JPH0971505A - Cross-linked type silicone-containing cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cosmetic improved in water repellency and compatibility with formulation component and having excellent functional characteristics and good in make-up persistence. SOLUTION: This cosmetic uses a cross-linked silicone obtained by cross- linking a silicone of formula I [R is a hydrocarbon which may have a substituent group; A is a divalent hydrocarbon which may have a substituent group; (n) is 0 or a natural number; (m) is a natural number, with the proviso that in either one of R and A, at least one H atom is replaced with F] with a cross- linking agent of formula II (X is a halogen other than F; Q is a divalent hydrocarbon which may have a substituent group). A compound of formula III [(p) is a natural number] is especially preferably used as the cross-linked silicone. Further, a compound of formula IV [(s), (t) and (u) are each a natural number; R<9> is an alkyl; R<10> and R<11> are each a fluoroalkyl or an alkyl (at least either one thereof is a fluoroalkyl)] is preferably used as the cross-linked silicone. The content of the cross-linked silicone is 0.1-80wt.% based on total amount.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cosmetic containing a crosslinkable silicone.

[0002]

2. Description of the Related Art In the field of cosmetics, makeup breakage is an important problem, and it has been said that makeup breakage is caused by a hydrophilic component in a cosmetic material. It has been said that it is effective to mix a highly water-repellent component with a cosmetic material to form a film strong against water, in order to prevent makeup deterioration. Further, in makeup cosmetics and the like, it has been known that maintaining the luster improves makeup retention. From this point of view, silicones are important raw materials as a substance causing gloss and water repellency. Among them, silicone having a three-dimensional structure has been remarkably improved in water repellency, and has been a material of interest in recent years.

In the field of cosmetics as well, conventionally known three-dimensional silicones have a polymethylsilsesquioxane structure or a silica structure (silicone varnish) having a trialkylsilyl group at the terminal. The coating film produced lacks flexibility, and when coating powders or the like, this coating property often suffers from damage. In particular, in the case of holding makeup, since the coating film lacks flexibility, it may fall off from the skin and cause makeup loss.

Further, in recent years, it has been pointed out that one of the causes of makeup deterioration is the breakage due to sebum, and the advent of raw materials having oil repellency as well as water repellency has been desired. There is fluorinated silicone as a silicone having oil repellency as well, but fluorinated silicone which has good compatibility with other components for cosmetics and forms a strong film has not been obtained yet.

A silicone obtained by crosslinking the silicone represented by the general formula (I) with a crosslinking agent represented by the general formula (II), especially the silicone represented by the general formula (III) is a novel silicone. It is a compound, and it has not been known at all that this compound has water repellency and oil repellency and forms a flexible and strong film. Further, it has not been known at all that the compound represented by the general formula (II) described below is a useful crosslinking agent for silicones.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of such a situation, and an object of the present invention is to provide a cosmetic having a long lasting makeup.

[0007]

In view of the above situation, the present inventors have earnestly studied for a material for forming a flexible film having water repellency and oil repellency, which is useful for improving makeup retention. As a result, the silicone represented by the following general formula (I) is cross-linked with the crosslinking agent represented by the following general formula (II), especially the silicone represented by the following general formula (III). The present invention has been completed by finding out that it has various properties.

That is, the present invention is a cosmetic containing a crosslinkable silicone obtained by crosslinking a compound represented by the general formula (I) with a crosslinking agent represented by the general formula (II),

[0009]

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(In the formula (I), each R independently represents a hydrocarbon group which may have a substituent, and these may be the same or different from each other. A has a substituent. Represents a divalent hydrocarbon group which may be represented, n represents 0 or a natural number, and m represents a natural number, provided that at least one hydrogen atom of R or A is substituted with a fluorine atom. Be present.)

[0011]

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(In the formula (II), X represents a halogen atom other than a fluorine atom, and Q represents a divalent hydrocarbon group which may have a substituent.)

Cosmetics containing a cross-linking silicone, preferably having a structure represented by the general formula (III),

[0014]

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(In formula (III), R's each independently represent a hydrocarbon group which may have a substituent, which may be the same or different from each other. A and Q are each a substituent. Represents a divalent hydrocarbon group which may have n and o.
Each represents 0 or a natural number, and m and p each represent a natural number. However, at least one hydrogen atom of either R or A is substituted with a fluorine atom. )

[0016]

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below.

(1) Crosslinking type silicone which is an essential component of the present invention The silicone of the present invention is obtained by crosslinking the silicone represented by the general formula (I) with a crosslinking agent represented by the general formula (II). The silicone of the general formula (II
It has a structure represented by I).

In the general formulas (I) and (III), R is a hydrocarbon group which may have a substituent, and the hydrocarbon group is an alkyl group, an alkenyl group, an alkynyl group,
It is a phenyl group. The carbon number of these groups is preferably 1 to 20, and more preferably 1 to 10. This is because if the hydrocarbon group is too large, the hydrocarbon group will have too strong properties. Among them, the methyl group is preferable as the alkyl group containing no fluorine atom from the viewpoint of easy production.

Q in the general formulas (II) and (III) is
Represents a divalent hydrocarbon group which may have a substituent,
Preferred are low chain length aliphatic or aromatic hydrocarbon groups. This is because if the crosslinked portion is too long, the properties of the silicone portion will be impaired. Preferred groups for Q are low-chain-length polymethylene groups and phenylene groups. Of these, 1,2- and 1,4-phenylene groups are preferable. This is because by adopting such a structure, a film having a good balance between strength and flexibility can be obtained. Here, specific examples of the compound represented by the general formula (II) include adipic dichloride, 1,4
-Cyclohexanedicarbonyl dichloride, 2,5-
Bis (pentyloxy) -1,4-benzenedicarbonyl chloride, succinyl dichloride, perfluorosuccinyl chloride (ClCOCF ₂ CF ₂ COCl)
And the like.

A in the general formulas (I) and (III) is a divalent hydrocarbon group which may have a substituent. Preferred hydrocarbon groups are an alkylene group, an alkenylene group, An alkynylene group, a phenylene group, and a polymethylene group. The carbon number of these groups is preferably 1 to 20, and more preferably 1 to 10. This is because if the hydrocarbon group is too large, the hydrocarbon group will have too strong properties.

In the above formulas (I) and (III), either R or A has at least one hydrogen atom substituted with a fluorine atom. Here, the ratio of the fluorine-containing hydrocarbon group to the total hydrocarbon groups in the silicone of the present invention is preferably 40 to 90 mol%, more preferably 60 to 80 mol%. This is because the ratio of the fluorinated hydrocarbon group to the total hydrocarbon group has an appropriate range for the balance between compatibility and water repellency.

The degree of polymerization of the silicone of the present invention, that is, n +
The value of m or o + p is preferably 10 to 1000, and more preferably 16 to 200. Further, the cross-linking rate, m
The average value of / m + n and p / o + p is 0.0001 to 0.8
Is preferable, and more preferably 0.001 to 0.5. This is because if this value is too large, the solubility is impaired,
This is because if it is too small, the coating properties will be impaired.

Since the silicone of the present invention has two amide bonds in one crosslinked structure and forms a flexible film while having a three-dimensional structure, it has a higher ratio than ordinary silicones having a three-dimensional structure. As a result, it has good adhesion and is less likely to peel off from the skin. Among these silicones, the silicone represented by the general formula (VII) is preferable.

[0025]

[Chemical 12]

(In the formula (VII), s, t, and u are respectively
Represents a natural number. R⁹Represents an alkyl group having 1 to 4 carbon atoms
But these may be the same or different from each other
Yes. R^TenAnd R¹¹Is a fluoroalkyl group or carbon number
1 to 4 alkyl groups, and R ^TenAnd R¹¹Nozomi
It is a fluoroalkyl group. A and Q are as above
Is synonymous with )

(2) Method for producing crosslinked silicone which is an essential component of the present invention The silicone of the present invention comprises, for example, a compound represented by the general formula (IV) and a compound represented by the general formula (V). After copolymerizing or polymerizing only the compound represented by the general formula (V), the compound represented by the general formula (VI) is reacted with the compound represented by the general formula (I). It can be produced by a method including a step of producing and a step of reacting the compound represented by the general formula (I) obtained in the above step with the compound represented by the general formula (II).

[0028]

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(In the formula (IV), R has the same meaning as in the formula (I), and q represents an integer of 4 or more.)

[0030]

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(In the formula (V), R'represents a hydrocarbon group which may have a substituent or a hydrogen atom, and r represents an integer of 4 or more.)

[0032]

[Chemical 15]

(In the formula (VI), R¹Is a hydrogen atom; R²,
R^Three, R^FourOr a hydrocarbon group which may be bonded to T;
Or C₍₂₎Represents a bond with R²Is a hydrogen atom; or R
¹, R^Three, R ^FourOr a hydrocarbon which may be bonded to T
Represents a group. R^ThreeIs a hydrogen atom; R¹, R², R^FourOr with T
An optionally bonded hydrocarbon group; or C₍₁₎Bond with
Represents T is R¹, R², R^Three, Or R^FourCombined with
Represents a hydrocarbon group. R^FourIs a hydrogen atom; or R¹,
R², R^ThreeAlternatively, a hydrocarbon group which may be bonded to T is
Represent. The hydrocarbon group referred to here is a fluorine atom or oxygen.
Can have atoms, nitrogen atoms, or carbonyl groups
Wear. )

[0034]

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(In the formula (VIII), R ⁵ represents a hydrogen atom; or R ⁶ , R ⁷ or a hydrocarbon group which may be bonded to R ^8. R ⁶ represents a hydrogen atom; R ⁵ and R ⁷ Or a hydrocarbon group which may be bonded to R ⁸ ; or a bond with C ₍₂₎ , R ⁷ is a hydrogen atom; and a hydrocarbon which may be bonded to R ⁵ , R ⁶ or R ^8. R ⁸ is a hydrogen atom; R ⁵ ,
It represents a hydrocarbon group which may be bonded to R ⁶ or R ⁷ ; or a bond to C ₍₁₎ . The hydrocarbon group here may have an oxygen atom, a nitrogen atom, a carbonyl group or a halogen group. )

The method for producing the silicone of the present invention is shown in the following reaction formula (1). Specifically, the method of the present invention comprises polymerizing a compound of the general formula (IV) with a compound of the general formula (V), and then converting the compound of the general formula (VII
The compound shown in I) is reacted, and then the remaining hydrogen atom bonded to the silicon atom is reacted with the compound of the general formula (VI) to introduce an amino group into the side chain to give the compound of the general formula (I). The compound represented by the formula (II)
The silicone of the general formula (III) can be obtained by reacting a crosslinking agent represented by and introducing a crosslinked structure. These can be easily produced according to the usual method for producing silicones.

The silicone of the present invention has the general formula (V)
In the ring-opening polymerization of only the compound represented by the formula (1), a part of the silicon-bonded hydrogen atoms is reacted with the compound represented by the general formula (VIII), and then the remaining silicon-bonded hydrogen atoms and the general formula ( VI) with a compound represented by
It can also be obtained by reacting this with a crosslinking agent represented by the general formula (II).

[0038]

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(R, A, m, n, X, Q, o, p, q,
r, T, W and Y have the same meanings as described above. )

Specific examples of the compound represented by the general formula (IV) include polydimethylsiloxane cyclic tetramer, polydiethylsiloxane cyclic tetramer, polydipropylsiloxane cyclic tetramer and polydibutylsiloxane. Examples thereof include a cyclic tetramer, a polymethylvinylsiloxane cyclic tetramer, a polydiphenylsiloxane cyclic tetramer, and a polyphenylmethylsiloxane cyclic tetramer.

Specific examples of the compound represented by the general formula (V) include polymethyl hydrogen siloxane cyclic tetramer, polyethyl hydrogen siloxane cyclic tetramer, polydiphenyl hydrogen siloxane cyclic tetramer and the like. Is mentioned.

Specific examples of the compound represented by the general formula (VI) include 2-butenylamine, 3-butenylamine, propargylamine, 2-cyclohexenylamine, 1-allylpiperazine, 1-propargylpiperazine, acrylamide and methacryl. Examples thereof include amide and 1- (4-fluoro-2-butenyl) piperazine.

Specific examples of the compound represented by the general formula (VIII) include 1-pentene, butyl acrylate, methyl oleate, 2-butene-1,4-diol diacetate, N-allylpiperidine, 1, 4-bis (allylpiperazine), 4,4,4-trifluoro-1
-Butene, 2,2,3,4,4,4-hexafluorobutyl acrylate, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, 1- (2-butenyl) -4- (2 2,3,4,4,4-hexafluorobutyl) piperazine and the like.

The silicone thus obtained has excellent water repellency and oil repellency, and is therefore extremely useful as a raw material for cosmetics.

The production method will be described in more detail below with reference to production examples.

<Production Example 1> 100 g of polydimethylsiloxane cyclic tetramer, 96 g of polymethylhydrogensiloxane cyclic tetramer and 10 g of concentrated sulfuric acid were heated and stirred in toluene to polymerize, and 30 g of hexamethyldiene was added thereto. Siloxane was added and end capped. After the reaction,
It was washed with water and a saturated aqueous solution of sodium hydrogen carbonate, and the solvent was distilled off to obtain a polymer. When the average degree of polymerization of this polymer was determined from the viscosity, it was about 96. Also,
From the ratio of methyl groups to hydrogen bonded to silicon in proton NMR, it was found that the ratio of dimethylsiloxane to methylhydrogensiloxane in the polymer was approximately 1: 1.

The total amount of this polymer, 10 g of allylamine and 10 g of 1,1,1-trifluoro-3-butene were added,
Using 500 mL of toluene as a solvent, the mixture was heated and stirred in the presence of chloroplatinic acid to introduce a fluorinated hydrocarbon group and an amino group.
Further, 200 mL of triethylamine was added to this reaction product, 17 g of phthalic acid dichloride dissolved in 200 mL of toluene was added under ice cooling, and the white precipitate formed was removed by filtration, and then the solvent was distilled off, followed by silica gel column chromatography. The product was purified by (elution solvent; normal hexane: diethyl ether = 100: 0 → 0: 100) to obtain 110 g of the silicone represented by the general formula (I). Both the infrared spectrum and carbon-13 NMR of this product supported the structure of the chemical formula (1) shown below in the general formula (I). (Silicone 1)

[0048]

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<Production Example 2> 100 g of polydiethylsiloxane cyclic tetramer, 45 g of polymethylhydrogensiloxane cyclic tetramer and 10 g of concentrated sulfuric acid were heated and stirred in toluene to polymerize, and 40 g of hexaethyl was added thereto. Disiloxane was added and end capped. After completion of the reaction, washed with water and saturated aqueous sodium hydrogen carbonate solution,
The solvent was distilled off to obtain a polymer. With respect to the obtained polymer, the average degree of polymerization was determined from the viscosity, and it was about 140. Also, from the ratio of methyl groups to hydrogen bonded to silicon in proton NMR, it was found that the ratio of diethyl siloxane to methyl hydrogen siloxane was about 2: 1.

The total amount of this polymer, 5 g of allylamine and 6
g of 1,1,1-trifluoro-4-pentene was heated and stirred in the presence of chloroplatinic acid using 500 mL of toluene as a solvent to introduce a fluoroalkyl group and an amino group. Furthermore, 200 mL of triethylamine was added to this reaction product, 8 g of terephthalic acid dichloride dissolved in 200 mL of toluene was added under ice cooling, the white precipitate formed was removed by filtration, and then the solvent was distilled off, followed by silica gel column chromatography. (Elution solvent: normal hexane:
Diethyl ether = 100: 0 → 0: 100) to obtain 98 g of the silicone represented by the general formula (I).
The infrared spectrum and carbon 13 NMR of this product are
All of them supported the structure of the chemical formula (2) shown below in the general formula (I). (Silicone 2)

[0051]

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<Example 3: Production example 3 of silicone> 50 g of polydimethylsiloxane cyclic tetramer, 100 g of polyethylhydrogensiloxane cyclic tetramer and 10% of concentrated sulfuric acid.
g and were polymerized by heating and stirring in toluene, and
End capping was performed by adding 0 g of hexaethyldisiloxane. After completion of the reaction, the polymer was washed by washing with water and a saturated aqueous solution of sodium hydrogen carbonate, and the solvent was distilled off. The average degree of polymerization of the obtained polymer was found to be about 190 as determined from its viscosity. Further, from the ratio of methyl groups to hydrogen bonded to silicon in proton NMR, the ratio of dimethylsiloxane to ethylhydrogensiloxane is approximately 1: 2.
It turned out to be.

The total amount of this polymer, 15 g of allylamine and 5 g of 1,1,1-trifluoro-4-pentene were added,
Using 500 mL of toluene as a solvent, the mixture was heated and stirred in the presence of chloroplatinic acid to introduce a fluoroalkyl group and an amino group. Further, 200 mL of triethylamine was added to this reaction product, and the solution was dissolved in 200 mL of toluene under ice cooling to give 23 g.
Terephthalic acid dichloride of was added, the resulting white precipitate was removed by filtration, the solvent was distilled off, and the residue was purified by silica gel column chromatography (elution solvent; normal hexane: diethyl ether = 100: 0 → 0: 100), 88 g of the silicone represented by the general formula (I) was obtained. Infrared spectrum and carbon 13 NMR of this product
Are all of the following chemical formula (3) in the general formula (I):
Supported the structure of. (Silicone 3)

[0054]

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Production Example 4 100 g of polydibutylsiloxane cyclic tetramer, 50 g of polyethylhydrogensiloxane cyclic tetramer and 10 g of concentrated sulfuric acid were heated and stirred in toluene to polymerize them, and hexabutyldisiloxane was added thereto. 50 g was added for end capping.

After the completion of the reaction, the polymer was washed by washing with water and a saturated aqueous solution of sodium hydrogencarbonate, and the solvent was distilled off. The average degree of polymerization of the obtained polymer was found to be about 64 when determined from its viscosity. In addition, the ratio of dibutyl siloxane to ethyl hydrogen siloxane is approximately 1: 1 based on the ratio of hydrogen bonded to silicon in proton NMR.
It turned out to be.

The total amount of this polymer and 5 g of allylamine and 5
1,500 g of 1,1,1-trifluoro-3-butene was heated and stirred in the presence of 500 mL of toluene as a solvent in the presence of chloroplatinic acid to introduce a fluoroalkyl group and an amino group.
Further, 200 mL of triethylamine was added to this reaction product, 15 g of terephthalic acid dichloride dissolved in 200 mL of toluene was added under ice cooling, the white precipitate formed was removed by filtration, and then the solvent was distilled off, followed by silica gel column chromatography. (Elution solvent; normal hexane: diethyl ether = 100: 0 → 0: 100), and
72 g of silicone represented by the general formula (I) was obtained. Both the infrared spectrum and carbon-13 NMR of this product supported the structure of the chemical formula (4) shown below in the general formula (I). (Silicone 4)

[0058]

[Chemical 21]

<Production Example 5> To 200 g of polymethyl hydrogen siloxane cyclic tetramer, 10 g of concentrated sulfuric acid and 300 mL of toluene were added, and the mixture was heated under reflux for 3 hours and 30 g of hexamethyldisiloxane was added for end capping. This was washed with water and further with a saturated aqueous sodium hydrogen carbonate solution, and the solvent was distilled off to obtain a polymer.

20 g of allylamine and 20 g of 1,1-difluoro-3-butene were added to the obtained polymer, and the mixture was heated under reflux in toluene in the presence of chloroplatinic acid for 4 hours to introduce an amino group and a fluoroalkyl group. . 2 more in this reaction
Add 00 mL of triethylamine and under ice cooling 200 mL
30 g of terephthalic acid dichloride dissolved in toluene was added, and the white precipitate formed was removed by filtration.
The solvent was distilled off, and silica gel column chromatography (eluting solvent; normal hexane: diethyl ether = 1)
(0: 0 → 0: 100) to obtain 63 g of silicone represented by the general formula (I). The introduction ratio of the amino group and the fluoroalkyl group was almost the same. The infrared spectrum and carbon 13 NMR of this product both supported the structure of the chemical formula (5) shown below in the general formula (I). (Silicone 5)

[0061]

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<Production Example 6> 100 g of polydimethylsiloxane cyclic tetramer, 96 g of polymethylhydrogensiloxane cyclic tetramer and 10 g of concentrated sulfuric acid were heated and stirred in toluene to polymerize, and 30 g of hexamethyldiene was added thereto. Siloxane was added and end capped. After the reaction,
It was washed with water and a saturated aqueous solution of sodium hydrogen carbonate, and the solvent was distilled off to obtain a polymer. When the average degree of polymerization of this polymer was determined from the viscosity, it was about 96. Also,
From the ratio of methyl groups to hydrogen bonded to silicon in proton NMR, it was found that the ratio of dimethylsiloxane to methylhydrogensiloxane in the polymer was approximately 1: 1.

The total amount of this polymer, 10 g of allylamine and 78 g of 1,1,1,2,2,3,3,4,5,5
5,6,6,7,7,8,8-heptadecafluoro-9
-Decene was heated and stirred in the presence of chloroplatinic acid using 500 mL of toluene as a solvent to introduce an amino group and a fluorohydrocarbon group. Furthermore, 200 mL of triethylamine was added to this reaction product, 35 g of phthalic acid dichloride dissolved in 200 mL of toluene was added under ice-cooling, and the generated white precipitate was removed by filtration, and then the solvent was distilled off, followed by silica gel column chromatography ( The solvent was purified with an elution solvent: normal hexane: diethyl ether = 100: 0 → 0: 100) to obtain 135 g of the silicone represented by the general formula (I). Infrared spectrum of this and carbon 13NM
All of the Rs supported the structure of the chemical formula (6) shown below in the general formula (I). (Silicone 6)

[0064]

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<Production Example 7> 100 g of polydimethylsiloxane cyclic tetramer, 96 g of polymethylhydrogensiloxane cyclic tetramer and 10 g of concentrated sulfuric acid were heated and stirred in toluene to polymerize, and 30 g of hexamethyldiene was added thereto. Siloxane was added and end capped. After the reaction,
It was washed with water and a saturated aqueous solution of sodium hydrogen carbonate, and the solvent was distilled off to obtain a polymer. When the average degree of polymerization of this polymer was determined from the viscosity, it was about 96. Also,
From the ratio of methyl groups to hydrogen bonded to silicon in proton NMR, it was found that the ratio of dimethylsiloxane to methylhydrogensiloxane in the polymer was approximately 1: 1.

The total amount of this polymer, 10 g of allylamine, and 42 g of 1,1,1,2,2,3,3,4,4-nonafluoro-5-hexene were treated with 500 mL of toluene as a solvent to form chloroplatinic acid. The mixture was heated and stirred in the presence of to introduce an amino group and a fluorohydrocarbon group. Further 200m to this reaction product
L triethylamine was added, 35 g of terephthalic acid dichloride dissolved in 200 mL of toluene under ice cooling was added, and the produced white precipitate was removed by filtration, and then the solvent was distilled off, followed by silica gel column chromatography (eluting solvent: normal hexane). : Diethyl ether = 100: 0
→ 0: 100) to obtain 114 g of silicone represented by the general formula (I). Both the infrared spectrum and carbon-13 NMR of this product supported the structure of the chemical formula (7) shown below in the general formula (I). (Silicone 7)

[0067]

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Production Example 8 100 g of polydimethylsiloxane cyclic tetramer and 96 g of polymethylhydrogensiloxane cyclic tetramer were heated and stirred in toluene to polymerize, and 30 g of hexamethyldisiloxane was added thereto. End capped. After completion of the reaction, the mixture was washed with water and a saturated aqueous solution of sodium hydrogencarbonate and the solvent was distilled off to obtain a polymer. When the average degree of polymerization of this polymer was determined from the viscosity, it was about 96. Further, from the ratio of methyl groups to hydrogen bonded to silicon in proton NMR, it was found that the ratio of dimethylsiloxane to methylhydrogensiloxane in the polymer was about 1: 1.

The total amount of this polymer, 10 g of allylamine and 78 g of 1,1,1,2,2,3,3,4,5,5
5,6,6,7,7,8,8-heptadecafluoro-9
-Decene was heated and stirred in the presence of chloroplatinic acid using 500 mL of toluene as a solvent to introduce an amino group and a fluorohydrocarbon group. Further, 200 mL of triethylamine was added to this reaction product, 17 g of terephthalic acid dichloride dissolved in 200 mL of toluene was added under ice cooling, and the white precipitate formed was removed by filtration, and then the solvent was distilled off, followed by silica gel column chromatography ( Elution solvent; normal hexane: diethyl ether = 100: 0 → 0: 10
0) and the silicone represented by the general formula (I)
1 g was obtained. Infrared spectrum of this and carbon 13
Each of the NMR supports the structure of the chemical formula (8) shown below in the general formula (I). (Silicone 8)

[0070]

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(3) Cosmetic of the present invention The cosmetic of the present invention is characterized by containing the above-mentioned specific cross-linking silicone. The cosmetic of the present invention is not particularly limited in dosage form, and examples thereof include basic cosmetics, makeup cosmetics, hair cosmetics, and cleaning cosmetics.
The preferred content of the crosslinkable silicone in the cosmetic of the present invention varies depending on the dosage form of the cosmetic, but is 0.1-8.
It is 0% by weight, more preferably 0.5 to 40% by weight in basic cosmetics such as cream, and 0.5 to 20% by weight in makeup cosmetics such as foundation.

The cosmetic of the present invention may contain optional components usually used in cosmetics, in addition to the above-mentioned crosslinkable silicone which is an essential component. As an optional component, hydrocarbons such as petrolatum, liquid paraffin and microcrystalline wax, silicones such as polydimethylsiloxane, jojoba oil, esters such as cetyl stearate, triglycerides such as beef tallow and olive oil, stearic acid, olein. Fatty acids such as acids, higher alcohols such as cetanol, octadecyl alcohol and oleyl alcohol, nonionic surfactants, anionic surfactants, surfactants such as amphoteric surfactants, glycerin, 1,3-butanediol, polyethylene glycol And the like, water-soluble polymers such as carbopol and guar gum, preservatives, ultraviolet absorbers, antioxidants, inorganic salts, powders, pigments, vitamins, crude drug extracts and the like. The cosmetic of the present invention can be obtained by formulating these optional components and the above-mentioned crosslinkable silicone by a usual method.

Among the crosslinkable silicones obtained by crosslinking the silicone represented by the above general formula (I) of the present invention with the crosslinking agent represented by the general formula (II), the preferable one is the general formula (III). The silicone represented by formula (VII) is more preferable, and the silicone represented by formula (VII) is more preferable.

[0074]

The present invention will be described in more detail with reference to the following examples, but it goes without saying that the present invention is not limited to these examples.

<Examples 1 to 4: Formulation example> Basic cosmetics were prepared in accordance with the formulations shown in Table 1 below. That is, A and B are 80 ℃
It was heated to dissolve each component, B was gradually added to A, emulsified and stirred to cool to obtain a cream. At this time, since silicone, which is an essential component of the present invention, has good compatibility, it is easy to emulsify, and special attention is not required in emulsification.
In addition, when the same amount of fomblin was used in place of the silicone, which is an essential component of the present invention in Example 1, emulsification was not possible and two layers were separated. It was confirmed that the makeup lasts long when the makeup is made after conditioning the skin with these basic cosmetics. That is, it was found that these are basic cosmetics and at the same time have an undermake-up function.

[0076]

[Table 1]

<Examples 5 to 8: Formulation example> A foundation was prepared according to the following Table 2. That is, the formulation components were weighed in a kneader, kneaded while being heated to 80 ° C., packed in a gold plate and pressure-molded to obtain a foundation. When these foundations were applied to the upper arm and rubbed with running fingers under running water, no drop was observed in any of the foundations. In the same manner except that the silicone was changed to the conventional polydimethylsiloxane, the resistance to rubbing under running water was low.

[0078]

[Table 2]

<Examples 9 to 12: Formulation example> Lip colors were prepared according to the formulations shown in Table 3 below. That is, the prescription components were dissolved and dispersed by heating at 80 ° C, heated at 60 ° C, heated to 90 ° C again, poured into a mold, cooled and taken out to obtain a lip color. The cross-linkable silicone, which is an essential constituent of the present invention in this lip color, was compared with an ordinary silicone varnish (three-dimensional structure) replaced for ease of color transfer. Was better. Furthermore, when comparing these conventional products with a commercially available lipstick overcoat and the case of only the example, the difficulty of color transfer is equivalent to this conventional product combination, and The fee is only one item,
It was found to have the function of combining two conventional products.

[0080]

[Table 3]

<Examples 13 to 16: Formulation example> Table 4 below.
A hair blow spray was prepared according to the prescription. That is, the prescription components were heated, dissolved and cooled, filled in a pressure resistant container with a spray nozzle, and natural gas was injected and sealed to obtain a spray. This is a conventional polydimethylsiloxane (100
c. s. ), The hair passed for a long time as compared to the one replaced with.

[0082]

[Table 4]

<Example 17: Sensory evaluation> Professional panelist 1
Sensory evaluation of the cosmetics of the present invention (Example 1) was performed by 0 persons. As a comparative example, one in which silicone 1 was replaced with polydimethylsiloxane (100 c.s.) was used (Comparative Example 1). The evaluation items are moist feeling, water repellency when water drops are dropped, good skin familiarity, difficulty in breaking makeup applied on the skin, and comprehensive evaluation, and "good" is given a score of 5 and "somewhat good". The evaluation was carried out on a five-point scale, with a rating of 4, a rating of 3 for "normal", a rating of 2 for "slightly bad" and a rating of 1 for "bad". Table 5 shows the results. This shows that the cosmetic composition of the present invention has excellent sensory characteristics.

[0084]

[Table 5]

<Example 18: Sensory evaluation> Professional panelist 1
Sensory evaluation of the cosmetic composition of the present invention (Example 8) was performed by 0 persons. As a comparative example, a silicone varnish in which the silicones 4 and 5 were replaced was used (Comparative Example 2). Evaluation items are
Moisture sensation, water repellency when water drops are dropped, skin familiarity, difficulty in breaking up makeup, and comprehensive evaluation. "Good" is given a score of 5, "somewhat good" is given a score of 4, and "normal" is given a rating. The evaluation was carried out on a scale of 5 with a rating of 3, "slightly bad" and a rating of 1 for "bad". Table 6 shows the results. This shows that the cosmetic composition of the present invention has excellent sensory characteristics.

[0086]

[Table 6]

<Example 19: Sensory evaluation> Special panelist 1
Sensory evaluation of the cosmetics of the present invention (Example 12) was performed by 0 persons. As a comparative example, a silicone varnish replacing the silicones 4 and 5 was used (Comparative Example 3). Evaluation items are
Difficulty in color transfer, water repellency when water drops are dropped, good familiarity with lips, difficulty in disintegration, and comprehensive evaluation,
The evaluation was carried out on a five-point scale with a rating of 5 for "good", a rating of 4 for "slightly good", a rating of 3 for "normal", a rating of 2 for "slightly bad" and a rating of 1 for "bad". Table 7 shows the results. This shows that the cosmetic composition of the present invention has excellent sensory characteristics.

[0088]

[Table 7]

<Example 20: Sensory evaluation> Professional panelist 1
Sensory evaluation of the cosmetic composition of the present invention (Example 14) was carried out by 0 persons. As a comparative example, one in which silicones 2, 3, and 4 were replaced by polydimethylsiloxane was used (Comparative Example 4). The evaluation items were gloss continuity, water repellency when water drops were dropped, combability, difficulty in collapsing the set, and comprehensive evaluation. "Good" was given a score of 5, "somewhat good" was given a score of 4,
The evaluation was carried out on a five-point scale with a rating of "normal" being 3, a rating of "bad" being 2 and a rating of 1 being "bad". Table 8 shows the results.
This shows that the cosmetic composition of the present invention has excellent sensory characteristics.

[0090]

[Table 8]

<Example 21: Formulation example> A foundation was prepared based on the following formulation. That is, Part A was weighed in a Henschel mixer, mixed at low speed, the speed was switched to high speed, and Part B was gradually added to perform coating. Next, this was finished and crushed with a palberizer equipped with a 1 mm herringbone screen, packed in a gold plate and pressure-molded to obtain a foundation.

(Part A) Sericite: 30 parts by weight Talc: 40 parts by weight Titanium oxide: 15 parts by weight Yellow iron oxide: 4 parts by weight Red iron oxide: 1 part by weight (part B) Squalane: 5 parts by weight Silicone 8: 5 parts by weight Department

[0093]

EFFECTS OF THE INVENTION The cosmetic composition of the present invention has improved water repellency and compatibility with formulation components, and thus has excellent organoleptic properties and functions.

Claims (7)

[Claims] 1. A cosmetic containing a crosslinked silicone obtained by crosslinking a compound represented by the general formula (I) with a crosslinking agent represented by the general formula (II). Embedded image (In the formula (I), R's each independently represent a hydrocarbon group which may have a substituent, and these may be the same or different from each other. A represents a substituent. Represents a divalent hydrocarbon group, n is 0 or a natural number, and m is a natural number, provided that either R or A is at least 1.
It is assumed that each hydrogen atom is replaced by a fluorine atom. ) (In the formula (II), X represents a halogen atom other than a fluorine atom, and Q represents a divalent hydrocarbon group which may have a substituent.) 2. The cosmetic according to claim 1, wherein the crosslinkable silicone has a structure represented by the general formula (III). Embedded image (In formula (III), R's each independently represent a hydrocarbon group which may have a substituent, which may be the same or different from each other. A and Q each have a substituent. And n and o each represent 0 or a natural number, and m and p each represent a natural number, provided that either R or A has at least one hydrogen atom as a fluorine atom. It shall be substituted with atoms.) 3. The crosslinkable silicone is represented by the general formula (VII).
The cosmetic according to claim 1 or 2, which has the structure described below. Embedded image(In the formula (VII), s, t, and u each represent a natural number.
You. R⁹Represents an alkyl group having 1 to 4 carbon atoms, and these are
They may be the same or different from each other. R^Tenand
R¹¹Is a fluoroalkyl group or an alkyl group having 1 to 4 carbon atoms.
Represents a radical and R ^TenAnd R¹¹At least of
The difference is a fluoroalkyl group. A and Q are respectively
It represents a divalent hydrocarbon group which may have a substituent. ) 4. R ^{9 of} formula (VII) is a methyl group,
The cosmetic according to claim 3. 5. The crosslinkable silicone is represented by the general formula (IV).
The compound represented by the general formula (V)
Or only compounds represented by general formula (V)
After polymerizing, the compound represented by the general formula (VI)
To produce a compound represented by the general formula (I)
Represented by the formula and the general formula (I) obtained in the process
By reacting a compound represented by the general formula (II) with
Manufactured by a method including a step of
The cosmetics described in the gap. Embedded image(In formula (IV), R has the same meaning as in formula (I),
q represents an integer of 4 or more. )(In the formula (V), R'is a hydrocarbon which may have a substituent.
It represents an elementary group or a hydrogen atom, and r represents an integer of 4 or more. )(In formula (VI), R¹Is a hydrogen atom; R², R^Three, R^FourOr
A hydrocarbon group which may be bonded to T; or C₍₂₎With
Represents a bond. R²Is a hydrogen atom; or R¹, R^Three, R ^Fourif
Represents a hydrocarbon group which may be bonded to T. R^ThreeIs
Hydrogen atom; R¹, R², R^FourOr even if it is bound to T
Good hydrocarbon radical; or C₍₁₎Represents a bond with T is
R¹, R², R^Three, Or R^FourCarbonized water that may be combined with
Represents an elementary group. R^FourIs a hydrogen atom; or R¹, R², R^Threeif
Represents a hydrocarbon group which may be bonded to T. In addition, this
The hydrocarbon group here means a fluorine atom, an oxygen atom, a nitrogen atom.
Can have a child or a carbonyl group. ) 6. The crosslinkable silicone copolymerizes the compound represented by the general formula (IV) and the compound represented by the general formula (V), or only the compound represented by the general formula (V). And then reacting the compound represented by the general formula (VI) with the compound represented by the general formula (VIII) to produce a compound represented by the general formula (I). The cosmetic according to any one of claims 1 to 5, which is produced by a method. Embedded image (In the formula (VIII), R ⁵ is a hydrogen atom; represents or R ^6, R ^7, or may be bonded to R ⁸ hydrocarbon group .R ⁶
Represents a hydrogen atom; a hydrocarbon group which may be bonded to R ⁵ , R ⁷ , or R ⁸ ; or a bond with C ₍₂₎ . R ⁷ represents a hydrogen atom; R ⁵ , R ⁶ , or a hydrocarbon group which may be bonded to R ⁸ . R ⁸ represents a hydrogen atom; a hydrocarbon group which may be bonded to R ⁵ , R ⁶ or R ⁷ ; or a bond to C ₍₁₎ . The hydrocarbon group here may have an oxygen atom, a nitrogen atom, a carbonyl group or a halogen group. ) 7. The cosmetic according to claim 1, wherein the content of the crosslinkable silicone is 0.1 to 80% by weight based on the total amount of the cosmetic.