JP2002029921A - Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cosmetic excellent in a preventing effect on color transfer, excellent in water repellency and oil repellency and yet excellent in sense of use. SOLUTION: This cosmetic contains a fluorinated polymer having a cross- linking structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic having excellent rub resistance, water resistance and oil resistance, and having a long-lasting effect on makeup, particularly having a high effect of preventing color transfer.

[0002]

2. Description of the Related Art Cosmetics such as make-up cosmetics and sunscreen cosmetics have a film-forming ability in order to prevent the migration of cosmetics due to contact with clothing, tableware, skin, etc. after application, for example, color transfer. High molecular compounds are used. For example, a cosmetic (Japanese Patent Application Laid-Open No. H10-194930) has been proposed which uses a film formed on the skin surface using a three-dimensionally crosslinked silicone and a volatile oil agent to prevent color transfer.

[0003]

However, although this cosmetic composition forms a water-repellent film on the skin after application, it has very poor oil repellency, and the strength of the film is reduced due to sebum and the like, and the cosmetic composition is not sufficiently coated. No color transfer prevention function was obtained. In addition, it was not satisfactory in terms of friction resistance. The object of the present invention is excellent in friction resistance, water resistance and oil resistance,
An object of the present invention is to provide a cosmetic having a long lasting effect on makeup, particularly having a high effect of preventing color transfer.

[0004]

The present inventors have found that a fluorinated polymer having a three-dimensional cross-linked structure forms a film having a low surface energy, and that the film does not lose its properties due to sebum. It has been found that it is possible to obtain a cosmetic film which is a difficult-to-make cosmetic film and which solves all of the above problems and has a good feeling in use. The present invention relates to a fluorinated polymer (A) having a crosslinked structure
And a cosmetic containing the same.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The crosslinked structure of a fluorinated polymer having a crosslinked structure of component (A) used in the present invention may be a structure in which polymer chains are chemically bonded by a covalent bond, The united chain may form a crosslinked structure by physical interaction.

Specifically, in a vinyl polymerization, a polymer having a crosslinked structure by a covalent bond can be synthesized by reacting a polyfunctional compound such as a divinyl compound. Here, a fluorine compound is used as a vinyl monomer or divinyl compound. What is used may be used. At this time, the fluorination may be performed on both the vinyl monomer and the divinyl compound. For example, a copolymer of perfluoroalkyl methacrylate and alkyl methacrylate (JP-A-63-54411)
In the production of, a fluorinated polymer having a crosslinked structure by a covalent bond can be produced by further crosslinking with a bifunctional monomer such as a divinyl compound.

The fluorinated polyether may be crosslinked.
For example, a commercially available perfluoropolyether, fomblin (manufactured by FOMBLIN Ausimont) can be crosslinked using a crosslinking monomer.

A fluorinated organopolysiloxane having a crosslinked structure, for example, a fluorine-modified silicone polymer described below is also a fluorinated polymer having a crosslinked structure formed by this covalent bond.

On the other hand, a cross-linked structure by physical interaction is formed by a hydrogen bond between polymer chains having a fluorine group, a hydrophobic interaction, a Coulomb force, or a coordination bond such as chelate formation. For example, when a block copolymer of perfluoroalkyl methacrylate and silicone (JP-A-11-100307) is used, a fluorinated polymer having a crosslinked structure by hydrophobic interaction can be obtained.

As the component (A), a fluorinated organopolysiloxane having a crosslinked structure is preferable, and in particular, hydrogen silicones represented by the formula (1) (wherein R ¹ is the same or different and has a substituent An alkyl group, an aryl group or an aralkyl group having 1 to 18 carbon atoms which may have a is an integer of 0 to 1000, and b is 1 to 100;
An integer of 0) and a fluorinated unsaturated compound represented by the formula (2) (wherein Rf represents a fluorinated hydrocarbon group having 1 to 16 carbon atoms, R ² represents a hydrogen atom or a carbon atom having 1 to 4 carbon atoms). Wherein X represents a divalent group containing any one of an ether group, an ester group, an amide group and a sulfonamide group), and a bifunctional unsaturated siloxane compound represented by the formula (3): (In the formula, R ³ is the same or different and may have a substituent, and may have a substituent.
A fluorine-modified silicone polymer produced by a hydrosilylation reaction of an aryl group or an aralkyl group with d representing an integer of 0 to 1000) is preferred.

[0011]

Embedded image

[0012]

Embedded image

[0013]

Embedded image

The alkyl group represented by R ¹ in the formula (1) preferably has 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms. The aryl group has 6 to 10 carbon atoms, particularly preferably a phenyl group. The aralkyl group preferably has 7 to 12 carbon atoms, particularly a phenyl-C _1-4 -alkyl group. The group which can be substituted with these groups is preferably a halogen atom such as a chlorine atom and a fluorine atom. Specific examples of preferred R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group,
Examples thereof include a chloromethyl group, a trifluoropropyl group, a phenyl group, a benzyl group, and a phenethyl group, and a methyl group, a phenyl group, and a trifluoropropyl group are particularly preferable.
Note that R ¹ in the formula may be the same or different. a is an integer of 0 to 1000, b is an integer of 1 to 1000, and a preferred range of a is 10 to 200;
Is preferably 2 to 200.

Fluorinated carbon represented by Rf in the formula (2)
As the hydrogen group, a linear or branched perfluoroalkyl
A fluoroalkyl group having a hydrogen group or a terminal hydrogen,
F (CF _Two)_e-, H (CF_Two)_e-, (CF_Three)_TwoCF (CF_Two)_e-3-(Where e
Is an integer of 1 to 16, preferably 4 to 12)
More preferably, F (CF_Two)_e-Is particularly preferred. R^TwoIndicated by
Among the alkyl groups having 1 to 4 carbon atoms, a methyl group is particularly preferred.
New X represents an ether bond, an ester bond, an amide bond or
Is a divalent group containing a sulfonamide bond, for example,-
(CH_Two)_pO (CH_Two)_q-,-(CH_Two)_pCOO (CH_Two)_q-,-(CH_Two)_pCONH (C
H_Two)_q-,-(CH_Two)_pSO_TwoNH (CH_Two)_q-(Where p and q are
A total of 1 to 16). formula
Specific examples of the compound (2) include RfCH_TwoCH2OCH_TwoCH = CH
_Two, RfCH_TwoCH_TwoOCOCH = CH_Two, RfCH_TwoCH_TwoOCOC (CH_Three) = CH_Two, RfCH_Two
CH_TwoOCO (CH_Two)₈CH = CH_Two, RfSO_TwoNHCH = CH_Two, RfCONHCH = CH_TwoBut
And especially RfCH_TwoCH_TwoOCH_TwoCH = CH_Two, RfCH_TwoCH_TwoOCOCH = CH
_Two, RfCH_TwoCH_TwoOCOC (CH_Three) = CH_Two, RfCH_TwoCH_TwoOCO (CH_Two)₈CH = CH_Two
Is preferred.

Examples of R ³ in the formula (3) include all those described above as examples of R ¹ , and specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a chloromethyl group and a trimethyl group. Examples thereof include a fluoropropyl group, a phenyl group, a benzyl group, and a phenethyl group, and a methyl group, a phenyl group, and a trifluoropropyl group are particularly preferable. Note that R ³ in the formula may be the same or different. The preferred range of d is 0-100.

The preferred fluorine-modified silicone polymer in component (A) is obtained by hydrosilylating a hydrogen silicone (1), a fluorine compound (2) and an unsaturated siloxane compound (3). The ratio of the hydrogen silicones (1) to the fluorine compound (2) is determined based on the compatibility of the obtained fluorine-modified silicone polymer with the oil agent with respect to the weight of the fluorocarbon group Rf based on the weight of the reaction product of the two. Weight percent is 20 to 90
%, Particularly preferably 30 to 80%. On the other hand, hydrogen silicones (1) and unsaturated siloxane compounds (3)
Is the ratio of the molecule of the unsaturated siloxane compound (3) to one molecule of the hydrogen silicone (1) (Y) in view of the compatibility of the obtained fluorine-modified silicone polymer with the oil agent and the film-forming property. Is 0.5 or more, and further 0.5
To 5, particularly preferably 1 to 3. If Y is too small, the crosslinking density is low, so that the compatibility with the oil agent is poor and a film is not formed. On the other hand, if Y is too large, the compatibility is good, but the crosslinking density is high, so that powder is formed. No film is formed.

In the hydrosilylation reaction of these three components, first, the hydrosilylation of a hydrogen silicone (1) and a fluorine compound (2) is performed, and then the hydrosilylation of an unsaturated siloxane compound (3) is performed. Is preferred. The first-stage hydrosilylation reaction may be performed, for example, under heating at 10 to 200 ° C. in the presence of a catalyst. As a catalyst, Bogdan Marciniec edited "Comprehensive H
andbook on Hydrosilylation "(Pergamon Press, 199
2) Those described on pages 29 to 32, for example, platinum-based catalysts such as chloroplatinic acid, divinyltetramethyldisiloxane platinum complex (Karlstedt catalyst), rhodium-based catalysts and the like can be used. Particularly, a platinum-based catalyst is preferable from the viewpoint of high activity. An organic solvent may be used for this reaction, such as aliphatic hydrocarbons such as hexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chloroform, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. Low viscosity silicone oils and the like can be used. When a solvent is used, the solvent is distilled off to obtain a fluorine-modified silicone.

The hydrosilylation reaction between the obtained fluorine-modified silicone and unsaturated siloxane compound (3) is preferably carried out in one or more oils selected from silicone oils, fluorine-based oils and fluorine-modified silicone oils. The reaction is carried out in the presence of the same catalyst as in the first stage reaction, from 10 to
It is preferable to carry out the heating at 200 ° C. After completion of the reaction, the oil may be distilled off to obtain the component (A), or the reaction solution containing the oil may be used as it is for the formulation of the cosmetic.

In the cosmetic of the present invention, the component (A) comprises:
Two or more kinds may be used in combination, and 0.001 to 3 in the total composition.
0% by weight (hereinafter simply referred to as%), preferably 0.0%
The content is preferably 1 to 20%, particularly preferably 0.1 to 10%.

The cosmetic composition of the present invention can be smoothly applied by adding an oil agent selected from the group consisting of component (B) silicone oil, fluorine-based oil and fluorine-modified silicone oil in addition to component (A). This is preferable in terms of feeling of use and finish. This is because the polymer of the component (A) is generally a hard polymer, and becomes easier to handle by swelling or dissolving in an oil agent.

Examples of the silicone oil include dimethylpolysiloxane, dimethylcyclopolysiloxane, methylhydrogenpolysiloxane and the like (for example, “Silicone Handbook” edited by Ito, Nikkan Kogyo Shimbun, 1998, 1
12 and the like, and polydimethylsiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane having a low viscosity of 100 mm ² / s or less are particularly preferable.

Fluorinated oils are perfluoro organic compounds which are liquid at normal temperature, such as perfluorodecalin, perfluoroadamantane, perfluorobutyltetrahydrofuran, perfluorooctane, perfluorononane, perfluoropentane, perfluorodecane , Perfluorododecane, etc., and a perfluoropolyether represented by the formula (4)

[0024]

Embedded image

Wherein R ¹¹ , R ¹³ , R ¹⁴ and R ¹⁵ may be the same or different and each represents a fluorine atom, a perfluoroalkyl group or a perfluoroalkyloxy group,
R ¹² represents a fluorine atom or a perfluoroalkyl group, p,
q and r are 0 so that the molecular weight becomes 500 to 100,000.
The above numbers are shown. However, p = q = r = 0 never occurs. The perfluoro groups need not be arranged in this order, and may be random polymerization or block polymerization. And formula (5) Rf ^2- (CH ₂ ) _l -OR ¹⁶ (5)

[In the formula, Rf ² represents a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms, and R ¹⁶ represents a linear or branched alkyl group having 3 to 9 carbon atoms or 3 carbon atoms. -9 represents a cycloalkyl group. l shows the number of 1-8. ] (JP-A-10-175)
No. 900, for example, perfluorohexylethyl-
1,3-dimethylbutyl ether).

Examples of the fluorine-modified silicone oil include compounds represented by the formula (6) or (7) (for example, JP-A-6-184312).

[0028]

Embedded image

(Wherein, R ⁵ is the same or different, substituted or unsubstituted alkyl, aryl or aralkyl group having 1 to 18 carbon atoms, and Rf ² is a straight or branched chain having 1 to 16 carbon atoms.) A fluorinated hydrocarbon group, m is from 0 to 1000
And n represents an integer of 1 to 1000)

As the component (B), two or more kinds may be used in combination, and 5 to 90%, preferably 20 to 80%,
In particular, it is preferable to contain 40 to 60%.

The cosmetics of the present invention include, for example, oily cosmetics, emulsified cosmetics, oily solid cosmetics and the like, such as lipsticks, lip balms, cheeks, liquid foundations, oily foundations, powder foundations, eye shadows, and towels. It is applied as basic cosmetics such as up cosmetics, emulsions and creams, and medicated cosmetics such as sunscreen emulsions.

[0032]

Example 1 A fluorinated polymer having a crosslinked structure of component (A) was produced according to the following method. -Fluorinated polymer (1) hydrogen silicone (in the formula (1), R ¹ = C
35 g of H ₃ , a = 20, b = 10) and perfluoroalkyl allyl ether (in the formula (2), X = CH ₂ OCH ₂ CH ₂ , R ² = H, Rf
= CF ₂ (CF ₂ ) ₆ CF ₃ ) (58.9 g) was reacted in the presence of Karstedt's catalyst. Next, 94 g of decamethylcyclopentasiloxane (D ₅ ) and divinyl silicone (formula (3)
In the above, 18.1 g of R ³ = CH ₃ , d = 10) was added, and a cross-linking reaction was carried out by adding a Karstedt's catalyst to obtain a fluorinated polymer (1) 50% decamethylcyclopentasiloxane 5%.
A 0% mixture was obtained.

A fluorinated polymer (2) hydrogen silicone (in the formula (1), R¹= C
H_Three, A = 100, b = 100) 10 g and perfluoroalkylun
Decylene acid ester (in the formula (2), X = (CH_Two )₈COO
(CH_Two)_Two, R^Two= H, Rf = CF_Two(CF_Two)₆CF_Three41.8 g of hexa
Reaction in the presence of Karstedt's catalyst in 200 g
I was After distilling off hexane, decamethylcyclopentane
52.8 g of siloxane and divinyl silicone (formula (3)
In, R^Three= CH_Three, D = 10) and add 1.0 g
Tet catalyst is added to carry out the cross-linking reaction,
Form (2) 50% and decamethylcyclopentasiloxane
A 50% mixture was obtained.

Example 1 A foundation having the composition shown in Table 1 was prepared, and the results of evaluating the effect of preventing color transfer, water resistance and oil resistance are also shown in Table 1.

(Evaluation Method) (1) Effect of Preventing Color Transfer 12.3 mg of a foundation was uniformly applied to 5 cm × 7 cm artificial leather and allowed to stand in a constant temperature room at 37 ° C. for 4 hours. A metal plate on which a white cloth was stuck was placed on this artificial leather and reciprocated three times on the application section with a load of 500 g (apparatus: surface tester, HEIDON TYPE 14DR: Shinto Kagaku Co., Ltd.). The results of the visual evaluation of the surface condition of the white cloth by 25 panelists were classified according to the following criteria. Evaluation Number of panelists evaluated as good color transfer prevention ◎ 20 or more ○ 15 to 19 △ 10 to 14 × 9 or less

(2) Water repellency and oil repellency A foundation was applied in the same manner as in (1), and the contact angle of water and squalane on the surface of the artificial leather left at 37 ° C. for 4 hours was measured at 25 ° C. Evaluation was made according to the following criteria. Water repellency (contact angle of water) ○ Contact angle 120 ° or more △ 100 to less than 120 ° × less than 100 ° Oil repellency (Squalane contact angle) ◎ Contact angle 90 ° or more ○ 50 to less than 90 ° △ 30 to less than 50 ° × Less than 30 °

(3) Feeling of Use Twenty-five panelists sensory-evaluated the feeling of use mainly based on the good elongation and smoothness when using the foundation, and ranked according to the following criteria. Evaluation Number of panelists who evaluated the usability as good ◎ 20 or more ○ 15 to 19 △ 10 to 14 × 9 or less

[0038]

[Table 1]

Each of the foundations of the present invention was excellent in the effect of preventing color transfer, and was also excellent in water resistance, oil resistance and usability.

[0040]

According to the present invention, the color transfer prevention effect is excellent, the water repellency and the oil repellency are excellent, and the usability is also excellent.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C083 AC102 AC342 AC811 AC812 AD151 AD152 AD161 AD162 AD172 BB21 CC01 CC12 EE06 EE07 4J035 BA02 CA02U CA021 CA16M CA161 FB01 FB02 FB05 LA02 LB14

Claims (4)

[Claims] 1. A cosmetic containing (A) a fluorinated polymer having a crosslinked structure. 2. The cosmetic according to claim 1, wherein the fluorinated polymer is a fluorinated organopolysiloxane. 3. A hydrogen silicone represented by the formula (1) wherein component (A) is the same or different, wherein R ¹ is the same or different and has 1 to 18 carbon atoms which may have a substituent. , An aryl group or an aralkyl group, a is 0 to 100
An integer of 0, b represents an integer of 1 to 1000) and a fluorinated unsaturated compound represented by the formula (2) (wherein Rf
Represents a fluorinated hydrocarbon group having 1 to 16 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents any one of an ether group, an ester group, an amide group and a sulfonamide group. And a difunctional unsaturated siloxane compound represented by the formula (3) wherein R ³ is the same or different and has 1 to 1 carbon atoms which may have a substituent. The cosmetic according to claim 1 or 2, which is a fluorine-modified silicone polymer produced by a hydrosilylation reaction of an alkyl group, an aryl group or an aralkyl group of 18 with d representing an integer of 0 to 1000). Embedded image Embedded image Embedded image 4. The cosmetic according to claim 1, further comprising (B) an oil selected from the group consisting of silicone oil, fluorine-based oil and fluorine-modified silicone oil.