, Cordillera edulis.

  The plant-derived extract may contain one or more of the above. Although the compounding quantity is not specifically limited, Although it changes with kinds of cosmetic composition, 0.0001-5 mass% is preferable with respect to cosmetic composition whole quantity, and 0.001-1 mass% is more preferable.

  Examples of the zinc compound include zinc acetate, zinc laurate, zinc myristate, zinc palmitate, zinc ricinoleate, zinc undecylenate, zinc aspartate, zinc acetylmethionine, zinc gluconate, zinc citrate, polypyrrolidone carboxylic acid Organic acid zinc salts such as zinc and zinc picolinate; Zinc sulfonic acid zinc salts such as zinc p-phenolsulfonate, Ascorbyl zinc phosphate, Sodium cetyl phosphate, zinc zinc phosphate such as DNA zinc; Zinc pyrithione and other zinc complexes Zinc supported zeolite such as (silver / zinc / ammonium) zeolite and silicic acid (ammonium / silver / zinc / aluminum); aluminum hydroxide such as aluminum oxide / zinc, aluminum oxide / zinc / cerium, aluminum oxide / zinc / iron Baked products such as sulfuric acid , Zinc sulfide, zinc chloride, zinc bromide, zinc nitrate, ammonium zinc chloride, zinc aluminum sulfate, potassium zinc sulfate, zinc iodide, basic zinc carbonate and other inorganic zinc salts; (hydroxide / carbonic acid) (Mg / Al / Zinc), zinc oxide and the like. Among these, a compound that easily dissolves in water to become zinc ions is preferable, the solubility in 100 g of water at 20 ° C. is preferably 5 g or more, and the solubility is more preferably 10 g or more. Examples of such zinc compounds include zinc sulfate, zinc chloride, zinc gluconate, zinc bromide, zinc nitrate, zinc ammonium chloride, zinc aluminum sulfate, potassium zinc sulfate, and zinc iodide.

  A zinc compound may mix said 1 type (s) or 2 or more types. Although the compounding quantity is not specifically limited, Although it changes with the kind of cosmetic composition, 0.001-10 mass% is preferable with respect to cosmetic composition whole quantity, and 0.01-3 mass% is more preferable.

  Examples of the thickener include dimethyldiallylammonium chloride / acrylamide copolymer, acrylamide / acrylic acid / dimethyldiallylammonium chloride copolymer, cellulose or derivatives thereof, keratin and collagen or derivatives thereof, calcium alginate, pullulan, agar , Gelatin, tamarind seed polysaccharide, xanthan gum, carrageenan, high methoxyl pectin, low methoxyl pectin, guar gum, gum arabic, crystalline cellulose, arabinogalactan, caraya gum, tragacanth gum, alginic acid, albumin, casein, curdlan, β-glucan and β-glucan Derivatives (excluding the cationized β-glucan of the present invention), gellan gum, dextran, α-glucose and α-glucose derivatives, and the like.

  A thickener may mix | blend said 1 type (s) or 2 or more types. Although the compounding quantity is not specifically limited, Although it changes with kinds of cosmetic composition, 0.01-20 mass% is preferable with respect to cosmetics composition whole quantity, and 0.05-10 mass% is more preferable.

  Oils include volatile and non-volatile oils and solvents and resins that are usually used in skin cosmetics, and may be liquids, pastes, or solids at room temperature, but liquids that are excellent in handling are preferred. Examples of the oil agent include higher alcohols such as cetyl alcohol, isostearyl alcohol, lauryl alcohol, hexadecyl alcohol, octyldodecanol; lauric acid, undecylenic acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, 12 -Higher fatty acids such as hydroxystearic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, isostearic acid, 12-hydroxystearic acid, lanolin fatty acid; myristyl myristate, hexyl laurate, oleic acid Decyl, isopropyl myristate, hexyl decyl dimethyloctanoate, glyceryl monostearate, diethyl phthalate, ethylene glycol monostearate, oxystearate Octylate, diisopropyl adipate, cetyl octanoate, isononyl isononanoate, isopropyl palmitate, stearyl stearate, isotridecyl myristate, 2-ethylhexyl palmitate, octyldodecyl ricinoleate, fatty acids having 10 to 30 carbon atoms Cholesteryl / lanosteryl, cetyl lactate, lanolin acetate, ethylene glycol di-2-ethylhexanoate, pentaerythritol fatty acid ester, dipentaerythritol fatty acid ester, cetyl caprate, glyceryl tricaprylate, diisostearyl malate, dioctyl succinate, and Esters such as cetyl 2-ethylhexanoate; hydrocarbons such as liquid paraffin, petrolatum, squalane; waxes such as lanolin, reduced lanolin and carnauba wax; mink Oils such as cocoa butter, palm oil, palm kernel oil, camellia oil, sesame oil, castor oil, olive oil; dimethylpolysiloxane, methylhydropolysiloxane, methylphenylpolysiloxane, polyether-modified organopolysiloxane, fluoroalkyl poly Oxyalkylene co-modified organopolysiloxane, alkyl-modified organopolysiloxane, terminal-modified organopolysiloxane, fluorine-modified organopolysiloxane, amodimethicone, amino-modified organopolysiloxane, silicone gel, acrylic silicone, trimethylsiloxysilicic acid, silicone RTV rubber, etc. Silicone compounds; fluorine compounds such as perfluoropolyether, fluorinated pitch, fluorocarbon, fluoroalcohol; polybutene, polyisobutene, hydrogenated poly Polyolefins or olefin oligomers such as sobutene, ethylene / α-olefin / co-oligomer; hydrocarbons such as mineral oil, light liquid isoparaffin, petrolatum, squalane and the like.

  An oil agent may mix | blend said 1 type (s) or 2 or more types. Although the compounding quantity is not specifically limited, Although it changes with kinds of cosmetic composition, 0.1-90 mass% is preferable with respect to the cosmetic composition whole quantity, and 0.5-70 mass% is more preferable.

  Examples of the dye include dyes such as Red No. 201, Yellow No. 4, Blue No. 1, and Black No. 401, and Lake Dye such as Yellow No. 4 Al lake and Yellow No. 203 Ba lake.

  Examples of the pigment include white pigments such as titanium oxide, extender pigments such as silica, talc, mica, sericite, and kaolin, and pearl pigments such as mica titanium. There are no particular restrictions on the shape of these pigments (spherical, rod-like, needle-like, plate-like, indeterminate, flake-like, spindle-like, etc.). These pigments are conventionally known surface treatments such as fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, oil agent treatment, N-acylated lysine treatment, polyacrylic. The surface treatment may be performed in advance by acid treatment, metal soap treatment, amino acid treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment or the like.

  The dye and / or pigment may be blended with one or more of the above. Although the compounding quantity is not specifically limited, Although it changes with kinds of cosmetic composition, 0.1-90 mass% is preferable with respect to the cosmetic composition whole quantity, and 0.5-70 mass% is more preferable.

  Examples of the antibacterial agent include paraben antibacterial agents such as methylparaben and ethylparaben; imidazole antibacterial agents such as thiabendazole and 2-benzimidazolylcarbamate methylpreventol; and carbanide antibacterial agents such as trichlorocarbanilide and cloflucarban A thiazole antibacterial agent such as benzothiazole; a triazine antibacterial agent such as debuconazole and cabinone; and a biguanide antibacterial agent such as chlorhexidine hydrochloride and polyhexamethylene biguanide.

  One or more antibacterial agents may be added, but when these antibacterial agents are used in combination, they should be used carefully in consideration of irritation to the human body. The blending amount is generally preferably from 0.01 to 10% by weight, more preferably from 0.03 to 3% by weight, based on the total amount of the cosmetic composition.

  Examples of the pH adjuster include potassium carbonate, sodium hydrogen carbonate, ammonium hydrogen carbonate and the like. These pH adjusters may be the same as or different from the acid base used for the preparation of the cationic surfactant composed of the tertiary amine and amidoamine.

  A pH adjuster may mix | blend said 1 type (s) or 2 or more types. Although the compounding quantity is not specifically limited, Although it changes with kinds of cosmetic composition, 0.001-10 mass% is preferable with respect to cosmetic composition whole quantity, and 0.01-5 mass% is more preferable.

  Examples of the antioxidant include tocopherol, butylhydroxyanisole, dibutylhydroxytoluene, phytic acid and the like.

  An antioxidant may mix | blend said 1 type (s) or 2 or more types. Although the compounding quantity is not specifically limited, Although it changes with kinds of cosmetic composition, 0.001-10 mass% is preferable with respect to cosmetic composition whole quantity, and 0.01-5 mass% is more preferable.

  Examples of the ultraviolet absorber include salicylic acid series such as homomenthyl salicylate, octyl salicylate, triethanolamine salicylate; paraaminobenzoic acid, ethyldihydroxypropylparaaminobenzoic acid, glycerylparaaminobenzoic acid, octyldimethylparaaminobenzoic acid, paradimethylaminobenzoic acid. PABA type such as amyl, 2-ethylhexyl paradimethylaminobenzoate; 4- (2-β-glucopyranosyloxy) propoxy-2-hydroxybenzophenone, dihydroxydimethoxybenzophenone, sodium dihydroxydimethoxybenzophenone disulfonate, 2-hydroxy -4-methoxybenzophenone, hydroxymethoxybenzophenonesulfonic acid and its trihydrate, hydroxymethoxybenzophenonesulfone Sodium, 2-hydroxy-4-methoxybenzophenone-5-sulfate, 2,2′-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2′4,4′-tetrahydroxybenzophenone, 2, 2 Benzophenones such as' -dihydroxy-4,4'-dimethoxybenzophenone and 2-hydroxy-4-N-octoxybenzophenone; 2-ethylhexyl paramethoxycinnamate (also known as octyl paramethoxycinnamate), diparamethoxy Glyceryl mono-2-ethylhexanoate, methyl 2,5-diisopropylcinnamate, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5- Triazine, methyl bis (trimethylsiloxy) silyli trimethoxycinnamate Cinnamic acid systems such as pentyl, isopropyl paramethoxycinnamate / diisopropyl cinnamate ester, p-methoxyhydrocinnamic acid diethanolamine salt; 2-phenyl-benzimidazole-5-sulfuric acid, 4-isopropyldibenzoylmethane, Benzoylmethane such as 4-tert-butyl-4′-methoxydibenzoylmethane; 2-cyano-, 3-diphenylprop-2-enoic acid 2-ethylhexyl ester (also known as octocrylene), dimethoxybenzylidene dioxoimidazolidinepropion 2-ethylhexyl acid, 1- (3,4-dimethoxyphenyl) -4,4-dimethyl-1,3-pentanedione, synoxate, methyl-O-aminobenzoate, 2-ethylhexyl-2-cyano-3, 3-diphenyl acrylate, 3 -(4-Methylbenzylidene) camphor, octyltriazone, 4- (3,4-dimethoxyphenylmethylene) -2,5-dioxo-1-imidazolidinepropionate 2-ethylhexyl, their polymer derivatives, and silane derivatives Is mentioned.

  An ultraviolet absorber may mix | blend said 1 type (s) or 2 or more types. Although the compounding quantity is not specifically limited, Although it changes with the kind of cosmetic composition, 0.01-10 mass% is preferable with respect to the cosmetic composition whole quantity, and 0.1-1 mass% is more preferable.

  Examples of moisturizing components include deoxyribonucleic acid, mucopolysaccharide, hyaluronic acid, chondroitin sulfate, collagen, elastin, chitin, chitosan, hydrolyzed eggshell membrane, polyoxyethylene methyl glucoside, polyoxypropylene methyl glucoside, sodium lactate, urea, Examples include sodium pyrrolidone carboxylate, betaine, and whey.

  One or two or more moisturizing components may be blended. Although the compounding quantity is not specifically limited, Although it changes with kinds of cosmetic composition, 0.001-30 mass% is preferable with respect to the cosmetic composition whole quantity, and 0.01-20 mass% is more preferable.

  Examples of the enzyme include acylcoenzyme A desaturase, aminopeptidase, amyloglucosidase, oxidoreductase, catalase, glucose oxidase, superoxide dismutase, soybean peroxidase, dextran-immobilized protease, transglutaminase, hyaluronidase, protease, hesperidinase, lactoperoxidase, lipase Etc.

  An enzyme may mix | blend said 1 type (s) or 2 or more types. Although the compounding quantity is not specifically limited, Although it changes with kinds of cosmetic composition, 0.001-10 mass% is preferable with respect to cosmetic composition whole quantity, and 0.01-5 mass% is more preferable.

  A fragrance | flavor is mix | blended in order to provide a fragrance and fragrance to a cosmetic composition, or to mask an unpleasant odor. It is not particularly limited as long as it is a fragrance generally blended in a cosmetic composition, including various extracts exemplified as the above-mentioned physiologically active ingredients, flowers, seeds, leaves, roots, etc. of various plants. Fragrance extracted from seaweed, fragrance extracted from seaweed, fragrance extracted from animal parts or secretions (eg, pepper, sperm), artificially synthesized fragrance (eg, menthol, musk, acetate ester, vanilla) Is exemplified.

  A fragrance | flavor may mix | blend said 1 type, or 2 or more types. Although the compounding quantity is not specifically limited, Although it changes with the kind of cosmetic composition, 0.001-10 mass% is preferable with respect to cosmetic composition whole quantity, and 0.01-3 mass% is more preferable.

  The cosmetic composition of the present invention includes, for example, shampoo, dry shampoo, rinse-integrated shampoo, hair rinse, hair conditioner, hair pack, hair treatment, hair tonic, pomade, tic, hair cream, hair wax, hair gel, hair foam, Hair care cosmetics such as hair mousse, hair mist, hair lotion, permanent wave agent, hair dye, etc .; facial cleanser, facial cleansing cream, facial cleansing foam, cleansing cream, cleansing foam, hand soap, body soap, body lotion, sunscreen, lotion , Milky lotion, serum, face cream, cold cream, face pack, antiperspirant, shaving soap, shaving foam, shaving oil, shaving lotion, aftershave broth Skin care cosmetics such as foundation, concealer, face powder, blusher, mascara, eyeliner, eyeshadow, etc .; can be used for lip balm, bathing agent, shampoo, Hair Rinse, Rinse Integrated Shampoo, Hair Conditioner, Hair Pack, Hair Treatment, Hair Cream, Hair Wax, Hair Gel, Hair Foam, Hair Mousse, Hair Mist, Hair Lotion, Hair Liquid, Mascara, Foundation, Eyeliner, Eyeshadow, Body Soap, Preferred for hand soap, face wash, lotion, serum, face pack, cleansing cream, lip balm, shaving lotion, after sun lotion, bath preparation, face cream It can be used.

  Next, the compounding example according to the kind of cosmetic composition of this invention is shown. Of the components of the following formulation examples, “cationized β-glucan” is the cationized β-glucan of the present invention. Further, the unit of the blending amount is mass%, and the blending amount of “remainder” means that the blending amount is adjusted so that the total blending amount becomes 100 mass%.

  First, the following formulation examples 1 to 50 are shown as shampoo formulation examples.

The following prescription examples 51 to 56 are shown as prescription examples of hair rinse.

As prescription examples of the rinse integrated shampoo, the following prescription examples 57 to 58 are shown.

The following prescription examples 59 to 61 are shown as prescription examples of the hair conditioner.

The following formulation examples 62 to 63 are shown as examples of hair pack formulations.

The following formulation example 64 is shown as a hair treatment formulation example.

The following formulation examples 65-67 are shown as hair cream formulation examples.

The following formulation examples 68 to 70 are shown as hair wax formulation examples.

The following prescription examples 71 to 73 are shown as prescription examples of the hair gel.

As prescription examples of hair foams, the following prescription examples 74 to 75 are shown.

The following formulation example 76 is shown as a hair mousse formulation example.

The following formulation example 77 is shown as a formulation example of hair mist.

The following formulation examples 78-79 are shown as formulation examples of hair lotions.

As a hair liquid formulation example, the following formulation example 80 is shown.

The following formulation examples 81-88 are shown as mascara formulation examples.

The following formulation examples 89-99 are shown as foundation formulation examples.

The following prescription examples 103 to 110 are shown as eye shadow prescription examples.

The following prescription examples 111 to 112 are shown as prescription examples of body soap.

The following prescription examples 135 to 136 are shown as prescription examples of whitening lotions.

The following prescription examples 137 to 145 are shown as examples of the cosmetic liquid formulation.

The following prescription examples 146 to 159 are shown as prescription examples of the emulsion.

The following formulation examples 164 to 166 are shown as formulation examples of cleansing creams.

The following formulation examples 167 to 168 are shown as formulation examples of the foundation.

The following formulation examples 169 to 170 are shown as lip balm formulation examples.

The following formulation examples 171 to 172 are shown as examples of shaving lotions.

The following prescription examples 173 to 184 are shown as prescription examples of after sun lotion.

The following prescription examples 175 to 176 are shown as prescription examples of bathing agents.

The following prescription examples 177 to 187 are shown as prescription examples of the face cream.

As prescription examples of hand soap, the following prescription examples 188 to 189 are shown.

  Among the cationized β-glucans of the present invention, the cationized β-1,3-1,6-glucan of the present invention, that is, the unit represented by the general formula (1a) and the unit represented by (4a). The β-glucan in which some of the hydroxyl group hydrogen atoms are substituted with a group represented by the general formula (5) is excellent in antibacterial properties, and is particularly high against Staphylococcus aureus. Shows antibacterial properties. The cationized β-1,3-1,6-glucan of the present invention can impart antibacterial properties to a cosmetic composition and can exert an effect by adhering to hair and skin. Antibacterial effect on hair and skin even when used in cleansing cosmetic compositions such as dry shampoos, rinse-in-one shampoos, facial cleansers, facial cleansing creams, facial cleansing foams, cleansing creams, cleansing foams, hand soaps, body soaps, etc. Can be given.

  Further, the cationized cationized β-1,3-1,6-glucan of the present invention is used in the same manner as known antibacterial agents, disinfectants and antifungal agents for the purpose of antibacterial, sterilization, disinfection, antifungal and the like In addition to cosmetic compositions, for example, medical cleaning agents for the purpose of disinfecting and cleaning medical equipment and affected areas, household cleaning agents for sterilizing dishes, cleaning agents for food industry, clothing It can be suitably used for softeners, wet tissues, toilet seat cleaners and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these Examples. Unless otherwise specified, “parts” and “%” in the examples are based on mass.
[Production of cationized β-glucan 1]
In a 200 ml flask equipped with a stirrer, 25 g of water, 125 ml of isopropyl alcohol, β-1,3-1,6-glucan extracted from fermentation broth by black yeast (Aureobasidium spp.) [Mass average molecular weight 310000, The molar ratio of the unit represented by (1a) to the unit represented by general formula (4a) is 2.26 g of powder of 1.3], 5 g of sodium hydroxide as a catalyst, and glycidyltrimethylammonium chloride as a cationizing agent. 2.12 g (10 mmol) was added and stirred at 25 ° C. for 30 minutes. Thereafter, the temperature in the system was raised to 50 ° C., and the reaction was continued by stirring at 50 ° C. for 5 hours. After completion of the reaction, the system was neutralized with acetic acid, and the stirring was stopped. When the mixture was allowed to stand for 3 hours with natural cooling, the cationized β-glucan obtained by the cationization reaction was precipitated in the system. The precipitate was filtered, washed with isopropyl alcohol, and dried to obtain a powder of cationized β-glucan 1. The degree of cationization of cationized β-glucan 1 was 0.47.

  In addition, the used β-1,3-1,6-glucan contains water, and corresponds to 1 mol of glucose unit at 226 g and 10 mmol of glucose unit at 2.26 g. The purity of β-1,3-1,6-glucan was determined by measuring the water content by the Karl Fischer method and measuring the glucose unit content by the phenol-sulfuric acid method described below. The degree of cationization was determined from the molar concentration of the glucose unit in the measurement sample determined by the following phenol-sulfuric acid method and the molar concentration of the cationic group in the measurement sample determined by the measurement of the following colloid titration method.

<Measurement method of monosaccharide unit content>
The monosaccharide unit content in the sample was determined by a general phenol-sulfuric acid method (based on Methods in Carbohydrate Chemistry vol.1, pp. 380-394) as a quantitative method for sugar. Glucose was used as a standard substance for the calibration curve.

<Measurement method of cationic group content>
A 0.1% by mass toluidine blue aqueous solution was used as an indicator, and titration was performed with potassium polyvinyl sulfate (N / 400), and the cationic group content in the sample was determined from the titration amount.

<Calculation of degree of cationization>
Cation degree = cationic group content in sample / monosaccharide unit content in sample

[Production of Cationized β-Glucan 2-4]
Except having changed the usage-amount of glycidyl trimethyl ammonium chloride, operation similar to the manufacture example of the cationized beta glucan 1 was performed, and the cationized beta glucan 2-4 was obtained. Table 86 below shows the mass average molecular weight and degree of cationization of the cationized β-glucans 2-4. The degree of cationization was calculated by the above method.

[Production of cationized β-glucan 5]
The same procedure as in the production example of cationized β-glucan 1 was performed except that β-1,3-glucan (mass average molecular weight 320,000) was used instead of β-1,3-1,6-glucan. Β-glucan 5 was obtained. Table 86 below shows the mass average molecular weight and degree of cationization of cationized β-glucan 5.

[Test polymer of comparative example]
As comparative examples, cationized hyaluronic acid, cationized cellulose, cationized β guar gum, and β-1,3-1,6-glucan were used. Each mass average molecular weight and degree of cationization are shown in Table 86 below. Since cationized hyaluronic acid is difficult to measure the cationic group content by the above method, the nitrogen content of the sample is measured, and the nitrogen content and monosaccharide units (glucuronic acid unit and N-acetoglucosamine unit) are measured. From the content, the degree of cationization was calculated.

  The test polymers of Examples 1 to 5 and Comparative Examples 1 to 4 were subjected to a chargeability test, a static electricity generation test, and a friction coefficient measurement by using hair as follows. The results are shown in Table 89.

[Preparation of test hair]
Test hair was prepared by the following steps. In addition, the test hair of only the washing | cleaning process was made into healthy hair, and the test hair which repeated the damage process 5 times was made into damaged hair.
<Washing process>
1 g of hair of the same person having a length of 10 cm was washed by stirring in 40 ml of an aqueous solution of 2.5% by mass nonionic surfactant (sodium polyoxyethylene lauryl ether sulfate) at 40 ° C. for 30 minutes. Rinse for a minute and then dry with a dryer.
<Damage process>
After damaging the hair by putting 1 g of normal hair in 200 ml of a mixture of 4.5% by mass aqueous hydrogen peroxide and 2.5% by mass aqueous ammonia and stirring at 25 ° C. for 30 minutes, Rinse with running water for 2 minutes and dry with a dryer.
<Adsorption process>
1 g of damaged hair is immersed in 200 ml of 0.1% by mass test polymer at 40 ° C. for 20 minutes, rinsed with running water for 2 minutes, and then dried with a dryer.

[Chargeability test]
Using a static electricity meter (model FMX003, manufactured by Simco Japan), the surface potential of the test hair was measured under the conditions of a temperature of 22 ° C. and a humidity of 25%. The measurement was performed 10 times on different parts of the test hair, and the average value was defined as the surface potential. Normally, healthy hair is known to be positively charged and damaged hair is negatively charged, and the more the cationic substance adsorbs to the damaged hair, the more positively charged. That is, the larger the amount of adsorption, the higher the treatment effect.

[Static generation test]
The test hair was rubbed against a polyethylene terephthalate resin sheet (PET sheet) 30 times under the conditions of a temperature of 22 ° C. and a humidity of 25% to generate static electricity on the test hair. FMX003) was used to measure the static electricity of the test hair under the conditions of a temperature of 22 ° C. and a humidity of 25%. The smaller the amount of static electricity, the smaller the amount of static electricity generated due to external influences such as brushing, and the better the unity of hair by brushing and the like, the easier it is to set.

[Friction coefficient measurement]
The average friction coefficient of the test hair was measured under conditions of a temperature of 22 ° C. and a humidity of 25% using a friction tester (manufactured by Kato Tech, model KES-SE). In the test, 20 test hairs attached to a glass plate were used, a weight of 25 g, a moving speed of 1 mm / second, and a fingerprint type sensor (made of metal) was used as a sensor. The lower the average coefficient of friction, the better the feel and fingering of the hair.

  From the results in Table 89, it can be seen that the cationized β-glucan of the present invention has a high conditioning effect on the hair. That is, in Table 89, it can be seen that all of the cationized β-glucans of the present invention are positively charged in the chargeability test and fall down, have a large amount of adsorption to damaged hair, and have a high treatment effect. Is shown. From the static electricity generation test, all of the cationized β-glucan of the present invention generates little static electricity, and by blending it with shampoo or rinse, it is easy to set the hair by brushing etc. . From the results of the friction coefficient measurement, it is shown that the cationized β-glucan of the present invention has a great effect of improving the touch and fingering of damaged hair. These effects are particularly remarkable in the cationized β-1,3-1,6-glucan of the present invention.

Evaluation with lotion Using the lotion formulated according to the formulation shown in Table 90 below based on Formulation Example 122 above, the panelists (10 persons) actually used the skin to feel moist and fluffy (the skin has elasticity). A sensory evaluation was performed on the feeling of freshness. The evaluation was made by calculating the average score of 10 people according to the following evaluation point criteria. The results are shown in Table 92.

(Evaluation criteria for moist feeling)
5 points: moist feeling 4 points: somewhat moist feeling 3 points: normal 2 points: no moist feeling 1 point: no moist feeling (evaluation point standard for fluffy feeling)
5 points: Fluffy 4 points: Slightly fluffy 3 points: Normal 2 points: Slightly fluffy 1 point: Fluffy

Evaluation with facial cleansers Based on prescription example 120, using facial cleansers formulated according to the prescription in Table 91 below, the actual use by professional panelists (10 persons) resulted in a moist and soft feeling after use (the skin has elasticity). A sensory evaluation was performed on the feeling of freshness. The evaluation was made by calculating the average score of 10 people based on the same evaluation criteria as the evaluation with the lotion.

  From the results in Table 92, it can be seen that the cationized β-glucan of the present invention has a high conditioning effect on the skin. That is, in Table 92, both the lotion and the face wash formulated with the cationized β-glucan of the present invention are excellent in the moist and fluffy feeling of the skin after use. , 3-1,6-glucan.

The antibacterial property was measured by the following method using the test polymers of Examples 1 to 5 or Comparative Examples 1 to 4 and a general phenoxyethanol as an antibacterial agent of the cosmetic composition. The results are shown in Table 93.
[Antimicrobial test method]
The test sample was diluted with sterilized water to prepare a test solution having a test sample concentration of 10240 μg / ml. Thereafter, the test solution was repeatedly diluted 2-fold with a bouillon medium (Mueller Hinton medium) to prepare test solutions having a total of 11 levels of test sample concentrations of 10 to 10240 μg / ml. Using the bacterial solution which had been pre-cultured in broth medium, the bacterial solution which had been adjusted to 10 ⁷ levels, placed in 0.01ml microplate, test solutions of various concentrations and stirred well with adding 0.2 ml. This mixed solution was cultured at 37 ° C. for 24 hours. After completion of the culture, the turbidity of the microplate was measured, and the lowest concentration that inhibited the growth of the test bacteria was defined as the minimum growth concentration (MIC). The lower the minimum growth concentration, the higher the antibacterial property. In the test, Staphylococcus aureus NBRC12732 was used.

  From the results of Table 93, it can be seen that among the cationized β-glucans of the present invention, the cationized β-1,3-1,6-glucan of the present invention has high antibacterial properties.

  Since the cationized β-glucan of the present invention has a high conditioning effect, the cationized β-glucan can be suitably used in a cosmetic composition for the purpose of washing and treating the body and hair such as shampoo, rinse, body soap, and facial cleanser. . Furthermore, since the cationized β-1,3-1,6-glucan of the present invention has high antibacterial properties, households that sterilize medical detergents, dishes, etc. for the purpose of disinfecting and cleaning medical instruments and affected areas. Can be suitably used for applications such as cleaning agents for foods, cleaning agents for food industry, softeners for clothing, wet tissues, toilet seat cleaners and the like.

Claims (7)

Cationized β-glucan containing at least one of units represented by the following general formulas (1) to (4):
General formula (1)

[Wherein R ^{1 to} R ³ represent a hydrogen atom or a group represented by the following general formula (5). However, at least one of R ^{1 to} R ³ must be a group represented by the following general formula (5). ]
General formula (2)

[Wherein, R ^{4 to} R ⁶ represent a hydrogen atom or a group represented by the following general formula (5). However, at least one of R ^{4 to} R ⁶ must be a group represented by the following general formula (5). ]
General formula (3)

[Wherein, R ⁷ and R ⁸ represent a hydrogen atom or a group represented by the following general formula (5). However, at least one of R ⁷ and R ⁸ must be a group represented by the following general formula (5). ]
General formula (4)

[Wherein R ^{9 to} R ¹⁴ represent a hydrogen atom or a group represented by the following general formula (5). However, at least one of R ^{9 to} R ¹⁴ must be a group represented by the following general formula (5). ]
General formula (5)

(In the formula, R ^{15 to} R ¹⁷ represent an alkyl group having 1 to 3 carbon atoms, R ¹⁸ represents an alkylene group having 1 to 6 carbon atoms or a hydroxyalkylene group having 2 to 6 carbon atoms, and X is Represents a halogen atom.) The β-glucan in which the cationized β-glucan is composed of at least one unit selected from the group consisting of units represented by the following general formulas (1a) to (4a) is a hydrogen atom of a part of hydroxyl groups. The cationized β-glucan according to claim 1, which is a cationized β-glucan substituted with a group represented by (5):
General formula (1a)

General formula (2a)

General formula (3a)

General formula (4a)

  A group in which hydrogen atoms of some hydroxyl groups of β-glucan, in which the cationized β-glucan is composed of the unit represented by the general formula (1a) and the unit represented by (4a), are represented by the general formula (5) The cationized β-glucan according to claim 1 or 2, which is a cationized β-glucan substituted with.   Selected from the group consisting of the unit represented by the general formula (1), the unit represented by the general formula (1a), the unit represented by the general formula (4), and the unit represented by the (4a). The cationized β-glucan according to claim 1 or 2, comprising at least three units.   The cationized β-glucan according to any one of claims 1 to 4, wherein the degree of cationization is 0.1 to 2.   A cosmetic composition comprising the cationized β-glucan according to any one of claims 1 to 5.   Surfactant, chelating agent, low molecular polyol, plant-derived extract, zinc compound, thickener, oil agent, dye, pigment, antibacterial agent, moisturizer, pH adjuster, antioxidant, ultraviolet absorber, moisturizing component and perfume The cosmetic composition according to claim 6, comprising one or more components selected from the group consisting of:

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