JPH0892376A - New fluorosilicone resin and its production - Google Patents

Abstract

PURPOSE: To obtain a new fluorosilicone resin capable of uniformly forming a flexible, firm and thin water-repellent film on a base such as a plastic, metal or the skin. CONSTITUTION: A silicon compound of formula Q<n> [Si(X)3 ]n (Q<n> is a n-valent organic group; (n) is an integer of 2-6; X is a hydrolyzable group) is subjected to hydrolyzing polycondensation followed by reaction of silicon compound(s) of formula (R<1> )3 SiX (R<1> is a hydrocarbon group or another hydrocarbon group with fluorine atom(s) substituted for part or the whole of the hydrogen atoms, and at least one R is the latter hydrocarbon group) and/or formula (R<1> )3 SiOSi(R<1> )3 as terminal blocking agent, thus affording the objective silicone resin consisting mainly of at least one kind of constituent unit of formula Q<n> (SiO3/2 )n with the terminal blocked with unit of formula (R<1> )3 SiO1/2 .

Description

Detailed Description of the Invention

[0001]

The present invention relates to plastics, metals,
TECHNICAL FIELD The present invention relates to a coating agent which provides a thin and uniform water-repellent and oil-repellent protective film on the surface of various substrates such as the skin, particularly a novel fluorinated silicone resin useful as a coating agent for cosmetics, and a method for producing the same.

[0002]

2. Description of the Related Art Silicone has been widely used as a coating agent for providing a water-repellent coating. Attempts have been made to further impart oil repellency by introducing a fluorine substituent into this silicone. As such an example, a polymer silicone composed of a unit (R) ₂ SiO (where R represents an organic group; the same applies hereinafter) and a RSiO _3/2 unit and a unit (R) ₃ SiO _1/2 and / or Alternatively, a silicone resin to which a unit SiO ₂ is added and a fluorine substituent is introduced into the side chain or terminal thereof can be used (Japanese Patent Laid-Open No. 64-83086 and Japanese Patent Laid-Open No. 5-78491).
No. 61-358185).

[0003]

However, most of the conventional fluorine-substituted silicones are two-dimensional type (straight chain type), and even if they are three-dimensional silicones, the network structure has an organic group R.
Since the resulting water-repellent and oil-repellent coating is flexible, the strength of the coating is insufficient and the durability of the coating is problematic because it is cut by the above-mentioned process and the continuity of the molecule is reduced. In order to obtain a certain degree of film strength, it is sufficient to increase the proportion of SiO ₂ units, but this method also has a limit, and if the proportion of this unit is increased too much, the flexibility of the molecule becomes insufficient, As a result, there is a drawback that the flexibility of the coating is significantly reduced. Further, although a certain degree of coating strength can be obtained even if it is applied thickly, it is of course desirable to apply it thinly and uniformly.

A conventional typical three-dimensional silicone resin network structure is shown in the following formula.

[0005]

[Chemical 1]

(However, R represents an organic group independent from each other, and Y represents an end-capping group.) Therefore, the object of the present invention is to form a flexible and strong water- and oil-repellent coating thinly and uniformly on various substrates. It is to provide a novel fluorinated silicone resin and a method for producing the same.

[0007]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies in view of the above-mentioned circumstances in the prior art, and as a result, a unit in which a silicon atom-a silicon atom are bonded by an organic chain and a terminal blocking unit are obtained. It was found that a flexible and strong water- and oil-repellent coating can be thinly and uniformly formed on various substrates by using a fluorinated silicone resin containing as a main constituent unit as a coating agent, and completed the present invention.

That is, the fluorinated silicone resin of the present invention has the general formula (I): Q ⁿ (SiO _3/2 ) _n (where Q ⁿ represents an n-valent organic group, and n is an integer of 2 to 6). At least one of the units represented by the formula (I)
I): (R ¹ ) ₃ SiO _1/2 (provided that R ^{1 s} may be the same as or different from each other, and are a hydrocarbon group or a hydrocarbon in which at least a part of hydrogen atoms is substituted with a fluorine atom. Represents a group and has three R ¹
At least one of them must be the above-mentioned fluorine-substituted hydrocarbon group. ) Is closed by the unit shown.

The method for producing a fluorinated silicone resin according to the present invention has the general formula (III): Q ⁿ [Si (X) ₃ ] _n (wherein Q ⁿ represents an n-valent organic group, and n is Represents any one of the integers of 2 to 6. X may be the same or different from each other and represents a hydrolyzable group.) After hydrolytic polycondensation of the hydrolyzable silicon compound represented by General formula (IV): (R ¹ ) ₃ SiX (provided that R ^{1 s} may be the same or different from each other, and a hydrocarbon group or at least a part of hydrogen atoms is substituted with a fluorine atom). Represents a hydrocarbon group and has three R ¹
At least one of them must be the above-mentioned fluorine-substituted hydrocarbon group. X represents a hydrolyzable group. ) Is used to react the silicon compound represented by the formula (1) as an end-capping agent to cap the ends of the polycondensate.

The present invention will be described in more detail below. <Fluorinated Silicone Resin> The fluorinated silicone resin of the present invention is basically the same as ^Qn (SiO 2) of the general formula (I).
_3/2 ) _n units are at least one main constituent unit, and the end is blocked with the (R ¹ ) ₃ SiO _1/2 unit of the general formula (II).
An iO ₂ unit can be included. in this case,
The content of the SiO ₂ unit is SiO ₂ / Q ⁿ (SiO _3/2 )
_{The n} molar ratio is preferably (3/2) or less, particularly preferably (1/2) or less. Q ⁿ (SiO _3/2 ) _{n of} (R ¹ ) ₃ SiO _1/2 unit
The molar ratio to the unit and the SiO ₂ unit is not particularly limited.

In the Q ⁿ (SiO _3/2 ) _n unit of the general formula (I), n is preferably 2, 3 or 4. In the Q ⁿ (SiO _3/2 ) _n unit of the general formula (I), specific examples of Q ⁿ are: 1) alkylene group; 2) polymethylene group; 3) phenylene group; 4) arylene group; ) To 4), wherein the hydrogen atom of the group is further substituted with at least one selected from the group consisting of an alkyl group, a phenyl group, an aryl group, an alkylene group, a polymethylene group, a phenylene group and an arylene group;
6) A group containing at least one functional group of the group consisting of ether, thioether, ester, ketone, amide, imide, amine and imine in the structure of the groups 1) to 4); and 7) 1) above. At least one of the groups in which the hydrogen atom of the groups (1) to (6) is substituted with a chlorine atom or a bromine atom can be exemplified.

More specific Q ⁿ is exemplified as follows. In the formulas below, a, b, c, d, e and f each represent an integer of 1 or more. Q ² (divalent organic group):

[0013]

[Image 2] _{- (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
_{2 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)

[0014]

[Chemical 3]

Q ³ (trivalent organic group):

[0016]

[Chemical 4]

Q ⁴ (tetravalent organic group):

[0018]

[Chemical 5]

The main constituent unit of the fluorinated silicone resin of the present invention is composed of at least one kind of the unit of the above general formula (I), but in the present invention, the main constituent unit is preferably a general constituent unit. A unit obtained by introducing a divalent organic group containing a dicarboxylic acid diamide as Q ⁿ into the formula (I) and a divalent organic group other than the divalent organic group containing a dicarboxylic acid diamide as Q ^{n in the} general formula (I) It is composed of a unit in which a group is introduced.

[0020] Then the general formula (II) (R ¹⁾ is a ₃ SiO _1/2 units, R ¹ of the unit, which may be the being the same or different, a hydrocarbon group, or hydrogen At least a part of the atoms represents a hydrocarbon group substituted with a fluorine atom, and at least one of the three R ¹ should be the fluorine-substituted hydrocarbon group, preferably an alkyl group or 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, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n- group.
Examples thereof include an alkyl group such as a butyl group, a sec-butyl group, and a tert-butyl group; a phenyl group; an aryl group; or a group in which at least a part of hydrogen atoms of these groups are substituted with a fluorine atom.

An example of the network structure of the fluorinated silicone resin of the present invention composed of the above units is
^For example, when ⁿ of n is 2, that is, a divalent organic group,
Shown below.

[0022]

[Chemical 6]

(In the formula 6, Q ² represents a divalent organic group. R ^{1 s} may be the same or different, and a hydrocarbon group or at least a part of hydrogen atoms is fluorine. Represents a hydrocarbon group substituted with atoms and has three R
^At least one of ¹ must be the above-mentioned fluorine-substituted hydrocarbon group. )

Specific examples of the fluorinated silicone resin of the present invention are as follows. _{B) [{CF 3 (CF 2} ) 2} 3 SiO 1/2] units and ^{_{[O 3/2 SiQ 2 SiO 3/}} 2] ( where, Q ² is - (C
H ₂ ) represents a divalent organic group represented by _3- . ) Fluorinated silicone resin consisting of a unit.

(B) A unit of [(CF ₃ CH ₂ ) ₃ SiO _1/2 ], [O _3/2 SiQ ² SiO _3/2 ] (wherein Q ² is a divalent group represented by the following formula (1a)) And an unit of [O _3/2 SiQ ′ ² SiO _3/2 ] (provided that Q ′ ² is — (C
It represents a divalent organic group represented by _{- H 2) 2 S (CH} 2) 3. ) Fluorinated silicone resin consisting of a unit.

[0026]

[Chemical 7]

C) [{CF ₃ (CF ₂ ) ₅ } (CH ₃ ) ₂ S
iO _1/2 ] unit, [SiO ₂ ] unit and [O
_3/2 SiQ ² SiO _3/2 ] (wherein Q ² represents a divalent organic group represented by the following formula (2a)).

[0028]

Embedded image

D) [{CF ₃ (CF ₂ ) ₃ } ₂ (C ₂ H ₅ ) S
fluorinated silicone resin composed of a unit of [iO _1/2 ] and a unit of [(O _3/2 Si) ₃ Q ³ ] (wherein Q ³ represents a trivalent organic group represented by the formula (3a)). .

[0030]

[Chemical 9]

E) [{CF ₃ (CF ₂ ) ₅ } (CH ₃ ) ₂ S
iO _1/2 ] unit, [SiO ₂ ] unit and [(O _3/2 Si) ₃ Q ³ ] (wherein Q ³ represents a trivalent organic group represented by the formula (4a)). Fluorinated silicone resin composed of units.

[0032]

[Chemical 10]

F) [{CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ }
₂ (C ₂ H ₅₎ units of SiO _1/2] and [(O _3/2 S
i) ₃ Q ³ ] (wherein Q ³ represents a trivalent organic group represented by the formula (5a)).

[0034]

[Chemical 11]

[0035] g) Unit _{[(CF 3 CH 2) 3} SiO 1/2], units of _{[SiO 2], [O 3} /2 SiQ 2 SiO
_3/2 ] (however, Q ² represents a divalent organic group represented by — (CH ₂ ) ₂ S (CH ₂ ) ₃ —) and [(O _3/2
Si) ₄ Q ⁴ ] (wherein Q ⁴ represents a tetravalent organic group represented by the formula (6a)).

[0036]

[Chemical 12]

H) [{CF ₃ (CF ₂ ) ₂ } ₃ SiO _1/2 ]
Fluorination of a unit of [(O _3/2 Si) ₄ Q ⁴ ] (where Q ⁴ represents a tetravalent organic group represented by the formula (7a)) and a unit of [SiO ₂ ] Silicone resin.

[0038]

[Chemical 13]

I) [{CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ }
₂ (C ₂ H ₅ ) SiO _1/2 ] unit and [(O _3/2 S
i) ₄ Q ⁴ ] (wherein Q ⁴ represents a tetravalent organic group represented by the formula (8a)).

[0040]

Embedded image

N) [{CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ }
₂ {C ₂ H ₅ } SiO _1/2 ] unit, [O _3/2 SiQ ² S
iO _3/2] (where, Q ² is - (CH _{2) 3} - represents a.) the unit and ^{_{[O 3/2 SiQ 2 'SiO 3/2}} ] ( where, Q ^2' has the formula (9a) Represents a divalent organic group as shown).

[0042]

[Chemical 15]

Le) [{CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ }
{C ₂ H ₅ } ₂ SiO _1/2 ] unit, [O _3/2 SiQ ² S
iO _3/2 ] (however, Q ² represents — (CH ₂ ) ₂ S (CH ₂ ) ₃ —) and [O _3/2 SiQ ² 'SiO _3/2 ].
(However, Q ² 'represents a divalent organic group represented by the above formula (9a).) A fluorinated silicone resin comprising a unit.

W) [{CF ₃ (CF ₂ ) ₅ } {CH ₃ } ₂ S
iO _1/2 ] unit, [O _3/2 SiQ ² SiO _3/2 ] (wherein Q ² represents a divalent organic group represented by the formula (1a)), [O _{3 / 2} SiQ ² 'SiO _3/2 ] (wherein Q ² ' represents a divalent organic group represented by the formula (9a)) and a unit of [SiO ₂ ].

<Method for producing fluorinated silicone resin>
Regarding the method for producing the fluorinated silicone resin of the present invention
explain. In the method of the present invention, first, the water of the general formula (III) is added.
Degradable silicon compound Qⁿ[Si (X) ₃]_nAdd water to
Perform hydrolysis polycondensation. In this case, if necessary, siliconization
Compound Si (X)_Four Are mixed with the silicon compound (III)
You may perform the cohydrolysis polycondensation of. The amount of water added is
Hydrolysis of the silicon compound used to control the reaction progress
The amount below the theoretical amount required to hydrolyze the volatile group X is
preferable.

At this time, it is preferable to use an organic solvent in order to allow the reaction to proceed uniformly. The organic solvent is not particularly limited as long as it can dissolve the silicon compound used in the reaction. The reaction temperature is preferably 0 to 80 ° C. If it is too low, coagulation of the solvent occurs, and if it is too high, extreme evaporation of the solvent occurs and the reaction progresses unevenly.

Further, in order to accelerate the progress of the reaction, it is preferable to use a base and / or an acid as a catalyst. The amount of base and / or acid catalyst added is 5 for the silicon compound used in the reaction.
It is preferably not more than mol%.

An example of the reaction formula of this hydrolysis polycondensation is shown below.
6 and an example of the network structure of the polycondensate obtained is shown in Chemical formula 17.

[0049]

[Chemical 16]

(However, Q ² in Chemical formula 16 represents a divalent organic group.)

[0051]

[Chemical 17]

(However, Q ² in Chemical Formula 17 represents a divalent organic group.)

Details of the materials used in the above-mentioned hydrolysis polycondensation step are as follows. The hydrolyzable silicon compound of the general formula (III) Q ⁿ [Si (X)
₃ ] _n : Synthesized by a known organic reaction of a known silicon compound. For example, alkoxysilane having an amino group, chlorosilane [NH ₂ C ₃ H ₆ Si (OR) ₃ , NH ₂ C ₃ H ₆ C
[ ₃ ] etc. with an acid derivative such as acid chloride or anhydride; addition reaction of hydrogensilane or mercaptosilane to a compound having an unsaturated bond; alkoxysilane compound or chlorosilane compound and Grignard reagent or organolithium compound It is synthesized by the reaction of. This hydrolyzable silicon compound of the general formula (III) Q ⁿ [Si
For Q ⁿ in the (X) _{3] n,} it is the same as Q ⁿ in the above general formula (I). In general formula (III), X is not particularly limited as long as it is a hydrolyzable group,
They may be the same or different from each other.

In the production method of the present invention, at least one of the hydrolyzable silicon compounds is used as a raw material, and preferably the hydrolyzable silicon compound is represented by the general formula (III)
A hydrolyzable silicon compound in which a divalent organic group containing a diamide of a dicarboxylic acid is introduced as Q ⁿ , and a general formula (III)
Is used in combination with a hydrolyzable silicon compound in which a divalent organic group other than the divalent organic group containing a diamide of dicarboxylic acid is introduced as Q ⁿ .

Silicon compound Si (X) ₄ : added to adjust the hardness of the resin. The resin will be harder if the added amount is larger, and softer if the added amount is smaller. Xs in the general formula are not particularly limited as long as they are hydrolyzable groups, and they may be the same or different. Specific examples of such a silicon compound include silicon tetrachloride, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane and the like, preferably silicon tetrachloride, tetramethoxysilane and tetraethoxysilane. .

Organic solvent: not particularly limited as long as it can dissolve the above-mentioned two kinds of silicon compounds, water, catalysts and the like, alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; Cellosolves such as methyl cellosolve and ethyl cellosolve; tetrahydroxyfuran; dimethylsulfoxide and the like.

Base and / or acid catalyst: inorganic acids such as hydrochloric acid and nitric acid; organic acids such as acetic acid and citric acid; sodium hydroxide,
Inorganic bases such as aqueous ammonia; organic bases such as amines and morpholines; basic group-containing silanes such as 3-aminoalkoxysilanes; preferably basic groups such as amino substituents and 4,5-dihydroimidazole substituents Containing silanes, such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (4,5-dihydroimidazole) propyltriethoxysilane, N-β
Examples thereof include-(aminoethyl) -γ-aminopropyltrimethoxysilane.

Next, after carrying out a polycondensation reaction for a certain period of time, in order to stably take out the polycondensate by blocking the reaction end of the obtained polycondensate, a silicon compound of the general formula (IV) is used as an end-capping agent. (R ¹ ) ₃ SiX is added and reacted. At this time, water and an acid catalyst are also added together in order to accelerate the hydrolysis of the terminal blocking agent and facilitate the progress of the terminal blocking reaction. The amount of water added is not particularly limited, but it is desirable to add water in an amount not less than the 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 end capping agent of the general formula (IV).

The end-blocking step is carried out 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, if the polycondensate undergoes phase separation, decantation is carried out. If the phase separation is not carried out, the intended product is taken out by a method such as solvent removal or freeze drying.

An example of the terminal blocking state in the network structure of the fluorinated silicone resin obtained by the reaction of the above polycondensate and the terminal blocking agent is shown below.

[0061]

[Chemical 18]

(However, Q ² in the chemical formula 18 represents a divalent organic group. R ^{1 s} may be the same or different from each other, and a hydrocarbon group or at least a part of hydrogen atoms is fluorine. Represents a hydrocarbon group substituted with atoms and has three R
^At least one of ¹ must be the above-mentioned fluorine-substituted hydrocarbon group. )

Details of the materials used in the above end-capping step are as follows. (R ¹ ) ₃ SiX of the general formula (IV): the above general formula (IV)
R ¹ may be the same or different from each other,
A hydrocarbon group, or a hydrocarbon group in which at least a part of hydrogen atoms are substituted with fluorine atoms, and at least one of three R ¹ 's must be the above-mentioned fluorine-substituted hydrocarbon group, preferably , 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, and examples thereof include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. , N-butyl group, sec-butyl group, tert-
Examples thereof include an alkyl group such as a butyl group; a phenyl group; an aryl group; or a group in which at least a part of hydrogen atoms of these groups are substituted with a fluorine atom. Further, in the general formula (IV), X is not particularly limited as long as it is a hydrolyzable group, and an alkoxy group, a halogen atom, an alkoxyalkoxy group or the like can be preferably mentioned.

Specific examples of such a compound include (CF _{3
CH 2) 3 Si (OCH 3} ), [CF 3 (CF 2) 2] 2 (CH 3) Si
_{Cl, [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 and the like,
It can be easily synthesized by reacting a Grignard reagent or lithium salt having a corresponding fluoroalkyl group with a known silicon compound. Ie

[0065]

Embedded image (R) _n Si (OR) _4-n + mR _f MgZ → (R _f ) _m Si (OR) _4-nm + _m Mg (OR) Z (R) _n SiCl _4-n + mR _f MgZ → (R _f ) _m SiCl _4-nm + mMgClZ R _n SiCl _4-n + mR _f Li → (R _f ) _m SiCl _4-nm + mLiCl (wherein R _f is a fluoroalkyl group, R is a hydrocarbon group,
Z represents Br or I, n represents 0 to 2 and m represents 1 to 3. )

Acid catalysts: Specifically, inorganic acids such as hydrochloric acid and nitric acid; organic acids such as acetic acid and citric acid; preferably volatile acids such as hydrochloric acid, nitric acid and acetic acid.

[0067]

In the conventional three-dimensional silicone resin, as shown in Chemical formula 1, the network structure is broken by the R group and the continuity of the molecule is low, whereas the three-dimensional fluorinated silicone resin of the present invention is represented by Chemical formula 18, for example. As shown, since the organic group represented by Q ⁿ is a part of the network structure of the resin, the continuity of molecules is improved, whereby a flexible, strong and uniform thin film can be obtained.

[0068]

EXAMPLES The present invention will be described below with reference to production examples of a silicon compound Q ⁿ [Si (X) ₃ ] _n of the general formula (III) and a fluorine-substituted end-capped silicon compound (R ¹ ) ₃ SiX of the general formula (IV). The production example of the fluorinated silicone resin will be described together with the production example of. <Production Example of ^Qn [Si (X) ₃ ] _n >

[0069]

[Production Example 1] 70.2 g of allyltrichlorosilane and 54.2 g of monohydrogentrichlorosilane were placed in a pressure-resistant bottle type reaction vessel and mixed. Next, chloroplatinic acid H ₂ Pt
After Cl 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, 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. IR, ¹ H-NMR, ¹³ C-N
When MR and ²⁹ Si-NMR measurements were performed, it was confirmed that this liquid was a compound represented by the formula (1b).

[0070]

Embedded image Cl ₃ Si (CH ₂ ) ₃ SiCl ₃ ... (1b)

[0071]

[Production Example 2] 49.3 g of diallyl terephthalate was placed in a three-necked flask equipped with a reflux condenser, a stirrer and a gas inlet tube.
-Mercaptotrimethoxysilane 78.6 g and benzene 450 ml were taken and mixed with stirring. Furthermore, to this solution, 0.5 g of azobisisobutyronitrile was added to 5 parts of benzene.
A solution dissolved in 0 ml was added and mixed with stirring. While continuing to stir, bubbling dry nitrogen gas at room temperature 1
After the reaction was carried out for a period of time, it was heated and refluxed at the boiling point of benzene for 24 hours to complete the reaction. Benzene was removed by a rotary evaporator to obtain a viscous liquid. IR, ¹ H-N
When MR, ¹³ C-NMR, and ²⁹ Si-NMR measurements were performed, it was confirmed that this liquid was a compound represented by the formula (2b).

[0072]

[Chemical 21]

[0073]

[Production Example 3] Vinyltrimethoxysilane 44.5 was placed in a three-necked flask equipped with a reflux condenser, a stirrer and a gas inlet tube.
g, 58.9 g of 3-mercaptotrimethoxysilane and 400 ml of benzene were taken and mixed with stirring. Furthermore, 0.5 g of azobisisobutyronitrile was added to benzene 5 in this solution.
A solution dissolved in 0 ml was added and mixed with stirring. While continuing to stir, bubbling dry nitrogen gas at room temperature 1
After the reaction was carried out for a period of time, it was heated and refluxed at the boiling point of benzene for 24 hours to complete the reaction. Benzene was removed by a rotary evaporator to obtain a viscous liquid. IR, ¹ H-N
When MR, ¹³ C-NMR, and ²⁹ Si-NMR measurements were performed, it was confirmed that this liquid was a compound represented by the formula (3b).

[0074]

Embedded image (CH ₃ O) ₃ Si (CH ₂ ) ₂ S (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ... (3b)

[0075]

[Production Example 4] 110.7 g of 3-aminopropyltriethoxysilane, 400 ml of diethyl ether, and 100 ml of triethylamine were placed in a three-necked flask equipped with a reflux condenser, a stirrer, and a gas introduction tube, and mixed with stirring while cooling with ice.
Further, 45.3 g of 3-butenoyl chloride was added to 100 ml of diethyl ether while stirring with ice cooling.
The solution dissolved in 1 was added dropwise. After the dropping, stirring was continued for another hour. The white precipitate formed was filtered off, and then diethyl ether and triethylamine were removed by a rotary evaporator to obtain a viscous liquid.

The above liquid 82.
7 g, monohydrogentriethoxysilane 49.3
g and mixed. Next, chloroplatinic acid H ₂ PtCl ₆・ 6H
₂ O was heated in tetrahydrofuran and this solution corresponding to 0.2 mmol 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. IR, ¹ H-NMR, ¹³ C-NMR, ²⁹ S
As a result of i-NMR measurement, this liquid was found to have the formula (4b).
It was confirmed that the compound was represented by

[0077]

[Chemical formula 23]

[0078]

[Production Example 5] Glycerin tri-1 was placed in a pressure-resistant bottle type reaction vessel.
177.3 g of 0-undecenoate and 110.0 g of monohydrogentrimethoxysilane 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. . Filtration and fractional distillation were performed to remove tetrahydrofuran and chloroplatinic acid to obtain a transparent liquid. IR, ¹ H
By -NMR, ¹³ C-NMR, and ²⁹ Si-NMR measurements, it was confirmed that this liquid was a compound represented by the formula (5b).

[0079]

[Chemical formula 24]

[0080]

[Production Example 6] 1,3,4-trivinylcyclohexane 48.7 g, 3-mercaptotris (β-methoxymethoxy) silane 257.8 g, and benzene were placed in a three-necked flask equipped with a reflux condenser, a stirrer, and a gas inlet tube. 800 ml was taken and mixed by stirring. Further, a solution prepared by dissolving 0.8 g of azobisisobutyronitrile in 100 ml of benzene was added to this solution, and the mixture was stirred and mixed. 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 viscous liquid. IR, ¹ H-NMR, ¹³ C-NM
When R, ²⁹ Si-NMR measurement was performed, it was confirmed that this liquid was a compound represented by the formula (6b).

[0081]

[Chemical 25]

[0082]

[Production Example 7] 57.9 g of 3-aminopropyltrichlorosilane, 320 ml of diethyl ether and 80 ml of triethylamine were placed in a three-necked flask equipped with a reflux condenser, a stirrer and a gas inlet tube, and the mixture was stirred and mixed while cooling with ice. Further, a solution prepared by dissolving 26.8 g of trimesoyl chloride in 100 ml of diethyl ether was added dropwise to this solution while continuing stirring with ice cooling. After the dropping, stirring was continued for another hour. After the generated white precipitate was filtered off, diethyl ether and triethylamine were removed by a rotary evaporator to obtain a white solid. IR, ¹ H-NMR, ¹³ C-NM
When R, ²⁹ Si-NMR measurement was performed, it was confirmed that this solid was a compound represented by the formula (7b).

[0083]

[Chemical formula 26]

[0084]

[Production Example 8] 3,3′-diaminobenzidine 64. was added to a three-necked flask equipped with a reflux condenser, a stirrer and a gas inlet tube.
3 g, 900 ml of tetrahydrofuran and 200 ml of triethylamine were taken and mixed with stirring while cooling with ice. Further, a solution prepared by dissolving 108.6 g of acryloyl chloride in tetrahydrofuran ml was added dropwise to this solution while continuing stirring with ice cooling. After the dropping, stirring was continued for another hour. The white precipitate thus formed was filtered off, and then tetrahydrofuran triethylamine was removed by a rotary evaporator to obtain a white solid.

The solid 86.
1 g, monohydrogentrimethoxysilane 97.8
g and mixed. Next, chloroplatinic acid H ₂ PtCl ₆・ 6H
₂ O was heated in tetrahydrofuran and this solution corresponding to 0.2 mmol 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 white solid. IR, ¹ H-NMR, ¹³ C-NMR, ²⁹ S
As a result of i-NMR measurement, this solid was found to have the formula (8b).
It was confirmed that the compound was represented by

[0086]

[Chemical 27]

[0087]

[Production Example 9] Pentaerythritol tetramethacrylate (81.7 g), 3-mercaptotriethoxysilane (190.7 g) and benzene (800 ml) were placed in a three-necked flask equipped with a reflux condenser, a stirrer and a gas inlet tube, and mixed with stirring. Further, to this solution, a solution prepared by dissolving 0.5 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 viscous liquid. IR, ¹ H-NMR, ¹³ C-NMR, ²⁹ Si
-By NMR measurement, it was confirmed that this liquid was a compound represented by the formula (9b).

[0088]

[Chemical 28]

[0089]

[Production Example 10] 27.6 g of glycerol-1,3-diallyl ether, 200 ml of tetrahydrofuran and 50 ml of triethylamine were placed in a three-necked flask equipped with a reflux condenser, a stirrer and a gas introduction tube, and the mixture was stirred and mixed while cooling with ice. Further, 14.6 g of adipoyl chloride was added to 100 parts of tetrahydrofuran while stirring with ice cooling.
The solution dissolved in ml was added dropwise. After the dropping, stirring was continued for another hour. The white precipitate formed was filtered off, and then diethyl ether and triethylamine were removed by a rotary evaporator to obtain a viscous liquid.

The above liquid 28.
2 g, monohydrogentrichlorocysilane 54.2
g and mixed. Next, chloroplatinic acid H ₂ PtCl ₆・ 6
H ₂ O was heated in tetrahydrofuran and this solution corresponding to 0.2 mmol platinum was added to the above mixed solution and then the reaction vessel was heated at 80 ° C. for 4 hours. Fractional distillation was performed to remove tetrahydrofuran and chloroplatinic acid to obtain a transparent liquid. IR, ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-N
When MR measurement was performed, it was confirmed that this liquid was a compound represented by the formula (10b).

[0091]

[Chemical 29]

[0092]

[Production Example 11] 107.6 g of 3-aminopropyltrimethoxysilane, 600 ml of tetrahydrofuran in a three-necked flask equipped with a reflux condenser, a stirrer and a gas introduction tube,
200 ml of triethylamine was taken and mixed with stirring while cooling with ice. Further, while continuing stirring with ice cooling, 60.9 g of terephthaloyl chloride was added to 20 ml of tetrahydrofuran in this solution.
A solution dissolved in 0 ml was added dropwise. After the dropping, stirring was continued for another hour. The white precipitate formed was filtered off, and then tetrahydrofuran and triethylamine were removed by a rotary evaporator to obtain a white solid. IR, ¹ H-NMR, ¹³
When C-NMR and ²⁹ Si-NMR measurements were performed, it was confirmed that this solid was a compound represented by the formula (11b).

[0093]

[Chemical 30]

[0094]

[Production Example 12] 96.5 g of 3-aminopropyltrichlorocysilane, 500 ml of diethyl ether and 150 ml of triethylamine were placed in a three-necked flask equipped with a reflux condenser, a stirrer and a gas inlet tube, and the mixture was stirred and mixed while cooling with ice. Further, while continuing ice-cooling stirring, 50.8 g of isophthalic acid chloride was added to 150 ml of diethyl ether in this solution.
The solution dissolved in 1 was added dropwise. After the dropping, stirring was continued for another hour. After the generated white precipitate was filtered off, diethyl ether and triethylamine were removed by a rotary evaporator to obtain a white solid. IR, ¹ H-NMR, ¹³ C-N
When MR and ²⁹ Si-NMR measurements were performed, it was confirmed that this solid was a compound represented by (12b).

[0095]

[Chemical 31]

<Production Example of (R ¹ ) ₃ SiX>

[0097]

MANUFACTURING EXAMPLE 13 8.7 g of metal magnesium was placed in a three-necked flask equipped with a reflux condenser, a stirrer and a gas inlet tube, which had been sufficiently dried, and was sufficiently replaced with dry nitrogen gas. Further, 150 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 to this solution,
A solution prepared by dissolving 63.0 g of 2,2,2-trifluoroethyl iodide in 200 ml of the above-mentioned tetrahydrofuran was added dropwise. While continuing stirring, a solution prepared by dissolving 15.2 g of tetramethoxysilane in 150 ml of the above-mentioned tetrahydrofuran was added dropwise under ice cooling. After the dropping is completed,
Refluxing was carried out for 24 hours at the boiling point of tetrahydrofuran to complete the reaction. After filtering the formed precipitate, fractional distillation was performed to isolate the target compound. All operations were performed under a dry nitrogen gas stream. IR, ¹ H-NMR, ¹³ C-NMR,
^{When 29} Si-NMR measurement was performed, it was confirmed that the target compound represented by the formula (13b) was isolated.

[0098]

Embedded image (CF ₃ CH ₂ ) ₃ Si (OCH ₃ ) (13b)

[0099]

[Production Example 14] 3.0 g of metal 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 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 to this solution,
A solution of 44.6 g of perfluorohexyl iodide in 300 ml of the above-mentioned tetrahydrofuran was added dropwise. While continuing stirring, dimethyldiethoxysilane 1 was added to 200 ml of the above-mentioned tetrahydrofuran under ice cooling.
A solution in which 4.8 g was dissolved 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. After filtering the formed precipitate, fractional distillation was performed to isolate the target compound. All operations were performed under a dry nitrogen gas stream. IR, ¹ H-NMR, ¹³ C-NMR, ²⁹ S
It was confirmed that the target compound represented by the formula (14b) was isolated by performing i-NMR measurement.

[0100]

Embedded image [CF ₃ (CF ₂ ) ₅ ] (CH ₃ ) ₂ Si (OC ₂ H ₅ ) (14b)

[0101]

[Production Example 15] 5.3 g of metal magnesium and 0.05 g of iodine were placed in a three-necked flask equipped with a reflux condenser, a stirrer, and a gas introduction tube, which had been sufficiently dried, and the nitrogen gas was sufficiently replaced with dry nitrogen gas. Furthermore, perfluorobutyl iodide 6 was added to 500 ml of diethyl ether dehydrated and purified by refluxing with sodium metal and distillation in this reaction vessel.
A solution in which 9.2 g and 15.0 g of ethyltrimethoxylane were dissolved was added dropwise. After completion of the dropping, the reaction was completed by leaving it for 2 hours at room temperature while continuing stirring. After filtering the formed precipitate, fractional distillation was performed to isolate the target compound. All the operations were performed under a dry nitrogen gas stream. IR, ¹ H-NM
When R, ¹³ C-NMR and ²⁹ Si-NMR measurements were performed, it was confirmed that the target compound represented by the formula (15b) was isolated.

[0102]

Embedded image [CF ₃ (CF ₂ ) ₃ ] ₂ (C ₂ H ₅ ) Si (OCH ₃ ) (15b)

[0103]

[Production Example 16] 5.6 g of metal 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 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 to this solution,
A solution prepared by dissolving 52.3 g of perfluoropropyl bromide in 300 ml of the above-mentioned tetrahydrofuran was added dropwise.
While continuing stirring, a solution prepared by dissolving 11.9 g of tetrachlorosilane in 100 ml of the above-mentioned tetrahydrofuran was added dropwise under ice cooling. After completion of the dropwise addition, reflux was carried out at the boiling point of tetrahydrofuran for 24 hours to complete the reaction.
After filtering the formed precipitate, fractional distillation was performed to isolate the target compound. All operations were performed under a dry nitrogen gas stream. IR, ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NM
When R measurement was performed, it was confirmed that the target compound represented by the formula (16b) was isolated.

[0104]

Embedded image [CF ₃ (CF ₂ ) ₂ ] ₃ SiCl ... (16b)

[0105]

[Production Example 17] 1 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.
50.8 g of H, 1H, 2H, 2H-nonafluorohexyl lithium and 400 ml of diethyl ether dehydrated and purified by refluxing with sodium metal and distillation were taken and mixed with stirring. While continuing to stir, add 100 ml of the above diethyl ether to 1 ml of ethyltrichlorosilane in the solution.
A solution in which 6.4 g was dissolved was added dropwise. 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 the formed precipitate, fractional distillation was performed to isolate the target compound. All operations were performed under a dry nitrogen gas stream. IR, ¹ H-NMR, ¹³ C-NMR, ²⁹ S
When i-NMR measurement was performed, it was confirmed that the target compound represented by the formula (17b) was isolated.

[0106]

Embedded image [CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ ] ₂ (C ₂ H ₅ ) SiCl ... (17b)

[0107]

MANUFACTURING EXAMPLE 18 5.8 g of metallic magnesium was placed in a three-necked flask equipped with a reflux condenser, a stirrer and a gas inlet tube, which had been sufficiently dried, and was sufficiently replaced with dry nitrogen gas. Furthermore, diethyl ether 200 was produced by dehydration in this reaction vessel by refluxing with sodium metal and distillation.
ml was taken and mixed by stirring. While continuing to stir, add 1H, 1H, 2 to 300 ml of the above diethyl ether.
H, 2H heptadecafluorodexyl iodide 11
A solution in which 4.8 g was dissolved was added dropwise. Further, while continuing stirring, the above-mentioned diethyl ether 200 m
A solution of 29.7 g of diethyldimethoxysilane dissolved in 1 was added dropwise. After completion of the dropping, reflux was carried out at the boiling point of diethyl ether for 24 hours to complete the reaction. After separating the formed precipitate by filtration, fractional distillation was performed to isolate the target compound. All the operations were performed under a stream of dry nitrogen gas. IR, ¹ H
By -NMR, ¹³ C-NMR, and ²⁹ Si-NMR measurements, it was confirmed that the target compound represented by the formula (18b) was isolated.

[0108]

Embedded image [CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ ] [C ₂ H ₅ ] ₂ Si (OCH ₃ ) (18b) <Production Example of Fluorinated Silicone Resin>

[0109]

Example 1 In a three-necked flask equipped with a condenser and a stirrer, 64.0 g of the silicon compound of Production Example 1 and 1 of methyl ethyl ketone
50 ml was taken and mixed and dissolved. A solution of 9.0 g of water in 50 ml of methyl ethyl ketone was added to this solution while continuing stirring. After the addition was completed, the mixture was left at 40 ° C. for 30 minutes while continuing stirring. In this mixed solution, Production Example 1
A solution consisting of 285.2 g of the silicon compound of No. 6, 40.5 g of water, 100 ml of methyl ethyl ketone, and 1.3 ml of concentrated hydrochloric acid was added, and the mixture was allowed to stand at 40 ° C. for 4 hours while continuing stirring. After the reaction was completed, the system 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 dried at 80 ° C for one day. The polycondensate was isolated. IR, ¹³ C-NMR, ¹ H-NMR, ²⁹ Si-
When NMR measurement was performed, this polycondensate was found to have [{CF ₃
(CF ₂ ) ₂ } ₃ SiO _1/2 ] unit and [O _3/2 Si
Q ² SiO _3/2 ] (wherein Q ² represents a divalent organic group represented by — (CH ₂ ) ₃ —) was confirmed to be a fluorinated silicone resin.

[0110]

Example 2 In a three-necked flask equipped with a condenser and a stirrer, 89.6 g of the silicon compound of Production Example 2, 48.2 g of the silicon compound of Production Example 3, 0.8 g of 3-aminopropyltrimethoxysilane and ethyl alcohol / 300 ml of tetrahydrofuran mixed solvent (7/3 by weight ratio) was taken and mixed and dissolved. A solution in which 9.1 g of water was dissolved in 100 ml of the above-mentioned mixed solvent was added to this solution while continuing stirring. After the addition was completed, the mixture was left at 25 ° C. for 4 hours while continuing stirring.
To this mixed solution, 159.3 g of the silicon compound of Production Example 13,
A solution consisting of 100.8 g of water, 200 ml of the mixed solvent described above, and 2.8 ml of concentrated hydrochloric acid was added, and the mixture was allowed to stand at 25 ° C. for 10 hours while continuing stirring. After the reaction was completed, the system 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 dried at 80 ° C for one day. The polycondensate was isolated. IR, ¹³ C-NM
When R, ¹ H-NMR and ²⁹ Si-NMR measurements were performed, the polycondensate was a unit of [(CF ₃ CH ₂ ) ₃ SiO _1/2 ], [O _3/2 SiQ ² SiO _3/2 ]. (However, Q ² represents a divalent organic group represented by the above formula (1a)) and [O _3/2 SiQ ′ ² SiO _3/2 ] (where Q ′ ² is −
It represents a divalent organic group represented by _{- (CH 2) 2 S (} CH 2) 3. It was confirmed to be a fluorinated silicone resin composed of the unit (1).

[0111]

Example 3 In a three-necked flask equipped with a condenser and a stirrer, 44.0 g of the silicon compound of Production Example 4, 22.8 g of tetramethoxysilane and 2.1 g of 3- (4,5-dihydroimidazole) propyltriethoxysilane. And 400 ml of isopropyl alcohol were taken and mixed and dissolved. A solution of 10.1 g of water dissolved in 100 ml of isopropyl alcohol was added to this solution while continuing stirring. After the addition was completed, the mixture was left at 60 ° C. for 2 hours while continuing stirring. 506.8 g of the silicon compound of Production Example 14 and 5 parts of water were added to this mixed solution.
A solution consisting of 4.0 g, 200 ml of isopropyl alcohol, and 3.0 ml of concentrated nitric acid was added, and the mixture was left standing at 60 ° C. for 16 hours while continuing stirring. After completion of the reaction, 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, and then water was removed by freeze-drying to isolate a polycondensate. .
When IR, ¹³ C-NMR, ¹ H-NMR and ²⁹ Si-NMR measurements were performed, this polycondensate was [{CF ₃ (CF ₂ )
₅ } (CH ₃ ) ₂ SiO _1/2 ] unit, [SiO ₂ ] unit, and [O _3/2 SiQ ² SiO _3/2 ] (however, Q ²
Represents a divalent organic group represented by the above formula (2a). It was confirmed to be a fluorinated silicone resin composed of the unit (1).

[0112]

Example 4 In a three-necked flask equipped with a condenser and a stirrer, 76.6 g of the silicon compound of Production Example 5 and triethylamine (0.1%) were added.
45 g and 300 ml of ethyl cellosolve were taken and mixed and dissolved. A solution of 3.9 g of water dissolved in 100 ml of ethyl cellosolve was added to this solution while continuing stirring. After the addition was completed, the mixture was left for 2 hours at 5 ° C. while continuing stirring. To this mixed solution, the silicon compound 252.
A solution consisting of 6 g, 43.2 g of water, 150 ml of ethyl cellosolve and 3.0 ml of concentrated nitric acid was added, and the mixture was allowed to stand at 20 ° C. for 8 hours while continuing stirring. 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, and then water was removed by decantation again, followed by drying at 80 ° C. for one day. The polycondensate was isolated. IR, ¹³ C-NMR,
^{When 1} H-NMR and ²⁹ Si-NMR measurements were performed, this polycondensate was found to be [{CF ₃ (CF ₂ ) ₃ } ₂ (C ₂ H ₅ ) SiO _2.
1/2 ] unit and [(O _3/2 Si) ₃ Q ³ ] (however, Q
³ represents a trivalent organic group represented by the above formula (3a). )
It was confirmed to be a fluorinated silicone resin composed of a unit of.

[0113]

Example 5 32.2 g of the silicon compound of Production Example 6, 2.8 g of tetraethoxysilane, 0.18 g of acetic acid and 250 ml of dimethyl sulfoxide were placed in a three-necked flask equipped with a condenser and a stirrer and mixed and dissolved. While continuing stirring, 5.5 g of water was added to 50 ml of dimethyl sulfoxide.
A solution dissolved in ml was added. After the addition was completed, the mixture was left at 60 ° C. for 6 hours while continuing stirring. To this mixed solution was added a solution of 114.0 g of the silicon compound of Production Example 14, 13.4 g of water, 150 ml of dimethyl sulfoxide, and 4.0 g of citric acid, and the mixture was allowed to stand at 60 ° C. for 18 hours while continuing stirring. . After the reaction was completed, the system separated into two phases, so the solvent phase was removed by decantation, and the
After washing with a% sodium hydrogen carbonate solution and water, the polycondensate was isolated by removing water by freeze-drying. IR, ¹³ C-N
When MR, ¹ H-NMR and ²⁹ Si-NMR measurements were performed, this polycondensate was found to be [{CF ₃ (CF ₂ ) ₅ } (CH ₃ ) ₂
SiO _1/2 ] unit, [SiO ₂ ] unit and [(O _3/2 Si) ₃ Q ³ ] (wherein Q ³ represents a trivalent organic group represented by the formula (4a)). It was confirmed to be a fluorinated silicone resin composed of a unit of.

[0114]

Example 6 In a three-necked flask equipped with a condenser and a stirrer, 88.5 g of the silicon compound of Production Example 7 and 5 tetrahydrofuran
00 ml was taken and mixed and dissolved. A solution of 15.6 g of water and 1.5 ml of concentrated aqueous ammonia in 100 ml of tetrahydrofuran was added to this solution while continuing stirring. After the addition was completed, the mixture was left standing at 10 ° C. for 1 hour while continuing stirring. To this mixed solution, the silicon compound 366.
1 g, water 45. Og, 300 ml of tetrahydrofuran,
A solution consisting of 5.0 g of acetic acid was added and left to stand at 10 ° C. for 4 hours with further stirring. After the reaction was completed, the system 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 dried at 80 ° C for one day. The polycondensate was isolated. IR, ¹³ C-NM
When R, ¹ H-NMR and ²⁹ Si-NMR measurements were performed, this polycondensate was found to be [{CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ } ₂
(C ₂ H ₅₎ units of SiO _1/2] and [(O _3/2 S
i) ₃ Q ³ ] (wherein Q ³ is ³ represented by the above formula (5a))
Represents a valent organic group. It was confirmed to be a fluorinated silicone resin composed of the unit (1).

[0115]

Example 7 In a three-necked flask equipped with a condenser and a stirrer, 18.1 g of the silicon compound of Production Example 8, 4.1 g of the silicon compound of Production Example 3, 0.9 g of tetramethoxysilane, 300 ml of tetrahydrofuran and 3-aminopropyl were added. 0.6 g of methoxysilane was taken and mixed and dissolved. While continuing stirring, 6.0 g of water was added to 100 m of tetrahydrofuran in this solution.
The solution dissolved in 1 was added. After the addition was completed, the mixture was left standing at 20 ° C. for 3 hours while continuing stirring. To this mixed solution was added a solution of 85.3 g of the silicon compound of Production Example 13, 59.4 g of water, 250 ml of tetrahydrofuran, and 3.0 ml of concentrated hydrochloric acid, and the mixture was allowed to stand at 20 ° C. for 12 hours while continuing stirring. After the reaction was completed, the system 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 dried at 80 ° C for one day. The polycondensate was isolated. IR, ¹³ C-NMR, ¹ H-NMR, ²⁹ Si
As a result of NMR measurement, it was confirmed that this polycondensate had [(CF
₃ CH _{2) 3} units of SiO _1/2], [Unit _{SiO 2], [O 3/2 SiQ} 2 SiO 3/2] ( where, Q ² is - (C
It represents a divalent organic group represented by _{- H 2) 2 S (CH} 2) 3. ) Unit and [(O _3/2 Si) ₄ Q ⁴ ] (however,
Q ⁴ represents a tetravalent organic group represented by the above formula (6a). It was confirmed to be a fluorinated silicone resin composed of the unit (1).

[0116]

Example 8 In a three-necked flask equipped with a condenser and a stirrer, 98.1 g of the silicon compound of Production Example 9, 1.7 g of tetraethoxysilane, 700 ml of an isopropyl alcohol / tetrahydrofuran mixed solvent (weight ratio 7/3) and morpholine. 2.1 g was taken and mixed and dissolved. While continuing stirring, a solution prepared by dissolving 3.1 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 standing at 20 ° C. for 4 hours while continuing stirring. A solution consisting of 456.4 g of the silicon compound of Production Example 16, 64.8 g of water, 400 ml of the mixed solvent described above, and 7.5 ml of concentrated hydrochloric acid was added to this mixed solution, and the mixture was allowed to stand at 20 ° C. for 12 hours while continuing stirring. After the reaction was completed, the system 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 dried at 80 ° C for one day. The polycondensate was isolated. IR, ¹³ C-NMR, ¹ H-NMR, ²⁹ Si-N
When MR measurement was performed, this polycondensate was [{CF
₃ (CF ₂ ) ₂ } ₃ SiO _1/2 ] unit, [(O _3/2 S
i) ₄ Q ⁴ ] (wherein Q ⁴ is ⁴ in the formula (7a)).
Represents a valent organic group. It was confirmed to be a fluorinated silicone resin composed of the unit (1) and the unit [SiO ₂ ].

[0117]

Example 9 82.4 g of the silicon compound of Production Example 10 and 400 ml of acetone were placed in a three-necked flask equipped with a condenser and a stirrer.
Were collected and mixed and dissolved. While continuing to stir, add to this solution
A solution of 21.6 g of water dissolved in 100 ml of acetone was added. After the addition was completed, the mixture was left at 20 ° C. for 1 hour while continuing stirring. The silicon compound 2 of Production Example 17 was added to this mixed solution.
A solution consisting of 34.7 g, water 36.0 g, acetone 200 ml, and concentrated hydrochloric acid 7.0 ml was added, and the mixture was left at 20 ° C. for 4 hours while continuing stirring. After the reaction was completed, the system 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 dried at 80 ° C for one day. The polycondensate was isolated. IR, ¹³ C-NM
When R, ¹ H-NMR and ²⁹ Si-NMR measurements were performed, this polycondensate was found to be [{CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ } ₂
(C ₂ H ₅ ) SiO _1/2 ] unit and [(O _3/2 Si)
₄ Q ⁴ ] (provided that Q ⁴ represents a tetravalent organic group represented by the formula (8a)) and is a fluorinated silicone resin.

[0118]

Example 10 24.9 g of the compound of Production Example 1 and the compound 6 of Production Example 12 were placed in a three-necked flask equipped with a condenser and a stirrer.
1.9 g and 250 ml of tetrahydrofuran were taken and mixed and dissolved. While continuing stirring, a solution prepared by dissolving 16.2 g of water in 70 ml of tetrahydrofuran was added to this solution.
After completion of the addition, the mixture was left standing at 20 ° C. for 1 hour while continuing stirring.
To this mixed solution, 469.3 g of the silicon compound of Production Example 17,
A solution consisting of 24.3 g of water, 150 ml of tetrahydrofuran and 3 ml of concentrated hydrochloric acid was added, and the mixture was left at 20 ° C. for 8 hours while further stirring. When a small amount of water was added after the reaction, the system separated into two phases, so the solvent phase was removed by decantation and the remaining volatile components were removed by a rotary evaporator to isolate the polycondensate. IR, ¹ H-NMR,
^{When 13} C-NMR and ²⁹ Si-NMR measurements were carried out, this polycondensate was found to be [{CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ } ₂ {C ₂
H ₅ } SiO _1/2 ] unit, [O _3/2 SiQ ² SiO
_3/2] (wherein, Q ² is - (CH _{2) 3} -. A representative) units and _{^{[O 3/2 SiQ 2 'SiO 3}} /2] ( where Q ^2' is the above formula (9a) It was confirmed to be a fluorinated silicone resin composed of a unit of the divalent organic group shown below.

[0119]

Example 11 38.8 g of the compound of Production Example 3 and the compound 1 of Production Example 11 were placed in a three-necked flask equipped with a condenser and a stirrer.
8.3 g, 3-aminopropyltrimethoxysilane 1.
1 g and 100 ml of ethyl alcohol were taken and mixed and dissolved. A solution of 8.2 g of water in 40 ml of ethyl alcohol was added to this solution while continuing stirring. After the addition was completed, the mixture was left standing at 20 ° C. for 2 hours while continuing stirring. To this mixed solution, 169.2 g of the silicon compound of Production Example 18 and 12.
A solution consisting of 2 g, 60 ml of ethyl alcohol and 1.5 ml of concentrated hydrochloric acid was added, and the mixture was allowed to stand at 20 ° C. for 16 hours while continuing stirring. After the reaction, the system was separated into two phases, so the solvent phase was removed by decantation, and the polycondensate was isolated by removing the volatile components remaining on the rotary evaporator after washing with a 5% sodium hydrogen carbonate solution and water.
When IR, ¹ H-NMR, ¹³ C-NMR, and ²⁹ Si-NMR measurements were performed, this polycondensate was [{CF ₃ (CF ₂ )
₇ (CH ₂ ) ₂ } {C ₂ H ₅ } ₂ SiO _1/2 ] unit,
[O _3/2 SiQ ² SiO _3/2 ] (however, Q ² is — (CH ₂ ) ₂
Represents S (CH ₂ ) ₃ −. ) Unit and [O _3/2 Si
Q ² 'SiO _3/2 ] (wherein Q ² ' represents a divalent organic group represented by the above formula (9a)) was confirmed to be a fluorinated silicone resin.

[0120]

[Example 12] A three-necked flask equipped with a condenser and a stirrer
57.5 g of the compound of Production Example 2 and the compound 1 of Production Example 11
4.7 g, tetramethoxysilane 4.6 g, 3-amino
Propyltrimethoxysilane 0.3g, ethyl alcohol
Solvent / tetrahydrofuran mixed solvent (weight ratio 7/3) 2
00 ml was taken and mixed and dissolved. While continuing to stir this melt
Water (15.0 g) was dissolved in the mixed solvent (50 ml).
The solution was added. After the addition is complete, continue stirring at 20 ° C.
It was left for 2 hours. A silicon compound of Production Example 14 was added to this mixed solution.
253.4 g, water 20.0 g, mixed solvent 10 at 20 ° C.
Add a solution consisting of 0 ml and 2.5 ml of concentrated nitric acid and stir.
Was continued for 12 hours at room temperature. After reaction
The system was separated into two phases by the addition of an amount of water.
Solution to remove the solvent phase, and add 5% sodium bicarbonate.
Solution and water, then leave on rotary evaporator.
The volatile components present were removed and the polycondensate was isolated. IR,
¹H-NMR,¹³C-NMR,²⁹Si-NMR measurement
When I found that this polycondensate was [{CF₃(CF₂)_Five}
{CH₃}₂SiO_1/2] Unit, [O_3/2SiQ²S
iO _3/2] (However, Q²Is a divalent group represented by the above formula (1a).
Represents an organic group. ) Unit, [O_3/2SiQ²'Si
O_3/2] (However, Q²'Is a divalent group represented by the above formula (9a)
Represents an organic group. ) Unit and [SiO₂] Uni
Confirmed to be a fluorinated silicone resin consisting of
Was done.

[0121]

Comparative Example 1 <Production of C ₄ F ₉ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ > Production Example 1
3, magnesium 8.7 g was changed to 2.9 g, and 2,2,2-trifluoroethyl iodide 6 was added.
A target compound was prepared in the same manner by using 37.4 g of 1H, 1H, 2H, 2H-nonafluorohexyl iodide instead of 3.0 g.

<Production of Fluorinated Silicone Resin> The same operation as in Example 2 is performed using the above silicon compound and the following silicon compound. That is, in a three-necked flask equipped with a cooler and a stirrer, 77.3 g of a silicon compound of C ₄ F ₉ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ and 13.7 of a silicon compound of Si (OCH ₃ ) ₄ were used.
g, 0.8 g of 3-aminopropyltrimethoxysilane and 300 ml of an ethyl alcohol / tetrahydrofuran mixed solvent (7/3 by weight) were taken and mixed and dissolved.
A solution in which 8.9 g of water was dissolved in 100 ml of the above-mentioned mixed solvent was added to this solution while continuing stirring. After the addition was completed, the mixture was left at 25 ° C. for 4 hours while continuing stirring. To this mixed solution, 125.0 g of (CH ₃ ) ₃ SiOCH ₃ and water 9
7.2 g, 200 ml of the above-mentioned mixed solvent, 3.5 m of concentrated hydrochloric acid
Add a solution consisting of 1 and add 25
It was left at 0 ° C. for 10 hours. Thereafter, the same operation as in Example 2 was carried out, and the unit of [(CH ₃ ) ₃ SiO _1/2 ], [C ₄ F ₉ (C
A silicone resin composed of units of [H ₂ ) ₂ SiO _3/2 ] and [SiO ₂ ] was prepared.

<Film Performance Test> Each fluorinated silicone resin of the examples and comparative examples obtained as described above was dissolved in tetrahydrofuran to prepare a solution having a concentration of 10% by weight. This solution was applied onto a commercially available slide glass by a spray method, dried at room temperature for 12 hours, and then further dried at 60 ° C. for 1 hour.
It was dried for 2 hours to form a film.

Next, this coating was strongly rubbed with a sponge under running water at a constant strength to observe the water and oil repellency of the coating. As a result, the coating films obtained from the silicone resins of Examples 1 to 12 were difficult to peel off, and showed longer water and oil repellency than the coating films obtained from the silicone resin of Comparative Example 1.

The above-mentioned tests proved that the silicone resin of the present invention gives a strong and flexible water / oil repellent coating as compared with the conventional silicone resin.

[0126]

EFFECTS OF THE INVENTION According to the method for producing a fluorinated silicone resin of the present invention, a three-dimensional bond, which is mostly an organic bond, is generated between all silicon-silicon atoms in the network, and the continuity of molecules and the flexibility are improved. Since the fluorinated silicone resin obtained by such a method can be used, a flexible, strong and durable water / oil repellent coating can be thinly formed on various substrates such as plastic, metal and skin. It can be formed uniformly.

Claims (14)

[Claims] 1. General formula (I): Q ⁿ (SiO _3/2 ) _n (wherein Q ⁿ represents an n-valent organic group, and n represents any one of integers of 2 to 6. At least one of the units represented by the formula ( ¹ ) is a main constituent unit, and the terminal is represented by the formula (II): (R ¹ ) ₃ SiO _1/2 (provided that R ^1's may be the same or different from each other; A hydrogen group or a hydrocarbon group in which at least a part of hydrogen atoms is replaced by a fluorine atom, and three R ¹
At least one of them must be the above-mentioned fluorine-substituted hydrocarbon group. ) A fluorinated silicone resin blocked with a unit represented by 2. The SiO ₂ unit further comprises SiO ₂ / Q.
The fluorinated silicone resin according to claim 1, which is contained in a molar ratio of ⁿ (SiO _3/2 ) _n of (3/2) or less. 3. The fluorinated silicone resin according to claim 1, wherein n in the general formula (I) is 2, 3, or 4. Q ⁿ of 4. A general formula (I), 1) an alkylene group; 2) a polymethylene group; 3) a phenylene group; 4) an arylene group; 5) the 1) group hydrogen atoms to 4) further A group substituted with at least one member selected from the group consisting of an alkyl group, a phenyl group, an aryl group, an alkylene group, a polymethylene group, a phenylene group and an arylene group; 6) 1) to 1) above
A group containing at least one functional group of the group consisting of ether, thioether, ester, ketone, amide, imide, amine and imine in the structure of the group 4); and 7) a group of the above 1) to 6). The fluorinated silicone resin according to claim 1, which is one of the group consisting of a group in which a hydrogen atom is replaced with a chlorine atom or a bromine atom; 5. The main constituent unit contains a divalent organic group containing a dicarboxylic acid diamide as Q ^{n in the} general formula (I) and a dicarboxylic acid diamide as Q ^{n in the} general formula (I). The fluorinated silicone resin according to claim 1, comprising a unit having a divalent organic group other than the divalent organic group introduced therein. 6. R ¹ of the general formula (II) is ^one of a group consisting of 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. Item 5. A fluorinated silicone resin according to item 1. 7. General formula (III): Q ⁿ [Si (X) ₃ ] _n (wherein Q ⁿ represents an n-valent organic group, and n represents any one of integers of 2 to 6). X may be the same or different from each other and represent a hydrolyzable group.) After hydrolytic polycondensation of the hydrolyzable silicon compound represented by the formula (IV): (R ¹ ) ₃ SiX (provided that R ^{1 s} may be the same or different from each other and represent a hydrocarbon group or a hydrocarbon group in which at least a part of hydrogen atoms is substituted with a fluorine atom, and 3 R ³
At least one of them must be the above-mentioned fluorine-substituted hydrocarbon group. X represents a hydrolyzable group. The method for producing a fluorinated silicone resin according to claim 1, wherein the silicon compound represented by the formula (4) is reacted as an end-capping agent to cap the end of the polycondensate. 8. In the polycondensation step, Si (X) ₄ (provided that
X is the same as X in the general formula (III). ) Is added, The manufacturing method of the fluorinated silicone resin of Claim 7. 9. The method for producing a fluorinated silicone resin according to claim 7, wherein n in the general formula (III) is 2, 3, or 4. Q ⁿ of 10. Formula (III) is 1) an alkylene group; 2) a polymethylene group; 3) a phenylene group; 4) an arylene group; 5) the 1) group hydrogen atoms to 4) further Alkyl group, phenyl group, aryl group, alkylene group,
Group substituted with at least one member selected from the group consisting of polymethylene group, phenylene group and arylene group; 6) above 1) to
A group containing at least one functional group of the group consisting of ether, thioether, ester, ketone, amide, imide, amine and imine in the structure of the group 4); and 7) a group of the above 1) to 6). The method for producing a fluorinated silicone resin according to claim 7, which is one of the group consisting of a group in which a hydrogen atom is replaced by a chlorine atom. 11. The hydrolyzable silicon compound has the general formula (II
A hydrolyzable silicon compound in which a divalent organic group containing a diamide of dicarboxylic acid is introduced as Q ⁿ into I) and a compound represented by the general formula (II
The method for producing a fluorinated silicone resin according to claim 7, which comprises a hydrolyzable silicon compound in which a divalent organic group other than the divalent organic group containing a dicarboxylic acid diamide as Q ⁿ is introduced into I). 12. R ¹ of the general formula (IV) is an alkyl group, a phenyl group, an aryl group or a group in which at least a part of hydrogen atoms of these groups is substituted with a fluorine atom.
The method for producing a fluorinated silicone resin according to claim 7, which is a seed. 13. One of the group consisting of an alkoxy group, a halogen atom and an alkoxyalkoxy group as X in the general formula (IV).
The method for producing a fluorinated silicone resin according to claim 7, which is a seed. 14. An amount of water which is equal to or less than a theoretical amount necessary for completely hydrolyzing a hydrolyzable group of the silicon compound represented by the general formula (III) and an amount of 5 mol% or less of the silicon compound. 8. The method for producing a fluorinated silicone resin according to claim 7, wherein the hydrolytic polycondensation is carried out in the presence of a silane having an amino substituent or a 4,5-dihydroimidazole substituent.