JP7781633B2 - Cosmetics - Google Patents

Description

The present invention relates to cosmetics.

It has been known that unsaturated fatty acids, such as oleic acid and palmitoleic acid, in sebum have effects on the skin, such as mild inflammation, rough surface, noticeable irregularities in pores, makeup breakdown, etc. Various studies have been conducted to improve the effects of such unsaturated fatty acids on the skin.
For example, Patent Document 1 describes that an unsaturated fatty acid adsorbent made of hexagonal plate-shaped zinc oxide coated with an oleic acid ester surfactant can suitably adsorb and fix unsaturated fatty acids contained in sebum, and can prevent makeup from coming off when blended into cosmetics.
Patent Document 2 describes that a cosmetic containing silicone microparticles having silicone elastomer spherical microparticles and polyorganosilsesquioxane coating the surfaces thereof can suppress changes in makeup cosmetic properties, color changes, shine, etc. caused by sebum.
Patent Document 3 describes that a composition for suppressing skin secretion containing butcher's broom extract can improve skin symptoms associated with excessive sebum secretion.

On the other hand, hydroxypropyl cellulose has conventionally been used as a water-soluble thickener in pharmaceuticals, cosmetics, etc.
For example, Patent Document 4 describes that an alcohol-in-oil-in-water emulsion composition having (a) an alcohol phase containing hydroxypropyl cellulose and exhibiting a gel-like state, (b) an oil phase containing dextrin palmitate and exhibiting a gel-like state, and (c) an aqueous phase containing polyvinyl alcohol and a carboxyvinyl polymer with a degree of saponification of 70 to 98 mol % and exhibiting a gel-like state, causes little irritation when applied to the skin and is highly stable.

JP 2018-83766 A JP 2011-105662 A Japanese Patent Application Laid-Open No. 2017-178858 JP 2009-114180 A

In the case of conventional technologies such as those disclosed in Patent Documents 1 and 2, where sebum is adsorbed using powder, the powder's ability to locally trap sebum on the skin surface provides a cosmetic effect that lasts, but does not improve the skin itself. Furthermore, in the case of those using plant extracts, as disclosed in Patent Document 3, although sebum secretion is suppressed, the effect on the skin by trapping unsaturated fatty acids is not improved.

The inventors have discovered that highly substituted hydroxypropyl cellulose specifically captures unsaturated fatty acids, such as oleic acid, which are components of sebum, from the outside, improving skin condition; furthermore, by using it in combination with a liquid dihydric alcohol and a specific water-insoluble polymer, it is possible to obtain a cosmetic product that is highly effective in suppressing skin roughness caused by sebum, and that provides an excellent finish and water resistance when foundation is applied.

The present invention comprises the following components (A), (B) and (C):
(A) a polymer having a cellulose skeleton in which 2.4 or more substituents selected from hydroxypropyl groups, hydroxybutyl groups, and amide groups are substituted per glucose;
(B) a water-insoluble polymer having a silicone backbone with a cationic charge;
(C) The cosmetic contains a liquid dihydric alcohol, the content of component (A) is 0.7 to 7.5 mass %, and the mass ratio of component (A) to component (B), (A)/(B), is 0.42 to 5.2.

The cosmetic product of the present invention can improve skin conditions such as uneven redness, brightness, and smoothness (roughness of the skin surface). When foundation or the like is applied, it adheres well and provides a uniform finish without unevenness, has excellent water resistance against sweat, etc., and ensures long-lasting makeup.

The component (A) used in the present invention is a polymer having a cellulose skeleton in which 2.4 or more substituents selected from hydroxypropyl groups, hydroxybutyl groups and amide groups are substituted per glucose.
Component (A) is a cellulose in which 2.4 or more hydroxyl groups per glucose are substituted with substituents selected from hydroxypropyl groups, hydroxybutyl groups, and amide groups (substitution degree of 2.4 or more), and the substitution degree is preferably 3 or more.
Here, the degree of substitution is the average number of substituted hydroxyl groups per glucose. When the substituents, such as hydroxypropyl groups, also contain hydroxyl groups, the hydroxyl groups of these substituents are also etherified during the reaction, and the molar substitution, which is the number of substituents per glucose, becomes, for example, greater than 3 for the hydroxypropyl group.
Hydroxypropyl cellulose is preferred as component (A) from the viewpoint of improving the capturing ability by gelling unsaturated fatty acids, improving skin condition, improving the application and unevenness of makeup when foundation or the like is applied, and increasing the durability of the makeup.
Furthermore, the polymer of component (A) preferably has no substituents other than hydroxypropyl groups, hydroxybutyl groups, and amide groups.

Furthermore, from the viewpoints of improving the capturing ability by gelling the unsaturated fatty acid, improving skin condition, improving the smoothness and unevenness of makeup application when foundation or the like is applied, and increasing the durability, component (A) preferably has an average molecular weight of 40,000 to 2,500,000, and more preferably 100,000 to 2,500,000.
Here, the average molecular weight is measured by GPC (Gel Permeation Chromatograph).

Such polymers can be produced, for example, by adding propylene oxide to alkali cellulose activated by alkali mercerization. For example, hydroxypropyl cellulose, which has hydroxypropyl groups as substituents, is produced by subjecting cellulose to a slurry-like process called alkali cellulose activation, known as alkali mercerization, in which a large amount of water and a large excess of an alkali metal hydroxide such as sodium hydroxide are mixed together to form an alkali cellulose, a very complicated activation process known as alkali mercerization, and then reacting this alkali cellulose with propylene oxide.

In addition, commercially available products such as HPC-SSL, HPC-SL, HPC-L, HPC-M, HPC-H, and HPC-VH (all manufactured by Nippon Soda Co., Ltd.), KLUCEL MF Pharm, and KLUCEL HPC (manufactured by Ashland) can be used as component (A).

Component (A) can be used alone or in combination with two or more types. Its content is 0.7% by mass or more, preferably 0.8% by mass or more, and more preferably 0.9% by mass or more, based on the viewpoints of improving skin condition, smoothness and unevenness of makeup application when foundation or the like is applied, and enhancing its durability by gelling the unsaturated fatty acids. Also, from the viewpoint of usability, improving smoothness and unevenness of makeup application when foundation or the like is applied, and enhancing its durability, it is 7.5% by mass or less, preferably 7% by mass or less, and more preferably 6.5% by mass or less. Furthermore, the content of component (A) is 0.7 to 7.5% by mass, preferably 0.8 to 7% by mass, and more preferably 0.9 to 6.5% by mass, based on the viewpoint of usability, improving smoothness and unevenness of makeup application when foundation or the like is applied, and enhancing its durability.

Component (B) is a water-insoluble polymer with a cationic silicone main chain. Component (B) has a cationic charge, which allows it to have high adsorption to the skin, and the silicone main chain improves water resistance after application.
The polymer of component (B) has a cationic group (cationic charge), and may have the cationic group in the main chain or in the side chain, with those having the cationic group in the side chain being preferred.
Here, the cationic group is a concept that encompasses not only groups having a cation such as a quaternary ammonium group, but also groups that can become a cation when a proton is present in the system. Examples include primary to tertiary amino groups, quaternary ammonium groups, biguanide residues, and the like. Among these, from the viewpoints of preventing unevenness when a foundation is applied over the coating film, and improving the skin's makeup application and makeup staying power when makeup is applied, primary to tertiary amino groups and quaternary ammonium groups are preferred, primary to tertiary amino groups are more preferred, and secondary amino groups are even more preferred.

The charge density of the polymer of component (B) is preferably 0.01 meq/g or more, more preferably 0.03 meq/g or more, even more preferably 0.05 meq/g or more, even more preferably 0.08 meq/g or more, even more preferably 0.1 meq/g or more, even more preferably 0.15 meq/g or more, and even more preferably 0.2 meq/g or more, from the viewpoints of preventing unevenness when a foundation is applied over the coating film and improving smooth makeup application and smooth makeup wear when makeup is applied. Furthermore, the charge density of the polymer of component (B) is preferably 10.0 meq/g or less, more preferably 9.0 meq/g or less, even more preferably 8.0 meq/g or less, and even more preferably 2.0 meq/g or less, from the viewpoints of preventing unevenness when a foundation is applied over the coating film and improving smooth makeup application and smooth makeup wear when makeup is applied. As a specific range, 0.01 meq/g or more and 10.0 meq/g or less is preferable, 0.1 meq/g or more and 9.0 meq/g or less is more preferable, 0.15 meq/g or more and 8.0 meq/g or less is even more preferable, and 0.2 meq/g or more and 2.0 meq/g or less is even more preferable.
In the present invention, the charge density of a cationic polymer refers to the amount of charge distribution per unit weight, and can be measured using a zeta potential measuring device or the like.

Furthermore, as the polymer of component (B), from the viewpoints of being able to improve skin conditions such as uneven redness of bare skin, brightness, and smoothness (roughness of the skin surface), of providing good adhesion and a uniform finish without unevenness when foundation or the like is applied, of excellent water resistance against sweat and the like, and of long-lasting makeup, preferred are those having one or more segments selected from organopolysiloxane segments, polyoxyalkylene segments, and segments containing repeating structural units derived from unsaturated monomers as their main chain, and more preferred are those having organopolysiloxane segments as their main chain.
As the polymer of component (B), a polymer having an organopolysiloxane segment in the main chain and a cationic group in the side chain is preferred, from the viewpoints of being able to improve skin conditions such as uneven redness of bare skin, brightness, and smoothness (roughness of the skin surface), being able to provide good adhesion and a uniform finish without unevenness when foundation or the like is applied, being excellent in water resistance against sweat and the like, and being able to ensure that makeup lasts.
Furthermore, the polymer of component (B) may further contain a poly(N-acylalkyleneimine) segment, etc., in addition to the segments contained in the main chain described above. Among such polymers, a graft polymer having an organopolysiloxane segment in the main chain and a poly(N-acylalkyleneimine) segment and a cationic group in the side chain is preferred.

Specific examples of the cationic polymer of component (B) include poly(N-acylalkyleneimine)-modified silicones (e.g., oxazoline-modified silicones), amino-modified silicones, etc. These may be used alone or in combination of two or more.
Among these, poly(N-acylalkyleneimine)-modified silicones are more preferred from the viewpoints of being able to improve skin conditions such as uneven redness, brightness, and smoothness (roughness of the skin surface) of bare skin, providing good adhesion and a uniform finish without unevenness when foundation or the like is applied, and having excellent water resistance against sweat and the like, and lasting makeup.

The poly(N-acylalkyleneimine)-modified silicone is preferably an organopolysiloxane in which poly(N-acylalkyleneimine) segments consisting of repeating units represented by the following general formula (1) are bonded via cationic divalent linking groups to at least two silicon atoms in the organopolysiloxane segments that make up the main chain, in which the number-average molecular weight of the poly(N-acylalkyleneimine) segments is 500 to 4,000 and the weight-average molecular weight of the organopolysiloxane segments that make up the main chain is 10,000 to 200,000 (hereinafter, this organopolysiloxane will also be referred to as organopolysiloxane (OX)).

[wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an aralkyl group, or an aryl group, and t represents 2 or 3.]

Here, the organopolysiloxane (OX) will be described in detail.
At least two poly(N-acylalkyleneimine) segments are bonded to any silicon atom constituting the organopolysiloxane segment via a cationic divalent linking group, but it is preferred that the poly(N-acylalkyleneimine) segment is bonded to one or more silicon atoms excluding those at both ends of the organopolysiloxane segment via a cationic divalent linking group, and it is more preferred that the poly(N-acylalkyleneimine) segment is bonded to two or more silicon atoms excluding those at both ends via a cationic divalent linking group.

The cationic divalent linking group functions as a linking group for the poly(N-acylalkyleneimine) segment.
Examples of the cationic divalent linking group include alkylene groups containing a cationic group, and alkylene groups having 2 to 20 carbon atoms and containing 1 to 3 cationic groups are preferred, and alkylene groups having 2 to 20 carbon atoms and containing 1 to 3 cationic groups of one or more types selected from a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium group are more preferred.
Among these cationic divalent linking groups, from the viewpoints of being able to improve skin conditions such as uneven redness of bare skin, brightness, and smoothness (rough skin surface), of providing good adhesion and a uniform finish without unevenness when a foundation or the like is applied, of excellent water resistance against sweat and the like, and of long-lasting makeup, preferred are groups represented by any of the following formulas (A1) to (A6), of which groups represented by formula (A1) or (A2) are more preferred, and of which groups represented by formula (A1) are even more preferred.
In the formula, An ⁻ represents a counter ion of the quaternary ammonium salt, such as a halide ion (e.g., chloride ion, iodide ion), sulfate ion, phosphate ion, acetate ion, lactate ion, p-toluenesulfonate ion, perchlorate ion, or monoalkyl nitrate ion (e.g., methyl sulfate ion, ethyl sulfate ion).

In the N-acylalkyleneimine unit constituting the poly(N-acylalkyleneimine) segment, the alkyl group represented by ^R1 in general formula (1) has 1 to 22 carbon atoms, preferably 1 to 14 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. The alkyl group may be linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, and a hexyl group.
The aralkyl group represented by ^R1 is preferably an aralkyl group having 7 to 15 carbon atoms, such as a benzyl group, a phenethyl group, a trityl group, a naphthylmethyl group, and an anthracenylmethyl group.
The aryl group represented by ^R1 is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group, an anthracenyl group, or a phenanthryl group.
Among these, R ¹ is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 3 carbon atoms.
In formula (1), t represents 2 or 3, with 2 being preferred.

The mass ratio (a/b) of the organopolysiloxane segment (a) constituting the main chain to the poly(N-acylalkyleneimine) segment (b) is preferably 45/55 to 82/18, more preferably 50/50 to 80/20, and even more preferably 65/35 to 80/20, from the viewpoints of improving skin conditions such as uneven redness, brightness, and smoothness (roughness of the skin surface) of bare skin, providing good adhesion and a uniform finish without unevenness when foundation or the like is applied, excellent water resistance against sweat and the like, and long-lasting makeup.
In the present invention, the mass ratio (a/b) refers to a value determined by dissolving 5% by mass of organopolysiloxane (OX) in deuterated chloroform and subjecting the solution to nuclear magnetic resonance ( ^H -NMR) analysis to determine the integral ratio of alkyl groups or phenyl groups in the organopolysiloxane segment to methylene groups in the poly(N-acylalkyleneimine) segment.

In the organopolysiloxane (OX), the weight-average molecular weight (hereinafter also referred to as "MWg") of the organopolysiloxane segment between adjacent poly(N-acylalkyleneimine) segments can improve skin conditions such as uneven redness, brightness, and smoothness (roughness of the skin surface), and from the standpoints of providing good adhesion and a uniform finish without unevenness when foundation or the like is applied, excellent water resistance against sweat, etc., and long-lasting makeup, it is preferably 1,000 to 40,000, more preferably 1,500 to 30,000, and even more preferably 1,750 to 5,000.

In the present invention, the term "organopolysiloxane segment between adjacent poly(N-acylalkyleneimine) segments" refers to the portion enclosed by the dashed line between the attachment point (attachment point A) of the poly(N-acylalkyleneimine) segment to the organopolysiloxane segment and the attachment point (attachment point B) of the adjacent poly(N-acylalkyleneimine) segment, as shown in formula (2) below, and is a segment composed of one ^R2SiO unit, one ^R3 , and y+1 ( ^R2 ) _2SiO units. Furthermore, the term "poly(N-acylalkyleneimine) segment" refers to ^-Z1 - ^R4 bonded to the above ^R3 .

(In the formula, ^R2 's each independently represent an alkyl group or a phenyl group having 1 to 22 carbon atoms, ^R3 represents a cationic divalent linking group, ^-Z1 - ^R4 represents a poly(N-acylalkyleneimine) segment, ^R4 represents a residue of a polymerization initiator or a hydrogen atom, and y represents a positive number. Note that multiple ^R2's , R3 ^'s , and ^R4 's may be the same or different.)

MWg is the molecular weight of the portion enclosed by the dashed line in formula (2) above, and can be interpreted as the mass (g/mol) of organopolysiloxane segments per mole of poly(N-acylalkyleneimine) segments. Note that when 100% of the functional groups in the modified organopolysiloxane raw material compound are substituted with poly(N-acylalkyleneimine), this corresponds to the functional group equivalent (g/mol) of the modified organopolysiloxane.

The molecular weight of the poly(N-acylalkyleneimine) segment can be calculated from the molecular weight and degree of polymerization of the N-acylalkyleneimine unit or measured by gel permeation chromatography (GPC). In this specification, however, it refers to the polystyrene-equivalent number average molecular weight (hereinafter also referred to as MNox) measured by GPC under the measurement conditions described below. MNox can improve skin conditions such as uneven redness, brightness, and smoothness (roughness of the skin surface), and when foundation or the like is applied, it provides good adhesion, a uniform finish without unevenness, excellent water resistance against sweat, and makeup wear that lasts. From these viewpoints, MNox is preferably 800 to 3500, and more preferably 1000 to 3000.

MWg can be calculated using the content (mass%) of organopolysiloxane segments (hereinafter also referred to as Csi) that make up the main chain according to the following formula (I):

MWg = Csi×MNox/(100-Csi) (I)

The weight-average molecular weight (hereinafter also referred to as MWsi) of the organopolysiloxane segment constituting the main chain is preferably 15,000 to 160,000, more preferably 20,000 to 150,000, and even more preferably 25,000 to 100,000, from the viewpoints of being able to improve skin conditions such as uneven redness, brightness, and smoothness (roughness of the skin surface) of bare skin, providing good adhesion and a uniform finish without unevenness when foundation or the like is applied, excellent water resistance against sweat and the like, and long-lasting makeup.
Since the organopolysiloxane segments constituting the main chain share a skeleton in common with the modified organopolysiloxane of the raw material compound, MWsi is substantially the same as the weight average molecular weight of the modified organopolysiloxane of the raw material compound. The weight average molecular weight of the modified organopolysiloxane of the raw material compound is a polystyrene-equivalent weight average molecular weight measured by GPC under the following measurement conditions:

(Conditions for measuring the weight-average molecular weight of modified organopolysiloxane)
Column: Super HZ4000 + Super HZ2000 (Tosoh Corporation)
Eluent: 1 mM triethylamine/THF
Flow rate: 0.35mL/min
Column temperature: 40°C
Detector: UV
Sample: 50 μL

The weight-average molecular weight (hereinafter also referred to as MWt) of organopolysiloxane (OX) can improve skin conditions such as uneven redness, brightness, and smoothness (roughness of the skin surface), and from the standpoints of providing good adhesion and a uniform finish without unevenness when foundation or the like is applied, excellent water resistance against sweat, and long-lasting makeup, it is preferably 12,000 to 200,000, more preferably 25,000 to 160,000, and even more preferably 35,000 to 150,000. MWt refers to the polystyrene-equivalent value measured by GPC under the measurement conditions described below.

(Measurement conditions for MNox and MWt)
Column: K-804L (Tosoh Corporation), two columns connected in series Eluent: 1 mM dimethyldodecylamine/chloroform Flow rate: 1.0 mL/min
Column temperature: 40°C
Detector: RI
Sample: 50 μL

When the poly(N-acylalkyleneimine) segment is a poly(N-propionylethyleneimine) segment, ^{the 1} H-NMR measurement for calculating the mass ratio (a/b) can be carried out, for example, under the following conditions.
( ^1H -NMR measurement conditions)
0.5 g of the polymer sample is dissolved in 2 g of a measurement solvent (deuterated chloroform), and the solution is measured by ¹ H-NMR (400 MHz, manufactured by Varian). The ratio of silicone to poly(N-propionylethyleneimine) is calculated from each integral value.
PULSE SEQUENCE
・Relax. delay: 30 seconds ・Pulse: 45 degrees
Number of integrations: 8 Confirmed peaks Around 0 ppm: methyl group of polydimethylsiloxane,
Around 3.4 ppm: methylene moiety of ethyleneimine.

The organopolysiloxane (OX) can be one obtained by synthesis according to the methods described in JP 2008-143820 A, JP 2009-24114 A, JP 2015-67603 A, etc. For example, it can be produced by reacting an organopolysiloxane modified with a functional group that induces the above-mentioned cationic divalent linking group with a terminally reactive poly(N-acylalkyleneimine) obtained by ring-opening polymerization of a cyclic iminoether corresponding to the repeating unit represented by general formula (1).

Specific examples of the organopolysiloxane (OX) used in the present invention include one prepared in accordance with the description in Example 8 of JP-A No. 2009-24114 (charge density: 0.3 meq/g) and one prepared in accordance with the description in Synthesis Example 2 of JP-A No. 2008-143820 (charge density: 0.1 meq/g).

An example of an amino-modified silicone is one represented by the following general formula (3):

[During the ceremony,
R ¹¹ to R ¹³ each independently represent a hydrogen atom, a hydroxyl group, or a monovalent organic group having 1 to 20 carbon atoms;
R ¹⁴ represents a group represented by the following general formula (4):
R ¹⁵ and R ¹⁶ each independently represent a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, a monovalent organic group having 1 to 20 carbon atoms, or a group represented by the following general formula (4):
R ¹⁷ to R ²⁰ each independently represent a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, a monovalent organic group having 1 to 20 carbon atoms, or a group represented by the following general formula (4):
d represents a number in the range of 10≦d≦10,000;
e represents a number in the range of 0.1≦e≦1000.

[In formula (4),
R ²¹ and R ²² each independently represent an alkanediyl group having 1 to 8 carbon atoms;
R ^{to R} each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms;
f represents a number in the range of 0≦f≦6,
* indicates a bond.

In formula (3), examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ¹¹ to R ¹³ , R ¹⁵ to R ¹⁶ , and R ¹⁷ to R ²⁰ include straight-chain or branched-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl and tolyl; and halogenoalkyl groups such as 3,3,3-trifluoropropyl, 2-(perfluorobutyl)ethyl, 2-(perfluorohexyl)ethyl, and 2-(perfluorooctyl)ethyl.

R ¹¹ to R ¹³ are preferably monovalent organic groups having 1 to 20 carbon atoms. Of all R ¹¹ to R ¹³ contained in formula (3), 90 mol % or more are preferably methyl groups.

The alkoxy groups represented by R ¹⁵ to R ¹⁶ and R ¹⁷ to R ²⁰ have 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms. The alkoxy group may be linear or branched. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.
R ¹⁵ to R ¹⁶ and R ¹⁷ to R ²⁰ are preferably a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or a monovalent organic group having 1 to 20 carbon atoms, and more preferably a hydroxyl group, a methoxy group, or a methyl group.

Furthermore, d is a number in the range of 10≦d≦10,000, but preferably in the range of 100≦d≦2,000.
Furthermore, e is a number satisfying 0.1≦e≦1000, but 1≦e≦100 is preferred.
The sum of d and e is preferably 10 or more and less than 1,000 on the number average, more preferably 30 or more and less than 1,000 on the number average, and even more preferably 40 or more and less than 800 on the number average.

In formula (4), R ²¹ and R ²² each independently represent an alkanediyl group having 1 to 8 carbon atoms.
The alkanediyl group represented by R ²¹ preferably has 1 to 6 carbon atoms, while the alkanediyl group represented by R ²² preferably has 1 to 4 carbon atoms.
The alkanediyl groups represented by R ²¹ and R ²² may be linear or branched. Examples of the alkanediyl group include a methane-1,1-diyl group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a propane-2,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. Among these, a propane-1,3-diyl group (trimethylene group) is preferred as R ²¹ , and an ethane-1,2-diyl group (dimethylene group) is preferred as R ²² .

R ²³ to R ²⁵ each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. Examples of the organic groups represented by R ^{to R} include linear or branched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl and tolyl; alkanoyl groups such as acetyl and propionyl, as well as groups in which some or all of the hydrogen atoms of these groups have been substituted with substituents selected from halogen atoms, hydroxyl groups, alkoxy groups, and hydroxyalkoxy groups, such as halogenoalkyl groups such as 3,3,3-trifluoropropyl, 2-(perfluorobutyl)ethyl, 2-(perfluorohexyl)ethyl, and 2-(perfluorooctyl)ethyl; and monovalent organic groups obtained by reaction with acid anhydrides, epoxy compounds, and acrylic compounds (for example, —COCH ₃ , —CH ₂ CH(OH)CH ₂ OH, —CH ₂ CH(OH)CH ₂ OCH ₂ CH ₂ OH).
R ²³ to R ²⁵ are preferably hydrogen atoms, but when at least one of R ²³ to R ²⁵ is a hydrogen atom, some or all of the remaining groups may be groups such as monovalent organic groups obtained by reaction with the above-mentioned acid anhydrides, epoxy compounds, and acrylic compounds.
Furthermore, f represents a number in the range of 0≦f≦6, but is preferably a number in the range of 0≦f≦3.

Specific examples of such R ¹⁴ include the following:

The amino equivalent of the amino-modified silicone is preferably 200 g/mol to 30,000 g/mol, more preferably 400 g/mol to 10,000 g/mol, and even more preferably 600 g/mol to 5,000 g/mol.
The amino-modified silicone is preferably amodimethicone, aminoethylaminopropyldimethicone, or aminopropyldimethicone.

The amino-modified silicone may be commercially available or synthesized according to conventional methods. Commercially available amino-modified silicones include amino-modified silicone oils such as SF8451C, SF8452C, and SF8457C (manufactured by Dow Corning Toray Silicone Co., Ltd.), KF8003 and KF867 (manufactured by GE Toshiba Silicone Co., Ltd.), and amodimethicone emulsions such as SM8704C (manufactured by Dow Corning Toray Silicone Co., Ltd.). Amino-modified silicone oils may also be formulated in the form of emulsions. Amino-modified silicone emulsions can be prepared by mechanical emulsification (high-shear mechanical mixing of amino-modified silicone and water), chemical emulsification (emulsifying amino-modified silicone with water and an emulsifier), a combination of these, or emulsion polymerization.

Component (B) can be used singly or in combination of two or more types. From the viewpoints of achieving good adhesion, a uniform finish without unevenness, excellent water resistance against sweat, and long-lasting makeup when applying foundation, etc., the content is preferably 0.2% by mass or more of the total composition, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more. Furthermore, from the viewpoints of capturing unsaturated fatty acids and improving skin conditions such as uneven redness, brightness, and smoothness (roughness of the skin surface), the content is preferably 6% by mass or less, more preferably 5.5% by mass or less, and even more preferably 5.2% by mass or less. Furthermore, the content of component (B) is preferably 0.2 to 6% by mass of the total composition, more preferably 0.3 to 5.5% by mass, and even more preferably 0.5 to 5.2% by mass.

In the present invention, the mass ratio (A)/(B) of component (A) to component (B) is 0.42 or more, preferably 0.45 or more, and more preferably 0.48 or more, from the viewpoints of improving skin conditions such as uneven redness, brightness, and smoothness (rough skin surface) of bare skin, and of providing good adhesion and a uniform finish without unevenness when foundation or the like is applied, excellent water resistance against sweat, etc., and long-lasting makeup. Furthermore, from the viewpoints of capturing unsaturated fatty acids and improving skin conditions such as uneven redness, brightness, and smoothness (rough skin surface) of bare skin, the mass ratio (A)/(B) of component (A) to component (B) is 0.42 to 5.2, preferably 0.45 to 4.5, and even more preferably 0.48 to 4.

In the liquid dihydric alcohol of component (C), the term "liquid" refers to one that is fluid at 25°C.
Examples of liquid dihydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-butylene glycol, 1,3-propanediol, 1,2-propanediol, and pentylene glycol.
Among these, from the viewpoints of enhancing the unsaturated fatty acid capturing effect, improving skin condition, improving makeup application and unevenness when foundation or the like is applied, and enhancing the durability, it is preferable to contain at least one or more selected from propylene glycol, dipropylene glycol, 1,3-butylene glycol, and propanediol, and it is more preferable to contain 1,3-butylene glycol or propanediol.

Component (C) can be used singly or in combination of two or more types. Its content is preferably 2% by mass or more of the total composition, more preferably 3% by mass or more, and even more preferably 4% by mass or more, from the viewpoints of improving the dispersibility of component (A), enhancing the capture effect of unsaturated fatty acids, improving skin conditions such as uneven redness, brightness, and smoothness (roughness of the skin surface), improving makeup application and unevenness when foundation is applied, and enhancing water resistance and durability. From the viewpoint of usability, it is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 23% by mass or less. Furthermore, the content of component (C) is preferably 2 to 30% by mass of the total composition, more preferably 3 to 25% by mass, and even more preferably 4 to 23% by mass.

In the present invention, the mass ratio (A)/(C) of component (A) to component (C) is preferably 0.01 or more, more preferably 0.02 or more, and even more preferably 0.04 or more, from the viewpoints of gelling unsaturated fatty acids, enhancing the unsaturated fatty acid capture effect, improving skin conditions such as uneven redness, brightness, and smoothness (roughness of the skin surface), improving makeup application and unevenness when foundation or the like is applied, and enhancing water resistance and durability. Furthermore, from the viewpoints of improving makeup application and unevenness, the mass ratio (A)/(C) of component (A) to component (C) is preferably 0.01 to 0.8, more preferably 0.02 to 0.7, and even more preferably 0.04 to 0.65.

The cosmetic of the present invention may further contain (D) a water-soluble polymer having a carboxyl group.
Here, "water-soluble" refers to a substance that dissolves in pure water at 25°C at a rate of at least 0.1% by mass.
The polymer of component (D) may have any suitable carboxyl group, and is preferably an acrylic acid-based polymer from the viewpoints of gelling unsaturated fatty acids to enhance the capturing effect, improving skin condition, and improving makeup application and unevenness when foundation or the like is applied, as well as enhancing the durability of the makeup.

Acrylic acid-based polymers include polymers containing acrylic acid or methacrylic acid as structural units, such as polyacrylic acid, polymethacrylic acid, carboxyvinyl polymer, acrylic acid/alkyl methacrylate copolymer, and acrylic acid/alkyl acrylate (C10-30) crosspolymer.

In addition, examples of the polymer of component (D) that can be used include commercially available products such as acrylates/C10-30 alkyl acrylate crosspolymer (product name: PEMULEN TR-1 POLYMER (Lubrizol Advanced Materials)), carboxyvinyl polymer (product name: Carbopol 980 POLYMER (Lubrizol Advanced Materials)), and methacrylic acid copolymer (product name: Eudragit L100 (Evonic)).

Component (D) can be used alone or in combination of two or more types. From the viewpoints of gelling unsaturated fatty acids to enhance the capture effect, improving skin condition, and improving makeup application and unevenness when foundation or the like is applied, as well as increasing the durability, the content is preferably 0.001% by mass or more of the total composition, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more, and preferably 0.15% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.08% by mass or less. Furthermore, the content of component (D) is preferably 0.001 to 0.15% by mass of the total composition, more preferably 0.005 to 0.1% by mass, and even more preferably 0.01 to 0.08% by mass.

In the present invention, the mass ratio (D)/(A) of component (D) to component (A) is 0.001 or more, preferably 0.005 or more, more preferably 0.008 or more, and 0.3 or less, preferably 0.15 or less, more preferably 0.12 or less, from the viewpoints of gelling unsaturated fatty acids to enhance the capture effect, improving skin condition, and improving makeup application and unevenness when applying foundation or the like, as well as enhancing durability. Furthermore, the mass ratio (D)/(A) of component (D) to component (A) is 0.001 to 0.3, preferably 0.005 to 0.15, and more preferably 0.008 to 0.12.

In addition to the above-mentioned components, the cosmetic of the present invention may contain ingredients commonly used in cosmetics, such as oily components, polyhydric alcohols other than those mentioned above, surfactants, powders, polymeric compounds other than those mentioned above, antioxidants, fragrances, preservatives, pH adjusters, blood circulation promoters, cooling agents, antiperspirants, disinfectants, skin activators, moisturizers, and cooling agents.

The cosmetic of the present invention can be produced according to conventional methods and can be any of a water-in-oil emulsion cosmetic, an oil-in-water emulsion cosmetic, an aqueous cosmetic, etc. It can also be made into a dosage form such as a liquid, emulsion, paste, cream, gel, or solid.

The cosmetic of the present invention is preferably applied as an oil-in-water emulsion cosmetic or an aqueous cosmetic, and can be applied as a lotion, emulsion, serum, cream, makeup base, foundation, sunscreen emulsion, sunscreen cream, and other UV protective cosmetics.

Examples 1 to 9 and Comparative Examples 1 to 9
Oil-in-water emulsion cosmetics were prepared with the compositions shown in Tables 1 and 2, and evaluated for improvement in skin brightness, reduction in uneven redness on the cheeks, improvement in skin smoothness, even makeup application, good makeup application, makeup durability, and water resistance. The results are also shown in Table 1.

(Manufacturing method)
1) The oil phase components were uniformly mixed and dissolved by heating to 80°C to obtain an oil phase mixture. Water in an amount of 5% by mass of the entire cosmetic was heated to 80°C and added thereto, and the mixture was cooled to 40°C to obtain an oil-water mixture.
2) Separately, the other aqueous phase ingredients were heated to 50°C, mixed uniformly, and then cooled to 40°C while stirring.
3) The mixture of 1) and 2) above was mixed uniformly at 40°C and cooled to room temperature while stirring to obtain an oil-in-water emulsion cosmetic.

(Evaluation method)
(1) Improved skin brightness:
800 mg of each cosmetic product was applied twice a day, morning and evening, for 7 consecutive days, and the brightness of bare skin was evaluated in the mirror before and after application. Five expert evaluators evaluated each skin according to the following criteria, and the results are shown as the total score of the five evaluators.
5: There is a clear improvement compared to before continuous use.
4: There is some improvement compared to before continuous use.
3: No change.
2: Slightly worse than before continuous use.
1: It has worsened compared to before continuous use.

(2) Improves uneven redness on bare cheeks:
800 mg of each cosmetic product was applied twice daily, morning and evening, for seven consecutive days, and the unevenness of redness was evaluated in the mirror on bare cheek skin after cleansing, both before and after application. Five expert evaluators evaluated each skin type according to the following criteria, and the results are shown as the total score of the five evaluators.
5: The redness and unevenness have clearly decreased compared to before continuous use.
4: The redness has slightly decreased compared to before continuous use.
3: No change.
2: Redness has become slightly more uneven compared to before continuous use.
1: The redness has become more uneven compared to before continuous use.

(3) Improved skin smoothness:
800 mg of each cosmetic was applied twice a day, morning and evening, for 7 consecutive days, and the smoothness of the bare skin was evaluated before and after application when touched after cleansing. Five expert evaluators evaluated each skin according to the following criteria, and the results are shown as the total score of the five evaluators.
5: My skin is noticeably smoother than before I started using it.
4: My skin feels a little smoother than before I started using it.
3: No change.
2: My skin feels a little rougher than before I started using it.
1: My skin is clearly rougher than before I started using it.

(4) Makeup stays even:
Five expert evaluators applied 800 mg of each cosmetic product to the entire face, and then applied a commercially available powder foundation, and evaluated the unevenness of the application according to the following criteria. The results are shown as the total score of the five evaluators.
5: Uniform and without unevenness.
4: Some unevenness but mostly uniform.
3: Slightly uneven and not uniform.
2: Uneven and not uniform.
1: Uneven and not uniform.

(5) Makeup goes on well:
Five expert evaluators applied 800 mg of each cosmetic product to the entire face twice a day, morning and evening, for three days, then cleansed the skin, applied a regular lotion and emulsion, and then applied a commercially available powder foundation. The degree of makeup application was evaluated according to the following criteria. The results are shown as the total score of the five experts.
5: Makeup goes on very well.
4: Makeup goes on well.
3: Makeup goes on fairly well.
2: Makeup doesn't stick well.
1: Makeup does not stick very well.

(6) Makeup lasts:
Five expert evaluators applied 800 mg of each cosmetic product to the entire face, followed by 60 mg of a commercially available powder foundation. Five hours after application, the degree of makeup wear was evaluated according to the following criteria. The results are shown as the total score of the five evaluators.
5: Foundation remains on the skin.
4: Most of the foundation remains on the skin.
3: Some foundation remains on the skin.
2: There is almost no foundation left on the skin.
1: No foundation remains on the skin.

(7) Water resistance:
Each cosmetic was applied at 3 mg/ ^cm² to a glass substrate (76 mm x 26 mm), and after drying, a line was drawn on the coating with a black marker. The substrate was then immersed in a 500 mL beaker of water for 30 minutes, removed, and wiped clean. The degree to which the black marker remained after wiping was taken as the water resistance of the formulation, and five expert evaluators evaluated it according to the following criteria. The results are shown as the total score of the five evaluators.
5: The black marker remains almost intact on the glass substrate.
4: Most of the black marker remains on the glass substrate.
3: Some black marker remains on the glass substrate.
2: Almost no black marker remains on the glass substrate.
1: The black marker has disappeared and not remained on the glass substrate at all.

The symbols in the table indicate the following:
*1: Prepared according to the description of Example 8 of JP 2009-24114 A, manufactured by Kao Corporation, OS-75 (charge density: 0.3 meq/g)
*2: Prepared according to the description of Synthesis Example 2 of JP 2008-143820 A, manufactured by Kao Corporation, OS-51 (charge density: 0.1 meq/g)
* 3: Shin-Etsu Chemical Co., Ltd., KF-8003 (charge density: 0.4 meq/g)
* 4: Akzo Nobel Structure XL (charge density: 0 meq/g)
* 5: Shin-Etsu Chemical Co., Ltd., KF96-10000CS (charge density: 0 meq/g)

Claims (3)

The following components (A), (B), and (C):
(A) a polymer having a cellulose skeleton in which 2.4 or more substituents selected from hydroxypropyl groups, hydroxybutyl groups, and amide groups are substituted per glucose;
(B) a water-insoluble polymer having a silicone backbone with a cationic charge;
(C) A cosmetic preparation containing a liquid dihydric alcohol, in which component (A) is hydroxypropyl cellulose, component (B) is one or more polymers selected from poly(N-acylalkyleneimine)-modified silicones and amino-modified silicones, the content of component (A) is 0.7 to 7.5 mass%, and the mass ratio of component (A) to component (B), (A)/(B), is 0.42 to 5.2. 2. The cosmetic according to claim 1 , wherein the mass ratio (A)/(C) of component (A) to component (C) is 0.01 to 0.8. The cosmetic according to claim 1 or 2 , further comprising (D) a water-soluble polymer having a carboxyl group.