CN105456045B - Transparent gel-like aqueous cosmetic - Google Patents

Transparent gel-like aqueous cosmetic Download PDF

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CN105456045B
CN105456045B CN201510565999.9A CN201510565999A CN105456045B CN 105456045 B CN105456045 B CN 105456045B CN 201510565999 A CN201510565999 A CN 201510565999A CN 105456045 B CN105456045 B CN 105456045B
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aqueous cosmetic
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gel
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CN105456045A (en
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柳辉一
北冈弘行
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Fujifilm Corp
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Abstract

The present invention provides a transparent gel-like aqueous cosmetic composition containing 0.5 to 5 mass% of a compound represented by the general formula (1) relative to the total mass of the cosmetic composition, 0.1 to 1000ppm of an acyl ceramide represented by the general formula (I) relative to the total mass of the cosmetic composition, 0.1-fold or more of a nonionic surfactant relative to the amount of the acyl ceramide, 0.01-fold or more of an anionic surfactant relative to the amount of the acyl ceramide, and water, wherein the transparent gel-like aqueous cosmetic composition has an absorbance at a wavelength of 625nm of 0.04 or less. In the general formula (1), R1: hydrocarbyl radical, R2、R4: hydrocarbyl radical, R3: h + 1-valent hydrocarbon radical, R5: hydrocarbyl radical, R6: hydrogen atom or hydroxyl group, m: 2 or more, h: 1 or more, k and n: 0 to 1000; in the general formula (I), R31: hydrocarbyl radicals containing ester linkages in the carbon chain, R32: an alkyl or alkenyl group. General formula (1) R1‑{(O‑R2)k‑OCONH‑R3[‑NHCOO‑(R4‑O)n‑R5]h}m‑R6General formula (I)

Description

Transparent gel-like aqueous cosmetic
Technical Field
The present invention relates to a transparent gel-like aqueous cosmetic.
Background
In the fields of cosmetics, foods, pharmaceuticals, and the like, a gelling agent is generally used to impart viscosity or elasticity to a product. For example, in the field of cosmetics, a gelling agent is used to impart unique viscosity or elasticity to a product for the purpose of improving the feeling of use when applied to the skin, preventing dripping, or the like.
As cosmetics containing a gelling agent, for example, a jelly-like cosmetic using a PEG-240/decyltetradecylpolyether-20/hexamethylene diisocyanate copolymer has been reported (see, for example, Japanese patent laid-open publication No. 2013-6775).
Disclosure of Invention
However, in recent years, skin care effects of ceramides have been expected, and various techniques for blending ceramides in cosmetics have been developed.
However, ceramide is a substance having high crystallinity, does not dissolve in water, has low solubility in other oil agents, and precipitates at low temperature, and therefore, when ceramide is blended in a cosmetic, it is sometimes difficult to ensure stability. For example, a ceramide can be dispersed by using a large amount of an oil agent, a surfactant, or the like, but it is difficult to sufficiently reduce the particle size of dispersed particles of a ceramide, and a cosmetic lacking transparency is easily formed.
Among ceramides, acylceramides having an excellent skin-care effect have particularly high crystallinity, and even when a stable dispersion is prepared, when mixed with a general cosmetic ingredient, crystals may precipitate when stored for a long period of time, and transparency may be impaired in some cases.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a transparent gel-like aqueous cosmetic composition containing an acylceramide, which is excellent in transparency and can maintain the transparency for a long period of time.
The present specification discloses the following.
[1] A transparent gel-like aqueous cosmetic composition which comprises (i) to (v) and has an absorbance at a wavelength of 625nm of 0.04 or less:
(i) a compound represented by the general formula (1), wherein the content thereof is 0.5 to 5% by mass relative to the total mass of the transparent gel-like aqueous cosmetic;
(ii) an acylceramide represented by the general formula (I) in an amount of 0.1 to 1000ppm based on the total mass of the transparent gel-like aqueous cosmetic;
(iii) a nonionic surfactant, the content of which is 0.1 times or more the amount of the acyl ceramide;
(iv) an anionic surfactant, the content of which is 0.01 times or more the amount of the acyl ceramide;
(v) the amount of water is controlled by the amount of water,
general formula (1)
R1-{(O-R2)k-OCONH-R3[-NHCOO-(R4-O)n-R5]h}m-R6
In the general formula (1), R1R represents a C2-36 and m-valent hydrocarbon group2And R4Each independently represents a C1-4 and C2-valent hydrocarbon group, R3Represents a h +1 valent hydrocarbon group containing a linear, branched, or aliphatic or aromatic ring which may have a urethane bond, R5Represents a 2-valent hydrocarbon group, R6Represents a hydrogen atom or a hydroxyl group. m is an integer of 2 or more, h is an integer of 1 or more, k and n are integers each independently ranging from 0 to 1000 representing the number of repetitions of the structure in parentheses, and both k and n are not 0 at the same time.
General formula (I)
Figure BDA0000797835270000021
In the general formula (I), R31Represents a linear or branched hydrocarbon group having 40 to 55 carbon atoms in total and containing an ester bond in a carbon chain, R31The hydrocarbon group may have 1 or 2 or more partial structures selected from the group consisting of a multiple bond, an aromatic ring, and an aromatic heterocycle in a carbon chain; r32Represents an alkyl group having 11 to 21 carbon atoms which may have a hydroxyl group, or an alkenyl group having 11 to 21 carbon atoms which may have a hydroxyl group.
[2] The transparent gel-like aqueous cosmetic according to [1], wherein the acyl ceramide is a human-type acyl ceramide.
[3] The transparent gel-like aqueous cosmetic according to [1] or [2], which comprises a dispersion obtained by dispersing an acylceramide with a nonionic surfactant and an anionic surfactant.
[4] The transparent gel-like aqueous cosmetic preparation according to any one of [1] to [3], wherein the nonionic surfactant is a polyglycerin fatty acid ester.
[5] The transparent gel-like aqueous cosmetic according to any one of [1] to [4], wherein the anionic surfactant is lecithin.
[6] The transparent gel-like aqueous cosmetic according to any one of [1] to [5], wherein the compound represented by the general formula (1) is at least one compound selected from the group consisting of a compound represented by the following general formula (1-1) and a compound represented by the following general formula (1-2):
general formula (1-1)
R11-{(O-R12)k1-OCONH-R13[-NHCOO-(R14-O)n1-R15]h1}m1
In the general formula (1-1), R11R represents a C2-12 hydrocarbon group having a valence of m112And R14Each independently represents a C1-4 and C2-valent hydrocarbon group, R13Represents a h1+1 valent hydrocarbon group containing a linear, branched, or aliphatic or aromatic ring which may have a urethane bond, R15Represents a 1-valent hydrocarbon group. m1 is an integer of 2 or more, h1 is an integer of 1 or more, k1 and n1 represent the number of repetitions of the parenthesis structure, each independently is an integer in the range of 0 to 1000, and both k1 and n1 are not 0 at the same time.
General formula (1-2)
R21-[OCONH-R22-NHCO(-O-CHR23CH2)n2]m2-OH
In the general formula (1-2), R21R represents a C6-36 hydrocarbon group having a valence of m222Represents methyldiphenylene, hexamethylene, methyldicyclohexyl, 3-methyl-3, 5, 5-trimethylcyclohexylene, dimethylphenylene or tolylene, R23Represents a hydrogen atom or a methyl group. n2 represents an integer of 90 to 900, and m2 represents an integer of 1 to 5.
[7] The transparent gel-like aqueous cosmetic preparation according to item [6], wherein the compound represented by general formula (1) is at least one copolymer selected from the group consisting of a PEG-240/decyltetradecylpolyether-20/hexamethylene diisocyanate copolymer which is a compound represented by general formula (1-1), and a distearyl PEG/PPG-8/6 (methylenediphenyl diisocyanate/PEG-400) copolymer which is a compound represented by general formula (1-2).
[8] The transparent gel-like aqueous cosmetic according to any one of [1] to [7], which further contains cholesterol.
[9] The transparent gel-like aqueous cosmetic according to [8], which further comprises a fatty acid or a salt thereof.
The present invention can provide a transparent gel-like aqueous cosmetic composition which contains an acylceramide, has good transparency, and can maintain the transparency for a long period of time.
Detailed Description
The present invention is not limited to the embodiments described below, and can be carried out with appropriate modifications within the intended scope of the present invention.
In the present specification, the numerical range expressed by the term "to" means a range including numerical values before and after the term "to" as a minimum value and a maximum value, respectively.
In the present specification, in the case where reference is made to the amount of each component in the transparent gel-like aqueous cosmetic, when there are a plurality of substances belonging to each component in the transparent gel-like aqueous cosmetic, the total amount of the plurality of substances present in the transparent gel-like aqueous cosmetic is referred to unless otherwise noted.
In the present specification, the term "aqueous phase" is used as a term for "oil phase" regardless of the type of solvent.
In the present specification, the term "step" is not limited to an independent step, and is also included in the term as long as the intended purpose of the step can be achieved even when the step cannot be clearly distinguished from other steps.
In the present invention, the term "gel-like" refers to a state in which the object to be measured exhibits a hardness of 1g to 1000g when measured using a durometer under a measurement condition of 25 ℃.
In the present invention, the "aqueous cosmetic" refers to a cosmetic containing water and containing a total content of water and a water-soluble liquid component contained as desired of 50 mass% or more and a content of the liquid component of 10 mass% or less with respect to the total mass of the cosmetic, and an amount of dissolution of the liquid component in water at 25 ℃ is 1 mass% or less with respect to the mass of water.
The "water-soluble liquid component" referred to herein is a liquid component in which the amount of a target substance dissolved in water at 25 ℃ is more than 1 mass% based on the mass of water.
In the present invention, "PEG" means polyethylene glycol. The number appended after PEG represents the average number of ethylene glycol units constituting the PEG.
In the present invention, "PPG" refers to polypropylene glycol. The number appended after PPG represents the average number of propylene glycol units constituting the PPG.
[ transparent gel-like aqueous cosmetics ]
The transparent gel-like aqueous cosmetic of the present invention (hereinafter, appropriately referred to as "gel-like aqueous cosmetic") contains: (i) a compound represented by the general formula (1) (hereinafter, appropriately referred to as "specific compound (1)") in an amount of 0.5 to 5% by mass based on the total mass of the gel-like aqueous cosmetic composition, (ii) an acylceramide represented by the general formula (I) (hereinafter, appropriately referred to as "specific acylceramide") in an amount of 0.1 to 1000ppm based on the total mass of the gel-like aqueous cosmetic composition, (iii) a nonionic surfactant in an amount of 0.1 times or more the amount of the specific acylceramide, (iv) an anionic surfactant in an amount of 0.01 times or more the amount of the specific acylceramide, and (v) water; and the transparent gel-like aqueous cosmetic has an absorbance at a wavelength of 625nm of 0.04 or less.
The gel-like aqueous cosmetic of the present invention may contain other components than the components (i) to (v) as necessary within a range not impairing the effects of the present invention.
Since acyl ceramide has particularly high crystallinity in ceramide, it is difficult to obtain stability with time in cosmetics containing acyl ceramide due to crystal precipitation with time, decrease in transparency, and the like. In addition, in aqueous cosmetics, it is difficult to sufficiently reduce the particle size of dispersed particles of acylceramide, and it is easy to form cosmetics that lack transparency.
The gel-like aqueous cosmetic composition of the present invention contains a specific amount of each of the specific compound (1), the specific acylceramide, the nonionic surfactant, the anionic surfactant, and water in combination, and thus has good transparency such that the absorbance at a wavelength of 625nm is 0.04 or less, and the transparency can be maintained for a long period of time.
The reason why the gel-form aqueous cosmetic of the present invention can exhibit such an effect is not clear, and the present inventors presume as follows.
In the gel-like aqueous cosmetic of the present invention, by combining the specific acyl ceramide, the nonionic surfactant, and the anionic surfactant in specific amounts, respectively, the dispersed particles containing the specific acyl ceramide (hereinafter, appropriately referred to as "acyl ceramide dispersed particles") can be contained in a fine and stable manner. In addition, in the gel-like aqueous cosmetic of the present invention, by containing a specific amount of the specific compound (1) having a hydrophobic portion and a hydrophilic portion in a molecule, the dispersion stability of the acylceramide dispersed particles in an aqueous system is improved. As a result, a gel-like aqueous cosmetic containing an acylceramide, which has excellent transparency and can maintain the transparency for a long period of time, can be realized.
The above estimation is not intended to be a content for explaining the effects of the present invention in a limiting manner, but is described as an example.
[ transparency of gel-like aqueous cosmetic ]
The gel-like aqueous cosmetic of the present invention is a transparent gel-like aqueous cosmetic having an absorbance at a wavelength of 625nm of 0.04 or less, preferably 0.035 or less, more preferably 0.03 or less. The lower limit of the absorbance at a wavelength of 625nm is not particularly limited, but is preferably 0.001 or more in general.
In the gel-like aqueous cosmetic composition of the present invention, by containing the specific compound (1), the specific acylceramide, the nonionic surfactant, the anionic surfactant, and water in specific amounts in combination, the acylceramide dispersed particles can be finely and stably contained, and good transparency can be achieved with an absorbance at a wavelength of 625nm of 0.04 or less.
In the present invention, "having good transparency and maintaining transparency for a long period of time" means that the absorbance at a wavelength of 625nm is maintained at 0.04 or less regardless of time when the cosmetic is stored at room temperature (25 ℃) as long as the function, shape, and the like expected for the cosmetic are maintained.
The absorbance at a wavelength of 625nm of the gel-like aqueous cosmetic of the present invention can be measured by a usual method for measuring absorbance. In the present invention, for example, when the defoaming treatment is preferably performed, the following method can be employed as a method for measuring absorbance.
For example, the gel-like aqueous cosmetic of the present invention is placed in a disposable cuvette made of Polystyrene (PS) and having an optical path length of 0.4cm, and a defoaming treatment is performed by centrifugation at 4000rpm for 2 minutes using a small-sized refrigerated centrifuge (model: CF5RX, Hitachi Ltd., cantilever rotator: T4SS31) per cuvette. The gel-like aqueous cosmetic composition after defoaming treatment was measured for its absorbance at a wavelength of 625nm using a spectrophotometer (model: U-3310, manufactured by Hitachi, Ltd.).
Hereinafter, each component contained in the gel-like aqueous cosmetic of the present invention will be described in detail.
[ Compound represented by the general formula (1) ]
The gel-like aqueous cosmetic of the present invention contains a compound represented by the following general formula (1) (specific compound (1)).
General formula (1)
R1-{(O-R2)k-OCONH-R3[-NHCOO-(R4-O)n-R5]h}m-R6
In the general formula (1), R1R represents a C2-36 and m-valent hydrocarbon group2And R4Each independently represents a C1-4 and C2-valent hydrocarbon group, R3Represents a h +1 valent hydrocarbon group containing a linear, branched, or aliphatic or aromatic ring which may have a urethane bond, R5Represents a 2-valent hydrocarbon group, R6Represents a hydrogen atom or a hydroxyl group, m is an integer of 2 or more, h is an integer of 1 or more, and k is (O-R)2) An integer ranging from 0 to 1000 in the number of repetitions of the structure, n represents (R)40 of the number of repetitions of the structure-O)And an integer ranging from 1000, both k and n not being 0 at the same time.
The specific compound (1) is a modified hydrophobic urethane copolymer having a urethane structure and a hydrophilic alkyleneoxy group in the main chain and a hydrophobic hydrocarbon group at the end, as is clear from the general formula (1).
In the general formula (1), R1Represents a C2-36 and m-valent hydrocarbon group, preferably a C2-8 hydrocarbon group. R1The hydrocarbon group represented may contain an oxygen atom between carbon atoms.
In the general formula (1), R2And R4Each independently represents a C1-4 and 2-valent hydrocarbon group, preferably a C2-4 alkylene group.
In the general formula (1), R3Represents a h + 1-valent hydrocarbon group which may have a urethane bond and includes a linear, branched, or aliphatic ring or an aromatic ring, and preferably a 2-to 4-valent hydrocarbon group. R3The number of carbon atoms of the hydrocarbon group is preferably 1 to 10.
In the general formula (1), R5Represents a 2-valent hydrocarbon group. R5The number of carbon atoms of the hydrocarbon group is preferably 8 to 36, more preferably 12 to 24. As R5Examples of the 2-valent hydrocarbon group include 2-valent groups obtained by removing one hydrogen atom from an alkyl group, an alkenyl group, an alkylaryl group, a cycloalkyl group, a cycloalkenyl group, and the like. Wherein, as R5The 2-valent hydrocarbon group is preferably an alkylene group obtained by removing one hydrogen atom from an alkyl group.
In the general formula (1), R6Represents a hydrogen atom or a hydroxyl group.
At R6In the case of a hydrogen atom, R6And R5The 2-valent hydrocarbon groups shown together form the terminal group.
In the general formula (1), m and R1The valences of the hydrocarbon groups are the same and are integers of 2 or more.
In the general formula (1), h is R3The valence of the hydrocarbon group represented by-1 is an integer of 1 or more. h is preferably 1.
In the general formula (1), k is (O-R)2) Number of repetitions of structureThe polymerization degree may be an integer in the range of 0 to 1000.
In the general formula (1), n is (R)4The number of repetition of the structure of-O) (polymerization degree) may be an integer in the range of 0 to 1000.
In the general formula (1), k and n are not 0 at the same time.
< Compound represented by the general formula (1-1) >
The compound represented by the general formula (1) in the present invention is preferably a compound represented by the following general formula (1-1) (hereinafter, appropriately referred to as "specific compound (1-1)").
General formula (1-1)
R11-{(O-R12)k1-OCONH-R13[-NHCOO-(R14-O)n1-R15]h1}m1
In the general formula (1-1), R11R represents a C2-12 hydrocarbon group having a valence of m112And R14Each independently represents a C1-4 and C2-valent hydrocarbon group, R13Represents a h1+1 valent hydrocarbon group containing a linear, branched, or aliphatic or aromatic ring which may have a urethane bond, R15Represents a hydrocarbon group having a valence of 1, m1 is an integer of 2 or more, h1 is an integer of 1 or more, and k1 is (O-R)12) An integer of 0 to 1000 of the number of repetition of the structure, n1 represents (R)14O) an integer in the range of 0 to 1000, and both k1 and n1 are not 0 at the same time.
R in the general formula (1-1)11And R in the general formula (1)1And (7) corresponding.
R in the general formula (1-1)11Except the carbon number and R in the general formula (1)1The description of the carbon number and the other embodiments are omitted here because they are synonymous.
R11The number of carbon atoms of the hydrocarbon group is 2 to 12, preferably 2 to 4. R11The hydrocarbon group is preferably a chain or branched aliphatic hydrocarbon group, and more preferably a chain aliphatic hydrocarbon group.
R in the general formula (1-1)12And R14Are respectively connected with R in the general formula (1)2And R4And (7) corresponding.
R in the general formula (1-1)12And R14Are respectively connected with R in the general formula (1)2And R4The same applies to the preferred embodiments, and therefore, the description thereof is omitted here.
R in the general formula (1-1)13And R in the general formula (1)3And (7) corresponding.
R in the general formula (1-1)13And R in the general formula (1)3Therefore, descriptions other than the preferred embodiments are omitted here.
R13The hydrocarbon group represented is preferably an aliphatic hydrocarbon group.
M1, h1, k1 and n1 in the general formula (1-1) correspond to m, h, k and n in the general formula (1), respectively.
M1, h1, k1 and n1 in the general formula (1-1) are synonymous with m, h, k and n in the general formula (1), respectively, and therefore descriptions other than the preferred embodiment are omitted here.
m1 is preferably 2 and h1 is preferably 1.
k1 is preferably an integer of 1 to 500, more preferably an integer of 100 to 300.
n1 is preferably an integer of 1 to 200, more preferably an integer of 10 to 100.
R in the general formula (1-1)15With R in the general formula (1)6"R" in the case of a hydrogen atom5-R6The groups represented by "are equivalent.
In the general formula (1-1), R15Preferably an alkyl group (i.e., R in the formula (1))5The 2-valent hydrocarbon group is a branched alkylene group and R6A structure of a hydrogen atom).
The specific compound (1-1) is preferably obtained, for example, as follows: let' R11-[(O-R12)k1-OH]m1(Here, R is11、R12K1 and m1 are as defined above), "and" R "are used as the main components13-(NCO)h1+1(Here, R is13And h1 is the same as defined above) "and" HO- (R)14-O)n1-R15(Here, R is14、R15And n1 and the definitions given aboveThe same) "is obtained by reacting polyether monools represented by the formula (I).
The polyether polyol, polyisocyanate and polyether monool which are raw materials used in the reaction may be 1 kind or 2 or more kinds, respectively.
In the case where the specific compound (1-1) is obtained by the above-mentioned method, R in the general formula (1-1)11、R12、R13、R14And R15The hydrocarbon groups represented by the above are represented by "R" as the 3 kinds of raw materials used11-[(O-R12)k1-OH]m1”、“R13-(NCO)h1+1And HO- (R)14-O)n1-R15"determine.
The charge ratio of the 3 kinds of raw materials is not particularly limited, and for example, the ratio of the isocyanate group derived from the polyisocyanate to the hydroxyl group derived from the polyether polyol and the polyether monool is preferably NCO: OH ═ 0.8: 1-1.4: 1, in the above range.
“R11-[(O-R12)k1-OH]m1The polyether polyol can be obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin and the like to m 1-valent polyol.
Therefore, R can be determined according to the structure of the m1 valent polyol used in the synthesis of the specific compound (1-1)11A hydrocarbon group represented by the formula (I). Further, R can be determined from alkylene oxide or the like addition-polymerized with m1 valent polyol12A hydrocarbon group represented by the formula (I).
The polyhydric alcohol is preferably a polyhydric alcohol having a valence of 2 to 8, and specific examples thereof include glycols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, and neopentyl glycol; triols such as glycerol, trioxyisobutane, 1,2, 3-butanetriol, 1,2, 3-pentanetriol, 2-methyl-1, 2, 3-propanetriol, 2-methyl-2, 3, 4-butanetriol, 2-ethyl-1, 2, 3-butanetriol, 2,3, 4-pentanetriol, 2,3, 4-hexanetriol, 4-propyl-3, 4, 5-heptanetriol, 2, 4-dimethyl-2, 3, 4-pentanetriol, pentamethylglycerol, pentaglycerol, 1,2, 4-butanetriol, 1,2, 4-pentanetriol, trimethylolethane, trimethylolpropane and the like; tetrahydric alcohols such as pentaerythritol, 1,2,3, 4-pentaerythriol, 2,3,4, 5-hexanetetrol, 1,2,4, 5-pentaerythriol, and 1,3,4, 5-hexanetetrol; pentahydric alcohols such as adonitol, arabitol and xylitol; hexahydric alcohols such as dipentaerythritol, sorbitol, mannitol, and iditol; octahydric alcohols such as sucrose, etc.
In the present invention, as the polyhydric alcohol, a dihydric alcohol is preferable, and ethylene glycol is particularly preferable.
The alkylene oxide to be addition polymerized with the m1 valent polyol is preferably an alkylene oxide having 2 to 4 carbon atoms, and particularly preferably ethylene oxide, from the viewpoint of being particularly easily available and exerting excellent effects.
The addition polymerization form of alkylene oxide or the like may be a single polymerization, or 2 or more kinds of copolymerization may be used. In the case of copolymerization, the form of copolymerization may be random polymerization or block polymerization. Among them, the method for their addition polymerization may be a usual method.
The k1 representing the polymerization degree may be in the range of 0 to 1000, preferably in the range of 1 to 500, and more preferably in the range of 100 to 300.
Ethylene being based on all R12Preferably all of R12In the range of 50 to 100 mass%.
“R11-[(O-R12)k1-OH]m1The molecular weight of (A) is preferably 500 to 10 ten thousand, and particularly preferably 1000 to 5 ten thousand.
“R13-(NCO)h1+1The polyisocyanate "is not particularly limited as long as it is a polyisocyanate having 2 or more isocyanate groups in the molecule.
Thus, R13The hydrocarbon group represented may be determined depending on the polyisocyanate used in the synthesis of the specific compound (1-1).
Examples of the polyisocyanate used in the present invention include aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate, biphenyl diisocyanate, diisocyanate of phenyl methane, triisocyanate, tetraisocyanate, and the like. Among these, aliphatic diisocyanates are preferable as the polyisocyanate used in the present invention.
Examples of the aliphatic diisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, 2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, octamethylene diisocyanate, 2, 4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1, 4-butanediol dipropyl ether diisocyanate, thiodihexyl diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, and tetramethylxylylene diisocyanate. Among these, hexamethylene diisocyanate is preferable as the aliphatic diisocyanate used in the present invention.
Examples of the aromatic diisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, xylylene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, dimethylbiphenyl diisocyanate, 1, 4-naphthalene diisocyanate, 1, 5-naphthalene diisocyanate, 2, 6-naphthalene diisocyanate, and 2, 7-naphthalene diisocyanate.
Examples of the alicyclic diisocyanate include hydrogenated xylylene diisocyanate and isophorone diisocyanate.
Examples of the biphenyl diisocyanate include biphenyl diisocyanate, 3 '-dimethylbiphenyl diisocyanate, and 3, 3' -dimethoxybiphenyl diisocyanate.
Examples of the diisocyanate of phenylmethane include diphenylmethane-4, 4 '-diisocyanate, 2' -dimethyldiphenylmethane-4, 4 '-diisocyanate, diphenyldimethylmethane-4, 4' -diisocyanate, 2,5,2 ', 5' -tetramethyldiphenylmethane-4, 4 '-diisocyanate, cyclohexylbis (4-isocyanatophenyl) methane, 3' -dimethoxydiphenylmethane-4, 4 '-diisocyanate, 4' -dimethoxydiphenylmethane-3, 3 '-diisocyanate, 4' -diethoxydiphenylmethane-3, 3 '-diisocyanate, 2' -dimethyl-5, 5 ' -dimethoxydiphenylmethane-4, 4 ' -diisocyanate, 3 ' -dichlorodiphenyldimethylmethane-4, 4 ' -diisocyanate, benzophenone-3, 3 ' -diisocyanate, and the like.
Examples of the triisocyanate of phenylmethane include 1-toluene-2, 4, 6-triisocyanate, 1,3, 5-trimethylbenzene-2, 4, 6-triisocyanate, 1,3, 7-naphthalene triisocyanate, biphenyl-2, 4,4 '-triisocyanate, diphenylmethane-2, 4, 4' -triisocyanate, 3-methyldiphenylmethane-4, 6,4 '-triisocyanate, triphenylmethane-4, 4', 4' -triisocyanate, 1,6, 11-undecane triisocyanate, 1, 8-diisocyanate-4-isocyanate methyloctane, 1,3, 6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanatophenyl) thiophosphate, and the like.
As the polyisocyanate, a dimer or trimer (isocyanurate bond) of the above polyisocyanate can be used. Also, biurets obtained by reacting the above-mentioned polyisocyanates with amines may be used.
Further, polyisocyanates having urethane bonds, which can be obtained by reacting these polyisocyanates with polyols, can be used. The polyol used herein is preferably a 2-to 8-valent polyol, and is preferably the above-mentioned polyol.
Further, as "R13-(NCO)h1+1", in the case of using a polyisocyanate having a valence of 3 or more, the polyisocyanate is preferably the above-mentioned polyisocyanate having a urethane bond.
“HO-(R14-O)n1-R15The polyether monool "is not particularly limited as long as it is a polyether of a monovalent alcohol.
“HO-(R14-O)n1-R15The polyether monool represented by "can be obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin and the like to a monovalent alcohol.
Thus, R14The hydrocarbon group represented can be determined according to alkylene oxide addition polymerized with monovalent alcohol, and the like. In addition, R15A hydrocarbon group represented byCan be determined according to the monovalent alcohol used in the synthesis of the specific compound (1-1).
The monovalent alcohol referred to herein is an alcohol represented by the following general formula (2), (3) or (4). Thus, R15Corresponds to groups obtained by removing hydroxyl groups in the following general formulae (2) to (4).
General formula (2): ra-OH
General formula (3): rb-CH(Rc)-Rd-OH
General formula (4): re-CH(Rf)-OH
In the general formulae (2) to (4), Ra、Rb、Rc、ReAnd RfEach independently represents a hydrocarbon group, and specific examples thereof include hydrocarbon groups such as an alkyl group, an alkenyl group, an alkylaryl group, a cycloalkyl group, and a cycloalkenyl group.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, an isotridecyl group, a myristyl group, a palmityl group, a stearyl group, an isostearyl group, an eicosyl group, a docosyl group, a tetracosyl group, a triacontyl group, a 2-octyldodecyl group, a 2-dodecylhexadecyl group, a 2-tetradecyl.
Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a pentenyl group, an isopentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tetradecenyl group, and an oleyl group.
Examples of the alkylaryl group include a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a benzyl group, a phenethyl group, a cinnamyl group, a benzhydryl group, a trityl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a pentylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, and a nonylphenyl group.
Examples of the cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, and methylcycloheptyl.
Examples of the cycloalkenyl group include cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, and methylcycloheptenyl.
In the general formula (3), RdRepresents a 2-valent hydrocarbon group. As RdExamples of the 2-valent hydrocarbon group include groups having a valence of 2 obtained by removing one hydrogen atom from an alkyl group, an alkenyl group, an alkylaryl group, a cycloalkyl group, a cycloalkenyl group, and the like. Specifically, as RdExamples of the 2-valent hydrocarbon group include an alkylene group, an alkenylene group, an alkylarylene group, a cycloalkylene group, and a cycloalkenylene group.
The alkylene oxide to be addition polymerized with a monovalent alcohol is preferably an alkylene oxide having 2 to 4 carbon atoms, and particularly preferably ethylene oxide, from the viewpoint of being particularly easily available and exerting excellent effects.
As for the addition polymerization form of alkylene oxide or the like, it is possible to use a single polymerization, or 2 or more kinds of copolymerization. In the case of copolymerization, the form of copolymerization may be random polymerization or block polymerization. Among them, the method for their addition polymerization may be a usual method.
N1 representing the degree of polymerization may be in the range of 0 to 1000, preferably in the range of 1 to 200, and more preferably in the range of 10 to 200.
Ethylene being based on all R14Preferably all of R14In (3), the content is in the range of 50 to 100% by mass, and more preferably in the range of 65 to 100% by mass.
The method for producing the specific compound (1-1) is similar to the reaction between a general polyether and an isocyanate, and can be obtained by, for example, heating a polyether and an isocyanate at 80 to 90 ℃ for 1 to 3 hours and reacting them.
In the reaction of "R11-[(O-R12)k1-OH]m1Polyether polyol (a) and "R" each of which is represented by13-(NCO)h1+1Polyisocyanate (b) represented by the formula and "HO- (R)14-O)n1-R15Polyether monools of(c) In the case of the reaction, products other than the compound (copolymer) represented by the general formula (1-1) may be produced as by-products.
For example, when diisocyanate is used, a c-b-a-b-c type copolymer represented by the general formula (1-1) is produced as a main product, but other c-b-c type and c-b- (a-b) x-a-b-c type copolymers may be produced as by-products.
In this case, the c-b-a-b-c type copolymer represented by the general formula (1-1) may be used in the gel-like aqueous cosmetic of the present invention in a state of containing a mixture of the copolymer without separating it.
As the specific compound (1-1) used in the present invention, the compounds exemplified in Japanese patent laid-open No. 9-71766 are suitable.
As the specific compound (1-1) used in the present invention, in particular, PEG-240/decyltetradecylpolyether-20/Hexamethylene Diisocyanate (HDI) copolymer is suitable.
Such a copolymer is commercially available from the company ADEKA as "ADEKA NOL GT-700".
< Compound represented by the general formula (1-2) >
The compound represented by the general formula (1) in the present invention is preferably a compound represented by the following general formula (1-2) (hereinafter, appropriately referred to as "specific compound (1-2)").
General formula (1-2)
R21-[OCONH-R22-NHCO(-O-CHR23CH2)n2]m2-OH
In the general formula (1-2), R21R represents a saturated hydrocarbon group having 6 to 36 carbon atoms and a valence of m222Represents methyldiphenylene, hexamethylene, methyldicyclohexyl, 3-methyl-3, 5, 5-trimethylcyclohexylene, dimethylphenylene or tolylene, R23Represents a hydrogen atom or a methyl group, n2 represents an integer of 90 to 900, and m2 represents an integer of 1 to 5.
In the general formula (1-2), R21Is a C6-36 saturated hydrocarbon group, preferably a C6-36 linear alkyl or branched alkyl group.
Specific compound(1-2) can be obtained as follows: will be "H- (O-CHR)23CH2)n2-OH (here, R23And n2 is the same as defined above), "HO-R21(Here, R is21The same as defined above) "1-valent hydrophobic alcohol and" R22<(NCO)2(Here, R is22The same as defined above) "as a raw material, and reacting these raw materials.
As "H- (O-CHR)23CH2)n2Specific examples of the polyalkylene oxide compound represented by-OH "include polyethylene oxide, polypropylene oxide, and a copolymer of ethylene oxide and propylene oxide (for example, polyethylene oxide/polypropylene oxide having a block copolymer of a polyethylene oxide segment and a polypropylene oxide segment).
Wherein, H- (O-CHR)23CH2)n2The polyalkylene oxide compound represented by-OH "is preferably a polyalkylene oxide compound containing an ethylene oxide group in an amount of 70% by mass or more, and more preferably a polyalkylene oxide compound having an ethylene oxide group in an amount of 95% by mass or more.
As "HO-R21The hydrophobic alcohol having a valence of 1 represented by "is preferably an alcohol having a solubility in water of 0.4 mass% or less, and specific examples thereof include hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, palmitol, pentadecanol, octadecanol, nonadecanol, arachidyl alcohol, 2-octyldodecanol, and behenyl alcohol, and preferred examples thereof include hydrophobic alcohols having a valence of 1 selected from the group consisting of palmitol and behenyl alcohol.
These hydrophobic alcohols having a valence of 1 may be used alone or in combination of two or more.
The hydrophobic alcohol having a valence of 1 is used preferably in a proportion of 0.2 to 1.0 mol, more preferably in a proportion of 0.25 to 0.70 mol, based on 1mol of the polyalkyleneoxide compound.
As "R22<(NCO)2Specific examples of the diisocyanate compound represented by the above formula4,4 '-diphenylmethane diisocyanate (MDI), 1, 6-Hexamethylene Diisocyanate (HDI), dicyclohexylmethane-4, 4' -diisocyanate (HMDI), 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate (IPDI), 1, 8-dimethylbenzene-2, 4-diisocyanate, 2, 4-Tolylene Diisocyanate (TDI), and the like.
Wherein, as "R22<(NCO)2The diisocyanate compound represented by "is preferably a diisocyanate compound selected from the group consisting of dicyclohexylmethane-4, 4' -diisocyanate (HMDI) and 1, 6-Hexamethylene Diisocyanate (HDI).
These diisocyanate compounds may be used alone or in combination of two or more.
Regarding the diisocyanate compound, it is preferable that the number of moles of isocyanate groups ([ -NCO ] mole) of the isocyanate compound is used in the range of 0.67 to 0.91, preferably 0.70 to 0.90, relative to the total number of moles of terminal hydroxyl groups ([ -OH ]) (i.e., ([ -NCO ]/([ -OH ])) of the polyalkyleneoxide compound and the 1-valent hydrophobic alcohol compound.
Examples of the method for reacting the polyalkylene oxide compound, the 1-valent hydrophobic alcohol and the diisocyanate compound include a method in which the compounds are dissolved or dispersed in a reaction solvent such as toluene, xylene or dimethylformamide and reacted; a method in which a solid is pulverized into a powder or melted into a liquid, the two are uniformly mixed, and then heated to a predetermined temperature to cause a reaction.
As a method for synthesizing the specific compound (1-2), the methods described in paragraphs [ 0049 ] to [ 0051 ] of Japanese patent application laid-open No. 2013-116941 can be preferably used.
As the specific compound (1-2) in the present invention, a distearyl PEG/PPG-8/6 (methylene diphenyl diisocyanate/PEG-400) copolymer, i.e., a compound commercially available from Sumitomo Seiki Kabushiki Kaisha under the trade name "AQUPEC HU type C", is suitable.
The content of the specific compound (1) in the gel-like aqueous cosmetic of the present invention is 0.5 to 5% by mass, preferably 1 to 3% by mass, and more preferably 1.3 to 2% by mass, based on the total mass of the gel-like aqueous cosmetic.
When the content of the specific compound (1) is within the above range, the transparency of the gel-like aqueous cosmetic composition is improved by containing the specific acylceramide, the nonionic surfactant and the anionic surfactant, which will be described later, in combination in specific amounts. When the content of the specific compound (1) is within the above range, a suitable hardness as a gel-like aqueous cosmetic can be obtained.
[ acylceramide represented by the general formula (I) ]
The gel-like aqueous cosmetic of the present invention contains an acylceramide represented by the following general formula (I) (hereinafter, appropriately referred to as "specific acylceramide").
General formula (I)
Figure BDA0000797835270000161
In the general formula (I), R31Represents a linear or branched hydrocarbon group having 40 to 55 carbon atoms in total and containing an ester bond in a carbon chain, R31The hydrocarbon group may have 1 or 2 or more partial structures selected from the group consisting of a multiple bond, an aromatic ring and an aromatic heterocycle in a carbon chain, and R is32Represents an alkyl group having 11 to 21 carbon atoms which may have a hydroxyl group, or an alkenyl group having 11 to 21 carbon atoms which may have a hydroxyl group.
The following is a detailed description of the general formula (I).
R31The total carbon number of the hydrocarbon group is 40 to 55, preferably 42 to 52, and more preferably 45 to 48.
R31The number of ester bonds contained in the carbon chain of the hydrocarbon group represented may be 1 or 2 or more, and more preferably 1.
As R31The hydrocarbon group represented by the above-mentioned group may have multiple bonds in the carbon chain, and examples thereof include a carbon-carbon double bond and a carbon-carbon triple bond, and a carbon-carbon double bond is preferable.
As R31The hydrocarbon group may be an aromatic ring contained in a carbon chain, and examples thereof include benzeneA ring, a naphthalene ring, an anthracene ring, and the like.
As R31Examples of the aromatic heterocyclic ring which may be contained in the carbon chain of the hydrocarbon group include a pyridine ring and a pyrazine ring.
R31The hydrocarbon group may be a saturated or unsaturated hydrocarbon group having 25 to 30 carbon atoms, which is linked to a saturated or unsaturated hydrocarbon group having 16 to 18 carbon atoms via 1 ester bond.
As R31The preferable hydrocarbon group is a hydrocarbon group having a total carbon number of 40 to 55 and having a structure in which a linear fatty acid such as linoleic acid or stearic acid is ester-bonded to an ω terminal of a linear ω -hydroxy linear saturated fatty acid.
R31The hydrocarbon group may further have a substituent, and examples of the substituent include a carbonyl group, an oxy group, and an amide group.
Shown below is R31Without being limited thereto.
Figure BDA0000797835270000171
Denotes the junction site.
R32The alkyl group has 11 to 21 carbon atoms, preferably 13 to 21 carbon atoms, and more preferably 14 to 20 carbon atoms. R32The alkyl group represented by the above general formula (I) may be linear or branched, and is preferably linear.
R32The alkenyl group has 11 to 21 carbon atoms, preferably 13 to 21 carbon atoms, and more preferably 14 to 20 carbon atoms. R32The alkenyl group represented may be linear or branched, and is preferably linear.
R32The alkyl or alkenyl group represented may have 1 or 2 or more hydroxyl groups, preferably 1 or 2 hydroxyl groups.
As R in the general formula (I)31And R32In a preferred combination of (A) and (B), containing the above-mentioned R31And R32In combination with the preferred embodiments of (a).
Shown below is R32Specific examples of (2), howeverAnd is not limited thereto.
Figure BDA0000797835270000181
Denotes the junction site.
The specific acyl ceramide includes a human-type acyl ceramide (hereinafter, appropriately referred to as "human-type acyl ceramide").
In the present invention, "human-type acyl ceramide" refers to an acyl ceramide having the same optical isomer structure as an acyl ceramide present in the stratum corneum of human skin.
The human-type acylceramide may be a natural product (extract), a product obtained by a microbial fermentation method, a synthetic product or a product derived from an animal.
Among the specific acylceramides, human type acylceramides are particularly poorly soluble and easily crystallized. Gel-like aqueous cosmetics containing human acyl ceramide tend to be cosmetics lacking in transparency, and show a significant decrease in transparency with time. The gel-like aqueous cosmetic of the present invention has a specific structure, and can realize good transparency and suppress deterioration of good transparency with time even when a human-type acylceramide is contained.
Examples of the human-type acyl ceramide which can be used as the specific acyl ceramide in the present invention include ceramide I, ceramide IV, ceramide IX, and the like.
Such human-type acylceramides are also commercially available, and examples thereof include Ceramide I, Ceramide EOP27, and Ceramide EOS27 (all of which are trade names, Evonik).
Specific examples of the specific acylceramide are given below, but the present invention is not limited to these examples.
Figure BDA0000797835270000191
Specific examples of the specific acylceramide include, in addition to the above, the following.
Figure BDA0000797835270000192
The gel-like aqueous cosmetic of the present invention may contain a specific acyl ceramide alone or in combination of 2 or more.
The gel-like aqueous cosmetic of the present invention may be used in combination with another ceramide other than the specific acyl ceramide, within a range not impairing the effect of the present invention.
The gel-like aqueous cosmetic of the present invention preferably contains a dispersion obtained by dispersing a specific acylceramide in a nonionic surfactant and an anionic surfactant, which are described later. The dispersion method will be described later.
The content of the specific acylceramide in the gel-like aqueous cosmetic of the present invention is 0.1 to 1000ppm, preferably 0.5 to 100ppm, and more preferably 1 to 10ppm based on the total mass of the gel-like aqueous cosmetic, from the viewpoint of transparency and deposition with time.
[ nonionic surfactant ]
The gel-like aqueous cosmetic of the present invention contains a nonionic surfactant.
The nonionic surfactant used in the present invention is not particularly limited, and known ones can be used.
In the specific compound (1), for example, a substance having a surface-active action such as a PEG-240/decyltetradecylpolyether-20/Hexamethylene Diisocyanate (HDI) copolymer as the specific compound (1-1) is present, but such a high molecular compound is not included in the nonionic surfactant of the present invention.
In the present invention, the weight average molecular weight of the "nonionic surfactant" is preferably 1000 or less. The weight average molecular weight of the nonionic surfactant can be calculated by a standard polystyrene conversion method using Gel Permeation Chromatography (GPC) described below.
Condition ^ E
Figure BDA0000797835270000201
Examples of the nonionic surfactant in the present invention include glycerin fatty acid esters, polyglycerin fatty acid esters, organic acid monoglycerides, propylene glycol fatty acid esters, polyglycerin condensed ricinoleic acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and the like. These nonionic surfactants are not necessarily highly purified substances by distillation or the like, and may be reaction mixtures.
In the above examples, the nonionic surfactant is preferably a polyglycerin fatty acid ester, and more preferably a polyglycerin fatty acid ester having a hydrophilic-lipophilic Balance (HLB) of 10 or more and 16 or less, from the viewpoint of maintaining more excellent transparency for a long period of time. The polyglycerin fatty acid ester can greatly reduce the surface tension of the dispersed phase/continuous phase, and as a result, the acylceramide dispersed particles can be contained more finely and stably, which is preferable from this point of view.
HLB is a balance parameter indicating hydrophilicity-hydrophobicity, which is generally used in the field of surfactants, and can be calculated by a commonly used calculation formula such as the formula above. In the present invention, the following formula is used.
HLB=7+11.7log(Mw/Mo)
Here, Mw is the molecular weight of the hydrophilic group, and Mo is the molecular weight of the hydrophobic group.
HLB can be represented by a numerical value described in a product catalog or the like. As is clear from the above formula, a surfactant having an arbitrary HLB value can be obtained by utilizing the additivity of HLB.
The polyglycerin fatty acid ester is preferably an ester of a polyglycerin having an average polymerization degree of 10 and a fatty acid having a fatty acid skeleton with 8 to 18 carbon atoms, such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, or linoleic acid.
More preferable examples of such polyglycerin fatty acid esters include hexaglycerin monooleate, hexaglycerin monopalmitate, hexaglycerin monomyristate, hexaglycerin monolaurate, decaglycerin monooleate, decaglycerin monostearate, decaglycerin monopalmitate, decaglycerin monomyristate, and decaglycerin monolaurate. All of them have HLB values of 10 to 16.
Among the polyglycerin fatty acid esters, at least one selected from the group consisting of decaglyceryl monolinoleate (HLB ═ 12), decaglyceryl monooleate (HLB ═ 12), decaglyceryl monostearate (HLB ═ 12), decaglyceryl monopalmitate (HLB ═ 13), decaglyceryl monomyristate (HLB ═ 14), and decaglyceryl monolaurate (HLB ═ 16) is more preferable, and decaglyceryl monomyristate is particularly preferable.
As the polyglycerin fatty acid ester, 1 or more selected from polyglycerin fatty acid esters having HLB of 10 or more and 16 or less and 1 or more selected from polyglycerin fatty acid esters having HLB of 5 or more and 15 or less different from the molecular structure thereof may be used in combination. The polyglycerin fatty acid ester having HLB of 5 to 15 may be a polyglycerin fatty acid ester contained in the polyglycerin fatty acid ester, or may be other polyglycerin fatty acid esters.
Commercially available polyglycerin fatty acid esters may be used.
Examples of commercially available products of polyglycerol fatty acid esters include NIKKOL DGMS, NIKKOL DGMO-CV, NIKKOL DGMO-90V, NIKKOL DGDO, NIKKOL DGMIS, NIKKOLDGTIS, NIKKOL Tetraglyn 1-SV, NIKKOL Tetraglyn 1-O, NIKKOL Tetraglyn 3-S, NIKKOLTetraglyn 5-S, NIKKOL Tetraglyn 5-O, NIKKOL Hexaglyn 1-L, NIKKOL Hexaglyn 1-M, NIKKOL Hexaglyn 1-SV, NIKKOL Hexaglyn 1-O, NIKKOL Hexaglyn 3-S, NIKKOL Hexaglyn4-B, NIKKOL Hexaglyn 5-S, NIKKOL Hexatol 5-Hexaglyn 1-SV, NIKKOL Hexaglyn 1-O, NIKKOL Dexaglyn 3-S, NIKK Hexaglyn4-B, NIKK Hexaglyn 5-S, NIKKOL Hexaol 5-NIKK Hexaglyn 1-SV, NIKK Hexaglyn 1-O, NIKK Dexaglyn 1-O, NIKK Dexaglyn-1-SV, NIKK-K-O, NIKK-1-K-O, NIKK-D-1-O, NIKK-D-O, NIKK-O-D-1-D-O, NIKK, NIKKOLDecaglyn 1-LN, NIKKOL Decaglyn 2-SV, NIKKOL Decaglyn 2-ISV, NIKKOL Decaglyn 3-SV, NIKKOL Decaglyn 3-OV, NIKKOL Decaglyn 5-SV, NIKKOL Decaglyn 5-HS, NIKKOL Decaglyn 5-IS, NIKKOL Decaglyn 5-OV, NIKKOL Decaglyn 5-O-R, NIKKOL Decaglyn 7-S, NIKKOL Decaglyn 7-O, NIKKOL Decaglyn 10-SV, NIKKOL Decaglyn 10-IS, NIKKOL Decaglyn 10-OV, NIKKOL Decaglyn 10-MAC, NIKKOL Decaglyn PR-20 etc. ("NIKKOL" IS registered for all); RYOTO POLYGLYESTER L-7D, L-10D, M-10D, P-8D, SWA-10D, SWA-15D, SWA-20D, S-24D, S-28D, O-15D, O-50D, B-70D, B-100D, ER-60D, LOP-120DP, DS13W, DS3, HS11, HS9, TS4, TS2, DL15, DO13, etc., from Mitsubishi-Kagaku Foods Corporation; SUNSOFT Q-17UL, SUNSOFT Q-14S, SUNSOFT A-141C, and the like ("SUNSOFT" is a registered trademark); POEM DO-100, POEM J-0021, and the like ("POEM" are all registered trademarks) by RikenVitamin Co., Ltd.
Among the above, preferred commercially available products of the polyglycerin fatty acid ester are NIKKOL Decaglyn 1-L, NIKKOLDecaglyn 1-M, NIKKOL Decaglyn 1-SV, NIKKOL Decaglyn 1-50SV, NIKKOL Decaglyn 1-ISV, NIKKOL Decaglyn 1-O, NIKKOL Decaglyn 1-OV, NIKKOL Decaglyn 1-LN, YOTOPOLYGLYESTER L-7D, L-10D, M-10D, P-8D, SWA-10D, SWA-15D, SWA-20D, S-24D, S-28D, O-15D, O-50D, B-70D, B-100D, ER-60D, and LOP-120 DP.
The gel-like aqueous cosmetic of the present invention may contain 1 kind of nonionic surfactant alone or a combination of 2 or more kinds thereof.
The content of the nonionic surfactant in the gel-like aqueous cosmetic composition of the present invention is 0.1 times or more, preferably 1 to 70 times, more preferably 3 to 40 times, and further preferably 5 to 20 times the content of the specific acylceramide, from the viewpoint of maintaining good transparency for a long period of time.
[ anionic surfactant ]
The gel-like aqueous cosmetic of the present invention contains an anionic surfactant.
The anionic surfactant in the present invention is not particularly limited, and known ones can be used.
From the viewpoint of maintaining further good transparency over a long period of time, lecithin is preferred as the anionic surfactant in the present invention.
The gel-like aqueous cosmetic of the present invention contains a polyglycerol fatty acid ester as a nonionic surfactant and lecithin as an anionic surfactant, and thus can maintain a further excellent transparency over a long period of time.
Lecithin has a hydrophilic group and a hydrophobic group in its molecule, and has been widely used as an emulsifier in the fields of foods, pharmaceuticals, cosmetics, and the like.
In the present invention, lecithin having a lecithin purity of 60% or more is industrially used, and such lecithin can be used. From the viewpoint of more finely and stably containing the dispersed particles of acyl ceramide, lecithin is preferably lecithin having a lecithin purity of 80% or more, and more preferably 90% or more, which is generally called high-purity lecithin.
Examples of the lecithin include various kinds of lecithin known to be extracted and isolated from plants, animals, or microorganisms.
Specific examples of such lecithins include various lecithins derived from plants such as soybean, corn, peanut, rapeseed, and wheat, animals such as egg yolk and bovine, and microorganisms such as Escherichia coli.
When such lecithins are exemplified by the name of a compound, there may be exemplified glycerolecithins such as phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, phosphatidylethanolamine, phosphatidylmethylethanolamine, phosphatidylcholine, phosphatidylserine, bisphosphatidic acid, and diphosphatidylglycerol (cardiolipin); sphingomyelin such as sphingomyelin.
In the present invention, in addition to the high-purity lecithin, hydrogenated lecithin, enzymatically decomposed hydrogenated lecithin, hydroxy lecithin, and the like can be used. The gel-like aqueous cosmetic of the present invention may contain lecithin in 1 kind alone or in combination of 2 or more kinds.
The content of the anionic surfactant in the gel-like aqueous cosmetic of the present invention is 0.01-fold or more, preferably 0.01-fold to 20-fold, more preferably 0.1-fold to 10-fold, and further preferably 0.4-fold to 5-fold relative to the content of the specific acylceramide, from the viewpoint of maintaining good transparency for a long period of time.
In the gel-like aqueous cosmetic of the present invention, the ratio of the content of the nonionic surfactant to the content of the anionic surfactant (nonionic surfactant content: anionic surfactant content) is preferably 0.01: 1-1: 0.01, more preferably 0.1: 1-1: 0.1.
[ Water ]
The gel-like aqueous cosmetic of the present invention contains water.
The water is not particularly limited as long as it can be used in cosmetics.
The content of water in the present invention is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and still more preferably 70 to 88% by mass, based on the total mass of the gel-like aqueous cosmetic.
[ other Components ]
The gel-like aqueous cosmetic of the present invention may contain, in addition to the specific compound (1), the specific acylceramide, the nonionic surfactant, the anionic surfactant, and water, other components other than these, as desired. Hereinafter, other components that can be used in the gel-like aqueous cosmetic of the present invention will be described.
< cholesterol >
The gel-like aqueous cosmetic of the present invention preferably further contains cholesterol.
In the gel-like aqueous cosmetic of the present invention, cholesterol can function as an oil agent for dissolving a specific acylceramide therein, for example.
The gel-like aqueous cosmetic composition of the present invention further contains cholesterol, whereby the crystallization-preventing effect of the specific acylceramide is further improved.
As cholesterol, a purified product of crude cholesterol obtained by extraction in the form of a main component of lanolin can be suitably used. As the cholesterol, commercially available products can be used, and examples of the commercially available products include "cholesterol JSQI" of Japan kosher and "cholesterol" of Croda Japan KK..
When the gel-like aqueous cosmetic of the present invention contains cholesterol, the content thereof is not particularly limited. The content of cholesterol in the gel-like aqueous cosmetic of the present invention is preferably 0.1 to 1000ppm, more preferably 0.5 to 100ppm, and still more preferably 1 to 100ppm based on the total mass of the gel-like aqueous cosmetic.
< fatty acid or salt thereof >
When the gel-like aqueous cosmetic of the present invention contains cholesterol, it preferably further contains a fatty acid or a salt thereof.
The gel-like aqueous cosmetic composition of the present invention contains a fatty acid or a salt thereof together with a specific acylceramide and cholesterol, and thereby improves the barrier function of the skin against external irritation, the moisturizing ability of the skin, and the like.
The fatty acid or a salt thereof in the present invention is not particularly limited, and may be natural or synthetic.
The carbon chain in the fatty acid or salt thereof may be a straight chain or a branched chain, or may be a saturated or unsaturated carbon chain. The carbon chain in the fatty acid or a salt thereof is preferably a branched or unsaturated carbon chain from the viewpoint of solubility in the gel-like aqueous cosmetic and prevention of precipitation.
The number of carbon atoms in the fatty acid skeleton of the fatty acid or salt thereof is not particularly limited, but is preferably 12 to 22, more preferably 16 to 20, and still more preferably 16 to 18.
When the number of carbon atoms in the fatty acid skeleton in the fatty acid or salt thereof is within the above range, the stability of transparency with time is further improved.
Specific examples of the fatty acid include caprylic acid (C8: 0), capric acid (C10: 0), lauric acid (C12: 0), myristic acid (14: 0), palmitic acid (C16: 0), stearic acid (C18: 0), isostearic acid (C18: 0), oleic acid (C18: 1), linoleic acid (C18: 2), α -linolenic acid (C18: 3), γ -linolenic acid (C18: 3), arachidic acid (C20: 0), behenic acid (C22: 0), and the like, and the number of carbon atoms and the number of double bonds of the fatty acid skeleton are shown in parentheses, and for example, "C18: 1" shows that the number of carbon atoms of the fatty acid skeleton is 18 and the number of double bonds is 1.
The fatty acid in the present invention is preferably at least one selected from the group consisting of isostearic acid, oleic acid and linoleic acid, and more preferably at least one selected from the group consisting of isostearic acid and oleic acid, from the viewpoints of improving the emulsion stability and dispersion stability of the ingredients of the gel-like aqueous cosmetic composition and preventing the fatty acid or the salt thereof from precipitating itself.
The salt structure of the salt constituting the fatty acid includes salts of alkali metals such as sodium and potassium, salts of basic amino acids such as L-arginine, L-histidine and L-lysine, and alkanolamine salts such as triethanolamine. The kind of the salt is appropriately selected depending on the kind of the fatty acid used, and the like. From the viewpoint of solubility, the salt structure of the salt constituting the fatty acid is preferably an alkali metal salt such as a sodium salt.
The salt of a fatty acid in the present invention is preferably at least one selected from the group consisting of an alkali metal salt of isostearic acid, an alkali metal salt of oleic acid, and an alkali metal salt of linoleic acid, and more preferably at least one selected from sodium isostearate and sodium oleate.
The gel-like aqueous cosmetic of the present invention may contain 1 kind of the above-mentioned fatty acid or a salt thereof alone, or 2 or more kinds thereof in combination.
When the gel-like aqueous cosmetic of the present invention contains a fatty acid or a salt thereof, the content thereof is not particularly limited. The content of the fatty acid or a salt thereof in the gel-like aqueous cosmetic of the present invention is preferably 0.1ppm to 100000ppm, more preferably 1ppm to 50000ppm, and still more preferably 10ppm to 10000ppm, based on the total mass of the gel-like aqueous cosmetic.
In the present invention, "the content of a fatty acid or a salt thereof" refers to a fatty acid equivalent.
< polyol >
The gel-like aqueous cosmetic of the present invention may contain a polyhydric alcohol. The gel-like aqueous cosmetic composition of the present invention contains a polyhydric alcohol, and thus has improved moisture retention and a good feeling in use.
Examples of the polyhydric alcohol include glycerin, ethylhexylglycerin, 1, 3-butylene glycol, and ethylene glycol; reducing syrup, sucrose, erythritol, xylitol, glucose, galactose, sorbitol, maltotriose, trehalose, and other polysaccharides.
The gel-like aqueous cosmetic of the present invention may contain 1 kind of the above-mentioned polyhydric alcohol alone, or 2 or more kinds of the above-mentioned polyhydric alcohols in combination.
When the gel-like aqueous cosmetic of the present invention contains a polyhydric alcohol, the content thereof is not particularly limited. The content of the polyhydric alcohol in the gel-like aqueous cosmetic of the present invention is preferably 1 to 50% by mass, more preferably 2 to 20% by mass, and still more preferably 5 to 10% by mass, based on the total mass of the gel-like aqueous cosmetic.
< other additional ingredients >
The gel-like aqueous cosmetic of the present invention may contain, as appropriate, additives that are generally used in the field of cosmetics, within a range that does not impair the effects of the present invention.
Examples of the additive component include functional components exhibiting a cosmetic effect (e.g., moisturizing effect, whitening effect, and skin-conditioning effect) useful for use in cosmetics, and examples of such functional components include β carotenoids such as carotene, astaxanthin, zeaxanthin, lycopene, and lutein, vitamin E such as tocopherol and tocotrienol, ubiquinones such as coenzyme Q10, polysaccharides such as hyaluronic acid, glycosphingolipids such as glucosylceramide and galactosylceramide, collagens such as hydrolyzed collagen and water-soluble collagen, amino acids such as acetylhydroxyproline, hydrolyzed lupin protein, and ascorbyl palmitate 3 Na.
Examples of the additive components include preservatives such as phenoxyethanol, antioxidants, colorants, thickeners, aqueous sodium hydroxide solutions, pH adjusters such as hydrochloric acid, buffers, perfumes, antibacterial agents, ultraviolet absorbers, active oxygen scavengers, antimicrobial agents, anti-inflammatory agents, minerals, and the like.
[ method for producing gel-like aqueous cosmetic preparation ]
The method for producing the gel-like aqueous cosmetic of the present invention is not particularly limited. The gel-like aqueous cosmetic of the present invention can be obtained by a known method for producing a gel-like aqueous cosmetic using a specific amount of the specific compound (1), a specific amount of the specific acylceramide, a specific amount of the nonionic surfactant, a specific amount of the anionic surfactant, water, and other components as needed.
One of preferred methods for producing the gel-like aqueous cosmetic of the present invention includes a method comprising the steps of: a dispersion composition containing a specific acyl ceramide, which comprises at least a specific amount of a specific acyl ceramide, a specific amount of a nonionic surfactant, and a specific amount of an anionic surfactant, that is, a dispersion obtained by dispersing a specific acyl ceramide with a nonionic surfactant and an anionic surfactant, is prepared in advance, and a mixture of the dispersion composition containing a specific acyl ceramide, a specific amount of a specific compound (1) and water, and other components as required are mixed under heating.
The dispersion composition containing a specific acylceramide can be obtained by a production method comprising the following steps: mixing a dispersed phase component comprising at least a specific acyl ceramide and a continuous phase component.
The mixing method of the continuous phase component (aqueous phase component) and the dispersed phase component (oil phase component) is not particularly limited, and known mixing methods such as an ultrasonic dispersion method, a high-pressure emulsification method, and a spray injection method for directly injecting the dispersed phase component into the continuous phase component can be used.
As one of preferable production methods of the dispersion composition containing the specific acyl ceramide, there is a production method including: a step of obtaining a crude dispersion by performing a dispersion treatment in a state in which a pre-dispersion treatment liquid containing a specific amount of a specific acylceramide, a specific amount of a nonionic surfactant, and a specific amount of an anionic surfactant in combination is heated to 100 ℃ or higher (hereinafter, appropriately referred to as a "pre-dispersion treatment step"); and a mixed liquid obtained by mixing the crude dispersion liquid with water or the like is subjected to a dispersion treatment by an ultrasonic dispersion method or a high-pressure emulsification method (hereinafter, appropriately referred to as a "main dispersion treatment step").
The production method of the present embodiment will be explained below.
In the preparation of the crude dispersion in the preliminary dispersion treatment step, a solution (dispersion pretreatment solution) containing a specific amount of a specific acyl ceramide, a specific amount of a nonionic surfactant, and a specific amount of an anionic surfactant is heated to 100 ℃ or higher, and then dispersion treatment is performed, whereby a crude dispersion in which dispersed particles (dispersion phase) containing a specific acyl ceramide in a molten state are coarsely dispersed in a continuous phase can be obtained.
In the liquid before the dispersion treatment, the specific acylceramide, the nonionic surfactant, and the anionic surfactant may be simply mixed. The method of mixing the specific acylceramide, the nonionic surfactant, and the anionic surfactant is not particularly limited, and examples thereof include a method of mixing by stirring.
The liquid before dispersion treatment may contain other components than the specific acylceramide, the nonionic surfactant, and the anionic surfactant, as necessary. Examples of the other components include components such as a polyol and cholesterol.
In the preparation of the crude dispersion, the liquid before dispersion treatment is heated to 100 ℃ or higher from the viewpoint of melting the specific acylceramide. The temperature of 100 ℃ or higher may be attained when the dispersion treatment is performed on the liquid before the dispersion treatment. The dispersion treatment may be performed by heating the liquid before the dispersion treatment to 100 ℃ or higher in advance and maintaining the liquid temperature at 100 ℃ or higher, or the dispersion treatment may be performed while heating the liquid before the dispersion treatment to 100 ℃ or higher.
The apparatus for heating the liquid before dispersion treatment to 100 ℃ or higher is not particularly limited, and a general heating apparatus can be used. Examples of the heating device include a thermostatic chamber.
The apparatus for obtaining the crude dispersion by dispersing the dispersion liquid before the dispersion treatment is not particularly limited, and a general stirring apparatus can be used. Examples of the stirring apparatus include a magnetic stirrer, a home mixer, a paddle mixer, an impeller mixer, a homogenizer, a disperser mixer, and a super mixer.
The time of the dispersion treatment is not particularly limited, and may be appropriately set in accordance with the kind of the stirring apparatus, the composition of the liquid before the dispersion treatment, and the like.
In the main dispersion treatment step, after the coarse dispersion liquid obtained in the preliminary dispersion treatment is mixed with water or the like, dispersion treatment by an ultrasonic dispersion method (hereinafter, appropriately referred to as "ultrasonic dispersion treatment") or dispersion treatment by a high-pressure emulsification method (hereinafter, appropriately referred to as "high-pressure emulsification treatment") may be performed.
In the main dispersion treatment step, a molten crude dispersion of the specific acyl ceramide and water or the like are mixed and subjected to a dispersion treatment, whereby a dispersion composition containing the specific acyl ceramide, which contains dispersed particles containing the specific acyl ceramide, can be obtained.
The temperature of the crude dispersion when it is mixed with water or the like is preferably set to 100 ℃ or lower, more preferably 90 to 100 ℃ from the viewpoint of preventing bumping.
The temperature of water or the like is not particularly limited, but is preferably set to 50 ℃ to 90 ℃.
The crude dispersion may be mixed with water or the like at once, or may be mixed while gradually adding one to the other. The crude dispersion may be simply mixed with water or the like, and examples of a method of mixing include mixing by stirring.
The mixing ratio of the crude dispersion and water is not particularly limited, but from the viewpoint of miniaturization of the acylceramide dispersed particles, the ratio of the crude dispersion/water (on a mass basis) is preferably 1/20 to 10/1, more preferably 1/10 to 5/1, and still more preferably 1/2 to 2/1.
From the viewpoint of the miniaturization and the stability with time of the acylceramide dispersed particles, the ratio of the dispersed phase to the continuous phase in the dispersion composition containing the specific acylceramide is preferably 1/1000 to 1/5 in terms of the ratio of the dispersed phase to the continuous phase (mass basis), more preferably 1/100 to 1/10, and still more preferably 1/50 to 1/10 by mixing, for example, water.
As the dispersion treatment in the main dispersion step, high-pressure emulsification treatment is preferably performed from the viewpoint of miniaturization of the acylceramide dispersed particles.
The high-pressure emulsification treatment is a dispersion treatment in which a shearing force of 50MPa or more is applied to a material to be dispersed. From the viewpoint of miniaturization of the acylceramide dispersed particles, the shear force applied to the dispersed material is preferably 100MPa or more, and more preferably 180MPa or more. In a commercially available apparatus, the upper limit value is preferably 300MPa or less from the viewpoint of temperature rise and pressure resistance.
The apparatus for the high-pressure emulsification treatment is not particularly limited, and a general high-pressure emulsification apparatus can be used. Examples of the high-pressure emulsifying apparatus include altizer HJP-25005(SUGINO MACHINE LIMITED), microfluidizer (microfluidics), NanoMizer (jida mechanical industry), Gaulin type homogenizer (APV), Lanier type homogenizer (Lanier), high-pressure homogenizer (Niro-Soavi), homogenizer (san and mechanical co., Ltd.), high-pressure homogenizer (IzumiFood Machinery co., Ltd.), ultra high-pressure homogenizer (Ika), and the like.
The temperature in the high-pressure emulsification treatment is preferably set to 20 to 80 ℃ and more preferably 40 to 70 ℃.
The number of times of the high-pressure emulsification treatment may be 1, but in order to improve the uniformity of the whole solution, the high-pressure emulsification treatment is preferably performed 2 or more times, and more preferably 2 to 5 times. Further, it is preferable that the emulsion of the emulsified and dispersed composition is cooled by passing through an arbitrary cooler within 30 seconds, preferably within 3 seconds immediately after passing through the chamber, from the viewpoint of stably maintaining the particle diameter of the acylceramide dispersed particles.
The dispersion treatment in the main dispersion step may be ultrasonic dispersion treatment. From the viewpoint of further improving the dispersion effect, it is preferable to perform ultrasonic dispersion treatment after mixing the coarse dispersion liquid with water or the like and before performing high-pressure emulsification treatment. In the dispersion treatment by imparting ultrasound, a general ultrasonic dispersion device may be used.
Examples of the ultrasonic dispersion device include an ultrasonic homogenizer US-600, US-1200T, RUS-1200T, MUS-1200T (manufactured by Nippon Seiko Co., Ltd.), an ultrasonic processor UIP2000, UIP-4000, UIP-8000 and UIP-16000 (manufactured by Hielscher). These ultrasonic dispersion devices can be used at a frequency of 25kHz or less, preferably 15kHz to 20 kHz.
The method for producing a dispersion composition containing a specific acyl ceramide may include other steps as necessary, in addition to the preliminary dispersion treatment step and the main dispersion treatment step described above.
The apparatus for mixing the thus obtained dispersion composition containing the specific acylceramide with the mixture of the specific compound (1) and water and the apparatus for mixing the specific compound (1) and water are not particularly limited, and any commercially available mixing apparatus can be used. Examples of the mixing device include a stirrer, a paddle mixer, an impeller mixer, a homogenizer, a disperser mixer, a super mixer, a high-pressure homogenizer, and an ultrasonic homogenizer. Among these mixing devices, at least one selected from a homogenizer and a disperser is preferable.
The temperature at the time of mixing the components is not particularly limited, and may be set to an appropriate preferable range, and is usually preferably set to a range of 4 to 80 ℃.
The stirring conditions for mixing the components are not particularly limited as long as the components can be sufficiently mixed, and may be appropriately set according to the mixing equipment. For example, when a homogenizer is used as the mixing device, each component may be usually stirred at 500 to 8000rpm for 5 to 60 minutes.
In the method for producing the gel-like aqueous composition of the present invention, it is preferable that the mixture obtained by mixing the specific compound (1) and water is cooled, and then the mixture is mixed with a dispersion composition containing the specific acylceramide. The cooling temperature is not particularly limited, and may be appropriately set in consideration of the inhibition of crystallization of the specific acylceramide, and is preferably set in the range of 4 to 50 ℃.
The method for producing a gel-like aqueous cosmetic of the present invention may include other steps than the above-described steps as necessary. Examples of the other steps include a defoaming step, a heat sterilization step, a cooling step, and a taking-out step. The defoaming step, the heat sterilization step, the cooling step, the taking-out step, and the like may be performed by methods known in the art.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
< preparation of acyl ceramide-containing Dispersion composition >
(acylceramide dispersion D-101)
39.5g of solution A having the following composition was stirred and mixed at 110 ℃ for 10 minutes to obtain a crude dispersion. The resulting crude dispersion was cooled to 100 ℃ and added with a solution B obtained by dissolving 60.51g of the following components at 70 ℃ and then dispersed for 3 minutes using an ultrasonic homogenizer (type: US-600, manufactured by Nippon Seiko Seisaku-Sho Ltd.) to obtain a crude dispersion. Next, the resultant crude dispersion was cooled to about 60 ℃ and then subjected to high-pressure emulsification (dispersion) treatment under a pressure of 245MPa using an ultrahigh-pressure emulsification apparatus (model name: altizer HJP-25005, SUGINO MACHINE LIMITED), thereby obtaining an acylceramide dispersion D-101.
[ solution A ]
10.3 parts by mass of ceramide
(specific acyl ceramides, trade name: Ceramide I, INCI name: Ceramide 1, Evonik)
0.3 parts by mass of Cholesterol
(trade name: Cholesterol JSQI, Nippon Kogyo Co., Ltd.)
0.9 parts by mass of 1, 3-butanediol (Daicel, Ltd.)
Decaglycerol monomyristate 3.0 parts by mass
(nonionic surfactant, trade name: NIKKOL (registered trademark) Decaglyn 1-M, HLB: 14.0, Nikko Chemicals Co., Ltd.)
35.0 parts by mass of glycerin (cosmetic concentrated glycerin, Kao corporation)
[ solution B ]
Lecithin 4.0 parts by mass
(anionic surfactant, trade name: SLP-PC70, Tsuji oil Co., Ltd.)
0.01 part by mass of iodopropynyl butylcarbamate
(trade name: GLYCACIL, Lonza Japan K.K.)
56.5 parts by mass of pure water
(acylceramide dispersion D-102)
An acylceramide dispersion D-102 was obtained in the same manner as the acylceramide dispersion D-101, except that decaglycerol monomyristate was not added to the acylceramide dispersion D-101.
(acylceramide dispersion D-103)
An acylceramide dispersion D-103 was obtained in the same manner as the acylceramide dispersion D-101, except that lecithin was not added to the acylceramide dispersion D-101.
< preparation of ceramide-containing Dispersion composition >
The following ingredients were stirred at room temperature for 1 hour to obtain an oil phase composition.
Composition of the oil phase composition
Figure BDA0000797835270000321
1mol/L hydrochloric acid (adjusted so that the pH immediately after dispersion is 7 or less)
The resulting oil phase composition (oil phase) and pure water (water phase) were mixed in a ratio of 1: the dispersion was obtained by micro-mixing at a ratio (mass ratio) of 7 using a KM type micro-mixer 100/100 as an impact type. The conditions for using the micromixer are as follows.
Conditions for use of micromixer
Micro-channels
Micro-channels on the oil phase side
Cross-sectional shape/width/depth/length ═ rectangle/70 μm/100 μm/10mm
Micro-channels on the water phase side
Cross-sectional shape/width/depth/length ═ rectangle/490 μm/100 μm/10mm
Flow rate-
The aqueous phase was introduced at a flow rate of 21.0 ml/min in the outer ring, and the oil phase was introduced at a flow rate of 3.0 ml/min in the inner ring, and micro-mixing was performed.
The obtained dispersion was desolventized with a centrifugal thin film vacuum evaporator (model name: EVAPOR CEP-lab, manufactured by Dachuan Kabushiki Kaisha) until the ethanol concentration became 0.1% by mass or less, and concentrated and adjusted so that the dispersion concentration became 2.0% by mass, to obtain a ceramide-containing dispersion composition. The dispersion concentration referred to herein is a concentration based on the total of solid components added to the oil phase.
< preparation of astaxanthin-containing emulsion composition >
The following components were heated at 70 ℃ for 1 hour to dissolve them, thereby obtaining an aqueous phase composition a.
Composition of the aqueous composition A-
Figure BDA0000797835270000331
The following components were heated at 70 ℃ for 1 hour to dissolve them, thereby obtaining oil phase composition a.
Composition of the oil phase composition A-
15.0g of astaxanthin-containing oil
(trade name: ASTOTS-S (derived from Haematococcus, astaxanthin: 20% by mass content), Kogya paper products of Wutian Co., Ltd.)
Mixed tocopherols 32.0g
(trade name: Liyan E Oil 800, Riken Vitamin Co., Ltd.)
93.0g of medium-chain fatty glyceride
(trade name: COCONARD (registered trademark) MT, Kao corporation)
Lecithin 10.0g
(trade name: レシオン P, from Glycine max, Riken Vitamin Co., Ltd.)
The resulting aqueous phase composition A was stirred at 10000rpm using an ultrasonic homogenizer (type: HP93, SMTCcorporation) while maintaining the temperature at 70 ℃ and the oil phase composition A was added to obtain a crude emulsion.
Next, the resulting crude emulsion was cooled to about 40 ℃ and subjected to high-pressure emulsification at a pressure of 200MPa using an ultrahigh-pressure emulsification apparatus (model name: AltimizerHJP-25005, SUGINO MACHINE LIMITED). Then, the mixture was filtered through a microfilter having an average pore size of 1 μm to obtain an astaxanthin-containing emulsion composition (astaxanthin content: 0.3% by mass).
The obtained astaxanthin-containing emulsion composition was diluted with Milli-Q water to a concentration of 1% by mass, and the particle diameter of the dispersed particles was measured with a particle diameter analyzer (type: FPAR-1000, Otsuka Denshi Co., Ltd.), whereby the particle diameter was 58nm (median diameter (d 50)).
Preparation of an emulsified composition containing lycopene
The following components were mixed with stirring in a thermostatic bath at 70 ℃ under heating to obtain an aqueous composition B.
Composition of the aqueous composition B-
Oleic acid decaglycerol ester-108.0 g
(trade name: Decaglyn 1-OV, HLB ═ 12.0, Nikko Chemicals Co., Ltd.)
Sucrose stearate 2.0g
(trade name: RYOTO SUGAR ESTERS-1670, Mitsubishi-Kagaku Foods Corporation)
45.0g of glycerol
The balance of pure water to 100g
The following components were mixed by heating for 5 minutes while stirring on a hot plate at 150 ℃ to obtain oil phase composition B.
Composition of the oil phase composition B-
1.14g of Tomato oleoresin (Tomato oleoresin)
(trade name: Lyc-O-Mato (registered trademark) 15% (lycopene: containing 15% by mass), Sunbright Co., LTD.)
Lecithin 1.0g
(trade name: レシオン P, from Glycine max, Riken Vitamin Co., Ltd.)
12.8g of medium-chain fatty glyceride
(trade name: COCONARD (registered trademark) MT, Kao corporation)
The resulting aqueous composition B was added to the oil composition B, followed by mixing with stirring and dispersing for a predetermined period of time using an ultrasonic homogenizer (type: US-150T, Nippon Kogyo Co., Ltd.) to obtain a crude emulsion.
Then, the obtained crude emulsion was further subjected to high-pressure emulsification under a pressure of 200MPa using an ultra-high pressure emulsification apparatus (model name: altizer HJP-25005, SUGINO MACHINE LIMITED) to obtain an emulsified composition containing lycopene (lycopene content: 0.17 mass%).
The obtained lycopene-containing emulsion composition was diluted with Milli-Q water to a concentration of 1% by mass, and the particle diameter of the dispersed particles was measured using a particle diameter analyzer (type: FPAR-1000, Otsuka Denshi Co., Ltd.), whereby the particle diameter was 52nm (median diameter (d 50)).
[ preparation of aqueous cosmetics ]
[ example 1]
1.7g of PEG-240/decyltetradecanolpolyether-20/HDI copolymer (ADEKANOL GT-700, manufactured by ADEKA Co., Ltd.), 0.5g of ascorbyl palmitate phosphate 3Na (trade name: APPRECIER (registered trademark), Showa Denko K.K.), 6.0g of glycerin, 0.2g of ethylhexylglycerin, 0.63g of 1, 3-butanediol, 0.5g of phenoxyethanol, 0.54g of a 1mol/L aqueous solution of sodium hydroxide (pH adjuster), and 35g of pure water were mixed as the specific compound (1). The resulting mixture (pH: 7.8) was warmed to 60 ℃ and stirred at 2000rpm for 5 minutes using a homogenizer (model name: homogenizer HM-310, AS ONE Corporation), and then cooled to 40 ℃.
Subsequently, 0.1g of the above-mentioned acylceramide dispersion D-101 prepared in advance, 6.0g of the above-mentioned ceramide-containing emulsified composition prepared in advance, 0.22g of the above-mentioned astaxanthin-containing emulsified composition prepared in advance, 0.1g of the above-mentioned lycopene-containing emulsified composition prepared in advance, 0.1g of hydrolyzed collagen, 0.1g of acetylhydroxyproline, 0.1g of hydrolyzed lupin protein, and 0.1g of a perfume were added to the cooled mixture, and further, pure water was added so that the total amount became 100g, followed by stirring at 2000rpm for 20 minutes using a homogenizer (model name: homogenizer HM-310, AS ONE Corporation), and then vacuum defoaming was carried out, to obtain the aqueous cosmetic of example 1.
[ example 2]
The procedure of example 1 was repeated to obtain an aqueous cosmetic preparation of example 2, except that 0.01g of the acylceramide dispersion D-101 was added to the aqueous cosmetic preparation of example 1 instead of adding 0.1g of the acylceramide dispersion D-101.
[ example 3]
The procedure of example 1 was repeated to obtain an aqueous cosmetic preparation of example 3, except that 0.1g of the acylceramide dispersion D-101 was added to the aqueous cosmetic preparation of example 1, and 1g of the acylceramide dispersion D-101 was added thereto.
[ example 4]
The procedure of example 1 was repeated to obtain an aqueous cosmetic preparation of example 4, except that 20g of the acylceramide dispersion D-101 was added to the aqueous cosmetic preparation of example 1 instead of 0.1g of the acylceramide dispersion D-101.
[ example 5]
The procedure of example 1 was repeated in the same manner as in example 1 except that 1g of acylceramide dispersion D-101 was blended in place of 0.1g of acylceramide dispersion D-101 in the aqueous cosmetic composition of example 1, and the blending amount of PEG-240/decyltetradecyltetradecanol polyether-20/HDI copolymer as the specific compound (1) was changed from 1.7g to 2g, to obtain an aqueous cosmetic composition of example 5.
[ example 6]
The procedure of example 3 was repeated in the same manner as in example 3 except that 0.5g of ascorbyl palmitate, phosphoric acid 3Na and 0.25g of oleic acid Na were blended in the aqueous cosmetic of example 3 to obtain an aqueous cosmetic of example 6.
[ example 7]
The procedure of example 3 was repeated to obtain the aqueous cosmetic preparation of example 7, except that 0.5g of ascorbyl palmitate phosphate 3Na was added, 0.25g of isostearic acid was added, and a ceramide-containing dispersion composition, an astaxanthin-containing emulsion composition, and a lycopene-containing emulsion composition were not added to the aqueous cosmetic preparation of example 3.
[ example 8]
The procedure of example 3 was repeated to obtain an aqueous cosmetic preparation of example 8, except that the aqueous cosmetic preparation of example 3 did not contain the ceramide-containing dispersion composition, the astaxanthin-containing emulsion composition, and the lycopene-containing emulsion composition.
[ example 9]
The aqueous cosmetic preparation of example 9 was obtained in the same manner as in example 4, except that the ceramide-containing dispersion composition, the astaxanthin-containing emulsion composition, and the lycopene-containing emulsion composition were not blended in the aqueous cosmetic preparation of example 4.
[ comparative example 1]
An aqueous cosmetic preparation of comparative example 1 was obtained in the same manner as in example 1, except that 0.1g of acylceramide dispersion D-102 was added to the aqueous cosmetic preparation of example 1 instead of 0.1g of acylceramide dispersion D-101.
[ comparative example 2]
An aqueous cosmetic preparation of comparative example 2 was obtained in the same manner as in example 1, except that 0.1g of acylceramide dispersion D-103 was added to the aqueous cosmetic preparation of example 1 instead of 0.1g of acylceramide dispersion D-101.
[ comparative example 3]
An aqueous cosmetic preparation of comparative example 3 was obtained in the same manner as in example 1, except that 0.1g of the acylceramide dispersion D-101 was added to the aqueous cosmetic preparation of example 1, and 40g of the acylceramide dispersion D-101 was added to the aqueous cosmetic preparation of example 1.
[ measurement of hardness ]
Each 100g of the aqueous cosmetics of examples 1 to 9 and comparative examples 1 to 3 immediately after the preparation was put in a glass container having a diameter of 47mm X a height of 90mm, and stored at 25 ℃ for 24 hours in a state of being capped. The hardness (hereinafter, appropriately referred to as "initial hardness") of each aqueous cosmetic after storing the cosmetic at 25 ℃ for 24 hours was measured using a rheometer (model name: FUDOH REHOMER, Rheotech Co.). Specifically, the peak value of the stress measured when the tip of an adapter having a diameter of 20mm was inserted into the tip of the adapter at a load of 2kg for 20mm at a rate of 60 mm/min under a measurement temperature of 25 ℃ was used as the measurement value (unit: g) of the hardness for each aqueous cosmetic. The details of the measurement conditions are shown below.
Conditions for measurement
Figure BDA0000797835270000371
As a result, it was found that the measured values of the hardness of the aqueous cosmetics of examples 1 to 9 and comparative examples 1 to 3 were all in the range of 1g to 1000g, and were all referred to as "gel-like" in the present invention.
[ evaluation ]
[ stability of transparency over time ]
Each 100g of the aqueous cosmetics of examples 1 to 9 and comparative examples 1 to 3 immediately after the preparation was put in a glass container having a diameter of 47mm X a height of 90mm, and stored at 25 ℃ for 24 hours in a state of being capped. Each of the aqueous cosmetics stored at 25 ℃ for 24 hours was placed in a Polystyrene (PS) disposable cuvette having an optical path length of 0.4cm, and a small-sized cooling centrifuge (type: CF5RX, Hitachi Ltd., cantilever rotator: T4SS31) was used for each cuvette, and centrifuged at 4000rpm for 2 minutes to remove bubbles.
The absorbance of each of the defoamed aqueous cosmetics was measured for light having a wavelength of 625nm using a spectrophotometer (model: U-3310, manufactured by Hitachi, Ltd.), and the measured value was defined as "initial absorbance".
The aqueous cosmetic having the initial absorbance of 0.04 or less was evaluated to have excellent transparency.
As another series, 100g of each of the aqueous cosmetics of examples 1 to 9 and comparative examples 1 to 3 immediately after the preparation was put in a glass container having a diameter of 47mm X a height of 90mm, and stored at 50 ℃ for 45 days in a state of being capped. The absorbance of each aqueous cosmetic composition after storage at 50 ℃ for 45 days was measured by the same method as described above for light having a wavelength of 625nm, and the obtained measurement value was defined as "absorbance with time".
The results are shown in table 1 together with the compositions of the aqueous cosmetics of examples 1 to 9 and comparative examples 1 to 3.
The absorbance with time is 0.04 or less, and the smaller the difference between the initial absorbance and the absorbance with time, the more excellent the stability with time.
Figure BDA0000797835270000391
As shown in table 1, the aqueous cosmetics of examples 1 to 9 all had low initial absorbance and excellent transparency, and the transparency thereof was maintained for a long period of time.
On the other hand, the aqueous cosmetics of comparative examples 1 and 2 had low initial absorbance and excellent transparency, but the transparency thereof was significantly reduced with time. In addition, the aqueous cosmetic of comparative example 3 had high initial absorbance and poor transparency.

Claims (6)

1. A transparent gel-like aqueous cosmetic composition which comprises (i) to (v) and a dispersion obtained by dispersing an acylceramide in (iii) and (iv), and has an absorbance at a wavelength of 625nm of 0.04 or less:
(i) a compound represented by the general formula (1), wherein the content thereof is 0.5 to 5% by mass relative to the total mass of the transparent gel-like aqueous cosmetic;
(ii) an acylceramide represented by the general formula (I) in an amount of 0.1 to 1000ppm based on the total mass of the transparent gel-like aqueous cosmetic;
(iii) a nonionic surfactant containing a polyglycerol fatty acid ester in an amount of 0.1 to 70 times the amount of an acylceramide, wherein the polyglycerol fatty acid ester has a weight average molecular weight of 1000 or less and an HLB of 10 or more and 16 or less, and at least one of the polyglycerol fatty acid esters is an ester of a polyglycerol having an average polymerization degree of 10 and a fatty acid having a fatty acid skeleton with 8 to 18 carbon atoms;
(iv) an anionic surfactant containing lecithin in an amount of 0.1 to 10 times the amount of the acyl ceramide;
(v) the amount of water is controlled by the amount of water,
general formula (1)
R1-{(O-R2)k-OCONH-R3[-NHCOO-(R4-O)n-R5]h}m-R6
In the general formula (1), R1R represents a C2-36 and m-valent hydrocarbon group2And R4Each independently represents a C1-4 and C2-valent hydrocarbon group, R3Represents a h +1 valent hydrocarbon group containing a linear, branched, or aliphatic or aromatic ring which may have a urethane bond, R5Represents a 2-valent hydrocarbon group, R6Represents a hydrogen atom or a hydroxyl group, m is an integer of 2 or more, h is an integer of 1 or more, and k is (O-R)2) An integer ranging from 0 to 1000 in the number of repetitions of the structure, n represents (R)4-O) an integer ranging from 0 to 1000 in the number of repetitions of the structure, both k and n not being 0 at the same time;
general formula (I)
Figure FDA0002262483750000021
In the general formula (I), R31Represents a linear or branched hydrocarbon group having 40 to 55 carbon atoms in total and containing an ester bond in a carbon chain, R31The hydrocarbon group may have 1 or 2 or more partial structures selected from the group consisting of a multiple bond, an aromatic ring and an aromatic heterocycle in a carbon chain, and R is32Represents an alkyl group having 11 to 21 carbon atoms which may have a hydroxyl group, or an alkenyl group having 11 to 21 carbon atoms which may have a hydroxyl group.
2. The transparent gel-like aqueous cosmetic according to claim 1, wherein the acyl ceramide is a human-type acyl ceramide.
3. The transparent gel-like aqueous cosmetic according to claim 1, wherein the compound represented by the general formula (1) is at least one compound selected from the group consisting of a compound represented by the following general formula (1-1) and a compound represented by the following general formula (1-2):
general formula (1-1)
R11-{(O-R12)k1-OCONH-R13[-NHCOO-(R14-O)n1-R15]h1}m1
In the general formula (1-1), R11R represents a C2-12 hydrocarbon group having a valence of m112And R14Each independently represents a C1-4 and C2-valent hydrocarbon group, R13Represents a h1+1 valent hydrocarbon group containing a linear, branched, or aliphatic or aromatic ring which may have a urethane bond, R15Represents a hydrocarbon group having a valence of 1, m1 is an integer of 2 or more, h1 is an integer of 1 or more, and k1 is (O-R)12) An integer of 0 to 1000 of the number of repetition of the structure, n1 represents (R)14-O) an integer in the range of 0 to 1000 in the number of repetitions of the structure, both k1 and n1 not being 0 at the same time;
general formula (1-2)
R21-[OCONH-R22-NHCO(-O-CHR23CH2)n2]m2-OH
In the general formula (1-2),R21R represents a saturated hydrocarbon group having 6 to 36 carbon atoms and a valence of m222Represents methyldiphenylene, hexamethylene, methyldicyclohexyl, 3-methyl-3, 5, 5-trimethylcyclohexylene, dimethylphenylene or tolylene, R23Represents a hydrogen atom or a methyl group, n2 represents an integer of 90 to 900, and m2 represents an integer of 1 to 5.
4. The transparent gel-like aqueous cosmetic according to claim 1, wherein the compound represented by general formula (1) is at least one copolymer selected from the group consisting of PEG-240/decyltetradecylpolyether-20/hexamethylene diisocyanate copolymer and distearyl PEG/PPG-8/6 (methylenediphenyl diisocyanate/PEG-400) copolymer.
5. The transparent gel-like aqueous cosmetic according to any one of claims 1 to 4, which further contains cholesterol.
6. The transparent gel-like aqueous cosmetic according to claim 5, which further contains a fatty acid or a salt thereof.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5162377A (en) * 1988-06-20 1992-11-10 Shiseido Company, Ltd. Transparent composition
EP2295032A4 (en) * 2008-05-29 2014-08-13 Fujifilm Corp Ceramide dispersion

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5162377A (en) * 1988-06-20 1992-11-10 Shiseido Company, Ltd. Transparent composition
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