JPH10139623A - Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water- and oil-repellent cosmetic excellent in resistance to sweat and sebum, and highly adhesive to the skin, by compounding a combination of a fluorine-based lubricant with a specific copolymer. SOLUTION: This cosmetic is a combination of (A) pref. 2-98wt.% of a fluorine-based lubricant (pref. perfluoropolyether or fluorinemodified silicone) with (B) a copolymer composed of hydrophilic segment and organopolysiloxane segment and soluble to or dispersible in water or lower alcohol. In this case, the hydrophilic segment in the component B is pref. a terminal-blocked N- acylalkyleneimine, polyalkylene glycol, saccharide-derived residue), and it is preferable that the weight ratio of the hydrophilic segment to organopolysiloxane segment is (1:50) to (20:1) and the weight-average molecular weight of the copolymer 500-500,000. Furthermore, this cosmetic may also be incorporated with hydrophilicized powder.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to water repellency and oil repellency, excellent sweat resistance and sebum resistance, high adhesion to skin, and re-adhesion of cosmetic ingredients to other parts. The present invention relates to a cosmetic that can prevent bleeding.

[0002]

2. Description of the Related Art Conventionally, powders treated with silicone or metal soap or silicone oil such as dimethylpolysiloxane are blended in a blending amount according to the purpose to impart water repellency to cosmetics and to reduce sweat and sweat. Prevention of makeup loss due to moisture. However, there is a problem that makeup is lost for sebum and oil. Therefore, in recent years, as a measure against sebum, a powder or a liquid fluorine compound treated with a fluorine compound has been blended to impart water repellency and oil repellency to cosmetics. However, since fluorine compounds are poorly applied to the skin, no satisfactory cosmetics containing the fluorine compounds and preventing reattachment to other parts have not yet been proposed.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to have water repellency, oil repellency, excellent sweat resistance and sebum resistance,
Another object of the present invention is to provide a cosmetic that has high adhesion to the skin and is difficult to re-adhere to other parts.

[0004]

Under such circumstances, the inventors of the present invention have conducted intensive studies and as a result, have found that a fluorine-containing oil, a hydrophilic segment and an organopolysiloxane, which are dissolved or dispersed in water or a lower alcohol. Cosmetics having water repellency, oil repellency, excellent sweat resistance and sebum resistance and high adhesion to skin by using one or more polymer compounds selected from polymers in combination And completed the present invention.

[0005] That is, the present invention comprises the following components (A) and (B): (A) a fluorinated oil agent (B) a hydrophilic segment and an organopolysiloxane segment, which are dissolved or dispersed in water or a lower alcohol. It is intended to provide a cosmetic containing a polymer.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As the fluorinated oil agent which is the component (A) of the present invention, perfluoropolyethers and fluorine-modified silicones which are liquid at room temperature are preferable, such as perfluorodecalin and perfluorodecalin. Adamantane, perfluorobutyltetrahydrofuran, perfluorooctane, perfluorononane,
Perfluoropentane, perfluorodecane, perfluorododecane, fluorine-modified silicone, general formula (13)

[0007]

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(Wherein R ²¹ , R ²³ , R ²⁴ and R ²⁵ may be the same or different and each represents a fluorine atom, a perfluoroalkyl group or a perfluoroalkyloxy group, and R ²² represents a fluorine atom or a perfluoroalkyloxy group) Represents a fluoroalkyl group, and a, b, and c each represent a number of 0 or more at which the molecular weight becomes 500 to 100,000, provided that a = b = c = 0. Polyether and the like. Here, the perfluoro groups shown in parentheses need not be arranged in this order, and may be random polymerization or block polymerization. As such perfluoropolyether, particularly, the viscosity is 5 to 5,000.
A liquid of 0 cs (centistokes) is preferred,
For example, the following general formula (14)

[0009]

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(Wherein d and e each have a molecular weight of 500 to 1)
It indicates a number that is 0000, and d / e is 0.2 to 2. ) Represented by FOMBLIN HC-04 (average molecular weight 1,500), HC-25 (3,200) and HC-R (6,600) (all manufactured by Montefros)
And the following general formula (15)

[0011]

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Wherein f is a number from 4 to 500. Demnum S-20 (weight average molecular weight 25,000)
0), S-65 (4,500), S-100 (5,600), and S-200 (8,400) (all manufactured by Daikin Industries, Ltd.). Can be.

As the fluorine-modified silicone, for example, a silicone having at least one of the structural units represented by the following general formulas (16) to (19) and a structural unit represented by the following general formula (20) is used. Can be mentioned.

[0014]

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Wherein Rf and Rf ′ are the same or different
And may be a linear or branched chain having 1 to 20 carbon atoms.
-Fluoroalkyl group or the following formula: H (CF_Two)_g− (G is
Represents an integer of 1 to 20).
R represents a cycloalkyl group;²⁶, R ²⁹And R³⁰Are the same or
It may be different, and may be a straight or branched chain having 1 to 20 carbon atoms.
A branched aliphatic hydrocarbon group or an alicyclic group having 5 to 10 carbon atoms
Or an aromatic hydrocarbon group;²⁷Is a hydrogen atom, charcoal
Linear or branched aliphatic hydrocarbon having a prime number of 1 to 20
Group, alicyclic or aromatic hydrocarbon having 5 to 10 carbon atoms
Group, a perfluoroalkyl group having 1 to 20 carbon atoms or
Formula: H (CF_Two)_g-(G represents an integer of 1 to 20)
R—H-perfluoroalkyl group represented by
²⁸Represents a divalent hydrocarbon group having 2 to 6 carbon atoms; X^TwoPassing
And Y^TwoIs a single bond, -CO- or a divalent group having 1 to 6 carbon atoms.
Represents a hydrocarbon group; i represents a number of 2 to 16, j and k
Represents the number of 1 to 16 respectively, and h represents the number of 1 to 200
And w represents a number from 0 to 20, and v represents a number from 0 to 200.
Show)

In the structural units represented by the general formulas (16) to (20), as the perfluoroalkyl group represented by Rf and Rf ', any of a linear or branched chain can be used. , CF _3- , C ₂ F _5- , C ₄ F
_{9 -, C 6 F 13 -} , C 8 F 17 -, C 10 F 21 -, H (CF 2)
_{2 -, H (CF 2)} 4 -, H (CF 2) 6 -, H (CF 2) 8
—, (C ₃ F ₇ ) C (CF ₃ ) ₂ — and the like. Further, _{g in} H (CF ₂ ) _g − is 6 to 2
An integer of 0 is preferred. Examples of the hydrocarbon group represented by R ²⁶ , R ²⁹ and R ³⁰ include direct groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. Branched alkyl group such as isopropyl group, s-butyl group, t-butyl group, neopentyl group, 1-ethylpropyl group, and 2-ethylhexyl group; cyclic alkyl group such as cyclopentyl group and cyclohexyl group; phenylnaphthyl And an aromatic hydrocarbon group such as a group. As the divalent hydrocarbon group represented by R ^28, preferably is a linear or branched alkylene group having 2 to 4 carbon atoms, particularly an ethylene group, a propylene group are preferable.

As the fluorine-modified silicone having such a structural unit, for example, the following general formula (21)

[0018]

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[In the formula, at least one of Z ² and Z ³ represents a structural unit selected from the general formulas (16) to (19), the remainder represents a single bond, and v, R ²⁹ and R ³⁰ are as defined above. Having the same meaning] or the following general formula (2
2)

[0020]

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[Wherein, Z ⁴ is a general formula (16) to (1)
9) a structural unit selected from 9), wherein R ³¹ has 1 to 2 carbon atoms
0 represents a linear or branched aliphatic hydrocarbon group or an alicyclic or aromatic hydrocarbon group having 5 to 10 carbon atoms,
p represents a number of 0 to 200, and v, R ²⁹ and R ³⁰ have the same meanings as described above].

The structural units represented by the general formulas (16) to (20) and the groups in each formula in the fluorine-modified silicone represented by the general formulas (21) and (22) are used to prevent makeup loss and improve usability. In consideration of the following, the following are preferable. Rf and Rf 'each represent a linear or branched perfluoroalkyl group having 6 to 20 carbon atoms or the following formula;
An ω-H-perfluoroalkyl group represented by (CF ₂ ) _q- (q is an integer of 6 to 20) is preferable. R ²⁶ , R
²⁹ and R ³⁰ may be the same or different, and are preferably a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms. R ²⁷ is a hydrogen atom, a perfluoroalkyl group having 6 to 20 carbon atoms, or ω-H-perfluoro represented by the following formula: H (CF ₂ ) _q- (q is an integer of 6 to 20) Alkyl groups are preferred. R ²⁸ has 2 to 4 carbon atoms
Are preferred. X ² and Y ² are preferably a single bond, —CO— or a divalent hydrocarbon group having 1 to 4 carbon atoms, i is preferably a number of 2 to 10, particularly preferably 2 to 5, and j
And k are each preferably a number of 2 to 10, particularly 1 to 6, h is preferably a number of 1 to 100, particularly preferably 1 to 10, w
Is preferably a number of 0 to 20, particularly 0 to 5, and v is 0 to 10.
A number of 0, especially 0-10 is preferred. The general formula (2)
The arrangement of the structural units of the fluorine-modified silicone represented by 2) may be alternate, block or random.

Further, as a preferred example of the fluorine-modified silicone, a polymerization degree of from 2 to 200 described in JP-A-5-247214, having structural units represented by the general formulas (17) and (20), is preferable. Of fluorine-modified silicone,
Japanese Unexamined Patent Application Publication No.
No. 184312, a fluorine-modified silicone having a polymerization degree of 2 to 200, a commercially available FSL manufactured by Asahi Glass Co., Ltd.
-300, Shin-Etsu Chemical's X-22-819, X-
22-820, X-22-821, X-22-822 and FL-100, FS-1265 manufactured by Dow Corning Toray Silicone Co., Ltd., and the like.

These fluorinated oils can be used alone or in combination of two or more. If the total amount of the fluorinated oil is 2 to 98% by weight, more preferably 5 to 60% by weight, the feeling of use will be good, so that it is preferable. .

The copolymer containing the hydrophilic segment and the organopolysiloxane segment of the component (B) and dissolved or dispersed in water or a lower alcohol is not particularly limited, but intermolecular cross-linking is caused by a bond other than a covalent bond. It is a viscous liquid or solid copolymer at normal temperature and normal pressure, and preferably has a physical property that does not cause breakage or plastic deformation at an elongation of 0 to 15% at a temperature of 20 ° C. and a relative humidity of 65%. -It is a copolymer that is solid at normal pressure.
As lower alcohols, C ₁ -C ₆ alcohols are preferred.

The bond other than the covalent bond includes a bond which is easily cleaved in water or a lower alcohol, for example, an ionic bond, a hydrogen bond, a hydrophobic interaction, a dipole-dipole interaction, or a bond by van der Waals attractive force. Although ionic bonding, hydrogen bonding, and dipole-dipole interaction are preferred, the component (B) has one or more functional groups that cause such bonding.

Preferably, the component (B) does not break or undergo plastic deformation when the elongation percentage at a temperature of 20 ° C. and a relative humidity of 65% is in the range of 0 to 15%. Usually, the polymer recovers its original shape when the deformation is small,
It is known that the greater the deformation, the more difficult it is to recover. Such deformation that does not return to its original shape is called plastic deformation. Some hard, brittle polymers break before plastic deformation occurs. Therefore, the above-mentioned properties of the polymer having orientation at the oil-water interface of the present invention need to be rubber elasticity.

Whether or not plastic deformation occurs when the elongation is in the range of 0 to 15% can be confirmed by, for example, a simple experiment as follows. That is, about 0.2 mm thick, 20 mm long,
Prepare a 5mm wide specimen, temperature 20 ℃, relative humidity 65%
While recording the stress-strain curve under the conditions of (1), the crosshead is extended 3 mm (15%) at a crosshead speed of 20 mm / min. Ten minutes later, it was stretched again, and the stress-strain curve at the second stretching was 1
Following the same trajectory as the first curve indicates that it has completely recovered and no plastic deformation has occurred. In contrast,
When plastic deformation occurs, stress is applied with a delay in the second elongation since the first reciprocation has already caused the elongation, and as a result, the stress-strain curve does not follow the same locus.

The component (B) is not particularly limited as long as it causes intramolecular and intermolecular cross-links by bonds other than covalent bonds. It is necessary to have some polar functional group at the terminal or side chain in the polymer, and another polymer compound may be used as a linking group between the organopolysiloxane and the polar functional group.

Examples of such polar functional groups include those having a hydroxyl group such as saccharides and polyvinyl alcohols which generate dipole-dipole interactions, such as N-acylalkyleneimine and pyrrolidone. And C ₁ -C ₄ such as poly (meth) acrylamide, polydimethylacrylamide, polydiethylacrylamide, etc.
A mono- or dialkyl (meth) acrylamide polymer,
Poly-N-morpholine (meth) acrylamide, poly-
Those having an amide group such as N-vinylpyrrolidone, poly-N-vinylacetamide, and polyamino acid are exemplified. Carbobetaine, which produces ionic bonds,
Betaine polymers such as sulfobetaine and phosphobetaine and anionic monomers such as (meth) acrylic acid and N,
N-dimethylaminoethyl (meth) acrylate and N,
Examples include amphoteric ionomers such as copolymers of cationic monomers such as N-dimethylaminopropyl (meth) acrylamide and amine oxides.

In the cosmetic composition of the present invention, particularly in the emulsified cosmetic composition, the component (B) is mixed with water droplets of the W / O emulsion by the action of the hydrophilic segment contained in the component (B) (external phase = oil). Phase) at the interface to prevent coalescence and sedimentation of water droplets. At this time, the component (B) becomes a protective film having an elastic property with respect to water droplets. In the case of a W / O emulsion containing ethanol and silicone oil, component (B) is an elastic protective film against separation due to coalescence or sedimentation of water droplets due to destruction of the interface film, which is likely to occur with a normal emulsifier. In addition, a stable emulsion can be obtained by suppressing coalescence and sedimentation of water droplets.
In order to obtain such a protective film having an elastic property against water droplets, it is preferable that the polymer contains a hydrophilic segment exhibiting a special property.

As the component (B), a protective film for water droplets oriented at the interface between water droplets and an oil phase in a cosmetic and having strong lower alcohol resistance (more silicone resistance when the oil phase contains silicone oil). Is preferably formed. As the component (B) alone, those exhibiting rubber elasticity at normal temperature and normal pressure are preferable, but those which alone do not exhibit rubber elasticity may be substances such as lower alcohols / silicone oils which constitute cosmetics, especially emulsified cosmetics. When alone and at the same time, the physical properties at normal temperature and normal pressure alone are not particularly limited as long as they are oriented at the interface between the water droplet and the oil phase and the same effect can be obtained.

As the hydrophilic segment, specifically, N-acylalkyleneimine, polyalkyleneglycol, polyalkyleneglycol monoalkylether, acrylic acid, methacrylic acid, N, N-dimethylacrylamide, dimethylaminoethyl, whose terminal is blocked Methacrylate, quaternary dimethylaminoethyl methacrylate, methacrylamide, Nt-butylacrylamide, maleic acid, maleic anhydride, maleic anhydride half-esters, crotonic acid, itaconic acid, acrylamide, acrylate alcohols, hydroxyethyl methacrylate, Diallyl dimethyl ammonium chloride, vinyl pyrrolidone, vinyl ethers, vinyl pyridine, vinyl imidazole, styrene sulfonate, allyl alcohol, vinyl alcohol , Vinyl caprolactam, N-
Examples thereof include segments derived from one or more selected from alkylenecarbobetaine and sugar-derived residues. Preferably, N-acylalkyleneimine, polyalkylene glycol, polyalkylene glycol monoalkyl ether, acrylic acid, N, N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternary dimethylaminoethyl methacrylate, vinylpyrrolidone, N-alkylenecarbobetaine and It is derived from one or more selected from those represented by sugar-derived residues.

In the component (B), the weight ratio of the hydrophilic segment to the segment other than the hydrophilic segment (including the organopolysiloxane) is from 1/50 to 20/1, preferably from 1/50 to 20/1. Those having a molecular weight of from 40 to 2/1 and a molecular weight of from 500 to 500,000, preferably from 1,000 to 300,000 are preferred because the effect of the present invention is enhanced. Further, as the hydrophilic segment derived from N-acylalkyleneimine, a compound represented by the formula (1):

[0035]

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Wherein R ¹ is a hydrogen atom and has 1 to 22 carbon atoms.
Represents an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group, and n is 2 or 3. A) a poly (N-acylalkyleneimine) segment comprising a repeating unit represented by the formula (1) and an organopolysiloxane segment, wherein at least one of the terminal or side chain silicon atoms of the organopolysiloxane segment is hetero- It is preferable that the poly (N-acylalkyleneimine) segment composed of the repeating unit represented by the formula (1) is bonded via an alkylene group containing an atom. In such a poly (N-acylalkylenimine) -modified silicone, the weight ratio of the segment of the poly (N-acylalkylenimine) to the segment of the organopolysiloxane is 1/50 to 20/1, preferably 1/40 to 20/1.
A ratio of 2/1 and a molecular weight of 500 to 500,000, preferably 1,000 to 300,000 is preferred because the effect of the present invention is enhanced.

In the formula (1), the cycloalkyl group represented by R ¹ includes one having 3 to 6 carbon atoms; the aralkyl group includes phenylalkyl and naphthylalkyl; the aryl group includes Phenyl, naphthyl, alkyl-substituted phenyl and the like. Examples of the alkylene group containing a heteroatom bonded to at least one silicon atom at the terminal or side chain of the organopolysiloxane segment include a nitrogen atom, an oxygen atom or a sulfur atom having 1 to 3 carbon atoms having 2 to 20 carbon atoms. Examples of the alkylene group include specific examples of the formula (3);

[0038]

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And the group represented by

Preferred examples of the poly (N-acylalkyleneimine) -modified silicone include poly (N-acylalkyleneimine).
Formylethyleneimine) modified silicone, poly (N-
Acetylethyleneimine) modified silicone, poly (N-
Propionylethyleneimine-modified silicone, poly (Nn-octanoylethyleneimine) -modified silicone, poly (Nn-dodecanoylethyleneimine) -modified silicone, poly (N-formylpropyleneimine) -modified silicone, poly (N- Acetyl propylene imine)
Modified silicone, poly (N-propionylpropyleneimine) -modified silicone, poly (Nn-octanoylpropyleneimine) -modified silicone, poly (Nn-dodecanoylpropyleneimine) -modified silicone, and the like.

The above poly (N-acylalkyleneimine)
The modified silicone can be prepared by a known method (Japanese Unexamined Patent Publication No. Hei 2-27682).
4, JP-A-4-85334, JP-A-4-8
No. 5,335, JP-A-5-112423, JP-A-7-133352, etc.)
For example, it is synthesized by the following method. First, a segment of poly (N-acylalkyleneimine) composed of the repeating unit represented by the formula (1) is represented by the formula (23);

[0042]

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(Wherein R ¹ is a hydrogen atom and has 1 to 22 carbon atoms)
Represents an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group, and n is 2 or 3. ) Is obtained by ring-opening polymerization of the cyclic imino ether compound represented by The cyclic imino ether compound represented by the formula (23) is a 2-oxazoline or a 2-oxazine as exemplified below. That is, 2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-butyl-2-oxazoline, 2-pentyl-2
-Oxazoline, 2-heptyl-2-oxazoline, 2
-Octyl-2-oxazoline, 2-nonyl-2-oxazoline, 2-decyl-2-oxazoline, 2-undecyl-2-oxazoline, 2-dodecyl-2-oxazoline, 2-tridecyl-2-oxazoline, 2-tetradecyl -2-oxazoline, 2-pentadecyl-2-oxazoline, 2-hexadecyl-2-oxazoline, 2
-Heptadecyl-2-oxazoline, 2-octadecyl-2-oxazoline, 2-nonadecyl-2-oxazoline, 2-eicosyl-2-oxazoline, 2-heneicosyl-2-oxazoline, 2-docosyl-2-oxazoline, 2-benzyl -2-oxazoline, 2-phenyl-2-oxazoline, 2-naphthyl-2-oxazoline, 2-anthryl-2-oxazoline, 2-pyrenyl-2-oxazoline, 2-perylenyl-2-oxazoline, 2-cyclohexyl-2 -Oxazoline, 2-oxazine, 2-methyl-2-oxazine, 2-ethyl-2
-Oxazine, 2-propyl-2-oxazine, 2-butyl-2-oxazine, 2-pentyl-2-oxazine, 2-hexyl-2-oxazine, 2-heptyl-2
-Oxazine, 2-octyl-2-oxazine, 2-nonyl-2-oxazine, 2-decyl-2-oxazine,
2-undecyl-2-oxazine, 2-dodecyl-2-
Oxazine, 2-tridecyl-2-oxazine, 2-tetradecyl-2-oxazine, 2-pentadecyl-2-
Oxazine, 2-hexadecyl-2-oxazine, 2-
Heptadecyl-2-oxazine, 2-octadecyl-2
-Oxazine, 2-nonadecyl-2-oxazine, 2-
Eicosyl-2-oxazine, 2-heneicosyl-2
-Oxazine, 2-docosyl-2-oxazine, 2-benzyl-2-oxazine, 2-phenyl-2-oxazine, 2-naphthyl-2-oxazine, 2-anthryl-
2-oxazine, 2-pyrenyl-2-oxazine, 2-
Perylenyl-2-oxazine, 2-cyclohexyl-2
-Oxazine and the like.

These cyclic imino ethers are, for example, Li
ebigs Ann. Chem. , P996-p100
9 (1974). These compounds may be used alone as a monomer for ring-opening polymerization, or may be used in combination of two or more.

Examples of the polymerization initiator for ring-opening polymerization of the above cyclic imino ether include toluenesulfonic acid alkyl ester, dialkyl sulfate ester, trifluoromethanesulfonic acid alkyl ester and alkyl halide, but are not limited thereto. Absent. These initiators can be used alone or in a mixture.

The cyclic imino ether compound represented by the above formula (23) is subjected to ring-opening polymerization using these initiators to obtain a molecular chain of poly (N-acylalkyleneimine). The chains may be homopolymer chains or copolymer chains, which may be random copolymer chains or block copolymer chains.

The above poly (N-acylalkyleneimine)
Is preferably 150 or more and 50,000 or less, more preferably 500 or more and 10,000 or less. When the molecular weight is smaller than 150, the properties of poly (N-acylalkylenimine) are lost, and 5
If it is larger than 000, production becomes difficult, which is not preferable.

In the component (B), the one in which the hydrophilic segment is derived from N-acylalkyleneimine may be a polymerization active species formed by ring-opening polymerization of a cyclic imino ether compound represented by the formula (23). And an organopolysiloxane having a functional group capable of reacting therewith.

The functional group capable of reacting with the above-mentioned polymerization active species includes a primary, secondary or tertiary amino group, a mercapto group, a hydroxyl group, a carboxylate group and the like. Among them, an amino group or a mercapto group is preferred. is there. The organopolysiloxane containing an amino group or a mercapto group in the molecule preferably has a molecular weight of 300 or more and 400,000 or less, more preferably 800 or more and 250,000 or less. May be provided. If the molecular weight of the organopolysiloxane is less than 300, the adhesion to the skin is poor, which is not preferable. If the molecular weight is more than 400,000, a gel is formed and the reaction is difficult, which is not preferable. The amino group or mercapto group contained may be introduced at any position of the main chain and the side chain.

The reaction between an organopolysiloxane containing an amino group or a mercapto group and a reactive terminal of poly (N-acylalkyleneimine) obtained by cationic polymerization of a cyclic imino ether can be carried out as follows. .

The initiator may be used in combination with a polar solvent, preferably a single solvent such as acetonitrile, valeronitrile, dimethylformamide, dimethylacetamide, chloroform, methylene chloride, ethylene chloride, ethyl acetate, methyl acetate, or if necessary, another solvent. Dissolved in a mixed solvent of 40-1
The temperature is raised to 50 ° C, preferably 60 to 100 ° C. Therein, the cyclic imino ether represented by the above general formula (23) is charged at once, or, if the reaction is severe, dropped to carry out polymerization. The progress of the polymerization can be monitored by quantifying the residual amount of the cyclic imino ether which is a monomer using an analytical instrument such as gas chromatography. Even when the cyclic imino ether is consumed and the polymerization is completed, the active species at the growth terminal maintains the reactivity. Without isolating the polymer,
Subsequently, the polymer solution and an organopolysiloxane containing an amino group or a mercapto group in the molecule are mixed and reacted at 5 to 100 ° C, preferably 20 to 60 ° C. The mixing ratio can be appropriately selected as desired, but the reaction is carried out at a ratio of 0.1 to 1.3 mole equivalent of poly (N-acylalkylenimine) per mole of amino group or mercapto group in the organopolysiloxane. Is preferred. If it is less than 0.1 molar equivalent, it is difficult to impart the properties of the poly (N-acylalkylenimine) intended in the present invention due to a small modification rate, and more than 1.3 molar equivalent is unnecessary.

By the above-mentioned reaction, a block copolymer or graft polymer having a poly (N-acylalkylenimine) segment as a hydrophilic segment added to an organopolysiloxane can be obtained.

Further, as the component (B), at least one silicon atom at the terminal or side chain of the organopolysiloxane segment may be represented by the following general formula (4):

[0054]

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(Wherein, m represents an integer of 1 to 8).

In this copolymer, the number of silicon atoms to which the group represented by the general formula (4) is bonded is 10 to 90% (more preferably 40 to 80%) of the total number of silicon atoms in the molecule, and the weight The average molecular weight is preferably from 1,000 to 500,000 (more preferably from 5,000 to 300,000).

When the weight average molecular weight of the organopolysiloxane containing the group (4) is smaller than 1,000, the effect of the present invention is not exerted, and the weight average molecular weight becomes 500,0.
Those exceeding 00 are difficult to manufacture. General formula (4)
When the number of silicon atoms bonded to the group represented by is less than 10% of the total number of silicon atoms in the molecule, adhesion to the skin is not sufficient, and when it exceeds 90%, water repellency is poor. Become.

The organopolysiloxane containing such a group (4) can be used, for example, as a precursor of the following general formula (24)
Can be synthesized by using an organohydrogenpolysiloxane represented by the following formula, and reacting this with an N-alkylenepyrrolidone represented by the following general formula (25), that is, a so-called hydrosilylation reaction. The hydrosilylation reaction is carried out using a halogen-based solvent such as dichloromethane, chloroform, or 1,2-dichloroethane, or an aliphatic ether such as tetrahydrofuran, diisopropyl ether, or dibutyl ether as a reaction solvent at room temperature to 100 ° C. And a transition metal complex such as chloroplatinic acid as a catalyst.

[0059]

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(Wherein R ¹¹ is the same or different and represents a saturated alkyl group having 1 to 22 carbon atoms or a phenyl group;
R ¹² , R ¹³ and R ¹⁴ each represent the same group as R ¹¹ or a group selected from a saturated alkyl group having 1 to 22 carbon atoms or a phenyl group, and p ² represents an integer of 30 to 3,000. shows, q ² is an integer of 60~1,500, m are as defined above)

Further, as the component (B), a copolymer in which a sugar-derived residue is bonded to at least one of the terminal or side chain silicon atoms of the organopolysiloxane segment can be used.

In this organopolysiloxane, the sugar-derived residue includes a sugar lactone amide alkyl group (a group in which a sugar lactone compound and an aminoalkyl group are amide-bonded). Also, as the organopolysiloxane,
40 to 97% by weight of silicone chain (more preferably 50 to 97% by weight)
９５95% by weight), having a weight average molecular weight of 1,000-
500,000 (more preferably 5,000 to 300,
000) is preferred. If the silicone chain is less than 40% by weight, the water repellency is poor, while if it exceeds 97% by weight, the adhesion to the skin is poor. If the weight average molecular weight is less than 1,000, the effect of the present invention is not exhibited, and if the weight average molecular weight exceeds 500,000, production is difficult.

The organopolysiloxane having a sugar-derived residue bonded thereto is, for example, an organopolysiloxane having at least one aminoalkyl group, a sugar lactone compound (in which aldonic acid or uronic acid is dehydrated and cyclized in the molecule).
To produce an amide bond.

Here, the aminoalkyl group is preferably an aminoalkyl group having 1 to 20 carbon atoms, particularly preferably an aminoalkyl group having 1 to 8 carbon atoms. Examples of lactone compounds in which aldonic acid or uronic acid is intramolecularly cyclized include D-glucose, D-galactose, D-allose, D-aldose, D-mannose, D-gulose, D-idose,
Lactone of aldonic acid derived from reducing monosaccharide such as talose; lactone of aldonic acid derived from reducing disaccharide such as maltose, cellobiose, lactose, xylobiose, isomaltose, nigerose, kojibiose; maltotriose, panose; Lactone of aldonic acid derived from reducing trisaccharide such as isomalttriose; lactone of aldonic acid derived from reducing oligosaccharide of four or more sugars; D
-Lactones of uronic acids such as -glucuronic acid, L-iduronic acid and mannuronic acid. These can be subjected to the reaction alone or as a mixture.

The reaction between the organopolysiloxane precursor having an aminoalkyl group and the sugar lactone is preferably carried out by using the sugar lactone in an amount of 1.0 to 1.3 times the mole of the amino group of the organopolysiloxane precursor in a solvent. And stirring at a solution concentration of 5 to 30% by weight under reflux for 3 to 20 hours. As the solvent used at this time, lower alcohols such as methanol, ethanol, 1-propanol and 2-propanol are suitable.

Further, at least one silicon atom in the terminal or side chain of the organopolysiloxane segment is linked via an alkylene group containing a hetero atom to the following general formula (2):

[0067]

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(Wherein R ² is a hydrogen atom and has 1 to 22 carbon atoms)
Represents an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or an alkoxycarbonylalkyl group,
Represents a number of 1 to 5), and a copolymer formed by bonding poly (N-propylenecarbobetaine) composed of repeating units represented by the following formulas can also be used.

In this copolymer, the weight ratio of the organopolysiloxane segment to the poly (N-propylenecarbobetaine) segment is from 98/2 to 40 /
It is preferably 60 (more preferably 95/5 to 60/40) and the weight average molecular weight is 1,000 to 500,000 (more preferably 5,000 to 300,000). When the weight ratio between the organopolysiloxane segment and the poly (N-propylenecarbobetaine) segment is 9
When it is more than 8/2, or less than 40/60, or when the weight average molecular weight is less than 1,000, elasticity does not occur and adhesion to skin is insufficient, which is not preferable.
On the other hand, those having a weight average molecular weight exceeding 500,000 are difficult to produce.

The alkylene group containing a hetero atom intervening in the bond between the organopolysiloxane segment and the poly (N-propylenecarbobetaine) segment includes nitrogen, oxygen and / or sulfur atoms of 1 to 3
Examples thereof include an alkylene group having 2 to 20 carbon atoms, and specific examples thereof include:

[0071]

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And the like. Examples of the cycloalkyl group represented by R ² include those having 3 to 6 carbon atoms; examples of the aralkyl group include phenylalkyl and naphthylalkyl; and examples of the aryl group include phenyl and
Naphthyl, alkyl-substituted phenyl and the like.

The above copolymer is composed of an organopolysiloxane and the following formula (26):

[0074]

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(Wherein R ² is the same as defined above), and the terminal-reactive poly (N-
First, an organopolysiloxane in which poly (N-propyleneimine) is bonded is produced. This is further reacted with sodium chloroacetate, β-propiolactone, γ-butyrolactone, and ε-caprolactone to produce an organopolysiloxane having poly (N-propylenecarbobetaine) bonded thereto.

As still another production method, the obtained poly (N-propyleneimine) -bonded organopolysiloxane is quaternized with an alkyl halide having 1 to 22 carbon atoms, a cycloalkyl halide, an aryl halide or the like. After the reaction, a hydrolysis reaction of an alkoxycarbonylethyl group or an alkoxycarbonylmethyl group is carried out under basic conditions to produce an organopolysiloxane to which poly (N-propylenecarbobetaine) is bonded.

Here, the ring-opening polymerization of the cyclic amine is carried out by a compound such as a Lewis acid, a protonic acid, or an alkylating agent, for example, triethyloxonium tetrafluoroborate, benzyl chloride, benzyl bromide, benzyl iodide, methyl bromide, or the like. Methyl iodide, ethyl bromide, ethyl iodide, dimethyl sulfate, diethyl sulfate, trifluoromethanesulfonic acid, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, benzenesulfonic acid, methyl benzenesulfonate, ethylbenzenesulfonate, p -Toluenesulfonic acid, p-toluenemethyl sulfonate, p-
It is carried out using ethyl toluenesulfonate or the like as an initiator. When N-substituted-azetidine is used as the cyclic amine, poly (N-substituted-propylenecarbobetaine) can be obtained.

Solvents used for the ring-opening polymerization of cyclic amines and the production of the copolymer of the present invention include acetates such as ethyl acetate and propyl acetate, and ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran. Ketones such as acetone, methyl ethyl ketone, etc .; halogen solvents such as chloroform and methylene chloride; nitrile solvents such as acetonitrile and benzonitrile; aprotic polar such as N, N-dimethylformamide, N, N-dimethylacetamide and dimethyl sulfoxide Solvents can be used.

The method for connecting the poly (N-propyleneimine) chain to the silicone chain can be the same as the method for connecting the poly (N-acylalkyleneimine) chain to the silicone chain.

JP-B-63-16418 discloses a siloxane having a betaine group similar to the organopolysiloxane to which the above-mentioned poly (N-propylenecarbobetaine) is bonded, and a method for producing the same. Also in the examples, the effect of improving the adhesion to the skin and suppressing the re-adhesion to other parts is not shown. Further, as the component (B), the following three segments (i) and (i)
Copolymers consisting of i) and (iii) can also be used because they have the effect of improving the adhesion to the skin.

(I) 1 to 98% by weight of a segment derived from a radical polymerizable vinyl monomer (ii) 1.5 to 60% by weight of a hydrophilic segment (iii) 0.1 to 90% by weight of an organopolysiloxane segment

The segments (i), (ii) and (ii)
The copolymer comprising i) is described in JP-A-3-128311, JP-A-3-128312, WO95 / 060.
78, WO95 / 06079, etc., disclose similar copolymers and a method for producing the same, but the field of application of the copolymer relates to hair cosmetics, which has high adhesiveness and is re-adhered to other places. There is no indication of the effect of difficulty.

The copolymer comprising the above segments (i), (ii) and (iii) will be described below.

Representative examples of the radically polymerizable vinyl monomer used for constituting the segment (i) include acrylic acid and salts, esters and amides thereof. Acrylates include those derived from normal non-toxic metal ions, ammonium ions or substituted ammonium ions. Examples of the acrylate include those derived from an alcohol having a C ₁ -C ₄₀ linear, C ₃ -C ₄₀ branched or C ₃ -C ₄₀ cyclic structure, and 2 to 8 hydroxyl groups. Derived from a C ₂ -C ₈ polyhydric alcohol (eg, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerin, 1,2,6-hexanetriol, etc.), and an amino alcohol (eg, amino Examples thereof include those derived from ethanol, dimethylaminoethanol, diethylaminoethanol, and quaternized derivatives thereof, and those derived from alcohol ethers (eg, methoxyethanol, ethoxyethanol, and the like). Examples of the acrylamide include unsubstituted acrylamide, N-alkylmonosubstituted or N-alkylaminomonosubstituted acrylamide, N, N-dialkyldisubstituted or N, N-dialkylaminodisubstituted acrylamide (as the alkyl group or alkylamino group). Is C ₁ −
Straight-chain C _40, of branched C ₃ -C _40, or may be mentioned those having a cyclic structure C ₃ -C _40, also the alkylamino groups may optionally be quaternized. ).

Further, a substituted acrylic acid (for example, methacrylic acid, α-amino acid) in which a substituent selected from a C ₁ -C ₄ alkyl group, a cyano group and a carboxyl group is bonded to the 2- or 3-position carbon atom of acrylic acid. Ethyl acrylic acid, 3-cyanoacrylic acid and the like), and salts, esters and amides thereof can also be used. Examples of the salts, esters and amides of these substituted acrylic acids include those similar to the salts, esters and amides of acrylic acid. Other radically polymerizable vinyl monomers that can be used include C ₁ -C ₄₀ linear, C ₃ -C ₄₀ branched or C
Vinyl esters or allyl esters of carboxylic acids having a cyclic structure ₃ -C _40, vinyl halides or allyl halides (e.g. vinyl chloride, allyl chloride), vinyl-substituted or allyl-substituted heterocyclic compounds (such as vinyl pyridine, allyl pyridine, etc.) , Vinylidene chloride, hydrocarbons having at least one carbon-carbon double bond (e.g.,
Styrene, α-methylstyrene, t-butylstyrene,
Butadiene, isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutylene, vinyltoluene, etc.), and mixtures thereof.

Among these, preferred radically polymerizable vinyl monomers include acrylic acid, methacrylic acid,
α-ethylacrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid n-butyl, isobutyl methacrylate, t-butyl methacrylate, methacrylic acid 2
-Ethylhexyl, decyl methacrylate, methyl α-ethyl acrylate, ethyl α-ethyl acrylate, n-butyl α-ethyl acrylate, isobutyl α-ethyl acrylate, t-butyl α-ethyl acrylate, α-ethyl acryl 2-ethylhexyl acid, decyl α-ethyl acrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate 2-hydroxyethyl α-ethyl acrylate, glyceryl acrylate, glyceryl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl α-ethyl acrylate, 2-ethoxyethyl acrylate, Methacrylic acid - ethoxyethyl, 2-ethoxyethyl alpha-ethyl acrylate, acrylamide, methacrylamide, alpha-ethyl acrylamide, N- methylacrylamide, N, N- dimethylacrylamide,
N, N-dimethylmethacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-butylacrylamide, Nt-butylacrylamide,
N, N-di-n-butylacrylamide, N, N-diethylacrylamide, N-octylacrylamide, N
-Octadecylacrylamide, N-phenylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-dodecylmethacrylamide, N, N
-Dimethylaminoethylacrylamide, quaternized N, N
-Dimethylaminoethyl acrylamide, N, N-dimethylaminoethyl methacrylamide, quaternized N, N-dimethylaminoethyl methacrylamide, acrylic acid N,
N-dimethylaminoethyl, quaternized acrylate N, N-
Dimethylaminoethyl, N, N-dimethylaminoethyl methacrylate, quaternized N, N-dimethylaminoethyl methacrylate, maleic acid, maleic anhydride, maleic acid half ester, crotonic acid, itaconic acid, angelic acid, chloride Diallyl dimethyl ammonium, vinyl pyrrolidone, methyl vinyl ether, methyl vinyl ketone,
Maleimide, vinylpyridine, vinylimidazole, vinylfuran, styrenesulfonic acid, allyl alcohol,
Examples include vinyl alcohol, vinyl caprolactam, and mixtures thereof. As more preferred radical polymerizable monomers, methyl acrylate, methyl methacrylate,
α-ethyl methyl acrylate, ethyl acrylate, ethyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, n-butyl α-ethyl acrylate, 2-ethylhexyl acrylate, methacrylic acid 2 -Ethylhexyl, 2-ethylhexyl α-ethylacrylate, N-octylacrylamide, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, N, N-dimethylaminoethyl acrylate,
And quaternized N, N-dimethylaminoethyl acrylate and mixtures thereof. The most preferred radically polymerizable monomers are n-butyl acrylate and acrylate 2
-Ethylhexyl, N-octylacrylamide, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, N, N-dimethylaminoethyl acrylate, quaternized acrylate N, N-dimethylacrylamide, and mixtures thereof. .

A preferred radical polymerizable monomer used for constituting the segment (i) can be represented by the following general formula (5):

[0088]

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Wherein X ¹ is —OH, —NH ₂ , —OM (M is Na
⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Zn ²⁺ , NH ₄ ⁺ , cations such as alkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium), —OR ³ , —NHR ³ and -N (R ³ ) ₂ (R ³ has 1 to 1 carbon atoms)
8 linear or branched alkyl groups, N, N-dimethylaminoethyl groups, methyl quaternized N, N-dimethylaminoethyl groups, 2-hydroxyethyl groups, 2-methoxyethyl groups or 2-ethoxyethyl groups Wherein R ⁴ and R ⁵ are a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a methoxyl group, an ethoxyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group. Or a group selected from an ethoxyethyl group).

Examples of the hydrophilic segment (ii) include the same ones as described above.

The segment consisting of the organopolysiloxane of (iii) includes the following general formula (6): E (Y) _s Si (R ⁶ ) _3-t (Z) _t (6) A monomer constituting (i) or (ii) or a vinyl group copolymerizable with the macromonomer thereof (optionally having a substituent), Y represents a divalent linking group, and R ⁶ represents hydrogen Represents an atom, a lower alkyl group, an aryl group or an alkoxyl group, Z represents a monovalent siloxane polymer portion having an average molecular weight of 500 or more, and s represents 0 or 1
And t represents an integer of 1 to 3]. The weight average molecular weight of the organopolysiloxane (6) is from about 1,000 to about 50.
Of about 5,000 to about 4,000 to about 400,000.
0 is particularly preferred, and about 5,000 to about 300,000 is more preferred. Examples of the organopolysiloxane (6) include dimethylpolysiloxane represented by the following formulas (7) to (12).

[0092]

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[Wherein R ⁷ represents a hydrogen atom or an alkyl group, R ⁸ represents a hydrogen atom or a carboxyl group (preferably a hydrogen atom), and R ⁹ represents a hydrogen atom, a methyl group or a carboxymethyl group (preferably A methyl group), R ¹⁰ represents an alkyl group, an alkoxyl group, an alkylamino group, an aryl group or a hydroxyl group (preferably an alkyl group), x represents an integer of 2 to 6, and y represents an integer of 5 to 700. (Preferably about 250), u represents 0 or 1,
t represents an integer of 1 to 3]

The copolymer comprising the segments (i), (ii) and (iii) contains 1 to 98% by weight of the segment (i).
(Preferably 1 to 90% by weight, more preferably 50 to 9% by weight.
0% by weight), segment (ii) 1.5 to 60% by weight (preferably 7.5 to 50% by weight) and segment (iii)
0.1 to 90% by weight (preferably 0.5 to 90% by weight,
(More preferably 2 to 60% by weight).

In the copolymer comprising the segments (i), (ii) and (iii), the segment (i) is preferably selected from t-butyl acrylate, t-butyl methacrylate and a mixture thereof. This is because such polymers dissolve directly in cyclomethicone solvents without the need for co-solvents.

Particularly preferred copolymers containing segments (i), (ii) and (iii) include the following (weight percentages below relate to the amount of reactants added to the polymerization reaction and are not necessarily in the final polymer). It is not about the amount of).

Acrylic acid / n-butyl methacrylate /
Polydimethylsiloxane (PDMS) macromer-molecular weight 20,000 (10/70/20 v / v / v) (I) N, N-dimethylacrylamide / isobutyl methacrylate / PDMS macromer-molecular weight 20,000 (2
0/60/20 v / v / v) (II) t-butyl acrylate / t-butyl methacrylate /
PDMS macromer-molecular weight 10,000 (56/24
/ 20 v / v / v) (III) n-butyl acrylate / 2-methoxyethyl acrylate / poly (N-propionylethyleneimine) / polydimethylsiloxane 36/22/40/2 (IV) n-butyl acrylate / 2- Methoxyethyl acrylate / poly (N-propionylethyleneimine) / polydimethylsiloxane 33/22/40/5 (V) n-butyl acrylate / 2-methoxyethyl acrylate / poly (N-propionylethyleneimine) / polydimethylsiloxane 30 0.5 / 22/40 / 7.5
(VI) n-butyl acrylate / 2-methoxyethyl acrylate / poly (N-propionylethyleneimine) / polydimethylsiloxane 28/22/40/10 (VII) n-butyl acrylate / 2-methoxyethyl acrylate / poly (N -Propionylethyleneimine) / polydimethylsiloxane 23/22/40/15 (VIII) n-butyl acrylate / poly (N-propionylethyleneimine) / polydimethylsiloxane 53/40/7
(IX) n-butyl acrylate / 2-ethylhexyl methacrylate / poly (N-propionylethyleneimine) / polydimethylsiloxane 35/20/40/5 (X) n-butyl acrylate / 2-methoxyethyl acrylate / poly (ethylene glycol ) / Polydimethylsiloxane 36/22/40/2 (XI)

The above segments (i), (ii) and (ii)
The copolymer containing i) can be synthesized at a time by a radical polymerization method, or each macromonomer can be polymerized in advance and finally made into a copolymer. For example, it can be synthesized by a radical polymerization method as follows.

The general principles are well understood [eg Odian; "Principles of polymerization", 2nd edition,
John Wiley & Sons, 1
981, 179, 318]. The desired monomers are all introduced into the reactor with sufficient amounts of mutual solvent to ensure that the viscosity of the reaction is reasonable when the reaction is complete. Typical monomer concentrations are from about 20 to about 50% by weight. It is desirable to remove undesired terminators, especially oxygen. This is done by purging or evacuation with an inert gas such as argon or nitrogen. An initiator is introduced, but if a thermal initiator is used, the reaction is brought to the temperature required for initiation. On the other hand, redox or radical initiation can also be applied if desired. The polymerization is allowed to proceed for hours to days as needed to achieve high levels of conversion. The solvent is then removed, usually by evaporation or by precipitating the polymer with the addition of a non-solvent. The polymer is further purified if necessary.

The amount of the polymer having orientation at the oil-water interface is preferably 0.05 to 30% by weight, more preferably 0.1 to 10% by weight, and even more preferably 0.1 to 5% by weight.
It is. Within this range, the adhesive effect is high and stickiness does not occur during use, and the feeling of use is good.

The cosmetic of the present invention may contain a hydrophobized powder (C) in addition to the above essential components.
The hydrophobized powder of the component (C) includes not only ordinary hydrophobic pigments but also pigments whose surfaces are hydrophobized. As the surface treatment method, for example, an oil or fat is adsorbed on the surface of the pigment, or a functional group such as a hydroxyl group is used to cause esterification or etherification to make the pigment lipophilic, a zinc salt of a fatty acid or magnesium. A metal soap treatment using a salt, a silicone treatment using dimethyl polysiloxane or methyl hydrogen polysiloxane, a treatment using a fluorine compound having a perfluoroalkyl group such as the following (where the fluorine compound is, for example, [ _{C m F 2m + 1 C n} H 2n O ]
_y PO (OH) _3-y (where m is an integer of 4 to 18, n is 1
An integer of from 1 to 12, and y represents a number of from 1 to 3. (US Pat. No. 3,632,744)
No.), fluoroalkyldi (oxyethyl) amine phosphate (Japanese Patent Application Laid-Open No. 62-250074), and a resin having a perfluoroalkyl group (Japanese Patent Application Laid-Open No. 55-167).
209), a tetrafluoroethylene resin, a perfluoroalcohol, a perfluoroepoxy compound, a sulfoamide-type fluorophosphoric acid, a perfluorosulfate, a perfluorocarboxylate, and a perfluoroalkylsilane (JP-A-2-218603). And the like).

The base powder to be treated is not particularly limited as long as it is substantially insoluble in water and oil. For example, titanium oxide, iron oxide, ultramarine, zinc white, magnesium oxide, zirconium oxide, mica, Inorganic pigments such as sericite, talc, silica, kaolin, and chromium hydroxide; organic powders such as nylon powder, carbon black, polymethyl methacrylate, styrene-divinylbenzene copolymer, and polyethylene powder; and organic pigments.

These hydrophobized powders can be used alone or in combination of two or more.
When it is blended in an amount of from 70 to 70% by weight, especially from 0.1 to 40% by weight, a stable product is obtained, which is preferable.

In the cosmetic of the present invention, in addition to the above components,
If necessary, the purpose of the present invention, qualitative that does not impair the effect,
Within the quantitative range, components that are blended with ordinary cosmetics can be blended. Such components include, for example, petrolatum, lanolin, ceresin, microcrystalline wax, carnauba wax, candelilla wax, higher fatty acids, solid and semi-solid oils such as higher alcohols; olive oil, jojoba oil, castor oil, squalane, liquid paraffin, Fluid oils such as ester oils, diglycerides, triglycerides, silicone oils; water-soluble and oil-soluble polymers; inorganic and organic pigments;
Coloring agents such as organic dyes; surfactants such as cationic surfactants, anionic surfactants and nonionic surfactants; ethanol,
Preservatives, antioxidants, pigments, thickeners, pH adjusters, fragrances,
UV absorbers, moisturizers, blood circulation enhancers, cooling sensation agents, antiperspirants,
Skin activators and the like.

The skin cosmetic of the present invention can be produced according to a usual method, and can be cream, emulsion, foundation, eyeshadow, blush, lipstick and the like.

[0106]

Industrial Applicability The cosmetic of the present invention has water repellency and oil repellency, is excellent in sweat resistance and sebum resistance, and has high adhesion to the skin. It has the property that adhesion can be prevented.

Next, the present invention will be further described with reference to examples, but the present invention is not limited to these examples.
The percentages in the examples are on a weight basis unless otherwise specified. Also,
In this synthesis example, the weight average molecular weight is determined by gel permeation type liquid chromatography using chloroform as a developing solvent, and the value is a value in terms of polystyrene.

Synthesis Example 1 (Synthesis of poly (N-acetylethyleneimine) -modified silicone) 13.03 g (0.070 mol) of methyl-p-toluenesulfonate (methyl tosylate), 2-methyl-2
A mixture of 70 g (0.82 mol) of oxazoline, 10 ml of acetonitrile, and 30 ml of chloroform was refluxed for 6 hours to synthesize a poly (N-acetylethyleneimine) terminal reactive polymer (molecular weight: 1,000). To this reaction solution, polydimethylsiloxane substituted with 3-aminopropyl at both ends (FM3311, molecular weight 1,000, manufactured by Chisso Corporation).
A solution prepared by dissolving 31.8 g in 50 ml of chloroform was added thereto, and reacted at 55 ° C. for 24 hours. By distilling off the solvent under reduced pressure, a block copolymer (molecular weight: 3,000) having poly (N-acetylethyleneimine) chains at both ends of polydimethylsiloxane was obtained. The copolymer was a pale yellow brittle solid (yield 110.2 g,
Yield 96%).

Synthesis Example 2 (Synthesis of poly (Nn-dodecanoylpropyleneimine) -modified silicone) 1.45 g (7.8 × 10 ⁻³ mol) of methyl tosylate,
7.8 g of 2-n-undecyl-2-oxazine (0.0
33 mol) and 10 ml of dimethylacetamide in 1
While maintaining the temperature at 00 ° C. for 24 hours, poly (Nn-dodecanoylpropyleneimine) (molecular weight: 1,000) was synthesized. This reaction solution was mixed with a polydimethylsiloxane substituted at both ends with 3-aminopropyl (manufactured by Chisso, FM3325, molecular weight 1).
A solution of 38.9 g of (0000) dissolved in 50 ml of chloroform was added and refluxed for 72 hours. Then, it was reprecipitated with methanol, and the residue was dried under reduced pressure. The obtained polymer was a yellow viscous liquid and had a molecular weight of 12,000 (yield 45.7 g, 95%).

Synthesis Example 3 (Synthesis of poly (N-acetylethyleneimine) -modified silicone) 3.26 g (0.018 mol) of methyl tosylate, 2-
A mixture of 70 g (0.82 mol) of methyl-2-oxazoline, 10 ml of acetonitrile and 40 ml of chloroform was added to 6
After refluxing for an hour, poly (N-acetylethyleneimine) (molecular weight: 4,000) was synthesized. In this reaction solution, 3
Polydimethylsiloxane substituted with an aminopropyl group (KF865, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 4,40)
0, molecular weight 2,000) 63.6 g of chloroform 15
The solution dissolved in 0 ml was added and reacted at 55 ° C. for 24 hours. By evaporating the solvent under reduced pressure, a graft polymer (molecular weight: 6,000) having a poly (N-acetylethyleneimine) chain attached to polydimethylsiloxane and a molecular weight of 2,0
A mixture of 100 silicones formed. This polymer was a pale yellow brittle solid (134.1 g, yield 9).
8%).

Synthesis Example 4 Synthesis of (N-acetylethyleneimine) · (Nn-octanoylethyleneimine) random copolymer-modified silicone 1.86 g (0.01 mol) of methyl tosylate, 2-n
-Heptyl-2-oxazoline 10 g (0.059 mol), 2-methyl-2-oxazoline 10 g (0.11 mol)
A mixture of (N-acetylethyleneimine) and (Nn-octanoylethyleneimine) random copolymer (molecular weight 2,000) was synthesized by refluxing a mixture of 74 mol) and 20 ml of chloroform for 6 hours. Polydimethylsiloxane having a 2-aminoethylaminopropyl group substituted on the side chain (KF857, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 830, viscosity 7)
0cs (25 ° C)) 43.34 g in chloroform 150 g
Put the above random copolymer solution in the solution dissolved in,
Refluxed for 10 hours. The solvent was distilled off under reduced pressure to obtain a copolymer (molecular weight: 19,000) in which poly (N-acylethyleneimine) was grafted to polydimethylsiloxane. This copolymer was a pale yellow viscous liquid (yield 64.5 g, 99%).

Synthesis Example 5 (Synthesis of poly (N-formylpropyleneimine) -modified silicone) 13.03 g (0.070 mol) of methyl tosylate, 2
A mixture of 70 g (0.82 mol) of oxazine, 10 ml of acetonitrile and 30 ml of chloroform was refluxed for 6 hours,
A terminally reactive polymer of poly (N-formylpropyleneimine) (molecular weight 1,000) was synthesized. This reaction solution was mixed with polydimethylsiloxane having a 3-mercaptopropyl group substituted on the side chain (X-22-980, manufactured by Shin-Etsu Chemical Co., Ltd.).
1.7% sulfur content, 150 cs viscosity (25 ° C) 50
g in 100 ml of chloroform,
The reaction was carried out at a temperature of 60 ° C for 3 hours and then at 60 ° C for 24 hours. By evaporating the solvent under reduced pressure, a graft polymer (molecular weight: 6,200) having poly (N-formylpropyleneimine) chain attached to polydimethylsiloxane was obtained. This copolymer was a pale yellow viscous liquid (yield: 129.0 g, 97%).

Synthesis Example 6 (Synthesis of Amino-Modified Silicone Containing Tertiary Amino Group in Side Chain (Precursor of Synthesis Example 7)) 6.00 g (0.031 mol) of N, N-dimethylaminopropylmethyldimethoxysilane 1.46 g of water (0.
(081 mol) at 60 ° C. for 5 hours, and the resulting methanol and water are removed under reduced pressure at 60 ° C. and 2-5 mmHg. After the temperature was raised to 80 ° C., 228 g (0.769 mol) of octamethylcyclotetrasiloxane, 1.92 g (1.18 × 10 ⁻² mol) of hexamethyldisiloxane and 0.90 g of polymerization catalyst (tetramethylammonium hydroxide 0 .12 g (1.32 × 10 ⁻³ mol) contained; tetramethylammonium hydroxide pentahydrate dissolved in octamethylcyclotetrasiloxane and toluene, reacted at 80 ° C. for 12 hours, and dried in vacuum at 80 ° C./2 mmHg The tetramethylammonium hydroxide content was determined by a hydrochloric acid titration method), and the mixture was heated under a nitrogen atmosphere for 72 hours. 1
By removing the oligomer at 20 ° C. under a vacuum of 2 to 5 mmHg, an amino-modified silicone having a tertiary amino group in the side chain represented by the following formula was synthesized. The product was a clear, colorless oil (225 g). The weight average molecular weight is 22,
000. The amine equivalent was determined by a hydrochloric acid titration method to be 7,200.

[0114]

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Synthesis Example 7 (Synthesis of poly (N-propionylethyleneimine) -modified silicone) 2.36 g (0.0153 mol) of diethyl sulfate and 30.3 g (0.306 mol) of 2-ethyl-2-oxazoline
Was dissolved in 43 ml of chloroform and heated under reflux in a nitrogen atmosphere for 5 hours to obtain poly (N-propionylethyleneimine).
Was synthesized (molecular weight: 2,000). A solution of 100 g of the tertiary amino-modified silicone synthesized in Synthesis Example 6 (0.0139 mol as an amino group) in 270 ml of chloroform was added all at once, and the mixture was heated under reflux for 16 hours. The reaction mixture was concentrated under reduced pressure, and a graft copolymer (molecular weight: 28,90) having N-propionylethyleneimine chain attached to polydimethylsiloxane represented by the following formula:
0) was obtained. This polymer was a pale yellow rubbery solid (yield 129 g, 97%).

[0116]

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Synthesis Example 8 (Synthesis of poly (N-propionylethyleneimine) -modified silicone) 3.55 g (0.0230 mol) of diethyl sulfate and 27.4 g (0.276 mol) of 2-ethyl-2-oxazoline
Was dissolved in 60 g of dehydrated ethyl acetate, and the solution was dissolved in a nitrogen atmosphere.
The mixture was heated under reflux for an hour to synthesize a poly (N-propionylethyleneimine) terminal-reactive polymer (molecular weight 1,200). Here, a side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight 110,000, amine equivalent 2
(0,800) 400 g (0.0192 mol based on amino group) of a 50% ethyl acetate solution was added all at once, and the mixture was refluxed for 8 hours. The reaction mixture was concentrated under reduced pressure to obtain a graft copolymer (molecular weight 115,000) in which N-propionylethyleneimine chain was attached to polydimethylsiloxane. This copolymer was a pale yellow rubbery solid (yield 4
27g, 99% yield).

Synthesis Example 9 (Synthesis of poly (N-propionylethyleneimine) -modified silicone) 3.77 g (0.0244 mol) of diethyl sulfate and 48.4 g (0.488 mol) of 2-ethyl-2-oxazoline
Was dissolved in 107 g of dehydrated chloroform, and the mixture was heated under reflux in a nitrogen atmosphere for 5 hours to synthesize a poly (N-propionylethyleneimine) terminal-reactive polymer (molecular weight: 2,000). Here, a 50% ethyl acetate solution of 400 g (0.0407 mol in terms of amino group) of side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight 110,000, amine equivalent 9,840) was added all at once, and the mixture was added for 13 hours. Heated to reflux. The reaction mixture was concentrated under reduced pressure to obtain a graft copolymer (molecular weight: 137,000) having N-propionylethyleneimine chain attached to polydimethylsiloxane. The obtained copolymer was a pale yellow rubbery solid (yield 444).
g, 98% yield).

Synthesis Example 10 (Synthesis of alkylpyrrolidone-modified silicone) Methyl hydrogen polysiloxane 500 g (SiH
2.91 mol, weight average molecular weight 100,000,
2.0 g of a 5% isopropyl alcohol solution of chloroplatinic acid was added to the SiH equivalent 172), and N- (3-propenyl) pyrrolidone 382 was added thereto while stirring under a nitrogen atmosphere.
g (3.06 mol) was added dropwise at such a rate that the temperature in the system did not exceed 60 ° C. After the completion of the dropping, the inside of the system is kept at 65 ° C.
Stirring was continued for another 3 hours to return to room temperature. To this, 3,530 g of ethanol was added to make a homogeneous solution, and 10 g of activated carbon powder was further added. The obtained solution is concentrated under reduced pressure, ethanol and unreacted N- (3-propenyl) pyrrolidone are distilled off, and 847 g (yield 98%) of methylpolysiloxane having an alkylpyrrolidone group in a side chain is colorless. Obtained as a clear rubbery solid. The weight average molecular weight was 155,000. In the FT-IR spectrum, no Si-H stretching vibration absorption (2125 cm ^-1 ) was observed.

Synthesis Example 11 (Synthesis of Silicone Containing Residue Derived from Sugar) The amine equivalent was 996 and the weight average molecular weight was 108,000.
Of γ-aminopropyl-modified dimethylpolysiloxane (0.201 mol in terms of amino group), 39.3 g (0.221 mol) of δ-gluconolactone, and 200 g of methanol were mixed and stirred vigorously under a nitrogen atmosphere. While heating, the mixture was refluxed for 8 hours. The solution was diluted three times with methanol and added dropwise to 10 liters of vigorously stirred water at room temperature. The stirring was stopped, the precipitate was collected by filtration, washed with water, and dried under reduced pressure to obtain 204 g (86% yield) of a saccharide-derived residue-containing dimethylpolysiloxane as a colorless transparent elastic solid.
As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that no amino group remained. The content of the silicone segment was 86%.

Synthesis Example 12 (Synthesis of Carbobetaine-Modified Silicone) 30.6 g (0.198 mol) of diethyl sulfate and 1- (2
-Carboethoxyethyl) azetidine 1498.2 g
(9.53 mol) was dissolved in 3058 g of dehydrated ethyl acetate, and the mixture was heated under reflux in a nitrogen atmosphere for 15 hours to synthesize a terminal-reactive poly (N-propylene imine). Here, 800 g of side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight 110,000, amine equivalent 4,840)
A 50% ethyl acetate solution (0.165 mol based on amino group) was added all at once, and the mixture was refluxed for 12 hours. The reaction mixture was concentrated under reduced pressure to give an N-propyleneimine-dimethylsiloxane copolymer as a pale yellow solid (2,212 g, yield 95
%). The resulting reaction mixture was dissolved in 5,000 g of diethyl ether, and β-propiolactone 824 was dissolved.
g (11.4 mol) was added at room temperature, and reacted at room temperature for 24 hours. The obtained solution was concentrated under reduced pressure to obtain an N-propylenecarbobetaine-dimethylsiloxane copolymer as a pale yellow solid.

Synthesis Example 13 [Synthesis of poly (2-ethyl-2-oxazoline) macromonomer end-blocked with vinylbenzyl (precursor of synthesis example 14)] 50 g of 2-ethyl-2-oxazoline (0.5044 mol) ), Meta-paravinylbenzyl chloride 0.381
6 g (0.0025 mol) [manufactured by Aldrich Chemical Co.], sodium iodide 0.562 g (0.0037 mol), N, N'-diphenyl-p-phenylenediamine 0.06 g (0.00023 mol), acetonitrile 5
0 ml of the mixture was refluxed for 16 hours at 90 ° C. and the reaction was terminated by adding 100 ml of dichloromethane. The mixed solution containing the synthesized product was filtered, further precipitated in 800 ml of ether, filtered out with suction, and dried under vacuum to obtain a poly (2-ethyl-2-oxazoline) macromonomer ( (40 g, 90% yield).

Synthesis Example 14 [n-butyl acrylate /
Synthesis of 2-methoxyethyl acrylate / poly (N-propionylethyleneimine) / polydimethylsiloxane copolymer (36/22/40/5)] 3.6 g (0.0281 mol) of n-butyl acrylate, 2-methoxy 2.2 g of ethyl acrylate (0.
0169 mol), dimethylpolysiloxane (Mw = 10,
000 (manufactured by Chisso), 0.2 g (0.00002 mol) of the poly (2-ethyl-2-oxazoline) macromonomer prepared in Synthesis Example 13, 4.0 g (0.001 mol), and 90 ml of acetone as an initiator. As azobisisobutyronitrile (AIBN) 0.015 g (0.0
001 mol), and refluxed for 24 hours.
Was added to stop the synthesis. The reaction mixture is poured into a Teflon coat pan and placed in a vacuum drier to dry the acetone at room temperature. The obtained synthesized product was dissolved in ethanol, the insolubles were filtered, the filtrate was taken out, and the ethanol was distilled off under reduced pressure to obtain [n-butyl acrylate / 2-methoxyethyl acrylate / poly (N-propionylethyleneimine) / Polydimethylsiloxane copolymer].
This copolymer was a rubbery solid (yield 9.0 g).

Synthesis Example 15 [Acrylic acid / n-butyl methacrylate / polydimethylsiloxane copolymer (10
Synthesis of / 70/20)] Polymer I: 10 parts of acrylic acid, 70 parts of n-butyl methacrylate and 20 parts of 20K PDMS macromer were placed in a flask. Add enough ethyl acetate to obtain a final monomer concentration of 40%. The initiator benzoyl peroxide was added to a level of 0.1% by weight relative to the amount of monomer. The vessel was evacuated and refilled with nitrogen. Heated to 60 ° C. and maintained this temperature under stirring for 48 hours. The reaction was terminated by cooling to room temperature, and the reaction mixture was poured into a Teflon coat pan and placed in a vacuum oven to dry out ethyl acetate, and acrylic acid / n-butyl methacrylate / polydimethylsiloxane (= 10/70/20) ) (Molecular weight 100,000).

Production Example 1 150 g of a pigment in a round-bottomed flask (or kneader) was charged and heated to 60 ° C. while mixing. In addition, (C ₈ F ₁₇ C ₂
13 g of H ₄ O) ₂ P (O) OH dissolved in 1500 g of isopropyl alcohol by heating (50 ° C.) was added and mixed at 60 ° C. for 4 hours. Thereafter, isopropyl alcohol was distilled off under reduced pressure at 50 to 60 ° C. and dried to obtain 157 g of a fluorine compound-treated powder.

Production Example 2

[0127]

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In a 100 ml two-necked flask equipped with a condenser and a magnetic stirrer, the following formula:

[0129]

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The methyl hydrogen polysiloxane represented by
6.0 g (14.0 mmol) of Shiba Silicone Co., Ltd.
₆F₁₃-CH_TwoCH_Two-O-CH_Two)_TwoCH-O-CH_TwoCH
= CH _Two27.6 g (33.5 mmol), 2 of chloroplatinic acid
110.5 μl (4.0%)
× 10^-3mmol), and in the same manner as in Production Example 3,
The desired fluorine-modified silicone represented by the above formula (A
-1) 23.2 g was obtained as a colorless and transparent liquid oil.
Rate 80%).

Production Example 3

[0132]

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The apparatus used in Production Example 2 was placed under a nitrogen atmosphere.
Xylene 12 ml, methyl hydrogen polysiloxane ^(H MD ₄
^{M H) 12.0g (27.8mmol),} C 10 F 21 -CH 2 C
_{H 2 -O-CH 2 CH =} CH 2 40.4g (66.8mmo
l) 2% chloroplatinic acid solution in isopropyl alcohol 1
01μl (3.1 × 10 ^-3 mmol) was added, in the same manner as in Production Example 3, a fluorine-modified silicone represented by the above formula of the maximum endothermic peak 37.0 ° C. by DSC of interest (A-2) 41.0 g was obtained as a white solid fat (yield 90%).

Production Example 4

[0135]

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In the apparatus used in Production Example 2, 19.0 g (44.1 mmol) of methyl hydrogen polysiloxane (MD ₂ ^DH ₂ M) (manufactured by Toshiba Silicone Co., Ltd.) and C ₈ F ₁₇ —CH ₂ CH ₂ —
_{O-CH 2 CH = CH 2} 53.3g (105.8mmol)
Was charged. Next, after the temperature in the flask was raised to 80 ° C., 174.5 μl of a 2% isopropyl alcohol solution of chloroplatinic acid was added, and the mixture was stirred for 5 hours. After the reaction mixture was cooled to room temperature, 50 ml of hexane and 2.2 g of activated carbon were added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the activated carbon was filtered off, and the solvent was distilled off. The unreacted compound was distilled off under reduced pressure to obtain 49.4 g of the objective fluorine-modified silicone (A-3) represented by the above formula as a colorless and transparent liquid oil (yield 78%).

Production Example 5

[0138]

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The apparatus used in Production Example 2 was charged with 25.0 g (58.0 mmol) of methyl hydrogen polysiloxane (MD ₂ ^DH ₂ M) (manufactured by Toshiba Silicone Co., Ltd.) and CH ₂ ＣＨCH—CH ₂ —C.
50.1 g (139.2 mmol) of (CF ₃ ) ₂ C ₃ F ₇ was charged. Next, after raising the temperature in the flask to 80 ° C., a 2% chloroplatinic acid solution in isopropyl alcohol 23 was added.
0.0 μl (7.0 × 10 ⁻³ mmol) was added, and the mixture was stirred for 5 hours. Hereinafter, in the same manner as in Production Example 6, 58.3 g of the intended fluorine-modified silicone (A-4) represented by the above formula is obtained.
Was obtained as a colorless and transparent liquid oil (yield 87%).

Production Example 6

[0141]

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In the apparatus used in Production Example 2, toluene 20 m
l, methyl hydrogen polysiloxane (MD _TwoD^H _TwoM) 6.4 g
(14.9 mmol), C₆F₁₃-CH_TwoCH_Two-O-CH_TwoC
H (OCOC₇F_Fifteen) -CH_Two-O-CH_TwoCH = CH_Two
31.2 g (35.6 mmol), 2% isoprate of chloroplatinic acid
58.9 μl of propyl alcohol solution (0.89 × 10 ^-3
mmol), and the target was prepared in the same manner as in Production Example 3.
Fluorine-modified silicone (A-5) 2 represented by the above formula
5.2 g was obtained as a colorless and transparent liquid oil (yield 78).
%).

Examples 1 to 8 and Comparative Examples 1 to 3 (Two-layered liquid foundation) Two-layered liquid foundations having the compositions shown in Table 1 were prepared by the following method, and were used for holding makeup, floating oil, and applying skin. The difficulty of removal was evaluated by the following evaluation method.
Table 1 shows the results.

(Production method) After the oil phase was dissolved at room temperature, a pigment was added and dispersed with a disper. Next, the aqueous phase was added with stirring to obtain a two-layer liquid foundation.

(Evaluation method) Make-up, oil floating: Sensory evaluation was carried out by 12 specialized panelists, and evaluated on a 5-point scale according to the following criteria. 5:10 to 12 people judged good. 4: 8 to 9 persons are judged to be good. 3: 6 to 7 persons are judged to be good. 2: 4 to 5 people judged good. 1: 0 to 3 people are judged to be good.

Difficulty of removal from the skin after application: A fixed amount of a two-layer liquid foundation was applied thinly and uniformly to the center of the forehead of a man, and after 4 hours, the portion applied with tissue paper was applied under a pressure of 200 g / cm ² . I held it down. At that time, the difficulty of removing the cosmetic was evaluated based on the degree to which the tissue paper was colored by the foundation transferred to the tissue paper. The evaluation criteria are as follows. A: Almost no coloring. ：: Slightly colored. Δ: Colored. X: considerably colored.

[0147]

[Table 1]

As is clear from Table 1, the cosmetic of the present invention was excellent in all aspects of long-lasting makeup, oil floating (no oil floating), and difficulty in removing from the skin after application. These results indicate that the cosmetic of the present invention is excellent in water resistance, sebum resistance and resistance to reattachment. On the other hand, none of the cosmetics of Comparative Examples 1 to 3 had excellent test results.

Example 9 (Cream foundation)
In the same manner as in Example 1, a cream foundation having the following composition was obtained.

[0150]

(Composition) (%) (1) Fluorine compound-treated powder (manufactured in the same manner as in Production Example 1) Titanium oxide 6.0 Sericite 8.0 Iron oxide (red, yellow, black) 1.2 (2) Poly (N-propionylethyleneimine) -modified silicone (Synthesis Example 7) 3.0 (3) Perfluoropolyether (FOMBLIN HC-04, manufactured by Ausimont) 10.0 (4) Decamethylcyclopentasiloxane 15 4.0 (5) Dimethylpolysiloxane / methylpolyoxyethylene copolymer (KF-6015, manufactured by Shin-Etsu Chemical Co., Ltd.) 4.0 (6) Ethanol 7.0 (7) Glycerin 5.0 (8) Purified water residue amount

Example 10 (Powder Foundation) In the following composition, first, a pigment and a poly (N-propionylethyleneimine) -modified silicone of the component (2) were mixed and pulverized through a pulverizer. This was transferred to a high-speed blender, the other components were mixed, and the resulting mixture was added to the pigment and further mixed to make the mixture uniform. This was treated with a pulverizer, and the particle size was adjusted through a sieve. Then, the mixture was allowed to stand for several days and then compression-molded in a container such as a gold plate to obtain a powder foundation.

[0152]

(Composition) (%) (1) Fluorine compound-treated pigment (produced in the same manner as in Production Example 1) Titanium oxide 15.0 Sericite Remaining talc 20.0 Kaolin 5.0 Bengala 2.0 Yellow oxidation Iron 2.5 Black iron oxide 0.1 Polyethylene powder 4.0 (2) Poly (N-propionylethyleneimine) -modified silicone (Synthesis Example 8) 2.0 (3) Fluorine-modified silicone (A) obtained in Production Example 2 -1) 8.0 (4) Squalane 2.0 (5) Preservative appropriate amount (6) Fragrance trace amount

Example 11 (Red) A reddish red having the following composition was obtained in the same manner as in Example 10.

[0154]

(Composition) (%) (1) Fluorine compound-treated pigment (produced in the same manner as in Production Example 1) Kaolin 40.0 Mica Remaining amount Titanium oxide 12.0 Iron oxide (red, yellow, black) 0 (2) Poly (N-propionylethyleneimine) -modified silicone (Synthesis Example 9) 2.0 (3) Organic pigment (Red No. 202) 2.4 (4) Fluorine-modified silicone obtained in Production Example 3 (A- 2) 8.0 (5) Preservative 0.1 (6) Fragrance trace

Example 12 (Powder Eye Shadow) Pigments other than titanium mica were first mixed and pulverized, and then titanium mica was mixed. Others are the same as in Example 10,
A powder eye shadow having the following composition was obtained.

[0156]

(Composition) (%) (1) Fluorine compound-treated pigment (manufactured in the same manner as in Production Example 1) Titanium mica 5.0 Sericite Remaining amount of mica 20.0 Iron oxide (red, yellow, black) 2 6.0 ultramarine 10.0 navy blue 6.0 (2) Poly (N-propionylethyleneimine) -modified silicone (Synthesis Example 9) 3.0 (3) Fluorine-modified silicone (A-3) obtained in Production Example 4 7. 0 (4) Candelilla wax 7.0 (5) Squalane 3.0 (6) Preservative appropriate amount (7) Fragrance trace amount

Example 13 (Sunscreen emulsion) A sunscreen emulsion having the following composition was obtained in the same manner as in Example 1.

[0158]

(Composition) (%) (1) Octamethylcyclotetrasiloxane 20.0 (2) Fluorine-modified silicone (A-4) 8.0 obtained in Production Example 5 (3) Copolymer (Synthesis Example) 10) 2.0 (4) Dimethylsiloxane / methylpolyoxyethylene copolymer (manufactured by Dow Corning Toray, SH3775C) 2.0 (5) Ethanol 8.0 (6) Octyl methoxycinnamate 2.0 (7 ) Silicone coated zinc oxide 7.5 (8) Fragrance trace amount (9) Glycerin 2.0 (10) Purified water balance

Example 14 (Sunscreen emulsion) A sunscreen emulsion was prepared in the same manner as in Example 13, except that the copolymer of component (3) used in Synthesis Example 11 was used.

Example 15 (Sunscreen emulsion) A sunscreen emulsion was prepared in the same manner as in Example 13 except that the copolymer of component (3) used in Synthesis Example 12 was used.

Example 16 (Sunscreen emulsion) A sunscreen emulsion was prepared in the same manner as in Example 13 except that the copolymer of Component (3) used in Synthesis Example 14 was used.

Example 17 (Sunscreen emulsion) A sunscreen emulsion was prepared in the same manner as in Example 13, except that the copolymer of Component (3) used in Synthesis Example 15 was used.

Example 18 (Sunscreen emulsion) A sunscreen was prepared in the same manner as in Example 13 except that the fluorine-modified silicone (A-5) of Production Example 6 was used as the component (2). An emulsion was prepared.

The cosmetics of Examples 9 to 18 were excellent in water resistance, sebum resistance and resistance to reattachment.

Claims (19)

[Claims] 1. The following components (A) and (B): (A) a fluorinated oil agent (B) a copolymer containing a hydrophilic segment and an organopolysiloxane segment, which is dissolved or dispersed in water or a lower alcohol. Cosmetics. 2. The component (B) causes intramolecular and intermolecular crosslinks due to bonds other than covalent bonds, and breaks or undergoes plastic deformation at an elongation of 0 to 15% at a temperature of 20 ° C. and a relative humidity of 65%. The cosmetic according to claim 1, which is a copolymer which is a solid at ordinary temperature and ordinary pressure and exhibits physical properties that do not occur. 3. The method according to claim 1, wherein the hydrophilic segment of the component (B) has a terminal-blocked N-acylalkyleneimine, polyalkylene glycol, polyalkylene glycol monoalkyl ether, acrylic acid, methacrylic acid, N, N-dimethylacrylamide, Dimethylaminoethyl methacrylate, quaternary dimethylaminoethyl methacrylate, methacrylamide, Nt-butylacrylamide, maleic acid, maleic anhydride, half esters of maleic anhydride, crotonic acid, itaconic acid, acrylamide, acrylate alcohols, hydroxy Ethyl methacrylate, diallyl dimethyl ammonium chloride, vinyl pyrrolidone, vinyl ethers, vinyl pyridine, vinyl imidazole, styrene sulfonate, allyl alcohol, vinyl alcohol , Vinyl caprolactam, N-
The cosmetic according to claim 1, wherein the cosmetic is derived from one or more selected from alkylenecarbobetaine and a residue derived from sugar. 4. The weight ratio of the hydrophilic segment of the component (B) to the segment of the organopolysiloxane is from 1/50 to
20/1, and the weight average molecular weight of the copolymer is 500 to
The cosmetic according to claim 1 or 2, wherein the cosmetic is 500,000. 5. The component (B) wherein the hydrophilic segment is a segment which is bonded to at least one of the terminal or side chain silicon atoms of the organopolysiloxane segment via an alkylene group containing a hetero atom. Formula (1): (Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group, and n represents a number of 2 or 3). The cosmetic according to any one of claims 1 to 4, which is (N-acylalkylenimine). 6. The component (B) wherein the hydrophilic segment is a segment which is bonded to at least one of the terminal or side chain silicon atoms of the organopolysiloxane segment via an alkylene group containing a hetero atom. Formula (2): (Wherein, R ² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group, an aralkyl group, an aryl group or an alkoxycarbonylalkyl group, and r represents a number of 1 to 5). Poly (N-
The cosmetic according to any one of claims 1 to 4, wherein the cosmetic is propylene carbobetaine. 7. An alkylene group containing a heteroatom bonded to at least one silicon atom at a terminal or side chain of a segment of an organopolysiloxane is represented by the formula (3): The cosmetic according to claim 5, which is selected from the groups represented by: 8. Component (B) comprises at least one terminal or side chain silicon atom of the organopolysiloxane segment.
The following general formula (4): The cosmetic according to claim 1, wherein a group represented by the formula (where m represents an integer of 1 to 8) is bonded. 9. The component (B) is characterized in that the number of silicon atoms to which the group represented by the general formula (4) is bonded is 1 to the total number of silicon atoms in the molecule.
0 to 90%, and a weight average molecular weight of 1,000 to 50.
9. The cosmetic according to claim 8, which is a 000 copolymer. 10. The cosmetic according to claim 1, wherein the component (B) is a copolymer in which a sugar-derived residue is bonded to at least one silicon atom in the terminal or side chain of the organopolysiloxane segment. . 11. The cosmetic according to claim 10, wherein the sugar-derived residue is a sugar lactone amide alkyl group. 12. Component (B) comprises a silicone chain of from 40 to
97% by weight, weight average molecular weight 1,000-500,
The cosmetic according to claim 10, wherein the cosmetic is a 000 copolymer. 13. The weight ratio of the organopolysiloxane segment of the component (B) to the poly (N-propylenecarbobetaine) segment is from 98/2 to 40/60,
The cosmetic according to claim 12, having a weight average molecular weight of 1,000 to 500,000. 14. The component (B) is composed of the following segments (i), (ii) and (iii): (i) a segment derived from a radical polymerizable vinyl monomer 1 to 98% by weight (ii) a hydrophilic segment 2. The cosmetic according to claim 1, which is a copolymer comprising 1.5 to 60% by weight (iii) 0.1 to 90% by weight of an organopolysiloxane segment. 15. The segment (i) is represented by the following general formula (5): [In the formula, X ¹ represents —OH, —NH ₂ , —OM (M represents a cation), —OR ³ , —NHR ^3, and —N (R ³ ) ₂ (where R ³ represents 1 to 8 carbon atoms) A linear or branched alkyl group, N, N-dimethylaminoethyl group, methyl quaternized N, N-dimethylaminoethyl group, 2-hydroxyethyl group, 2-methoxyethyl group or 2-ethoxyethyl group And R ⁴ and R ⁵ are a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a methoxyl group, an ethoxyl group,
A group selected from a 2-hydroxyethyl group, a 2-methoxyethyl group and an ethoxyethyl group]. 16. A segment (ii) having a terminal-blocked N-acylalkyleneimine, polyalkylene glycol, polyalkylene glycol monoalkyl ether, acrylic acid, methacrylic acid, N, N-dimethylacrylamide, dimethylaminoethyl methacrylate , Quaternary dimethylaminoethyl methacrylate, methacrylamide, Nt-butylacrylamide, maleic acid, maleic anhydride, maleic anhydride half-esters, crotonic acid, itaconic acid, acrylamide, acrylate alcohols, hydroxyethyl methacrylate, diallyl Dimethylammonium chloride, vinylpyrrolidone,
15. It is derived from one or more selected from vinyl ethers, vinyl pyridine, vinyl imidazole, styrene sulfonate, allyl alcohol, vinyl alcohol, vinyl caprolactam, N-alkylenecarbobetaine and residues derived from sugars. The cosmetic described. 17. The segment (iii) is represented by the following general formula (6): E (Y) _s Si (R ⁶ ) _3-t (Z) _t (6) wherein E is a segment (i) or ( ii) a vinyl group (which may have a substituent) which can be copolymerized with the monomer constituting the monomer or its macromonomer, Y represents a divalent linking group, R ⁶ represents a hydrogen atom, a lower alkyl group , An aryl group or an alkoxyl group, Z represents a monovalent siloxane polymer portion having an average molecular weight of 500 or more, and s represents 0 or 1.
And t represents an integer of 1 to 3]. The cosmetic according to claim 14, which is an organopolysiloxane. 18. An organopoly represented by the general formula (6)
The siloxane is represented by the following general formulas (7) to (12);(Wherein t has the same meaning as described above;⁷Is a hydrogen atom or
Represents an alkyl group; ⁸Is a hydrogen atom or carboxyl
A group represented by R⁹Represents a hydrogen atom, a methyl group or a carboxy group.
A tyl group;^TenRepresents an alkyl group, an alkoxyl group,
Shows a rukylamino group, aryl group or hydroxyl group
And x represents a number of 2 to 6, and y represents a number of 5 to 700.
And u represents 0 or 1).
Silicone containing with a weight average molecular weight of 00000
15. The cosmetic according to claim 14, comprising a macromer.
Fees. 19. The cosmetic according to claim 1, further comprising a hydrophobized powder as the component (C).