JP7110722B2 - FLUORINE-CONTAINING ORGANOSILIC COMPOUND AND METHOD FOR PRODUCING THEREOF, ROOM-TEMPERATURE-CURABLE FLUORINE-CONTAINING RUBBER COMPOSITION AND ITS CURED MATERIAL AND ARTICLES - Google Patents

Description

The present invention provides a fluorine-containing organosilicon compound which is useful as a base polymer for a fluorine-containing elastomer (cured product of fluorine-containing rubber) which is useful, for example, as a rubber material and a release agent and has excellent acid resistance and amine resistance, and its production. The present invention relates to a method, a room-temperature-curable fluorine-containing rubber composition containing the fluorine-containing organosilicon compound, a cured product thereof (cured fluorine-containing rubber product), and articles and applications using the same.

Organic fluorine compounds are used in various fields. For example, a fluorine-containing elastomer (cured product of fluorine-containing rubber) obtained by mixing an organic fluorine compound with a crosslinking agent and crosslinking the mixture at a high temperature of 150° C. or higher is used as a rubber material and a release agent. However, the thermosetting materials described above are not suitable for non-heatable applications such as large parts due to the fact that they require high temperature conditions. In addition, many elastomers obtained from conventional organic fluorine compounds have insufficient chemical resistance such as solvent resistance, acid resistance and base resistance. In particular, elastomers used for sealants, molded parts, and the like are desirable to be excellent in releasability, water repellency, and low moisture permeability in addition to the chemical resistance described above, and to cure at room temperature. Patent Document 1 (Japanese Patent No. 3121245) and the like report an organic fluorine compound and a composition containing the same, which can provide an elastomer satisfying such properties. Since a perfluoropolyether compound having a bonded phenylene structure in the molecule is used as a base polymer, the cured product (fluorine-containing elastomer) obtained from the composition has chemical resistance, especially high-concentration acid and amine compounds. It cannot be said that the long-term durability against

Japanese Patent No. 3121245

The present invention has been devised in view of the above circumstances, and provides a novel elastomer suitable for obtaining an elastomer excellent in releasability, water repellency, and low moisture permeability, and further enhanced in chemical resistance, particularly acid resistance and amine resistance. An object of the present invention is to provide a fluoroorganosilicon compound, a method for producing the same, and a room-temperature-curing fluorine-containing rubber composition containing the fluoroorganosilicon compound.

［式中、Ａは独立に非置換又は置換の脂肪族２価炭化水素基であり、Ｒ¹及びＲ²は独立に非置換又は置換の１価炭化水素基であり、Ｒ³は独立に非置換又は置換の飽和脂肪族２価炭化水素基であり、Ｒｆは独立にパーフルオロアルキレン基又は２価のパーフルオロポリエーテル基であり、Ｘは独立に加水分解性基であり、Ｐｈはフェニル基であり、Ｑは下記一般式（２）又は下記一般式（３）：

（式中、Ｒ⁴は結合途中に酸素原子、窒素原子及びケイ素原子からなる群より選ばれる少なくとも１種を介在させてもよい非置換又は置換の２価炭化水素基であり、Ｐｈはフェニル基である。）

（式中、Ｒ⁵及びＲ⁶は独立に非置換又は置換の２価炭化水素基である。）
で表される基であり、ａは０以上の整数であり、ｂは１、２又は３である。］
で表される含フッ素有機ケイ素化合物をベースポリマーとして用いた室温硬化性含フッ素ゴム組成物が、離型性、撥水性、低透湿性に優れ、耐薬品性、特に耐酸性及び耐アミン性をさらに高めたエラストマーとなり得ることを見出し、本発明をなすに至った。 As a result of extensive studies to achieve the above object, the present inventors have found the following general formula (1):

[In the formula, A is independently an unsubstituted or substituted aliphatic divalent hydrocarbon group, R ¹ and R ² are independently unsubstituted or substituted monovalent hydrocarbon groups, and R ³ is independently a non- A substituted or substituted saturated aliphatic divalent hydrocarbon group, Rf is independently a perfluoroalkylene group or a divalent perfluoropolyether group, X is independently a hydrolyzable group, Ph is a phenyl group and Q is the following general formula (2) or the following general formula (3):

(Wherein, R ⁴ is an unsubstituted or substituted divalent hydrocarbon group which may be interposed by at least one selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom in the middle of the bond, and Ph is a phenyl group. is.)

⁽ Wherein, R5 and ^R6 are independently unsubstituted or substituted divalent hydrocarbon groups.)
is a group represented by, a is an integer of 0 or more, and b is 1, 2 or 3; ]
A room-temperature curable fluorine-containing rubber composition using a fluorine-containing organosilicon compound represented by as a base polymer has excellent releasability, water repellency, low moisture permeability, and chemical resistance, especially acid resistance and amine resistance. The inventors have found that the elastomer can be further enhanced, and have completed the present invention.

［式中、Ａは独立に非置換又は置換の脂肪族２価炭化水素基であり、Ｒ¹及びＲ²は独立に非置換又は置換の１価炭化水素基であり、Ｒ³は独立に非置換又は置換の炭素数２以上の飽和脂肪族２価炭化水素基（ただし、該炭素数２以上の飽和脂肪族２価炭化水素基はヒドロシリル化付加反応由来の－ＣＨＲ－基（Ｒは水素原子又はハロゲン原子である）を含む。）であり、Ｒｆは独立にパーフルオロアルキレン基又は２価のパーフルオロポリエーテル基であり、Ｘは独立に加水分解性基であり、Ｐｈはフェニル基であり、Ｑは下記一般式（２）又は下記一般式（３）：

（式中、Ｒ⁴は、下記式：
－（ＣＨ₂）₂－、
－（ＣＨ₂）₃－、
－（ＣＨ₂）₆－、
－（ＣＨ₂）₂－Ｒｆ－（ＣＨ₂）₂－、

－（ＣＨ₂）₂－Ｏ－（ＣＨ₂）₂－、
－（ＣＨ₂）₂－ＮＨ－（ＣＨ₂）₂－、

（式中、Ｒｆは上記と同じであり、Ｒ¹⁰は独立にアルキル基又はアリール基であり、Ｒ¹¹は独立にアルキレン基であり、ｃは０～１０の整数である。Ｍｅはメチル基である。）
から選ばれる基であり、Ｐｈはフェニル基である。）

（式中、Ｒ⁵及びＲ⁶は独立に非置換又は置換の２価炭化水素基である。）
で表される基であり、ａは１以上の整数であり、ｂは１、２又は３である。］
で表される含フッ素有機ケイ素化合物。
２．
一般式（１）におけるＱが下記式：

（式中、Ｍｅはメチル基であり、Ｐｈはフェニル基であり、Ｒｆはパーフルオロアルキレン基又は２価のパーフルオロポリエーテル基である。）
から選ばれるいずれかである１に記載の含フッ素有機ケイ素化合物。
３．
一般式（１）におけるＲ³ がエチレン基、プロピレン基（トリメチレン基）、メチルエチレン基、ブチレン基、ヘキサメチレン基及びシクロヘキシレン基から選ばれる少なくとも１種である１又は２に記載の含フッ素有機ケイ素化合物。
４．
下記一般式（４）：

［式中、Ａは独立に非置換又は置換の脂肪族２価炭化水素基であり、Ｒ²は独立に非置換又は置換の１価炭化水素基であり、Ｒｆは独立にパーフルオロアルキレン基又は２価のパーフルオロポリエーテル基であり、Ｒ¹²は独立に脂肪族不飽和結合を有する非置換又は置換の１価炭化水素基であり、Ｐｈはフェニル基であり、Ｑは下記一般式（２）又は下記一般式（３）：

（式中、Ｒ⁴は、下記式
－（ＣＨ₂）₂－、
－（ＣＨ₂）₃－、
－（ＣＨ₂）₆－、
－（ＣＨ₂）₂－Ｒｆ－（ＣＨ₂）₂－、

－（ＣＨ₂）₂－Ｏ－（ＣＨ₂）₂－、
－（ＣＨ₂）₂－ＮＨ－（ＣＨ₂）₂－、

（式中、Ｒｆは上記と同じであり、Ｒ¹⁰は独立にアルキル基又はアリール基であり、Ｒ¹¹は独立にアルキレン基であり、ｃは０～１０の整数である。Ｍｅはメチル基である。）
から選ばれる基であり、Ｐｈはフェニル基である。）

（式中、Ｒ⁵及びＲ⁶は独立に非置換又は置換の２価炭化水素基である。）
で表される基であり、ａは１以上の整数である。］
で表される脂肪族不飽和結合を有する含フッ素有機ケイ素化合物と、下記一般式（５）：

（式中、Ｒ¹は非置換又は置換の１価炭化水素基であり、Ｘは加水分解性基であり、ｂは１、２又は３である。）
で表される（オルガノ）ハイドロジェンシラン化合物とを触媒の存在下でヒドロシリル化付加反応させることを特徴とする下記一般式（１’）で表される含フッ素有機ケイ素化合物の製造方法。

（式中、Ａ、Ｒ¹、Ｒ²、Ｒｆ、Ｘ、Ｑ、ａ及びｂは上記と同じであり、Ｒ^3’は独立に、一般式（４）のＲ¹²における脂肪族不飽和結合と一般式（５）で表される（オルガノ）ハイドロジェンシラン化合物における－ＳｉＨとのヒドロシリル化付加反応により形成される非置換又は置換の炭素数２以上の飽和脂肪族２価炭化水素基であり、Ｐｈはフェニル基である。）
５．
一般式（４）におけるＱが下記式：

（式中、Ｍｅはメチル基であり、Ｐｈはフェニル基であり、Ｒｆはパーフルオロアルキレン基又は２価のパーフルオロポリエーテル基である。）
から選ばれるいずれかである４に記載の含フッ素有機ケイ素化合物の製造方法。
６．
一般式（１’）におけるＲ^3’ がエチレン基、プロピレン基（トリメチレン基）、メチルエチレン基、ブチレン基、ヘキサメチレン基及びシクロヘキシレン基から選ばれる少なくとも１種である４又は５に記載の含フッ素有機ケイ素化合物の製造方法。
７．
１～３のいずれかに記載の含フッ素有機ケイ素化合物及び硬化触媒を含有する室温硬化性含フッ素ゴム組成物。
８．
更に、架橋剤、充填剤、接着助剤、耐熱性付与剤及び着色剤から選ばれる少なくとも一種を含有する７に記載の室温硬化性含フッ素ゴム組成物。
９．
７又は８に記載の室温硬化性含フッ素ゴム組成物の硬化物からなる含フッ素ゴム。
１０．
７又は８に記載の室温硬化性含フッ素ゴム組成物を室温で硬化して含フッ素ゴム硬化物を得る工程を含む含フッ素ゴム硬化物の耐熱性、耐薬品性、耐溶剤性、撥水性及び／又は低透湿性を向上させる方法。
１１．
７又は８に記載の室温硬化性含フッ素ゴム組成物の硬化物層を有する物品。 Accordingly, the present invention provides the following fluorine-containing organosilicon compounds, methods for producing the same, room-temperature-curable fluorine-containing rubber compositions, cured products thereof, and the like.
1.
The following general formula (1):

[In the formula, A is independently an unsubstituted or substituted aliphatic divalent hydrocarbon group, R ¹ and R ² are independently unsubstituted or substituted monovalent hydrocarbon groups, and R ³ is independently a non- A substituted or substituted saturated aliphatic divalent hydrocarbon group having 2 or more carbon atoms (wherein the saturated aliphatic divalent hydrocarbon group having 2 or more carbon atoms is a -CHR- group derived from a hydrosilylation addition reaction (R is a hydrogen atom or a halogen atom) , Rf is independently a perfluoroalkylene group or a divalent perfluoropolyether group, X is independently a hydrolyzable group, and Ph is a phenyl group , Q is the following general formula (2) or the following general formula (3):

(Wherein, R ⁴ is the following formula:
-( _CH2 ) _2- ,
-( _CH2 ) _3- ,
-( _CH2 ) _6- ,
—(CH ₂ ) ₂ —Rf—(CH ₂ ) ₂ —,

—(CH ₂ ) ₂ —O—(CH ₂ ) ₂ —,
-( _CH2 ) ₂ -NH-( _CH2 ) _2- ,

(wherein Rf is the same as above, R ¹⁰ is independently an alkyl group or an aryl group, R ¹¹ is independently an alkylene group, c is an integer of 0 to 10, Me is a methyl group, be.)
and Ph is a phenyl group. )

( ^In the ^formula , R5 and R6 are independently unsubstituted or substituted divalent hydrocarbon groups.)
is a group represented by, a is an integer of 1 or more, and b is 1, 2 or 3; ]
A fluorine-containing organosilicon compound represented by.
2.
Q in the general formula (1) is the following formula:

(In the formula, Me is a methyl group, Ph is a phenyl group, and Rf is a perfluoroalkylene group or a divalent perfluoropolyether group.)
2. The fluorine-containing organosilicon compound according to 1, which is any one selected from
3.
3. The fluorine-containing according to 1 or 2, wherein R ³ in general formula (1) is at least one selected from ethylene group, propylene group (trimethylene group), methylethylene group, butylene group, hexamethylene group and cyclohexylene group. Organosilicon compound.
4.
The following general formula (4):

[wherein A is independently an unsubstituted or substituted aliphatic divalent hydrocarbon group, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group, and Rf is independently a perfluoroalkylene group or is a divalent perfluoropolyether group, R ¹² is independently an unsubstituted or substituted monovalent hydrocarbon group having an aliphatic unsaturated bond, Ph is a phenyl group, and Q is represented by the following general formula (2 ) or the following general formula (3):

(In the formula, R ⁴ is the following formula -(CH ₂ ) ₂ -,
-( _CH2 ) _3- ,
-( _CH2 ) _6- ,
—(CH ₂ ) ₂ —Rf—(CH ₂ ) ₂ —,

—(CH ₂ ) ₂ —O—(CH ₂ ) ₂ —,
-( _CH2 ) ₂ -NH-( _CH2 ) _2- ,

(wherein Rf is the same as above, R ¹⁰ is independently an alkyl group or an aryl group, R ¹¹ is independently an alkylene group, c is an integer of 0 to 10, Me is a methyl group, be.)
and Ph is a phenyl group. )

( ^In the ^formula , R5 and R6 are independently unsubstituted or substituted divalent hydrocarbon groups.)
and a is an integer of 1 or more. ]
and a fluorine-containing organosilicon compound having an aliphatic unsaturated bond represented by the following general formula (5):

(Wherein, R ¹ is an unsubstituted or substituted monovalent hydrocarbon group, X is a hydrolyzable group, and b is 1, 2 or 3.)
A method for producing a fluorine-containing organosilicon compound represented by the following general formula (1′), which comprises hydrosilylation addition reaction with a (organo)hydrogensilane compound represented by the following general formula (1′) in the presence of a catalyst.

(Wherein, A, R ¹ , R ² , Rf, X, Q, a and b are the same as above, and R ^3′ is independently the aliphatic unsaturated bond in R ¹² of general formula (4) An unsubstituted or substituted saturated aliphatic divalent hydrocarbon group having 2 or more carbon atoms formed by a hydrosilylation addition reaction with —SiH in the (organo)hydrogensilane compound represented by the general formula (5), Ph is a phenyl group.)
5.
Q in the general formula (4) is the following formula:

(In the formula, Me is a methyl group, Ph is a phenyl group, and Rf is a perfluoroalkylene group or a divalent perfluoropolyether group.)
5. The method for producing a fluorine-containing organosilicon compound according to 4, which is any one selected from
6.
4 or 5, wherein R ^3' in general formula (1') is at least one selected from an ethylene group, a propylene group (trimethylene group), a methylethylene group, a butylene group, a hexamethylene group and a cyclohexylene group. A method for producing a fluorine-containing organosilicon compound.
7.
A room-temperature curable fluorine-containing rubber composition containing the fluorine-containing organosilicon compound according to any one of 1 to 3 and a curing catalyst.
8.
8. The room temperature curable fluororubber composition according to 7, which further contains at least one selected from a cross-linking agent, a filler, an adhesion promoter, a heat resistance imparting agent and a colorant.
9.
9. A fluorine-containing rubber comprising a cured product of the room-temperature-curable fluorine-containing rubber composition according to 7 or 8 above.
10.
heat resistance, chemical resistance, solvent resistance, water repellency and / Or a method for improving low moisture permeability.
11.
9. An article having a cured product layer of the room temperature curable fluorine-containing rubber composition according to 7 or 8.

Since the fluorinated organosilicon compound of the present invention has a hydrolyzable silyl group at its terminal, it can be crosslinked, for example, by reacting with moisture (moisture) in the air to form a fluorinated elastomer (cured fluorinated rubber). In addition, since the fluorine-containing organosilicon compound of the present invention has a high fluorine content, the room-temperature-curing fluorine-containing rubber composition containing it is excellent in solvent resistance, chemical resistance, particularly acid resistance and amine resistance. Furthermore, it is possible to obtain building materials, industrial plant members, sealants, molded parts, extruded parts, coating materials, release agents, etc., which are excellent in releasability, water repellency and low moisture permeability. The fluorine-containing rubber composition of the present invention can be used to coat the surface of specific substrates such as metals, rubbers, resins, and fibers. Thereby, it is possible to impart the above-mentioned properties derived from the fluororubber composition and its cured product (fluorine-containing rubber cured product) to the target substrate, or to improve the above-mentioned properties of the target substrate. . The first use is to improve solvent resistance and chemical resistance (acid resistance, amine resistance) by coating the surface of general-purpose rubbers such as nitrile rubber, polyurethane, silicone rubber, and butyl rubber, which have poor solvent resistance or water resistance. , low moisture permeability and water repellency can be imparted to the target substrate, and the above properties can be improved. This approach works well for all other rubber and elastomeric substrates. Furthermore, since the cured product obtained from the fluorine-containing rubber composition is rubbery, there is also the advantage that the flexibility, stretchability and other functionality derived from the target rubber base material and elastomer base material are not impaired. .

［式中、Ａは独立に非置換又は置換の脂肪族２価炭化水素基であり、Ｒ¹及びＲ²は独立に非置換又は置換の１価炭化水素基であり、Ｒ³は独立に非置換又は置換の飽和脂肪族２価炭化水素基であり、Ｒｆは独立にパーフルオロアルキレン基又は２価のパーフルオロポリエーテル基であり、Ｘは独立に加水分解性基であり、Ｐｈはフェニル基であり、Ｑは下記一般式（２）又は下記一般式（３）：

（式中、Ｒ⁴は結合途中に酸素原子、窒素原子及びケイ素原子からなる群より選ばれる少なくとも１種を介在させてもよい非置換又は置換の２価炭化水素基であり、Ｐｈはフェニル基と同じである。）

（式中、Ｒ⁵及びＲ⁶は独立に非置換又は置換の２価炭化水素基である。）
で表される基であり、ａは０以上の整数であり、ｂは１、２又は３である。］ The present invention will be described in detail below.
[Fluorine-containing organosilicon compound]
The fluorine-containing organosilicon compound of the present invention is represented by the following general formula (1).

[In the formula, A is independently an unsubstituted or substituted aliphatic divalent hydrocarbon group, R ¹ and R ² are independently unsubstituted or substituted monovalent hydrocarbon groups, and R ³ is independently a non- A substituted or substituted saturated aliphatic divalent hydrocarbon group, Rf is independently a perfluoroalkylene group or a divalent perfluoropolyether group, X is independently a hydrolyzable group, Ph is a phenyl group and Q is the following general formula (2) or the following general formula (3):

(Wherein, R ⁴ is an unsubstituted or substituted divalent hydrocarbon group which may be interposed by at least one selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom in the middle of the bond, and Ph is a phenyl group. is the same as

⁽ Wherein, R5 and ^R6 are independently unsubstituted or substituted divalent hydrocarbon groups.)
is a group represented by, a is an integer of 0 or more, and b is 1, 2 or 3; ]

In general formula (1), R ¹ and R ² are independently unsubstituted or substituted monovalent hydrocarbon groups, preferably unsubstituted or substituted saturated or unsaturated hydrocarbon groups having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms. Saturated monovalent hydrocarbon groups, and examples of the unsubstituted saturated or unsaturated monovalent hydrocarbon groups represented by R ¹ and R ² include saturated aliphatic monovalent hydrocarbon groups such as alkyl groups and cycloalkyl groups. groups, aromatic monovalent hydrocarbon groups such as aryl groups and aralkyl groups, unsaturated aliphatic monovalent hydrocarbon groups such as alkenyl groups, and the like.
Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group and octyl group. 2-ethylhexyl group, nonyl group, decyl group and other linear or branched alkyl groups having 1 to 10 carbon atoms, more representative ones being methyl group, ethyl group, propyl group, butyl group, tert-butyl group, hexyl group and octyl group, and particularly preferred are lower alkyl groups having 1 to 3 carbon atoms such as methyl group, ethyl group and propyl group.
Examples of the cycloalkyl group include cycloalkyl groups having 3 to 8 carbon atoms such as cyclopentyl group, cyclohexyl group and cycloheptyl group. It is a cycloalkyl group of number 5 or 6.
Examples of the aryl group include aryl groups having 6 to 15 carbon atoms such as phenyl group, tolyl group, xylyl group, naphthyl group and biphenylyl group. It is an aryl group having 6 to 8 carbon atoms such as a xylyl group.
Examples of the aralkyl group include aralkyl groups having 7 to 10 carbon atoms such as a benzyl group, a phenylethyl group, a phenylpropyl group and a methylbenzyl group, and more typical ones are a benzyl group and a phenylethyl group. is an aralkyl group having 7 or 8 carbon atoms such as
Examples of the alkenyl group include alkenyl groups having 2 to 10 carbon atoms such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, hexenyl group, and cyclohexenyl group. Typical examples are alkenyl groups having 2 to 4 carbon atoms such as vinyl group, allyl group and butenyl group.
As the substituted saturated or unsaturated monovalent hydrocarbon group represented by R ¹ and R ² , at least part of the hydrogen atoms in the unsubstituted saturated or unsaturated monovalent hydrocarbon group is fluorine atom, chlorine a group substituted with a halogen atom such as an atom, a bromine atom, an iodine atom, and representative examples include, for example, a chloromethyl group, a 2-bromoethyl group, a 3-chloropropyl group and a 3,3,3-trifluoropropyl and halogen-substituted alkyl groups having 1 to 8 carbon atoms such as 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, more representative ones being 3,3 ,3-trifluoropropyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group and other halogen-substituted alkyl groups having 3 to 8 carbon atoms.
Among these, R ¹ is preferably a methyl group, an ethyl group, or a propyl group, and R ² is preferably a methyl group, an ethyl group, or a propyl group.

In general formula (1), A is independently an unsubstituted or substituted aliphatic divalent hydrocarbon group, and the unsubstituted or substituted aliphatic divalent hydrocarbon group includes, for example, 1 to 20 carbon atoms , In particular, 2 to 10 unsubstituted or substituted saturated or unsaturated aliphatic divalent hydrocarbon groups are mentioned, and typical ones are methylene group, ethylene group, propylene group (trimethylene group), methylethylene group , a butylene group (tetramethylene group), a hexamethylene group, and other linear, branched or cyclic alkylene groups having 1 to 10 carbon atoms; A linear alkylene group having 1 to 4 atoms; a saturated aliphatic divalent hydrocarbon group such as a cycloalkylene group having 3 to 7 carbon atoms such as a cyclohexylene group; a 1-butenylene group, a 3-heptenylene group, etc. A linear or branched alkenylene group having 4 to 10 carbon atoms; or a combination of these unsubstituted or substituted alkylene groups and cycloalkylene groups; or some or all of the hydrogen atoms of these groups are fluorine atoms, Examples include groups substituted with halogen atoms such as chlorine, bromine and iodine atoms. Among them, straight-chain alkylene groups such as ethylene group and propylene group are preferable from the viewpoint of ease of synthesis, stability of the compound, and the like.

In general formula (1), R ³ is independently an unsubstituted or substituted saturated aliphatic divalent hydrocarbon group, and the unsubstituted or substituted saturated aliphatic divalent hydrocarbon group for R ³ includes, for example, Linear, branched or cyclic saturated aliphatic divalent hydrocarbon groups having 1 to 20 carbon atoms, particularly 2 to 10 carbon atoms, and typical examples thereof include methylene group, ethylene group and propylene. linear, branched or cyclic alkylene groups having 1 to 10 carbon atoms such as a group (trimethylene group), methylethylene group, butylene group, hexamethylene group, and further typical examples are methylene group, ethylene group and propylene. linear alkylene group having 1 to 4 carbon atoms such as group (trimethylene group); saturated aliphatic divalent hydrocarbon group such as cycloalkylene group having 3 to 7 carbon atoms such as cyclohexylene group; Groups in which some or all of the hydrogen atoms in the group are substituted with halogen atoms such as fluorine, chlorine, bromine and iodine atoms are exemplified. Among them, an ethylene group and a propylene group are preferable from the viewpoints of ease of synthesis, stability of the compound, and the like.

In the general formula (1), Rf is independently a perfluoroalkylene group or a divalent perfluoropolyether group, and among these Rf, the perfluoroalkylene group is a linear or branched chain represented by the following general formula belongs to.
_{-CmF2m- _}
(Wherein, m is an integer of 1 to 10, preferably an integer of 1 to 6.)

（式中、Ｙは独立にフッ素原子又はトリフルオロメチル基であり、ｐ、ｑ及びｒは、ｐ≧１、ｑ≧１、２≦ｐ＋ｑ≦２００を満足する整数であり、好ましくは３≦ｐ＋ｑ≦１１０、０≦ｒ≦６を満足する整数である。）

（式中、ｒは前記と同じであり、ｓ及びｔは、ｓ≧０、ｔ≧０、２≦ｓ＋ｔ≦２００を満足する整数であり、好ましくは３≦ｓ＋ｔ≦１１０を満足する整数である。）

（式中、Ｙは前記と同じであり、ｕ及びｖは１≦ｕ≦１００、１≦ｖ≦１００を満足する整数である。）

（式中、ｗは１≦ｗ≦１００を満足する整数である。） Among these Rf, the divalent perfluoropolyether group includes, for example, those represented by the following general formula.

(Wherein Y is independently a fluorine atom or a trifluoromethyl group, p, q and r are integers satisfying p ≥ 1, q ≥ 1, 2 ≤ p + q ≤ 200, preferably 3 ≤ p + q is an integer satisfying ≤110 and 0≤r≤6.)

(Wherein, r is the same as above, and s and t are integers satisfying s ≥ 0, t ≥ 0, 2 ≤ s + t ≤ 200, preferably 3 ≤ s + t ≤ 110. .)

(In the formula, Y is the same as above, and u and v are integers satisfying 1 ≤ u ≤ 100 and 1 ≤ v ≤ 100.)

(Wherein, w is an integer that satisfies 1≤w≤100.)

（式中、ｐ１は平均で１～１００、ｑ１は平均で１～１００、ｐ１＋ｑ１は平均で２～２００、好ましくは３０～１１０である。）

（式中、ｐ２は平均で１～１００、ｑ２は平均で１～１００、ｐ２＋ｑ２は平均で２０～１１０、例えば３０である。）

（式中、ｕ１は平均で５～５０、例えば８であり、ｖ１は平均で１～１０、例えば２である。）

（式中、ｕ２は平均で５～５０、例えば１５であり、ｖ２は平均で１～１０、例えば２である。）

（式中、ｗ１は５～１００の整数、例えば１０である。） Specific examples of such Rf include those shown below.

(In the formula, p1 is 1 to 100 on average, q1 is 1 to 100 on average, and p1+q1 is 2 to 200 on average, preferably 30 to 110.)

(In the formula, p2 is 1 to 100 on average, q2 is 1 to 100 on average, and p2+q2 is 20 to 110 on average, for example 30.)

(Wherein, u1 is 5 to 50, for example 8 on average, and v1 is 1 to 10, for example 2 on average.)

(Wherein, u2 is an average of 5 to 50, such as 15, and v2 is an average of 1 to 10, such as 2.)

(Wherein, w1 is an integer from 5 to 100, such as 10.)

In the present invention, the degree of polymerization (or molecular weight) of the perfluoroalkylene group or divalent perfluoropolyether group represented by Rf is, for example, a polystyrene equivalent in gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent. It can be obtained as a number average polymerization degree (or number average molecular weight) at.

In the general formula (1), X is independently a hydrolyzable group, and the hydrolyzable group represented by X includes, for example, a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom; Examples thereof include groups represented by general formulae.

（式中、Ｒ⁷及びＲ⁸はそれぞれ水素原子又は非置換もしくは置換の１価炭化水素基である。）

( ^In the formula, ^R7 and R8 are each a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group.)

Here, the unsubstituted or substituted monovalent hydrocarbon group represented by R ⁷ and R ⁸ includes, for example, carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group. Alkyl groups having a number of 1 to 10, typical examples include alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl and isobutyl; cyclo groups having 3 to 7 carbon atoms such as cyclohexyl; Alkyl group; Alkenyl group having 2 to 10 carbon atoms such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group and isobutenyl group; typical examples are carbon atoms such as vinyl group and isopropenyl group an alkenyl group having a number of 2 to 4; an aryl group having 6 to 10 carbon atoms such as a phenyl group; or a group in which the hydrogen atoms of these groups are partially substituted with an alkoxy group or the like, such as a methoxymethyl group or methoxyethyl alkoxy-substituted alkyl groups having 2 to 4 carbon atoms such as ethoxymethyl group and ethoxyethyl group.

Ｘとしては、これらの中でもメトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基等のアルコキシ基が好ましい。 Specific examples of X include those shown below.

Among these, X is preferably an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or an isopropoxy group.

（式中、Ｒ⁴は結合途中に酸素原子、窒素原子及びケイ素原子からなる群より選ばれる少なくとも１種を介在させてもよい非置換又は置換の２価炭化水素基であり、Ｐｈはフェニル基である。）

（式中、Ｒ⁵及びＲ⁶は独立に非置換又は置換の２価炭化水素基である。） In general formula (1), Q is a group represented by general formula (2) or general formula (3) below.

(Wherein, R ⁴ is an unsubstituted or substituted divalent hydrocarbon group which may be interposed by at least one selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom in the middle of the bond, and Ph is a phenyl group. is.)

⁽ Wherein, R5 and ^R6 are independently unsubstituted or substituted divalent hydrocarbon groups.)

(i) a group represented by the general formula (2) In the general formula (2), R ⁴ is non-bonded and may be interposed by at least one selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom. It is a substituted or substituted divalent hydrocarbon group, and as this R ⁴ , in addition to the unsubstituted or substituted aliphatic divalent hydrocarbon group (for example, (cyclo)alkylene group) exemplified as A, aromatic 2 A valent hydrocarbon group (e.g., an arylene group) or a combination thereof (e.g., an alkylene-arylene group), and an unsubstituted or Substituted, aliphatic or aromatic divalent hydrocarbon groups are included. In the aliphatic or aromatic divalent hydrocarbon group for R ⁴ , the oxygen atom may exist as —O— (ether bond), and the nitrogen atom may be —NR ⁹ — (with the proviso that R ⁹ is a hydrogen atom, an alkyl group or an aryl group.) can be interposed as an imino group represented by the silicon atom is a divalent group containing a linear or cyclic organosiloxane structure, or a divalent group It can be interposed as an organosilylene group.

Here, the alkyl group for R ⁹ includes, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group and the like, and particularly representative ones are methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, etc. 1 to 6 alkyl groups. Examples of the aryl group for R ⁹ include aryl groups having 6 to 8 carbon atoms such as phenyl group, tolyl group and xylyl group. Among these, ^R9 is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group.

（式中、Ｒ¹⁰は独立にアルキル基又はアリール基であり、Ｒ¹¹は独立にアルキレン基であり、ｃは０～１０の整数、代表的には０～５の整数である。） Examples of the divalent group or diorganosilylene group containing a linear or cyclic organosiloxane structure are given below.

(In the formula, R ¹⁰ is independently an alkyl group or an aryl group, R ¹¹ is independently an alkylene group, and c is an integer of 0-10, typically 0-5.)

Here, examples of the alkyl group or aryl group for R ¹⁰ include those similar to the alkyl group or aryl group for R ⁹ above.
Examples of the alkylene group for R ¹¹ include alkylene groups having 1 to 10 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group and decylene group. groups. Among these, R ¹¹ is preferably a lower alkylene group such as a methylene group, an ethylene group and a propylene group.

（式中、Ｒｆは上記と同じであり、Ｍｅはメチル基である。） Specific examples of the unsubstituted or substituted divalent hydrocarbon group in which at least one selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom may be interposed in the middle of the bond of R ⁴ include, for example, , and those represented by the following formulas.
-( _CH2 ) _2- ,
-( _CH2 ) _3- ,
-( _CH2 ) _6- ,
—(CH ₂ ) ₂ —Rf—(CH ₂ ) ₂ —,

(Wherein, Rf is the same as above and Me is a methyl group.)

（式中、Ｍｅはメチル基であり、Ｐｈはフェニル基であり、Ｒｆは上記と同じである。） Specific examples of the group Q represented by the general formula (2) include the following.

(Wherein, Me is a methyl group, Ph is a phenyl group, and Rf is the same as above.)

(ii) a group represented by general formula (3) In general formula (3), R ⁵ and R ⁶ are independently unsubstituted or substituted divalent hydrocarbon groups, and this unsubstituted or substituted divalent hydrocarbon group. Examples of the hydrogen group include those exemplified for R ³ in the general formula (1). Typical examples include methylene, ethylene, propylene, methylethylene, butylene, hexa an alkylene group having 1 to 20 carbon atoms such as a methylene group, particularly an alkylene group having 1 to 10 carbon atoms, more representative alkylene groups having 1 to 3 carbon atoms such as a methylene group, an ethylene group and a propylene group; Examples thereof include groups in which some or all of the hydrogen atoms in the group are substituted with halogen atoms such as fluorine, chlorine, bromine and iodine atoms. As R ⁵ and R ⁶ , ethylene group and propylene group are preferable among them.

（式中、Ｍｅはメチル基である。） Specific examples of the group Q represented by the general formula (3) include the following.

(In the formula, Me is a methyl group.)

In general formula (1), a is an integer of 0 or more, typically an integer of 0-10, more typically an integer of 0-6. Accordingly, one molecule of the fluorine-containing organosilicon compound of general formula (1) contains one or more perfluoroalkylene groups or divalent perfluoropolyether groups.
In general formula (1), b is independently 1, 2 or 3, preferably 2 or 3, more preferably 3. Therefore, the fluorine-containing organosilicon compound of general formula (1) contains 1 to 3 hydrolyzable groups X (ie, 2 to 6 in the molecule) at both ends of the molecular chain.

（式中、Ｒｆ、Ｑ及びａは前記と同じである。Ｍｅはメチル基であり、Ｐｈはフェニル基である。） Examples of the fluorine-containing organosilicon compound represented by formula (1) include those shown below.

(Wherein, Rf, Q and a are the same as above. Me is a methyl group and Ph is a phenyl group.)

The fluorine-containing organosilicon compound represented by the general formula (1) of the present invention includes low-viscosity polymers of several tens of mPa·s to solid gum-like polymers. For example, for heat-vulcanized rubber, raw rubber-like polymers may be used in consideration of ease of handling. For liquid rubber, one having a viscosity of about 100 to 100,000 mPa·s at 25° C. may be used. If the viscosity is too low, the resulting cured product may lose its elasticity and become brittle. In the present invention, viscosity can be measured by a rotational viscometer (eg, BL type, BH type, BS type, cone plate type, rheometer, etc.).

［式中、Ａ、Ｒ²、Ｒｆ、Ｑ及びａは上記と同じであり、Ｐｈはフェニル基であり、Ｒ¹²は独立に脂肪族不飽和結合を有する非置換又は置換の１価炭化水素基である。］

（式中、Ｒ¹、Ｘ、ｂは上記と同じである。） [Method for Producing Fluorine-Containing Organosilicon Compound]
The fluorine-containing organosilicon compound represented by the general formula (1) of the present invention comprises a fluorine-containing organosilicon compound having an aliphatic unsaturated bond represented by the following general formula (4), and a fluorine-containing organosilicon compound represented by the following general formula (5). It can be produced by hydrosilylation addition reaction with the represented (organo)hydrogensilane compound in the presence of a catalyst.

[Wherein, A, R ² , Rf, Q and a are the same as above, Ph is a phenyl group, and R ¹² is independently an unsubstituted or substituted monovalent hydrocarbon group having an aliphatic unsaturated bond. is. ]

(In the formula, R ¹ , X, and b are the same as above.)

[Fluorinated Organosilicon Compound of General Formula (4)]
In general formula (4), R ¹² is an unsubstituted or substituted monovalent hydrocarbon group having an aliphatic unsaturated bond capable of hydrosilylation reaction with a hydrogen atom independently bonded to a silicon atom. Examples of R ¹² include vinyl, allyl, propenyl, isopropenyl, butenyl, butenyl, hexenyl, cyclohexenyl, etc., having 2 to 8 carbon atoms. Aliphatic unsaturated monovalent hydrocarbon groups such as 2 to 6 alkenyl groups, or some or all of the hydrogen atoms in these groups are substituted with halogen atoms such as fluorine, chlorine, bromine and iodine atoms. and the like. R ¹² is preferably a vinyl group.

（式中、Ｒｆ、Ｑ及びａは前記と同じである。Ｍｅはメチル基であり、Ｐｈはフェニル基である。） Examples of the fluorine-containing organosilicon compound having an aliphatic unsaturated bond represented by formula (4) include those shown below.

(Wherein, Rf, Q and a are the same as above. Me is a methyl group and Ph is a phenyl group.)

（式中、Ａ、Ｒ²、Ｒ¹²及びＲｆは前記と同じである。Ｐｈはフェニル基である。） [Method for Producing Fluorine-Containing Organosilicon Compound of Formula (4)]
(i) A method for producing a fluorine-containing organosilicon compound in which a is 0 in formula (4)
The fluorine-containing organosilicon compound [the following general formula (4-1)] in which a in the general formula (4) is 0 is, for example, as shown in the following reaction formula, both terminals represented by the following general formula (6) Synthesized by reacting a fluorine-containing compound having an acid fluoride group and an amine compound having an aliphatic unsaturated group-containing silyl group represented by the following general formula (7) in the presence of an acid acceptor such as triethylamine can do.

(In the formula, A, R ² , R ¹² and Rf are the same as above. Ph is a phenyl group.)

（式中、ｐ１は平均で１～１００、ｑ１は平均で１～１００、ｐ１＋ｑ１は平均で２～２００、好ましくは３０～１１０である。）

（式中、ｐ２は平均で１～１００、ｑ２は平均で１～１００、ｐ２＋ｑ２は平均で２０～１１０、例えば３０である。）

（式中、ｕ１は平均で５～５０、例えば８であり、ｖ１は平均で１～１０、例えば２である。）

（式中、ｕ２は平均で５～５０、例えば１５であり、ｖ２は平均で１～１０、例えば２である。）

（式中、ｗ１は５～１００の整数、例えば１０である。） Specific examples of the fluorine-containing compound represented by the formula (6) having acid fluoride groups at both ends are given below.

(In the formula, p1 is 1 to 100 on average, q1 is 1 to 100 on average, and p1+q1 is 2 to 200 on average, preferably 30 to 110.)

(In the formula, p2 is 1 to 100 on average, q2 is 1 to 100 on average, and p2+q2 is 20 to 110 on average, for example 30.)

(Wherein, u1 is 5 to 50, for example 8 on average, and v1 is 1 to 10, for example 2 on average.)

(Wherein, u2 is an average of 5 to 50, such as 15, and v2 is an average of 1 to 10, such as 2.)

(Wherein, w1 is an integer from 5 to 100, such as 10.)

The viscosity at 25° C. of the fluorine-containing compound represented by the formula (6) having acid fluoride groups at both ends, measured by a rotational viscometer, is 300 to 15,000 mPa s, particularly 400 to 7,500 mPa s. is preferred.

Specific examples of the amine compound having an aliphatically unsaturated group-containing silyl group represented by formula (7) are given below.

In the above reaction, the compounding ratio of the fluorine-containing compound of general formula (6) and the amine compound of general formula (7) is not particularly limited. The amount of the amine compound of formula (7) used (B) [molar ratio] is preferably from 0.2 to 0.5, more preferably from 0.4 to 0.5. If the molar ratio is too small, a colored product may be obtained, and if it is too large, part of the COF groups at both ends of the molecular chain of the fluorine-containing compound of general formula (6) may remain and the reaction may not be completed. There is

Examples of the acid acceptor used in the above reaction include triethylamine, diisopropylethylamine, pyridine and the like. The amount of the acid acceptor used is not particularly limited, but it should be 1.1 to 1.5 equivalents (molar conversion) with respect to the amount of COF groups at both ends of the molecular chain of the fluorine-containing compound of general formula (6). is preferred.

The reaction conditions are not particularly limited, and the reaction may be carried out at 20 to 100° C. for 1 to 8 hours, preferably 20 to 50° C. for 2 to 4 hours.

（式中、Ａ、Ｒ²、Ｒ¹²、Ｑ、ａ及びＲｆは前記と同じである。Ｐｈはフェニル基である。） (ii) Method for producing a fluorine-containing organosilicon compound in which a is 1 or more in formula (4). Then, a fluorine-containing compound represented by the following general formula (6) having acid fluoride groups at both ends and a compound represented by the following general formula (8) having active hydrogen atoms at both ends are combined with an acceptor such as triethylamine. After reacting in the presence of an acid agent, an amine compound having an aliphatic unsaturated group-containing silyl group represented by the following general formula (7) is added to the resulting reaction product represented by the following general formula (9). can be synthesized by reacting

(In the formula, A, R ² , R ¹² , Q, a and Rf are the same as above. Ph is a phenyl group.)

Examples of the fluorine-containing compound having an acid fluoride group at both ends represented by formula (6) and the amine compound having an aliphatic unsaturated group-containing silyl group represented by formula (7) include those described above.

Further, specific examples of the compound having active hydrogen atoms at both terminals represented by the formula (8) include those shown below.

In the above reaction, the compounding ratio of the fluorine-containing compound of general formula (6) and the active hydrogen atom-containing compound of general formula (8) is the molar amount (A) of the fluorine-containing compound of formula (6) in terms of moles. Although it is not particularly limited as long as it is not less than the molar amount (C) of the active hydrogen atom-containing compound in (8), the molar amount ratio (A)/(C) is 1.0 to 3.0, In particular, it is preferable to set it to 1.0 to 2.0. Incidentally, a in the general formula (4) can be set to a value according to the purpose by adjusting the molar ratio (A)/(C). If (A)/(C) is increased, a polymer with a relatively small molecular weight can be synthesized, and if the value of (A)/(C) is close to 1, a polymer with a large molecular weight can be synthesized.

In the above reaction, the compounding ratio of the reaction product of general formula (9) and the amine compound of general formula (7) is not particularly limited, but the amount of the reaction product of formula (9) used The amount of (D)/(B) [molar ratio] of the amine compound of formula (7) is preferably from 0.2 to 0.5, more preferably from 0.4 to 0.5. If the molar ratio is too small, a colored product may be obtained, and if it is too large, part of the COF groups at both ends of the molecular chain of the fluorine-containing compound of general formula (9) will remain and the reaction will not be completed. Sometimes.

In addition, examples of the acid acceptor used in the above reaction are the same as those exemplified in (i) above. The amount of the acid acceptor used is not particularly limited, but it should be 1.1 to 1.5 equivalents (molar conversion) with respect to the amount of COF groups at both ends of the molecular chain of the fluorine-containing compound of general formula (9). is preferred.

The reaction conditions of the fluorine-containing compound of formula (6) and the active hydrogen atom-containing compound of formula (8), and the reaction conditions of the reaction product of formula (9) and the amine compound of formula (7) are the same as those described above. The same reaction conditions as in (i) may be used.

（式中、Ａ、Ｒ²、Ｒ¹²、ａ及びＲｆは上記と同じである。Ｐｈはフェニル基である。Ｐは末端にケイ素原子を有する２価の有機基であり、Ｒ¹³は独立に炭素原子数２～８の非置換又は置換の２価炭化水素基である。） (iii) Another method for producing a fluorine-containing organosilicon compound in which a in formula (4) is 1 or more As another method for producing a fluorine-containing organosilicon compound in which a in formula (4) is 1 or more, For example, first, a fluorine-containing organosilicon compound having an aliphatically unsaturated group-containing silyl group at the end represented by the formula (4-1) in which a is 0 in the formula (4) is synthesized by the method (i) above. , as shown in the following reaction formula, with the obtained fluorine-containing organosilicon compound having an aliphatic unsaturated group-containing silyl group at the end represented by the following general formula (4-1), and the following general formula (10): By reacting with a compound having silicon-bonded hydrogen atoms at both ends shown in the presence of an addition reaction catalyst, an aliphatic unsaturated compound represented by the following general formula (4-2), that is, general formula (4) A fluorine-containing organosilicon compound having a bond can be synthesized.

(wherein A, R ² , R ¹² , a and Rf are the same as above; Ph is a phenyl group; P is a divalent organic group having a silicon atom at the end; R ¹³ is independently It is an unsubstituted or substituted divalent hydrocarbon group having 2 to 8 carbon atoms.)

（式中、Ａ、Ｒ²、Ｒ¹³及びＰは上記と同じである。Ｐｈはフェニル基である。） The following structure in formula (4-2) corresponds to Q in formula (4), and the compound of formula (4-2) is included in the fluorine-containing organosilicon compound of formula (4). is.

(In the formula, A, R ² , R ¹³ and P are the same as above. Ph is a phenyl group.)

（式中、Ｒｆ及びＱは前記と同じである。Ｍｅはメチル基であり、Ｐｈはフェニル基である。） Examples of the fluorine-containing organosilicon compound having a terminal aliphatic unsaturated group-containing silyl group represented by the above formula (4-1) include the following.

(Wherein, Rf and Q are the same as above. Me is a methyl group and Ph is a phenyl group.)

（式中、Ｍｅはメチル基である。） In the above formula (10), P is a divalent organic group having a silicon atom at its terminal, preferably having a siloxane bond, and specific examples thereof are shown below.

(In the formula, Me is a methyl group.)

In the above formula (4-2), R ¹³ is independently an unsubstituted or substituted divalent hydrocarbon group having 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms, preferably unsubstituted or substituted A saturated aliphatic divalent hydrocarbon group, specifically, a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group (trimethylene group), a methylethylene group, a butylene group, and a hexamethylene group , or groups obtained by substituting some or all of the hydrogen atoms of these groups with halogen atoms such as fluorine, chlorine, bromine and iodine atoms. Among them, an ethylene group and a propylene group are preferable.

In the above reaction, the compounding ratio of the fluorine-containing compound of general formula (4-1) and general formula (10) is such that the molar amount (E) of the fluorine-containing compound of formula (4-1) is expressed by the formula ( Although it is not particularly limited as long as it is not less than the molar amount (F) of the compound of formula (10), the amount (E) of the fluorine-containing organosilicon compound of formula (4-1) used/the amount of the compound of formula (10) The amount (F) [molar ratio] used is preferably from 1.0 to 3.0, more preferably from 1.0 to 2.0. If the molar ratio (E)/(F) is increased within the range described above, a polymer with a relatively small molecular weight can be synthesized, and if the value of (E)/(F) approaches 1 Polymers with large molecular weights can be synthesized.

Examples of the addition reaction catalyst used in the above reaction include platinum group metal-based catalysts known as catalysts used in hydrosilylation reactions, such as chloroplatinic acid and alcohol-modified chloroplatinic acid (see U.S. Pat. No. 3,220,972). ), complexes of chloroplatinic acid and olefins (see U.S. Pat. Nos. 3,159,601, 3,159,662, and 3,775,452), platinum and alcohols or a complex with vinyl siloxane, platinum black or palladium supported on a carrier such as alumina, silica, carbon, rhodium-olefin complex, chlorotris (triphenylphosphine) rhodium (Wilkinson's catalyst), and the like. Among these, the complex type is preferably dissolved in an organic solvent such as alcohol, ketone, ether or toluene before use.
The amount of the addition reaction catalyst used may be a so-called catalytic amount, and the fluorine-containing organosilicon compound having a terminal aliphatic unsaturated group-containing silyl group represented by the general formula (4-1) and the general formula (9) It is preferably in the range of 10 to 2,000 ppm, more preferably 100 to 1,000 ppm in terms of the mass of the platinum group metal, based on the total mass of the compound having silicon-bonded hydrogen atoms at both ends.

In the above reaction, the reaction temperature may be about 50-150°C, preferably 80-120°C. The reaction time may be about 2 to 4 hours, preferably about 2 to 3 hours.

（式中、Ｍｅはメチル基である。） [(Organo)hydrogensilane compound of general formula (5)]
Examples of the (organo)hydrogensilane compound represented by formula (5) include trimethoxysilane, triethoxysilane, dimethoxymethylsilane, dimethoxyethylsilane, diethoxyethylsilane, and the following.

(In the formula, Me is a methyl group.)

The amount of the (organo)hydrogensilane compound of general formula (5) to be used is generally 2 to 10 mol, preferably 2 to 5 mol, per 1 mol of the fluorine-containing organosilicon compound of general formula (4). If the amount of the (organo)hydrogensilane compound of formula (5) is too large, the amount of distillate will be too large during stripping, which is a post-treatment step, and the time required to complete stripping may become longer. Fluorine-containing organosilicon compound of general formula (4)) A portion of terminal alkenyl groups such as terminal Si--CH=CH ₂ groups may remain and the addition reaction may not be completed.

Examples of the catalyst include platinum group metal-based catalysts known as catalysts used in hydrosilylation reactions, such as chloroplatinic acid, alcohol-modified chloroplatinic acid (see U.S. Pat. No. 3,220,972), and chloroplatinic acid. and an olefin complex (see U.S. Pat. Nos. 3,159,601, 3,159,662, and 3,775,452), platinum black or palladium on alumina, Examples include those carried on carriers such as silica and carbon, rhodium-olefin complexes, chlorotris(triphenylphosphine) rhodium (Wilkinson's catalyst), and the like. Among these, the complex type is preferably used by dissolving it in an organic solvent such as an alcohol type, a ketone type or an ether type.
The amount of the catalyst to be used may be a so-called catalytic amount. It is preferably in the range of 10 to 2,000 ppm, more preferably 100 to 1,000 ppm in terms of the mass of the platinum group metal relative to the total mass of the compound.

The fluorine-containing organosilicon compound represented by the general formula (1) of the present invention comprises, as described above, the fluorine-containing organosilicon compound represented by the general formula (4) and the (organo)hydrogensilane compound represented by the general formula (5). can be obtained by hydrosilylation addition reaction in the presence of the catalyst.
In this reaction, the reaction temperature may be about 50-150°C, preferably 70-120°C. The reaction time may be about 2 to 4 hours, preferably about 2 to 3 hours. After completion of the reaction, the compound of formula (5) remaining in the reaction product can be removed by vacuum stripping.

The fluorine-containing organosilicon compound of the present invention thus obtained has hydrolyzable groups (X in formula (1)) at both ends of the molecular chain. It decomposes and undergoes condensation polymerization to form a rubber-like cured product. Therefore, the fluorine-containing organosilicon compound of the present invention can be used as a base polymer for a room-temperature-curable fluorine-containing rubber composition.

[Room temperature curable fluorine-containing rubber composition]
The room-temperature-curable fluorine-containing rubber composition of the present invention essentially contains the fluorine-containing organosilicon compound represented by the general formula (1) as a main agent (base polymer). In addition to including a curing catalyst, adhesion aids may be added to the composition.

などのグアニジル基含有シランもしくはシロキサン等のグアニジル化合物；を挙げることができ、これらは１種単独でも２種以上を組み合わせても使用することもできる。なお、上記のうち、特にグアニジル化合物は、硬化反応を良好に進行させると共に接着性向上機能を併せて有しているので好ましい。
これらの硬化触媒は、通常、前記一般式（１）で表される含フッ素有機ケイ素化合物１００質量部に対し、０．０１～５質量部、特に０．０５～５質量部程度の範囲が好適である。 Said curing catalyst further accelerates the curing speed of the composition, for example lead-2-ethyloctoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, butyltin tri-2-ethylhexoate, iron-2-ethylhexoate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate, zinc-2-ethylhexoate, stannous caprylate, tin naphthenate, tin oleate, Metal salts of organic carboxylic acids such as tin butylate, titanium naphthenate, zinc naphthenate, cobalt naphthenate, zinc stearate; tetrabutyl titanate, tetra-2-ethylhexyl titanate, triethanolamine titanate, tetra(isopropenyloxy) Organic titanate esters such as titanates; Organo-titanium compounds such as organosiloxytitanium and β-carbonyl titanium; Alkoxyaluminum compounds; Aminoalkyl group-substituted alkoxy such as 3-aminopropyltriethoxysilane and N-(trimethoxysilylpropyl)ethylenediamine Amine compounds such as silane, hexylamine and dodecylamine phosphate and salts thereof; Quaternary ammonium salts such as benzyltriethylammonium acetate; Alkali metal lower fatty acids such as potassium acetate, sodium acetate and lithium oxalate; Dialkylhydroxylamine such as diethylhydroxylamine; tetramethylguanidine, formula:

A guanidyl compound such as silane or siloxane containing a guanidyl group such as; These can be used singly or in combination of two or more. In addition, among the above, guanidyl compounds are particularly preferable because they have a function of improving adhesion while allowing the curing reaction to progress well.
These curing catalysts are usually preferably in the range of about 0.01 to 5 parts by weight, particularly about 0.05 to 5 parts by weight, per 100 parts by weight of the fluorine-containing organosilicon compound represented by the general formula (1). is.

で表されるもの等が挙げられる。
これらの接着助剤は、通常、前記一般式（１）で表される含フッ素有機ケイ素化合物１００質量部に対し、０．１～５．０質量部、特に１．０～３．０質量部程度の範囲が好適である。 The above-mentioned adhesion promoter further improves the adhesion between the cured product and various substrates when the composition is cured. Such adhesion promoters include, for example, vinylchlorosilane, vinyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrisilane. Ethoxysilane, γ-Methacryloxypropyltrimethoxysilane, γ-Methacryloxypropylmethyldiethoxysilane, N-β-(Aminoethyl)γ-Aminopropyltrimethoxysilane, γ-Aminopropyltriethoxysilane, γ-Chloropropyl trimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, as well as partially fluorinated silanes such as 3,3,3-trifluoropropyltrimethoxysilane, as well as the formula: _{CF3 ( CF2} ) _{7CH2CH2 -} Si ₍ OCH3) ₃ and

and the like.
These adhesion promoters are usually 0.1 to 5.0 parts by weight, particularly 1.0 to 3.0 parts by weight, per 100 parts by weight of the fluorine-containing organosilicon compound represented by the general formula (1). A range of degrees is preferred.

In addition to the curing catalyst and adhesion aid described above, the room-temperature-curable fluorine-containing rubber composition of the present invention may contain various additives conventionally used in such compositions, such as tetramethoxysilane, 2 or 3 alkoxy groups in the molecule such as tetraalkoxysilane such as tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, etc. Cross-linking agents such as hydrolyzable silane compounds such as (organo)alkoxysilanes that do not have functional groups in the molecule other than hydrolyzable groups, such as alkylalkoxysilanes and arylalkoxysilanes with groups, fumed silica ( dry silica), precipitated silica (wet silica), fused silica, calcined silica, crystalline silica (quartz powder), sol-gel silica, colloidal silica, and other silica-based fillers, as well as titanium dioxide, aluminum oxide, carbon, and talc. and reinforcing or non-reinforcing fillers such as bentonite, fillers such as fibrous fillers such as asbestos, glass fibers and organic fibers, colorants such as potassium methacrylate, dyes, pigments, red iron oxide (iron oxide) and oxides A heat resistance-imparting agent such as cerium can also be blended. These may be added in predetermined amounts depending on the purpose.

In addition, the room-temperature-curable fluorine-containing rubber composition of the present invention can be stored or used as a solution diluted with a non-aqueous organic solvent, if necessary. In particular, use as an organic solvent solution is suitable for forming a thin cured film. Examples of such organic solvents include hydrocarbon solvents such as n-hexane, cyclohexane, toluene, petroleum ether and xylene; ether solvents such as diethyl ether, n-butyl ether, dioxane and tetrahydrofuran; acetone, methyl ethyl ketone, dibutyl ketone solvents such as ketones and ethyl acetate; chlorinated hydrocarbon solvents such as methylene chloride, chlorobenzene and chloroform; nitrile solvents such as acetonitrile; fluorine solvents such as trifluorobenzene and meta-xylene hexafluoride; Alcoholic solvents such as ethanol, isopropanol and n-butanol can be mentioned, and two or more of these may be used in combination if necessary.

The room-temperature-curable fluororubber composition of the present invention is cured (crosslinked) by hydrolysis and condensation reaction at room temperature (25° C.±10° C.) due to moisture (moisture) in the atmosphere. In addition to the properties unique to solvent-resistant fluorine-containing coatings, such as water repellency, oil repellency, chemical resistance, low moisture permeability, and weather resistance, It is possible to form a cured film (fluorine-containing rubber cured product) having excellent properties such as adhesion to materials and strength. Therefore, the room-temperature-curable fluorine-containing rubber composition of the present invention is useful as a coating agent, sealant, and paint for construction, industrial plants, and various types of equipment. In addition, since it has excellent adhesion to base materials such as various metals, resins, rubbers, and concrete, especially when coated on exterior materials, it not only maintains its appearance for a long time, but also has solvent resistance, chemical resistance, and repellency. Properties such as water resistance and low moisture permeability can be imparted to the base material, or the main properties of the base material can be improved. Furthermore, the room-temperature-curing fluororubber composition of the present invention can be applied to various powders such as silica filler, quartz powder, ceramic powder, metal powder, and surface treatment agents such as sand to improve water and oil repellency. There is an effect that it can be given.

The room-temperature-curable fluororubber composition of the present invention can be obtained as a one-component room-temperature-curable fluororubber composition by uniformly mixing predetermined amounts of the above components in a dry atmosphere. This composition undergoes hydrolysis and polycondensation reaction due to moisture in the air, for example, to form a cured rubber elastic body. The composition of the present invention cures at room temperature, but can be accelerated by heating. The obtained cured product has excellent solvent resistance, chemical resistance, heat resistance, cold resistance, water repellency, low Excellent in both properties of moisture permeability. This composition is suitable for sealing agents, coating materials, etc. in the construction and civil engineering industries, and is also very useful as an adhesive and sealing material for electrical and electronic parts, and as an FIPG material in the automobile industry.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In this example, "Me" represents a methyl group, "Ph" represents a phenyl group, and "PhN" represents a phenylene group. The viscosity is a value measured by a rotational viscometer at 25° C., and the degree of polymerization is the number-average degree of polymerization in terms of polystyrene in gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent. Further, the refractive index is a value measured by an Abbe refractometer DR-A1 (manufactured by Atago Co., Ltd.).

（式中、ｐ’＋ｑ’の平均は３８である。）
で示される両末端に酸フロライド基を有する化合物１８９．２ｇ（０．０３０モル、２５℃における粘度：４３０ｍＰａ・ｓ）を投入した。そしてこれを室温（２５℃、以下同じ）下に攪拌しながら滴下ロートより下記式：

で示される化合物１５．８ｇ（０．０７２モル）とトリエチルアミン６．５ｇ（０．０６４モル）との混合物を滴下した。滴下終了後、６０℃で２時間撹拌した。次に、反応混合物を加圧濾過して得られた濾液を、１２０℃／３ｍｍＨｇで減圧ストリップし、淡黄色がかった透明の液状化合物１９５．３ｇを得た。この液状化合物を前記と同様のフラスコに投入し、これにメタキシレンヘキサフロライド５０．０ｇを加え、撹拌しながら１００℃に昇温した後、塩化白金酸のイソプロピルアルコール２質量％溶液０．２ｇを添加した。次いで、これに滴下ロートから下記式：

で示されるシクロテトラシロキサン４．９ｇ（０．０１５モル）を滴下し、２時間反応を行った。滴下終了後、反応生成物を熟成させながらガスクロマトグラフで前記のシクロテトラシロキサンが消失するのを確認し、フラスコ内容物を室温まで冷却した。次に、フラスコ内に、活性炭１．５ｇを投入して２時間撹拌した後、反応混合物を加圧濾過し、得られた濾液を１２０℃／３ｍｍＨｇで減圧ストリップし、透明な液状化合物１９６．１ｇを得た。 [Example 1]
In a 300 ml four-necked flask equipped with a stir bar, thermometer, Dimroth and dropping funnel, the following formula:

(Where the average of p'+q' is 38.)
189.2 g (0.030 mol, viscosity at 25° C.: 430 mPa·s) of a compound having acid fluoride groups at both ends represented by is charged. Then, while stirring this at room temperature (25° C., hereinafter the same), the following formula was added from the dropping funnel:

A mixture of 15.8 g (0.072 mol) of the compound represented by and 6.5 g (0.064 mol) of triethylamine was added dropwise. After completion of dropping, the mixture was stirred at 60°C for 2 hours. Next, the filtrate obtained by pressure filtration of the reaction mixture was vacuum stripped at 120° C./3 mmHg to obtain 195.3 g of a pale yellowish transparent liquid compound. This liquid compound was charged into the same flask as above, 50.0 g of meta-xylene hexafluoride was added thereto, and the temperature was raised to 100° C. with stirring. was added. Then, from the dropping funnel, the following formula is added to this:

4.9 g (0.015 mol) of cyclotetrasiloxane represented by was added dropwise, and the reaction was carried out for 2 hours. After completion of the dropwise addition, disappearance of the cyclotetrasiloxane was confirmed by gas chromatography while aging the reaction product, and the contents of the flask were cooled to room temperature. Next, 1.5 g of activated carbon was charged into the flask and stirred for 2 hours, and then the reaction mixture was filtered under pressure. got

This liquid compound had a viscosity of 13,700 mPa·s (25° C.) and a refractive index of 1.335. As a result of ¹ H-NMR measurement of this liquid compound, the following absorption was observed.
1H ^- NMR (TMS standard)
δ = 3.4 to 3.9 ppm (m, N—C H ₂ -, 8H)
δ = 5.4 to 6.2 ppm (m, SiCH = CH ₂ , 6H)
δ = 6.9 to 7.4 ppm (m, N- Ph , 20H)

（式中、Ｒｆ¹は下記式：

（式中、ｐ’＋ｑ’は平均で３８である。）
で表される基であり、Ｑ¹は下記式：

で表される基であり、ａ１は平均で１である。）
で表される含フッ素有機ケイ素化合物であることが確認された。 Further, when the vinyl group content of this compound was quantified, it was 0.014 mol/100 g. The obtained compound has the following structural formula (11):

(Wherein, Rf ¹ is the following formula:

(Where p'+q' is 38 on average.)
and Q ¹ is a group represented by the following formula:

and a1 is 1 on average. )
It was confirmed to be a fluorine-containing organosilicon compound represented by

Into a 500 ml four-necked flask equipped with a stirring rod, a thermometer, a Dimroth and a dropping funnel, 276.2 g of the fluorine-containing organosilicon compound having vinyl groups at both ends represented by the structural formula (11) obtained above (0.020 mol) and 55 g of meta-xylene hexafluoride were added and heated in an oil bath while stirring so that the temperature of the contents of the flask reached 80°C. Next, 0.3 g of a 2% by mass solution of chloroplatinic acid in isopropyl alcohol was added into the flask, and then 7.3 g (0.06 mol) of trimethoxysilane was added dropwise from the dropping funnel, followed by reaction for 2 hours. After completion of the dropwise addition, disappearance of the vinyl group (--CH=CH ₂ : δ=5.4-6.2 ppm) of the compound of formula (11) was confirmed by ¹ H-NMR analysis while aging the reaction product. After that, vacuum stripping was carried out at 100° C./10 mmHg to remove unreacted silane components, and 278.3 g of a pale yellowish transparent liquid compound was obtained. The resulting liquid compound had a viscosity of 33,400 mPa·s (25° C.) and a refractive index of 1.338. As a result of ¹ H-NMR measurement of this liquid compound, the following absorption was observed.
1H ^- NMR (TMS standard)
δ = 3.4 to 3.9 ppm (m, N—C H ₂ -, 8H)
δ=3.67 ppm (s, Si—OC H ₃ , 18H)
δ = 6.9 to 7.4 ppm (m, N- Ph , 20H)

（式中、Ｒｆ¹、Ｑ¹及びａ１は前記と同じである。）
で示される含フッ素有機ケイ素化合物であることが確認された。 Further, when this liquid compound was hydrolyzed and the amount of desorbed methanol was quantified, it was 0.044 mol/100 g, and the following structural formula (12):

(In the formula, Rf ¹ , Q ¹ and a1 are the same as above.)
It was confirmed to be a fluorine-containing organosilicon compound represented by

で示されるシラン化合物７．９ｇ（０．０５０モル）を用いた以外は、実施例１と同様に反応、後処理を行い、淡黄色がかった透明のオイル状化合物２７９．３ｇを得た。得られたオイル状化合物は粘度が３４，７００ｍＰａ・ｓ（２５℃）であり、屈折率が１．３４０（２５℃）であった。この液状化合物を¹Ｈ－ＮＭＲ測定した結果、以下に示す吸収が認められた。
¹Ｈ－ＮＭＲ（ＴＭＳ標準）
δ＝３．３～３．８ｐｐｍ（ｍ，Ｎ－ＣＨ ₂－，８Ｈ）
δ＝４．１～４．２ｐｐｍ（ｍ，ＯＣ＝ＣＨ ₂，８Ｈ）
δ＝６．９～７．４ｐｐｍ（ｍ，Ｎ－Ｐｈ，２０Ｈ） [Example 2]
In Example 1, instead of 7.3 g of trimethoxysilane, the following formula (13):

Except for using 7.9 g (0.050 mol) of the silane compound represented by the following, the reaction and post-treatment were carried out in the same manner as in Example 1 to obtain 279.3 g of a pale yellowish transparent oily compound. The resulting oily compound had a viscosity of 34,700 mPa·s (25°C) and a refractive index of 1.340 (25°C). As a result of ¹ H-NMR measurement of this liquid compound, the following absorption was observed.
1H ^- NMR (TMS standard)
δ = 3.3 to 3.8 ppm (m, N—C H ₂ -, 8H)
δ = 4.1 to 4.2 ppm (m, OC = CH ₂ , 8H)
δ = 6.9 to 7.4 ppm (m, N- Ph , 20H)

（式中、Ｒｆ¹、Ｑ¹及びａ１は前記と同じである。）
で表される含フッ素有機ケイ素化合物であることが確認された。 Further, when this compound was hydrolyzed and the amount of acetone released was quantified, it was 0.028 mol/100 g, and the following structural formula (14):

(In the formula, Rf ¹ , Q ¹ and a1 are the same as above.)
It was confirmed to be a fluorine-containing organosilicon compound represented by

で示されるシラン化合物８．１ｇ（０．０５０モル）を用いた以外は実施例２と同様に反応、後処理を行い、淡黄色がかった透明の液状化合物２８０．４ｇを得た。得られた液状化合物は、粘度が３５，２００ｍＰａ・ｓ（２５℃）であり、屈折率が１．３４１（２５℃）であった。この液状化合物を¹Ｈ－ＮＭＲ測定した結果、以下に示す吸収が認められた。
¹Ｈ－ＮＭＲ（ＴＭＳ標準）
δ＝１．９４ｐｐｍ（ｓ，ＳｉＯＣＣＨ ₃，１２Ｈ）
δ＝３．３～３．８ｐｐｍ（ｍ，Ｎ－ＣＨ ₂－，８Ｈ）
δ＝６．９～７．４ｐｐｍ（ｍ，Ｎ－Ｐｈ，２０Ｈ） [Example 3]
In Example 2, instead of 7.9 g of the silane compound represented by the formula (13), the following formula (15):

The reaction and post-treatment were carried out in the same manner as in Example 2 except that 8.1 g (0.050 mol) of the silane compound represented by was used to obtain 280.4 g of a pale yellowish transparent liquid compound. The obtained liquid compound had a viscosity of 35,200 mPa·s (25° C.) and a refractive index of 1.341 (25° C.). As a result of ¹ H-NMR measurement of this liquid compound, the following absorption was observed.
1H ^- NMR (TMS standard)
δ=1.94 ppm (s, SiOCC H ₃ , 12H)
δ = 3.3 to 3.8 ppm (m, N—C H ₂ -, 8H)
δ = 6.9 to 7.4 ppm (m, N- Ph , 20H)

（式中、Ｒｆ¹、Ｑ¹及びａ１は前記と同じである。）
で表される含フッ素有機ケイ素化合物であることが確認された。 Further, when this compound was hydrolyzed and the amount of acetic acid released was quantified, it was 0.028 mol/100 g, and the following structural formula (16):

(In the formula, Rf ¹ , Q ¹ and a1 are the same as above.)
It was confirmed to be a fluorine-containing organosilicon compound represented by

（式中、ｐ’＋ｑ’の平均は３８である。）
で示される両末端に酸フロライド基を有する化合物１８９．２ｇ（０．０３０モル、２５℃における粘度：４３０ｍＰａ・ｓ）を投入した。そしてこれを室温下に攪拌しながら滴下ロートより下記式：

で示される化合物２．３ｇ（０．０２モル）とトリエチルアミン６．５ｇ（０．０６４モル）との混合物を滴下した。滴下終了後、６０℃で２時間撹拌した。次に、これに滴下ロートから下記式：

で示される化合物５．３ｇ（０．０２４モル）を滴下し、反応を行った。滴下終了後、反応生成物を熟成させながら¹⁹Ｆ－ＮＭＲで前記の両末端に酸フロライド基を有する化合物のＣＯＦ由来のシグナルの消失を確認し、フラスコ内容物を室温まで冷却した。次に、フラスコ内に、活性炭１．５ｇを投入して２時間撹拌した後、反応混合物を加圧濾過し、得られた濾液を１２０℃／３ｍｍＨｇで減圧ストリップし、薄黄色の液状化合物１８４．９ｇを得た。 [Example 4]
In a 300 ml four-necked flask equipped with a stir bar, thermometer, Dimroth and dropping funnel, the following formula:

(Where the average of p'+q' is 38.)
189.2 g (0.030 mol, viscosity at 25° C.: 430 mPa·s) of a compound having acid fluoride groups at both ends represented by is charged. Then, while stirring this at room temperature, the following formula was added from the dropping funnel:

A mixture of 2.3 g (0.02 mol) of the compound represented by and 6.5 g (0.064 mol) of triethylamine was added dropwise. After completion of dropping, the mixture was stirred at 60°C for 2 hours. Next, the following formula is added to this from the dropping funnel:

5.3 g (0.024 mol) of the compound represented by was added dropwise to carry out the reaction. After completion of the dropwise addition, disappearance of the signal derived from the COF of the compound having acid fluoride groups at both ends was confirmed by ¹⁹ F-NMR while aging the reaction product, and the contents of the flask were cooled to room temperature. Next, 1.5 g of activated carbon was put into the flask, and after stirring for 2 hours, the reaction mixture was pressure-filtered, and the resulting filtrate was stripped under reduced pressure at 120° C./3 mmHg to obtain a pale yellow liquid compound 184. 9 g was obtained.

This liquid compound had a viscosity of 35,300 mPa·s (25° C.) and a refractive index of 1.346. As a result of ¹ H-NMR measurement of this liquid compound, the following absorption was observed.
1H ^- NMR (TMS standard)
δ=0.45 ppm (s, Si—C H ₃ , 12H)
δ=1.1 to 1.5 ppm (m, C—C H ₃ , 12H)
δ=3.3 to 3.8 ppm (m, CON—C H ₂ —, 4H)
δ = 5.4 to 6.2 ppm (m, SiCH = CH ₂ , 6H)
δ = 6.9 to 7.4 ppm (m, N- Ph , 10H)

（式中、Ｒｆ¹は上記と同じであり、Ｑ²は下記式：

で表される基であり、ａ２は平均で２である。）
で表される含フッ素有機ケイ素化合物であることが確認された。 Further, when the vinyl group content of this compound was quantified, it was 0.01 mol/100 g. The obtained compound has the following structural formula (17):

(wherein Rf ¹ is the same as above and Q ² is the following formula:

and a2 is 2 on average. )
It was confirmed to be a fluorine-containing organosilicon compound represented by

Into a 500 ml four-necked flask equipped with a stirring rod, a thermometer, a Dimroth and a dropping funnel, 393.9 g of the fluorine-containing organosilicon compound having vinyl groups at both ends represented by the structural formula (17) obtained above (0.020 mol) and 64.8 g of meta-xylene hexafluoride were added and heated in an oil bath with stirring so that the temperature of the contents of the flask reached 70°C. Next, 0.3 g of a 2% by mass solution of chloroplatinic acid in isopropyl alcohol was added into the flask, and then 9.5 g (0.078 mol) of trimethoxysilane was added dropwise from the dropping funnel, followed by reaction for 2 hours. Thereafter, reaction and post-treatment were carried out in the same manner as in Example 1 to obtain 397.0 g of a pale yellowish transparent liquid compound.

The obtained compound had a viscosity of 84,200 mPa·s (25° C.) and a refractive index of 1.324 (25° C.). As a result of ¹ H-NMR measurement, the following absorption was confirmed.
1H ^- NMR (TMS standard)
δ=0.45 ppm (s, Si—C H ₃ , 12H)
δ=1.1 to 1.5 ppm (m, C—C H ₃ , 12H)
δ=3.3 to 3.8 ppm (m, CON—C H ₂ —, 4H)
δ=3.63 ppm (s, SiO—C H ₃ , 18H)
δ = 6.9 to 7.4 ppm (m, N- Ph , 10H)

（式中、Ｒｆ¹、Ｑ²、ａ２は上記と同じである。）
で示される含フッ素有機ケイ素化合物であることが確認された。 Further, when this compound was hydrolyzed and the amount of desorbed methanol was quantified, it was 0.031 mol/100 g, and the following structural formula (18):

(In the formula, Rf ¹ , Q ² and a2 are the same as above.)
It was confirmed to be a fluorine-containing organosilicon compound represented by

［式中、Ｒｆ²は下記式：

（式中、ｐ’＋ｑ’は平均で９４である。）
で表される基である。］
で表される化合物３２０．２ｇ（０．０２０モル）を用い、メタキシレンヘキサフロライドの使用量を６０．０ｇにした以外は実施例１と同様に反応、後処理を行い、淡黄色がかった透明の液状化合物３２４．１ｇを得た。 [Comparative Example 1]
In Example 1, instead of 276.2 g of the compound of formula (11), the following formula (19):

[In the formula, Rf ² is the following formula:

(Where p'+q' is 94 on average.)
is a group represented by ]
The reaction and post-treatment were carried out in the same manner as in Example 1 except that 320.2 g (0.020 mol) of the compound represented by was used and the amount of meta-xylene hexafluoride used was changed to 60.0 g. 324.1 g of a clear liquid compound were obtained.

The obtained liquid compound had a viscosity of 18,300 mPa·s (25° C.) and a refractive index of 1.320 (25° C.). As a result of ¹ H-NMR measurement of this liquid compound, the following absorptions were confirmed.
1H ^- NMR (TMS standard)
δ=0.42 ppm (s, Si—C H ₃ , 12H)
δ=3.56 ppm (s, Si—OC H ₃ , 18H)

（式中、Ｒｆ²は上記と同じである。）
で示される含フッ素有機ケイ素化合物であることが確認された。 Further, when this compound was hydrolyzed and the amount of desorbed methanol was quantified, it was 0.039 mol/100 g, and the following structural formula (20):

⁽ Wherein, Rf2 is the same as above.)
It was confirmed to be a fluorine-containing organosilicon compound represented by

（式中、ｐ’＋ｑ’の平均は３８である。）
で示される両末端に酸フロライド基を有する化合物１８９．２ｇ（０．０３０モル、２５℃における粘度：４３０ｍＰａ・ｓ）を投入した。そしてこれを室温下に攪拌しながら滴下ロートより下記式：

で示される化合物１３．８ｇ（０．０７２モル）とトリエチルアミン６．５ｇ（０．０６４モル）との混合物を滴下した。滴下終了後、６０℃で２時間撹拌した。次に、反応混合物を加圧濾過して得られた濾液を、１２０℃／３ｍｍＨｇで減圧ストリップし、淡黄色がかった透明の液状化合物１９５．３ｇを得た。この液状化合物を前記と同様のフラスコに投入し、これにメタキシレンヘキサフロライド５０．０ｇを加え、撹拌しながら１００℃に昇温した後、塩化白金酸のイソプロピルアルコール２質量％溶液０．２ｇを添加した。次いで、これに滴下ロートから下記式：

で示されるシクロテトラシロキサン４．９ｇ（０．０１５モル）を滴下し、２時間反応を行った。滴下終了後、反応生成物を熟成させながらガスクロマトグラフで前記のシクロテトラシロキサンが消失するのを確認し、フラスコ内容物を室温まで冷却した。次に、フラスコ内に、活性炭１．５ｇを投入して２時間撹拌した後、反応混合物を加圧濾過し、得られた濾液を１２０℃／３ｍｍＨｇで減圧ストリップし、透明な液状化合物１９７．４ｇを得た。 [Comparative Example 2]
In a 300 ml four-necked flask equipped with a stir bar, thermometer, Dimroth and dropping funnel, the following formula:

(Where the average of p'+q' is 38.)
189.2 g (0.030 mol, viscosity at 25° C.: 430 mPa·s) of a compound having acid fluoride groups at both ends represented by is charged. Then, while stirring this at room temperature, the following formula was added from the dropping funnel:

A mixture of 13.8 g (0.072 mol) of the compound represented by and 6.5 g (0.064 mol) of triethylamine was added dropwise. After completion of dropping, the mixture was stirred at 60°C for 2 hours. Next, the filtrate obtained by pressure filtration of the reaction mixture was vacuum stripped at 120° C./3 mmHg to obtain 195.3 g of a pale yellowish transparent liquid compound. This liquid compound was charged into the same flask as above, 50.0 g of meta-xylene hexafluoride was added thereto, and the temperature was raised to 100° C. with stirring. was added. Then, from the dropping funnel, the following formula is added to this:

4.9 g (0.015 mol) of cyclotetrasiloxane represented by was added dropwise, and the reaction was carried out for 2 hours. After completion of the dropwise addition, disappearance of the cyclotetrasiloxane was confirmed by gas chromatography while aging the reaction product, and the contents of the flask were cooled to room temperature. Next, 1.5 g of activated carbon was charged into the flask and stirred for 2 hours, and then the reaction mixture was filtered under pressure. got

This liquid compound had a viscosity of 15,200 mPa·s (25° C.) and a refractive index of 1.335. As a result of ¹ H-NMR measurement of this liquid compound, the following absorption was observed.
1H ^- NMR (TMS standard)
δ=3.42 ppm (S, N—C H ₃ , 12H)
δ = 5.5 to 6.3 ppm (m, SiCH = CH ₂ , 6H)
δ = 7.1 to 7.8 ppm (m, PhN , 16H)

（式中、Ｒｆ¹は下記式：

（式中、ｐ’＋ｑ’は平均で３８である。）
で表される基であり、Ｑ³は下記式：

で表される基であり、ａ１は平均で１である。）
で表される含フッ素有機ケイ素化合物であることが確認された。 Further, when the vinyl group content of this compound was quantified, it was 0.014 mol/100 g. The obtained compound has the following structural formula (21):

(Wherein, Rf ¹ is the following formula:

(Where p'+q' is 38 on average.)
and Q ³ is a group represented by the following formula:

and a1 is 1 on average. )
It was confirmed to be a fluorine-containing organosilicon compound represented by

276.2 g (0.020 mol), and 55 g of meta-xylene hexafluoride were added and heated in an oil bath while stirring so that the temperature of the content of the flask reached 80°C. Next, 0.3 g of a 2% by mass solution of chloroplatinic acid in isopropyl alcohol was added into the flask, and then 7.3 g (0.060 mol) of trimethoxysilane was added dropwise from the dropping funnel, followed by a reaction for 2 hours. After completion of the dropwise addition, disappearance of the vinyl group (--CH=CH ₂ : δ=5.5 to 6.3 ppm) of the compound of formula (21) was confirmed by ¹ H-NMR analysis while aging the reaction product. After that, vacuum stripping was carried out at 100° C./10 mmHg to remove unreacted silane components, and 278.3 g of a pale yellowish transparent liquid compound was obtained. The obtained liquid compound had a viscosity of 34,200 mPa·s (25° C.) and a refractive index of 1.103. As a result of ¹ H-NMR measurement of this liquid compound, the following absorption was observed.
1H ^- NMR (TMS standard)
δ=3.44 ppm (S, N—C H ₃ , 12H)
δ=3.67 ppm (S, Si—OC H ₃ , 18H)
δ = 7.1 to 7.8 ppm (m, PhN , 16H)

（式中、Ｒｆ¹、Ｑ³及びａ１は前記と同じである。）
で示される含フッ素有機ケイ素化合物であることが確認された。 Further, when this liquid compound was hydrolyzed and the amount of desorbed methanol was quantified, it was 0.044 mol/100 g, and the following structural formula (22):

(In the formula, Rf ¹ , Q ³ and a1 are the same as above.)
It was confirmed to be a fluorine-containing organosilicon compound represented by

[Example 5]
100 g of the fluorine-containing organosilicon compound of formula (12) obtained in Example 1 and 20 g of MT carbon (medium particle pyrolytic carbon, manufactured by Denka Co., Ltd.; hereinafter the same) were mixed, and the mixture was passed through three rolls. Composition I was obtained by mixing once with 0.1 g of dibutyltin dioctoate. This composition I was formed into a sheet having a thickness of 2 mm, and the sheet was allowed to stand for 14 days in an atmosphere at a temperature of 20° C. and a relative humidity of 55% to cure. The rubber physical properties (hardness, tensile strength, elongation at break) of the obtained sheet-like rubber elastic body (hereinafter referred to as elastic body I) were measured according to JIS C 2123. Table 1 shows the results.
In addition, the composition I was stored in a sealed state at room temperature. Composition I was stable for more than 6 months. A sheet-like rubber elastic body (hereinafter referred to as "elastic body I'") was prepared from composition I after 6 months had passed, in the same manner as described above, and the rubber physical properties of this rubber elastic body were measured in the same manner as described above. Table 1 shows the results.
The hardness values in the table are values measured using a spring-type hardness tester (type A) (the same shall apply hereinafter).

[Comparative Example 3]
100 g of the fluorine-containing organosilicon compound of formula (22) obtained in Comparative Example 2 and 20 g of MT carbon were mixed, the mixture was passed through a triple roll once, and then 0.1 g of dibutyltin dioctoate was mixed. Composition II was obtained. This composition II was formed into a sheet having a thickness of 2 mm, and the sheet was allowed to stand for 14 days in an atmosphere of 20° C. and 55% relative humidity to cure. The rubber physical properties of the obtained sheet-like rubber elastic body (hereinafter referred to as elastic body II) were measured according to JIS C 2123. Table 1 shows the results.
In addition, the composition II was stored in a sealed state at room temperature. Composition II was stable for more than 6 months. A sheet-like rubber elastic body (hereinafter referred to as elastic body II') was prepared from composition II after 6 months had passed, and the rubber physical properties of this rubber elastic body were measured in the same manner as described above. Table 1 shows the results.

Next, the following solvent resistance, acid resistance, heat resistance, cold resistance, moisture permeability, and amine resistance were evaluated for the elastic bodies I and II.

Solvent Resistance An elastic body was immersed in each solvent shown in Table 2 at 25° C. for 7 days, and the solvent resistance was evaluated from the volume change rate. Table 2 shows the results. The fluororubber in Table 2 is DuPont Viton E-60C used for comparison.

The elastic body was immersed in acid (98 mass% sulfuric acid and 60 mass% nitric acid) at 40°C shown in Acid Resistance Table 3 for 1 week, and the hardness change rate and mass change rate (heat loss: mass%) showed acid resistance. evaluated. Table 3 shows the results. The hardness values in the table are values measured using a spring-type hardness tester (A type). Compared with the elastic body II obtained from the composition II of Comparative Example 3, the elastic body I obtained from the composition I of Example 5 had a hardness change rate and The mass change rate tended to decrease. In particular, when immersed in 98 mass % sulfuric acid, Elastic I maintained its shape, whereas Elastic II decomposed. The silicone rubber in Table 3 is a cured product of KE-951, a condensation-curable room-temperature-curable silicone rubber composition manufactured by Shin-Etsu Chemical Co., Ltd., used for comparison.

Before and after heating the heat-resistant elastic body at 250° C. for 120 hours, the physical properties of the rubber (according to JIS C 2123) were measured and evaluated. Table 4 shows the results. Table 4 also shows the reduction rate of the mass after heating with respect to the mass before heating (loss on heating: mass %).

According to cold resistance JIS K 6301, the test piece was cooled to -70°C in dry ice/ethanol and then heated at a rate of 1°C/min. Then, the rigidity at each temperature at this time was measured with a Gehmann torsion tester manufactured by Ueshima Seisakusho, and the temperature at which the rigidity at room temperature was doubled, five times, ten times and 100 times was calculated as T ₂ . , T ₅ , T ₁₀ , T ₁₀₀ . Table 5 shows the results. The fluororubber in Table 5 is DuPont Viton E-60C used for comparison.

The moisture- permeable elastic body was placed in a Lyssy L80-5000 water vapor permeability meter to measure the water vapor transmission rate. Table 6 shows the results.

Amine resistance An elastic body was immersed in amine at 40°C for one week, and the amine resistance was evaluated based on the amount of change in hardness. Table 7 shows the results. The hardness in the table is the value measured using a spring type hardness tester (A type). Elastic body I obtained from composition I of Example 5 tended to show a smaller hardness change rate when immersed in ethylenediamine and diethylamine than elastic body II obtained from composition II of Comparative example 3. .

[Example 6]
A mixture of 100 parts by mass of the fluorine-containing organosilicon compound of formula (12) obtained in Example 1 and 2 parts by mass of methyltrimethoxysilane was dissolved in meta-xylene hexafluoride to prepare a 20% by mass solution of the mixture. did. After dipping the slide glass in this solution for 30 seconds, it was allowed to stand at 20° C. and 55% RH for 18 hours to form a cured film on the surface of the slide glass. When one drop of n-hexadecane and one drop of pure water were placed on the slide glass on which this cured film was formed, the contact angle of each drop with respect to the slide glass was measured. Table 8 shows the results.

[Example 7]
A mixture of 100 parts by mass of the fluorine-containing organosilicon compound of formula (12) obtained in Example 1, 2 parts by mass of methyltrimethoxysilane, and 0.2 parts by mass of dibutyltin dilaurate was dissolved in meta-xylene hexafluoride, and the above-mentioned A 50% by weight solution of the mixture was prepared. This solution was applied to the surface of a slide glass and allowed to stand at 20° C. and 55% RH for 6 hours to form a cured film on the surface of the slide glass. The contact angle was measured in the same manner as in Example 6 for the slide glass on which this cured film was formed. Table 8 shows the results.

[Comparative Example 4]
A mixture of 100 parts by weight of the fluorine-containing organosilicon compound of formula (22) obtained in Comparative Example 2 and 2 parts by weight of methyltrimethoxysilane was dissolved in meta-xylene hexafluoride to prepare a 20% by weight solution of the mixture. did. After dipping the slide glass in this solution for 30 seconds, it was allowed to stand at 20° C. and 55% RH for 18 hours to form a cured film on the surface of the slide glass. The contact angle was measured in the same manner as in Example 6 for the slide glass on which this cured film was formed. Table 8 shows the results.

Claims (11)

The following general formula (1):

[In the formula, A is independently an unsubstituted or substituted aliphatic divalent hydrocarbon group, R ¹ and R ² are independently unsubstituted or substituted monovalent hydrocarbon groups, and R ³ is independently a non- A substituted or substituted saturated aliphatic divalent hydrocarbon group having 2 or more carbon atoms (wherein the saturated aliphatic divalent hydrocarbon group having 2 or more carbon atoms is a -CHR- group derived from a hydrosilylation addition reaction (R is a hydrogen atom or a halogen atom) , Rf is independently a perfluoroalkylene group or a divalent perfluoropolyether group, X is independently a hydrolyzable group, and Ph is a phenyl group , Q is the following general formula (2) or the following general formula (3):

(Wherein, R ⁴ is the following formula:
-( _CH2 ) _2- ,
-( _CH2 ) _3- ,
-( _CH2 ) _6- ,
—(CH ₂ ) ₂ —Rf—(CH ₂ ) ₂ —,

—(CH ₂ ) ₂ —O—(CH ₂ ) ₂ —,
-( _CH2 ) ₂ -NH-( _CH2 ) _2- ,

(wherein Rf is the same as above, R ¹⁰ is independently an alkyl group or an aryl group, R ¹¹ is independently an alkylene group, c is an integer of 0 to 10, Me is a methyl group, be.)
and Ph is a phenyl group. )

⁽ Wherein, R5 and ^R6 are independently unsubstituted or substituted divalent hydrocarbon groups.)
is a group represented by, a is an integer of 1 or more, and b is 1, 2 or 3; ]
A fluorine-containing organosilicon compound represented by. Q in the general formula (1) is the following formula:

(In the formula, Me is a methyl group, Ph is a phenyl group, and Rf is a perfluoroalkylene group or a divalent perfluoropolyether group.)
2. The fluorine-containing organosilicon compound according to claim 1, which is any one selected from ^3. The method according to claim 1 or 2, wherein R3 in general formula (1) is at least one selected from ethylene , propylene (trimethylene), methylethylene, butylene, hexamethylene and cyclohexylene. Fluorine-containing organosilicon compounds. The following general formula (4):

[wherein A is independently an unsubstituted or substituted aliphatic divalent hydrocarbon group, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group, and Rf is independently a perfluoroalkylene group or is a divalent perfluoropolyether group, R ¹² is independently an unsubstituted or substituted monovalent hydrocarbon group having an aliphatic unsaturated bond, Ph is a phenyl group, and Q is represented by the following general formula (2 ) or the following general formula (3):

(In the formula, R ⁴ is the following formula -(CH ₂ ) ₂ -,
-( _CH2 ) _3- ,
-( _CH2 ) _6- ,
—(CH ₂ ) ₂ —Rf—(CH ₂ ) ₂ —,

—(CH ₂ ) ₂ —O—(CH ₂ ) ₂ —,
-( _CH2 ) ₂ -NH-( _CH2 ) _2- ,

(wherein Rf is the same as above, R ¹⁰ is independently an alkyl group or an aryl group, R ¹¹ is independently an alkylene group, c is an integer of 0 to 10, Me is a methyl group, be.)
and Ph is a phenyl group. )

⁽ Wherein, R5 and ^R6 are independently unsubstituted or substituted divalent hydrocarbon groups.)
and a is an integer of 1 or more. ]
and a fluorine-containing organosilicon compound having an aliphatic unsaturated bond represented by the following general formula (5):

(Wherein, R ¹ is an unsubstituted or substituted monovalent hydrocarbon group, X is a hydrolyzable group, and b is 1, 2 or 3.)
A method for producing a fluorine-containing organosilicon compound represented by the following general formula (1′), which comprises subjecting a hydrosilylation addition reaction with a (organo)hydrogensilane compound represented by the following general formula (1′) in the presence of a catalyst.

(Wherein, A, R ¹ , R ² , Rf, X, Q, a and b are the same as above, and R ^3′ is independently the aliphatic unsaturated bond in R ¹² of general formula (4) An unsubstituted or substituted saturated aliphatic divalent hydrocarbon group having 2 or more carbon atoms formed by a hydrosilylation addition reaction with —SiH in the (organo)hydrogensilane compound represented by the general formula (5), Ph is a phenyl group.) Q in the general formula (4) is the following formula:

(In the formula, Me is a methyl group, Ph is a phenyl group, and Rf is a perfluoroalkylene group or a divalent perfluoropolyether group.)
5. The method for producing a fluorine-containing organosilicon compound according to claim 4, which is any one selected from wherein R ^3' in general formula (1') is at least one selected from ethylene group, propylene group (trimethylene group), methylethylene group, butylene group, hexamethylene group and cyclohexylene group; A method for producing the fluorine-containing organosilicon compound described. A room temperature curable fluorine-containing rubber composition comprising the fluorine-containing organosilicon compound according to any one of claims 1 to 3 and a curing catalyst. 8. The room temperature curable fluorine-containing rubber composition according to claim 7, further comprising at least one selected from a cross-linking agent, a filler, an adhesion promoter, a heat resistance imparting agent and a colorant. A fluorine-containing rubber comprising a cured product of the room-temperature-curable fluorine-containing rubber composition according to claim 7 or 8. Heat resistance, chemical resistance, solvent resistance, and repellency of the cured fluorine-containing rubber product, comprising the step of curing the room temperature-curable fluorine-containing rubber composition according to claim 7 or 8 at room temperature to obtain a cured fluorine-containing rubber product. A method for improving water and/or low moisture permeability. An article having a cured product layer of the room temperature curable fluorine-containing rubber composition according to claim 7 or 8.