WO2022113724A1

WO2022113724A1 - Silicon-containing monomer, mixture, polysiloxane, and method for producing same

Info

Publication number: WO2022113724A1
Application number: PCT/JP2021/041158
Authority: WO
Inventors: 毅増渕; 友大片村; 一広山中
Original assignee: セントラル硝子株式会社
Priority date: 2020-11-24
Filing date: 2021-11-09
Publication date: 2022-06-02
Also published as: TW202227461A; JPWO2022113724A1; KR20230110761A; CN116457363A

Abstract

The present invention pertains to a silicon-containing monomer represented by formula (1). Furthermore, a mixture according to the present invention includes: (I) at least one silicon-containing monomer represented by formula (1); and (II) at least one monomer selected from the group consisting of silicon-containing monomers represented by formula (2-1) and silicon-containing monomers represented by formula (2-2).

Description

Silicon-containing monomers, mixtures, polysiloxanes, and methods for producing them

The present disclosure relates to silicon-containing monomers and mixtures containing them, polysiloxanes containing siloxane bonds, and methods for producing them.

Polymer compounds containing siloxane bonds (hereinafter sometimes referred to as polysiloxane) utilize their high heat resistance and transparency, and are used as coating materials for liquid crystal displays and organic EL displays, coating materials for image sensors, and semiconductor fields. It is used as a sealing material in. It is also used as a hard mask material for multilayer resists because it has high oxygen plasma resistance. In order to use polysiloxane as a photosensitive material capable of patterning and forming, it is required to be soluble in an alkaline aqueous solution such as an alkaline developer. As a means for making it soluble in an alkaline developer, it is possible to use a silanol group in the polysiloxane or to introduce an acidic group into the polysiloxane. Examples of such an acidic group include a phenol group, a carboxyl group, a fluorocarbinol group and the like.

Patent Document 1 discloses a polysiloxane having a silanol group as a soluble group in an alkaline developer. On the other hand, Patent Document 2 discloses a polysiloxane having a phenol group, Patent Document 3 discloses a polysiloxane having a carboxyl group, and Patent Document 4 discloses a hexafluoroisopropanol group (2-hydroxy-1,1). , 1, 3, 3, 3-Fluoroisopropyl groups [-C (CF ₃ ) ₂ OH] are disclosed. These polysiloxanes are photosensitive such as having a photoacid generator or a quinonediazide group. It is used as a positive resist composition in combination with a compound.

Hexafluoroisopropanol group (2-hydroxy-1,1,1,3,3,3-fluoroisopropyl group [-C (CF ₃ ) ₂ OH] disclosed in Patent Documents 4 and 5 relating to a positive resist composition]. The polysiloxane comprising the above has good transparency, heat resistance, and acid resistance, and the pattern structure based on the polysiloxane is promising as a permanent structure in various devices.

Japanese Unexamined Patent Publication No. 2012-242600 Japanese Unexamined Patent Publication No. 4-130324 Japanese Unexamined Patent Publication No. 2005-330488 JP-A-2015-129908 Japanese Unexamined Patent Publication No. 2014-156461

The silicon-containing monomer having a hexafluoroisopropanol group {2-hydroxy-1,1,1,3,3,3-fluoroisopropyl group [-C (CF ₃ ) ₂ OH]} described in Patent Documents 4 and 5 is described above. As mentioned above, it is a promising raw material for polysiloxane. On the other hand, for example, 3- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) -1-trimethoxysilylbenzene and 3- (2-hydroxy-1,1,1) , 3,3,3-Hexafluoroisopropyl) -1-triethoxysilylbenzene, when purified and purified by distillation, is stored at room temperature (23 ° C) even though it is a liquid immediately after distillation. It has been found by the present inventors that there is room for improvement in terms of handleability when it becomes a solid and is used on an industrial scale.

Therefore, the present inventors include a silicon-containing monomer that is liquid at room temperature (23 ° C.) or a silicon-containing monomer thereof as a raw material thereof so as to facilitate the production of an industrial scale of a polysiloxane having a hexafluoroisopropanol group. One of the purposes is to provide a mixture. Another object of the present invention is to provide a method for producing the above mixture. Another object of the present invention is to provide a polysiloxane obtained by polymerizing the above mixture and a method for producing the polysiloxane.

As a result of diligent studies to solve the above problems, the present inventors have completed the inventions provided below.

The silicon-containing monomer according to one embodiment of the present invention is represented by the formula (1).

R ¹ is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be replaced.
R ² , R ³ , and R ⁴ are linear or branched alkyl groups having 1 to 5 carbon atoms independently of each other, and all or part of the hydrogen atoms in the alkyl groups are fluorine atoms. N is an integer of 1 to 5, p is an integer of 0 to 1, q is an integer of 0 to 1, r is an integer of 0 to 1, and s is an integer of 0 to 1. p + q + r + s = 3.
However, when p = 0, q = 1, r = 1, and s = 1, the structures of R ² = R ³ = R ⁴ = methyl group and R ² = R ³ = R ⁴ = ethyl group are excluded. Further, when p = 1, q = 1, r = 1, and s = 0, the structures of R ² = R ³ = methyl group and R ² = R ³ = ethyl group are excluded. Further, when p = 1, q = 1, r = 0, s = 1, the structures of R ² = R ⁴ = methyl group and R ² = R ⁴ = ethyl group are excluded. Further, when p = 1, q = 0, r = 1, and s = 1, the structures of R ³ = R ⁴ = methyl group and R ³ = R ⁴ = ethyl group are excluded.

The mixture containing the silicon-containing monomer according to the embodiment of the present invention contains at least one silicon-containing monomer represented by the formula (I) (1) and the silicon-containing monomer represented by the formula (II) (2-1). It contains at least one selected from the group consisting of a monomer and a silicon-containing monomer represented by the formula (2-2).

R ¹ is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where n is an integer of 1 to 5 and p is an integer of 0 to 1.

A method for producing a mixture containing a silicon-containing monomer according to an embodiment of the present invention comprises a silicon compound represented by the formula (3) and at least one of (III) methanol and ethanol, and is represented by the formula (4). React with mixed alcohols, including at least one of the represented alcohols. Thereby, (I) at least one kind of silicon-containing monomer (1) and (II) at least one selected from the group consisting of silicon-containing monomer (2-1) and silicon-containing monomer (2-2) are included. A method of producing a mixture.

R ¹ is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where X is a halogen atom, n is an integer of 1 to 5, and p is an integer of 0 to 1.

R ⁶ OH (4)
R ⁶ is a linear alkyl group having 3 to 5 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms, and all or a part of hydrogen atoms in the alkyl group may be substituted with fluorine atoms.

In the method for producing a mixture containing a silicon-containing monomer according to an embodiment of the present invention, the silicon compound represented by the formula (3) is reacted with a mixture of methanol and ethanol. As a result, a group consisting of at least one kind of silicon-containing monomer represented by the formula (5), a silicon-containing monomer represented by the formula (2-1), and a silicon-containing monomer represented by the formula (2-2). A mixture comprising a silicon-containing monomer is produced, comprising at least one selected from.

R ¹ is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, where X is a halogen atom, n is an integer of 1 to 5, and p is an integer of 0 to 1.

R ¹ is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be replaced.
R ⁷ , R ⁸ and R ⁹ are methyl or ethyl groups independently of each other, p is an integer of 0 to 1, q is an integer of 0 to 1, r is an integer of 0 to 1, and s is an integer of 0 to 1. It is an integer, and p + q + r + s = 3. However, when p = 0, q = 1, r = 1, and s = 1, the structures of R ⁷ = R ⁸ = R ⁹ = methyl group and R ⁷ = R ⁸ = R ⁹ = ethyl group are excluded.
Further, when p = 1, q = 1, r = 1, and s = 0, the structures of R ⁷ = R ⁸ = methyl group and R ⁷ = R ⁸ = ethyl group are excluded. Further, when p = 1, q = 1, r = 0, s = 1, the structures of R ⁷ = R ⁹ = methyl group and R ⁷ = R ⁹ = ethyl group are excluded. Further, when p = 1, q = 0, r = 1, and s = 1, the structures of R ⁸ = R ⁹ = methyl group and R ⁸ = R ⁹ = ethyl group are excluded.

The polysiloxane according to the embodiment of the present invention contains at least one kind of silicon-containing monomer represented by the formula (1), a silicon-containing monomer represented by the formula (2-1), and a formula (2-2). It comprises polymerizing a mixture comprising at least one selected from the group consisting of the represented silicon-containing monomers.

The method for producing a polysiloxane according to an embodiment of the present invention includes at least one kind of silicon-containing monomer represented by the formula (1), a silicon-containing monomer represented by the formula (2-1), and a formula (2-). It is a method for producing a polysiloxane in which a mixture is polymerized, which comprises at least one selected from the group consisting of the silicon-containing monomers represented by 2).

According to the present invention, a silicon-containing monomer or a mixture containing the same, which is a liquid at room temperature (23 ° C.), is provided. Also provided is a method of producing the above mixture. Further, a polysiloxane obtained by polymerizing the above mixture and a method for producing the polysiloxane are provided.

Hereinafter, a silicon-containing monomer according to an embodiment of the present invention, a mixture containing the same, and a method for producing the mixture will be described. However, the embodiments of the present invention are not construed as being limited to the contents described in the embodiments and examples shown below. In the present specification, the notation "XY" in the description of the numerical range means X or more and Y or less unless otherwise specified.

In the notation of a group (atomic group) in the present specification, the notation that does not indicate whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, the "cyclic alkyl group" includes not only a monocyclic structure but also a polycyclic structure. The same applies to the "cycloalkyl group".

Unless otherwise specified, the term "organic group" in the present specification means an atomic group obtained by removing one or more hydrogen atoms from an organic compound. For example, the "monovalent organic group" represents an atomic group obtained by removing one hydrogen atom from an arbitrary organic compound.

In the present specification, the hexafluoroisopropanol group represented by -C (CF ₃ ) ₂ OH may be referred to as "HFIP group".

<1. Silicon-containing monomer (1)>
First, the silicon-containing monomer (1) according to the embodiment of the present invention will be described. In the following, the silicon-containing monomer represented by the formula (1) will be referred to as a silicon-containing monomer (1).

In one embodiment, it is preferable that the following group (1 _HFIP ) of the formula (1) is any of the groups represented by the following formulas (1A) to (1D). Further, in the formula (1), it is preferable that p is 0. In the formula (1), it is preferable to have a structure in which p = 0, that is, a three-dimensional structure, because it is easy to satisfy the required physical properties such as heat resistance and solvent resistance in the case of a permanent film.

(In the equation, wavy lines indicate that the intersecting line segments are bonds.)

As an example of the silicon-containing monomer (1), for example, when p = 0, q = r = s = 1, R ² = R ³ = R ⁴ = propyl group structure, p = 0, q = When r = s = 1, R ² = R ³ = R ⁴ = Isobutyl group structure, and when p = 0, q = r = s = 1, R ² = R ³ = R ⁴ = Isoamyl Those having a basic structure are preferable. The silicon-containing monomer (1) having these structures is preferable because it remains liquid regardless of whether it is stored at room temperature or refrigerated.

Further, as an example of the silicon-containing monomer (1), for example, when p = 0, q = r = s = 1, a structure having a structure of R ² = R ³ = methyl group and R ⁴ = ethyl group, or p. When = 0, q = r = s = 1, R ² = R ³ = ethyl group and R ⁴ = methyl group structure, and when p = 0, q = r = s = 1, R ² Those having a structure of = R ³ = ethyl group and R ⁴ = propyl group are preferable. The silicon-containing monomer (1) having these structures is preferable because it remains liquid regardless of whether it is stored at room temperature or refrigerated.

In the silicon-containing monomer (1), when p = 0, q = 1, r = 1, s = 1, when R ² = R ³ = R ⁴ = methyl group structure, or when p = 0, q = When 1, r = 1 and s = 1, when the structure is R ² = R ³ = R ⁴ = ethyl group, it becomes a solid regardless of whether it is stored at room temperature or refrigerated. Further, in the silicon-containing monomer (1), when p = 1, q = 1, r = 1, s = 0, when the structure is R ² = R ³ = methyl group, or R ² = R ³ = ethyl. When it has a basic structure, it becomes solid whether it is stored at room temperature or refrigerated. Further, in the silicon-containing monomer (1), when p = 1, q = 1, r = 0, s = 1, when R ² = R ⁴ = methyl group structure is adopted, or R ² = R ⁴ = ethyl. It is also solid when it has a basic structure. Further, in the silicon-containing monomer (1), when p = 1, q = 0, r = 1, s = 1, when R ³ = R ⁴ = methyl group structure is adopted, or R ³ = R ⁴ = ethyl. It is also solid when it has a basic structure. Therefore, there is room for improvement in terms of handleability when used on an industrial scale.

The silicon-containing monomer (1) according to the embodiment of the present invention can be left as a liquid regardless of whether it is stored at room temperature or refrigerated. This makes it easy to handle even when used on an industrial scale.

<2. Mixtures containing silicon-containing monomers>
Next, a mixture containing a silicon-containing monomer according to an embodiment of the present invention will be described. The mixture containing the silicon-containing monomer is represented by (I) at least one of the silicon-containing monomers (1), (II) the silicon-containing monomer represented by the formula (2-1), and the formula (2-2). Includes at least one selected from the group consisting of silicon-containing monomers. In the following, the silicon-containing monomer represented by the formula (2-1) is referred to as a silicon-containing monomer (2-1), and the silicon-containing monomer represented by the formula (2-2) is referred to as a silicon-containing monomer (2-2). It is described as.

Of the mixture containing the silicon-containing monomer, the silicon-containing monomer (1) is described in <1. As described in Silicon-containing monomer (1)>.

The silicon-containing monomer (2-1) is as follows.

The silicon-containing monomer (2-2) is as follows.

The following group ( _1HFIP ) in the formula (1), the formula (2-1), and the formula (2-2) may be any of the groups represented by the following formulas (1A) to (1D). preferable. Further, it is preferable that p is 0 in the formula (1).

The silicon-containing monomer (2-1) has a structure of R ² = R ³ = R ⁴ = methyl group when p = 0, q = 1, r = 1, s = 1 in the silicon-containing monomer (1). Corresponds to the silicon-containing monomer when taken. The silicon-containing monomer (2-2) has a structure of R ² = R ³ = R ⁴ = ethyl group in the silicon-containing monomer (1) when p = 0, q = 1, r = 1, s = 1. Corresponds to the silicon-containing monomer when taken. As described above, the simple substance of these silicon-containing monomers and the mixture consisting of only these silicon-containing monomers can be stored at room temperature (23 ° C.) or refrigerated (4 ° C.). Also becomes solid.

However, silicon containing (I) at least one of silicon-containing monomers (1) and (II) at least one selected from the group consisting of silicon-containing monomers (2-1) and silicon-containing monomers (2-2). In the mixture containing the contained monomer, it can be made into a liquid even when stored at room temperature (23 ° C.). Furthermore, by selecting an appropriate mixing ratio as described later, it can be made into a liquid even when stored in a refrigerator (4 ° C.).
That is, at least selected from the group consisting of (II) silicon-containing monomer (2-1) and silicon-containing monomer (2-2), which have been solid at room temperature or refrigerated and may be difficult to use on an industrial scale. By mixing the silicon-containing monomer according to one embodiment of the present invention into a mixture, a liquid can be obtained at room temperature or in a refrigerator. Due to the effect that the silicon-containing monomer according to the embodiment of the present invention can be liquefied including the solid component (II), it can be liquefied at room temperature or refrigerated in a wider range of compositions.

In the silicon-containing monomer mixture according to the embodiment of the present invention, it is preferable that the ratio of the component (I) and the component (II) satisfies the following relationship in terms of mass ratio.
(I) component / {(I) component + (II) component} ≧ 0.10
When the ratio of the component (I) and the component (II) satisfies the above relationship in terms of mass ratio, the mixture containing the silicon-containing monomer can be made into a liquid at room temperature.

Further, in the mixture according to the embodiment of the present invention, it is more preferable that the ratio of the component (I) and the component (II) satisfies the following relationship in terms of mass ratio.
(I) component / {(I) component + (II) component} ≧ 0.17
By satisfying the above relationship in terms of the ratio of the component (I) and the component (II) in terms of mass ratio, the mixture containing the silicon-containing monomer can be made into a liquid both at room temperature and in refrigeration.

<3. Method for producing a mixture containing a silicon-containing monomer>
The mixture containing a silicon-containing monomer according to an embodiment of the present invention contains at least one of a silicon compound represented by the formula (3), methanol and ethanol, and at least one alcohol represented by the formula (4). It is obtained by reacting with a mixed alcohol containing. In the following, the silicon compound represented by the formula (3) will be referred to as a silicon compound (3). Further, the alcohol represented by the formula (4) is referred to as alcohol (4).

The raw material compounds, reaction products, reaction conditions, etc. in the method for producing a mixture containing a silicon-containing monomer will be described below.

(Silicon compound)
The silicon compound (3) is represented by the following formula.

(Mixed alcohol)
As the mixed alcohol, at least one of methanol and ethanol is contained, and at least one of alcohol (4) is contained. The alcohol (4) is selected depending on the mixture containing the silicon-containing monomer of interest. As the alcohol (4), specifically, 1-propanol, 2-propanol, 1-butanol, 2-butanol (isobutyl alcohol), 2-methyl-2-butanol, 1-pentanol, 3-methyl-1- Butanol (isoamyl alcohol), 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, 2-pentanol, 3-methyl-2-butanol, 3-pentanol, 2-methyl-2-butanol, 3-Fluoropropanol, 3,3-difluoropropanol, 3,3,3-trifluoropropanol, 2,2,3,3-tetrafluoropropanol, 2,2,3,3,3-pentafluoropropanol, 1, 1,1,3,3,3-hexafluoroisopropanol and the like can be used. If water is mixed in when the mixed alcohol is reacted, the hydrolysis reaction and condensation reaction of the silicon compound (3) will proceed, and the yield of the mixture containing the target silicon-containing monomer will decrease. , It is preferable to use a mixed alcohol containing a small amount of water. Specifically, the water content of the mixed alcohol is preferably 5 wt% or less, more preferably 1 wt% or less.

(Reaction condition)
The reaction method for producing the mixture according to the embodiment of the present invention is not particularly limited. Typical examples include a method in which a mixed alcohol is dropped and reacted with the silicon compound (3), and a method in which the silicon compound (3) is dropped and reacted with the mixed alcohol.

The amount of mixed alcohol used is not particularly limited. From the viewpoint of efficient progress of the reaction, 1 molar equivalent or more and 10 molar equivalents or less are preferable, and 1 molar equivalent or more and 3 molar equivalents or less are more preferable with respect to the Si—X bond contained in the silicon compound (3).

The addition time of the mixed alcohol or the silicon compound (3) is not particularly limited. The addition time is preferably, for example, 10 minutes or more and 24 hours or less, and more preferably 30 minutes or more and 6 hours or less. The optimum temperature of the reaction during dropping varies depending on the reaction conditions, but specifically, it is preferably 0 ° C. or higher and 70 ° C. or lower.

The reaction can be completed by aging while continuing stirring after the dropping is completed. The aging time is not particularly limited, and is preferably 30 minutes or more and 6 hours or less from the viewpoint of sufficiently advancing the desired reaction. Further, it is preferable that the reaction temperature during aging is the same as that at the time of dropping or higher than that at the time of dropping. Specifically, the reaction temperature during aging is preferably 10 ° C. or higher and 80 ° C. or lower.

The reactivity between the mixed alcohol and the silicon compound (3) is high, and the halogenosilyl group is rapidly converted to the alkoxysilyl group. However, in order to promote the reaction and suppress side reactions, the hydrogen halide generated during the reaction is removed. It is preferable to do so. As a method for removing hydrogen halide, it is produced by adding known hydrogen halide trapping agents such as amine compounds, orthoesters, sodium alkoxides, epoxy compounds and olefins, as well as heating, degassing, vacuum heating or bubbling dry nitrogen. There is a method of removing the hydrogen halide gas to the outside of the system. These methods may be performed alone or in combination of two or more.

Examples of the hydrogen halide scavenger include ortho ester and sodium alkoxide. Examples of the orthoester include trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropyl orthoformate, trimethyl orthoacetate, triethyl orthoformate, trimethyl orthopropionic acid, and trimethyl orthobenzoate. Since it is easily available, trimethyl orthoformate or triethyl orthoformate is preferable. Examples of the sodium alkoxide include sodium methoxide and sodium ethoxide.

The reaction solution of the mixed alcohol and the silicon compound (3) may be diluted with a solvent. The solvent used is not particularly limited as long as it does not react with the mixed alcohol used and the silicon compound (3), and pentane, hexane, heptane, octane, toluene, xylene, tetrahydrofuran, diethyl ether, dibutyl ether, diisopropyl ether, 1,2-. Dimethoxyethane, 1,4-dioxane and the like can be used. These solvents may be used alone or in combination.

It is preferable to terminate the reaction after confirming that the raw materials have been sufficiently consumed by a general-purpose analytical means such as gas chromatography. After completion of the reaction, purification is carried out by means such as filtration, extraction and distillation to obtain a mixture containing a silicon-containing monomer.

The mixture containing the silicon-containing monomer produced by the above-mentioned method includes (I) at least one of the silicon-containing monomers (1), (II) the silicon-containing monomer (2-1), and the silicon-containing monomer (2-2). Includes at least one selected from the group consisting of. The silicon-containing monomer (1) remains liquid regardless of whether it is stored at room temperature or refrigerated. On the other hand, both the silicon-containing monomer (2-1) and the silicon-containing monomer (2-2) remain solid regardless of whether they are stored at room temperature or refrigerated. By mixing the silicon-containing monomer (1) according to the embodiment of the present invention with at least one selected from the group consisting of the silicon-containing monomer (2-1) and the silicon-containing monomer (2-2), at room temperature. It can remain liquid even when stored. Furthermore, by selecting an appropriate mixing ratio, it can remain liquid even when stored in a refrigerator. This makes it easy to handle the mixture containing the silicon-containing monomer even when it is used on an industrial scale.

<4. Method for producing a mixture containing a silicon-containing monomer>
Further, the mixture containing the silicon-containing monomer according to the embodiment of the present invention can also be obtained by reacting the silicon compound (3) with a mixture of methanol and ethanol. In this case, the mixture containing the silicon-containing monomer contains at least one silicon-containing monomer represented by the formula (I-1) (5), (II) the silicon-containing monomer (2-1), and the silicon-containing monomer (2). -Including at least one selected from the group consisting of 2). In the following, the silicon-containing monomer represented by the formula (5) will be referred to as a silicon-containing monomer (5).

The silicon-containing monomer (5) is as follows.

R ¹ is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, and R ⁷ , R ⁸ , and R ⁹ are methyl groups or ethyl groups independently of each other, p is an integer of 0 to 1, q is an integer of 0 to 1, and r is an integer of 0 to 1. , S is an integer from 0 to 1, and p + q + r + s = 3. However, when p = 0, q = 1, r = 1, and s = 1, the structures of R ⁷ = R ⁸ = R ⁹ = methyl group and R ⁷ = R ⁸ = R ⁹ = ethyl group are excluded. Further, when p = 1, q = 1, r = 1, and s = 0, the structures of R ⁷ = R ⁸ = methyl group and R ⁷ = R ⁸ = ethyl group are excluded. Further, when p = 1, q = 1, r = 0, s = 1, the structures of R ⁷ = R ⁹ = methyl group and R ⁷ = R ⁹ = ethyl group are excluded. Further, when p = 1, q = 0, r = 1, and s = 1, the structures of R ⁸ = R ⁹ = methyl group and R ⁸ = R ⁹ = ethyl group are excluded.

The following group ( _1HFIP ) in the formula (3), the formula (2-1), and the formula (2-2) may be any of the groups represented by the following formulas (1A) to (1D). preferable. Further, it is preferable that p is 0 in the formula (1).

In the method for producing a mixture according to an embodiment of the present invention, it is preferable that the ratio of the component (I-1) and the component (II) satisfies the following relationship in terms of mass ratio.
(I-1) component / {(I-1) component + (II) component} ≧ 0.10
When the ratio of the component (I-1) and the component (II) satisfies the above relationship by mass ratio, the obtained mixture containing the silicon-containing monomer can be made into a liquid at room temperature.

Further, in the method for producing a mixture according to an embodiment of the present invention, it is more preferable that the ratio of the component (I-1) and the component (II) satisfies the following relationship in terms of mass ratio.
(I-1) component / {(I-1) component + (II) component} ≧ 0.17
When the ratio of the component (I-1) and the component (II) satisfies the above relationship by mass ratio, the resulting mixture containing the silicon-containing monomer can be made into a liquid at room temperature or in a refrigerator. ..

As an example of the silicon-containing monomer (5), for example, when p = 0, q = r = s = 1, a structure having a structure of R ⁷ = R ⁸ = methyl group and R ⁹ = ethyl group, or p = 0. , Q = r = s = 1, preferably having a structure of R ⁷ = R ⁸ = ethyl group and R ⁹ = methyl group. The silicon-containing monomer (5) having these structures is preferable because it remains liquid regardless of whether it is stored at room temperature or refrigerated. On the other hand, both the silicon-containing monomer (2-1) and the silicon-containing monomer (2-2) remain solid regardless of whether they are stored at room temperature or refrigerated. By mixing the silicon-containing monomer (5) according to the embodiment of the present invention with at least one selected from the group consisting of the silicon-containing monomer (2-1) and the silicon-containing monomer (2-2), at room temperature. It can remain liquid even when stored. Furthermore, by selecting an appropriate mixing ratio, it can remain liquid even when stored in a refrigerator. This makes it easy to handle the mixture containing the silicon-containing monomer even when it is used on an industrial scale.

<5. Polysiloxane>
Next, the polysiloxane according to the embodiment of the present invention will be described. The polysiloxane is represented by at least one kind of silicon-containing monomer represented by the formula (I) (1), the silicon-containing monomer represented by the formula (II) (2-1), and the formula (2-2). It is obtained by polymerizing (hydrolyzing and polycondensing reaction) a mixture containing a silicon-containing monomer containing at least one selected from the group consisting of silicon-containing monomers.

R ¹ is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. It is a branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or a part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group is formed by a fluorine atom. It may be substituted, and R ² , R ³ , and R ⁴ are linear or branched alkyl groups having 1 to 5 carbon atoms and having 3 to 5 carbon atoms independently of each other, and are the hydrogen atoms in the alkyl group. All or part of it may be substituted with a fluorine atom, where n is an integer of 1 to 5, p is an integer of 0 to 1, q is an integer of 0 to 1, r is an integer of 0 to 1, and s is 0. It is an integer of 1 and p + q + r + s = 3. However, when p = 0, q = 1, r = 1, and s = 1, the structures of R ² = R ³ = R ⁴ = methyl group and R ² = R ³ = R ⁴ = ethyl group are excluded. Further, when p = 1, q = 1, r = 1, and s = 0, the structures of R ² = R ³ = methyl group and R ² = R ³ = ethyl group are excluded. Further, when p = 1, q = 1, r = 0, s = 1, the structures of R ² = R ⁴ = methyl group and R ² = R ⁴ = ethyl group are excluded. Further, when p = 1, q = 0, r = 1, and s = 1, the structures of R ³ = R ⁴ = methyl group and R ³ = R ⁴ = ethyl group are excluded.

When the mixture according to the embodiment of the present invention is used as a raw material for polysiloxane, it is preferable that the ratio of the component (I) to the component (II) satisfies the following relationship in terms of mass ratio.
(I) component / {(I) component + (II) component} ≧ 0.10
When the ratio of the component (I) and the component (II) satisfies the above relationship in terms of mass ratio, the mixture containing the silicon-containing monomer can be made into a liquid at room temperature. Therefore, it is easy to handle the mixture on an industrial scale during the production of polysiloxane.

Further, when the mixture according to the embodiment of the present invention is used as a raw material for polysiloxane, it is more preferable that the ratio of the component (I) and the component (II) satisfies the following relationship in terms of mass ratio.
(I) component / {(I) component + (II) component} ≧ 0.17
By satisfying the above relationship in terms of the ratio of the component (I) and the component (II) in terms of mass ratio, the mixture containing the silicon-containing monomer can be made into a liquid both at room temperature and in refrigeration. Therefore, it is easier to handle the mixture on an industrial scale during the production of polysiloxane.

The present hydrolysis polycondensation reaction can be carried out by a general method in the hydrolysis and condensation reaction of hydrolyzable silane. Specifically, at least one of (I) a silicon-containing monomer (1) and at least one selected from the group consisting of (II) a silicon-containing monomer (2-1) and a silicon-containing monomer (2-2). , Containing, after collecting the mixture containing the silicon-containing monomer in the reaction vessel, water for hydrolysis, if necessary, a catalyst for advancing the polycondensation reaction, and the reaction solvent are added into the reactor and stirred. Then, if necessary, heating is carried out to allow the hydrolysis and polycondensation reaction to proceed, whereby a polysiloxane (solution) is obtained. A "polysiloxane solution" is obtained in which polysiloxane is miscible with the above water by hydrolysis without adding a special reaction solvent to obtain a uniform solution state. Although the details are unknown, it is derived from the above-mentioned silicon-containing monomer (1) and at least one selected from the group consisting of the silicon-containing monomer (2-1) and the silicon-containing monomer (2-2) by hydrolysis. The silanol group of the polysiloxane contributes to the mixing with the above water, and the by-produced solvent component (for example, when alkoxysilane is used, the corresponding alcohol is by-produced) is the polysiloxane and the above-mentioned water. It is thought that it contributes to mixing. Further, the same solvent as the reaction solvent described later may be further added to the polysiloxane (solution) obtained by performing the above hydrolysis polycondensation.

(catalyst)
The catalyst for advancing the polycondensation reaction is not particularly limited, and examples thereof include an acid catalyst and a base catalyst. Acid catalysts include hydrochloric acid, nitrate, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, tosylic acid, formic acid, maleic acid and malonic acid. , Or a polyvalent carboxylic acid such as succinic acid, or an anhydride of these acids can be exemplified. As the base catalyst, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, or sodium carbonate can be used. It can be exemplified.

(Reaction solvent)
In the hydrolysis and polycondensation reaction, it is not always necessary to use a reaction solvent, and a raw material compound, water and a catalyst can be mixed and hydrolyzed and polycondensed. On the other hand, when the reaction solvent is used, the type thereof is not particularly limited. Among them, a polar solvent is preferable, and an alcohol solvent is more preferable, because of its solubility in a raw material compound, water, and a catalyst. Examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol.

Further, after the reaction, a step of adjusting the pH of the polysiloxane solution by extraction, washing with water or the like may be carried out, if necessary, or a step of adjusting the concentration of the polysiloxane solution by solvent distillation, concentration, dilution or the like. May be carried out.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

In this example, the silicon compound represented by the following chemical formula is referred to as HFA-Ph-CS.

The silicon compound obtained in this example was identified by the method shown below.

(Gel Permeation Chromatography (GPC))
A high-speed GPC device manufactured by Tosoh Corporation, device name HLC-8320GPC, was used to measure the weight average molecular weight in terms of polystyrene.

(Gas Chromatography (GC) measurement)
The GC measurement was performed using the trade name Shimadzu GC-2010plus manufactured by Shimadzu Corporation, and the column was a capillary column DB5 (30 m × 0.25 mmφ × 0.25 μm).

(Example 1)

While performing _N2 bubbling, the HFA-Ph-CS (30 g, 79.6 mmol) was heated to an internal temperature of 50 ° C., and the mixed alcohol (12.1 g, 309.9 mmol, 3.9 eq.), (The breakdown of the mixed alcohol is EtOH (7.14 g, 154.9 mmol, 1.9 eq.) And MeOH (4.96 g, 154.9 mmol, 1.9 eq.) Were slowly added dropwise (maintaining an internal temperature of 45 to 55 ° C.). After the dropping of the mixed alcohol was completed, the mixture was stirred at an internal temperature of 50 ° C. for 30 minutes, and the HCl gas and the unreacted alcohol were distilled off by an evaporator (bath 40 ° C., 10 hPa, 1 hr). At this time, the yield was 30 g. Then, simple distillation was carried out to obtain 26.5 g of the mixture. As a result of identification of the obtained mixture by GC-MS, the mixture had silicon-containing monomer I having the structure shown in Table 1 at 6.8%, silicon-containing monomer II at 30.5%, and silicon-containing monomer. It was a mixture containing 40.5% of III and 17.2% of silicon-containing monomer IV. As a result of storing the obtained mixture at 23 ° C. (hereinafter, simply referred to as “room temperature”) and 4 ° C. (hereinafter, simply referred to as “refrigerator”) for 1 day, both were liquid.

(Example 2)

While performing _N2 bubbling, the HFA-Ph-CS (30 g, 79.6 mmol) was heated to an internal temperature of 50 ° C., and the mixed alcohol (15.4 g, 309.9 mmol, 3.9 eq.), (The breakdown of the mixed alcohol is EtOH (11.4 g, 247.9 mmol, 3.1 eq.), MeOH (0.5 g, 15.5 mmol, 0.2 eq.), 1-propanol (0.9 g, 15.5 mmol, 0.2 eq.), Isobutanol (1.2 g, 15.5 mmol, 0.2 eq.) And isoamyl alcohol (1.4 g, 15.5 mmol, 0.2 eq.) Were slowly added dropwise (maintaining an internal temperature of 45 to 55 ° C.). After the dropping of the mixed alcohol was completed, the mixture was stirred at an internal temperature of 50 ° C. for 30 minutes, and the HCl gas and the unreacted alcohol were distilled off by an evaporator (bath 40 ° C., 10 hPa, 1 hr). At this time, the yield was 32 g. Then, simple distillation was carried out to obtain 27.5 g of the mixture. As a result of identifying the obtained mixture by GC-MS, the mixture had a silicon-containing monomer V having a structure shown in Table 2 of 5.2%, a silicon-containing monomer VI of 43.1%, and a silicon-containing monomer. VII was 10.8%, silicon-containing monomer VIII was 12.9%, and silicon-containing monomer IX was 13.8%, which were the main components of the mixture. As a result of storing the obtained mixture at room temperature and refrigerating for 1 day, both were liquid.

(Example 3)

While performing _N2 bubbling, the HFA-Ph-CS (30 g, 79.6 mmol) was heated to an internal temperature of 50 ° C., and the mixed alcohol (12.1 g, 309.9 mmol, 3.9 eq.), (The breakdown of the mixed alcohol is MeOH (7.94 g, 247.9 mmol, 3.1 eq.), EtOH (0.71 g, 15.5 mmol, 0.2 eq.), 1-propanol (0.9 g, 15.5 mmol, 0.2 eq.), Isobutanol (1.2 g, 15.5 mmol, 0.2 eq.) And isoamyl alcohol (1.4 g, 15.5 mmol, 0.2 eq.) Were slowly added dropwise (maintaining an internal temperature of 45 to 55 ° C.). After the dropping of the mixed alcohol was completed, the mixture was stirred at an internal temperature of 50 ° C. for 30 minutes, and the HCl gas and the unreacted alcohol were distilled off by an evaporator (bath 40 ° C., 10 hPa, 1 hr). At this time, the yield was 29 g. Then, simple distillation was carried out to obtain 25.8 g of the mixture. As a result of identifying the obtained mixture by GC-MS, the mixture contained 39.4% of silicon-containing monomer X, 10.9% of silicon-containing monomer XI, and silicon-containing monomer having the structures shown in Table 3. It was a mixture containing 11.9% of XII, 10.0% of the silicon-containing monomer XIII, and 10.2% of the silicon-containing monomer XIV, which were the main components. As a result of storing the obtained mixture at room temperature and refrigerating for 1 day, both were liquid.

(Comparative Example 1) (corresponding to the structure of equation (2-2))
3- (2-Hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) -1-triethoxysilylbenzene (hereinafter referred to as "ethyl form") was obtained by a known method (GC). Purity 97%). As a result of storing the ethyl form at room temperature and refrigerating for 1 day, both were solid.

(Comparative Example 2) (corresponding to the structure of equation (2-1))
3- (2-Hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) -1-trimethoxysilylbenzene (hereinafter referred to as "methyl form") was obtained by a known method (GC). Purity 98%). As a result of storing the methyl form at room temperature and refrigerating for one day, both were solid.

(Synthesis Example 1) (Structure of p = 0, q = r = s = 1, R ² = R ³ = R ⁴ = n-propyl in the formula (1))
While _N2 bubbling, the HFA-Ph-CS (30 g, 79.6 mmol) was heated to an internal temperature of 50 ° C., and 1-propanol (18.6 g, 309.9 mmol, 3.9 eq.) Was slowly added dropwise (inside). The temperature was maintained at 45-55 ° C.). After the dropping of the alcohol was completed, the mixture was stirred at an internal temperature of 50 ° C. for 30 minutes, and the HCl gas and the unreacted alcohol were distilled off by an evaporator (bath 40 ° C., 10 hPa, 1 hr). At this time, the yield was 32 g. Then, simple distillation was carried out to refer to 3- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) -1-tri-n-propoxysilylbenzene (hereinafter referred to as "propyl form"). 29 g (described) was obtained (GC purity 99.3%). As a result of storing the propyl compound at room temperature and refrigerating for one day, both were liquid.

(Synthesis Example 2) (Structure of p = 0, q = r = s = 1, R ² = R ³ = R ⁴ = isobutyl in the formula (1))
While _N2 bubbling, the HFA-Ph-CS (30 g, 79.6 mmol) was brought to an internal temperature of 50 ° C., and isobutyl alcohol (23.0 g, 309.9 mmol, 3.9 eq.) Was slowly added dropwise (internal temperature). It was maintained at 45-55 ° C.). After the alcohol was added dropwise, the mixture was stirred at an internal temperature of 50 ° C. for 30 minutes, and the HCl gas and the unreacted alcohol were distilled off by an evaporator (bath 40 ° C., 10 hPa, 1 hr). At this time, the yield was 34 g. Then, simple distillation is carried out, and 3- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) -1-triisobutoxysilylbenzene (hereinafter referred to as "isobutyl form") is described. ) Was obtained (GC purity 99.4%). As a result of storing the isobutyl compound at room temperature and refrigerating for one day, both were liquid.

(Synthesis Example 3) (P = 0, q = r = s = 1, R ² = R ³ = R ⁴ = Isoamyl structure of the formula (1))
While performing _N2 bubbling, the HFA-Ph-CS (30 g, 79.6 mmol) was brought to an internal temperature of 50 ° C., and isoamyl alcohol (27.3 g, 309.9 mmol, 3.9 eq.) Was slowly added dropwise (internal temperature 45). It was maintained at ~ 55 ° C.). After the alcohol was added dropwise, the mixture was stirred at an internal temperature of 50 ° C. for 30 minutes, and the HCl gas and the unreacted alcohol were distilled off by an evaporator (bath 40 ° C., 10 hPa, 1 hr). At this time, the yield was 36 g. Then, simple distillation is carried out, and 3- (2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl) -1-triisoamyloxysilylbenzene (hereinafter referred to as "isoamyl form") is described. ) Was obtained (GC purity 99.2%). As a result of storing the isoamyl acetate at room temperature and refrigerating for one day, both were liquid.

(Example 4)
As a result of mixing 1 g of the ethyl form of Comparative Example 1 and 1 g of the propyl form of Synthetic Example 1 and storing them at room temperature and refrigerating for 1 week, both were liquid.

(Example 5)
As a result of mixing 0.75 g of the ethyl compound of Comparative Example 1 and 0.25 g of the propyl compound of Synthetic Example 1 and storing them at room temperature and refrigerating for 1 week, both were liquid.

(Example 6)
As a result of mixing 0.80 g of the ethyl compound of Comparative Example 1 and 0.20 g of the propyl compound of Synthetic Example 1 and storing them at room temperature and refrigerating for 1 week, both were liquid.

(Example 7)
As a result of mixing 0.85 g of the ethyl compound of Comparative Example 1 and 0.15 g of the propyl compound of Synthetic Example 1 and storing them at room temperature and refrigerating for 1 week, they remained liquid at room temperature and became solid when refrigerated.

(Example 8)
As a result of mixing 1 g of the ethyl compound of Comparative Example 1 and 1 g of the isobutyl compound of Synthesis Example 2 and storing them at room temperature and refrigerating for 1 week, both were liquid.

(Example 9)
As a result of mixing 0.75 g of the ethyl compound of Comparative Example 1 and 0.25 g of the isobutyl compound of Synthesis Example 2 and storing them at room temperature and refrigerating for 1 week, both were liquid.

(Example 10)
As a result of mixing 0.8 g of the ethyl compound of Comparative Example 1 and 0.2 g of the isobutyl compound of Synthesis Example 2 and storing them at room temperature and refrigerating for 1 week, both were liquid.

(Example 11)
As a result of mixing 0.85 g of the ethyl compound of Comparative Example 1 and 0.15 g of the isobutyl compound of Synthesis Example 2 and storing them at room temperature and refrigerating for 1 week, they remained liquid at room temperature and became solid when refrigerated.

(Example 12)
As a result of mixing 1 g of the ethyl form of Comparative Example 1 and 1 g of the isoamyl form of Synthesis Example 3 and storing them at room temperature and refrigerating for 1 week, both were liquid.

(Example 13)
As a result of mixing 0.75 g of the ethyl compound of Comparative Example 1 and 0.25 g of the isoamyl acetate of Synthetic Example 3 and storing them at room temperature and refrigerating for 1 week, both were liquid.

(Example 14)
As a result of mixing 0.8 g of the ethyl compound of Comparative Example 1 and 0.2 g of the isoamyl acetate compound of Synthesis Example 3 and storing them at room temperature and refrigerating for 1 week, both were liquid.

(Example 15)
As a result of mixing 0.85 g of the ethyl compound of Comparative Example 1 and 0.15 g of the isoamyl acetate of Synthetic Example 3 and storing them at room temperature and refrigeration for 1 week, they remained liquid at room temperature and became solid in refrigeration.

(Example 16)
As a result of mixing 1 g of the methyl form of Comparative Example 2 and 1 g of the propyl form of Synthetic Example 1 and storing them at room temperature and refrigerating for 1 week, both were liquid.

(Example 17)
As a result of mixing 0.75 g of the methyl form of Comparative Example 2 and 0.25 g of the propyl form of Synthetic Example 1 and storing them at room temperature and refrigerating for 1 week, both were liquid.

(Example 18)
As a result of mixing 0.80 g of the methyl form of Comparative Example 2 and 0.20 g of the propyl form of Synthetic Example 1 and storing them at room temperature and refrigerating for 1 week, both were liquid.

(Example 19)
As a result of mixing 0.85 g of the methyl form of Comparative Example 2 and 0.15 g of the propyl form of Synthetic Example 1 and storing them at room temperature and refrigerating for 1 week, they remained liquid at room temperature and became solid when refrigerated.

(Example 20)
As a result of mixing 1 g of the methyl compound of Comparative Example 2 and 1 g of the isobutyl compound of Synthesis Example 2 and storing them at room temperature and refrigerating for 1 week, both were liquid.

(Example 21)
As a result of mixing 0.75 g of the methyl compound of Comparative Example 2 and 0.25 g of the isobutyl compound of Synthetic Example 2 and storing them at room temperature and refrigerating for 1 week, both were liquid.

(Example 22)
As a result of mixing 0.8 g of the methyl compound of Comparative Example 2 and 0.2 g of the isobutyl compound of Synthetic Example 2 and storing them at room temperature and refrigerating for 1 week, both were liquid.

(Example 23)
As a result of mixing 0.85 g of the methyl compound of Comparative Example 2 and 0.15 g of the isobutyl compound of Synthetic Example 2 and storing them at room temperature and refrigerating for 1 week, they remained liquid at room temperature and became solid when refrigerated.

(Example 24)
As a result of mixing 1 g of the methyl compound of Comparative Example 2 and 1 g of the isoamyl acetate compound of Synthesis Example 3 and storing them at room temperature and refrigerating for 1 week, both were liquid.

(Example 25)
As a result of mixing 0.75 g of the methyl compound of Comparative Example 2 and 0.25 g of the isoamyl acetate compound of Synthesis Example 3 and storing them at room temperature and refrigerating for 1 week, both were liquid.

(Example 26)
As a result of mixing 0.8 g of the methyl compound of Comparative Example 2 and 0.2 g of the isoamyl acetate compound of Synthesis Example 3 and storing them at room temperature and refrigerating for 1 week, both were liquid.

(Example 27)
As a result of mixing 0.85 g of the methyl compound of Comparative Example 2 and 0.15 g of the isoamyl acetate compound of Synthesis Example 3 and storing them at room temperature and refrigeration for 1 week, they remained liquid at room temperature and became solid in refrigeration.

(Example 28)
As a result of mixing 0.25 g of the ethyl form of Comparative Example 1, 0.25 g of the methyl form of Comparative Example 2 and 0.5 g of the propyl form of Synthetic Example 1 and storing them at room temperature and refrigerating for 1 week, they were all liquid. rice field.

(Comparative Example 3)
Even when 0.85 g of the ethyl form of Comparative Example 1 and 0.15 g of the methyl form of Comparative Example 2 were mixed at room temperature, they remained solid.

(Comparative Example 4)
Even when 0.5 g of the ethyl form of Comparative Example 1 and 0.5 g of the methyl form of Comparative Example 2 were mixed at room temperature, they remained solid.

(Comparative Example 5)
Even when 0.15 g of the ethyl form of Comparative Example 1 and 0.85 g of the methyl form of Comparative Example 2 were mixed at room temperature, they remained solid.

From the above results, the simple substances of the above formulas (2-1) and (2-2) and their mixtures are solid at room temperature, whereas the above formulas (2-1) and (2-) are solid. It has been found that the mixture of 2) and a mixture thereof and a silicon-containing monomer represented by the above formula (1) becomes a liquid and can be easily handled at room temperature.

Next, the results of producing polysiloxane using the mixture containing the silicon-containing monomers obtained in Examples 1 to 3 will be described.

(Example 1-P)
At room temperature (23 ° C.), the silicon-containing monomer mixture (5.0 g, 10.2 mmol) obtained in Example 1, pure water (0.68 g, 37.5 mmol), acetic acid (0.02 g, 0.36 mmol). Was mixed. Since the above silicon-containing monomer mixture is a liquid at room temperature (23 ° C.), it can be added and mixed very easily. Then, the mixture was stirred at 100 ° C. under full reflux for 1 hr. The obtained reaction solution was returned to room temperature, and the weight average molecular weight (Mw) was measured by GPC and found to be 1740.

(Example 2-P)
Silicon-containing monomer mixture (5.0 g, 10.2 mmol), pure water (0.68 g, 37.5 mmol), acetic acid (0.02 g, 0.36 mmol) obtained in Example 2 at room temperature (23 ° C.). Was mixed. Since the above silicon-containing monomer mixture is a liquid at room temperature (23 ° C.), it can be added and mixed very easily. Then, the mixture was stirred at 100 ° C. under full reflux for 1 hr. The obtained reaction solution was returned to room temperature, and the weight average molecular weight (Mw) was measured by GPC. As a result, it was 1690.

(Example 3-P)
Silicon-containing monomer mixture (5.0 g, 10.2 mmol), pure water (0.68 g, 37.5 mmol), acetic acid (0.02 g, 0.36 mmol) obtained in Example 3 at room temperature (23 ° C.). Was mixed. Since the above silicon-containing monomer mixture is a liquid at room temperature (23 ° C.), it can be added and mixed very easily. Then, the mixture was stirred at 100 ° C. under full reflux for 1 hr. The obtained reaction solution was returned to room temperature, and the weight average molecular weight (Mw) was measured by GPC. As a result, it was 2060.

(Example 4-P)
At room temperature (23 ° C.), the silicon-containing monomer mixture (5.0 g, 10.2 mmol) obtained in Example 1 was dissolved in 2-butanol (2.5 g) and then pure water (0.68 g, 37). .5 mmol) and acetic acid (0.02 g, 0.36 mmol). Since the above silicon-containing monomer mixture is a liquid at room temperature (23 ° C.), it can be added, mixed and dissolved very easily. Then, the mixture was stirred at 100 ° C. under total reflux for 24 hours. The obtained reaction solution was returned to room temperature, and the weight average molecular weight (Mw) was measured by GPC and found to be 1080.

From the above results, polysiloxane could be easily produced by using a silicon-containing monomer mixture. The weight average molecular weight (Mw) of the polysiloxane in the obtained reaction solution was in the order of Example 3-P> Example 1-P> Example 2-P> Example 4-P. From the viewpoint of hydrolysis and polycondensation reaction rate, it was found that Example 3-P was the most excellent, followed by Example 1-P and Example 2-P. The detailed mechanism of this tendency is not clear, but it is because the hydrolysis and polycondensation reaction rates increase as the carbon number of the alkoxide moiety and the proportion of structures with less steric hindrance in the silicon-containing monomer mixture are shorter. Conceivable. It was also found that the hydrolysis and polycondensation reaction rates could be controlled using a reaction solvent as in Example 4-P.

Next, the result of producing polysiloxane using the mixture containing the silicon-containing monomer obtained in Example 2 and triethoxyphenylsilane will be described.

(Example 2-coP)
At room temperature (23 ° C.), the silicon-containing monomer mixture (5.0 g, 10.2 mmol) obtained in Example 2, triethoxyphenylsilane (22.9 g, 95.2 mmol), KBM-303 (manufactured by Shinetsu Silicone Co., Ltd.). , 2.9 g, 11.9 mmol), pure water (6.8 g, 374.8 mmol), and acetic acid (0.21 g, 3.57 mmol) were mixed. Since the above silicon-containing monomer mixture is a liquid at room temperature (23 ° C.), it can be added and mixed very easily. Then, the mixture was stirred at 40 ° C. for 1 hr, 70 ° C. for 1 hr, and 85 ° C. for 3 hr under full reflux. Alcohol by-produced by the evaporator was distilled off, 40 g of cyclohexanone was added, and washing with water was carried out twice with 20 g of water. Cyclohexanone in the organic layer obtained by the evaporator was distilled off to obtain 42 g of a solution having a solid content concentration of 50%. As a result of measuring the weight average molecular weight (Mw) by GPC, it was 1750.

The silicon-containing monomer and its mixture of the present invention are useful as a synthetic raw material for a polymer resin, a polymer modifier, a surface treatment agent for an inorganic compound, various coupling agents, and an intermediate raw material for organic synthesis. Further, the polysiloxane of the present invention and the film obtained from the polysiloxane are soluble in an alkaline developing solution, have patterning performance, and are excellent in heat resistance and transparency. Therefore, a protective film for semiconductors, a flattening material, and a microlens It can be used as a material, an insulating protective film for a touch panel, a liquid crystal display TFT flattening material, a core or clad forming material for an optical waveguide, a resist for an electron beam, a multilayer resist intermediate film, an underlayer film, an antireflection film and the like. Among these applications, when used for optical system members such as displays and image sensors, fine particles such as polytetrafluoroethylene, silica, titanium oxide, zirconium oxide, and magnesium fluoride are used in an arbitrary ratio for the purpose of adjusting the refractive index. Can be mixed and used in.

Claims

(I) A silicon-containing monomer represented by the formula (1).

[R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. , A branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group are fluorine atoms. R 2 , R 3 , and R 4 are linear or branched alkyl groups having 1 to 5 carbon atoms and hydrogen atoms in the alkyl groups independently of each other. All or part of may be substituted with a fluorine atom, n is an integer of 1 to 5, p is an integer of 0 to 1, q is an integer of 0 to 1, r is an integer of 0 to 1, and s is. It is an integer of 0 to 1, and p + q + r + s = 3. However, when p = 0, q = 1, r = 1, and s = 1, the structures of R 2 = R 3 = R 4 = methyl group and R 2 = R 3 = R 4 = ethyl group are excluded. Further, when p = 1, q = 1, r = 1, and s = 0, the structures of R 2 = R 3 = methyl group and R 2 = R 3 = ethyl group are excluded. Further, when p = 1, q = 1, r = 0, s = 1, the structures of R 2 = R 4 = methyl group and R 2 = R 4 = ethyl group are excluded. Further, when p = 1, q = 0, r = 1, and s = 1, the structures of R 3 = R 4 = methyl group and R 3 = R 4 = ethyl group are excluded. ]
The silicon content according to claim 1, wherein the following group (1 HFIP ) in the formula (1) is any of the groups represented by the following formulas (1A) to (1D), and p is 0. monomer.

(In the equation, wavy lines indicate that the intersecting line segments are bonds.)
(I) At least one kind of silicon-containing monomer represented by the formula (1) is used.
(II) At least one selected from the group consisting of the silicon-containing monomer represented by the formula (2-1) and the silicon-containing monomer represented by the formula (2-2).
Including, mixture.

[R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. , A branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group are fluorine atoms. R 2 , R 3 , and R 4 are linear or branched alkyl groups having 1 to 5 carbon atoms and hydrogen atoms in the alkyl groups independently of each other. All or part of may be substituted with a fluorine atom, n is an integer of 1 to 5, p is an integer of 0 to 1, q is an integer of 0 to 1, r is an integer of 0 to 1, and s is. It is an integer of 0 to 1, and p + q + r + s = 3. However, when p = 0, q = 1, r = 1, and s = 1, the structures of R 2 = R 3 = R 4 = methyl group and R 2 = R 3 = R 4 = ethyl group are excluded. Further, when p = 1, q = 1, r = 1, and s = 0, the structures of R 2 = R 3 = methyl group and R 2 = R 3 = ethyl group are excluded. Further, when p = 1, q = 1, r = 0, s = 1, the structures of R 2 = R 4 = methyl group and R 2 = R 4 = ethyl group are excluded. Further, when p = 1, q = 0, r = 1, and s = 1, the structures of R 3 = R 4 = methyl group and R 3 = R 4 = ethyl group are excluded. ]

[R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. , A branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group are fluorine atoms. May be replaced by, n is an integer of 1 to 5, and p is an integer of 0 to 1. ]

[R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. , A branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group are fluorine atoms. May be replaced by, n is an integer of 1 to 5, and p is an integer of 0 to 1. ]
The following group ( 1HFIP ) in the formula (1), the formula (2-1), and the formula (2-2) is any of the groups represented by the following formulas (1A) to (1D). The mixture according to claim 3, wherein p is 0.

(In the equation, wavy lines indicate that the intersecting line segments are bonds.)
The mixture according to claim 3, wherein the ratio of the component (I) to the component (II) satisfies the following relationship in terms of mass ratio.
(I) component / {(I) component + (II) component} ≧ 0.10
The mixture according to claim 3, wherein the ratio of the component (I) to the component (II) satisfies the following relationship in terms of mass ratio.
(I) component / {(I) component + (II) component} ≧ 0.17
The silicon compound represented by the formula (3) and
(III) Containing at least one of methanol and ethanol,
By reacting with a mixed alcohol containing at least one alcohol represented by the formula (4),
(I) At least one kind of silicon-containing monomer represented by the formula (1) is used.
(II) At least one selected from the group consisting of the silicon-containing monomer represented by the formula (2-1) and the silicon-containing monomer represented by the formula (2-2).
A method of producing a mixture, including.

[R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. , A branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group are fluorine atoms. In addition to, X is a halogen atom, n is an integer of 1 to 5, and p is an integer of 0 to 1. ]
R 6 OH (4)
[R 6 is a linear or branched alkyl group having 3 to 5 carbon atoms, and all or part of hydrogen atoms in the alkyl group may be replaced with fluorine atoms. .. ]

[R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. , A branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group are fluorine atoms. R 2 , R 3 , and R 4 are linear or branched alkyl groups having 1 to 5 carbon atoms and hydrogen atoms in the alkyl groups independently of each other. All or part of may be substituted with a fluorine atom, n is an integer of 1 to 5, p is an integer of 0 to 1, q is an integer of 0 to 1, r is an integer of 0 to 1, and s is. It is an integer of 0 to 1, and p + q + r + s = 3. However, when p = 0, q = 1, r = 1, and s = 1, the structures of R 2 = R 3 = R 4 = methyl group and R 2 = R 3 = R 4 = ethyl group are excluded. Further, when p = 1, q = 1, r = 1, and s = 0, the structures of R 2 = R 3 = methyl group and R 2 = R 3 = ethyl group are excluded. Further, when p = 1, q = 1, r = 0, s = 1, the structures of R 2 = R 4 = methyl group and R 2 = R 4 = ethyl group are excluded. Further, when p = 1, q = 0, r = 1, and s = 1, the structures of R 3 = R 4 = methyl group and R 3 = R 4 = ethyl group are excluded. ]

[R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. , A branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group are fluorine atoms. May be replaced by, n is an integer of 1 to 5, and p is an integer of 0 to 1. ]

[R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. , A branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group are fluorine atoms. May be replaced by, n is an integer of 1 to 5, and p is an integer of 0 to 1. ]
The following groups (1 HFIP ) in the above formula (3), formula (1), formula (2-1), and formula (2-2) are the groups represented by the following formulas (1A) to (1D). The method for producing a mixture according to claim 7, wherein p is 0.

(In the equation, wavy lines indicate that the intersecting line segments are bonds.)
The method for producing a mixture according to claim 7, wherein the reaction is carried out so that the ratio of the component (I) and the component (II) satisfies the following relationship in terms of mass ratio.
(I) component / {(I) component + (II) component} ≧ 0.10
The method for producing a mixture according to claim 7, wherein the reaction is carried out so that the ratio of the component (I) and the component (II) satisfies the following relationship in terms of mass ratio.
(I) component / {(I) component + (II) component} ≧ 0.17
The silicon compound represented by the formula (3) and
(III-1) Reacting with a mixture of methanol and ethanol,
(I-1) At least one kind of silicon-containing monomer represented by the formula (5) is used.
(II) At least one selected from the group consisting of the silicon-containing monomer represented by the formula (2-1) and the silicon-containing monomer represented by the formula (2-2).
A method of producing a mixture, including.

[R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. , A branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group are fluorine atoms. In addition to, X is a halogen atom, n is an integer of 1 to 5, and p is an integer of 0 to 1. ]

[R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. , A branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group are fluorine atoms. R 7 , R 8 and R 9 may be substituted with each other independently of each other as a methyl group or an ethyl group, p is an integer of 0 to 1, q is an integer of 0 to 1, and r is 0 to 1. The integer and s are integers from 0 to 1, and p + q + r + s = 3. However, when p = 0, q = 1, r = 1, and s = 1, the structures of R 7 = R 8 = R 9 = methyl group and R 7 = R 8 = R 9 = ethyl group are excluded. Further, when p = 1, q = 1, r = 1, and s = 0, the structures of R 7 = R 8 = methyl group and R 7 = R 8 = ethyl group are excluded. Further, when p = 1, q = 1, r = 0, s = 1, the structures of R 7 = R 9 = methyl group and R 7 = R 9 = ethyl group are excluded. Further, when p = 1, q = 0, r = 1, and s = 1, the structures of R 8 = R 9 = methyl group and R 8 = R 9 = ethyl group are excluded. ]

[R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. , A branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group are fluorine atoms. May be replaced by, n is an integer of 1 to 5, and p is an integer of 0 to 1. ]

[R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. , A branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group are fluorine atoms. May be replaced by, n is an integer of 1 to 5, and p is an integer of 0 to 1. ]
The following group ( 1HFIP ) in the formula (3), the formula (2-1), and the formula (2-2) is any of the groups represented by the following formulas (1A) to (1D). The method for producing a mixture according to claim 11, wherein p is 0.

(In the equation, wavy lines indicate that the intersecting line segments are bonds.)
The method for producing a mixture according to claim 11, wherein the reaction is carried out so that the ratio of the component (I-1) and the component (II) satisfies the following relationship in terms of mass ratio.
(I-1) component / {(I-1) component + (II) component} ≧ 0.10
The method for producing a mixture according to claim 11, wherein the reaction is carried out so that the ratio of the component (I-1) and the component (II) satisfies the following relationship in terms of mass ratio.
(I-1) component / {(I-1) component + (II) component} ≧ 0.17
(I) At least one kind of silicon-containing monomer represented by the formula (1) is used.
(II) At least one selected from the group consisting of the silicon-containing monomer represented by the formula (2-1) and the silicon-containing monomer represented by the formula (2-2).
Containing, polysiloxane obtained by polymerizing a mixture.

[R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. , A branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group are fluorine atoms. R 2 , R 3 , and R 4 are linear or branched alkyl groups having 1 to 5 carbon atoms and hydrogen atoms in the alkyl groups independently of each other. All or part of may be substituted with a fluorine atom, n is an integer of 1 to 5, p is an integer of 0 to 1, q is an integer of 0 to 1, r is an integer of 0 to 1, and s is. It is an integer of 0 to 1, and p + q + r + s = 3. However, when p = 0, q = 1, r = 1, and s = 1, the structures of R 2 = R 3 = R 4 = methyl group and R 2 = R 3 = R 4 = ethyl group are excluded. Further, when p = 1, q = 1, r = 1, and s = 0, the structures of R 2 = R 3 = methyl group and R 2 = R 3 = ethyl group are excluded. Further, when p = 1, q = 1, r = 0, s = 1, the structures of R 2 = R 4 = methyl group and R 2 = R 4 = ethyl group are excluded. Further, when p = 1, q = 0, r = 1, and s = 1, the structures of R 3 = R 4 = methyl group and R 3 = R 4 = ethyl group are excluded. ]

[R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. , A branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group are fluorine atoms. May be replaced by, n is an integer of 1 to 5, and p is an integer of 0 to 1. ]

[R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. , A branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group are fluorine atoms. May be replaced by, n is an integer of 1 to 5, and p is an integer of 0 to 1. ]
The following group ( 1HFIP ) in the formula (1), the formula (2-1), and the formula (2-2) is any of the groups represented by the following formulas (1A) to (1D). The polysiloxane according to claim 15, wherein p is 0.

(In the equation, wavy lines indicate that the intersecting line segments are bonds.)
The polysiloxane according to claim 15, wherein the ratio of the component (I) to the component (II) satisfies the following relationship in terms of mass ratio.
(I) component / {(I) component + (II) component} ≧ 0.10
The polysiloxane according to claim 15, wherein the ratio of the component (I) to the component (II) satisfies the following relationship in terms of mass ratio.
(I) component / {(I) component + (II) component} ≧ 0.17
(I) At least one kind of silicon-containing monomer represented by the formula (1) is used.
(II) At least one selected from the group consisting of the silicon-containing monomer represented by the formula (2-1) and the silicon-containing monomer represented by the formula (2-2).
A method for producing a polysiloxane, which comprises polymerizing a mixture.

[R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. , A branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group are fluorine atoms. R 2 , R 3 , and R 4 are linear or branched alkyl groups having 1 to 5 carbon atoms and hydrogen atoms in the alkyl groups independently of each other. All or part of may be substituted with a fluorine atom, n is an integer of 1 to 5, p is an integer of 0 to 1, q is an integer of 0 to 1, r is an integer of 0 to 1, and s is. It is an integer of 0 to 1, and p + q + r + s = 3. However, when p = 0, q = 1, r = 1, and s = 1, the structures of R 2 = R 3 = R 4 = methyl group and R 2 = R 3 = R 4 = ethyl group are excluded. Further, when p = 1, q = 1, r = 1, and s = 0, the structures of R 2 = R 3 = methyl group and R 2 = R 3 = ethyl group are excluded. Further, when p = 1, q = 1, r = 0, s = 1, the structures of R 2 = R 4 = methyl group and R 2 = R 4 = ethyl group are excluded. Further, when p = 1, q = 0, r = 1, and s = 1, the structures of R 3 = R 4 = methyl group and R 3 = R 4 = ethyl group are excluded. ]

[R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. , A branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group are fluorine atoms. May be replaced by, n is an integer of 1 to 5, and p is an integer of 0 to 1. ]

[R 1 is a hydrogen atom independently of each other, a linear group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. , A branched alkenyl group having 3 to 10 carbon atoms or a cyclic alkenyl group having 3 to 10 carbon atoms, or a phenyl group, and all or part of the hydrogen atoms in the above-mentioned alkyl group, alkenyl group, or phenyl group are fluorine atoms. May be replaced by, n is an integer of 1 to 5, and p is an integer of 0 to 1. ]
The following group ( 1HFIP ) in the formula (1), the formula (2-1), and the formula (2-2) is any of the groups represented by the following formulas (1A) to (1D). The method for producing a polysiloxane according to claim 19, wherein p is 0.

(In the equation, wavy lines indicate that the intersecting line segments are bonds.)
The method for producing a polysiloxane according to claim 19, wherein the ratio of the component (I) to the component (II) satisfies the following relationship in terms of mass ratio.
(I) component / {(I) component + (II) component} ≧ 0.10
The method for producing a polysiloxane according to claim 19, wherein the ratio of the component (I) to the component (II) satisfies the following relationship in terms of mass ratio.
(I) component / {(I) component + (II) component} ≧ 0.17