JPH09291010A - Fluorinated polysiloxane-containing cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject cosmetic, excellent in compatibility with an oil and fat, capable of providing a soft, strong, thin and uniform water and oil repellent protecting film and useful as a basic, a makeup cosmetics, etc. SOLUTION: This fluorinated polysiloxane-containing cosmetic comprises a fluorinated polysiloxane represented by formula I R is a monovalent hydrocarbon group or the one in which at least a part of hydrogen atoms are substituted with fluorine atoms; R' is a group represented by the formula O-Si(R)3 , or R; at least one of all the R groups is a monovalent hydrocarbon in which at least a part of the hydrogen atoms are substituted with fluorine atoms} in an amount of 0.1-20wt.% based on the whole cosmetic. The compound represented by formula I is obtained by carrying out the hydrolysis and polycondensation of a silicon compound represented by formula II and then reacting the resultant compound with a silicon compound represented by the formula (R)3 SiX and/or a silicon compound represented by the formula (R)3 Si-O-Si(R)3 or a silicon compound represented by formula III as a terminal blocking agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a ladder which has excellent compatibility with fats and oils and provides a flexible and strong water- and oil-repellent protective film on the surface of various human bodies such as skin, hair and nails, which is thin and uniform. The present invention relates to cosmetics containing a fluorine-modified silene derivative.

[0002]

2. Description of the Related Art Silicone has been widely used as a coating agent for providing a water-repellent coating. Attempts have also been made to impart oil repellency by introducing a fluorine substituent into this silicone compound. As such an example, a polymer silicone composed of a unit-(R ₀ ) ₂ SiO- (wherein R ₀ represents an organic group; the same applies hereinafter) and a unit (R ₀ ) ₃ SiO _1/ 2-, This unit R ₀ SiO _2/3, and / or units SiO
A silicone resin having ₂ added thereto has a fluorine substituent introduced into the side chain or terminal thereof (Japanese Patent Laid-Open No. 64-83).
086, JP-A-5-78491, JP-A-6
-358185 gazette).

However, most of the conventional fluorine-substituted silicones are two-dimensional type (straight-chain type), and even with three-dimensional silicone, the network structure is cleaved by the organic group R ₀ , and the continuity of the molecule is lowered. Therefore, although the obtained water and oil repellent coating film has flexibility, the coating film strength is insufficient and there is a problem in the durability of the coating film. By increasing the proportion of SiO ₂ units, it can be improved to some extent the film strength, on this method also has limitations, SiO ₂
The increase in the proportion of units reduces the flexibility of the molecule,
As a result, there is a drawback that the strength of the coating is significantly reduced. Further, although coating strength can be obtained by applying a thick coating, it is needless to say that a thin and uniform coating is desirable. Further, the three-dimensional fluorine-substituted silicone generally has a problem of poor compatibility with various fats and oils.

For this reason, although the physical properties it possesses are considered to be useful for cosmetics, very few silicones have been applied to cosmetics.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and is flexible and strong,
Moreover, it is an object of the present invention to provide cosmetics such as basic cosmetics, makeup cosmetics, hair cosmetics, cleansing agents, nail enamel, and bath agents that provide a thin and uniform water and oil repellent protective film.

[0006]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present inventors have found that a hydrocarbon having a specific structure having an organic bond between silicon and silicon atoms and substituted with a fluorine atom. The present invention has been completed by finding that the novel ladder-type fluorinated polysiloxane having a group is excellent in coating properties and also has good miscibility with other cosmetic raw materials.

That is, the cosmetic of the present invention contains a fluorinated polysiloxane having a structure represented by the following general formula (1).

[0008]

Embedded image

[In the formula (1), R represents a monovalent hydrocarbon group or a monovalent hydrocarbon group in which at least a part of hydrogen atoms are substituted with fluorine atoms, and they may be the same or different from each other. . R'represents a group represented by the following general formula (2) or R, and may be the same or different from each other.

[0010]

Embedded image —O—Si (R) ₃ (2)

However, at least one of all Rs contained in the general formulas (1) and (2) is a monovalent hydrocarbon group in which at least a part of hydrogen atoms is substituted with a fluorine atom. Q represents a divalent organic group. n represents an integer of 10 or more. In the present invention, the silicon compound represented by the following general formula (3) is hydrolyzed and polycondensed, and then the following general formula (4) is added thereto.
And / or the fluorinated poly (polysiloxane) obtained by reacting a silicon compound represented by the following general formula (5) or a silicon compound represented by the following general formula (6) as a terminal blocking agent. Siloxane.

[0012]

[Chemical 6]

[Equations (3), (4), (5) and (6)]
In the above, R and Q have the same meanings as in the general formula (1). Further, X represents a hydrolyzable group. ]

The fluorinated polysiloxane used in the present invention can improve the continuity of molecules by the skeleton structure represented by the following general formula (7) and can provide a flexible and strong coating film. Further, the fluorine substituent imparts water and oil repellency to the coating film, and due to the presence of the organic group represented by Q and the pseudo two-dimensional structure of the ladder type molecule, the solubility in oil and fat is excellent. Therefore, the cosmetic of the present invention containing such a fluorinated polysiloxane has excellent compatibility with oils and fats, is flexible and strong on the surface of various human bodies such as skin, hair, nails, etc., and is thin and uniform water and oil repellency. A protective film can be provided.

[0015]

Embedded image

[0016]

Embodiments of the present invention will be described below in detail.

(1) Fluorinated Polysiloxane The cosmetic material of the present invention is characterized by containing a fluorinated polysiloxane having a ladder structure represented by the general formula (1). Here, in the general formula (1), Q is not particularly limited as long as it is a divalent organic group, but preferably 1).
Alkylene group; 2) polymethylene group; 3) phenylene group; 4) arylene group; 5) at least a part of hydrogen atoms of the groups of 1) to 4) above is further an alkyl group, a phenyl group,
And a group substituted with at least one member selected from the group consisting of aryl groups; 6) a group containing a functional group having an oxygen atom, a nitrogen atom or a sulfur atom in the structure of the groups 1) to 5) above;
And 7) a divalent organic group selected from the group consisting of the groups 1) to 6) in which at least some of the hydrogen atoms are replaced with chlorine or bromine.

The alkylene group is preferably one having about 3 to 20 carbon atoms, the polymethylene group is preferably one having about 3 to 20 carbon atoms, and the arylene group is preferably one having about 6 to 20 carbon atoms. The substituted alkyl group has about 1 to 5 carbon atoms, and the aryl group has 6 to 1 carbon atoms.
It is preferably about 2. Examples of the functional group having an oxygen atom, a nitrogen atom or a sulfur atom include functional groups such as ether, thioether, ester, ketone, amide, imide, amine and imine.

Specifically, the following organic groups can be exemplified. In the formula below, a, b, c and d are each 1
Represents the above integer.

[0020]

[Of 8] _{- (CH 2) a - ...} (1), -CH (CH 3) - (CH
_{2) a - ... (2)} , - (CH 2) a -C (C 2 H 5) (CH 3) - ...
_{(3), -C 6 H 4} - ... (4), - (CH 2) a -C 6 H 4 - (CH
Cl) - ... (5), - CH (CH 3) -C 6 H 4 - (CH 2) a - ...
_{(6), - (CH 2} ) a -S- (CH 2) b - ... (7), - (CH 2) a
_{-S-C 6 H 4 - ...} (8), - CH (CH 3) -S- (CH 2) a - ...
(9)

[0021]

Embedded image

In the above general formula (1), R is a monovalent hydrocarbon group or a monovalent hydrocarbon group in which at least a part of hydrogen atoms are substituted with fluorine atoms, and preferably an alkyl group or phenyl. Examples thereof include a group, an aryl group, and a group selected from the group consisting of a group in which at least a part of hydrogen atoms of these groups are substituted with a fluorine atom. In the general formula (1),
R'represents the group represented by the general formula (2) or the R.

The alkyl group in R has 1 carbon atom.
It is preferable that the aryl group has about 5 to about 5 carbon atoms, and the aryl group has about 6 to 12 carbon atoms. R and R ′ may be the same or different from each other. That is, R and R'may each contain the same group in one polysiloxane molecule, or may contain different groups. Further, R and R'may be the same or different from each other. However, among all Rs in the general formulas (1) and (2), at least one is a monovalent hydrocarbon group in which at least a part of hydrogen atoms is substituted with a fluorine atom. 0.1 to 99.9%, preferably 15 with respect to the total amount of R in one molecule
It is preferable that ˜70% is a group substituted with a fluorine atom.

Specific examples of R include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
an alkyl group such as a sec-butyl group or a tert-butyl group; a phenyl group; an aryl group such as a methylphenyl group or an ethylphenyl group; or a group in which at least a part of hydrogen atoms of these groups are substituted with a fluorine atom. Can be mentioned.

In the general formula (1), n (degree of polymerization) is 10
It is an integer of the above or more, preferably 50 to 5000, and more preferably 100 to 2000. The fluorinated polysiloxane used in the cosmetic of the present invention is obtained by hydrolytically polycondensing the silicon compound represented by the general formula (3), and then adding the silicon compound represented by the general formula (4) and / Or the silicon compound represented by the general formula (5) or the silicon compound represented by the general formula (6) is reacted as an end-capping agent.

In this production method, first, a silicon compound having a hydrolyzable group X represented by the above general formula (3).
(Hereinafter, referred to as a silicon compound (3).) Water is added to one or more kinds of the compounds, and a hydrolysis polycondensation reaction is performed. Here, in order to control the progress of the reaction, the amount of water added is preferably an amount equal to or less than the theoretical amount necessary for hydrolyzing the hydrolyzable group X of the silicon compound (3) used. At this time, it is preferable to use an organic solvent in order to allow the reaction to proceed uniformly. The reaction temperature of the hydrolysis polycondensation reaction is not particularly limited, but is preferably 0 to 80 ° C. Within this range, it is less likely that the reaction temperature becomes too low and the solvent coagulates, or that the reaction temperature becomes too high and the solvent extremely evaporates and the reaction progresses unevenly. Further, in order to promote the progress of the reaction, it is preferable to appropriately use a base and / or an acid as a catalyst. The addition amount is preferably 5 mol% or less of the silicon compound (3) used in the reaction.

Next, after carrying out the polycondensation reaction for a certain period of time, an end-capping agent is added in order to block the reaction end of the obtained polycondensate and to stably take out the polycondensate. As the terminal blocking agent, any one of the following 1 to 4 is adopted.

1. Silicon compound represented by the general formula (4) (hereinafter referred to as silicon compound (4)) 1. 2. A silicon compound represented by the general formula (5) (hereinafter referred to as a silicon compound (5)). Silicon compound (4) and silicon compound (5) 4. The silicon compound represented by the general formula (6) (hereinafter referred to as the silicon compound (6)).

That is, these end-capping agents are added to the polycondensate obtained by the above-mentioned hydrolysis polycondensation reaction to further carry out the hydrolysis reaction. At this time, it is preferable to add water and a suitable acid catalyst together in order to promote the hydrolysis reaction of the end-capping agent and facilitate the progress of the end-capping reaction. The amount of water added is not particularly limited, but it is preferable to add an amount of at least a theoretical amount necessary for hydrolyzing the added end-blocking agent. Further, the addition amount of the acid catalyst is preferably 2 mol% or more of the terminal blocking agent. In addition, this end-blocking step is performed under stirring conditions in order to allow the reaction to proceed uniformly.
The reaction time is preferably 4 to 20 hours. After completion of the reaction, the target product is taken out by decantation when the polycondensate is phase-separated, or when the phase separation is not carried out, by distilling off the solvent, freeze-drying or the like.

Materials used in the above steps will be described below.

I. Silicon compound (3) represented by the general formula (3): In the general formula (3), X is not particularly limited as long as it is a hydrolyzable group, and preferably an alkoxy group, a halogen atom or an alkoxyalkoxy group. Can be mentioned. The alkoxy group preferably has about 1 to 5 carbon atoms. Further, R and Q have the same meaning as in the general formula (1), and R may be the same as or different from each other. The silicon compound (3) can be synthesized by a known organic reaction using a known silicon compound as a raw material. For example, reaction of an alkoxysilane having an amino group with an acid derivative such as acid chloride or acid anhydride; addition reaction of hydrogensilane or mercaptosilane to a compound having an unsaturated bond; alkoxysilane compound or chlorosilane compound and Grignard reagent Alternatively, a reaction with an organic lithium compound can be mentioned. The synthesis of the silicon compound by these reactions is specifically shown as follows. However, in the following formulas, R, Q, and X have the same meanings as described above, and A and P represent a divalent organic group. Also, R _f
Represents a monovalent hydrocarbon group substituted with fluorine, and Z represents a bromine atom or an iodine atom.

1. In case of not having fluorine substituent <1> Reaction of silane having amino group with acid derivative such as acid chloride;

[0033]

Embedded image

<2> Addition reaction of hydrogensilane or mercaptosilane to a compound having an unsaturated bond;

[0035]

Embedded image · 2H-Si (R) X 2 + CH 2 = CH-A-CH = CH 2 → X 2 (R) Si- (CH 2) 2 -A- (CH 2) 2 -Si (R ) X ₂ .2HS-PSi (R) X ₂ + CH ₂ = CH-A-CH = CH ₂ → X ₂ (R) SiP-S- (CH ₂ ) ₂ -A- (CH ₂ ) ₂ -S- PSi (R) X ₂

<3> Reaction of silane compound with Grignard reagent or organolithium compound;

[0037]

Embedded image 2Si (R) X ₃ + ZMgQMgZ → X ₂ (R) SiQSi (R) X ₂ 2Si (R) X ₃ + LiQLi → X ₂ (R) SiQSi (R) X ₂

<4><1> or a combination of <2> and <3>;

[0039]

Embedded image

2. In case of having fluorine substituent <1> Reaction of fluorosilane compound with Grignard reagent or organic lithium salt;

[0041]

Embedded image 2Si (R _f ) X ₃ + ZMgQMgZ → X ₂ (R _f ) SiQSi (R _f ) X ₂ · 2Si (R _f ) X ₃ + LiQLi → X ₂ (R _f ) SiQSi (R _f ). X ₂

<2> The above 1 (when fluorine is not included)
X synthesized by <1> to <3> of _ThreeSiQSiX_ThreeWhen
Reaction with Grignard reagents or organolithium salts;

[0043]

Embedded image X ₃ SiQSiX ₃ + 2R _f MgZ → X ₂ (R _f ) SiQSi (R _f ) X ₂ · X ₃ SiQSiX ₃ + 2R _f Li → X ₂ (R _f ) SiQSi (R _f ) X ₂

II. Silicon compound (4) represented by the general formula (4): In the general formula (4), R has the same meaning as in the general formula (1), and a monovalent hydrocarbon group or a part of the hydrogen atom is Represents a monovalent hydrocarbon group substituted with a fluorine atom,
Preferred are an alkyl group, a phenyl group, an aryl group, and a group in which at least a part of hydrogen atoms of these groups are substituted with a fluorine atom. The same molecule may be contained in one molecule, or different molecules may be contained in one molecule. Specific examples of R include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group; phenyl group; methylphenyl group, ethylphenyl group. Or an aryl group; or a group in which at least a part of hydrogen atoms of these groups are substituted with a fluorine atom. In the general formula (4), X is not particularly limited as long as it is a hydrolyzable group, as in the general formula (3), but an alkoxy group, a halogen atom or an alkoxyalkoxy group can be preferably mentioned. The alkoxy group preferably has about 1 to 5 carbon atoms.

Specific examples of the silicon compound (4) include trimethylchlorosilane, triethylchlorosilane, tert-butyldimethylchlorosilane, phenyldimethylchlorosilane, trimethylmethoxysilane and trimethylethoxysilane. Also,
Specific examples in the case of having a fluorine substituent include (CF ₃
CH ₂ ) ₃ Si (OCH ₃ ), [CF ₃ (CF ₂ ) ₂ ] ₂ (C
_{H 3) SiCl, [CF 3} (CF 2) 5] (CH 3) 2 Si
(OC ₂ H ₅ ), [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₂ (C _{2
H 5) SiCl, [CF 3} (CF 2) 7] (C 2 H 5) 2 Si
_{(OCH 3), [CF 3} (CF 2) 4] (C 2 H 5) 2 SiC
1 and the like, and is obtained by a reaction of a Grignard reagent or organolithium salt having a corresponding fluoroalkyl group with a known silicon compound, or a reaction of a silicon compound having a known fluorine substituent with a Grignard reagent or an organolithium salt. . That is, it is as shown by the following reaction formula. In the formula below, R _f and Z have the same meanings as above. R ¹ and R ² each represent a hydrocarbon group.

[0046]

Embedded image (R ¹ ) _n Si (OR ² ) _4-n + mR _f MgZ → (R _f ) _m (R ¹ ) _n Si (OR ² ) _4-nm + mMg (OR ² ) Z ・ (R ¹ ) _n SiCl _4-n + mR _f MgZ → (R _f ) _m (R ¹ ) _n SiCl _4-nm + m MgClZ ・ (R ¹ ) _n SiCl _4-n + mR _f Li → (R _f ) _m (R ¹ ) _n SiCl _4-nm + mLiCl · (R _f ) _n Si (OR ² ) _4-n + mR ¹ MgZ → (R ¹ ) _m (R _f ) _n Si (OR ² ) _4-nm + mMg (OR ² ) Z · (R _f ) _n SiCl _4-n + mR ¹ MgZ → (R ¹ ) _m (R _f ) _n SiCl _4-nm + m MgClZ ・ (R _f ) _n SiCl _4-n + mR ¹ Li → (R ¹ ) _m (R _f ) _n SiCl _4-nm + mLiCl

III. Silicon compound (5) represented by the general formula (5): In the general formula (5), R has the same meaning as in the general formula (4), and R may be the same in one molecule. Well, it may contain different things. Specific examples of such silicon compounds include hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, and hexaphenyldisiloxane.

IV. Silicon compound (6) represented by the general formula (6): In the general formula (6), R and Q have the same meanings as in the general formulas (1) and (3), and each is 1
The same molecule may be contained in the molecule, or different molecules may be contained in the molecule. X has the same meaning as in formula (3). Such a silicon compound (6) can be synthesized by a known organic reaction using a known silicon compound as a raw material, similarly to the above silicon compound (3). For example,
Alkoxysilane etc. having amino group and acid chloride,
Examples thereof include a reaction with an acid derivative such as an acid anhydride; an addition reaction of hydrogensilane or mercaptosilane to a compound having an unsaturated bond; a reaction between an alkoxysilane compound or a chlorosilane compound and a Grignard reagent or an organolithium compound. The synthesis of the silicon compound by these reactions is specifically shown as follows. However, in the following formulas, R, R _f , Q, X, A, P, and Z have the same meanings as described above.

1. In case of not having fluorine substituent <1> Reaction of silane having amino group with acid derivative such as acid chloride;

[0050]

Embedded image

<2> Addition reaction of hydrogensilane or mercaptosilane to a compound having an unsaturated bond;

[0052]

Embedded image 2H-Si (R) ₂ X + CH ₂ = CH-A-CH = CH ₂ → X (R) ₂ Si (CH ₂ ) ₂ -A- (CH ₂ ) ₂ Si (R) ₂ X 2HS-PSi (R) ₂ X + CH ₂ = CH-A-CH = CH ₂ → X (R) ₂ SiP-S- (CH ₂ ) ₂ -A- (CH ₂ ) _2- S-PSi ( R) ₂ X

<3> Reaction of silane compound with Grignard reagent or organolithium compound;

[0054]

2Si (R) ₂ X ₂ + ZMgQMgZ → X (R) ₂ SiQSi (R) ₂ X 2Si (R) ₂ X ₂ + LiQLi → X (R) ₂ SiQSi (R) ₂ X

<4> Reaction of silicon compound (3) with Grignard reagent or organolithium compound;

[0056]

Embedded image X ₂ (R) SiQSi (R) X ₂ + 2RMgZ → X (R) ₂ SiQSi (R) ₂ X ・ X ₂ (R) SiQSi (R) X ₂ + 2RLi → X (R) ₂ SiQSi (R) ₂ X

2. When it has a fluorine substituent <1><1> in 1 above (when it has no fluorine substituent)
Reaction with synthesized X ₃ SiQSiX ₃ and Grignard reagent or organic lithium salt by ~ <3>;

[0058]

Embedded image X ₃ SiQSiX ₃ + 4R _f MgZ → X (R _f ) ₂ SiQSi (R _f ) ₂ X ・ X ₃ SiQSiX ₃ + 4R _f Li → X (R _f ) ₂ SiQSi (R _f ) ₂ X

<2> Reaction of silicon compound (3) with Grignard reagent or organic lithium salt;

[0060]

Embedded image X ₂ (R) SiQSi (R) X ₂ + 2R _f MgZ → X (R _f ) (R) SiQSi (R _f ) (R) X · X ₂ (R) SiQSi (R) X ₂ + 2R _f Li → X (R _f ) (R) SiQSi (R _f ) (R) X

V. Solvent used for hydrolysis polycondensation reaction: not particularly limited as long as it can dissolve the silicon compound (3), water, catalyst, etc., but specifically, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, etc. Ketones such as acetone and methyl ethyl ketone; cellosolves such as methyl cellosolve and ethyl cellosolve; tetrahydrofuran; dimethyl sulfoxide and the like.

VI. Base and / or acid catalyst used in hydrolysis polycondensation reaction: The base and / or acid catalyst used in the hydrolysis polycondensation reaction is not particularly limited as long as it is used in a usual hydrolysis reaction, Include inorganic acids such as hydrochloric acid and nitric acid; organic acids such as acetic acid and citric acid; inorganic bases such as sodium hydroxide and ammonium hydroxide; organic bases such as amine and morpholine; basic such as 3-aminoalkoxysilane Examples include group-containing silanes.

VII. Acid catalyst used for end-capping reaction: The acid catalyst used for the end-capping reaction is not particularly limited as long as it is used in a usual hydrolysis reaction,
Specific examples thereof include inorganic acids such as hydrochloric acid and nitric acid; organic acids such as acetic acid and citric acid;

(2) Cosmetic of the present invention The cosmetic of the present invention contains the fluorinated polysiloxane represented by the general formula (1) obtained as described above as an essential component. As cosmetics, basic cosmetics such as lotion, milky lotion, cream, foundation, undermake-up, lipstick, blusher, mascara, eyeliner, eye color and other makeup cosmetics, nail enamel, nail coat, remover, etc. Examples thereof include cosmetics for hair, hair lotions, hair liquids, hair cosmetics such as hair sprays, shampoos, rinses, facial cleansers, cleaning agents such as soaps, and bath agents such as bath essences and bath salts. The content of the fluorinated polysiloxane represented by the general formula (1) in these cosmetics is preferably 0.1 to 20% by weight, more preferably 0.1 to 1% by weight based on the total amount of the cosmetic.
0% by weight.

The cosmetic of the present invention may contain optional components usually used in cosmetics, in addition to the fluorinated polysiloxane. Such optional components include
For example, hydrocarbons such as petrolatum and squalane, esters such as jojoba oil and gayleu, triglycerides such as beef tallow and olive oil, fatty acids such as stearic acid and oleic acid, higher alcohols such as cetanol and oleyl alcohol, nonionic interfaces. Activator, anionic surfactant, cationic surfactant, amphoteric surfactant, polyhydric alcohols,
Examples include water-soluble polymers, ethanol, preservatives, ultraviolet absorbers, antioxidants, various vitamins, medicinal ingredients, fragrances, colorants, powders and the like. These can be formulated into cosmetics according to a conventional method.

[0066]

Embodiments of the present invention will be described below.

[0067]

Production Example 1 <Production of Silicon Compound (3)> 5.4 g of 1,3-butadiene and 23.0 g of monohydrogenmethyldichlorosilane were taken and mixed in a pressure-resistant bottle-type reaction vessel. Then, chloroplatinic acid H ₂ PtCl ₆ .6H ₂ O was heated in tetrahydrofuran, and this solution corresponding to 0.2 mmol of platinum was added to the above mixed solution, and then the reaction vessel was heated at 80 ° C. for 4 hours. . Filtration and fractional distillation were performed to remove tetrahydrofuran and chloroplatinic acid to obtain the target compound. IR, ¹ H
-NMR, ¹³ C-NMR, and ²⁹ Si-NMR spectrum measurements were performed, and it was confirmed that the target compound represented by the following formula (1a) was isolated.

[0068]

Embedded image

[0069]

[Production Example 2] <Production of silicon compound (3)> In a pressure bottle type reaction vessel
1,3-Butadiene 5.4g, Monohydrogentri
27.1 g of chlorosilane was taken and mixed. Then platinum chloride
Acid H_TwoPtCl₆・ 6H _TwoAdd O in tetrahydrofuran
Heat and add this solution corresponding to 0.2 mmol platinum to
After adding to the mixed solution, heat the reaction vessel at 80 ° C for 4 hours.
did. After filtration and fractional distillation, tetrahydrofuran and salt
The platinized acid was removed to obtain a transparent liquid. Fully dried
Three-necked frass with reflux condenser, stirrer and gas inlet tube
Take 5.8g of magnesium metal and use dry nitrogen gas.
Substantially replaced. Furthermore, metal nato is placed in this reaction vessel.
Tetrahydrofuran produced by distillation with lithium
200 ml was taken and mixed by stirring.

While continuing stirring, add to the above solution the above-mentioned solution.
2,2,2-trifru in 200 ml of trahydrofuran
A solution of 42.0 g of oroethyl iodide was added dropwise.
did. Further, under ice cooling, the above-mentioned tetrahydrofuran 2
A solution prepared by dissolving 32.5 g of the transparent liquid obtained above in 00 ml.
The solution was added dropwise. Boiling point of tetrahydrofuran after completion of dropping
The mixture was refluxed for 24 hours to complete the reaction. In addition, all
The operation was performed under a stream of dry nitrogen gas. The generated precipitate is filtered
After separation, fractional distillation was performed to obtain the target compound. IR, ¹H-N
MR,¹³C-NMR, and²⁹Si-NMR spectrum measurement
The target compound represented by the following formula (2a)
It was confirmed that the product was isolated.

[0071]

Embedded image

[0072]

[Production Example 3] <Production of silicon compound (3)> In a three-necked flask equipped with a reflux condenser, a stirrer and a gas introduction tube, 29.6 g of vinyltrimethoxysilane, 39.3 g of 3-mercaptotrimethoxysilane and benzene were added. 400 ml was taken and mixed by stirring. Further, to this solution, a solution prepared by dissolving 0.2 g of azobisisobutyronitrile in 100 ml of benzene was added and mixed with stirring. After bubbling with dry nitrogen gas at room temperature for 1 hour while continuing stirring, the mixture was heated to reflux at the boiling point of benzene for 24 hours to complete the reaction.
Benzene was removed by a rotary evaporator to obtain a transparent liquid. In a three-necked flask equipped with a reflux condenser, a stirrer, and a gas introduction tube, which had been sufficiently dried,
8.9 g and 400 ml of diethyl ether dehydrated and refined by refluxing with sodium metal and distillation were taken and sufficiently replaced with dry nitrogen gas. While continuing cooling and stirring, a solution prepared by dissolving 53.3 g of ethylmagnesium bromide in 200 ml of the above-mentioned diethyl ether was added dropwise to this solution. After completion of the dropping, stirring was continued at room temperature for 20 hours to complete the reaction. All operations were performed under a stream of dry nitrogen gas.
After removing the generated precipitate, fractional distillation was further performed to obtain the target compound. IR, ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-
When the NMR spectrum was measured, the following formula (3a)
It was confirmed that the target compound represented by was isolated.

[0073]

Embedded image

[0074]

[Production Example 4] <Production of silicon compound (3)> In a three-necked flask equipped with a reflux condenser, a stirrer and a gas introduction tube, 29.6 g of vinyltrimethoxysilane, 39.3 g of 3-mercaptotrimethoxysilane and benzene were added. 400 ml was taken and mixed by stirring.
Furthermore, to this solution, azobisisobutyronitrile 0.2
A solution prepared by dissolving g in 100 ml of benzene was added and mixed with stirring. After bubbling with dry nitrogen gas at room temperature for 1 hour while continuing stirring, the mixture was heated to reflux at the boiling point of benzene for 24 hours to complete the reaction. Benzene was removed by a rotary evaporator to obtain a transparent liquid. 5.3 g of magnesium metal and 0.05 g of iodine are put into a three-necked flask equipped with a reflux condenser, a stirrer and a gas introduction tube, which has been sufficiently dried, and the nitrogen gas is sufficiently replaced with dry nitrogen gas. Furthermore, to this reaction vessel, a solution prepared by dissolving 69.2 g of perfluorobutyl iodide and 34.5 g of the transparent liquid obtained above in 500 ml of diethyl ether produced by dehydration and dehydrated by metallic sodium was added dropwise. After completion of the dropping, the reaction was completed by leaving it for 2 hours at room temperature while continuing stirring. All the operations were performed under a dry nitrogen gas stream. The formed precipitate was separated by filtration and fractionated to obtain the target compound. IR, ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NM
When the R spectrum was measured, it was confirmed that the target compound represented by the following formula (4a) was isolated.

[0075]

Embedded image

[0076]

Production Example 5 <Production of Silicon Compound (3)> 7.3 g of metal magnesium, 198.3 g of phenyltrimethoxysilane, in a sufficiently dried three-necked flask equipped with a reflux condenser, a stirrer and a gas introduction tube. Tetrahydrofuran 3 dehydrated and purified by 0.3 g of iodine, reflux with sodium metal and distillation
00 ml was taken and stirred and mixed while sufficiently substituting with dry nitrogen gas. While continuing to stir, 23.6 g of 1,4-dibromobenzene was added to this solution under reflux conditions at the boiling point of tetrahydrofuran to obtain 100 parts of tetrahydrofuran as described above.
The solution dissolved in ml was added dropwise. Reflux for 2 after the dropping.
The reaction was completed for 4 hours. All operations were performed under a stream of dry nitrogen gas. After removing the generated precipitate, fractional distillation was further performed to obtain the target compound. IR, ¹ H-NMR, ¹³
When C-NMR and ²⁹ Si-NMR spectrum measurements were performed, it was confirmed that the target compound represented by the following formula (5a) was isolated.

[0077]

Embedded image

[0078]

Production Example 6 <Production of Silicon Compound (3)> A three-necked flask equipped with a reflux condenser, a stirrer and a gas introduction tube, which was sufficiently dried,
Metallic magnesium 0.7 g, 1H, 1H, 2H, 2H-
29.4 g of nonafluorohexyltrimethoxysilane,
Iodine (0.01 g) and tetrahydrofuran (100 ml) dehydrated and refined by refluxing with sodium metal and distillation were taken and stirred and mixed while sufficiently substituting dry nitrogen gas. While continuing stirring, 1,4-dibromobenzene 2. was added to this solution under reflux conditions at the boiling point of tetrahydrofuran.
A solution of 4 g dissolved in 50 ml of the above-mentioned tetrahydrofuran was added dropwise. After completion of the dropping, reflux was continued for 24 hours to complete the reaction. All operations were performed under a stream of dry nitrogen gas. After removing the generated precipitate, fractional distillation was further performed to obtain the target compound. IR, ¹ H-NMR, ¹³ C-NMR, ²⁹ S
When the i-NMR spectrum was measured, it was confirmed that the target compound represented by the following formula (6a) was isolated.

[0079]

Embedded image

[0080]

Production Example 7 <Production of Silicon Compound (3)> Paradivinylbenzene 26.0 g and monohydrogenmethyldiethoxysilane 53.6 g were taken and mixed in a pressure resistant bottle type reaction vessel. Next, chloroplatinic acid H ₂ PtCl ₆ .6H ₂ O was heated in tetrahydrofuran, and this solution corresponding to 0.2 mmol of platinum was added to the above mixed solution.
Heated for hours. Filtration and fractional distillation were performed to remove tetrahydrofuran and chloroplatinic acid to obtain the target compound. IR,
^{When 1} H-NMR, ¹³ C-NMR, and ²⁹ Si-NMR spectrum measurements were performed, it was confirmed that the target compound represented by the following formula (7a) was isolated.

[0081]

Embedded image

[0082]

[Production Example 8] <Production of Silicon Compound (3)> Paradivinylbenzene 26.0 g and monohydrogentriethoxysilane 65.7 g were placed in a pressure bottle type reaction vessel and mixed. Then, chloroplatinic acid H ₂ PtCl ₆ .6H ₂ O was heated in tetrahydrofuran, and this solution corresponding to 0.2 mmol of platinum was added to the above mixed solution, and then the reaction vessel was heated at 80 ° C. for 4 hours. . Filtration and fractional distillation were performed to remove tetrahydrofuran and chloroplatinic acid to obtain a transparent liquid. 3.0 g of metallic magnesium was placed in a three-neck flask equipped with a reflux condenser, a stirrer, and a gas introduction tube, which was sufficiently dried, and was sufficiently replaced with dry nitrogen gas. Further, 200 ml of tetrahydrofuran produced and dehydrated by distillation with sodium metal was placed in this reaction vessel and mixed with stirring. While continuing to stir, add 400 ml of the above-mentioned tetrahydrofuran to this solution.
A solution having 44.6 g of perfluorohexyl iodide dissolved therein was added dropwise. Further, under ice cooling, 22.9 g of the transparent liquid obtained above in 100 ml of the above-mentioned tetrahydrofuran.
Was added dropwise.

After completion of the dropwise addition, reflux was carried out for 24 hours at the boiling point of tetrahydrofuran to complete the reaction. All the operations were performed under a dry nitrogen gas stream. The formed precipitate was separated by filtration and fractionated to obtain the target compound. IR, ¹ H-NM
When R, ¹³ C-NMR and ²⁹ Si-NMR spectrum measurements were performed, it was confirmed that the target compound represented by the following formula (8a) was isolated.

[0084]

Embedded image

[0085]

[Production Example 9] <Production of silicon compound (3)> 153.0 g of 3-aminopropylmethyldiethoxysilane, 700 ml of tetrahydrofuran, and 300 ml of triethylamine were placed in a three-necked flask equipped with a reflux condenser, a stirrer, and a gas introduction tube. ,
The mixture was stirred and mixed while cooling with ice. Further, a solution prepared by dissolving 73.2 g of adipic acid chloride in 300 ml of tetrahydrofuran was added dropwise to this solution while continuing stirring with ice cooling. After the dropping was completed, stirring was continued for another hour. After filtering off the generated white precipitate, benzene, and
Triethylamine was removed to obtain the target compound. IR,
¹ H-NMR, ¹³ was subjected to ^{C-NMR, 2 9 Si-} NMR spectrum measurement, it was confirmed that the target compound represented by the following formula (9a) has been isolated.

[0086]

Embedded image

[0087]

Production Example 10 <Production of Silicon Compound (3)> 123.0 g of diallyl terephthalate and 122.2 g of monohydrogentrimethoxysilane were placed in a pressure-resistant bottle-type reaction vessel and mixed. Next, chloroplatinic acid H ₂ PtCl ₆ .6H ₂ O was heated in tetrahydrofuran, and this solution corresponding to 0.2 mmol of platinum was added to the above mixed solution.
Heated for hours. Filtration and fractional distillation were performed to remove tetrahydrofuran and chloroplatinic acid to obtain a transparent liquid. 1H, 1H, 2H, 2H in a three-necked flask equipped with a reflux condenser, a stirrer and a gas introduction tube, which was sufficiently replaced with dry nitrogen gas.
-Nonafluorohexyllithium (50.8 g) and 400 ml of diethyl ether dehydrated and refined by refluxing with sodium metal and distillation were taken and mixed with stirring. With continued stirring, add 100 mL of the above-mentioned diethyl ether to this solution.
A solution in which 49.1 g of the transparent liquid prepared above was dissolved was added dropwise to ml. After the dropwise addition was completed, stirring was continued for another 2 hours, and then reflux was performed for 8 hours to complete the reaction. After filtering off the formed precipitate, fractional distillation was performed to obtain the target compound. IR, ¹
H-NMR, ¹³ C-NMR, and ²⁹ Si-NMR spectrum measurements were performed, and it was confirmed that the target compound represented by the following formula (10a) was isolated.

[0088]

Embedded image

[0089]

[Production Example 11] <Production of silicon compound (3)> 58.9 g of diallyl ether and 138.0 g of monohydrogenmethyldichlorosilane were taken and mixed in a pressure-resistant bottle-type reaction vessel. Next, chloroplatinic acid H ₂ PtCl ₆ .6H ₂ O was heated in tetrahydrofuran, and this solution corresponding to 0.6 mmol of platinum was added to the above mixed solution, and then the reaction vessel was heated at 80 ° C. for 4 hours. . Filtration and fractional distillation were performed to remove tetrahydrofuran and chloroplatinic acid to obtain the target compound. IR, ¹ H
-NMR, ¹³ C-NMR, and ²⁹ Si-NMR spectrum measurement were performed, and it was confirmed that the target compound represented by the following formula (11a) was isolated.

[0090]

Embedded image

[0091]

[Manufacturing Example 12] <Manufacturing of silicon compound (3)>
Allyl ether 58.9g, Monohydrogenlic
53.6 g of lorosilane was taken and mixed. Next, chloroplatinic acid
H_TwoPtCl₆・ 6H _TwoHeating O in tetrahydrofuran
Then, add this solution corresponding to 0.6 mmol of platinum to the above mixture.
After adding to the combined solution, heat the reaction vessel at 80 ° C for 4 hours.
Was. After filtration and fractional distillation, tetrahydrofuran and platinum chloride
The acid was removed to give a clear liquid. Reflux cooling with sufficient drying
Gold in a three-necked flask equipped with a reactor, a stirrer, and a gas inlet tube.
Take 11.6g of magnesium, and dry nitrogen gas is enough
Substitution was made. In addition, sodium metal was added to the reaction vessel.
Tetrahydro dehydrated and purified by reflux with water and distillation
400 ml of furan was taken and mixed by stirring. Keep stirring
400 ml of the above-mentioned tetrahydrofuran in this solution.
2,2,2-trifluoroethyl iodide 84.0
A solution in which g was dissolved was added dropwise.

Further, while continuing stirring, a solution prepared by dissolving 73.8 g of the above-prepared transparent liquid in 400 ml of tetrahydrofuran was added dropwise under ice cooling. After completion of the dropping, reflux was carried out at the boiling point of tetrahydrofuran to complete the reaction. The purified precipitate was separated by filtration and fractionated to obtain the target compound. IR, ¹ H-NMR, ¹³ C-NMR, ²⁹ S
When the i-NMR spectrum was measured, the following formula (1
It was confirmed that the target compound represented by 2a) was isolated.

[0093]

Embedded image

[0094]

MANUFACTURING EXAMPLE 13 <Manufacturing of Silicon Compound (3)> 39.6 g of divinyl adipate and 53.6 g of monohydrogenmethyldiethoxysilane were taken and mixed in a pressure bottle type reaction vessel. Then, chloroplatinic acid H ₂ PtCl ₆ .6H ₂ O was heated in tetrahydrofuran, this solution corresponding to 0.3 mmol of platinum was added to the above mixed solution, and then the reaction vessel was heated at 80 ° C. for 4 hours. . Filtration and fractional distillation were performed to obtain tetrahydrofuran,
Chloroplatinic acid was removed to obtain the target compound. IR, ¹ H-
When NMR, ¹³ C-NMR, and ²⁹ Si-NMR spectrum measurements were performed, it was confirmed that the target compound represented by the following formula (13a) was isolated.

[0095]

Embedded image

[0096]

Production Example 14 <Production of Silicon Compound (3)> 1 in a pressure-resistant bottle-type reaction vessel
H, 1H, 2H-perfluorodec-1-ene 89.2
g and 24.0 g of dihydrogendiethoxysilane were taken and mixed. Then, chloroplatinic acid H ₂ PtCl ₆ .6H ₂ O was heated in tetrahydrofuran, and this solution corresponding to 0.2 mmol of platinum was added to the above mixed solution, and then the reaction vessel was heated at 80 ° C. for 4 hours. . After cooling, 19.8 g of divinyl adipate was added and the reaction vessel was again heated to 80
Heated at 0 ° C for 4 hours. Filtration and fractional distillation were performed to remove tetrahydrofuran and chloroplatinic acid to obtain the target compound.
When IR, ¹ H-NMR, ¹³ C-NMR, and ²⁹ Si-NMR spectrum measurements were performed, it was confirmed that the target compound represented by the following formula (14a) was isolated.

[0097]

Embedded image

[0098]

MANUFACTURING EXAMPLE 15 <Manufacturing of Silicon Compound (3)>
Rylmethyldichlorosilane 46.5 g, monohydrogen
Take 53.1 g of phenyldichlorosilane and mix
Was. Next, chloroplatinic acid H _TwoPtCl₆・ 6H_TwoO for Tetrahi
Heated in drofuran, equivalent to 0.2 mmol platinum
After adding this solution to the above-mentioned mixed solution, the reaction vessel
Heated at 0 ° C. for 4 hours. After filtration and fractional distillation,
Drofuran and chloroplatinic acid are removed to obtain the target compound.
Was. IR,¹H-NMR,¹³C-NMR,²⁹Si-NM
When the R spectrum was measured, the following formula (15a) was used.
It was confirmed that the target compound represented was isolated.
Was.

[0099]

Embedded image

[0100]

Production Example 16 <Production of Silicon Compound (6)> In a pressure bottle type reaction vessel,
Paradivinylbenzene 19.5 g and monohydrogen dimethylethoxysilane 31.3 g were taken and mixed. Next, chloroplatinic acid H ₂ PtCl ₆ .6H ₂ O was heated in tetrahydrofuran, and this solution corresponding to 0.1 mmol of platinum was added to the above mixed solution, and then the reaction vessel was heated at 80 ° C. for 4 hours. . Filtration and fractional distillation were performed to remove tetrahydrofuran and chloroplatinic acid to obtain the target compound. I
When R, ¹ H-NMR, ¹³ C-NMR, and ²⁹ Si-NMR spectrum measurements were performed, it was confirmed that the target compound represented by the following formula (16a) was isolated.

[0101]

Embedded image

[0102]

[Production Example 17] <Production of silicon compound (6)> 0.1 g of metal magnesium and 81.7 g of diphenyldiethoxysilane were placed in a three-necked flask equipped with a reflux condenser, a stirrer and a gas introduction tube, which were sufficiently dried. Tetrahydrofuran 1 dehydrated and purified by 0.01 g of iodine, reflux with sodium metal and distillation
00 ml was taken and stirred and mixed while sufficiently substituting with dry nitrogen gas. While continuing stirring, 7.1 g of 1,4-dibromobenzene was added to this solution under reflux conditions at the boiling point of tetrahydrofuran in 50 ml of the above-mentioned tetrahydrofuran.
Was added dropwise. After completion of the dropping, reflux was continued for 24 hours to complete the reaction. All operations were performed under a stream of dry nitrogen gas. After removing the generated precipitate, the solvent was further removed to obtain the target compound. IR, ¹ H-NMR, ¹³ C
When -NMR and ²⁹ Si-NMR spectrum measurements were performed, it was confirmed that the target compound represented by the following formula (17a) was isolated.

[0103]

Embedded image

[0104]

Production Example 18 <Production of Silicon Compound (6)> 5.8 g of metallic magnesium was placed in a three-necked flask equipped with a reflux condenser, a stirrer and a gas introduction tube, which had been sufficiently dried, and was thoroughly replaced with dry nitrogen gas. went. Further, 200 ml of tetrahydrofuran dehydrated and refined by refluxing with sodium metal and distillation was placed in this reaction vessel and mixed with stirring. While continuing to stir
To this solution, 42.0 g of 2,2,2-trifluoroethyl iodide was added to 200 ml of the above-mentioned tetrahydrofuran.
Was added dropwise. Further, while continuing stirring, a solution prepared by dissolving 32.8 g of the silicon compound obtained in Production Example 11 above in 200 ml of tetrahydrofuran was added dropwise under ice cooling. After completion of the dropping, reflux was carried out at the boiling point of tetrahydrofuran to complete the reaction. After filtering the purified precipitate, fractional distillation was performed to obtain the target compound. IR, ¹ H
-NMR, ¹³ C-NMR, and ²⁹ Si-NMR spectrum measurements were performed, and it was confirmed that the target compound represented by the following formula (18a) was isolated.

[0105]

Embedded image

[0106]

Production Example 19 <Production of Silicon Compound (4) Having Fluorine Substituent> Ethyl magnesium bromide 19 was placed in a well-dried three-necked flask equipped with a reflux condenser, a stirrer and a gas inlet tube.
2.0 g and 800 ml of diethyl ether dehydrated and refined by refluxing with sodium metal and distillation were taken and sufficiently replaced with dry nitrogen gas. While continuing stirring, a solution prepared by dissolving 374.9 g of 1H, 1H, 2H, 2H-perfluorodecanoyltrimethoxysilane in 400 ml of the above-mentioned diethyl ether was added dropwise to this solution. After completion of dropping, stirring was continued for 20 hours to complete the reaction. All operations were performed under a stream of dry nitrogen gas.

After removing the produced precipitate, fractional distillation was further carried out to obtain the target compound. IR, ¹ H-NMR, ¹³ C-NM
When the R, ²⁹ Si-NMR spectrum was measured, it was confirmed that the target compound represented by the following formula (19a) was isolated.

[0108]

Embedded image

[0109]

MANUFACTURING EXAMPLE 20 <Manufacturing of Silicon Compound (4) Having Fluorine Substituent> 5.6 g of metallic magnesium was placed in a three-necked flask equipped with a reflux condenser, a stirrer and a gas introducing tube, which was sufficiently dried.
It was sufficiently replaced with dry nitrogen gas. Further, 100 ml of tetrahydrofuran dehydrated and refined by refluxing with sodium metal and distillation was placed in this reaction vessel and mixed with stirring. While continuing to stir, add 300 ml of the above-mentioned tetrahydrofuran to this solution and add 5 parts of perfluoropropyl bromide.
A solution in which 2.3 g was dissolved was added dropwise. While continuing stirring, under ice-cooling, 100 m of the above-mentioned tetrahydrofuran
A solution of 11.9 g of tetrachlorosilane dissolved in 1 was added dropwise. After completion of the dropwise addition, reflux was carried out at the boiling point of tetrahydrofuran for 24 hours to complete the reaction. All operations were performed under a stream of dry nitrogen gas. After removing the generated precipitate, the solvent was further removed to obtain the target compound. IR, ¹ H-N
When MR, ¹³ C-NMR and ²⁹ Si-NMR spectrum measurements were performed, it was confirmed that the target compound represented by the following formula (20a) was isolated.

[0110]

Embedded image [CF ₃ (CF ₂ ) ₂ ] ₃ SiCl ... (20a)

[0111]

Production Example 21 <Production of Fluorinated Polysiloxane> In a three-necked flask equipped with a condenser and a stirrer, 28.4 g of the silicon compound of Production Example 1,
42.0 g of the silicon compound of Production Example 2 and 1 of methyl alcohol
60 ml was taken and mixed and dissolved. While continuing stirring, a solution prepared by dissolving 10.8 g of water in 40 ml of methyl alcohol was added to this solution. After the addition is complete, continue to stir 4
It was left at 0 ° C. for 8 hours. 21.7 g of trimethylchlorosilane, 8.0 g of water, 1.0 m of concentrated hydrochloric acid were added to this mixed solution.
l, a solution consisting of 40 ml of methyl alcohol was added,
It was left at 40 ° C. for 4 hours. After the reaction was completed, the system was separated into two phases, so the solvent phase was removed by decantation, further washed with a 5% sodium hydrogen carbonate solution and water, the water was removed again by decantation, and vacuum dried at 80 ° C overnight. The polycondensate was isolated. IR, ¹ H-NMR,
^{When 13} C-NMR and ²⁹ Si-NMR spectrum measurements were performed, it was confirmed that the polycondensate was a ladder-type silicone represented by the following formula (1b). In addition, n ¹ and n ² are 1 respectively by gel permeation chromatography measurement.
It was 00-200 and 100-200.

[0112]

Embedded image

[0113] In the formula (1b), Q is - (CH _{2) 4} - represents a. ]

[0114]

Production Example 22 <Production of Fluorinated Polysiloxane> A silicon compound 71.5 of Production Example 3 and a silicon compound 62.0 g of Ethyl alcohol 250 of Production Example 4 were placed in a three-necked flask equipped with a condenser and a stirrer.
ml was taken and mixed and dissolved. While continuing stirring, a solution prepared by dissolving 1.3 g of triethanolamine and 7.2 g of water in 50 ml of ethyl alcohol was added to this solution. After the addition was completed, the mixture was left at 40 ° C. for 6 hours while continuing stirring. Hexapropyldisiloxane 132.3 was added to this mixed solution.
g, 10.8 g of water, 2.0 ml of concentrated nitric acid, and 100 ml of ethyl alcohol were added, and the mixture was allowed to stand at 40 ° C. for 2 hours. After the reaction was completed, the system was separated into two phases, so the solvent phase was removed by decantation, further washed with a 5% sodium hydrogen carbonate solution and water, the water was removed again by decantation, and vacuum dried at 80 ° C overnight. The polycondensate was isolated. IR, ¹ H-NMR, ¹³ C-NMR, ²⁹ S
When the i-NMR spectrum was measured, it was confirmed that the polycondensate was a ladder-type silicone represented by the following formula (2b). In addition, n ¹ and n ² are 30 to 100 and 70 to
It was 300.

[0115]

Embedded image

[In the formula (2b), Q is-(CH ₂ ) ₂ S (C
H ₂ ) ₃ −. ]

[0117]

Production Example 23 <Production of Fluorinated Polysiloxane> In a three-necked flask equipped with a condenser and a stirrer, 82.2 g of the silicon compound of Production Example 5,
225.0 g of the silicon compound of Production Example 6 and 500 ml of methyl ethyl ketone were taken and mixed and dissolved. While continuing stirring, a solution prepared by dissolving 1.2 g of acetic acid and 25.2 g of water in 100 ml of methyl ethyl ketone was added to this solution. After the addition was completed, the mixture was left at 60 ° C. for 4 hours while continuing stirring. 20 ° C
After cooling to, a solution consisting of 113.7 g of hexamethyldisiloxane, 18.9 g of water, 4.0 ml of concentrated hydrochloric acid and 100 ml of ethyl alcohol was added to this mixed solution, and the mixture was heated to 20 ° C.
For 16 hours. After the reaction was completed, the system was separated into two phases, so the solvent phase was removed by decantation, further washed with a 5% sodium hydrogen carbonate solution and water, the water was removed again by decantation, and vacuum dried at 80 ° C overnight. The polycondensate was isolated. IR, ¹ H-NMR, ¹³ C
When -NMR and ²⁹ Si-NMR spectrum measurements were performed, it was confirmed that the polycondensate was a ladder-type silicone represented by the following formula (3b). Further, n ¹ and n ² were each 150 from gel permeation chromatographic measurement.
Was ~ 300, 250-500.

[0118]

Embedded image

[0119] In Expression (3b), Q is -C ₆ H ₄ - represents a. ]

[0120]

Production Example 24 <Production of Fluorinated Polysiloxane> In a three-necked flask equipped with a condenser and a stirrer, 31.9 g of the silicon compound of Production Example 7,
20.1 g of the silicon compound of Production Example 8, 1.5 g of 3 aminopropyltrimethoxysilane, and 1 of isopropyl alcohol
00 ml was taken and mixed and dissolved. While continuing stirring, a solution prepared by dissolving 3.6 g of water in 50 ml of isopropyl alcohol was added to this solution. After the addition was completed, the mixture was left at 70 ° C. for 6 hours while continuing stirring. After cooling to 20 ° C., 6.8 g of the silicon compound of Production Example 16 and 1.5 of water were added to this mixed solution.
g, concentrated nitric acid 0.5 ml, isopropyl alcohol 20 m
The solution consisting of 1 was added and left at 20 ° C. for 12 hours. After the reaction was completed, the system was separated into two phases, so the solvent phase was removed by decantation, further washed with 5% sodium hydrogen carbonate solution and water, the water was removed again by decantation, and vacuum dried at 80 ° C for one day. The polycondensate was isolated. IR, ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NM
When the R spectrum was measured, it was confirmed that the polycondensate was a ladder-type silicone represented by the following formula (4b). In addition, n ¹ and n ² are 200 to 300 and 600 to 7, respectively, by gel permeation chromatography measurement.
It was 00.

[0121]

Embedded image

[In the formula (4b), Q is-(CH ₂ ) ₂ C ₆ H
₄ (CH _{2) 2} - represents a. ]

[0123]

Production Example 25 <Production of Fluorinated Polysiloxane> In a three-necked flask equipped with a condenser and a stirrer, 45.2 g of the silicon compound of Production Example 9,
200 ml of methyl cellosolve was taken and mixed and dissolved. While continuing stirring, a solution prepared by dissolving 0.1 ml of hydrochloric acid and 6.5 g of water in 50 ml of methyl cellosolve was added to this solution.
After the addition was completed, the mixture was left at 20 ° C. for 6 hours while continuing stirring. In this mixed solution, the silicon compound 89.4 of Production Example 19 was added.
g, 12.2 g of water, 1.0 ml of concentrated nitric acid, and 100 ml of isopropyl alcohol, and the solution is added at 20 ° C. for 12 hours.
Left for hours. The solvent and water were removed by freeze-drying, and the polycondensate was isolated by vacuum drying at 80 ° C. for 24 hours. I
When R, ¹ H-NMR, ¹³ C-NMR, and ²⁹ Si-NMR spectrum measurements were performed, the polycondensate had the following formula (5b).
It was confirmed to be a ladder-type silicone represented by.
In addition, from gel permeation chromatography measurement,
Was 200-600.

[0124]

Embedded image

[In the formula (5b), Q represents a group represented by the following formula. ]

[0126]

Embedded image

[0127]

[Production Example 26] <Production of fluorinated polysiloxane> A silicon compound 273. of Production Example 10 was placed in a three-necked flask equipped with a condenser and a stirrer.
8 g, 3- (4,5-dihydroimidazole) propyltriethoxysilane 4.0 g, ethyl alcohol / tetrahydrofuran mixed solvent (weight ratio 7/3) 350 ml
Were collected and mixed and dissolved. While continuing stirring, a solution prepared by dissolving 6.5 g of water in 100 ml of the above-mentioned mixed solvent was added to this solution. After the addition was completed, the mixture was left at 60 ° C. for 4 hours while continuing stirring. After cooling to 20 ° C., 5.3 g of the silicon compound of Production Example 17, 1.0 g of water, and 0.1 g of concentrated nitric acid were added to this mixed solution.
A solution consisting of 5 ml and 100 ml of the above mixed solvent was added, and the mixture was left at 20 ° C. for 12 hours. After the reaction was completed, the system was separated into two phases, so the solvent phase was removed by decantation, further washed with a 5% sodium hydrogen carbonate solution and water, the water was removed again by decantation, and vacuum dried at 80 ° C overnight. The polycondensate was isolated. IR, ¹ H-
When NMR, ¹³ C-NMR, and ²⁹ Si-NMR spectrum measurements were performed, it was confirmed that the polycondensate was a ladder-type silicone represented by the following formula (6b). In addition, n is 400-from gel permeation chromatography measurement.
600.

[0128]

Embedded image

[0129] In the formula (6b), Q ¹ represents a group represented by the following formula, Q ² is -C ₆ H ₄ - represents a. ]

[0130]

Embedded image

[0131]

Production Example 27 <Production of Fluorinated Polysiloxane> Silicon compound 49.2 of Production Example 11 was placed in a three-necked flask equipped with a condenser and a stirrer.
g, 162.4 g of the silicon compound of Production Example 12 and 500 ml of ethyl alcohol were taken and mixed and dissolved. While continuing stirring, a solution prepared by dissolving 4.7 g of citric acid and 12.6 g of water in 100 ml of ethyl alcohol was added to this solution. After the addition was completed, the mixture was left at 40 ° C. for 4 hours while continuing stirring. 8.5 g of the silicon compound of Production Example 18, 0.5 g of water, 3.2 g of citric acid, and 100 parts of ethyl alcohol were added to this mixed solution.
A solution consisting of ml was added and the mixture was allowed to stand at 40 ° C. for 12 hours.
After the reaction was completed, the system was separated into two phases, so the solvent phase was removed by decantation, further washed with a 5% sodium hydrogen carbonate solution and water, the water was removed again by decantation, and vacuum dried at 80 ° C overnight. The polycondensate was isolated. IR, 1 ^H -NMR, ¹³ C-NMR, ²⁹ Si-N
When the MR spectrum was measured, it was confirmed that the polycondensate was a ladder-type silicone represented by the following formula (7b). In addition, n ¹ and n ² are 300 to 400 and 700 to ¹ respectively by gel permeation chromatography measurement.
000.

[0132]

Embedded image

[In the formula (7b), Q is-(CH ₂ ) ₃ O (C
H ₂ ) ₃ −. ]

[0134]

[Production Example 28] <Production of fluorinated polysiloxane> Silicon compound 74.7 of Production Example 13 was placed in a three-necked flask equipped with a condenser and a stirrer.
g, 52.4 g of the silicon compound of Production Example 14 and 300 ml of tetrahydrofuran were mixed and dissolved. While continuing stirring, a solution prepared by dissolving 0.3 ml of concentrated hydrochloric acid and 13.0 g of water in 100 ml of tetrahydrofuran was added to this solution. After the addition was completed, the mixture was left standing at 20 ° C. for 4 hours while continuing stirring.
Trimethylmethoxysilane 26.1 was added to this mixed solution.
g, 14.4 g of water, 2.0 ml of concentrated hydrochloric acid, and 100 ml of tetrahydrofuran were added, and the mixture was allowed to stand at 20 ° C. for 12 hours. After the completion of the reaction, a small amount of water was added, and the system separated into two phases. Therefore, the solvent phase was removed by decantation, further washed with a 5% sodium hydrogen carbonate solution and water, and then water was removed again by decantation. The polycondensate was isolated by vacuum drying at 80 ° C. for 24 hours. IR, ¹ H-
When NMR, ¹³ C-NMR, and ²⁹ Si-NMR spectrum measurements were performed, it was confirmed that the polycondensate was a ladder-type silicone represented by the following formula (8b). Moreover, n ¹ and n ² are 1 from the gel permeation chromatographic measurement.
It was 50-300 and 250-500.

[0135]

Embedded image

[In the formula (8b), Q represents a group represented by the following formula. ]

[0137]

Embedded image

[0138]

Production Example 29 <Production of Fluorinated Polysiloxane> A silicon compound 136.4 of Production Example 1 was placed in a three-necked flask equipped with a condenser and a stirrer.
g, 148.5 g of the silicon compound of Production Example 12, and 700 ml of ethyl alcohol were taken and mixed and dissolved. While continuing stirring, a solution prepared by dissolving 6.2 g of morpholine and 34.6 g of water in 200 ml of ethyl alcohol was added to this solution.
After the addition was completed, the mixture was left standing at 20 ° C. for 8 hours while continuing stirring. To this mixed solution, the silicon compound 33.8 of Production Example 18 was added.
g, 2.0 g of water, 1.0 ml of concentrated hydrochloric acid, 200 ml of ethyl alcohol were added, and the mixture was allowed to stand at 20 ° C. for 16 hours. When a small amount of water was added after the reaction was completed, the system separated into two phases. Therefore, the solvent phase was removed by decantation, further washed with a 5% sodium hydrogen carbonate solution and water, and then water was removed again by decantation. The polycondensate was isolated by vacuum drying at ℃ for 24 hours. IR, ¹ H-NMR,
^{When 13} C-NMR and ²⁹ Si-NMR spectrum measurements were performed, it was confirmed that the polycondensate was a ladder-type silicone represented by the following formula (9b). In addition, ¹ H-NMR
N ¹ and n ² are 300 to 500 and 300 to 500, respectively, according to the integral value and gel permeation chromatographic measurement.
Met.

[0139]

Embedded image

[In the formula (9b), Q ¹ represents — (CH ₂ ) ₄ — and Q ² represents — (CH ₂ ) ₃ O (CH ₂ ) ₃ —. ]

[0141]

Production Example 30 <Production of Fluorinated Polysiloxane> A silicon compound 232.5 of Production Example 15 was placed in a three-necked flask equipped with a condenser and a stirrer.
g and 500 ml of ethyl cellosolve were taken and mixed and dissolved.
2.5m concentrated ammonia water in this solution while continuing to stir
1, and a solution of 30.2 g of water dissolved in 100 ml of ethyl cellosolve was added. After the addition is complete, continue to stir 5
It was left at 0 ° C. for 8 hours. After cooling to 20 ° C., 439.3 g of the silicon compound of Production Example 20 and 12.6 of water were added to this mixed solution.
g, 8.0 ml of concentrated hydrochloric acid, and 200 ml of ethyl cellosolve were added, and the mixture was allowed to stand at 20 ° C. for 12 hours. After the reaction was completed, the system was separated into two phases, so the solvent phase was removed by decantation, further washed with a 5% sodium hydrogen carbonate solution and water, the water was removed again by decantation, and vacuum dried at 80 ° C overnight. The polycondensate was isolated.
When IR, ¹ H-NMR, ¹³ C-NMR, and ²⁹ Si-NMR spectrum measurements were carried out, the polycondensate had the following formula (10
It was confirmed to be a ladder type silicone represented by b). Further, n was 1400 to 1600 according to gel permeation chromatography measurement.

[0142]

Embedded image

[In the formula (10b), Q represents-(CH ₂ ) _3- . ]

[0144]

Production Example 31 <Production of Fluorinated Polysiloxane> A silicon compound 314.5 of Production Example 14 was placed in a three-necked flask equipped with a condenser and a stirrer.
g, 23.9 g of the silicon compound of Production Example 7, and 300 ml of isopropyl alcohol were taken and mixed and dissolved. While continuing stirring, a solution prepared by dissolving 0.4 ml of concentrated hydrochloric acid and 19.4 g of water in 50 ml of isopropyl alcohol was added to this solution. After the addition was completed, the mixture was left standing at 20 ° C. for 8 hours while continuing stirring. Add triethylchlorosilane 4 to this mixed solution.
5.2 g, hexaethyldisiloxane 49.3 g, water 1
A solution consisting of 0.8 g, concentrated hydrochloric acid 3.0 ml, and isopropyl alcohol 100 ml was added, and the mixture was allowed to stand at 20 ° C. for 16 hours. After the completion of the reaction, a small amount of water was added, and the system separated into two phases. Therefore, the solvent phase was removed by decantation, further washed with a 5% sodium hydrogen carbonate solution and water, and then water was removed again by decantation. The polycondensate was isolated by vacuum drying at 80 ° C. for 24 hours. IR, ¹ H-
When NMR, ¹³ C-NMR, and ²⁹ Si-NMR spectrum measurements were performed, it was confirmed that the polycondensate was a ladder-type silicone represented by the following formula (11b). Also ¹
From the integrated value of H-NMR and gel permeation chromatography measurement, n ¹ and n ² were 300 to 500 and 70, respectively.
It was 0 to 1000.

[0145]

Embedded image

[In the formula (11b), Q ¹ is-(CH ₂ ) ₂ C ₆
H ₄ (CH _{2) 2} - represents, Q ² represents a group represented by the following formula. ]

[0147]

Embedded image

[0148]

Example 1 <Composition Examples 1 to 5 of Cosmetics> Using the fluorinated polysiloxanes 1b to 5b of the present invention obtained in the above Production Examples, 5 kinds of creams (Formulation Example 1 ~ 5) were produced. That is, the components of A, B, C, and D parts were separately heated to 80 ° C. and dissolved. Then A and B
And were mixed and kneaded well, and C was added to the mixture to dilute it, and D was gradually added with stirring to emulsify, followed by stirring and cooling to obtain a cream. Hereinafter, the numerical values in the table represent parts by weight.

[0149]

[Table 1]

[0150]

Example 2 <Cosmetic Formulation Examples 6 to 10> Using the fluorinated polysiloxanes 6b to 10b of the present invention obtained in the above Production Examples, 5 types of foundations (Formulation Examples 6 to
10) was manufactured. That is, the part A was weighed in a Hensyl mixer, mixed at a low speed, coated at a high speed while dropping the part B, finished pulverized with a pulverizer equipped with a 1 mm herringbone screen, and filled in a gold plate. Then, pressure molding was performed to obtain a foundation. All of these foundations had excellent makeup retention.

[0151]

[Table 2]

[0152]

Example 3 <Cosmetic Formulation Examples 11 to 15> Using the fluorinated polysiloxanes 7b to 11b of the present invention obtained in the above Production Example,
Five types of hair tonics according to the formulations in Table 3 (formulation examples 11 to 11)
15) was created. That is, the prescription ingredients in Table 3 were heated and dissolved to obtain a hair tonic. All of these hair tonics were excellent in improving the gloss of the hair.

[0153]

[Table 3]

[0154]

Example 4 <Composition Examples 16 to 20 of Cosmetics> Using the fluorinated polysiloxanes 2b to 6b of the present invention obtained in the above Production Example, 5 kinds of rinses (Formulation Examples 16 to 20) was created. That is, the prescription components in Table 4 were stirred under heating to be solubilized to obtain a rinse. These rinses were excellent in combing improvement.

[0155]

[Table 4]

[0156]

Example 5 <Evaluation of Cream> As a comparative example, a conventional dimethicone (dimethylpolysiloxane: 100 c.s.) was prepared by using the fluorinated polysiloxane obtained in the above Production Example in the formulation example 1.
The water repellency of the creams of Formulation Examples 1 to 5 was compared by using 5 those specialized panelists.
The evaluation was performed by applying an appropriate amount of cream to the inner part of the lower arm, dropping water droplets, observing the state of rubbing, ranking in order from the strongest, and obtaining the average of the rankings. The sample was run blind. Table 5 shows the results. It can be seen that the cosmetic containing the fluorinated polysiloxane represented by the general formula (1) of the present invention has excellent water repellency.

A cream having the same composition as in Formulation Example 1 was prepared by using a conventional fluorinated siloxane (Silicone FS1265 manufactured by Toray Industries, Inc.) instead of the fluorinated polysiloxane of the present invention obtained in the above Production Example. I tried to make it,
Did not emulsify.

[0158]

[Table 5]

[0159]

EFFECT OF THE INVENTION By using the fluorinated polysiloxane of the present invention, it has excellent compatibility with oils and fats, and is flexible and strong on the surface of various human bodies such as skin, hair, nails, etc. A cosmetic that gives a protective film is obtained, and it is useful as a basic cosmetic, a make-up cosmetic, a hair cosmetic, a cleansing agent, a nail varnish, a bath agent and the like.

Claims (6)

[Claims] 1. A cosmetic containing a fluorinated polysiloxane having a structure represented by the following general formula (1). Embedded image [In the formula (1), R represents a monovalent hydrocarbon group or a monovalent hydrocarbon group in which at least a part of hydrogen atoms are substituted with fluorine atoms, and they may be the same or different from each other. R'represents a group represented by the following general formula (2) or R, and may be the same or different from each other. ## STR2 ## -O-Si (R) ₃ · · · (2) provided that at least one of all R are included in the general formula (1) and (2), at least part of the hydrogen atoms fluorine It is a monovalent hydrocarbon group substituted with atoms. Q represents a divalent organic group. n represents an integer of 10 or more. ] 2. In the fluorinated polysiloxane represented by the general formula (1), Q is 1) an alkylene group; 2) a polymethylene group; 3) a phenylene group; 4) an arylene group;
5) A group in which at least a part of hydrogen atoms of the groups of 1) to 4) are further substituted with at least one selected from the group consisting of an alkyl group, a phenyl group and an aryl group; 6) 1) to 5 above A group containing a functional group having an oxygen atom, a nitrogen atom or a sulfur atom in the structure of the group)); and 7) the above 1) to
The cosmetic according to claim 1, which is a divalent organic group selected from the group consisting of a group in which at least a part of hydrogen atoms of the group 6) is substituted with a chlorine atom or a bromine atom; 3. In the fluorinated polysiloxane represented by the general formula (1), Q is 1) an alkylene group; 2).
Polymethylene group; 3) phenylene group; 4) arylene group; 5) at least one of the groups 1) to 4) wherein at least a part of the hydrogen atoms further comprises an alkyl group, a phenyl group, and an aryl group. A group substituted with 6) an ether, a thioether in the structure of the group of 1) to 5) above,
A group containing at least one functional group selected from the group consisting of esters, ketones, amides, imides, amines and imines; and 7) at least some of the hydrogen atoms of the groups 1) to 6) above are chlorine atoms or The cosmetic according to claim 1 or 2, which is a divalent organic group selected from the group consisting of a group substituted with a bromine atom; 4. R in the fluorinated polysiloxane represented by the general formula (1) is an alkyl group, a phenyl group,
An aryl group and a group selected from the group consisting of a group in which at least a part of hydrogen atoms of these groups are substituted with a fluorine atom, and at least one of R is at least a part of hydrogen atoms being a fluorine atom. The cosmetic according to any one of claims 1 to 3, which is a substituted group. 5. The fluorinated polysiloxane represented by the general formula (1) is hydrolyzed and polycondensed with a silicon compound represented by the following general formula (3), and then the silicon compound represented by the following general formula (4) is added thereto.
And a silicon compound represented by the following general formula (5) or a silicon compound represented by the following general formula (6) as a terminal blocking agent. The cosmetic according to any one of claims 1 to 4. Embedded image [R and Q in Formulas (3), (4), (5) and (6)
Is as defined in the above general formula (1). Also,
X represents a hydrolyzable group. ] 6. The content of the fluorinated polysiloxane represented by the general formula (1) is from 0.1 to 20% by weight based on the total amount of the cosmetic, and the content is from 1 to 5. Cosmetics.