JP2015091770A - Oil-in-water emulsion cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil-in-water emulsion cosmetic which suppresses unevenness caused by flipping after application, has excellent spread during application of powder foundation, and refines makeup deformation after a lapse of six hours since application.SOLUTION: An oil-in-water emulsion cosmetic comprises: (A) 0.1 to 15 mass% of an organopolysiloxane obtained by bonding poly(N-acylalkyleneimine) segments composed of a repeating unit represented by formula (1) where Ris H or a 1-3C alkyl group, and t is 2 or 3; (B) 0.05 to 5 mass% of hydrophobic modified polyether urethane represented by formula (5) where R, Rand Rare hydrocarbon groups, Ris a hydrocarbon group optionally containing an urethane bond, Ris a straight chain, branched chain or a secondary hydrocarbon group, m is 2 or more, h is 1 or more, and k and n are 0-1000; and (C) particulate zinc oxide with a specific surface area of 10-100 m/g. A mass ratio (A)/(B) of the component (A) to the component (B) is 0.1-50.

Description

  The present invention relates to an oil-in-water emulsified cosmetic.

  Various thickeners are used to maintain the shape retention and stability of cosmetics. For example, Patent Document 1 and Patent Document 2 describe a viscosity modifier having a specific urethane bond, and it is described that a composition containing the same maintains a constant viscosity even with changes in temperature and pH. Yes. Patent Document 3 describes that a cosmetic composition containing such a viscosity modifier is excellent in viscosity stability and usability.

JP-A-9-71766 JP 2000-239649 A JP 2000-239120 A

  The present inventor has found that, with a viscosity adjuster that has been used in the past, the viscosity of the cosmetic is high, but unevenness occurs after application, and when the foundation is overlaid, the foundation is overlaid for 6 hours. I found out that there is a problem with the makeup of the makeup.

  When the present inventors use a specific poly (N-acylalkylenimine) -modified organopolysiloxane, a hydrophobic-modified polyether urethane, and fine-particle zinc oxide in combination at a specific ratio, the oil-in-water emulsification that solves the above-mentioned problems is achieved. We found that cosmetics can be obtained.

The present invention includes the following components (A), (B) and (C):
(A) At least two silicon atoms of the organopolysiloxane segment constituting the main chain, via an alkylene group containing a hetero atom, the following general formula (1);

(Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and t represents 2 or 3)
An organopolysiloxane formed by bonding poly (N-acylalkylenimine) segments composed of repeating units represented by:
The number average molecular weight of the poly (N-acylalkylenimine) segment is 500 to 4000,
The mass average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 1000-40000,
0.1 to 15% by mass of an organopolysiloxane in which the mass average molecular weight of the organopolysiloxane segment constituting the main chain is 15000 to 200000,
(B) The following general formula (5):

(In the formula, R ¹¹ , R ¹² and R ¹⁴ are the same or different and each represents a hydrocarbon group, R ¹³ represents a hydrocarbon group which may have a urethane bond, and R ¹⁵ represents a linear or branched chain. Or a secondary hydrocarbon group, m represents a number of 2 or more, h represents a number of 1 or more, and k and n independently represent a number of 0 to 1000)
0.05 to 5% by mass of a hydrophobically modified polyether urethane represented by
(C) Oil-in-water emulsification containing fine particle zinc oxide having a specific surface area of 10 to 100 m ² / g and having a mass ratio (A) / (B) of components (A) and (B) of 0.1 to 50 Regarding cosmetics.

  The oil-in-water emulsified cosmetic of the present invention is excellent in shape retention, spreads well on the skin during application, has a fresh feeling of use and is not sticky, and suppresses uneven play. In addition, the sponge is prevented from being caught when the foundation is overlaid, and the spread of the overlaid foundation is excellent. Even after 6 hours of overcoating with the foundation, the unevenness is suppressed and the makeup and powder floating are not noticeable.

  Component (A) used in the present invention is represented by the following general formula (1) via an alkylene group containing a hetero atom in at least two silicon atoms of the organopolysiloxane segment constituting the main chain;

(Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and t represents 2 or 3)
An organopolysiloxane formed by bonding poly (N-acylalkylenimine) segments composed of repeating units represented by:
The number average molecular weight of the poly (N-acylalkylenimine) segment is 500 to 4000,
The mass average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 1000-40000,
The organopolysiloxane segment constituting the main chain is an organopolysiloxane having a mass average molecular weight of 15,000 to 200,000, and more excellent stability can be obtained by using this component.

  The poly (N-acylalkyleneimine) segment is bonded to any silicon atom constituting the organopolysiloxane segment via an alkylene group containing a hetero atom. Further, it is preferably bonded to one or more silicon atoms excluding both ends of the organopolysiloxane segment via the alkylene group, and bonded to two or more silicon atoms excluding both ends via the alkylene group. More preferably. That is, the organopolysiloxane of component (A) is a graft polymer having a poly (N-acylalkylenimine) segment composed of at least two or more repeating units represented by the general formula (1) as a side chain. is there.

The alkylene group containing a hetero atom functions as a linking group for the poly (N-acylalkylenimine) segment. Examples of the alkylene group include C2-C20 alkylene groups containing 1 to 3 nitrogen atoms, oxygen atoms or sulfur atoms, and are represented by any of the following formulas (i) to (vii). A group represented by the following formula (i) or (ii) is more preferred, and a group represented by the following formula (i) is more preferred. In the formula, An ⁻ represents a counter ion of a quaternary ammonium salt, for example, ethyl sulfate ion, methyl sulfate ion, chloride ion, iodide ion, sulfate ion, p-toluenesulfonate ion, perchlorate ion. Is exemplified.

In the N-acylalkyleneimine unit constituting the poly (N-acylalkylenimine) segment, in the general formula (1), examples of the alkyl group having 1 to 3 carbon atoms in R ¹ include a straight chain having 1 to 3 carbon atoms. Examples include a chain alkyl group or a branched or alkyl group having 3 carbon atoms, and specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

  In the general formula (1), t represents a number of 2 or 3, and is preferably 2 from the viewpoint of obtaining raw materials when producing the organopolysiloxane.

The mass ratio (a / b) between the organopolysiloxane segment (a) constituting the main chain and the poly (N-acylalkyleneimine) segment (b) is excellent in shape retention and spreads to the skin during application. 45/55 to 79/21 is preferable from the viewpoint that the stickiness is good, the stickiness is not noticeable, and the playing unevenness is suppressed, and 60/40 to 79 is preferable from the viewpoint that unevenness with time and unevenness of makeup are suppressed. / 21 is more preferable.
In this specification, the mass ratio (a / b) is determined by dissolving 5% by mass of the organopolysiloxane of component (A) in deuterated chloroform, and analyzing it by nuclear magnetic resonance ( ¹ H-NMR) analysis. The value obtained from the integral ratio of the alkyl group or phenyl group in the segment and the methylene group in the poly (N-acylalkylenimine) segment.

  In the organopolysiloxane of component (A), the mass average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments (hereinafter also simply referred to as “MWg”) is in the range of 1000 to 40000, From the point of the softness | flexibility of a film | membrane and the orientation to an oil-water interface, More preferably, it is 1500-30000, More preferably, it is 2000-10000.

In the present specification, the “organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments” means an organopolysiloxane of a poly (N-acylalkylenimine) segment as shown in the following formula (2). A portion surrounded by a broken line between two points from a bonding point to the segment (bonding point A) to a bonding point (bonding point B) of the poly (N-acylalkyleneimine) segment adjacent thereto, A segment composed of R ² SiO units, one R ³ and y + 1 (R ² ) ₂ SiO units. The “poly (N-acylalkylenimine) segment” refers to —Z—R ⁴ bonded to the above R ³ .

In the general formula (2), each R ² independently represents an alkyl group having 1 to 22 carbon atoms or a phenyl group, R ³ represents an alkylene group containing a hetero atom, and —Z—R ⁴ represents poly (N— Acylalkylimine) segment, R ⁴ represents the residue of the polymerization initiator, and y represents a positive number.

  MWg is the molecular weight of the portion surrounded by the broken line in the above general formula (2), but is understood as the mass (g / mol) of the organopolysiloxane segment per mole of the poly (N-acylalkylenimine) segment. Can do. In addition, when the functional group of the modified organopolysiloxane that is the raw material compound is 100% substituted with poly (N-acylalkyleneimine), it matches the functional group equivalent (g / mol) of the modified organopolysiloxane.

  The poly (N-acylalkylenimine) segment is represented by a number average molecular weight, and is calculated from the molecular weight of N-acylalkyleneimine units and the degree of polymerization, or gel permeation chromatography (hereinafter also simply referred to as “GPC”). ) It can be measured by the measuring method. In the present invention, the polystyrene-equivalent number average molecular weight (hereinafter, also simply referred to as “MNox”) measured by GPC measurement performed under the measurement conditions described later is used. When the MNox is in the range of 500 to 4000, the flexibility of the film and the solubility in the solvent can be increased. From this viewpoint, the MNox is preferably 800 to 3500, more preferably 1000 to 3000.

The MWg can be obtained by the following formula (I) using the content (mass%) of the organopolysiloxane segment constituting the main chain (hereinafter also simply referred to as “Csi”).
MWg = Csi × MNox / (100−Csi) (I)

  The mass average molecular weight (hereinafter also simply referred to as “MWsi”) of the organopolysiloxane segment constituting the main chain is 15000 to 200000, and preferably 20000 to 16000, more preferably from the viewpoint of flexibility and adhesion to the skin. 25,000 to 100,000. The organopolysiloxane of component (A) can be easily blended into various products by dissolving in a polar solvent such as water. Since the organopolysiloxane segment constituting the main chain has a skeleton common to the modified organopolysiloxane that is the raw material compound, MWsi is substantially the same as the mass average molecular weight of the modified organopolysiloxane that is the raw material compound. In addition, the mass average molecular weight of the modified organopolysiloxane which is a raw material compound is measured by GPC under the measurement conditions described later, and converted to polystyrene.

  The weight average molecular weight (hereinafter also simply referred to as “MWt”) of the organopolysiloxane of the component (A) is preferably 25,000 to 200,000, more preferably 30000 to 2,000 from the viewpoint of achieving both adhesion to the skin and emulsion stability. 160000, more preferably 35,000 to 150,000. MWt is a value measured by GPC under the measurement conditions described later and converted to polystyrene.

  In addition to the high elastic modulus and a large deformable amount, the organopolysiloxane of component (A) becomes extremely soft when heated to a temperature range of 50 to 220 ° C., and immediately after the heating is stopped and it returns to room temperature. It has a characteristic thermoplasticity that regains elasticity.

  The organopolysiloxane of component (A) is, for example, the following general formula (3)

(In the formula, R ² represents the same meaning as described above, and R ⁵ and R ⁶ each represent the same group as R ² , or the following formulas (viii) to (xiii)

R ⁷ represents a monovalent group represented by the above formulas (viii) to (xiii), and d represents a number from 91.5 to 1255.0. E represents a number of 2.0 to 62.5]
Modified organopolysiloxane represented by the following general formula (4)

(Wherein R ¹ and t have the same meaning as described above)
Is produced by reacting with a terminal reactive poly (N-acylalkyleneimine) obtained by ring-opening polymerization.

  A polymerization initiator can be used for the ring-opening polymerization of the cyclic imino ether represented by the general formula (4) (hereinafter also simply referred to as “cyclic imino ether (4)”). As the polymerization initiator, a compound having strong electrophilic reactivity, for example, a strong acid such as benzenesulfonic acid alkyl ester, p-toluenesulfonic acid alkyl ester, trifluoromethanesulfonic acid alkyl ester, trifluoroacetic acid alkyl ester, sulfuric acid dialkyl ester, etc. Alkyl esters can be used, and among them, dialkyl sulfate is preferably used.

  Examples of the polymerization solvent include acetates such as ethyl acetate and propyl acetate, ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, halogen solvents such as chloroform and methylene chloride, acetonitrile. , Nitrile solvents such as benzonitrile, aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, etc., among which acetates are preferred Is done. The usage-amount of a solvent is 20-2000 mass parts normally with respect to 100 mass parts of cyclic imino ether (4).

  The polymerization temperature is usually from 30 to 170 ° C., preferably from 40 to 150 ° C., and the polymerization time is not uniform depending on the polymerization temperature or the like, but is usually from 1 to 60 hours.

  When, for example, 2-substituted-2-oxazoline is used as the cyclic imino ether (4), poly (N-acylethyleneimine) of t = 2 in the general formula (1) is obtained, and 2-substituted-dihydro When 2-oxazine is used, in the above general formula (1), poly (N-acylpropyleneimine) having t = 3 is obtained.

  Poly (N-acylalkylenimine) obtained by living polymerization of cyclic iminoether (4) has a reactive group at the terminal. Therefore, the reactive group at the terminal of the poly (N-acylalkylenimine) and the reactive group represented by the above (viii) to (xiii) of the modified organopolysiloxane represented by the general formula (3) By reacting, the organopolysiloxane of component (A) can be obtained.

  In the production method by the living polymerization, the degree of polymerization can be easily controlled by the use amount of the cyclic imino ether (4) and the polymerization initiator as in the theoretical formula (II) shown below, and moreover than the normal radical polymerization. This is effective in that a substantially monodispersed poly (N-acylalkylenimine) having a narrow molecular weight distribution can be obtained.

  The amount of cyclic iminoether (4) used and the amount of polymerization initiator used is preferably such that MNi in formula (II) is 500-4000, more preferably 800-3500, The amount is more preferably 1000 to 3000.

  The mass average molecular weight of the modified organopolysiloxane represented by the general formula (3) is preferably 25000 to 200000 from the viewpoint of the solubility of the resulting organopolysiloxane in a polar solvent such as water and the ease of handling after dissolution. More preferably, it is 30000-160000, More preferably, it is 35000-150,000.

Further, the functional group equivalent of the modified organopolysiloxane represented by the general formula (3) has an upper limit to satisfy the mass ratio (a / b) and MWg of the organopolysiloxane of the component (A). From this viewpoint and the viewpoint of imparting appropriate hydrophobicity to the main chain, the functional group equivalent is preferably 1000 to 40000, more preferably 1500 to 30000, and still more preferably 2000 to 10000. Here, the functional group equivalent of the modified organopolysiloxane represented by the general formula (3) is the mass average molecular weight of the modified organopolysiloxane represented by the general formula (3). This is the value divided by the average value of the number of R ⁷ possessed around.

  The amount of the modified organopolysiloxane represented by the general formula (3) and the terminal reactive poly (N-acylalkyleneimine) is the mass ratio (modified organopolysiloxane / terminal reactive poly (N-acylalkylene). The imine)) is preferably in the range of 45/55 to 79/21 from the viewpoint of the elastic modulus and the deformable amount of the resulting organopolysiloxane. From the same viewpoint, 60/40 to 79/21 is more preferable. preferable.

  In the present invention, in the synthesis of each organopolysiloxane, various molecular weights were measured according to the following measurement conditions.

<Measurement conditions of mass 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

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

In addition, ¹ H-NMR measurement for calculating the mass ratio (a / b) was performed under the following conditions.
^<1 H-NMR measurement conditions>
The composition of the obtained polymer was confirmed by ¹ H-NMR (manufactured by 400 MHz Varian).
A sample amount of 0.5 g dissolved in 2 g of a measurement solvent (deuterated chloroform) was measured.
PULSE SEQUENCE
・ Relax.delay: 30 seconds ・ Pulse: 45degrees ・ Number of integration: 8 times Confirmation peak around 0ppm: Methyl group of polydimethylsiloxane,
Around 3.4ppm: Methylene part of ethyleneimine.
The ratio of silicone to poly (N-propionylethyleneimine) was calculated from each integrated value.

  Examples of the component (A) organopolysiloxane include poly (N-formylethyleneimine) organosiloxane, poly (N-acetylethyleneimine) organosiloxane, and poly (N-propionylethyleneimine) organosiloxane.

  Component (A) can be used alone or in combination of two or more, has excellent shape retention, spreads to the skin during application, has good stickiness, and suppresses stickiness with a fresh feeling of use, so the content is The total composition is 0.1% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, 15% by mass or less, preferably 12% by mass or less, and more preferably 10% by mass or less. . Moreover, content of a component (A) is 0.1-15 mass% in all the compositions, 1-12 mass% is preferable, and 2-10 mass% is more preferable.

The component (B) hydrophobically modified polyether urethane used in the present invention is represented by the general formula (5).
The hydrophobically modified polyether urethane represented by the general formula (5) is, for example, one or more polyether polyols represented by R ¹¹ -[(O—R ¹² ) _k —OH] _m , R ¹³ - and one or more polyisocyanates represented by (NCO) _{h + 1,} HO- and one or more polyether monoalcohols represented by (R ¹⁴ -O) _n -R ¹⁵ It can be obtained by reacting.

In this case, the general formula (5) R ¹¹ ~R ¹⁵ in the used ^{R 11 - [(O-R} 12) k -OH] m, R 13 - (NCO) h + 1, HO- (R 14 -O) It is determined by the _n -R ^15. The charge ratio of the three members is not limited, but the ratio of the hydroxyl group derived from polyether polyol and polyether monoalcohol to the isocyanate group derived from polyisocyanate is NCO / OH = 0.8: 1 to 1.4: 1. Preferably there is.

The polyether polyol represented by R ¹¹ — [(O—R ¹² ) _k —OH] _m is not limited as long as it is a polyether of m-valent alcohol. Such a compound can be obtained by addition polymerization of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide or the like to m-valent polyol.

  Here, as the polyol, those having 2 to 8 valences (m = 2 to 8) are preferable, for example, dihydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol and neopentyl glycol; glycerin and trioxy Isobutane, 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-pentanetriol, trimer Trivalent alcohols such as roll ethane and trimethylolpropane; pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol Tetrahydric alcohols such as 1,3,4,5-hexanetetrol; pentahydric alcohols such as adnit, arabit and xylit; hexahydric alcohols such as dipentaerythritol, sorbit, mannitol and exit; 8 such as sucrose And monohydric alcohols.

R ¹² is preferably a hydrocarbon group having 2 to 15 carbon atoms, and R ¹² is determined by the alkylene oxide, styrene oxide or the like to be added. Alkylene oxide or styrene oxide having 2 to 4 carbon atoms is preferable in order to easily obtain and exhibit an excellent effect.

Alkylene oxide, styrene oxide and the like to be added may be either homopolymerization, two or more kinds of random polymerization, or block polymerization, and the addition method may be a normal method. The degree of polymerization k is 0 to 1000, preferably 1 to 500, and more preferably 10 to 200. The ratio of ethylene to total R ¹² of preferably 50 to 100 wt% of the total R ^12, and more preferably 65 to 100 wt%.

R ¹¹ is preferably a hydrocarbon group having 2 to 15 carbon atoms, and k is preferably 10 to 200.
The polyether polyol represented by R ¹¹ — [(O—R ¹² ) _k —OH] _m preferably has a molecular weight of 500 to 100,000, more preferably 1,000 to 50,000.

R ¹³ - (NCO) a polyisocyanate represented by _{h + 1} is not limited as long as it has two or more isocyanate groups in the molecule, for example, aliphatic diisocyanates, aromatic diisocyanates, alicyclic diisocyanates, biphenyl Examples include diisocyanate, phenylmethane diisocyanate, triisocyanate, and tetraisocyanate.

  Examples of the aliphatic isocyanate 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 Isocyanate Include tetramethylxylylene diisocyanate and the like.

  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 biphenyl diisocyanate include biphenyl diisocyanate, 3,3′-dimethylbiphenyl diisocyanate, 3,3′-dimethoxybiphenyl diisocyanate, and the like.

  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 include 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, 1,3,7-naphthalene triisocyanate, and 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 (isocyanatephenyl) thiophosphate, etc. Is mentioned.

Moreover, you may use with the dimer and trimer (isocyanurate coupling | bonding) of these polyisocyanate compounds, and you may make it react with an amine and use it as a biuret.
Further, polyisocyanates having urethane bonds obtained by reacting these polyisocyanate compounds with polyols can also be used. As a polyol, the thing of 2-8 valence is preferable, and the above-mentioned polyol is preferable. In addition, when using polyisocyanate more than trivalence as R _< ¹³ _> -(NCO) _{h + 1} , the polyisocyanate which has this urethane bond is preferable. h is preferably 1 or 2.

The polyether monoalcohol represented by HO— (R ¹⁴ —O) _n —R ¹⁵ is not limited as long as it is a linear, branched or secondary monohydric alcohol polyether. Such a compound can be obtained by addition polymerization of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide or the like to a linear, branched or secondary monohydric alcohol.

  The linear alcohol is represented by the following general formula (6), the branched chain alcohol is represented by the general formula (7), and the secondary monohydric alcohol is represented by the general formula (8). Is.

(Wherein R ¹⁶ , R ¹⁷ , R ¹⁸ , R ²⁰ and R ²¹ represent a hydrocarbon group or a fluorocarbon group, and R ¹⁹ represents a divalent hydrocarbon group or a fluorocarbon group)

Accordingly, R ¹⁵ is a group obtained by removing a hydroxyl group in the above general formulas (6) to (8).
In the general formulas (6) to (8), R ¹⁶ , R ¹⁷ , R ¹⁸ , R ²⁰ and R ²¹ are a hydrocarbon group or a fluorocarbon group, and examples thereof include an alkyl group, an alkenyl group, an alkylaryl group, a cyclo An alkyl group, a cycloalkenyl group, etc. are mentioned.

  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 alkylaryl groups include phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonyl Examples include phenyl, α-naphthyl, β-naphthyl group and the like.

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

In the general formula (7), R ¹⁹ is a divalent hydrocarbon group or a fluorocarbon group, and examples thereof include an alkylene group, an alkenylene group, an alkylarylene group, a cycloalkylene group, and a cycloalkenylene group.

R ¹⁵ is preferably a linear, branched or secondary hydrocarbon group having 8 to 36 carbon atoms, more preferably a hydrocarbon group having 12 to 24 carbon atoms, and still more preferably an alkyl group.

R ¹⁴ is preferably a hydrocarbon group having 2 to 15 carbon atoms, and the alkylene oxide and styrene oxide to be added may be either homopolymerization, random polymerization of two or more types, or block polymerization, and the addition method is usually It may be the method of. The degree of polymerization n is 0 to 1000, preferably 1 to 200, and more preferably 10 to 200. The ratio of ethylene to total R ¹⁴ of preferably 50 to 100 wt% of the total R ^14, and more preferably 65 to 100 wt%.

  The method for producing the compound represented by the general formula (5) can be the same as the reaction of an ordinary polyether and isocyanate. For example, the reaction is carried out by heating at 80 to 90 ° C. for 1 to 3 hours. Can be obtained.

In addition, a polyether polyol (a) represented by R ¹¹ — [(O—R ¹² ) _k —OH] _m , a polyisocyanate (b) represented by R ¹³ — (NCO) _{h + 1} , and HO— ( When the polyether monoalcohol (c) represented by R ¹⁴ —O) _n —R ¹⁵ is reacted, other than the compound having the structure of the general formula (5) may be by-produced. For example, when diisocyanate is used, as the main product, a compound of the cb-a-b-c type represented by the general formula (5) is obtained. Compounds such as -b- (ab) _x -abc type may be by-produced. In this case, the compound of the general formula (5) type can be used in the form of a mixture containing the compound of the general formula (5) type without separation.

As the component (B), in general formula (5), R ¹¹ , R ¹² and R ¹⁴ represent a hydrocarbon group having 2 to 15 carbon atoms, and R ¹³ may have a urethane bond. R ¹⁵ represents a linear, branched or secondary hydrocarbon group having 8 to 36 carbon atoms, m represents a number of 2 to 8, h represents 1 or 2, and k and n are independent. Hydrophobically modified polyether urethane having a number of 10 to 200 is preferred.
Furthermore, a (PEG-240 / decyltetradeces-20 / hexamethyl diisocyanate) copolymer is preferable, and commercially available products such as Adecanol GT-700 (manufactured by ADEKA) can be used.

  Component (B) can be used singly or in combination of two or more. From the point of producing an elastic gel, the content is 0.05% by mass or more in the total composition, and 0.1% by mass or more. 0.5 mass% or more is more preferable, 5 mass% or less is preferable, 4 mass% or less is preferable, and 2 mass% or less is more preferable. Moreover, content of a component (B) is 0.05-5 mass% in the whole composition, 0.1-4 mass% is preferable, and 0.5-2 mass% is more preferable.

  In the present invention, the mass ratio (A) / (B) of the components (A) and (B) is excellent in shape retention, spreads on the skin during application, has good stickiness, and has no stickiness with a fresh feeling of use. Uneven playing is suppressed. In addition, the sticking of the sponge when the foundation is overlaid is suppressed, the spread of the overlaid foundation is excellent, and even after 6 hours of overcoating with the foundation, unevenness is suppressed and the makeup and powder floating are not noticeable. Therefore, it is 0.1 or more, preferably 1 or more, more preferably 2 or more, 50 or less, preferably 20 or less, and more preferably 15 or less. Moreover, mass ratio (A) / (B) of component (A) and (B) is 0.1-50, 1-20 are preferable and 2-15 are more preferable.

Particulate zinc oxide component (C) used in the present invention has a specific surface area be of 10 to 100 m ² / g, preferably from 15~95m ² / g. By using the fine particle zinc oxide having such a specific surface area, the cosmetic durability is excellent and a good feeling of use can be obtained.

  The finely divided zinc oxide of component (C) can be used as it is, but if necessary, water repellency and / or repellency with silicone, metal soap, lecithin, N-acylamino acid, fluorine compound, alkylalkoxysilane and the like. The oil-treated one can also be used. In view of preventing disintegration and improving dispersibility of fine zinc oxide in cosmetics, those treated with silicone or alkylalkoxysilane are preferred, and treated with methylhydrogenpolysiloxane; octyltriethoxysilane, It is more preferable to perform alkylalkoxysilane treatment using octyltrimethoxysilane, and it is more preferable to perform octyltriethoxysilane or octyltrimethoxysilane treatment. These processes can be performed by a normal method.

  The processing amount of the water and / or oil repellent treatment is preferably 0.1% by mass or more, more preferably 1% by mass or more, and more preferably 3% by mass with respect to 100% by mass of the fine particle zinc oxide of the component (C). % Or more is more preferable. The upper limit is preferably 30% by mass or less, more preferably 10% by mass or less, and further preferably 7% by mass or less. Taking these viewpoints together, the amount of water and / or oil repellent treatment is preferably 0.1 to 30% by mass with respect to 100% by mass of the fine particle zinc oxide of the component (C). 10 mass% is more preferable, and 3-7 mass% is further more preferable. With this treatment amount, the dispersibility of the fine particle zinc oxide is improved, the unevenness during application is suppressed, and the cover finish has a covering power, but it does not become thick and a natural finish can be obtained.

  Component (C) can be used singly or in combination of two or more. From the standpoint of superior makeup, the content is preferably 0.01% by mass or more, more preferably 0.1% by mass or more in the total composition. Preferably, 1% by mass or more is more preferable, 20% by mass or less is preferable, 15% by mass or less is more preferable, and 8% by mass or less is further preferable. Moreover, 0.01-20 mass% is preferable in the whole composition, as for content of a component (C), 0.1-15 mass% is more preferable, and 1-8 mass% is still more preferable.

  In the present invention, the mass ratio (C) / (B) of the components (B) and (C) suppresses the sponge from being stuck on the foundation, is excellent in spreading the foundation, and is overlaid with the foundation. Even after 6 hours, the unevenness is suppressed, makeup is not more noticeable, and powder floating is not more noticeable, preferably 0.02 or more, more preferably 0.5 or more, further preferably 1 or more, preferably 200 or less, 50 or less is more preferable, and 12 or less is still more preferable. Moreover, 0.02-200 are preferable, as for the mass ratio (C) / (B) of a component (B) and (C), 0.5-50 are more preferable, and 1-12 are still more preferable.

  The oil-in-water emulsified cosmetic of the present invention can further contain (D) an oil agent that is liquid at 25 ° C. Here, the liquid state means that the viscosity at 25 ° C. is 10,000 mPa · s or less. Viscosity was measured using a B-type viscometer (VISCOMETER TVB-10, manufactured by Toki Sangyo Co., Ltd.), Rotor No. It is measured at 4, 12 rpm for 1 minute.

Such a liquid oil agent is not limited as long as it is usually used in cosmetics. For example, linear or branched hydrocarbon oils such as liquid paraffin, light isoparaffin, liquid isoparaffin, squalane, squalene; jojoba oil Vegetable oil such as olive oil, animal oil such as liquid lanolin, ester oil such as monoalcohol fatty acid ester and polyhydric alcohol fatty acid ester; dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, higher alcohol modified Examples include silicone oils such as organopolysiloxanes; fluorine oils such as fluoropolyethers, perfluoroalkyl ether silicones, and fluorine-modified silicones.
Among these, liquid paraffin, light isoparaffin, liquid isoparaffin, squalane, octyl paramethoxycinnamate, diisostearyl malate, glyceryl tri-2-ethylhexanoate, neopentyl glycol dicaprate, dimethylpolysiloxane, dimethylcyclopolysiloxane Fluorine-modified silicone is preferred.
Among the components (D), as the fluorine-modified silicone, the following general formulas (9) and (10):

(In the formula, Rf represents a straight-chain or branched perfluoroalkyl group having 6 carbon atoms, and R ²² , R ²³ and R ²⁴ are the same or different and each represents a straight-chain or branched chain having 1 to 6 carbon atoms. Represents an alkyl group, v represents a number of 2 to 6, w represents a number of 1 to 6, p represents a number of 3 to 50, s represents a number of 1 to 5, and the ratio of p and s Is 0.66 ≦ p / (p + s) ≦ 0.9)
A fluorine-modified silicone having a polysiloxane unit represented by

In the formula, examples of the alkyl group represented by R ²² , R ²³ and R ²⁴ include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; an isopropyl group, sec- Examples thereof include branched alkyl groups such as butyl group, tert-butyl group, neopentyl group and 1-ethylpropyl group; cyclic alkyl groups such as cyclopentyl and cyclohexyl.

Moreover, v shows the number of 2-6, Preferably it is 2-5, More preferably, it is 3. w shows the number of 1-6, Preferably it is 1-4, More preferably, it is 2.
p shows the number of 3-50, Preferably it is 3-10, More preferably, it is 3-6. s shows the number of 1-5, Preferably it is 1-3, More preferably, it is 1.

  The ratio of p and s, that is, the modification rate of the polysiloxane unit p represented by the general formula (9) with respect to the total p + s of the polysiloxane units represented by the general formulas (9) and (10) is used. 0.66 ≦ p / (p + s) ≦ 0.9, and 0.75 ≦ from the viewpoint that it is excellent in feeling and makeup, is less likely to cause uneven appearance, and is less likely to cause uneven application after the cosmetic is applied. p / (p + s) ≦ 0.83 is preferable.

Such a fluorine-modified silicone can be produced, for example, according to the method described in JP-A-6-184212.
As the fluorine-modified silicone, those represented by the following general formula (11) are preferable.

(Wherein p and s have the same meaning as described above, and q represents a number of 5)

  The component (D) is preferably a fluorine-modified silicone, more preferably a fluorine-modified silicone having a polysiloxane unit represented by the general formulas (9) and (10), and a fluorine-modified silicone represented by the general formula (11). Silicone is more preferred.

  Component (D) can be used singly or in combination of two or more. From the viewpoint of good usability and finish, the content is preferably 1% by mass or more, more preferably 4% by mass or more in the total composition. 8 mass% or more is further preferable, 50 mass% or less is preferable, 40 mass% or less is more preferable, and 25 mass% or less is still more preferable. Moreover, 1-50 mass% is preferable in the whole composition, as for content of a component (D), 4-40 mass% is more preferable, and 8-25 mass% is still more preferable.

The oil-in-water emulsified cosmetic of the present invention can further contain (E) ethanol.
The content of ethanol is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, more preferably 20% by mass or less, and preferably 15% by mass in the total composition in terms of excellent usability. The following is more preferable, and 10 mass% or less is still more preferable. The ethanol content is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and still more preferably 3 to 10% by mass in the total composition.

  In the present invention, the content of water is preferably 1% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and 90% by mass or less in the total composition from the viewpoint of creating a balanced emulsion system. Is preferable, 80 mass% or less is more preferable, and 75 mass% or less is still more preferable. Moreover, 1-90 mass% is preferable in the whole composition, as for content of water, 30-80 mass% is more preferable, and 40-75 mass% is still more preferable.

  The oil-in-water emulsification of the present invention can further contain a powder other than the component (C). Such powders are not limited as long as they are extender pigments and coloring pigments used in ordinary cosmetics. For example, silicic acid, silicic anhydride, magnesium silicate, talc, sericite, mica, kaolin, clay, bentonite , Titanium coated mica, bismuth oxychloride, zirconium oxide, magnesium oxide, titanium oxide, zinc oxide other than component (C), aluminum oxide, calcium sulfate, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, bengara, yellow iron oxide , Black iron oxide, ultramarine, chromium oxide, chromium hydroxide, calamine and carbon black, inorganic powders such as these composites; polyamide, polyester, polypropylene, polystyrene, polyurethane, vinyl resin, urea resin, phenol resin, fluorine resin , Silicon resin, acrylic resin, Organic powders such as lamin resin, epoxy resin, polycarbonate resin, divinylbenzene / styrene copolymer, silk powder, cellulose, long-chain alkyl phosphate metal salt, N-mono long-chain alkyl acyl basic amino acid, and complexes thereof A composite powder of the above inorganic powder and organic powder.

  Powders other than the component (C) can be used as they are, but if necessary, silicone, metal soap, lecithin, N-acylamino acid, fluorine compound, alkylalkoxysilane, tridecafluorooctyltriethoxysilane, etc. According to the above, it is also possible to use those subjected to water and / or oil repellent treatment. In order to prevent disintegration and improve the dispersibility of fine zinc oxide in cosmetics, those treated with silicone, alkylalkoxysilane, and tridecafluorooctyltriethoxysilane are preferred, and methylhydrogenpolysiloxane is used. More preferably, octyltriethoxysilane, alkylalkoxysilane treatment using octyltrimethoxysilane, and tridecafluorooctyltriethoxysilane treatment, more preferably octyltriethoxysilane, octyltrimethoxysilane treatment. Further preferred. These processes can be performed by a normal method.

  The amount of water and / or oil repellent treatment varies depending on the type of powder other than the component (C), but the lower limit is 0.1% by mass with respect to 100% by mass of the powder other than the component (C). The above is preferable, 0.5 mass% or more is more preferable, and 1 mass% or more is more preferable. The upper limit is preferably 30% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. Taking these viewpoints together, the amount of water and / or oil repellent treatment is preferably 0.1 to 30% by mass with respect to 100% by mass of the powder other than the component (C). 10 mass% is more preferable, and 1-5 mass% is further more preferable. With this amount of treatment, unevenness during application can be suppressed, and although there is a covering power, a thick finish can be obtained and a natural finish can be obtained.

The powder other than the component (C) preferably has an average particle size of 0.01 to 50 μm, preferably 0.1 to 20 μm from the viewpoint of suppressing the powderiness at the time of application and improving the finish. More preferably.
The particle size of the powder other than the component (C) is measured by an electron microscope observation and a particle size distribution measuring device by a laser diffraction / scattering method. Specifically, in the case of the laser diffraction / scattering method, measurement is performed with a laser diffraction / scattering particle size distribution analyzer (for example, LA-920, manufactured by Horiba, Ltd.) using ethanol as a dispersion medium.

  Powders other than component (C) can be used singly or in combination of two or more, and are excellent in water resistance, sebum resistance, and long-lasting makeup, and in terms of finish and stability, the content is in the total composition 0.01 mass% or more is preferable, 1 mass% or more is more preferable, 3 mass% or more is further preferable, 30 mass% or less is preferable, 25 mass% or less is more preferable, 20 mass% or less is more preferable, 12 The mass% or less is still more preferable. Moreover, 0.01-30 mass% is preferable in the whole composition, and, as for content of powder other than a component (C), 1-25 mass% is more preferable, 3-20 mass% is more preferable, 3-12 A mass% is even more preferable.

  The oil-in-water emulsified cosmetic of the present invention is a component used in ordinary cosmetics in addition to the above components, as long as the effects of the present invention are not impaired, for example, oily components other than those described above, surfactants, polyhydric alcohols , Preservatives, antioxidants, pigments, thickeners other than component (B), pH adjusters, fragrances, UV absorbers other than those mentioned above, moisturizers, blood circulation promoters, cooling agents, antiperspirants, bactericides , Skin activator and the like can be contained.

The oil-in-water emulsified cosmetic of the present invention can be produced by a usual method, and can be made into a liquid form, an emulsion form, a paste form, a cream form, a gel form, etc. preferable.
Further, the oil-in-water emulsified cosmetic of the present invention comprises a makeup base, foundation, concealer; makeup cosmetics such as blusher, eyeshadow, mascara, eyeliner, eyebrow, overcoat agent, lipstick, etc .; sunscreen emulsion, suntan It can be applied as UV protection cosmetics such as a stop cream. Among these, a makeup base, a liquid foundation, and a concealer are more preferable.
The oil-in-water emulsified cosmetic of the present invention can be used in the case of using only a single product or in the case of overlaying powder cosmetics such as liquid foundation, powder foundation, and white powder.
This invention discloses the following compositions further regarding embodiment mentioned above.

<1> The following components (A), (B) and (C):
(A) At least two silicon atoms of the organopolysiloxane segment constituting the main chain, via an alkylene group containing a hetero atom, the following general formula (1);

(Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and t represents 2 or 3)
An organopolysiloxane formed by bonding poly (N-acylalkylenimine) segments composed of repeating units represented by:
The number average molecular weight of the poly (N-acylalkylenimine) segment is 500 to 4000,
The mass average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 1000-40000,
0.1 to 15% by mass of an organopolysiloxane in which the mass average molecular weight of the organopolysiloxane segment constituting the main chain is 15000 to 200000,
(B) The following general formula (5):

(In the formula, R ¹¹ , R ¹² and R ¹⁴ are the same or different and each represents a hydrocarbon group, R ¹³ represents a hydrocarbon group which may have a urethane bond, and R ¹⁵ represents a linear or branched chain. Or a secondary hydrocarbon group, m represents a number of 2 or more, h represents a number of 1 or more, and k and n independently represent a number of 0 to 1000)
0.05 to 5% by mass of a hydrophobically modified polyether urethane represented by
(C) Oil-in-water emulsification containing fine particle zinc oxide having a specific surface area of 10 to 100 m ² / g and having a mass ratio (A) / (B) of components (A) and (B) of 0.1 to 50 Cosmetics.

<2> The mass ratio (a / b) between the organopolysiloxane segment (a) constituting the main chain of the component (A) and the poly (N-acylalkyleneimine) segment (b) is preferably 45 / The oil-in-water emulsified cosmetic according to <1>, which is 55 to 79/21, more preferably 60/40 to 79/21.
<3> The mass average molecular weight of the organopolysiloxane of the component (A) is preferably 25000 to 200000, more preferably 30000 to 16000, and further preferably 35000 to 150,000. Oil-in-water emulsified cosmetic.
<4> The organopolysiloxane of component (A) is preferably poly (N-formylethyleneimine) organosiloxane, poly (N-acetylethyleneimine) organosiloxane, or poly (N-propionylethyleneimine) organosiloxane. The oil-in-water emulsion cosmetic according to any one of <1> to <3>, wherein poly (N-propionylethyleneimine) organosiloxane is more preferable.
<5> Content of component (A), Preferably it is 1-12 mass% in the whole composition, 2-10 mass% is more preferable, Any one of said <1>-<4>. Oil-in-water emulsified cosmetic.

<6> Component (B) is preferably, in General Formula (5), R ¹¹ , R ¹² and R ¹⁴ represent a hydrocarbon group having 2 to 15 carbon atoms, and R ¹³ has a urethane bond. R ¹⁵ represents a linear, branched or secondary hydrocarbon group having 8 to 36 carbon atoms, m represents a number of 2 to 8, h represents 1 or 2, The oil-in-water emulsified cosmetic according to any one of <1> to <5>, wherein k and n are hydrophobically modified polyether urethanes each independently representing a number of 10 to 200.
<7> The oil-in-water emulsion cosmetic according to any one of <1> to <6>, wherein the component (B) is preferably a (PEG-240 / decyltetradeceth-20 / hexamethyl diisocyanate) copolymer. .
<8> Any of the above <1> to <7>, wherein the content of the component (B) is preferably 0.1 to 4% by mass in the total composition, and more preferably 0.5 to 2% by mass. The oil-in-water emulsified cosmetic according to claim 1.

<9> Any of the above <1> to <8>, wherein the mass ratio (A) / (B) of the components (A) and (B) is preferably 1 to 20 and more preferably 2 to 15 1. The oil-in-water emulsified cosmetic according to 1.
<10> The oil-in-water emulsion cosmetic according to any one of <1> to <9>, wherein the particulate zinc oxide of component (C) preferably has a specific surface area of 15 to 95 m ² / g.
<11> Component (C) is water-repellent and / or oil-repellent treated, preferably treated with silicone or alkylalkoxysilane, and treated with methylhydrogenpolysiloxane; octyl Any one of the above items <1> to <10>, which is preferably treated with alkylalkoxysilane using triethoxysilane and octyltrimethoxysilane, more preferably treated with octyltriethoxysilane and octyltrimethoxysilane. 1. The oil-in-water emulsified cosmetic according to 1.
The treatment amount of the water repellent and / or oil repellent treatment of <12> component (C) is preferably 0.1 to 30% by mass with respect to 100% by mass of fine particle zinc oxide of component (C), 1-10 mass% is more preferable, 3-7 mass% is still more preferable The oil-in-water type emulsion cosmetic as described in said <11>.
The content of <13> component (C) is preferably 0.01 to 20% by mass in the total composition, more preferably 0.1 to 15% by mass, and further preferably 1 to 8% by mass. The oil-in-water emulsified cosmetic according to any one of <1> to <12>.
<14> The mass ratio (C) / (B) of the components (B) and (C) is preferably 0.02 to 200, more preferably 0.5 to 50, and still more preferably 1 to 12. The oil-in-water emulsion cosmetic according to any one of <1> to <13>.

<15> The oil-in-water emulsified cosmetic according to any one of <1> to <14>, further comprising (D) a liquid oil at 25 ° C.
<16> Component (D) is preferably liquid paraffin, light isoparaffin, liquid isoparaffin, squalane, octyl paramethoxycinnamate, diisostearyl malate, glyceryl tri-2-ethylhexanoate, neopentyl glycol dicaprate, The oil-in-water emulsified cosmetic according to <15>, which is dimethylpolysiloxane, dimethylcyclopolysiloxane, or fluorine-modified silicone.
The content of <17> component (D) is preferably 1 to 50% by mass in the total composition, more preferably 4 to 40% by mass, and even more preferably 8 to 25% by mass <15> or <16> The oil-in-water emulsified cosmetic according to <16>.
<18> The oil-in-water emulsified cosmetic according to any one of <1> to <17>, further comprising (E) ethanol.
The content of <19> component (E) is preferably 1 to 20% by mass in the total composition, more preferably 2 to 15% by mass, and still more preferably 3 to 10% by mass. Oil-in-water emulsified cosmetic.

The content of <20> water is preferably 1 to 90% by mass in the total composition, more preferably 30 to 80% by mass, and still more preferably 40 to 75% by mass. The oil-in-water emulsion cosmetic according to any one of <1> to <19>.
<21> The oil-in-water emulsified cosmetic according to any one of <1> to <20>, further containing a powder other than the component (C).
<22> The content of the powder other than the component (C) is preferably 0.01 to 30% by mass in the total composition, more preferably 1 to 25% by mass, and further 3 to 20% by mass. The oil-in-water emulsified cosmetic according to <21>, wherein 3 to 12% by mass is more preferable.

Synthesis Example 1 (Production of poly (N-propionylethyleneimine) -modified silicone)
23.3 g (0.54 mol) of 2-ethyl-2-oxazoline and 127.46 g of ethyl acetate were mixed, and the mixture was dehydrated with 9.0 g of molecular sieve (Zeoram A-4, manufactured by Tosoh Corporation) for 15 hours. went.
Further, 153.7 g of side chain primary aminopropyl-modified polydimethylsiloxane (KF-8003, manufactured by Shin-Etsu Silicone Co., Ltd., mass average molecular weight 40000, amine equivalent 2000) and 31.06 g of ethyl acetate were mixed, and the mixture was molecular sieve 23. .29 g and dehydrated at 28 ° C. for 15 hours.
9.48 g (0.061 mol) of diethyl sulfate was added to the above-mentioned ethyl acetate solution of dehydrated 2-ethyl-2-oxazoline, heated under reflux at 80 ° C. for 8 hours under a nitrogen atmosphere, and terminal reactive poly (N-propionyl). Ethyleneimine) was synthesized. The number average molecular weight measured by GPC was 1300.
To this terminal-reactive poly (N-propionylethyleneimine) solution, the dehydrated side chain primary aminopropyl-modified polydimethylsiloxane solution was added all at once and heated to reflux at 80 ° C. for 10 hours.
The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine-dimethylsiloxane copolymer as a pale yellow rubbery solid (200 g). In the final product, the mass ratio (a / b) of the organopolysiloxane segment (a) constituting the main chain to the poly (N-propionylethyleneimine) segment (b) is 71/29, and the mass average molecular weight is 56000. Met.

Synthesis Example 2 (Production of poly (N-propionylethyleneimine) -modified silicone)
7.57 g (0.049 mol) of diethyl sulfate and 263.3 g (2.66 mol) of 2-ethyl-2-oxazoline were dissolved in 550 g of dehydrated ethyl acetate and heated under reflux for 8 hours under a nitrogen atmosphere. Reactive poly (N-propionylethyleneimine) was synthesized. A 50% ethyl acetate solution of 250 g (0.065 mol in terms of amino group) of side chain primary aminopropyl-modified polydimethylsiloxane (mass average molecular weight 60,000, amine equivalent 3870) was added all at once and heated to reflux for 12 hours. . The number average molecular weight measured by GPC was 5400. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine / dimethylsiloxane copolymer as a pale yellow rubber-like solid (505 g, yield 97%). The mass ratio (a / b) of the organopolysiloxane segment (a) constituting the main chain to the poly (N-propionylethyleneimine) segment (b) in the final product is 51/49, and the mass average molecular weight is 88400. Met.

Synthesis Example 3 (Production of fluorine-modified silicone)

Synthesis of _{C 6 F 13 -CH 2 CH 2} -O-CH 2 CH = CH 2:
To a 2 L four-necked flask equipped with a thermometer and a cooling tube, 800 g (2.2 mol) of FA-6 (Unimatec) and 175.78 g (4.4 mol) of granular NaOH (Wako Pure Chemical Industries) were added. It was. While stirring at 200 rpm with a 12 cm crescent stirring blade made of Teflon (registered trademark) in a nitrogen atmosphere, the temperature in the flask was adjusted to 60 ° C. Thereto, 398.73 g (3.3 mol) of allyl bromide (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 70 ° C. for 1 hour and at 80 ° C. for 1 hour. Thereafter, the temperature was raised to 130 ° C. to remove excess allyl bromide. After cooling to 60 ° C., 800 g of ion-exchanged water was added, stirred for 30 minutes, and then allowed to stand to separate the layers. The upper aqueous layer was extracted, and 800 g of ion-exchanged water was further added, followed by stirring, standing still, and removal of the aqueous layer. Dried at 60 ℃ / 5KPa, 100 ℃ / distilled at 2 KPa, as a fraction, to obtain a _{C 6 F 13 -CH 2 CH 2} -O-CH 2 CH = CH 2 774.9g ( yield: 88 %).

  To a 300 mL four-necked flask equipped with a thermometer, 52.89 g (111 mmol) of hydrogen polysiloxane (Shin-Etsu Chemical Co., Ltd.) represented by the following formula was added, and Teflon (registered trademark) 8 cm crescent moon was added under a nitrogen atmosphere. The mixture was stirred with a blade at 200 rpm, 2% by mass of chloroplatinic acid hexahydrate / isopropyl alcohol 0.66 g was added, and the temperature was raised to 110 ° C.

C ₆ F ₁₃ —CH ₂ CH ₂ —O—CH ₂ CH═CH ₂ 197.11 g (488 mmol) was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 110 ° C. for 2 hours. Thereafter, the temperature was lowered to 70 ° C. 25.07 g of 0.1% NaOH solution was added and stirred for 2 hours. After dehydration at 60 ° C./5 KPa, 2.51 g of carborane 3 (manufactured by Nippon Environmental Chemicals) was added at the same temperature, and the mixture was stirred for 2 hours. The mixture was filtered through a 0.1 μm PTFE membrane filter, and the filtrate was subjected to steam distillation using 100 ° C./5 KPa and 62.5 g of water to obtain 206.3 g of the target compound (yield 89%).

Synthesis Example 4 (Production of polymer powder)
To a 1300 mL beaker, 56 g of lauryl methacrylate, 19 g of ethylene glycol dimethacrylate and 1.5 g of lauroyl peroxide were added to obtain a solution. In addition, (a) titanium oxide having an average particle diameter of 0.25 μm (CR-50, manufactured by Ishihara Sangyo Co., Ltd.), (b) Bengala having an average particle diameter of 0.38 μm (Bengara Cloisonne, manufactured by Morishita Bengala), (c) average Yellow iron oxide (yellow LLXLO, manufactured by Titanium Industry Co., Ltd.) having a particle size of 0.07 × 0.7 μm (because it is needle-shaped) is a ratio of (a) :( b) :( c) = 95: 1: 4 The mixture was mixed and subjected to water repellent treatment (2% with respect to the inorganic powder) using methylhydrogenpolysiloxane. Next, the obtained solution and the inorganic pigment subjected to water repellent treatment were mixed and dispersed so that the inclusion rate was 20% by mass to obtain a dispersion. To this dispersion was added 750 g of a 1% by weight polyvinyl alcohol (GOHSENOL GH-17, manufactured by Nippon Synthetic Chemical Industry) aqueous solution and dispersed using an ultrasonic disperser (the particle size can be controlled by time and strength). The obtained dispersion was added to a 1000 mL separable flask, and then the gas phase in the separable flask was purged with nitrogen. Next, while stirring the dispersion at 150 r / min, polymerization was carried out at 75 ° C. for 8 hours under a nitrogen atmosphere. After completion of the polymerization, the obtained product was filtered to collect a solid, washed with water, and then dried under reduced pressure to obtain 120 g of an inorganic pigment-containing polymer powder.
The obtained polymer powder had a total transmittance of 60% and a haze value of 69. As a result of analyzing the obtained particles using a scanning electron microscope, the shape was substantially spherical, and the average particle size was 10 μm.

Examples 1-19, Comparative Examples 1-7
Manufactures oil-in-water emulsified cosmetics (makeup bases) having the compositions shown in Tables 1 and 2 and maintains shape retention, good spreading during application, good adhesion to the skin, fresh feeling of use, non-stickiness and unevenness Sponge of powder foundation application and good spread, covering power after powder foundation application and natural finish, and non-uniformity after 6 hours of powder foundation application, The absence of powder floating was evaluated. The results are shown in Table 1 and Table 2 together.

(Production method)
After roughly mixing the powder components, the powder components were mixed and pulverized using an Admizer pulverizer (Fuji Paudal). The oil phase component was mixed, and the pulverized powder component was added and dispersed with a disper. Furthermore, the water phase component was mixed and added to the mixture of the oil phase and the powder to emulsify. Thereafter, the viscosity was adjusted with a homomixer to obtain an oil-in-water emulsified cosmetic (makeup base).

(Evaluation method)
Five expert panelists evaluated the “shape retention” when each oil-in-water emulsified cosmetic (makeup base) was placed on the back of the hand, and each oil-in-water emulsified cosmetic (makeup base) was applied to the skin by hand. The following criteria were used to evaluate the “goodness of spread”, “goodness of skin”, “freshness of use”, “non-stickiness”, and “nonuniformity of playing” when applied. A result is shown by the integrated value of 5 persons.

(1) Shape retention:
5; Cosmetics do not collapse when the back of the hand is tilted.
4; Cosmetics do not collapse much when the back of the hand is tilted.
3; Cosmetics collapse slightly when the back of the hand is tilted.
2; Cosmetics collapse when the back of the hand is tilted.
1; Cosmetics flow from the beginning just by placing it on the back of the hand.

(2) Good quality:
5: The spread during application is quite good.
4; Good spreading during application.
3; Slightly good spreading during application.
2; Slightly bad during application.
1: The spread during application is poor.

(3) Good skin contact:
5; Very good adhesion to skin during application.
4; Good adhesion to skin during application.
3: Slightly sticking to the skin during application.
2; poor adhesion to the skin during application.
1; The adhesion to the skin during application is very bad.

(4) Fresh feeling:
5; I feel a lot of freshness during application.
4; Feeling fresh during application.
3; A little freshness is felt during application.
2; Does not feel much freshness during application.
1; Does not feel fresh during application.

(5) No stickiness:
5: No stickiness during application.
4; almost no stickiness during application.
3; Some feel stickiness during application.
2; feels sticky during application.
1: The stickiness during application is considerably felt.

(6) Unevenness of playing:
5; Cosmetics are not flipped on the skin during application.
4; Cosmetics bounce on the skin during application and slight unevenness is seen 3; Cosmetics bounce on the skin during application and slight unevenness is seen 2; Cosmetics on the skin during application Unevenness is noticeable.
1: The cosmetics bounce on the skin during application, and the unevenness is considerably noticeable.

(Evaluation method)
Five professional panelists apply each oil-in-water emulsified cosmetic (makeup base) to the skin by hand, and then apply a powder foundation (Sophina Fine Fit Powder Foundation UV, manufactured by Kao Corporation) with a special sponge. Evaluate “no sponge feeling when applying powder foundation”, “goodness of spreading when applying powder foundation”, “covering power after applying powder foundation”, “natural finish after applying powder foundation” In addition, the following criteria are used: “no unevenness after 6 hours of powder foundation application”, “no makeup after 6 hours of powder foundation application”, “no powder lift after 6 hours of powder foundation application” It was evaluated with. A result is shown by the integrated value of 5 persons.

(7) Sponge is not caught when powder foundation is applied:
5: Feels not caught in the initial stage of application.
4; Almost no initial catching feeling.
3; A slight feeling of catching at the initial stage of application is felt.
2; Feeling a catch at the initial stage of application.
1; A feeling of catching at the initial stage of application is considerably felt.

(8) Good spread when applying powder foundation:
5: The spread during application is quite good.
4; Good spreading during application.
3; The spread during application is slightly good.
2: The spread during application is slightly bad.
1: The spread during application is poor.

(9) Covering power after applying powder foundation:
5; The skin can be covered firmly.
4; Can cover bare skin.
3; The skin can be covered a little.
2; Unable to cover bare skin.
1: The bare skin cannot be covered at all.

(10) Natural finish after powder foundation application:
5: The finish is quite natural.
4; The finish is natural.
3; The finish is somewhat natural.
2; The finish is not so natural.
1: The finish is not natural.

(11) Non-uniformity after 6 hours of powder foundation application:
5; There is no unevenness in the skin.
4; There is not much unevenness in the skin.
3; Somewhat uneven skin.
2; The skin is uneven.
1; Skin unevenness is remarkable.

(12) Poor makeup after 6 hours of powder foundation application:
5; No makeup is seen.
4; Slightly visible makeup 3; Slightly noticeable makeup
2; Shaking makeup is conspicuous.
1; Shaking makeup is very conspicuous.

(13) No powder floating after 6 hours of powder foundation application:
5; Powder floating is not seen 4; Powder floating is slightly seen 3; Powder floating is slightly conspicuous.
2; Powder floating is conspicuous.
1; Powder float is quite conspicuous.

Claims (10)

The following components (A), (B) and (C):
(A) At least two silicon atoms of the organopolysiloxane segment constituting the main chain, via an alkylene group containing a hetero atom, the following general formula (1);

(Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and t represents 2 or 3)
An organopolysiloxane formed by bonding poly (N-acylalkylenimine) segments composed of repeating units represented by:
The number average molecular weight of the poly (N-acylalkylenimine) segment is 500 to 4000,
The mass average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 1000-40000,
0.1 to 15% by mass of an organopolysiloxane in which the mass average molecular weight of the organopolysiloxane segment constituting the main chain is 15000 to 200000,
(B) The following general formula (5):

(In the formula, R ¹¹ , R ¹² and R ¹⁴ are the same or different and each represents a hydrocarbon group, R ¹³ represents a hydrocarbon group which may have a urethane bond, and R ¹⁵ represents a linear or branched chain. Or a secondary hydrocarbon group, m represents a number of 2 or more, h represents a number of 1 or more, and k and n independently represent a number of 0 to 1000)
0.05 to 5% by mass of a hydrophobically modified polyether urethane represented by
(C) Oil-in-water emulsification containing fine particle zinc oxide having a specific surface area of 10 to 100 m ² / g and having a mass ratio (A) / (B) of components (A) and (B) of 0.1 to 50 Cosmetics.   The mass ratio a / b of the organopolysiloxane segment (a) constituting the main chain of the component (A) to the poly (N-acylalkyleneimine) segment (b) is 45/55 to 79/21. Item 1. An oil-in-water emulsified cosmetic according to Item 1. Component (B) is a hydrocarbon group in which R ¹¹ , R ¹² and R ¹⁴ in the general formula (5) represent a hydrocarbon group having 2 to 15 carbon atoms, and R ¹³ may have a urethane bond. R ¹⁵ represents a linear, branched or secondary hydrocarbon group having 8 to 36 carbon atoms, m represents a number of 2 to 8, h represents 1 or 2, and k and n independently The oil-in-water emulsified cosmetic according to claim 1 or 2, which is a hydrophobically modified polyether urethane having a number of 10 to 200.   The mass ratio a / b of the organopolysiloxane segment (a) constituting the main chain of the component (A) and the poly (N-acylalkyleneimine) segment (b) is from 60/40 to 79/21. Item 4. The oil-in-water emulsified cosmetic according to any one of Items 1 to 3.   Content of a component (C) is 0.01-20 mass%, The oil-in-water type emulsified cosmetics of any one of Claims 1-4.   The oil-in-water emulsified cosmetic according to any one of claims 1 to 5, wherein the mass ratio (C) / (B) of the components (B) and (C) is 0.02 to 200.   The oil-in-water emulsion cosmetic according to any one of claims 1 to 6, wherein the component (C) is octyltriethoxysilane or octyltrimethoxysilane-treated fine particle zinc oxide.   The oil-in-water emulsion cosmetic according to claim 7, wherein the amount of octyltriethoxysilane or octyltrimethoxysilane treatment is 0.1 to 30% by mass with respect to 100% by mass of fine particle zinc oxide.   Furthermore, (D) Oil-in-water type emulsified cosmetics of any one of Claims 1-8 containing a liquid oil agent at 25 degreeC.   Furthermore, (E) The oil-in-water type emulsion cosmetics of any one of Claims 1-9 which contain 1 mass% or more of ethanol.