JP2016069336A - Gel aqueous cosmetics - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gel aqueous cosmetic in which temporal increase of hardness is suppressed and storage stability is excellent.SOLUTION: The invention provides a gel aqueous cosmetic containing a compound represented by the following general formula (1), fatty acid or a salt thereof, and water, wherein the content of fatty acid or a salt thereof is 0.01-5 mass% to the total mass of the gel aqueous cosmetic in terms of fatty acid, and hardness at the time of measurement at 25°C is 1-1000 g. In the general formula (1), Rrepresents a hydrocarbon group, Rand Reach independently represent a hydrocarbon group, Rmay have an urethane bond, h+1 represents an univalent hydrocarbon group, Rrepresents a hydrocarbon group, Rrepresents a hydrogen atom or a hydroxy group, m is an integer of 2 or more, h is an integer of 1 or more, k and n represent a repetition rate of structures in parentheses, and are each independently an integer of a range of 0-1000, and both k and n does not become 0.SELECTED DRAWING: None

Description

  The present invention relates to a gel-like aqueous cosmetic.

  In the fields of cosmetics, foods, pharmaceuticals and the like, gelling agents or thickeners are widely used to impart viscosity or elasticity to products. For example, in the cosmetics field, gelling agents or thickeners are used for the purpose of enhancing the feeling of use when applied to the skin, preventing dripping, etc. Is granted.

  Cosmetics containing a gelling agent or thickener include, for example, a jelly-like cosmetic liquid using PEG-240 / decyltetradeceth-20 / hexamethylene diisocyanate copolymer (see, for example, Patent Document 1), a specific Hair styling gel using a silylated urethane-based resin having a structure (for example, see Patent Document 2), gel-like detergent using a hydrophobic modified polyether urethane having a specific structure (for example, see Patent Document 3), etc. It has been reported.

JP 2013-199466 A JP 2009-40755 A JP 2002-105493 A

In gel-like cosmetics, hardness is an important characteristic that affects the feeling of use when applied to the skin, so it is desirable that the change in hardness over time be as small as possible.
The present inventor includes a hydrophobically modified polyether urethane having a specific structure such as PEG-240 / decyltetradeceth-20 / hexamethylene diisocyanate copolymer, which is widely used as a gelling agent or thickener in cosmetics. In gel-like cosmetics, an increase in hardness was observed over time.

  This invention is made | formed in view of the above situations, and makes it a subject to provide the gel-like aqueous cosmetics by which the raise of the hardness over time is suppressed and excellent in storage stability.

  Specific means for solving the above problems are as follows.

  [1] A compound represented by the following general formula (1), a fatty acid or a salt thereof, and water are contained, and the content of the fatty acid or the salt thereof is converted into the total mass of the gel-based aqueous cosmetic in terms of fatty acid. On the other hand, a gel-like aqueous cosmetic that has a hardness of 0.01 to 5% by mass and a hardness of 1 to 1000 g when measured at 25 ° C.

In the general formula (1), R ¹ represents an m-valent hydrocarbon group having ² to 36 carbon atoms, R ² and R ⁴ each independently represents a divalent hydrocarbon group having 1 to 4 carbon atoms, R ³ represents a straight chain, branched chain, or h + 1 valent hydrocarbon group containing an aliphatic ring or an aromatic ring, which may have a urethane bond, R ⁵ represents a divalent hydrocarbon group, and R ⁶ represents Represents a hydrogen atom or a hydroxy group. m is an integer greater than or equal to 2, h is an integer greater than or equal to 1, k and n represent the repeating number of the structure in a parenthesis, and are each independently an integer of the range of 0-1000, both k and n Will never be zero.

[2] The gel-like aqueous cosmetic according to [1], having a hardness of 10 g to 200 g when measured at 25 ° C.
[3] The gel-based aqueous cosmetic according to [1] or [2], wherein the fatty acid skeleton in the fatty acid or a salt thereof has 12 to 22 carbon atoms.
[4] The gel-based aqueous cosmetic according to any one of [1] to [3], wherein the fatty acid or a salt thereof is at least one fatty acid selected from oleic acid and isostearic acid or a salt thereof.

  [5] The compound represented by the general formula (1) is at least 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). The gel-based aqueous cosmetic according to any one of [1] to [4], which is one compound.

In general formula (1-1), R ¹¹ represents a m1-valent hydrocarbon group having 2 to 12 carbon atoms, and R ¹² and R ¹⁴ each independently represents a divalent hydrocarbon group having 1 to 4 carbon atoms. , R ¹³ represents a linear, branched, or h1 + 1 valent hydrocarbon group containing an aliphatic ring or an aromatic ring which may have a urethane bond, and R ¹⁵ represents a monovalent hydrocarbon group. m1 is an integer greater than or equal to 2, h1 is an integer greater than or equal to 1, k1 and n1 represent the repeating number of the structure in a parenthesis, and are each independently an integer of the range of 0-1000, both k1 and n1 Will never be zero.

In the general formula (1-2), R ²¹ represents a m2-valent saturated hydrocarbon group having 6 to 36 carbon atoms, and R ²² represents a methyldiphenylene group, a hexamethylene group, a methyldicyclohexylene group, 3-methyl. −3,5,5-trimethylcyclohexylene group, dimethylphenylene group, or tolylene group, and R ²³ represents a hydrogen atom or a methyl group. n2 represents an integer of 90 to 900, and m2 represents an integer of 1 to 5.

  [6] PEG-240 / decyltetradeceth-20 / hexamethylene diisocyanate copolymer in which the compound represented by the general formula (1) is a compound represented by the general formula (1-1), and the general formula (1) -2) The gel aqueous solution according to [5], which is at least one copolymer selected from the group consisting of bisstearyl PEG / PPG-8 / 6 (methylenediphenyl diisocyanate / PEG-400) copolymer, which is a compound represented by -2) Cosmetics.

[7] The gel-based aqueous cosmetic according to any one of [1] to [6], further containing at least one selected from astaxanthin and lycopene.
[8] The gelled aqueous cosmetic according to [7], further comprising an ascorbic acid derivative.
[9] The gelled aqueous cosmetic according to [8], wherein the ascorbic acid derivative is sodium ascorbyl phosphate.

  ADVANTAGE OF THE INVENTION According to this invention, the raise of the hardness over time can be suppressed and the gel-like aqueous cosmetics which are excellent in storage stability can be provided.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. be able to.

In the present specification, a numerical range indicated using “to” means a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In the present specification, the amount of each component in the gel aqueous cosmetic is determined in the gel aqueous cosmetic unless there is a specific indication when there are a plurality of substances corresponding to each component in the gel aqueous cosmetic. Means the total amount of a plurality of substances present in

  In this specification, the term “process” is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. It is.

In the present invention, “gel” means a state in which the hardness of an object to be measured is 1 g to 1000 g when measured under a temperature condition of 25 ° C. using a hardness meter.
In the present invention, the “aqueous cosmetic” includes water, the total content of water and optionally a water-soluble liquid component is 50% by mass or more, and the amount dissolved in water at 25 ° C. is 1% by mass. The cosmetics whose content of the following liquid components is 10 mass% or less with respect to the total mass of cosmetics.
The “water-soluble liquid component” as used herein refers to a liquid component in which the amount of the target substance dissolved in water at 25 ° C. exceeds 1% by mass.

[Gel water-based cosmetic]
The gel-based aqueous cosmetic of the present invention contains a compound represented by the general formula (1) (hereinafter referred to as “specific compound (1)” as appropriate), a fatty acid or a salt thereof, and water. Or the content of the salt is 0.01 mass%-5 mass% with respect to the total mass of gel-like aqueous cosmetics in conversion of a fatty acid, and hardness when it measures at 25 degreeC is 1g-1000g. is there.
The gel aqueous cosmetic composition of the present invention contains a compound represented by the general formula (1), a fatty acid or a salt thereof, and other components other than water as necessary, as long as the effects of the present invention are not impaired. May be.

The gel-like aqueous cosmetic of the present invention is a gel-like cosmetic having a hardness of 1 g to 1000 g when measured at 25 ° C. In the gel-like aqueous cosmetic of the present invention, the gelation of the aqueous cosmetic is realized by containing the specific compound (1). However, the gel cosmetic containing the specific compound (1) tends to increase in hardness over time.
In gel-like cosmetics, the hardness is an important characteristic that affects the feeling of use when applied to the skin, so it is desirable that the change in hardness over time be as small as possible.
In the gel-like aqueous cosmetic of the present invention, by containing the specific compound (1) forming the gel together with a specific amount of fatty acid or salt thereof and water, an increase in hardness over time is suppressed, and storage stability is maintained. It becomes an excellent gel-like water-based cosmetic.
The reason why the gel-like aqueous cosmetic of the present invention can exert such an effect is not clear, but the present inventor presumes as follows.

  The specific compound (1) is a polymer having hydrophobic groups at both ends, and forms so-called flower micelles in water with the hydrophobic groups facing inward and the hydrophilic groups facing outward. In the gel-like aqueous cosmetic of the present invention, the hydrophobicity inside the flower micelle formed by the specific compound (1) by containing the specific compound (1), a specific amount of fatty acid or a salt thereof, and water in combination. It is considered that the fatty acid is adsorbed on the basis and the state of the flower micelle is stabilized, so that the hardness hardly changes with time, and the gel-like aqueous cosmetic excellent in storage stability is obtained. In addition, the said estimation does not interpret the effect of this invention restrictively, but demonstrates it as an example.

[Hardness of gel-based water-based cosmetics]
The gel-like aqueous cosmetic of the present invention has a hardness (hereinafter referred to as “hardness” as appropriate) as measured at 25 ° C. of 1 g to 1000 g, preferably 5 g to 300 g, more preferably 10 g to 200 g. It is.
When the hardness of the gel-like aqueous cosmetic of the present invention is 1000 g or less, it is easy to stretch when applied to the skin. When the hardness of the gel-like aqueous cosmetic of the present invention is 1 g or more, it is difficult to spill when scooping with a spatula or the like, and it is easy to scoop. Therefore, when the hardness of the gel aqueous cosmetic of the present invention is within the above range, the usability as a cosmetic is excellent.

  The hardness of the gel aqueous cosmetic of the present invention is 60 mm / min under the measurement temperature of 25 ° C. with respect to the gel aqueous cosmetic of the present invention using a rheometer (FUDOH REHOMETER, Rheotech Co., Ltd.). It refers to the peak value (unit: g) of the stress measured when the tip of an adapter with a diameter of 20 mm is inserted 20 mm with a load of 2 kg.

  Hereinafter, each component contained in the gel aqueous cosmetic of the present invention will be described in detail.

[Compound represented by the general formula (1)]
The gelled aqueous cosmetic of the present invention contains a compound represented by the following general formula (1) (specific compound (1)).

In the general formula (1), R ¹ represents an m-valent hydrocarbon group having ² to 36 carbon atoms, R ² and R ⁴ each independently represents a divalent hydrocarbon group having 1 to 4 carbon atoms, R ³ represents a straight chain, branched chain, or h + 1 valent hydrocarbon group containing an aliphatic ring or an aromatic ring, which may have a urethane bond, R ⁵ represents a divalent hydrocarbon group, and R ⁶ represents Represents a hydrogen atom or a hydroxy group. m is an integer greater than or equal to 2, h is an integer greater than or equal to 1, k and n represent the repeating number of the structure in a parenthesis, and are each independently an integer of the range of 0-1000, both k and n Will never be zero.

  As is clear from the general formula (1), the specific compound (1) has a urethane structure and a hydrophilic alkyleneoxy group in the main chain, and has a hydrophobic hydrocarbon group at the terminal, and is modified to be hydrophobic. Urethane copolymer.

In the general formula (1), R ¹ represents an m-valent hydrocarbon group having 2 to 36 carbon atoms, preferably a divalent to octavalent hydrocarbon group. The hydrocarbon group represented by R ¹ may contain an oxygen atom between carbon atoms.

In the general formula (1), R ² and R ⁴ each independently represent a divalent hydrocarbon group having 1 to 4 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms.

In the general formula (1), R ³ represents a linear, branched, or h + 1 valent hydrocarbon group containing an aliphatic ring or an aromatic ring, which may have a urethane bond, preferably divalent to 4 Valent hydrocarbon group. The number of carbon atoms in the hydrocarbon group represented by R ^3, 1-10 are preferred.

In the general formula (1), R ⁵ represents a divalent hydrocarbon group. The hydrocarbon groups represented by R ⁵ is preferably 8 to 36, 12 to 24 is more preferable. Examples of the divalent hydrocarbon group represented by R ⁵ include divalent groups obtained by removing one hydrogen atom from an alkyl group, alkenyl group, alkylaryl group, cycloalkyl group, cycloalkenyl group, and the like. . Among these, the divalent hydrocarbon group represented by R ⁵ is preferably an alkylene group obtained by removing one hydrogen atom from an alkyl group.

In the general formula (1), R ⁶ represents a hydrogen atom or a hydroxy group.
When R ⁶ is a hydrogen atom, R ⁶ becomes a terminal group together with the divalent hydrocarbon group represented by R ⁵ .

In the general formula (1), m is the same as the valence of the hydrocarbon group represented by R ¹ and is an integer of 2 or more.
In the general formula (1), h is the valence -1 of the hydrocarbon group represented by R ^3, is an integer of 1 or more. h is preferably 1.

In the general formula (1), k is the number of repetitions (polymerization degree) of the (O—R ² ) structure and may be an integer in the range of 0 to 1000.
In the general formula (1), n is the number of repetitions of the (R ⁴ —O) structure (degree of polymerization) and may be an integer in the range of 0 to 1000.
In general formula (1), both k and n are not 0.

<Compound represented by formula (1-1)>
As the compound represented by the general formula (1) in the present invention, a compound represented by the following general formula (1-1) (hereinafter referred to as “specific compound (1-1)” as appropriate) is preferable.

In general formula (1-1), R ¹¹ represents a m1-valent hydrocarbon group having 2 to 12 carbon atoms, and R ¹² and R ¹⁴ each independently represents a divalent hydrocarbon group having 1 to 4 carbon atoms. , R ¹³ represents a linear, branched, or h1 + 1 valent hydrocarbon group containing an aliphatic ring or an aromatic ring which may have a urethane bond, and R ¹⁵ represents a monovalent hydrocarbon group. m1 is an integer greater than or equal to 2, h1 is an integer greater than or equal to 1, k1 and n1 represent the repeating number of the structure in a parenthesis, and are each independently an integer of the range of 0-1000, both k1 and n1 Will never be zero.

R ¹¹ in the general formula (1-1) corresponds to R ¹ in the general formula (1).
Since R ¹¹ in the general formula (1-1) has the same meaning as R ¹ in the general formula (1) except for the number of carbon atoms, description other than the number of carbon atoms and preferred embodiments is omitted here.
The hydrocarbon group represented by R ¹¹ has 2 to 12 carbon atoms, preferably 2 to 4 carbon atoms. The hydrocarbon group represented by R ¹¹ is preferably a chain or branched aliphatic hydrocarbon group, and more preferably a chain aliphatic hydrocarbon group.

R ¹² and R ¹⁴ in the general formula (1-1) correspond to R ² and R ⁴ in the general formula (1), respectively.
R ¹² and R ¹⁴ in the general formula (1-1) have the same meanings as R ² and R ⁴ in the general formula (1), respectively.

R ¹³ in the general formula (1-1) corresponds to R ³ in the general formula (1).
Since R ¹³ in the general formula (1-1) has the same meaning as R ³ in the general formula (1), descriptions other than the preferred embodiments are omitted here.
The hydrocarbon group represented by R ¹³ 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.
Since m1, h1, k1, and n1 in the general formula (1-1) have the same meanings as m, h, k, and n in the general formula (1), descriptions other than the preferred embodiments 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 ¹⁵ in the general formula (1-1) corresponds to a group represented by “R ⁵ -R ⁶ ” when R ⁶ in the general formula (1) is a hydrogen atom.
In the general formula (1-1), R ¹⁵ is an alkyl group (that is, the divalent hydrocarbon group represented by R ⁵ in the general formula (1) is a branched alkylene group, and R ⁶ is hydrogen. Preferably, the structure is an atom.

The specific compound (1-1) is, for example, “R ¹¹ — [(O—R ¹² ) _k1 —OH] _m1 (where R ¹¹ , R ¹² , k1, and m1 are the same as defined above”). a polyether polyol represented, _{^{"R 13 - (NCO) h1 +}} 1 ( ^{wherein, R 13} and h1 are the same as defined above)" and a polyisocyanate represented by the ^"HO- (R 14 _{-O) n1} -R ¹⁵ (wherein R ¹⁴ , R ¹⁵ , and n1 are as defined above) "is preferably obtained by a method of reacting with a polyether monoalcohol.
Each of the above-mentioned polyether polyol, polyisocyanate, and polyether monoalcohol, which are raw materials used in the reaction, may be one kind or two or more kinds.

When the specific compound (1-1) is obtained by the above method, the hydrocarbon groups represented by R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ in the general formula (1-1) are used. the three ingredients _{^{"R 11 - [(O-R}} 12) k1 -OH] m1 ", - by ^"R 13 _{(NCO) h1 + 1",} and _{^{"HO- (R 14 -O) n1 -R}} 15 ', Each is decided.
The charging ratio of the above three raw materials is not particularly limited. For example, the ratio of the isocyanate group derived from polyisocyanate to the hydroxyl group derived from polyether polyol and polyether monoalcohol is NCO: OH = 0. It is preferably in the range of 8: 1 to 1.4: 1.

“R ¹¹ -[(O—R ¹² ) _k1 -OH] The polyether polyol represented by _m1 is obtained by addition polymerization of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, etc. to m1 valent polyol. Is obtained.
Therefore, the hydrocarbon group represented by R ¹¹ is determined by the structure of the m1 valent polyol used for the synthesis of the specific compound (1-1). Further, the hydrocarbon group represented by R ¹² is determined by alkylene oxide or the like to be addition-polymerized to the m1-valent polyol.

As the polyol, divalent to octavalent polyols are preferable. Specifically, dihydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol and neopentyl glycol; glycerin, trioxyisobutane, 1, 2 , 3-butanetriol, 1,2,3-pentatriol, 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, Pentamethylglycerin, pentaglycerin, 1,2,4-butanetriol, 1,2,4-pen Trihydric alcohols such as Ntriol, Trimethylolethane, Trimethylolpropane; Pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5 -Tetravalent alcohols such as pentanetetrol, 1,3,4,5-hexanetetrol; pentavalent alcohols such as adnit, arabit and xylit; hexavalent alcohols such as dipentaerythritol, sorbit, mannitol and exit; Examples thereof include octahydric alcohols such as sucrose.
In the present invention, the polyol is preferably a divalent alcohol, and particularly preferably ethylene glycol.

  As the alkylene oxide or the like to be addition-polymerized to the above m1 polyol, an alkylene oxide having 2 to 4 carbon atoms is preferable, and ethylene oxide is particularly preferable from the viewpoint that it is easily available and can exhibit an excellent effect. .

The form of addition polymerization of alkylene oxide or the like may be homopolymerization or copolymerization using two or more kinds. In the case of copolymerization, the form of copolymerization may be random polymerization or block polymerization. These addition polymerization methods may be ordinary methods.
K1 which shows a polymerization degree should just be the range of 0-1000, the range of 1-500 is preferable, and the range of 100-300 is more preferable.
Ratio of ethylene groups in the total ^{R 12} is preferably in the range of 50 wt% to 100 wt% of the total ^{R 12.}

“R ¹¹ — [(O—R ¹² ) _k1 —OH] The molecular weight of _m1 is preferably 500 to 100,000, particularly preferably 1,000 to 50,000.

Polyisocyanates represented by ^- "R ¹³ (NCO) h1 + _1" as long as they have two or more isocyanate groups in the molecule is not particularly limited.
Therefore, the hydrocarbon group represented by R ¹³ is determined by the polyisocyanate used for 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, phenylmethane diisocyanate, triisocyanate, and tetraisocyanate. 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, 2,2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, Octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate, thiodihexyl diisocyanate, metaxylylene diisocyanate, paraxylylene Range isocyanine DOO, tetramethylxylylene diisocyanate, and the like. Among these, hexamethylene diisocyanate is preferable as the aliphatic diisocyanate used in the present invention.

  Examples of the aromatic diisocyanate include metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, 1,4- Examples include 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, 3,3′-dimethylbiphenyl diisocyanate, and 3,3′-dimethoxybiphenyl diisocyanate.

  Examples of the diisocyanate of phenylmethane include diphenylmethane-4,4′-diisocyanate, 2,2′-dimethyldiphenylmethane-4,4′-diisocyanate, diphenyldimethylmethane-4,4′-diisocyanate, 2,5,2 ′. , 5′-tetramethyldiphenylmethane-4,4′-diisocyanate, cyclohexylbis (4-isothiontphenyl) methane, 3,3′-dimethoxydiphenylmethane-4,4′-diisocyanate, 4,4′-dimethoxydiphenylmethane 3,3′-diisocyanate, 4,4′-diethoxydiphenylmethane-3,3′-diisocyanate, 2,2′-dimethyl-5,5′-dimethoxydiphenylmethane-4,4′-diisocyanate, 3,3′- Dichlorodiphenyldimethyl Tan-4,4'-diisocyanate, benzophenone-3,3'-diisocyanate, and the like.

  Examples of the triisocyanate of phenylmethane include 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, and 1,3,7-naphthalenetriisocyanate. Isocyanate, 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 (isocyanate phenyl) Such as thiophosphate It is below.

  As the polyisocyanate, dimer or trimer (isocyanurate bond) of the above polyisocyanate may be used. Moreover, you may use the biuret which made said polyisocyanate and amine react.

Furthermore, you may use the polyisocyanate which has the urethane bond which made these polyisocyanate and polyol react. As the polyol used here, divalent to octavalent polyols are preferable, and the aforementioned polyols are preferable.
Note that - as ^"R 13 _{(NCO) h1 + 1",} the case of using trivalent or more polyisocyanates, polyisocyanate, polyisocyanate having the above urethane bond.

The polyether monoalcohol represented by “HO— (R ¹⁴ —O) _n1 —R ¹⁵ ” is not particularly limited as long as it is a monohydric alcohol polyether.
The polyether monoalcohol represented by “HO— (R ¹⁴ —O) _n1 -R ¹⁵ ” is obtained by subjecting monovalent alcohol to addition polymerization of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, and the like. Can be obtained.
Therefore, the hydrocarbon group represented by R ¹⁴ is determined by alkylene oxide or the like that undergoes addition polymerization to a monovalent alcohol. The hydrocarbon group represented by R ¹⁵ is determined by a monovalent alcohol used for the synthesis of the specific compound (1-1).

The monovalent alcohol here is an alcohol represented by the following general formula (2), (3), or (4). Therefore, R ¹⁵ corresponds to a group excluding the hydroxyl group in the following general formulas (2) to (4).

Formula ^(2): R a -OH
Formula ^{(3): R b -CH (} R c) -R d -OH
General formula (4): R < ^e > -CH (R < ^f >)-OH

In the general formulas (2) to (4), R ^a , R ^b , R ^c , R ^e , and R ^f each independently represent a hydrocarbon group, specifically, an alkyl group, an alkenyl group, an alkyl group Examples thereof include hydrocarbon groups such as aryl groups, cycloalkyl groups, and cycloalkenyl groups.

  Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl. , Tridecyl, isotridecyl, myristyl, palmityl, stearyl, isostearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-octyldodecyl, 2-dodecylhexadecyl, 2-tetradecyloctadecyl, monomethyl branched-isostearyl and the like.

  Examples of the alkenyl group include vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like.

  Examples of the alkylaryl group include toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, etc. Is mentioned.

Examples of the cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, and the like.
Examples of the cycloalkenyl group include cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcycloheptenyl, and the like.

In the general formula (3), R ^d represents a divalent hydrocarbon group. Examples of the divalent hydrocarbon group represented by R ^d include a divalent group 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. Can be mentioned. Specifically, examples of the divalent hydrocarbon group represented by R ^d include an alkylene group, an alkenylene group, an alkylarylene group, a cycloalkylene group, and a cycloalkenylene group.

  As the alkylene oxide or the like to be addition-polymerized to the above monohydric alcohol, an alkylene oxide having 2 to 4 carbon atoms is preferable, and ethylene oxide is particularly preferable from the viewpoint of being easily available and capable of exhibiting an excellent effect. .

The form of addition polymerization of alkylene oxide or the like may be homopolymerization or copolymerization using two or more kinds. In the case of copolymerization, the form of copolymerization may be random polymerization or block polymerization. These addition polymerization methods may be ordinary methods.
N1 which shows a polymerization degree should just be the range of 0-1000, the range of 1-200 is preferable, and the range of 10-200 is more preferable.
Ratio of ethylene groups in the total ^{R 14} is preferably in the range of 50 wt% to 100 wt% of the total ^{R 14,} and more preferably in the range of 65 wt% to 100 wt%.

  As a method for producing the specific compound (1-1), for example, the polyether and the isocyanate are heated at 80 to 90 ° C. for 1 to 3 hours in the same manner as in the reaction of the usual polyether and isocyanate, It can be obtained by reacting.

A polyether polyol represented by ^- _{'[(O-R 12) k1} -OH] m1 R 11 "(a), - the" ^R 13 _{(NCO) h1 + 1} "represented by a polyisocyanate (b)," When the polyether monoalcohol (c) represented by “HO— (R ¹⁴ —O) _n1 —R ¹⁵ ” is reacted, other than the compound (copolymer) represented by the general formula (1-1) Things can also be a by-product.
For example, when a diisocyanate is used, the main product is a c-b-a-b-c type copolymer represented by the general formula (1-1). , Cb- (ab) _x -abc type copolymers may be by-produced.
In this case, the gel-like aqueous cosmetic of the present invention can be used in the state of a mixture containing the copolymer without separating the copolymer of the cbbabcc type represented by the general formula (1-1). May be used.

As the specific compound (1-1) used in the present invention, compounds described in JP-A-9-71766 are suitable.
As the specific compound (1-1) used in the present invention, PEG-240 / decyltetradeceth-20 / hexamethylene diisocyanate (HDI) copolymer is particularly suitable.
Such a copolymer is commercially available from ADEKA under the trade name “Adecanol GT-700”.

<Compound represented by formula (1-2)>
As the compound represented by the general formula (1) in the present invention, a compound represented by the following general formula (1-2) (hereinafter referred to as “specific compound (1-2)” as appropriate) is preferable.

In the general formula (1-2), R ²¹ represents a m2-valent saturated hydrocarbon group having 6 to 36 carbon atoms, and R ²² represents a methyldiphenylene group, a hexamethylene group, a methyldicyclohexylene group, 3-methyl. −3,5,5-trimethylcyclohexylene group, dimethylphenylene group, or tolylene group, and R ²³ represents 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), R ²¹ is a saturated hydrocarbon group having 6 to 36 carbon atoms, preferably a linear alkyl group or branched alkyl group having 6 to 36 carbon atoms.

The specific compound (1-2) includes a polyalkylene oxide compound represented by “H— (O—CHR ²³ CH ₂ ) _n2 —OH (wherein R ²³ and n2 are as defined above)”, “ A monovalent hydrophobic alcohol represented by “HO—R ²¹ (wherein R ²¹ is as defined above)”, and “R ²² <(NCO) ₂ (wherein R ²² is as defined above). It can be obtained by reacting these raw materials with a diisocyanate compound represented by “)” as a raw material.

Specific examples of the polyalkylene oxide compound represented by “H— (O—CHR ²³ CH ₂ ) _n2 —OH” include polyethylene oxide, polypropylene oxide, polyethylene oxide / polypropylene oxide (preferably ethylene oxide and propylene oxide). Copolymer) and the like.
Among these, the polyalkylene oxide compound represented by “H— (O—CHR ²³ CH ₂ ) _n2 —OH” is preferably a polyalkylene oxide compound containing 70% by mass or more of an ethylene oxide group, and more preferably. Is a polyalkylene oxide compound having 95% by mass or more of ethylene oxide groups.

The monovalent hydrophobic alcohol represented by “HO—R ²¹ ” is preferably an alcohol having a solubility in water of 0.4% by mass or less, and specifically includes hexyl alcohol, heptyl alcohol, octyl alcohol. , Nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, aralkyl alcohol, 2-octyldodecanol and Examples include behenyl alcohol, and preferably monovalent hydrophobic alcohol selected from the group consisting of cetyl alcohol and behenyl alcohol.
These monovalent hydrophobic alcohols may be used alone or in combination of two or more.

  The monovalent hydrophobic alcohol is preferably used in a proportion of 0.2 mol to 1.0 mol, and used in a proportion of 0.25 mol to 0.70 mol, relative to 1 mol of the polyalkylene oxide compound. It is more preferable.

Specific examples of the diisocyanate compound represented by “R ²² <(NCO) ₂ ” include 4,4′-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexylmethane-4, 4′-diisocyanate (HMDI), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,8-dimethylbenzole-2,4-diisocyanate, 2,4-tolylene diisocyanate (TDI), etc. Is mentioned.
Among these, the diisocyanate compound represented by “R ²² <(NCO) ₂ ” is selected from the group consisting of dicyclohexylmethane-4,4′-diisocyanate (HMDI) and 1,6-hexamethylene diisocyanate (HDI). Diisocyanate compounds are preferred.
These diisocyanate compounds may be used alone or in combination of two or more.

  The diisocyanate compound is composed of the number of moles of isocyanate groups of the isocyanate compound ([—NCO] relative to the total number of moles of terminal hydroxyl groups of the polyalkylene oxide compound and the monovalent hydrophobic alcohol compound (number of moles of [—OH]). ] Is preferably used at a ratio of 0.67 mol to 0.91 mol, and more preferably at a ratio of 0.70 mol to 0.90 mol.

Examples of the method of reacting the polyalkylene oxide compound, the monovalent hydrophobic alcohol, and the diisocyanate compound include a method of reacting by dissolving or dispersing in a reaction solvent such as toluene, xylene, dimethylformamide, etc .; Alternatively, there may be mentioned a method in which the mixture is melted in a liquid state and both are uniformly mixed, and then heated to a predetermined temperature for reaction.
As a method for synthesizing the specific compound (1-2), the method described in paragraphs [0049] to [0051] of JP2013-116941A is preferably used.

  As the specific compound (1-2) in the present invention, bisstearyl PEG / PPG-8 / 6 (methylenediphenyl diisocyanate / PEG-400) copolymer, that is, Sumitomo Seika Co., Ltd. under the trade name "Apeck HU type C" More commercially available compounds are preferred.

The content of the specific compound (1) in the gel aqueous cosmetic of the present invention is preferably 0.5% by mass to 15% by mass with respect to the total mass of the gel aqueous cosmetic, and is preferably 1% by mass. It is more preferable that it is 10 mass%, and it is still more preferable that it is 1.3 mass%-2 mass%.
When the content of the specific compound (1) in the aqueous gel cosmetic composition of the present invention is within the above range, it is possible to obtain a hardness suitable for the aqueous gel cosmetic composition. Moreover, the gel-like water-based cosmetics excellent in usability such as easy scooping with a spatula and ease of spreading to the skin at the time of application can be obtained.

[Fatty acid or its salt]
The gel aqueous cosmetic of the present invention contains a fatty acid or a salt thereof.
By containing the fatty acid or a salt thereof, the gel-based aqueous cosmetic of the present invention can suppress an increase in hardness over time and improve storage stability.

The fatty acid or salt thereof in the present invention is not particularly limited. The fatty acid or a salt thereof may be derived from a natural product or a synthetic product.
The carbon chain in the fatty acid or salt thereof may be a straight chain or branched chain, and may be a saturated or unsaturated carbon chain. From the viewpoint of solubility in a gel-based aqueous cosmetic, that is, from the viewpoint of preventing precipitation over time, the carbon chain in the fatty acid or salt thereof is preferably a branched chain. From the same viewpoint, the carbon chain in the fatty acid or salt thereof is preferably an unsaturated carbon chain having at least one double bond or triple bond, and an unsaturated carbon having at least one double bond. More preferably, it is a chain.

The number of carbon atoms of the fatty acid skeleton in the fatty acid or salt thereof is not particularly limited, and is preferably 12 to 22, more preferably 16 to 20, and still more preferably 16 to 18.
When the number of carbon atoms of the fatty acid skeleton in the fatty acid or salt thereof is 12 or more, the stability over time of the hardness of the gel aqueous cosmetic can be further improved. When the number of carbon atoms of the fatty acid skeleton in the fatty acid or salt thereof is 22 or less, the solubility in the gel-based aqueous cosmetic becomes better, so that precipitation with time does not easily occur.

Specific examples of fatty acids include 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), behen An acid (C22: 0) etc. are mentioned. The numbers in parentheses indicate the number of carbon atoms and the number of double bonds in the fatty acid skeleton. For example, “C18: 1” has 18 carbon atoms in the fatty acid skeleton and one double bond. Indicates that there is.
The fatty acid in the present invention includes oleic acid and isostearic acid in terms of the stability of the hardness of the gel aqueous cosmetic and the solubility in the gel aqueous cosmetic and the ease of application to the human body. At least one selected from is preferred, and isostearic acid is more preferred.

Examples of the salt structure constituting the salt of fatty acid include alkali metal salts such as sodium and potassium, basic amino acid salts such as L-arginine, L-histidine and L-lysine, and alkanolamine salts such as triethanolamine. . The type of salt is appropriately selected depending on the type of fatty acid used. From the viewpoint of solubility, the salt structure constituting the fatty acid salt is preferably an alkali metal salt such as a sodium salt.
The fatty acid salt in the present invention is preferably at least one selected from the group consisting of an alkali metal salt of oleic acid and an alkali metal salt of isostearic acid, more preferably at least one selected from sodium oleate and sodium isostearate, More preferred is sodium isostearate.
The gel-like aqueous cosmetic of the present invention may contain the above-mentioned fatty acid or a salt thereof alone or in combination of two or more.

  The content of the fatty acid or the salt thereof in the gel aqueous cosmetic of the present invention is 0.01% by mass to 5% by mass with respect to the total mass of the gel aqueous cosmetic from the viewpoint of stability over time of hardness. Yes, preferably 0.05 mass% to 1 mass%, more preferably 0.1 mass% to 0.5 mass%. Further, from the viewpoint of irritation to the skin, the upper limit of the content of the fatty acid or the salt thereof in the gel aqueous cosmetic of the present invention is 5% by mass or less with respect to the total mass of the gel aqueous cosmetic. is there.

Moreover, it is preferable that content of the fatty acid or its salt in the gelatinous aqueous cosmetics of this invention is 0.1 millimoles-1.0 millimoles with respect to 1 g of specific compounds (1), and 0.2 millimoles. More preferably, it is -0.8 mmol, and it is still more preferable that it is 0.4-0.7 mmol.
When the content of the fatty acid or salt thereof in the gel aqueous cosmetic composition of the present invention is within the above range, the increase in hardness with time is remarkably suppressed, and the gel aqueous cosmetic composition is excellent in storage stability. .
The “content of fatty acid or salt thereof” in the present invention means a fatty acid equivalent value.

〔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 for cosmetics.
The water content in the gelled aqueous cosmetic of the present invention is preferably 50% by mass to 95% by mass, and preferably 60% by mass to 90% by mass with respect to the total mass of the gelled aqueous cosmetic. Is more preferable, and it is still more preferable that it is 70 mass%-88 mass%.

[Other ingredients]
The gel-like aqueous cosmetic of the present invention may optionally contain other components other than the specific compound (1), fatty acid or salt thereof, and water. Hereinafter, other components that can be used in the gelled aqueous cosmetic of the present invention will be described.

<Carotenoid>
The gelled aqueous cosmetic of the present invention preferably further contains a carotenoid.
Carotenoids are yellow to red terpenoid pigments. Examples of carotenoids include carotenoids derived from plants, algae, bacteria, and the like.
The carotenoid in the present invention is not limited to a carotenoid derived from a natural product, and any carotenoid may be used as long as it is obtained according to a conventional method.

Specific examples of carotenoids include lycopene, α-carotene, β-carotene, γ-carotene, δ-carotene, actinioerythrol, bixin, canthaxanthin, capsorubin, β-8′-apo-carotenal (apocarotenal), β -12′-apo-carotenal, xanthophylls (for example, astaxanthin, fucoxanthin, lutein, zeaxanthin, capsanthin, β-cryptoxanthin, violaxanthin, and the like) and hydroxyl or carboxyl derivatives thereof.
Among these, the carotenoid is preferably at least one selected from the group consisting of astaxanthin, lycopene, β-carotene, fucoxanthin, and lutein because of high antioxidant effect, whitening effect, etc., and astaxanthin, lycopene, and β -At least one selected from the group consisting of carotenes is more preferable, and at least one selected from astaxanthin and lycopene is more preferable.
The gel-like aqueous cosmetic of the present invention may contain the carotenoids as described above alone or in combination of two or more.

  The carotenoid in the present invention is a crystalline carotenoid. Here, "crystalline carotenoid" does not represent a specific carotenoid, but when it is in the form of oil, paste, etc. containing carotenoid, due to various factors such as its production method, treatment method, storage method, It means a carotenoid that can exist as a crystal at any temperature in the temperature range of −5 ° C. to 35 ° C. In particular, lycopene and astaxanthin, which will be described later, β-carotene, δ-carotene, zeaxanthin, lutein and the like are carotenoids in which crystals are likely to exist.

(Astaxanthin)
Astaxanthin is one of the preferred carotenoids that the gel-like aqueous cosmetic of the present invention may contain. Astaxanthin in the present invention includes at least one selected from astaxanthin and derivatives thereof (for example, esters of astaxanthin). In the present invention, astaxanthin and its derivatives are collectively referred to as “astaxanthin”.

As astaxanthin, in addition to astaxanthin derived from natural products such as plants, algae, crustaceans, and bacteria, a synthetic product of astaxanthin obtained according to a conventional method can also be used.
Astaxanthin can be extracted from cultures such as red yeast Phaffia, green alga Hematococcus, marine bacteria, and krill.
From the viewpoint of quality and productivity, astaxanthin is particularly preferably astaxanthin derived from an extract from Haematococcus algae (hereinafter referred to as “Hematococcus alga extract”) or an extract from krill.

  Specific examples of Haematococcus algae include Haematococcus pluviaris, Haematococcus lacustris, Haematococcus genus, Haematococcus capecus, Examples thereof include Haematococcus zimbabwiens.

The hematococcus algae extract is obtained by crushing the above-mentioned hematococcus algae as necessary, for example, by the method disclosed in JP-A-5-68585, etc. to obtain acetone, ether, chloroform, alcohol (for example, , Ethanol, methanol, etc.) or an extraction solvent such as supercritical carbon dioxide can be added.
Examples of commercially available products of Haematococcus algae extract include ASTOTS-S, ASTOTS-2.5 O, ASTOTS-5 O, ASTOTS-10 O from Takeda Paper Co., Ltd., Asteryl from Fuji Chemical Industry Co., Ltd. Examples include Oil 50F, Asteryl Oil 5F, and BioAsin SCE7 manufactured by Toyo Enzyme Chemical Co., Ltd.

The content of astaxanthin in the Haematococcus alga extract as a pure pigment content is preferably 0.001% by mass to 50% by mass, more preferably 0.01% by mass to 25%, from the viewpoint of handling during production. % By mass.
In addition, the Haematococcus alga extract may contain astaxanthin or its ester as a pigment | dye pure part similarly to the pigment | dye described in Unexamined-Japanese-Patent No. 2-49091. A Haematococcus alga extract containing an ester of astaxanthin is generally preferably used in an amount of 50 mol% or more, preferably 75 mol% or more, more preferably 90 mol% or more.

(Lycopene)
Lycopene is one of the preferred carotenoids that the gel-like aqueous cosmetic of the present invention may contain. Lycopene is a carotenoid represented by the chemical formula C ₄₀ H ₅₆ , belongs to carotenes, and is a red pigment having an absorption maximum at 474 nm (acetone).

  Lycopene also has cis- and trans- isomers of conjugated double bonds at the center of the molecule, and examples thereof include all trans-, 9-cis, and 13-cis isomers. Any of these may be sufficient as the lycopene in this invention.

Lycopene is contained in natural products such as tomatoes, strawberries, watermelons, pink grapefruits, etc., and can be separated or extracted from these natural products. Isolates or extracts containing lycopene are commercially available in four forms: oil type, emulsion type, paste type, and powder type.
As lycopene, in addition to lycopene derived from natural products, a lycopene synthetic product obtained according to a conventional method can also be used.

One preferred form of lycopene is tomato-derived lycopene. The lycopene derived from tomato includes a fat-soluble extract extracted from tomato pulp. Lycopene contained in the fat-soluble extract extracted from tomato pulp is particularly preferable from the viewpoints of stability, quality, and productivity.
Here, the “fat-soluble extract extracted from tomato pulp” is extracted from a pulp-like solid obtained by centrifuging a pulverized product obtained by pulverizing tomato using an oily solvent. Means extract.
As the fat-soluble extract extracted from tomato pulp, a tomato extract widely marketed as lycopene-containing oil or paste can be used. For example, Lyc-O-Mato sold by Sunbright Co., Ltd. 15%, Lyc-O-Mato 6%, lycopene 18 sold by Kyowa Hakko Kogyo Co., Ltd. and the like.

The gel-like aqueous cosmetic composition of the present invention may contain carotenoid as a carotenoid-containing oil or paste. From the viewpoint of improving the stability of the carotenoid in the gel aqueous cosmetic composition of the present invention, it is preferable to contain the carotenoid in the form of a dispersion.
The dispersion containing carotenoids may be an oil-in-water dispersion (O / W dispersion) or a water-in-oil dispersion (W / O dispersion). The dispersion containing carotenoid is more preferably an oil-in-water dispersion containing carotenoid as one of the oil phase components.
A dispersion containing a carotenoid can be prepared by a conventional method.

<Ascorbic acid compound>
When the gel-like aqueous cosmetic of the present invention contains a carotenoid, it is preferable to further contain ascorbic acid or a derivative thereof, and a salt thereof (hereinafter referred to as “ascorbic acid compound” as appropriate). In the present invention, ascorbic acid derivatives and salts thereof are collectively referred to as “ascorbic acid derivatives”.
If the gel-like aqueous cosmetic of the present invention containing a carotenoid further contains an ascorbic acid compound, the ascorbic acid compound only exhibits its effectiveness as a functional ingredient having effects such as antioxidant and whitening. In addition, it suppresses the decomposition of carotenoids by light, etc., and contributes to improving the stability of carotenoids over time. Thereby, the discoloration resulting from decomposition | disassembly of a carotenoid is suppressed and a favorable external appearance is maintained.

Ascorbic acid may be any of L-form, D-form and DL-form, and L-form is preferred from the viewpoint of availability.
Examples of ascorbate include sodium ascorbate, potassium ascorbate, and calcium ascorbate.
Ascorbic acid derivatives include ascorbic acid phosphate, sodium ascorbyl phosphate (APS: sodium L-ascorbyl-2-phosphate), magnesium ascorbyl phosphate (APM: magnesium L-ascorbyl-2) -phosphate, ascorbic acid phosphate magnesium salt), ascorbic acid sulfate, ascorbic acid sulfate disodium salt, ascorbic acid 2-glucoside and the like.
The gel-like aqueous cosmetic of the present invention may contain the above ascorbic acid compound alone or in combination of two or more.

  The ascorbic acid compound is preferably an ascorbic acid derivative from the viewpoint that the degradation of carotenoids by light or the like is remarkably suppressed and the stability of carotenoids with time can be further improved, and at least selected from sodium ascorbyl phosphate and magnesium ascorbyl phosphate One is more preferable, and from the viewpoint of high whitening effect, sodium ascorbyl phosphate is particularly preferable.

  A commercially available product may be used as the ascorbic acid compound. L-ascorbic acid and L-ascorbic acid sodium are available from, for example, Takeda Pharmaceutical Co., Ltd., Fuso Chemical Industry Co., Ltd., BASF Japan, Daiichi Sankyo Co., Ltd. and the like. Examples of commercially available products of ascorbyl-2-glucoside include AA-2G (trade name, Hayashibara Biochemical Laboratories). Examples of commercially available products of sodium ascorbyl phosphate include ascorbic acid PS (trade name, Showa Denko KK), L-ascorbyl sodium phosphate (trade name, BASF Japan KK), and the like. Examples of commercially available products of magnesium ascorbyl phosphate include ascorbic acid PM (trade name, Showa Denko KK), NIKKOL (registered trademark) VC-PMG (trade name, Nikko Chemicals), Seamate (trade name, Takeda Pharmaceutical Co., Ltd.).

The content of the ascorbic acid compound in the aqueous gel cosmetic of the present invention is determined from the viewpoints of carotenoid stability, whitening effect, and the like.
When the gel-like aqueous cosmetic of the present invention contains an ascorbic acid compound, the content is preferably 0.25% by mass to 3% by mass with respect to the total mass of the gel-like aqueous cosmetic, More preferably, the content is 5% by mass to 2% by mass, and further preferably 1% by mass to 2% by mass.

The ratio of the content of carotenoid and the content of ascorbic acid compound (the content of carotenoid: the content of ascorbic acid compound) in the aqueous gel cosmetic of the present invention is 1: 1 to 1: 100000 on a mass basis. It is preferable that it is 1:10 to 1: 10000, and it is still more preferable that it is 1: 100 to 1: 5000.
When the ratio of the content of carotenoid and the content of ascorbic acid compound (the content of carotenoid: the content of ascorbic acid compound) in the aqueous gel cosmetic of the present invention is within the above range, the oxidative degradation of carotenoid Is remarkably suppressed, and a carotenoid-containing gel-like aqueous cosmetic is provided that is superior in storage stability.
The “content of ascorbic acid compound” in the present invention means an ascorbic acid conversion value when the ascorbic acid compound is ascorbic acid or a salt thereof, and in the case of an ascorbic acid derivative or a salt thereof, ascorbic acid. It means the acid derivative equivalent value.

<Polyhydric alcohol>
The gel aqueous cosmetic of the present invention can contain a polyhydric alcohol. When the gel-like aqueous cosmetic of the present invention contains a polyhydric alcohol, the moisture retention is improved and a good feeling of use is obtained.
Examples of the polyhydric alcohol include glycerin, ethylhexylglycerin, 1,3-butylene glycol, ethylene glycol; polysaccharides such as reduced starch syrup, sucrose, erythritol, xylitol, glucose, galactose, sorbitol, maltotriose, and trehalose. Can be mentioned.
The gel-like aqueous cosmetic of the present invention may contain the above-mentioned polyhydric alcohol alone or in combination of two or more.

  When the gel-like aqueous cosmetic of the present invention contains a polyhydric alcohol, the content is preferably 1% by mass to 50% by mass with respect to the total mass of the gel-like aqueous cosmetic, and 2% by mass. It is more preferably ˜20% by mass, and further preferably 5% by mass to 10% by mass.

<Other additive components>
The gel-based aqueous cosmetic of the present invention may appropriately contain an additive component that is usually used in the cosmetic field within a range not impairing the effects of the present invention.
Examples of the additive component include functional components that exhibit useful beauty effects (for example, a moisturizing effect, a whitening effect, a skin conditioning effect, etc.) when used in cosmetics. Examples of such functional components include vitamin E such as tocopherol and tocotrienol; ubiquinone such as coenzyme Q10; polysaccharide such as hyaluronic acid; active ceramide such as ceramide 1, ceramide 2, ceramide 3, ceramide 5, and ceramide 6. A glycosphingolipid such as glucosylceramide and galactosylceramide; a collagen such as hydrolyzed collagen and water-soluble collagen; an amino acid such as acetylhydroxyproline; and a hydrolyzed silavanal-protein.
Other additive components include, for example, preservatives such as phenoxyethanol, antioxidants, coloring agents, thickeners, aqueous sodium hydroxide, pH adjusting agents such as hydrochloric acid, buffers, fragrances, antibacterial agents, ultraviolet absorbers, Examples include active oxygen scavengers, antimicrobial agents, anti-inflammatory agents, and minerals.

[Method for producing gel-based aqueous cosmetic]
The method for producing the gelled aqueous cosmetic of the present invention is not particularly limited. The gel aqueous cosmetic of the present invention is a known gel aqueous cosmetic using the specific compound (1), a fatty acid or a salt thereof, water, and other components such as a polyhydric alcohol as necessary. It can be obtained according to the manufacturing method of the material.
As one of suitable production methods for the gel-like aqueous cosmetic of the present invention, the specific compound (1), a fatty acid or a salt thereof, water, and, if necessary, a polyhydric alcohol are heated. There is a production method including mixing (hereinafter referred to as “mixing step” as appropriate).

A mixing method for mixing the specific compound (1), the fatty acid or a salt thereof, and water is not particularly limited. For example, the specific compound (1), the fatty acid or a salt thereof, and water are mixed at a time. The specific compound (1) and the fatty acid or salt thereof may be added and mixed in the water while stirring the water.
When the gel-like aqueous cosmetic of the present invention contains a polyhydric alcohol as another component, the specific compound (1), a fatty acid or a salt thereof, water, and a polyhydric alcohol are mixed at a time. Alternatively, the specific compound (1) and the fatty acid or salt thereof may be added and mixed in the mixed solution while stirring the mixed solution of water and polyhydric alcohol.

  The mixing means is not particularly limited, and any commercially available mixing means may be used. Examples of the mixing means include a stirrer, paddle mixer, impeller mixer, homomixer, dispermixer, ultramixer, high pressure homogenizer, ultrasonic homogenizer, and the like. Among these mixing means, at least one selected from a homomixer and a disper mixer is preferable.

The temperature at the time of mixing each component is not specifically limited, A preferable range can be set suitably, and it is preferable to set normally in the range of 4 to 80 degreeC.
The stirring conditions for mixing the components are not particularly limited as long as the components can be sufficiently mixed, and can be set as appropriate according to the mixing means. For example, when using a homogenizer as a mixing means, each component can be normally stirred at 500 rpm to 8000 rpm for 5 minutes to 60 minutes.

  When blending other components other than polyhydric alcohol, from the viewpoint of further improving the temporal stability of the hardness of the gel aqueous cosmetic of the present invention, after cooling the mixture obtained by the above mixing step, It is preferable to mix other components other than the monohydric alcohol and further mix them. A mixing means is synonymous with the mixing means in the said mixing process, and its preferable example is also the same. The cooling temperature is not particularly limited, and can be set as appropriate in consideration of the stability of other components, and is usually preferably set within a range of 4 ° C to 80 ° C.

  The gel-like aqueous cosmetic composition of the present invention can include other steps than the mixing step as necessary. Examples of other processes include a defoaming process, a cooling process, and a taking-out process. A method known in the art may be applied to the defoaming step, the cooling step, the taking-out step and the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.

[Preparation of aqueous cosmetics]
[Example 1]
As specific compound (1), PEG-240 / decyltetradeces-20 / HDI copolymer (Adecanol GT-700, ADEKA) 1.7 g, fatty acid salt, sodium caprate 0.15 g, and glycerin 6 0.0 g, ethyl hexylglycerin 0.2 g, 1,3-butylene glycol 0.63 g, phenoxyethanol 0.5 g, 1 mol / L sodium hydroxide aqueous solution (pH adjuster) 0.54 g, 35 g of pure water was mixed. The obtained mixture was heated to 60 ° C., stirred for 5 minutes at 2000 rpm using a homogenizer (model name: Homomixer HM-310, ASONE Co., Ltd.), and then cooled to 40 ° C.
Next, 0.22 g of the astaxanthin-containing emulsion composition prepared in advance by the following method and 0.1 g of the lycopene-containing emulsion composition prepared in advance by the following method were prepared in advance by the following method. 6.0 g of ceramide-containing dispersion composition, 0.1 g of water-soluble collagen, 0.1 g of hydrolyzed collagen, 0.1 g of acetylhydroxyproline, a small amount of hydrolyzed silavanal-protein, and 0 fragrance After adding pure water so that the total amount becomes 100 g, the mixture was stirred at 2000 rpm for 20 minutes using a homogenizer (model name: Homomixer HM-310, ASONE Co., Ltd.). Then, vacuum defoaming was performed to obtain the aqueous cosmetic of Example 1.

<Preparation of an astaxanthin-containing emulsion composition>
The following components were heated at 70 ° C. for 1 hour and dissolved to obtain an aqueous phase composition A.
-Composition of aqueous composition A-
・ Sucrose stearate (HLB = 16) 33.0 g
・ Decaglyceryl monooleate (HLB = 12) 67.0 g
・ Glycerin 450.0g
・ Pure water 300.0g

The following components were heated at 70 ° C. for 1 hour and dissolved to obtain an oil phase composition A.
-Composition of oil phase composition A-
・ Astaxanthin-containing oil 15.0g
(Product name: ASTOTS-S (derived from Haematococcus algae, containing astaxanthin: 20% by mass), Takeda Shiki Co., Ltd.)
・ Mixed tocopherol 32.0g
(Product name: Riken E Oil 800, Riken Vitamin Co., Ltd.)
・ Medium chain fatty acid glyceride 93.0 g
(Product name: Coconut (registered trademark) MT, Kao Corporation)
・ Lecithin 10.0g
(Product name: Recion P, derived from soybean, Riken Vitamin Co., Ltd.)

The obtained aqueous phase composition A was stirred at 10000 rpm using an ultrasonic homogenizer (model: HP93, SMT Co., Ltd.) while maintaining the temperature at 70 ° C., and the oil phase composition A was added to roughly emulsify. I got a thing.
Next, the obtained crude emulsion was cooled to about 40 ° C., and high pressure emulsification was performed at a pressure of 200 MPa using an ultrahigh pressure emulsifier (model name: Ultimateizer HJP-25005, Sugino Machine Co., Ltd.). Then, it filtered using the micro filter with an average hole diameter of 1 micrometer, and obtained the astaxanthin containing emulsion composition (astaxanthin content rate: 0.3 mass%).

  The obtained astaxanthin-containing emulsion composition was diluted with milli-Q water so as to have a concentration of 1% by mass, and the dispersed particles were dispersed using a particle size analyzer (model: FPAR-1000, Otsuka Electronics Co., Ltd.). The particle diameter was measured and found to be 58 nm (median diameter (d50)).

<Preparation of lycopene-containing emulsion composition>
The following components were heated and mixed with stirring in a constant temperature bath at 70 ° C. to obtain an aqueous phase composition B.
-Composition of aqueous phase composition B-
・ Decaglyceryl oleate-10 8.0 g
(Product name: Decaglyn 1-OV, HLB = 12.0, Nikko Chemicals Corporation)
・ Sucrose stearate 2.0g
(Product name: Ryoto Sugar Ester S-1670, Mitsubishi Chemical Foods Corporation)
・ Glycerin 45.0g
・ Remaining amount of pure water up to 100g

The following components were heated and mixed for 5 minutes while stirring on a 150 ° C. hot plate to obtain an oil phase composition B.
-Composition of oil phase composition B-
・ Tomato oleoresin 1.14g
(Product name: Lyc-O-Mato (registered trademark) 15% (containing lycopene: 15% by mass), Sunbright Co., Ltd.)
・ Lecithin 1.0g
(Product name: Recion P, derived from soybean, Riken Vitamin Co., Ltd.)
・ Medium chain fatty acid glyceride 12.8g
(Product name: Coconut (registered trademark) MT, Kao Corporation)

The obtained aqueous phase composition B was added to the oil phase composition B, mixed with stirring, and dispersed for a predetermined time using an ultrasonic homogenizer (model: US-150T, Nippon Seiki Co., Ltd.). An emulsion was obtained.
Subsequently, the obtained crude emulsion was further subjected to high pressure emulsification at a pressure of 200 MPa using an ultrahigh pressure emulsifier (model name: Ultimateizer HJP-25005, Sugino Machine Co., Ltd.), and a lycopene-containing emulsion composition ( Lycopene content: 0.17% by mass).

  The obtained lycopene-containing emulsion composition was diluted with Milli-Q water so as to have a concentration of 1% by mass, and the particle size of dispersed particles was measured using a particle size analyzer (model: FPAR-1000, Otsuka Electronics Co., Ltd.). When the diameter was measured, it was 52 nm (median diameter (d50)).

<Preparation of ceramide-containing dispersion composition>
The following components were stirred at room temperature for 1 hour to obtain an oil phase composition.
-Composition of oil phase composition-
・ Ceramide 3 0.1g
・ Ceramide 6 0.1g
・ Phytosphingosine 0.07g
・ Ethanol 150g
-1 mol / L hydrochloric acid (adjusted so that pH immediately after dispersion is 7 or less)

  Micromixing the obtained oil phase composition (oil phase) and pure water (aqueous phase) at a ratio (mass ratio) of 1: 7 using a collision type KM micromixer 100/100 A dispersion was obtained. The conditions for using the micromixer are as follows.

<Usage conditions of micromixer>
-Microchannel-
Oil phase side microchannel cross-sectional shape / width / depth / length = rectangle / 70 μm / 100 μm / 10 mm
Water phase side microchannel cross-sectional shape / width / depth / length = rectangle / 490 μm / 100 μm / 10 mm
-Flow rate-
The aqueous phase is 21.0 ml / min. The oil phase was introduced at a flow rate of 3.0 ml / min. Introduced at a flow rate of

  Using the centrifugal thin film vacuum evaporator (model name: Evapor PEP-lab, Okawara Seisakusho Co., Ltd.), the resulting dispersion was desolvated and dispersed until the ethanol concentration was 0.1% by mass or less. It concentrated and adjusted so that a product concentration might be 2.0 mass%, and the ceramide containing dispersion composition was obtained. The dispersion concentration referred to here is a concentration based on the total amount of solids added to the oil phase.

[Example 2]
In the aqueous cosmetic composition of Example 1, the same procedure as in Example 1 was performed except that 0.18 g of sodium laurate was blended as the fatty acid salt instead of 0.15 g of sodium caprate. An aqueous cosmetic was obtained.

Example 3
In the aqueous cosmetic of Example 1, as a fatty acid salt, in place of 0.15 g of sodium caprate, 0.2 g of sodium myristate was blended in the same manner as in Example 1, except that 0.15 g of sodium myristate was blended. An aqueous cosmetic was obtained.

Example 4
In the aqueous cosmetic of Example 1, as a fatty acid salt, instead of blending 0.15 g of sodium caprate, 0.23 g of sodium palmitate was blended, the same as in Example 1, except that 0.13 g of sodium palmitate was blended. An aqueous cosmetic was obtained.

Example 5
In the water-based cosmetic of Example 1, as a fatty acid salt, in the same manner as in Example 1, except that 0.25 g of sodium stearate was added instead of 0.15 g of sodium caprate, An aqueous cosmetic was obtained.

Example 6
In the water-based cosmetic of Example 1, as a fatty acid salt, in the same manner as in Example 1, except that 0.25 g of sodium isostearate was blended instead of blending 0.15 g of sodium caprate. An aqueous cosmetic was obtained.

Example 7
In the water-based cosmetic of Example 1, as a fatty acid salt, in the same manner as in Example 1, except that 0.25 g of sodium oleate was blended instead of blending 0.15 g of sodium caprate. An aqueous cosmetic was obtained.

Example 8
In the water-based cosmetic of Example 1, as a fatty acid salt, in the same manner as in Example 1, except that 0.3 g of sodium behenate was blended instead of blending 0.15 g of sodium caprate, An aqueous cosmetic was obtained.

[Comparative Example 1]
In the aqueous cosmetic of Example 1, the aqueous cosmetic of Comparative Example 1 was obtained in the same manner as in Example 1 except that the fatty acid salt and the 1 mol / L sodium hydroxide aqueous solution were not blended.

[Evaluation]
The following evaluation was performed using each of the aqueous cosmetics of Examples 1 to 8 and Comparative Example 1. The evaluation results are shown in Table 1 together with the compositions of the aqueous cosmetics of Examples 1 to 8 and Comparative Example 1.

1. Storage stability (Hardness stability over time)
100 g of each of the aqueous cosmetics of Examples 1 to 8 and Comparative Example 1 immediately after the preparation was put into a glass container having a diameter of 47 mm and a height of 90 mm, respectively, and stored at 25 ° C. for 24 hours in a capped state. The hardness (hereinafter referred to as “initial hardness” as appropriate) of each aqueous cosmetic after being stored at 25 ° C. for 24 hours was measured using a rheometer (model name: FUDOH REHOMETER, Rheotech Co., Ltd.). Specifically, for each aqueous cosmetic, the peak of stress measured when the tip of an adapter with a diameter of 20 mm is inserted with a load of 2 kg at a speed of 60 mm / min at a measurement temperature of 25 ° C. The value was a measured value of hardness (unit: g). Details of the measurement conditions are shown below.

"Measurement condition"
Adapter: No. 3 (Diameter: 20mm)
Load: 2kg
Speed: 60mm / min Measurement temperature: 25 ° C
No load base: 0.1%
Sampling interval: 0.02 seconds X-axis table travel distance: 20 mm (forced termination: 20 mm)

As another system, 100 g of each of the water-based cosmetics of Examples 1 to 8 and Comparative Example 1 immediately after preparation was put in a glass container having a diameter of 47 mm and a height of 90 mm, respectively, and capped, at 50 ° C. And stored for 2 weeks. The hardness of each water-based cosmetic after storage at 50 ° C. for 2 weeks (hereinafter referred to as “time-dependent hardness” as appropriate) was measured by the same method as the above-mentioned initial hardness.
Then, using the measured values of the initial hardness and the hardness over time, the rate of change in hardness over time is calculated, and based on the obtained rate of change in hardness, the storage stability of the water-based cosmetic (the hardness over time) (Stability) was evaluated. "Hardness change rate over time" was obtained by dividing the higher value of the measured values of initial hardness and time-dependent hardness by the lower value and rounding off the second decimal place to the first decimal place. Value.
The smaller the rate of change in hardness over time, the better the storage stability of the aqueous cosmetic.

~Evaluation criteria~
AAA: Hardness change rate over time is 1.0 or more and less than 1.5 AA: Hardness change rate over time is 1.5 or more and less than 2.0 A: Hardness change rate over time is 2.0 B: Hardness change rate over time is 3.0 or more and less than 4.0 C: Hardness change rate over time is 4.0 or more

2. Feeling of use (freshness)
The freshness felt when applied to the skin was evaluated as one of the feeling of use. The term “freshness” as used herein means that when applied to the skin, the components in the aqueous cosmetic are separated, and a change in which water oozes out is felt.
100 g of each of the aqueous cosmetics of Examples 1 to 8 and Comparative Example 1 immediately after the preparation was put into a glass container having a diameter of 47 mm and a height of 90 mm, respectively, and stored at 25 ° C. for 24 hours in a capped state. Each of the 40 g of each water-based cosmetic after being stored at 25 ° C. for 24 hours was used by 10 panelists specializing in cosmetics evaluation, and the degree of freshness felt when applied to the skin was judged. The panel was scored as “3” when it felt strongly, “2” when it felt moderate, and “1” when it almost didn't feel fresh.
Each paneler's scoring results were averaged, and the value rounded off to the nearest decimal point was used as the evaluation result of the feeling of use (freshness).
It shows that the use feeling of water-based cosmetics is excellent, so that the numerical value of an evaluation result is large.

As shown in Table 1, each of the aqueous cosmetics of Examples 1 to 8 using a fatty acid salt together with the specific compound (1) had a small change in hardness and was excellent in stability over time of hardness. Moreover, the water-based cosmetics of Examples 1 to 8 had a strong feeling of freshness when applied to the skin and were excellent in usability.
On the other hand, in the aqueous cosmetic of Comparative Example 1 in which the fatty acid salt was not used together with the specific compound (1), the freshness felt when applied to the skin was the same as that of the aqueous cosmetic of Examples 1 to 8. However, the temporal stability of hardness was inferior to the aqueous cosmetics of Examples 1 to 8.
As the number of carbon atoms of the fatty acid skeleton in the fatty acid salt increased, a tendency to improve the temporal stability of hardness was recognized (see Examples 1 to 8). Moreover, when the carbon chain of the fatty acid in the fatty acid salt is a branched chain, a tendency to be more excellent due to the stability over time of hardness was observed (see Example 5 and Example 6). Furthermore, when the fatty acid in the fatty acid salt had an unsaturated double bond, a tendency to be more excellent in the stability over time of hardness was recognized (see Example 5 and Example 7).

[Preparation of aqueous cosmetics]
Example 9
In the aqueous cosmetic of Example 1, as a fatty acid salt, 0.25 g of sodium oleate was blended instead of 0.15 g of sodium caprate, and PEG-240 / decyltetra which is the specific compound (1) An aqueous cosmetic of Example 9 was obtained in the same manner as in Example 1 except that the blending amount of the Decess-20 / HDI copolymer was changed from 1.7 g to 1 g.

Example 10
In the aqueous cosmetic of Example 1, as a fatty acid salt, 0.25 g of sodium oleate was blended instead of 0.15 g of sodium caprate, and PEG-240 / decyltetra which is the specific compound (1) An aqueous cosmetic of Example 10 was obtained in the same manner as in Example 1 except that the blending amount of Decess-20 / HDI copolymer was changed from 1.7 g to 1.3 g.

Example 11
In the aqueous cosmetic of Example 1, as a fatty acid salt, 0.25 g of sodium oleate was blended instead of 0.15 g of sodium caprate, and PEG-240 / decyltetra which is the specific compound (1) An aqueous cosmetic of Example 11 was obtained in the same manner as in Example 1 except that the blending amount of the Decess-20 / HDI copolymer was changed from 1.7 g to 1.5 g.

Example 12
In the aqueous cosmetic of Example 1, instead of 0.15 g of sodium caprate as a fatty acid salt, 0.25 g of sodium isostearate was added, and PEG-240 / decyltetra which is the specific compound (1) The aqueous cosmetic of Example 12 was obtained in the same manner as in Example 1 except that the blending amount of the Decess-20 / HDI copolymer was changed from 1.7 g to 1.5 g.

Example 13
In the water-based cosmetic of Example 1, as a fatty acid salt, instead of blending 0.15 g of sodium caprate, 0.25 g of sodium oleate was blended. An aqueous cosmetic was obtained.

Example 14
In the aqueous cosmetic composition of Example 1, as a fatty acid salt, instead of blending 0.15 g of sodium caprate, 0.25 g of sodium isostearate was blended in the same manner as in Example 1, except that 0.15 g of sodium isostearate was blended. An aqueous cosmetic was obtained.

Example 15
In the aqueous cosmetic composition of Example 1, 0.5 g of sodium isostearate was blended as the fatty acid salt instead of 0.15 g of sodium caprate, and PEG-240 / decyltetradeces, which is the specific compound (1). Except that the blending amount of the -20 / HDI copolymer was changed from 1.7 g to 3.5 g and the blending amount of the 1 mol / L sodium hydroxide aqueous solution was changed from 0.54 g to 1.08 g, In the same manner as in Example 1, the aqueous cosmetic of Example 15 was obtained.

Example 16
In the aqueous cosmetic composition of Example 1, 0.5 g of sodium isostearate was blended as the fatty acid salt instead of 0.15 g of sodium caprate, and PEG-240 / decyltetradeces, which is the specific compound (1). Example except that the blending amount of the -20 / HDI copolymer was changed from 1.7 g to 5 g and the blending amount of the 1 mol / L sodium hydroxide aqueous solution was changed from 0.54 g to 1.08 g. In the same manner as in Example 1, the aqueous cosmetic of Example 16 was obtained.

Example 17
In the aqueous cosmetic composition of Example 1, 0.5 g of sodium isostearate was blended as the fatty acid salt instead of 0.15 g of sodium caprate, and PEG-240 / decyltetradeces, which is the specific compound (1). Example except that the blending amount of the -20 / HDI copolymer was changed from 1.7 g to 10 g and the blending amount of the 1 mol / L sodium hydroxide aqueous solution was changed from 0.54 g to 1.08 g. In the same manner as in Example 1, the aqueous cosmetic of Example 17 was obtained.

[Comparative Example 2]
In the aqueous cosmetic composition of Example 1, 0.5 g of sodium oleate was blended as the fatty acid salt in place of 0.15 g of sodium caprate and PEG-240 / decyltetra which is the specific compound (1) An aqueous cosmetic of Comparative Example 2 was obtained in the same manner as in Example 1 except that the blending amount of Decess-20 / HDI copolymer was changed from 1.7 g to 0.3 g.

[Evaluation]
Using each of the aqueous cosmetics of Examples 9 to 17 and Comparative Example 2, the storage stability (stability of hardness over time) of the aqueous cosmetic was evaluated by the same method as described above. In addition, using each of the aqueous cosmetics of Examples 9 to 17 and Comparative Example 2, usability of the aqueous cosmetics shown below (easiness of scooping with a spatula, and easiness of spreading to the skin when applied) Was evaluated. The evaluation results are shown in Table 2 together with the compositions of the aqueous cosmetics of Examples 9 to 17 and Comparative Example 2.

3. Usability (1) (Ease of scooping with a spatula)
Ease of scooping with a spatula was evaluated as one of the indicators of usability.
100 g of each of the aqueous cosmetics of Examples 9 to 17 and Comparative Example 2 immediately after the preparation was put into glass containers each having a diameter of 47 mm and a height of 90 mm and stored at 25 ° C. for 24 hours in a capped state. Each aqueous cosmetic after being stored at 25 ° C. for 24 hours is scooped for 10 panelists using a spatula (ASTALIFT Jerry Aquarista R) (sale name: AL Jerry Aquarista R) 40g exclusive spatula, FUJIFILM Corporation. I was asked to judge the level of ease of scooping. The panelists scored “2” when scooping without problems and “1” when scooping could not be scooped.
The scoring results of each panel were averaged, and the numerical value rounded off to the nearest decimal point was used as the evaluation result of usability (1) (easiness of scooping with a spatula).
The larger the numerical value of the evaluation result, the easier it is to scoop the water-based cosmetic with a spatula and the better the usability.

4). Usability (2) (easy extension to the skin when applied)
The ease of extension to the skin when applied was evaluated as one of usability indicators.
100 g of each of the aqueous cosmetics of Examples 9 to 17 and Comparative Example 2 immediately after the preparation was put into glass containers each having a diameter of 47 mm and a height of 90 mm and stored at 25 ° C. for 24 hours in a capped state. Each aqueous cosmetic after being stored at 25 ° C. for 24 hours was used by 10 specialist panelists for cosmetic evaluation, and the degree of ease of extension to the skin when applied was judged. The panelists scored “3” when they felt that they could stretch without problems, “2” when they could stretch but felt some resistance, and “1” when they felt it was difficult to stretch.
The scoring results of each paneler were averaged, and the numerical value rounded off to the nearest decimal point was used as the evaluation result of usability (2) (ease of extending to the skin during application).
The larger the numerical value of the evaluation result, the easier it is for the water-based cosmetic to extend to the skin when it is applied, and the usability is excellent.

As shown in Table 2, Examples 10 to 10 in which the content of the fatty acid or the salt thereof in the aqueous cosmetic is within the range of 0.48 mmol to 0.63 mmol with respect to 1 g of the specific compound (1). In the aqueous cosmetic of Example 14, the change in the hardness of the gel was small, and the stability over time of the hardness was excellent.
All of the aqueous cosmetics of Examples 9 to 17 were excellent in ease of scooping with a spatula and easy to extend to the skin when applied, and excellent in usability. On the other hand, the water-based cosmetic of Comparative Example 2 having a hardness of less than 1 spilled even if it was scooped with a spatula, resulting in poor usability.

Example 18
In the aqueous cosmetic of Example 6, the aqueous cosmetic of Example 18 was obtained in the same manner as in Example 6 except that 0.25 g of sodium ascorbyl phosphate (APS) was further added.

Example 19
The aqueous cosmetic of Example 19 was obtained in the same manner as in Example 6 except that 0.5 g of sodium ascorbyl phosphate (APS) was further added to the aqueous cosmetic of Example 6.

Example 20
The aqueous cosmetic of Example 20 was obtained in the same manner as in Example 6 except that 1 g of sodium ascorbyl phosphate (APS) was further added to the aqueous cosmetic of Example 6.

Example 21
In the aqueous cosmetic of Example 6, the aqueous cosmetic of Example 21 was obtained in the same manner as in Example 6 except that 2 g of sodium ascorbyl phosphate (APS) was further added.

[Example 22]
In the aqueous cosmetic of Example 6, the aqueous cosmetic of Example 22 was obtained in the same manner as in Example 6 except that 2 g of magnesium ascorbyl phosphate (APM) was further added.

Example 23
In the aqueous cosmetic of Example 6, the aqueous cosmetic of Example 23 was obtained in the same manner as in Example 6 except that 2 g of sodium ascorbate was further added.

[Evaluation]
Using each of the water-based cosmetics of Examples 18 to 23, the storage stability (stability of hardness over time) of the water-based cosmetics was evaluated by the same method as described above. Moreover, the storage stability of the aqueous cosmetics shown below (the stability over time as seen from the change in absorbance) was evaluated using each of the aqueous cosmetics of Examples 18 to 23. The evaluation results are shown in Table 3 together with the compositions of the aqueous cosmetics of Examples 18 to 23.

5. Storage stability (Stability over time from change in absorbance)
In cosmetics containing carotenoids such as astaxanthin and lycopene, a change in absorbance over time can occur due to decomposition of carotenoids by light or the like. Thus, the change in absorbance over time was evaluated as one of the storage stability indexes of cosmetics containing carotenoids.
Immediately after the preparation, 100 g of each of the aqueous cosmetics of Examples 18 to 23 was put in a glass container having a diameter of 47 mm and a height of 90 mm, and stored at 25 ° C. for 24 hours in a capped state. Each aqueous cosmetic after being stored at 25 ° C. for 24 hours is put into a polystyrene (PS) disposable cell having an optical path length of 0.4 cm, and a small cooling centrifuge (model: CF5RX, Hitachi Koki Co., Ltd.) , Swing rotor: T4SS31) was centrifuged at 4000 rpm for 2 minutes to perform defoaming treatment.
About each water-based cosmetic after a defoaming process, the light absorbency with respect to the light of wavelength 478nm is measured using a spectrophotometer (model | form: U-3310, Hitachi, Ltd.), and the measured value obtained is referred to as "initial absorbance. "

As another system, 100 g of each of the aqueous cosmetics of Examples 18 to 23 immediately after preparation was put into a glass container having a diameter of 47 mm and a height of 90 mm, and stored at 50 ° C. for 4 weeks in a capped state. did. The absorbance of each aqueous cosmetic after storing for 4 weeks at 50 ° C. was measured by the same method as above, and the obtained measurement value was defined as “absorbance with time”.
Then, using the initial absorbance and the absorbance over time, the absorbance change rate over time was calculated, and based on the obtained absorbance change rate, the storage stability of the water-based cosmetics (measured according to the change in absorbance over time) (Stability) was evaluated. The “absorbance change rate with time” was a value obtained by dividing the measured value of initial absorbance and absorbance with time by dividing the higher value by the lower value and rounding off the first decimal place.
The smaller the change rate of absorbance with time, the better the storage stability.

~Evaluation criteria~
AA: Absorbance change rate over time is 99% or more and less than 100% A: Absorbance change rate over time is 90% or more and less than 99% B: Absorbance change rate over time is 75% or more and less than 90% A: Absorbance change rate with time is less than 75%

  As shown in Table 3, all the aqueous cosmetics of Examples 18 to 23 using ascorbic acid derivatives together with astaxanthin and lycopene had little change in absorbance over time. This change in absorbance over time tended to be smaller as the amount of the ascorbic acid derivative was increased, so it is considered that the ascorbic acid derivative contributed to the temporal stability of astaxanthin and lycopene. (See Example 18 to Example 21).

  The aqueous cosmetic of Example 21 using sodium ascorbyl phosphate (APS) was the aqueous cosmetic of Example 22 using magnesium ascorbyl phosphate (APM), and the aqueous cosmetic of Example 23 using sodium ascorbate. Compared with the sample, the change in absorbance over time was small. In particular, APS showed the same effect as APM at a content of 1/4 (see Examples 19 to 22).

Claims (9)

It contains a compound represented by the following general formula (1), a fatty acid or salt thereof, and water, and the content of the fatty acid or salt thereof is 0 in terms of fatty acid with respect to the total mass of the gel-based aqueous cosmetic. Gel aqueous cosmetics having a hardness of 1 to 1000 g when measured at 25 ° C. of 0.01% to 5% by mass.

In the general formula (1), R ¹ represents an m-valent hydrocarbon group having ² to 36 carbon atoms, R ² and R ⁴ each independently represents a divalent hydrocarbon group having 1 to 4 carbon atoms, R ³ represents a straight chain, branched chain, or h + 1 valent hydrocarbon group containing an aliphatic ring or an aromatic ring, which may have a urethane bond, R ⁵ represents a divalent hydrocarbon group, and R ⁶ represents Represents a hydrogen atom or a hydroxy group. m is an integer greater than or equal to 2, h is an integer greater than or equal to 1, k and n represent the repeating number of the structure in a parenthesis, and are each independently an integer of the range of 0-1000, both k and n Will never be zero.   The gel-based aqueous cosmetic according to claim 1, having a hardness of 10 g to 200 g when measured at 25 ° C.   The gel-based aqueous cosmetic according to claim 1 or 2, wherein the fatty acid skeleton in the fatty acid or a salt thereof has 12 to 22 carbon atoms.   The gelled aqueous cosmetic according to any one of claims 1 to 3, wherein the fatty acid or a salt thereof is at least one fatty acid selected from oleic acid and isostearic acid or a salt thereof. 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) The gel-based aqueous cosmetic composition according to any one of claims 1 to 4.

In general formula (1-1), R ¹¹ represents a m1-valent hydrocarbon group having 2 to 12 carbon atoms, and R ¹² and R ¹⁴ each independently represents a divalent hydrocarbon group having 1 to 4 carbon atoms. , R ¹³ represents a linear, branched, or h1 + 1 valent hydrocarbon group containing an aliphatic ring or an aromatic ring which may have a urethane bond, and R ¹⁵ represents a monovalent hydrocarbon group. m1 is an integer greater than or equal to 2, h1 is an integer greater than or equal to 1, k1 and n1 represent the repeating number of the structure in a parenthesis, and are each independently an integer of the range of 0-1000, both k1 and n1 Will never be zero.

In the general formula (1-2), R ²¹ represents a m2-valent saturated hydrocarbon group having 6 to 36 carbon atoms, and R ²² represents a methyldiphenylene group, a hexamethylene group, a methyldicyclohexylene group, 3-methyl. −3,5,5-trimethylcyclohexylene group, dimethylphenylene group, or tolylene group, and R ²³ represents a hydrogen atom or a methyl group. n2 represents an integer of 90 to 900, and m2 represents an integer of 1 to 5.   PEG-240 / decyltetradeceth-20 / hexamethylene diisocyanate copolymer in which the compound represented by the general formula (1) is a compound represented by the general formula (1-1), and the general formula (1-2) The gel-like aqueous cosmetic according to claim 5, which is at least one copolymer selected from the group consisting of bisstearyl PEG / PPG-8 / 6 (methylenediphenyl diisocyanate / PEG-400) copolymer, which is a compound represented by the formula:   The gel-based aqueous cosmetic according to any one of claims 1 to 6, further comprising at least one selected from astaxanthin and lycopene.   Furthermore, the gelatinous aqueous cosmetics of Claim 7 containing an ascorbic acid derivative.   The gelled aqueous cosmetic according to claim 8, wherein the ascorbic acid derivative is sodium ascorbyl phosphate.