JP6614039B2 - Fluoropolyether rubber, method for suppressing foaming of hermetic cured fluoropolyether rubber, and rubber adhesive - Google Patents

Description

The present invention, foam rubber when cured in a closed system is improved, light, light cured product of the photocurable fluoropolyether rubber compositions which cure in particular by irradiation of ultraviolet light, full Oro polyether The present invention relates to a method for suppressing foaming during the sealing and curing of a rubber cured product , and a rubber adhesive .

  Conventionally, heat curable fluoropolyether rubber compositions have excellent properties such as heat resistance, low temperature, chemical resistance, solvent resistance, oil resistance, etc. It is applied in a wide range of fields (Patent Documents 1, 2 and 3: Japanese Patent Application Laid-Open Nos. 2001-192,546, 3,646,775, and 4,016,239). However, since the above-mentioned heat-curing type composition requires heating to obtain a cured product, it requires a relatively large space for installing a heating furnace, and large parts that do not enter the heating furnace. There are problems such as difficulty in application to non-heatable parts and reduction in productivity because the molding process is batch-type.

  On the other hand, room temperature curing type fluoropolyether rubber compositions have been found, and condensation curing type and amide crosslinking type have been invented as such compositions. These compositions do not require heat treatment to obtain a cured product, and the resulting cured product is excellent in heat resistance, low temperature properties, chemical resistance, solvent resistance, oil resistance, etc. Application is expected (Patent Documents 4, 5, 6, 7 and 8: Patent No. 3,232,221, Patent No. 3,183,624, Patent No. 3,350,347, Patent No. 3,617,568 and Japanese Patent No. 5,146,690). However, conventional room temperature curing type rubber compositions have problems in terms of both storage stability and fast curability, such as thickening over time during storage and curing takes 24 hours or more.

  On the other hand, in a silicone elastomer material, a photoactive hydrosilylation catalyst that is activated by UV light irradiation of 230 to 400 nm is used to provide sufficient storage stability when not irradiated with light and good curability when irradiated with light. The photocurable composition which combined has become conventionally well-known (patent document 9 and 10: patent 5,384,524 gazette, patent 5,342,830 gazette). However, in the case of the photocurable silicone elastomer, there is a problem that chemical resistance, solvent resistance, oil resistance and the like are not sufficient depending on applications.

  A photocurable fluoropolyether system that has both storage stability and fast curability by changing the hydrosilylation catalyst of a conventionally known heat-curable fluoropolyether rubber composition to the photoactive hydrosilylation catalyst. A rubber composition can be obtained. However, when the composition is cured in a closed system at room temperature after light irradiation, rubber foaming occurs, causing problems such as poor appearance and unstable physical properties.

JP 2001-192546 A Japanese Patent No. 3,646,775 Japanese Patent No. 4,016,239 Japanese Patent No. 3,232,221 Japanese Patent No. 3,183,624 Japanese Patent No. 3,350,347 Japanese Patent No. 3,617,568 Japanese Patent No. 5,146,690 Japanese Patent No. 5,384,524 Japanese Patent No. 5,342,830

The present invention has been made in view of the above circumstances, and in a photocurable fluoropolyether rubber composition using a photoactive hydrosilylation reaction catalyst, a photocurable fluoropolymer having reduced foaming of rubber during hermetic curing. It is an object of the present invention to provide a fluoropolyether rubber which is a photocured product of a polyether rubber composition , a method for suppressing foaming of a cured fluoropolyether rubber , and a rubber adhesive .

  As a result of diligent research to solve the above problems, the present inventor has (A) a linear polymer having two or more alkenyl groups in one molecule and a perfluoropolyether structure in the main chain. Fluoro compound, (B) Fluorine-containing compound having two or more hydrogen atoms directly bonded to silicon atoms in one molecule and having a fluorine content of a specific amount or more, so that solubility in component (A) is good A photocurable fluoropolyether rubber composition containing a predetermined amount of an organohydrogenpolysiloxane and (C) a photoactive hydrosilylation reaction catalyst has been found to suppress foaming of the rubber during the above-mentioned hermetic curing, and the present invention has been completed. did.

In the present invention, the “linear polyfluoro compound”, “linear perfluoropolyether structure” or “linear perfluoropolyether group” constitutes the main chain perfluoropolyether structure. It means that divalent fluorooxyalkylene repeating units are linked in a straight chain, and each divalent fluorooxyalkylene unit itself is, for example, a linear fluorooxyalkylene unit. Or a fluorooxyalkylene unit having a branched structure such as — [CF ₂ CF (CF ₃ ) O] —.

（式（Ｚ）中、Ｒ³、Ｒ⁴はそれぞれ独立に−ＣＨ₃又は−ＣＨ＝ＣＨ₂である。）
で示されるｏ−、ｍ−又はｐ−シリルフェニレン基であり、Ｒ¹は水素原子又は非置換若しくは置換の１価炭化水素基である。〕であり、Ｘ’は−ＣＨ₂−、−ＯＣＨ₂−、−ＣＨ₂ＯＣＨ₂−又は−ＣＯ−ＮＲ²−Ｙ’−〔ここで、Ｙ’は−ＣＨ₂−、−ＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＣＨ₃）₂−、−ＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＣＨ₃）（ＣＨ＝ＣＨ₂）−、−ＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＣＨ＝ＣＨ₂）₂−又は下記構造式（Ｚ’）

（式（Ｚ’）中、Ｒ^3’、Ｒ^4’はそれぞれ独立に−ＣＨ₃又は−ＣＨ＝ＣＨ₂である。）
で示されるｏ−、ｍ−又はｐ−シリルフェニレン基であり、Ｒ²は水素原子又は非置換若しくは置換の１価炭化水素基である。〕である。ａは独立に０又は１である。Ｒｆ¹は下記式（ｉ）又は（ｉｉ）

（式（ｉ）中、ｐ及びｑはそれぞれ０又は１〜１５０の整数であって、且つｐとｑの和の平均は２〜２００である。ｒは０〜６の整数、ｔは２又は３である。）

（式（ｉｉ）中、ｕは１〜２００の整数、ｖは１〜５０の整数、ｔは２又は３である。）
で示される２価の直鎖状パーフルオロポリエーテル基である。］
［４］
（Ｂ）成分の含フッ素オルガノハイドロジェンポリシロキサンが、１分子中に１個以上の１価のパーフルオロアルキル基、１価のパーフルオロオキシアルキル基、２価のパーフルオロアルキレン基、又は２価のパーフルオロオキシアルキレン基を有するものである［１］〜［３］のいずれかに記載のフルオロポリエーテル系ゴム。
［５］
（Ｂ）成分の含フッ素オルガノハイドロジェンポリシロキサンが、下記式で表される化合物群から選ばれる１種又は２種以上である［１］〜［４］のいずれかに記載のフルオロポリエーテル系ゴム。

［６］
（Ｃ）成分の光活性型ヒドロシリル化反応触媒が、（η⁵−シクロペンタジエニル）トリ（σ−アルキル）白金（ＩＶ）錯体化合物及び／又はβ−ジケトナト白金（ＩＩ）錯体化合物である［１］〜［５］のいずれかに記載のフルオロポリエーテル系ゴム。
［７］
上記光硬化性フルオロポリエーテル系ゴム組成物が、更に（Ｅ）成分として、ヒドロシリル化反応の反応制御剤を含むものである［１］〜［６］のいずれかに記載のフルオロポリエーテル系ゴム。
［８］
（Ａ）１分子中に２個以上のアルケニル基を有し、且つ主鎖中に直鎖状パーフルオロポリエーテル構造を有する直鎖状ポリフルオロ化合物： １００質量部、
（Ｂ）１分子中にケイ素原子に直結した水素原子（Ｓｉ−Ｈ基）を２個以上有し、且つ、フッ素含有量が４０質量％以上である含フッ素オルガノハイドロジェンポリシロキサン： （Ａ）成分中のアルケニル基１モルに対して（Ｂ）成分中のＳｉ−Ｈ基が０．５〜３モルとなる量、
（Ｃ）光活性型ヒドロシリル化反応触媒： （Ａ）成分の質量に対して金属原子換算で０．１〜５００ｐｐｍ、及び
（Ｄ）ＢＥＴ比表面積が５０ｍ ² ／ｇ以上の疎水性シリカ粉末： ０．５〜３０質量部
を含有する光硬化性フルオロポリエーテル系ゴム組成物に最大ピーク波長が３００〜４００ｎｍである近紫外線を照射することによってフルオロポリエーテル系ゴム硬化物を得る工程を含む、フルオロポリエーテル系ゴム硬化物の密閉硬化時の発泡を抑制する方法。
［９］
（Ｂ）成分の含フッ素オルガノハイドロジェンポリシロキサンが、（Ａ）成分中のアルケニル基１モルに対して（Ｂ）成分中のＳｉ−Ｈ基が０．５〜３モルとなる量で（Ａ）成分と混合した際に（Ａ）成分中に均一且つ透明に分散可能なものである［８］記載のフルオロポリエーテル系ゴム硬化物の密閉硬化時の発泡を抑制する方法。
［１０］
（Ａ）成分が、下記式（１）で表される直鎖状ポリフルオロ化合物である［８］又は［９］記載のフルオロポリエーテル系ゴム硬化物の密閉硬化時の発泡を抑制する方法。
ＣＨ ₂ ＝ＣＨ−（Ｘ） _a −Ｒｆ ¹ −（Ｘ’） _a −ＣＨ＝ＣＨ ₂ （１）
［式（１）中、Ｘは−ＣＨ ₂ −、−ＣＨ ₂ Ｏ−、−ＣＨ ₂ ＯＣＨ ₂ −又は−Ｙ−ＮＲ ¹ −ＣＯ−〔ここで、Ｙは−ＣＨ ₂ −、−Ｓｉ（ＣＨ ₃ ） ₂ ＣＨ ₂ ＣＨ ₂ ＣＨ ₂ −、−Ｓｉ（ＣＨ ₃ ）（ＣＨ＝ＣＨ ₂ ）ＣＨ ₂ ＣＨ ₂ ＣＨ ₂ −、−Ｓｉ（ＣＨ＝ＣＨ ₂ ） ₂ ＣＨ ₂ ＣＨ ₂ ＣＨ ₂ −又は下記構造式（Ｚ）

（式（Ｚ）中、Ｒ ³ 、Ｒ ⁴ はそれぞれ独立に−ＣＨ ₃ 又は−ＣＨ＝ＣＨ ₂ である。）
で示されるｏ−、ｍ−又はｐ−シリルフェニレン基であり、Ｒ ¹ は水素原子又は非置換若しくは置換の１価炭化水素基である。〕であり、Ｘ’は−ＣＨ ₂ −、−ＯＣＨ ₂ −、−ＣＨ ₂ ＯＣＨ ₂ −又は−ＣＯ−ＮＲ ² −Ｙ’−〔ここで、Ｙ’は−ＣＨ ₂ −、−ＣＨ ₂ ＣＨ ₂ ＣＨ ₂ Ｓｉ（ＣＨ ₃ ） ₂ −、−ＣＨ ₂ ＣＨ ₂ ＣＨ ₂ Ｓｉ（ＣＨ ₃ ）（ＣＨ＝ＣＨ ₂ ）−、−ＣＨ ₂ ＣＨ ₂ ＣＨ ₂ Ｓｉ（ＣＨ＝ＣＨ ₂ ） ₂ −又は下記構造式（Ｚ’）

（式（Ｚ’）中、Ｒ ^3’ 、Ｒ ^4’ はそれぞれ独立に−ＣＨ ₃ 又は−ＣＨ＝ＣＨ ₂ である。）
で示されるｏ−、ｍ−又はｐ−シリルフェニレン基であり、Ｒ ² は水素原子又は非置換若しくは置換の１価炭化水素基である。〕である。ａは独立に０又は１である。Ｒｆ ¹ は下記式（ｉ）又は（ｉｉ）

（式（ｉ）中、ｐ及びｑはそれぞれ０又は１〜１５０の整数であって、且つｐとｑの和の平均は２〜２００である。ｒは０〜６の整数、ｔは２又は３である。）

（式（ｉｉ）中、ｕは１〜２００の整数、ｖは１〜５０の整数、ｔは２又は３である。）
で示される２価の直鎖状パーフルオロポリエーテル基である。］
［１１］
（Ｂ）成分の含フッ素オルガノハイドロジェンポリシロキサンが、１分子中に１個以上の１価のパーフルオロアルキル基、１価のパーフルオロオキシアルキル基、２価のパーフルオロアルキレン基、又は２価のパーフルオロオキシアルキレン基を有するものである［８］〜［１０］のいずれかに記載のフルオロポリエーテル系ゴム硬化物の密閉硬化時の発泡を抑制する方法。
［１２］
（Ｂ）成分の含フッ素オルガノハイドロジェンポリシロキサンが、下記式で表される化合物群から選ばれる１種又は２種以上である［８］〜［１１］のいずれかに記載のフルオロポリエーテル系ゴム硬化物の密閉硬化時の発泡を抑制する方法。

［１３］
（Ｃ）成分の光活性型ヒドロシリル化反応触媒が、（η ⁵ −シクロペンタジエニル）トリ（σ−アルキル）白金（ＩＶ）錯体化合物及び／又はβ−ジケトナト白金（ＩＩ）錯体化合物である［８］〜［１２］のいずれかに記載のフルオロポリエーテル系ゴム硬化物の密閉硬化時の発泡を抑制する方法。
［１４］
上記光硬化性フルオロポリエーテル系ゴム組成物が、更に（Ｅ）成分として、ヒドロシリル化反応の反応制御剤を含むものである［８］〜［１３］のいずれかに記載のフルオロポリエーテル系ゴム硬化物の密閉硬化時の発泡を抑制する方法。
［１５］
（Ａ）１分子中に２個以上のアルケニル基を有し、且つ主鎖中に直鎖状パーフルオロポリエーテル構造を有する直鎖状ポリフルオロ化合物： １００質量部、
（Ｂ）１分子中にケイ素原子に直結した水素原子（Ｓｉ−Ｈ基）を２個以上有し、且つ、フッ素含有量が４０質量％以上である含フッ素オルガノハイドロジェンポリシロキサン： （Ａ）成分中のアルケニル基１モルに対して（Ｂ）成分中のＳｉ−Ｈ基が０．５〜３モルとなる量、
（Ｃ）光活性型ヒドロシリル化反応触媒： （Ａ）成分の質量に対して金属原子換算で０．１〜５００ｐｐｍ、及び
（Ｄ）ＢＥＴ比表面積が５０ｍ ² ／ｇ以上の疎水性シリカ粉末： ０．５〜３０質量部
を含有する光硬化性フルオロポリエーテル系ゴム組成物からなるゴム系接着剤。
［１６］
（Ｂ）成分の含フッ素オルガノハイドロジェンポリシロキサンが、（Ａ）成分中のアルケニル基１モルに対して（Ｂ）成分中のＳｉ−Ｈ基が０．５〜３モルとなる量で（Ａ）成分と混合した際に（Ａ）成分中に均一且つ透明に分散可能なものである［１５］記載のゴム系接着剤。
［１７］
（Ａ）成分が、下記式（１）で表される直鎖状ポリフルオロ化合物である［１５］又は［１６］記載のゴム系接着剤。
ＣＨ ₂ ＝ＣＨ−（Ｘ） _a −Ｒｆ ¹ −（Ｘ’） _a −ＣＨ＝ＣＨ ₂ （１）
［式（１）中、Ｘは−ＣＨ ₂ −、−ＣＨ ₂ Ｏ−、−ＣＨ ₂ ＯＣＨ ₂ −又は−Ｙ−ＮＲ ¹ −ＣＯ−〔ここで、Ｙは−ＣＨ ₂ −、−Ｓｉ（ＣＨ ₃ ） ₂ ＣＨ ₂ ＣＨ ₂ ＣＨ ₂ −、−Ｓｉ（ＣＨ ₃ ）（ＣＨ＝ＣＨ ₂ ）ＣＨ ₂ ＣＨ ₂ ＣＨ ₂ −、−Ｓｉ（ＣＨ＝ＣＨ ₂ ） ₂ ＣＨ ₂ ＣＨ ₂ ＣＨ ₂ −又は下記構造式（Ｚ）

（式（Ｚ）中、Ｒ ³ 、Ｒ ⁴ はそれぞれ独立に−ＣＨ ₃ 又は−ＣＨ＝ＣＨ ₂ である。）
で示されるｏ−、ｍ−又はｐ−シリルフェニレン基であり、Ｒ ¹ は水素原子又は非置換若しくは置換の１価炭化水素基である。〕であり、Ｘ’は−ＣＨ ₂ −、−ＯＣＨ ₂ −、−ＣＨ ₂ ＯＣＨ ₂ −又は−ＣＯ−ＮＲ ² −Ｙ’−〔ここで、Ｙ’は−ＣＨ ₂ −、−ＣＨ ₂ ＣＨ ₂ ＣＨ ₂ Ｓｉ（ＣＨ ₃ ） ₂ −、−ＣＨ ₂ ＣＨ ₂ ＣＨ ₂ Ｓｉ（ＣＨ ₃ ）（ＣＨ＝ＣＨ ₂ ）−、−ＣＨ ₂ ＣＨ ₂ ＣＨ ₂ Ｓｉ（ＣＨ＝ＣＨ ₂ ） ₂ −又は下記構造式（Ｚ’）

（式（Ｚ’）中、Ｒ ^3’ 、Ｒ ^4’ はそれぞれ独立に−ＣＨ ₃ 又は−ＣＨ＝ＣＨ ₂ である。）
で示されるｏ−、ｍ−又はｐ−シリルフェニレン基であり、Ｒ ² は水素原子又は非置換若しくは置換の１価炭化水素基である。〕である。ａは独立に０又は１である。Ｒｆ ¹ は下記式（ｉ）又は（ｉｉ）

（式（ｉ）中、ｐ及びｑはそれぞれ０又は１〜１５０の整数であって、且つｐとｑの和の平均は２〜２００である。ｒは０〜６の整数、ｔは２又は３である。）

（式（ｉｉ）中、ｕは１〜２００の整数、ｖは１〜５０の整数、ｔは２又は３である。）
で示される２価の直鎖状パーフルオロポリエーテル基である。］
［１８］
（Ｂ）成分の含フッ素オルガノハイドロジェンポリシロキサンが、１分子中に１個以上の１価のパーフルオロアルキル基、１価のパーフルオロオキシアルキル基、２価のパーフルオロアルキレン基、又は２価のパーフルオロオキシアルキレン基を有するものである［１５］〜［１７］のいずれかに記載のゴム系接着剤。
［１９］
（Ｂ）成分の含フッ素オルガノハイドロジェンポリシロキサンが、下記式で表される化合物群から選ばれる１種又は２種以上である［１５］〜［１８］のいずれかに記載のゴム系接着剤。

［２０］
（Ｃ）成分の光活性型ヒドロシリル化反応触媒が、（η ⁵ −シクロペンタジエニル）トリ（σ−アルキル）白金（ＩＶ）錯体化合物及び／又はβ−ジケトナト白金（ＩＩ）錯体化合物である［１５］〜［１９］のいずれかに記載のゴム系接着剤。
［２１］
更に、（Ｅ）成分として、ヒドロシリル化反応の反応制御剤を含むものである［１５］〜［２０］のいずれかに記載のゴム系接着剤。
［２２］
光硬化して２つの基材同士を接着する［１５］〜［２１］のいずれかに記載のゴム系接着剤。 Accordingly, the present invention is to provide the following full Oro polyether rubber, a method of suppressing the foaming at the time of sealing the curing of the full Oro polyether cured rubber, and a rubber-based adhesive.
[1]
(A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and a linear perfluoropolyether structure in the main chain: 100 parts by mass;
(B) Fluorinated organohydrogenpolysiloxane having two or more hydrogen atoms (Si-H groups) directly bonded to silicon atoms in one molecule and a fluorine content of 40% by mass or more: (A) The amount that the Si-H group in the component (B) is 0.5 to 3 mol with respect to 1 mol of the alkenyl group in the component,
(C) Photoactive hydrosilylation reaction catalyst: (A) Hydrophobic silica powder having a BET specific surface area of 50 m ² / g or more and 0.1 to 500 ppm in terms of metal atom with respect to the mass of the component: 0 fluoropolyether rubber made of a light cured product of the photocurable fluoropolyether rubber composition you containing .5～30 parts by weight.
[2]
The fluorine-containing organohydrogenpolysiloxane of the component (B) is an amount such that the Si—H group in the component (B) is 0.5 to 3 mol per mol of the alkenyl group in the component (A) (A The fluoropolyether rubber according to [1], which can be uniformly and transparently dispersed in the component (A) when mixed with the component.
[3]
The fluoropolyether rubber according to [1] or [2], wherein the component (A) is a linear polyfluoro compound represented by the following formula (1).
_{CH 2 = CH- (X) a} -Rf 1 - (X ') a -CH = CH 2 (1)
[In formula (1), X _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR ¹ -CO- [where, Y is -CH ₂ -, - Si (CH _{3) 2 CH 2 CH 2 CH} 2 -, - Si (CH 3) (CH = CH 2) CH 2 CH 2 CH 2 -, - Si (CH = CH 2) 2 CH 2 CH 2 CH 2 - or the following structure Formula (Z)

(In Formula (Z), R ³ and R ⁴ are each independently —CH ₃ or —CH═CH _2. )
O-, m- or p-silylphenylene group, and R ¹ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group. X ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ² —Y′—, where Y ′ is —CH ₂ —, —CH ₂ CH _2. CH ₂ Si (CH ₃ ) ₂ —, —CH ₂ CH ₂ CH ₂ Si (CH ₃ ) (CH═CH ₂ ) —, —CH ₂ CH ₂ CH ₂ Si (CH═CH ₂ ) ₂ — or the following structural formula (Z ')

(In formula (Z ′), R ^{3 ′} and R ^{4 ′} are each independently —CH ₃ or —CH═CH _2. )
O-, m-, or p-silylphenylene group, and R ² is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group. ]. a is independently 0 or 1. Rf ¹ represents the following formula (i) or (ii)

(In formula (i), p and q are each 0 or an integer of 1-150, and the average of the sum of p and q is 2-200. R is an integer of 0-6, t is 2 or 3)

(In formula (ii), u is an integer of 1 to 200, v is an integer of 1 to 50, and t is 2 or 3.)
It is a bivalent linear perfluoropolyether group shown by these. ]
[4]
The fluorine-containing organohydrogenpolysiloxane of component (B) is one or more monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group, or divalent in one molecule. The fluoropolyether rubber according to any one of [1] to [3], which has a perfluorooxyalkylene group .
[5]
(B) Fluoropolyether type | system | group in any one of [1]-[4] whose fluorine-containing organohydrogenpolysiloxane is 1 type, or 2 or more types chosen from the compound group represented by a following formula Rubber .

[6]
The photoactive hydrosilylation reaction catalyst of the component (C) is an (η ⁵ -cyclopentadienyl) tri (σ-alkyl) platinum (IV) complex compound and / or a β-diketonatoplatinum (II) complex compound [ [1] The fluoropolyether rubber according to any one of [5].
[7]
The photo-curable fluoropolyether base rubber composition, as further the (E) component, is intended to include reaction control agent hydrosilylation [1] fluoropolyether rubber according to any one of to [6].
[8]
(A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and a linear perfluoropolyether structure in the main chain: 100 parts by mass;
(B) Fluorinated organohydrogenpolysiloxane having two or more hydrogen atoms (Si-H groups) directly bonded to silicon atoms in one molecule and a fluorine content of 40% by mass or more: (A) The amount that the Si-H group in the component (B) is 0.5 to 3 mol with respect to 1 mol of the alkenyl group in the component,
(C) Photoactive hydrosilylation reaction catalyst: (A) 0.1 to 500 ppm in terms of metal atom with respect to the mass of the component, and
(D) Hydrophobic silica powder having a BET specific surface area of 50 m ² / g or more: 0.5 to 30 parts by mass
A cured fluoropolyether rubber comprising a step of obtaining a cured fluoropolyether rubber by irradiating a near-ultraviolet ray having a maximum peak wavelength of 300 to 400 nm to a photocurable fluoropolyether rubber composition containing To suppress foaming at the time of airtight curing.
[9]
The fluorine-containing organohydrogenpolysiloxane of the component (B) is an amount such that the Si—H group in the component (B) is 0.5 to 3 mol per mol of the alkenyl group in the component (A) (A (8) The method for suppressing foaming at the time of hermetically curing the fluoropolyether rubber cured product according to [8], which can be uniformly and transparently dispersed in the component (A) when mixed with the component.
[10]
( A) The method in which the component suppresses foaming at the time of hermetically curing the fluoropolyether rubber cured product according to [8] or [9], which is a linear polyfluoro compound represented by the following formula (1).
_{CH 2 = CH- (X) a} -Rf 1 - (X ') a -CH = CH 2 (1)
[In formula (1), X _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR ¹ -CO- [where, Y is -CH ₂ -, - Si (CH _{3) 2 CH 2 CH 2 CH} 2 -, - Si (CH 3) (CH = CH 2) CH 2 CH 2 CH 2 -, - Si (CH = CH 2) 2 CH 2 CH 2 CH 2 - or the following structure Formula (Z)

(In Formula (Z), R ³ and R ⁴ are each independently —CH ₃ or —CH═CH _2. )
O-, m- or p-silylphenylene group, and R ¹ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group. X ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ² —Y′—, where Y ′ is —CH ₂ —, —CH ₂ CH _2. CH ₂ Si (CH ₃ ) ₂ —, —CH ₂ CH ₂ CH ₂ Si (CH ₃ ) (CH═CH ₂ ) —, —CH ₂ CH ₂ CH ₂ Si (CH═CH ₂ ) ₂ — or the following structural formula (Z ')

(In formula (Z ′), R ^{3 ′} and R ^{4 ′} are each independently —CH ₃ or —CH═CH _2. )
O-, m-, or p-silylphenylene group, and R ² is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group. ]. a is independently 0 or 1. Rf ¹ represents the following formula (i) or (ii)

(In formula (i), p and q are each 0 or an integer of 1-150, and the average of the sum of p and q is 2-200. R is an integer of 0-6, t is 2 or 3)

(In formula (ii), u is an integer of 1 to 200, v is an integer of 1 to 50, and t is 2 or 3.)
It is a bivalent linear perfluoropolyether group shown by these. ]
[11]
The fluorine-containing organohydrogenpolysiloxane of component (B) is one or more monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group, or divalent in one molecule. The method of suppressing foaming at the time of sealing hardening of the fluoropolyether type rubber cured product according to any one of [8] to [10], which has a perfluorooxyalkylene group.
[12]
The fluoropolyether system according to any one of [8] to [11], wherein the fluorine-containing organohydrogenpolysiloxane of component (B) is one or more selected from the group of compounds represented by the following formula: A method of suppressing foaming during sealing and curing of a rubber cured product.

[13]
The photoactive hydrosilylation reaction catalyst of the component (C) is an (η ⁵ -cyclopentadienyl) tri (σ-alkyl) platinum (IV) complex compound and / or a β-diketonatoplatinum (II) complex compound [ The method of suppressing foaming at the time of the sealing hardening of the fluoropolyether type rubber cured product according to any one of [8] to [12].
[14]
The photopolymerizable fluoropolyether rubber composition according to any one of [8] to [13], wherein the photocurable fluoropolyether rubber composition further contains a reaction control agent for hydrosilylation reaction as component (E). To suppress foaming at the time of airtight curing.
[15]
(A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and a linear perfluoropolyether structure in the main chain: 100 parts by mass;
(B) Fluorinated organohydrogenpolysiloxane having two or more hydrogen atoms (Si-H groups) directly bonded to silicon atoms in one molecule and a fluorine content of 40% by mass or more: (A) The amount that the Si-H group in the component (B) is 0.5 to 3 mol with respect to 1 mol of the alkenyl group in the component,
(C) Photoactive hydrosilylation reaction catalyst: (A) 0.1 to 500 ppm in terms of metal atom with respect to the mass of the component, and
(D) Hydrophobic silica powder having a BET specific surface area of 50 m ² / g or more: 0.5 to 30 parts by mass
A rubber adhesive comprising a photocurable fluoropolyether rubber composition containing
[16]
The fluorine-containing organohydrogenpolysiloxane of the component (B) is an amount such that the Si—H group in the component (B) is 0.5 to 3 mol per mol of the alkenyl group in the component (A) (A The rubber adhesive according to [15], which can be uniformly and transparently dispersed in the component (A) when mixed with the component.
[17]
The rubber-based adhesive according to [15] or [16], wherein the component (A) is a linear polyfluoro compound represented by the following formula (1).
_{CH 2 = CH- (X) a} -Rf 1 - (X ') a -CH = CH 2 (1)
[In formula (1), X _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR ¹ -CO- [where, Y is -CH ₂ -, - Si (CH _{3) 2 CH 2 CH 2 CH} 2 -, - Si (CH 3) (CH = CH 2) CH 2 CH 2 CH 2 -, - Si (CH = CH 2) 2 CH 2 CH 2 CH 2 - or the following structure Formula (Z)

(In Formula (Z), R ³ and R ⁴ are each independently —CH ₃ or —CH═CH _2. )
O-, m-, or p-silylphenylene group, and R ¹ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group. X ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ² —Y′—, wherein Y ′ is —CH ₂ —, —CH ₂ CH _2. CH ₂ Si (CH ₃ ) ₂ —, —CH ₂ CH ₂ CH ₂ Si (CH ₃ ) (CH═CH ₂ ) —, —CH ₂ CH ₂ CH ₂ Si (CH═CH ₂ ) ₂ — or the following structural formula (Z ')

(In formula (Z ′), R ^{3 ′} and R ^{4 ′} are each independently —CH ₃ or —CH═CH _2. )
O-, m-, or p-silylphenylene group, and R ² is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group. ]. a is independently 0 or 1. Rf ¹ represents the following formula (i) or (ii)

(In formula (i), p and q are each 0 or an integer of 1-150, and the average of the sum of p and q is 2-200. R is an integer of 0-6, t is 2 or 3)

(In formula (ii), u is an integer of 1 to 200, v is an integer of 1 to 50, and t is 2 or 3.)
It is a bivalent linear perfluoropolyether group shown by these. ]
[18]
The fluorine-containing organohydrogenpolysiloxane of component (B) is one or more monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group, or divalent in one molecule. The rubber adhesive according to any one of [15] to [17], which has a perfluorooxyalkylene group.
[19]
The rubber adhesive according to any one of [15] to [18], wherein the fluorine-containing organohydrogenpolysiloxane of component (B) is one or more selected from the group of compounds represented by the following formula: .

[20]
The photoactive hydrosilylation reaction catalyst of the component (C) is an (η ⁵ -cyclopentadienyl) tri (σ-alkyl) platinum (IV) complex compound and / or a β-diketonatoplatinum (II) complex compound [ The rubber adhesive according to any one of 15] to [19].
[21]
Furthermore, the rubber-type adhesive in any one of [15]-[20] which contains the reaction control agent of hydrosilylation reaction as (E) component.
[22]
The rubber adhesive according to any one of [15] to [21], which is photocured to bond two substrates together.

According to the present invention, it is possible to provide a photocured product of a light curable fluoropolyether rubber composition foaming was reduced the rubber during sealing curing. By reducing the foaming of rubber, the physical properties of the rubber obtained at the time of hermetic sealing can be stabilized.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[(A) Linear polyfluoro compound]
The component (A) in the photocurable fluoropolyether rubber composition of the present invention acts as a main agent (base polymer) of the composition according to the present invention, and includes two or more alkenyl groups in one molecule. A linear polyfluoro compound having a linear perfluoropolyether structure in the main chain. Here, the number of alkenyl groups is preferably 2 to 30, and particularly preferably 2 to 6.

（式（Ｚ）中、Ｒ³、Ｒ⁴はそれぞれ独立に−ＣＨ₃又は−ＣＨ＝ＣＨ₂である。）
で示されるｏ−、ｍ−又はｐ−シリルフェニレン基であり、Ｒ¹は水素原子又は非置換若しくは置換の１価炭化水素基である。〕であり、Ｘ’は−ＣＨ₂−、−ＯＣＨ₂−、−ＣＨ₂ＯＣＨ₂−又は−ＣＯ−ＮＲ²−Ｙ’−〔ここで、Ｙ’は−ＣＨ₂−、−ＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＣＨ₃）₂−、−ＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＣＨ₃）（ＣＨ＝ＣＨ₂）−、−ＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＣＨ＝ＣＨ₂）₂−又は下記構造式（Ｚ’）

（式（Ｚ’）中、Ｒ^3’、Ｒ^4’はそれぞれ独立に−ＣＨ₃又は−ＣＨ＝ＣＨ₂である。）
で示されるｏ−、ｍ−又はｐ−シリルフェニレン基であり、Ｒ²は水素原子又は非置換若しくは置換の１価炭化水素基である。〕である。ａは独立に０又は１である。Ｒｆ¹は下記式（ｉ）又は（ｉｉ）

（式（ｉ）中、ｐ及びｑはそれぞれ０〜１５０の整数、好ましくは１〜１５０の整数であって、且つｐとｑの和の平均は２〜２００である。ｒは０〜６の整数、ｔは２又は３である。）

（式（ｉｉ）中、ｕは１〜２００の整数、ｖは１〜５０の整数、ｔは２又は３である。）
で示される２価の直鎖状パーフルオロポリエーテル基であり、好ましくは、分岐構造を有するフルオロオキシアルキレン単位である−［ＣＦ₂ＣＦ（ＣＦ₃）Ｏ］−を含有する２価の直鎖状パーフルオロポリエーテル基である。］ As the component (A), a linear polyfluoro compound represented by the following formula (1) is particularly preferable.
_{CH 2 = CH- (X) a} -Rf 1 - (X ') a -CH = CH 2 (1)
[In formula (1), X _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR ¹ -CO- [where, Y is -CH ₂ -, - Si (CH _{3) 2 CH 2 CH 2 CH} 2 -, - Si (CH 3) (CH = CH 2) CH 2 CH 2 CH 2 -, - Si (CH = CH 2) 2 CH 2 CH 2 CH 2 - or the following structure Formula (Z)

(In Formula (Z), R ³ and R ⁴ are each independently —CH ₃ or —CH═CH _2. )
O-, m- or p-silylphenylene group, and R ¹ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group. X ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ² —Y′—, where Y ′ is —CH ₂ —, —CH ₂ CH _2. CH ₂ Si (CH ₃ ) ₂ —, —CH ₂ CH ₂ CH ₂ Si (CH ₃ ) (CH═CH ₂ ) —, —CH ₂ CH ₂ CH ₂ Si (CH═CH ₂ ) ₂ — or the following structural formula (Z ')

(In formula (Z ′), R ^{3 ′} and R ^{4 ′} are each independently —CH ₃ or —CH═CH _2. )
O-, m-, or p-silylphenylene group, and R ² is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group. ]. a is independently 0 or 1. Rf ¹ represents the following formula (i) or (ii)

(In the formula (i), p and q are each an integer of 0 to 150, preferably an integer of 1 to 150, and the average of the sum of p and q is 2 to 200. r is 0 to 6) Integer, t is 2 or 3.)

(In formula (ii), u is an integer of 1 to 200, v is an integer of 1 to 50, and t is 2 or 3.)
A divalent linear perfluoropolyether group represented by the formula ( ₂ ), preferably a divalent linear chain containing — [CF ₂ CF (CF ₃ ) O] —, which is a fluorooxyalkylene unit having a branched structure. Perfluoropolyether group. ]

Here, as R ¹ and R ² , a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms is preferable, and as the monovalent hydrocarbon group, specifically, Alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group and octyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and phenylethyl group, etc. And a substituted monovalent hydrocarbon group in which part or all of the hydrogen atoms in the group are substituted with a halogen atom such as fluorine.

Rf ¹ in the above formula (1) is a divalent linear perfluoropolyether group, preferably a group represented by the following formula (i) or (ii). More preferably, it is a divalent linear perfluoropolyether group containing — [CF ₂ CF (CF ₃ ) O] — which is a fluorooxyalkylene unit having a branched structure.

（式（ｉ）中、ｐ及びｑはそれぞれ０〜１５０の整数、好ましくは１〜１５０の整数、更に好ましくは１０〜１００の整数であって、且つｐとｑの和の平均は２〜２００、好ましくは２０〜１６０である。また、ｒは０〜６の整数、好ましくは０〜４の整数であり、ｔは２又は３である。）

(In the formula (i), p and q are each an integer of 0 to 150, preferably an integer of 1 to 150, more preferably an integer of 10 to 100, and the average of the sum of p and q is 2 to 200. And preferably 20 to 160. Also, r is an integer of 0 to 6, preferably an integer of 0 to 4, and t is 2 or 3.)

（式（ｉｉ）中、ｕは１〜２００の整数、好ましくは２０〜１６０の整数であり、ｖは１〜５０の整数、好ましくは５〜４０の整数であり、ｔは２又は３である。）

(In the formula (ii), u is an integer of 1 to 200, preferably an integer of 20 to 160, v is an integer of 1 to 50, preferably an integer of 5 to 40, and t is 2 or 3. .)

Preferred examples of the Rf ¹ group include the following three groups. Of these, a divalent group having the structure of the first formula is particularly preferable.

（式中、ｐ１及びｑ１はそれぞれ１〜１５０の整数、ｐ１＋ｑ１（平均）＝２〜２００である。Ｌは２〜６の整数である。）

(In the formula, p1 and q1 are each an integer of 1 to 150 and p1 + q1 (average) = 2 to 200. L is an integer of 2 to 6)

（式中、ｐ２及びｑ２はそれぞれ１〜１５０の整数、ｐ２＋ｑ２（平均）＝２〜２００である。Ｌは２〜６の整数である。）

(In the formula, p2 and q2 are each an integer of 1 to 150, and p2 + q2 (average) = 2 to 200. L is an integer of 2 to 6)

（式中、ｕ１は１〜２００の整数、ｖ１は１〜５０の整数である。）

(In the formula, u1 is an integer of 1 to 200, and v1 is an integer of 1 to 50.)

［式（２）中、Ｘ¹は−ＣＨ₂−、−ＣＨ₂Ｏ−、−ＣＨ₂ＯＣＨ₂−又は−Ｙ−ＮＲ¹¹−ＣＯ−（Ｙは前記と同じものを示し、Ｒ¹¹は水素原子、メチル基、フェニル基又はアリル基である。）で表される基を示し、Ｘ¹’は−ＣＨ₂−、−ＯＣＨ₂−、−ＣＨ₂ＯＣＨ₂−又は−ＣＯ−ＮＲ¹²−Ｙ’−（Ｒ¹²は上記Ｒ¹¹と同じものを示し、Ｙ’は前記と同じものを示す。）で表される基であり、ａは独立に０又は１、Ｌは２〜６の整数、ｐ３及びｑ３はそれぞれ１〜１５０の整数、ｐ３＋ｑ３（平均）＝２〜２００である。］ (A) As a preferable example of a component, the compound represented by following formula (2) is mentioned.

Wherein (2), X ¹ is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR ¹¹ -CO- (Y have the same meanings as defined above, R ¹¹ is hydrogen X ¹ ′ represents —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ —, or —CO—NR ¹² —Y. A group represented by '-(R ¹² is the same as R ¹¹ and Y' is the same as described above), a is independently 0 or 1, L is an integer of 2-6, p3 and q3 are each an integer of 1 to 150, and p3 + q3 (average) = 2 to 200. ]

（式中、ｐ’及びｑ’はそれぞれ１〜１５０の整数、ｐ’＋ｑ’（平均）＝６〜２００である。） Specific examples of the linear polyfluoro compound represented by the formula (1) include those represented by the following formula.

(Wherein, p ′ and q ′ are each an integer of 1 to 150, and p ′ + q ′ (average) = 6 to 200)

（式中、ｐ’及びｑ’はそれぞれ１〜１５０の整数、ｐ’＋ｑ’（平均）＝６〜２００である。）

(Wherein, p ′ and q ′ are each an integer of 1 to 150, and p ′ + q ′ (average) = 6 to 200)

（式中、ｐ’及びｑ’はそれぞれ１〜１５０の整数、ｐ’＋ｑ’（平均）＝６〜２００である。）

(Wherein, p ′ and q ′ are each an integer of 1 to 150, and p ′ + q ′ (average) = 6 to 200)

（式中、ｐ”及びｑ”はそれぞれ１〜１５０の整数、ｐ”＋ｑ”（平均）＝２〜２００である。）

(In the formula, p ″ and q ″ are each an integer of 1 to 150, and p ″ + q ″ (average) = 2 to 200.)

  The amount of alkenyl group contained in the linear polyfluoro compound represented by formula (1) is preferably 0.005 to 0.050 mol / 100 g, more preferably 0.007 to 0.040 mol / 100 g. It is. If the amount of the alkenyl group contained in the linear polyfluoro compound is too small, the physical strength of the cured product may be reduced or the cured product may not be obtained. Moreover, when there are too many amounts of alkenyl groups, the hardened | cured material obtained may become brittle and it will be easy to crack, or the light transmittance of a polymer may fall and sufficient hardened | cured material may not be obtained.

In addition, the viscosity (23 degreeC) of the linear polyfluoro compound of Formula (1) becomes like this. Preferably it is 100-100,000 mPa * s, More preferably, it is 500-50,000 mPa * s, More preferably, it is 1,000-20. , 000 mPa · s. If a photocurable fluoropolyether rubber composition having a viscosity within this range is used for sealing, potting, coating, impregnation, etc., it is desirable because the photocured product has appropriate physical properties. The linear polyfluoro compound of formula (1) is selected to have the most appropriate viscosity according to the application. At this time, a low viscosity polymer and a high viscosity polymer can be mixed and adjusted to a desired viscosity.
In the present invention, the viscosity (23 ° C.) can be measured with a rotational viscometer (for example, BL type, BH type, BS type, cone plate type, rheometer, etc.), and in particular, according to JIS K7117-1. It is preferable to measure in accordance with prescribed conditions. In addition, the number of repeats (or degree of polymerization) of each perfluorooxyalkylene repeating unit in the linear perfluoropolyether structure constituting the main chain of the linear polyfluoro compound is usually determined using a fluorine-based solvent as a developing solvent. It can be calculated as a polystyrene-reduced number average degree of polymerization (or number average molecular weight) by gel permeation chromatography (GPC) analysis.

  Furthermore, in the present invention, in order to adjust the linear polyfluoro compound of the formula (1) to a desired number average molecular weight or weight average molecular weight according to the purpose, a linear perfluoropolyether compound is previously incorporated in the molecule. It is also possible to use as a component (A) a product obtained by subjecting an organosilicon compound containing two hydrosilyl groups (Si-H groups) to a hydrosilylation reaction in the usual manner and conditions and extending the chain length.

  These linear polyfluoro compounds may be used individually by 1 type, or may be used in combination of 2 or more type.

[(B) Fluorinated organohydrogenpolysiloxane]
Component (B) usually contains one or more, preferably 1 to 10, fluorine-containing organic groups (for example, a monovalent or divalent fluorine-containing hydrocarbon group which may contain an oxygen atom) in one molecule. And having 2 or more, preferably 3 to 50 hydrogen atoms (that is, a hydrosilyl group represented by Si—H) directly bonded to a silicon atom, and the fluorine content in the molecule is 40% by mass or more. Is a fluorine-containing organohydrogenpolysiloxane that functions as a crosslinking agent and / or a chain extender of component (A), and is preferably a component that is “soluble” in component (A) . Here, “soluble” in the component (A) means that at room temperature (23 ° C. ± 10 ° C.), the component (A) and the component (B) are converted to 1 mol of the alkenyl group contained in the component (A). On the other hand, when the Si-H group in the component (B) is mixed in an amount of 0.5 to 3 mol, the component (B) can be dispersed (mixed) transparently and uniformly in the component (A). Represents that.

  Component (B) is composed of one or more monovalent perfluoroalkyl groups and monovalent perfluorooxy in one molecule from the viewpoint of compatibility with (A) component, dispersibility, uniformity after curing, and the like. Those having a fluorine-containing group such as an alkyl group, a divalent perfluoroalkylene group, or a divalent perfluorooxyalkylene group are preferred. Examples of the monovalent or divalent fluorine-containing organic group include those represented by the following formulas such as a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group, and a perfluorooxyalkylene group. it can.

C _g F _{2g + 1} −
−C _g F _2g −
(In the formula, g is an integer of 1 to 20, preferably an integer of 4 to 6.)

（式中、ｆは１〜２００の整数、好ましくは１〜１００の整数、ｈは１〜３の整数である。）

(In the formula, f is an integer of 1 to 200, preferably an integer of 1 to 100, and h is an integer of 1 to 3.)

（式中、ｉ及びｊはそれぞれ１以上の整数、好ましくは１〜１００の整数、ｉ＋ｊの平均は２〜２００、好ましくは２〜１００である。）

(In the formula, i and j are each an integer of 1 or more, preferably an integer of 1 to 100, and the average of i + j is 2 to 200, preferably 2 to 100.)

_{- (CF 2 O) d -} (CF 2 CF 2 O) e -CF 2 -
(In the formula, d and e are each an integer of 1 to 50, preferably an integer of 1 to 40.)

The perfluoroalkyl group, perfluorooxyalkyl group, perfluoroalkylene group or perfluorooxyalkylene group described above and the silicon atom in the component (B) are preferably connected by a divalent linking group, Examples of the divalent linking group include an alkylene group, an arylene group and a combination thereof, or an ether bond oxygen atom, an amide bond, a carbonyl bond, an ester bond, a diorganosilylene group, or the like interposed between these groups. For example, the following C2-C12 bivalent coupling group etc. are mentioned.
-CH ₂ CH ₂ -,
-CH ₂ CH ₂ CH ₂ -,
-CH ₂ CH ₂ CH ₂ O-,
_{-CH 2 CH 2 CH 2 OCH 2} -,
_{-CH 2 CH 2 CH 2 -NH-} CO-,
_{-CH 2 CH 2 CH 2 -N (} Ph) -CO-,
_{-CH 2 CH 2 CH 2 -N (} CH 3) -CO-,
_{-CH 2 CH 2 CH 2 -N (} CH 2 CH 3) -CO-,
_{-CH 2 CH 2 -Si (CH 3} ) 2 -Ph'-N (CH 3) -CO-,
_{-CH 2 CH 2 CH 2 -Si (} CH 3) 2 -Ph'-N (CH 3) -CO-,
—CH ₂ CH ₂ CH ₂ —O—CO—
(In the formula, Ph is a phenyl group, and Ph ′ is a phenylene group.)

  In addition, as the monovalent substituent bonded to the silicon atom other than the monovalent or divalent fluorine-containing organic group and the hydrogen atom bonded to the silicon atom in the fluorine-containing organohydrogenpolysiloxane of the component (B), For example, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, octyl group, decyl group and other alkyl groups; vinyl group, allyl group and other alkenyl groups; phenyl group, tolyl group, naphthyl group and the like Aryl groups; aralkyl groups such as benzyl and phenylethyl groups, and some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as chlorine atoms, cyano groups, etc., for example, chloromethyl groups, chloropropyl groups C 1-20, preferably 1-12, such as cyanoethyl group, unsubstituted or substituted (especially halogen atom or cyano group) Include monovalent hydrocarbon groups of conversion).

  The fluorine content in the fluorine-containing organohydrogenpolysiloxane as the component (B) needs to be 40% by mass or more, preferably 40 to 80% by mass, more preferably 40 to 70% by mass, and still more preferably. Is 40.5 to 68% by mass. If the fluorine content is lower than this, the compatibility with the component (A) is insufficient, and there is a possibility that the rubber foams at the time of hermetic curing.

  Further, the fluorine-containing organohydrogenpolysiloxane as the component (B) may be any of cyclic, chain, three-dimensional network, and combinations thereof. The number of silicon atoms in the fluorine-containing organohydrogenpolysiloxane is not particularly limited, but is usually 2 to 60, preferably about 3 to 30.

  Examples of the component (B) having such a monovalent or divalent fluorine-containing organic group and a silicon atom-bonded hydrogen atom include the following compounds. The fluorine content is written next to the compound formula. These compounds may be used alone or in combination of two or more. In the following formulae, Me represents a methyl group, and Ph represents a phenyl group. In addition, the following fluorine content rate (%) is "mass%".

  The amount of Si—H groups contained in the fluorine-containing organohydrogenpolysiloxane as the component (B) is preferably 0.00050 to 0.01000 mol / g, more preferably 0.00100 to 0.00800 mol / g. g. If the amount of Si-H groups contained in the fluorine-containing organohydrogenpolysiloxane is too small, the crosslinking density may be insufficient, and the physical properties of the resulting cured product may be deteriorated. Conversely, the amount of Si-H groups is large. If it is too much, the cured product may be brittle and easily cracked.

  The blending amount of the component (B) is the hydrosilyl group in the component (B), that is, the Si-H group, with respect to 1 mol of alkenyl groups such as vinyl group, allyl group, cycloalkenyl group and the like contained in the component (A). Is 0.5 to 3 mol, preferably 0.8 to 2 mol. If the amount of hydrosilyl groups (≡Si—H) is too small, there is a possibility that a photocured product cannot be obtained as a result of insufficient crosslinking density, and if there are too many hydrosilyl groups, the photocurable fluoropolyether rubber The composition may foam during curing.

[(C) Photoactive hydrosilylation catalyst]
Component (C) is a photoactive hydrosilylation reaction catalyst. The photoactive hydrosilylation reaction catalyst is activated by irradiation with light, particularly 300 to 400 nm, and promotes the addition reaction between the alkenyl group in component (A) and the hydrosilyl group in component (B). It is. This photoactive hydrosilylation reaction catalyst is mainly a platinum group metal catalyst or nickel metal catalyst, and platinum group metal catalysts include platinum, palladium and rhodium metal complex compounds, nickel. Examples of the metal catalyst include nickel-based, iron-based, and cobalt-based metal complex compounds. Of these, platinum-based metal complex compounds are preferred because they are relatively easily available and exhibit good catalytic activity.

Examples of photoactive platinum-based metal complex compounds include (η ⁵ -cyclopentadienyl) tri (σ-alkyl) platinum complex compounds and β-diketonatoplatinum complex compounds. Specifically, (methyl (Cyclopentadienyl) trimethylplatinum (IV), (cyclopentadienyl) trimethylplatinum (IV), (1,2,3,4,5-pentamethylcyclopentadienyl) trimethylplatinum (IV), (cyclopenta (Dienyl) dimethylethylplatinum (IV), (cyclopentadienyl) dimethylacetylplatinum (IV), (trimethylsilylcyclopentadienyl) trimethylplatinum (IV), (methoxycarbonylcyclopentadienyl) trimethylplatinum (IV), (Dimethylphenylsilylcyclopentadienyl) trimethylcyclopentadienylplatinum (I ), Trimethyl (acetylacetonato) platinum (IV), trimethyl (3,5-heptanedionate) platinum (IV), trimethyl (methylacetoacetate) platinum (IV), bis (2,4-pentanedionato) platinum (II), bis (2,4-hexandionato) platinum (II), bis (2,4-heptanedionate) platinum (II), bis (3,5-heptanedionate) platinum (II), bis (1-phenyl) Examples include -1,3-butanedioato) platinum (II), bis (1,3-diphenyl-1,3-propanedionato) platinum (II), and bis (hexafluoroacetylacetonato) platinum (II).

  When these catalysts are used, they can be used in a solid state when they are solid catalysts. However, in order to obtain a more uniform cured product, a solution obtained by dissolving the catalyst in an appropriate solvent (A) It is preferable to use it by dissolving in the component linear polyfluoro compound.

  The type of the solvent to be used is not particularly limited as long as the catalyst is soluble, but a solvent in which part of the hydrogen atoms of the hydrocarbon group is substituted with fluorine atoms, or one of the hydrogen atoms of the hydrocarbon group. It is possible to disperse the catalyst more uniformly in the composition by using a mixed solvent of a solvent in which a part is substituted with a fluorine atom and a solvent in which all of the hydrogen atoms of the hydrocarbon group are substituted with a fluorine atom. More preferred.

  Examples of the solvent in which a part of the hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms include 1,3-bis (trifluoromethyl) benzene, 1,2-bis (trifluoromethyl) benzene, and 1,4-bis. (Trifluoromethyl) benzene, 1-methyl-3- (pentafluoroethyl) benzene, 1,1,1-trifluoro-3- [3- (trifluoromethyl) phenyl] propan-2-one, 4-fluoro Methyl 3- (trifluoromethyl) benzoate, n-butyl heptafluorobutyrate, ethyl 3,5-bis (trifluoromethyl) benzoate, 2-methyl-5- (trifluoromethyl) benzaldehyde, 2,3- And dimethoxybenzotrifluoride.

  Examples of the solvent in which all the hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms include octafluorotoluene, (1,1,2,3,3,3-hexafluoropropoxy) perfluorobenzene, pentafluoroethyl 2 , 2,2-trifluoroethyl ether, Fluorinert (manufactured by 3M), PF5060 (manufactured by 3M), perfluoropolyether oligomer and the like.

  When using a catalyst as a solution, the preferable mixing ratio of the polymer of the component (A) and the catalyst solution is in the range of 100: 0.01 to 100: 1 (mass ratio). When the addition amount of the catalyst solution is larger than this range, the physical properties of the photocured product may be lowered. On the other hand, when the amount is smaller than this range, the catalyst for the photocurable fluoropolyether rubber composition may be reduced. May cause poor dispersibility. Therefore, the concentration of the catalyst solution may be adjusted as appropriate so that it is within the range of the mixing ratio.

  Component (C) is used in an amount of 0.1 to 500 ppm in terms of mass of metal atoms (particularly in terms of mass of platinum group metal atoms or in terms of mass of nickel-based metal atoms) relative to the mass of component (A). , Preferably 1 to 100 ppm. If the amount used is too small, the photocurable fluoropolyether-based rubber composition cannot obtain sufficient photocurability, while if too large, the heat resistance of the photocured product may be adversely affected.

[(D) Hydrophobic silica powder]
In the photocurable fluoropolyether rubber composition of the present invention, as an optional component that may be added if necessary, the hydrophobic silica powder of component (D) is added as long as the effects of the present invention are not impaired. It can be added as a filler. Thereby, appropriate physical strength can be imparted to the photocured product obtained from the photocurable fluoropolyether rubber composition of the present invention. As the hydrophobic silica powder, BET specific surface area of 50 m ² / g or more, is preferred, especially those of finely divided silica of 50 to 400 m ² / g were treated hydrophobic.

When the BET specific surface area is less than 50 m ² / g, the desired physical strength of the obtained photocured product may not be obtained. When the BET specific surface area exceeds 400 m ² / g, the kneading operation becomes difficult, and the curability by light may be significantly reduced. Examples of the fine powder silica include fumed silica (dry silica), precipitated silica (wet silica), colloidal silica, and the like. Among these, fumed silica is most preferable.

  Examples of the hydrophobizing agent for the fine powder silica include organochlorosilane, organodisilazane, cyclic organopolysilazane, linear organopolysiloxane, etc. Among them, organochlorosilane, organodisilazane, cyclic organo Polysilazane is preferred.

  The amount of component (D) is 0 to 30 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 1 to 25 parts by weight, based on 100 parts by weight of component (A). is there. If the blending amount is less than 0.5 parts by mass, the physical properties of the resulting photocured product may not be adjusted. On the other hand, if it exceeds 30 parts by mass, the flow of the photocurable fluoropolyether rubber composition And the photocurability may be significantly reduced.

[(E) Reaction control agent]
In the photocurable fluoropolyether rubber composition of the present invention, as an optional component that may be added as necessary, a conventionally known reaction control agent for hydrosilylation reaction within a range not impairing the effects of the present invention. Can be blended as component (E). As a result, the photocurable fluoropolyether rubber composition can obtain better storage stability. Examples of the reaction control agent include 1-ethynyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 3-methyl-1-pentene. Examples include acetylene alcohols such as -3-ol and phenylbutynol, and acetylene compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne. In addition, a fluorine-containing acetylene alcohol compound represented by the following structural formula, a polymethylvinylsiloxane cyclic compound, an organic phosphorus compound, or the like can also be used as a reaction control agent.

  Since these reaction control agents have different control abilities depending on their chemical structures, the addition amount should be adjusted to an optimum amount. Generally, if the addition amount of the reaction control agent is too small, the long-term storage stability of the photocurable fluoropolyether rubber composition at room temperature cannot be obtained, and if the addition amount of the reaction control agent is too large, the photocuring is performed. There is a possibility that the curability of the functional fluoropolyether rubber composition becomes dull and sufficient curability cannot be obtained.

[Other ingredients]
In the photocurable fluoropolyether rubber composition of the present invention, in addition to the above components (A) to (E), a plasticizer, a viscosity modifier, a flexibility imparting agent, Various compounding agents such as an inorganic filler, an adhesion promoter, an adhesion assistant, and a silane coupling agent can be added as necessary. The compounding amount of these additives is arbitrary as long as the effects of the present invention are not impaired and the properties of the photocurable fluoropolyether rubber composition and the physical properties of the photocured product are not impaired.

  As optional plasticizers, viscosity modifiers, and flexibility-imparting agents that may be added as necessary, polyfluoromonoalkenyl compounds represented by the following formula (3) and / or the following formula (4) or The linear polyfluoro compound represented by (5) can be used.

（式（ｉｉｉ）中、ｆ１は１以上の整数、好ましくは２〜１００の整数であり、ｔは２又は３であり、且つｆ１は上記（Ａ）成分のＲｆ¹基に関するｐ＋ｑ（平均）及びｒの和、並びにｕ及びｖの和のいずれの和よりも小さいことが好ましい。）］ Rf ² − (X ′) _b CH═CH ₂ (3)
[In the formula (3), X ′ is the same as above, Rf ² is the following formula (iii), and b is 0 or 1.

(In the formula (iii), f1 is an integer of 1 or more, preferably an integer of 2 to 100, t is 2 or 3, and f1 is p + q (average) relating to the Rf ¹ group of the component (A) and preferably less than the sum of r and any sum of u and v)

_{D-O- (CF 2 CF 2} CF 2 O) c1 -D (4)
(In Formula (4), D is a group represented by the formula: C _s F _{2s + 1} — (s is 1 to 3), and c1 is an integer of 1 to 200, preferably an integer of 2 to 100. And c1 is preferably smaller than any of the sum of p + q (average) and r and the sum of u and v regarding the Rf ¹ group of the component (A).

_{D-O- (CF 2 O)} d1 (CF 2 CF 2 O) e1 -D (5)
(In the formula (5), D is a group represented by the formula: C _s F _{2s + 1} — (s is 1 to 3), and d1 and e1 are each an integer of 1 to 200, preferably 1 to 100. It is an integer, and the sum of d1 and e1 is preferably smaller than any sum of p + q (average) and r and the sum of u and v regarding the Rf ¹ group of the component (A).

Specific examples of the polyfluoromonoalkenyl compound represented by the above formula (3) include, for example, the following (note that f1 ′ below satisfies the requirements for f1).

Specific examples of the linear polyfluoro compound represented by the formulas (4) and (5) include the following (for example, the following c1 ′ and the sum of d1 ′ and e1 ′ are the above) c1 and the sum of d1 and e1 are satisfied.)
_{CF 3 O- (CF 2 CF 2} CF 2 O) c1 '-CF 2 CF 3
(In the formula, c1 ′ is an integer of 1 to 200.)
CF ₃ O — [(CF ₂ O) _{d1 ′} (CF ₂ CF ₂ O) _{e1 ′} ] —CF ₃
(In the formula, d1 ′ is an integer of 1 to 200, e1 ′ is an integer of 1 to 200, and d1 ′ + e1 ′ = 2 to 201.)

  When the compounds of formulas (3) to (5) are added, the blending amount is preferably based on (A) component in the present composition, particularly 100 parts by mass of the linear polyfluoro compound of formula (1). 1 to 300 parts by mass, more preferably 50 to 250 parts by mass. Further, the viscosity (23 ° C.) by the rotational viscometer is desirably in the range of 5 to 100,000 mPa · s for the same reason as that of the linear polyfluoro compound.

  In addition to the hydrophobic silica powder of the component (D) described above, the photocurable fluoropolyether rubber composition of the present invention can contain an inorganic filler as an optional component. As this inorganic filler, for example, , Quartz powder, fused silica powder, diatomaceous earth, calcium carbonate and other reinforcing or semi-reinforcing fillers, inorganic pigments such as iron oxide, carbon black, cobalt aluminate, titanium oxide, iron oxide, carbon black, cerium oxide, water Heat resistance improver such as cerium oxide, zinc carbonate, magnesium carbonate, manganese carbonate, thermal conductivity imparting agent such as alumina, boron nitride, silicon carbide, metal powder, conductivity imparting such as carbon black, silver powder, conductive zinc white An agent etc. can be mentioned.

  Moreover, in this invention, adhesion promoters, such as a carboxylic acid anhydride and a titanate ester, an adhesion imparting agent, and / or a silane coupling agent can further be added as needed.

[Photocurable fluoropolyether rubber composition]
The photocurable fluoropolyether-based rubber composition of the present invention has the components (A) to (C) described above, preferably components (A) to (D), more preferably components (A) to (E), Other optional components can be produced by uniformly mixing them using a mixing device such as a planetary mixer, a loss mixer, and a Hobart mixer, and if necessary, a kneading device such as a kneader or a three roll.

  The production method of the photocurable fluoropolyether rubber composition of the present invention is not particularly limited, and can be produced by kneading the above components. Also, it may be prepared as two kinds of compositions and mixed at the time of use.

  Hereinafter, an example of a method for producing a photocurable fluoropolyether rubber composition will be described for the case where the components (A) to (E) are blended. In the case of producing a composition from the components (A) to (C), the components (A) to (C) may be simply blended in order and mixed.

  As a manufacturing method of the photocurable fluoropolyether-type rubber composition containing the said (A)-(E) component, for example, (D) component is first heated or not with respect to a part or all of (A) component, for example. After blending with the component (A) under heating conditions and kneading the component (A) with the component (D) under heating / depressurization conditions or heating / pressurization conditions, finally, the predetermined A method of post-diluting with the remainder of the component (A) so that the blending ratio is obtained. According to this method, the photocuring characteristics of the photocurable fluoropolyether rubber composition can be improved.

  Here, the blending and kneading of a part or all of the component (A) and the component (D) is carried out by applying the surface of the hydrophobic silica powder as the component (D) to the linear polyfluoro compound as the component (A). In order to cover well. As a result, the (B) component is less likely to be adsorbed on the silica surface of the (D) component, or the (B) component and the (D) component are less likely to be aggregated together, whereby a photocurable fluoropolyether rubber composition. This is because the viscosity of the resin is reduced and the photocurability is improved. Mixing and kneading of part or all of the component (A) and the component (D) can be performed by a kneading apparatus such as a planetary mixer, a gate mixer, or a kneader.

  The mixing and kneading temperature and time may be appropriately determined, but the heat treatment temperature is preferably 120 to 180 ° C., and kneading is preferably performed for 1 hour or more so that the components are uniformly dispersed.

  Since the pressure at the time of blending and kneading varies depending on the apparatus used, it is preferably carried out under pressure or reduced pressure depending on the apparatus. For example, when kneading with a planetary mixer or a gate mixer, the pressure condition is preferably a reduced pressure of −0.05 MPa or less in terms of gauge pressure. Moreover, when knead | mixing with a kneader, it is preferable that the pressure conditions are under the pressurization of 0.4-0.6 MPa by a gauge pressure. The reason why the operation is performed under this condition is that the component (A) easily wets (is easy to coat) the surface of the component (D).

  In the liquid base comprising part or all of the component (A) and the component (D) obtained as described above, the remainder of the component (A), the component (B), the component (C) and the component (E) By blending, a photocurable fluoropolyether rubber composition can be obtained.

  In using the photo-curable fluoropolyether rubber composition of the present invention, an appropriate fluorine-based solvent such as 1,3-bis (trifluoromethyl) benzene, fluorinate (3M Co., Ltd.), perfluorobutyl methyl ether, perfluorobutyl ethyl ether, perfluoropolyether oligomer, or a mixture thereof may be used by dissolving it at a desired concentration. In particular, it is preferable to use a solvent in thin film coating applications.

[Photocuring Method for Photocurable Fluoropolyether Rubber Composition]
The produced photocurable fluoropolyether rubber composition can be cured by light irradiation. During curing, the irradiated light is in the region where the maximum peak wavelength in the emission spectrum is 300 to 400 nm, and the irradiance of each wavelength in the wavelength region shorter than 300 nm is preferably 5% or less of the irradiance of the maximum peak wavelength, preferably Is 1% or less, more preferably 0.1% or less, that is, the closer to 0, the better. Irradiation with light having a wavelength shorter than 300 nm and an irradiance greater than 5% of the irradiance of the maximum peak wavelength may cause degradation of polymer end groups, resulting in insufficient curability. .

The actinic ray species used for curing the photocurable fluoropolyether rubber composition of the present invention is not particularly limited, but ultraviolet rays, particularly near ultraviolet rays having a maximum peak wavelength of 300 to 400 nm are preferable. The ultraviolet irradiation amount (illuminance) for obtaining good photocurability is 100 to 100,000 mJ / cm ² , preferably 1,000 to 10,000 mJ / cm ² , more preferably 5,000 to 10 as the integrated light amount. 1,000 mJ / cm ² . When the ultraviolet irradiation amount (illuminance) is less than the above range, sufficient energy cannot be obtained to activate the photoactive hydrosilylation reaction catalyst in the photocurable fluoropolyether rubber composition. There is a possibility that a photocured product cannot be obtained. In addition, when the ultraviolet irradiation amount (illuminance) exceeds the above range, the photocurable fluoropolyether rubber composition is irradiated with more energy than necessary, and the polymer end groups are decomposed or a part of the catalyst is exposed. There is a possibility that a sufficient photocured product cannot be obtained due to inactivation.

  The ultraviolet irradiation may be light having a plurality of emission spectra or light having a single emission spectrum. The single emission spectrum may have a broad spectrum in the region from 300 nm to 400 nm. The light having a single emission spectrum is light having a peak (ie, maximum peak wavelength) in the range of 300 nm to 400 nm, preferably 350 nm to 380 nm. Examples of such a light source for irradiating light include ultraviolet light emitting semiconductor element light sources such as ultraviolet light emitting diodes (ultraviolet LEDs) and ultraviolet light emitting semiconductor lasers.

  Examples of light sources that emit light having a plurality of emission spectra include metal halide lamps, xenon lamps, carbon arc lamps, chemical lamps, sodium lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, etc. And gas lasers of organic dye solutions, liquid lasers of organic dye solutions, solid lasers in which rare earth ions are contained in inorganic single crystals, and the like.

  When the light has a peak in a wavelength region shorter than 300 nm in the emission spectrum, or a wavelength having an irradiance greater than 5% of the irradiance of the maximum peak wavelength in the emission spectrum exists in a wavelength region shorter than 300 nm When the light emission spectrum is broad (for example, when the emission spectrum is broad over a wide wavelength region), light having a wavelength in a wavelength region shorter than 300 nm is removed by the optical filter. Thereby, the irradiance of each wavelength in a wavelength region shorter than 300 nm is set to 5% or less, preferably 1% or less, more preferably 0.1% or less, more preferably 0% of the irradiance of the maximum peak wavelength. be able to. When a plurality of peaks exist in the wavelength region from 300 nm to 400 nm in the emission spectrum, the peak wavelength showing the maximum absorbance among them is set as the maximum peak wavelength. The optical filter is not particularly limited as long as it cuts a wavelength shorter than 300 nm, but a known one may be used. For example, a 365 nm band pass filter or the like can be used. The illuminance and spectral distribution of ultraviolet rays can be measured with a spectral irradiance meter such as USR-45D (USHIO).

  Although it does not specifically limit as a light irradiation apparatus, For example, irradiation apparatuses, such as a spot type irradiation apparatus, a surface type irradiation apparatus, a line type irradiation apparatus, a conveyor type irradiation apparatus, can be used.

  When the photocurable fluoropolyether rubber composition of the present invention is cured, the light irradiation time is, for example, 1 to 300 seconds, preferably 10 to 200 seconds, more preferably 30 to 150 seconds. After -60 minutes, particularly after 5 to 30 minutes, the photocurable fluoropolyether rubber composition loses fluidity, and a rubber elastic body (rubber cured product) can be obtained.

[Photocured fluoropolyether rubber cured product]
The photocurable fluoropolyether rubber composition of the present invention comprising the above components (A) to (C), preferably components (A) to (D), more preferably components (A) to (E). Can form a rubber cured product having excellent chemical resistance and solvent resistance and low moisture permeability by the photocuring method. In addition, since foaming of rubber is suppressed even when cured in a sealed state, for example, a cured rubber product having a smooth surface and providing stable rubber properties can be obtained even when cured by being sandwiched between substrates. Can do. It can also be used as a rubber-based adhesive that is sandwiched and cured between substrates that have previously been coated with a silane-based primer, and that provides adhesion between the substrates. Even in that case, since foaming of the rubber is suppressed, stable adhesive properties can be obtained.
The cured product is formed by injecting the photocurable fluoropolyether rubber composition of the present invention into a suitable container or coating it on a suitable substrate and then curing it by irradiation with light. It can be easily carried out by a conventionally known method such as sandwiching a curable fluoropolyether rubber composition and irradiating it through a transparent substrate to cure.

  The photocured fluoropolyether rubber cured product of the present invention is, for example, for automobiles, chemical plants, semiconductor production lines, analytical / physical equipment, medical equipment, fuel cells, inkjet printers, aircraft, It can be suitably used as a member for various uses such as for an organic EL panel.

  More specifically, the cured product and the rubber product containing the cured product of the present invention include, for example, automotive rubber parts, specifically diaphragms, valves, seal materials, etc .; chemical plant rubber parts, specifically Such as pump diaphragms, valves, hoses, packings, oil seals, gaskets, tank pipe repair seals, etc .; rubber parts for semiconductor production lines, specifically chemical contact devices Diaphragms for valves, valves, packing, gaskets, etc., valves that require low friction and wear resistance, etc .; rubber parts for analytical and physics equipment, specifically, diaphragms for valves, valves, seal parts ( Packing, etc.); Rubber parts for medical devices, specifically pumps, valves, joints, etc .; Rubber parts for fuel cells, specifically, sealing materials for fuel cells; Rubber parts for top printers; Rubber parts for aircraft; Rubber parts for organic EL panels; Other rubber parts, specifically, tent film materials, sealants, molded parts, extruded parts, coating materials, copier roll materials, moisture-proof for electrical use It is useful for coating materials, potting materials for sensors, sealing materials for machine tools, laminated rubber cloths, etc.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, Me represents a methyl group, and parts represent parts by mass. Moreover, a viscosity shows the measured value in 23 degreeC (based on JISK7117-1). The molecular weight indicates the number average molecular weight in terms of polystyrene in GPC analysis using a fluorinated solvent as a developing solvent. The fluorine content (%) indicates mass%.

（ｍ＋ｎ≒９０） Production of base compound for photocurable fluoropolyether rubber composition [Production Example]
Fumed silica (product name: AEROSIL) as a hydrophobic silica filler in 100 parts of a polymer represented by the following formula (6) (viscosity 9,000 mPa · s, vinyl group amount 0.013 mol / 100 g, number average molecular weight 15,700) 10 parts of R972: BET specific surface area 130 m ² / g: Nippon Aerosil Co., Ltd. product name) were added in portions using a planetary mixer and kneaded for 1 hour. Subsequently, the mixed compound pressure reduction (-0.08--0.10 MPa) heat processing was carried out at 150 degreeC for 1 hour, and after cooling, the base compound was manufactured by carrying out the dispersion process with a three roll.

(M + n ≒ 90)

[Confirmation of compatibility between linear polyfluoro compound and fluorine-containing organohydrogenpolysiloxane]
[Reference Example 1]
3.100 parts of fluorine-containing organohydrogenpolysiloxane represented by the following formula (7) with respect to 100 parts of the polymer represented by the above formula (6) (Si—H group amount 0.00500 mol / g, fluorine content; 41.1%) at room temperature (23 ° C.) with a mixing device (ARE-310 manufactured by THINKY) for 1 minute with stirring at 2,000 rpm, and then centrifuged at 2,200 rpm for 1 minute. After foaming, the mixture was allowed to stand at 23 ° C. for 1 hour, and the transparency of the mixed solution was visually confirmed. The results are shown in Table 1.

[Reference Example 2]
In Reference Example 1, from 6.12 parts of the fluorinated organohydrogenpolysiloxane represented by the above formula (7) to 6.29 parts of the fluorinated organohydrogenpolysiloxane represented by the following formula (8) (Si—H group) The transparency of the mixed solution was visually confirmed by the same operation except that the amount was changed to 0.00248 mol / g, fluorine content: 45.5%. The results are shown in Table 1.

[Reference Example 3]
In Reference Example 1, from 3.12 parts of fluorine-containing organohydrogenpolysiloxane represented by the above formula (7) to 4.16 parts of fluorine-containing organohydrogenpolysiloxane represented by the following formula (9) (Si—H group) The transparency of the mixed solution was visually confirmed by the same operation except that the amount was changed to 0.00375 mol / g, fluorine content: 46.3%. The results are shown in Table 1.

[Comparative Reference Example 1]
In Reference Example 1, from 2.12 parts of the fluorinated organohydrogenpolysiloxane represented by the above formula (7) to 2.60 parts of the fluorinated organohydrogenpolysiloxane represented by the following formula (10) (Si—H group) The transparency of the mixed solution was visually confirmed by the same operation except that the amount was changed to 0.00599 mol / g, fluorine content: 34.2%. The results are shown in Table 1.

[Comparative Reference Example 2]
In the above Reference Example 1, 2.28 parts (Si—H group) of fluorine-containing organohydrogenpolysiloxane represented by the following formula (11) from 3.12 parts of fluorine-containing organohydrogenpolysiloxane represented by the above formula (7) The transparency of the mixed solution was visually confirmed by the same operation except that the amount was changed to 0.00683 mol / g, fluorine content: 35.1%. The results are shown in Table 1.

[Comparative Reference Example 3]
In Reference Example 1, 2.55 parts of a fluorine-containing organohydrogenpolysiloxane represented by the following formula (12) (3.12 parts from the fluorine-containing organohydrogenpolysiloxane represented by the above formula (7) (Si—H group) The transparency of the mixed solution was visually confirmed by the same operation except that the amount was changed to 0.00612 mol / g, fluorine content: 37.8%. The results are shown in Table 1.

  From the results of Table 1, the fluorine-containing organohydrogenpolysiloxanes of Reference Examples 1 to 3 corresponding to the component (B) of the present invention are uniformly dissolved and dispersed with the linear polyfluoro compound of the component (A) ( On the other hand, it was confirmed that the fluorine-containing organohydrogenpolysiloxanes of Comparative Reference Examples 1 to 3 were insoluble in the linear polyfluoro compound.

[Preparation of photocurable fluoropolyether rubber composition]
[Preparation Example 1]
The base compound (110 parts) prepared in the above production example was charged with 100 parts of the polymer represented by the above formula (6) in a planetary mixer and mixed until uniform. To this, 0.11 part of 1,3-bis (trifluoromethyl) benzene solution (platinum concentration: 3.0% by mass) of (methylcyclopentadienyl) trimethylplatinum (IV), 1-ethynyl-1-hydroxycyclohexane 0.12 part of toluene solution (5.0% by mass), 6.24 parts of fluorine-containing organohydrogenpolysiloxane represented by the above formula (7) (Si-H group amount 0.00500 mol / g, fluorine content 41 .1%) were added sequentially and mixed to be uniform. Then, the photocurable fluoropolyether type rubber composition was prepared by performing defoaming operation.

[Preparation Example 2]
In Preparation Example 1, 6.24 parts of the fluorinated organohydrogenpolysiloxane represented by the formula (7) was replaced with the fluorinated organohydrogenpolysiloxane represented by the above formula (8) (Si—H group amount: 0.00248 mol). / G, fluorine content 45.5%) A photocurable fluoropolyether rubber composition was prepared in the same manner as in Preparation Example 1 except that the content was changed to 12.58 parts.

[Preparation Example 3]
In Preparation Example 1, 6.24 parts of the fluorinated organohydrogenpolysiloxane represented by the formula (7) was added to the fluorinated organohydrogenpolysiloxane represented by the above formula (9) (Si-H group content: 0.00375 mol). / G, fluorine content 46.3%) A photocurable fluoropolyether rubber composition was prepared in the same manner as in Preparation Example 1 except that the content was changed to 8.32 parts.

[Preparation Example 4]
In Preparation Example 1, 6.24 parts of the fluorinated organohydrogenpolysiloxane represented by the formula (7) was added to the fluorinated organohydrogenpolysiloxane represented by the above formula (10) (Si-H group content: 0.00599 mol). / G, fluorine content 34.2%) A photocurable fluoropolyether rubber composition was prepared in the same manner as in Preparation Example 1 except that the content was changed to 5.20 parts.

[Preparation Example 5]
In Preparation Example 1, 6.24 parts of the fluorinated organohydrogenpolysiloxane represented by the formula (7) was added to the fluorinated organohydrogenpolysiloxane represented by the above formula (11) (Si-H group content 0.00683 mol). / G, fluorine content 35.1%) A photocurable fluoropolyether rubber composition was prepared in the same manner as Preparation Example 1 except that the content was changed to 4.56 parts.

[Preparation Example 6]
In Preparation Example 1, 6.24 parts of the fluorinated organohydrogenpolysiloxane represented by the formula (7) was added to the fluorinated organohydrogenpolysiloxane represented by the above formula (12) (Si-H group content 0.00612 mol). / G, fluorine content 37.8%) A photocurable fluoropolyether rubber composition was prepared in the same manner as Preparation Example 1 except that the content was changed to 5.10 parts.

[Rubber evaluation of rubber during hermetic curing]
[Example 1]
The fluoropolyether rubber composition obtained in Preparation Example 1 was poured into a mold of (H) × (D) × (t) = 105 mm × 35 mm × 1 mm, degassed under reduced pressure, and then UV-LED (365 nm) Irradiation was performed with an irradiator at 100 mW / cm ^{2 for} 45 seconds so as to be 4,500 mJ / cm ² . After light irradiation, a glass plate was placed on the mold to form a closed system, and the state of the cured product after standing at 23 ° C. for 10 minutes was visually observed. As evaluation, the case where foaming of rubber was observed was evaluated as x, and the case where foaming was not observed was evaluated as ◯. The results are shown in Table 2.

[Example 2]
A cured product was prepared in the same manner as in Example 1 except that the fluoropolyether rubber composition used was changed from that in Preparation Example 1 to that in Preparation Example 2, and visual observation was performed. The results are shown in Table 2.

[Example 3]
A cured product was produced in the same manner as in Example 1 except that the fluoropolyether rubber composition used in Example 1 was changed from that in Preparation Example 1 to that in Preparation Example 3, and visual observation was performed. The results are shown in Table 2.

[Comparative Example 1]
A cured product was produced in the same manner as in Example 1 except that the fluoropolyether rubber composition used in Example 1 was changed from that in Preparation Example 1 to that in Preparation Example 4, and visual observation was performed. The results are shown in Table 2.

[Comparative Example 2]
A cured product was prepared in the same manner as in Example 1 except that the fluoropolyether rubber composition used in Example 1 was changed from that in Preparation Example 1 to that in Preparation Example 5, and visual observation was performed. The results are shown in Table 2.

[Comparative Example 3]
A cured product was produced in the same manner as in Example 1 except that the fluoropolyether rubber composition used in Example 1 was changed from that in Preparation Example 1 to that in Preparation Example 6, and visual observation was performed. The results are shown in Table 2.

  From the results of Table 2, in Examples 1 to 3 which are photocurable fluoropolyether rubber compositions of the present invention, foaming of rubber at the time of seal curing is suppressed, while in Comparative Examples 1 to 3, It was confirmed that foaming of rubber occurred during hermetic curing.

[Evaluation of adhesion between rubber and base material during sealing and evaluation of stability of rubber properties]
[Examples 4-6, Comparative Examples 4-6]
The photocurable fluoropolyether rubber compositions obtained in Preparation Examples 1 to 6 were each applied onto two aluminum substrates previously coated with a silane primer composition, and after degassing under reduced pressure, UV- Irradiation was performed at 100 mW / cm ^{2 for} 45 seconds with an LED (365 nm) irradiator at 4,500 mJ / cm ² . After the light irradiation, two aluminum base materials were bonded so that the thickness of the fluoropolyether rubber composition was 0.08 mm, and allowed to stand at 40 ° C./60% RH for 24 hours.
After 24 hours, the specimen was allowed to cool until it returned to room temperature (23 ° C.), and in accordance with JIS K6250, adhesion area: 25 mm × 10 mm, tensile speed: 50 mm / min. Tensile shear adhesion test was conducted to evaluate rubber adhesion. The results are shown in Table 3.

  From the results of Table 3, in Examples 4 to 6 using the photocurable fluoropolyether rubber composition of the present invention, it was confirmed that the adhesion between the rubber and the substrate was improved, and the variation in adhesion was also reduced. It has been confirmed. On the other hand, in Comparative Examples 4 to 6, it was confirmed that due to the influence of foaming of rubber during hermetic hardening, the adhesion with the base material was reduced and the variation was large.

Claims (22)

(A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and a linear perfluoropolyether structure in the main chain: 100 parts by mass;
(B) Fluorinated organohydrogenpolysiloxane having two or more hydrogen atoms (Si-H groups) directly bonded to silicon atoms in one molecule and a fluorine content of 40% by mass or more: (A) The amount that the Si-H group in the component (B) is 0.5 to 3 mol with respect to 1 mol of the alkenyl group in the component,
(C) Photoactive hydrosilylation reaction catalyst: (A) Hydrophobic silica powder having a BET specific surface area of 50 m ² / g or more and 0.1 to 500 ppm in terms of metal atom with respect to the mass of the component: 0 fluoropolyether rubber made of a light cured product of the photocurable fluoropolyether rubber composition you containing .5～30 parts by weight. The fluorine-containing organohydrogenpolysiloxane of the component (B) is an amount such that the Si—H group in the component (B) is 0.5 to 3 mol per mol of the alkenyl group in the component (A) (A The fluoropolyether rubber according to claim 1, which can be dispersed uniformly and transparently in the component (A) when mixed with the component (A). The fluoropolyether rubber according to claim 1 or 2, wherein the component (A) is a linear polyfluoro compound represented by the following formula (1).
_{CH 2 = CH- (X) a} -Rf 1 - (X ') a -CH = CH 2 (1)
[In formula (1), X _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR ¹ -CO- [where, Y is -CH ₂ -, - Si (CH _{3) 2 CH 2 CH 2 CH} 2 -, - Si (CH 3) (CH = CH 2) CH 2 CH 2 CH 2 -, - Si (CH = CH 2) 2 CH 2 CH 2 CH 2 - or the following structure Formula (Z)

(In Formula (Z), R ³ and R ⁴ are each independently —CH ₃ or —CH═CH _2. )
O-, m- or p-silylphenylene group, and R ¹ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group. X ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ² —Y′—, where Y ′ is —CH ₂ —, —CH ₂ CH _2. CH ₂ Si (CH ₃ ) ₂ —, —CH ₂ CH ₂ CH ₂ Si (CH ₃ ) (CH═CH ₂ ) —, —CH ₂ CH ₂ CH ₂ Si (CH═CH ₂ ) ₂ — or the following structural formula (Z ')

(In formula (Z ′), R ^{3 ′} and R ^{4 ′} are each independently —CH ₃ or —CH═CH _2. )
O-, m-, or p-silylphenylene group, and R ² is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group. ]. a is independently 0 or 1. Rf ¹ represents the following formula (i) or (ii)

(In formula (i), p and q are each 0 or an integer of 1-150, and the average of the sum of p and q is 2-200. R is an integer of 0-6, t is 2 or 3)

(In formula (ii), u is an integer of 1 to 200, v is an integer of 1 to 50, and t is 2 or 3.)
It is a bivalent linear perfluoropolyether group shown by these. ] The fluorine-containing organohydrogenpolysiloxane of component (B) is one or more monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group, or divalent in one molecule. The fluoropolyether rubber according to any one of claims 1 to 3, which has a perfluorooxyalkylene group . The fluoropolyether-based rubber according to any one of claims 1 to 4, wherein the fluorine-containing organohydrogenpolysiloxane of component (B) is one or more selected from the group of compounds represented by the following formula: .

The photoactive hydrosilylation reaction catalyst of component (C) is an (η ⁵ -cyclopentadienyl) tri (σ-alkyl) platinum (IV) complex compound and / or a β-diketonatoplatinum (II) complex compound. Item 6. The fluoropolyether rubber according to any one of Items 1 to 5. The photo-curable fluoropolyether base rubber composition, further to (E) as component fluoropolyether rubber according to any one of claims 1 to 6 is intended to include reaction control agent hydrosilylation reaction. (A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and a linear perfluoropolyether structure in the main chain: 100 parts by mass;
(B) Fluorinated organohydrogenpolysiloxane having two or more hydrogen atoms (Si-H groups) directly bonded to silicon atoms in one molecule and a fluorine content of 40% by mass or more: (A) The amount that the Si-H group in the component (B) is 0.5 to 3 mol with respect to 1 mol of the alkenyl group in the component,
(C) Photoactive hydrosilylation reaction catalyst: (A) 0.1 to 500 ppm in terms of metal atom with respect to the mass of the component, and
(D) Hydrophobic silica powder having a BET specific surface area of 50 m ² / g or more: 0.5 to 30 parts by mass
A cured fluoropolyether rubber comprising a step of obtaining a cured fluoropolyether rubber by irradiating a near-ultraviolet ray having a maximum peak wavelength of 300 to 400 nm to a photocurable fluoropolyether rubber composition containing To suppress foaming at the time of airtight curing. The fluorine-containing organohydrogenpolysiloxane of the component (B) is an amount such that the Si—H group in the component (B) is 0.5 to 3 mol per mol of the alkenyl group in the component (A) (A The method for suppressing foaming at the time of hermetic curing of the fluoropolyether rubber cured product according to claim 8, wherein the fluoropolyether rubber cured product can be uniformly and transparently dispersed in the component (A) when mixed with the component. ( A) A component is a linear polyfluoro compound represented by following formula (1), The method of suppressing the foaming at the time of sealing hardening of the fluoropolyether type rubber | gum cured product of Claim 8 or 9.
_{CH 2 = CH- (X) a} -Rf 1 - (X ') a -CH = CH 2 (1)
[In formula (1), X _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR ¹ -CO- [where, Y is -CH ₂ -, - Si (CH _{3) 2 CH 2 CH 2 CH} 2 -, - Si (CH 3) (CH = CH 2) CH 2 CH 2 CH 2 -, - Si (CH = CH 2) 2 CH 2 CH 2 CH 2 - or the following structure Formula (Z)

(In Formula (Z), R ³ and R ⁴ are each independently —CH ₃ or —CH═CH _2. )
O-, m- or p-silylphenylene group, and R ¹ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group. X ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ² —Y′—, where Y ′ is —CH ₂ —, —CH ₂ CH _2. CH ₂ Si (CH ₃ ) ₂ —, —CH ₂ CH ₂ CH ₂ Si (CH ₃ ) (CH═CH ₂ ) —, —CH ₂ CH ₂ CH ₂ Si (CH═CH ₂ ) ₂ — or the following structural formula (Z ')

(In formula (Z ′), R ^{3 ′} and R ^{4 ′} are each independently —CH ₃ or —CH═CH _2. )
O-, m-, or p-silylphenylene group, and R ² is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group. ]. a is independently 0 or 1. Rf ¹ represents the following formula (i) or (ii)

(In formula (i), p and q are each 0 or an integer of 1-150, and the average of the sum of p and q is 2-200. R is an integer of 0-6, t is 2 or 3)

(In formula (ii), u is an integer of 1 to 200, v is an integer of 1 to 50, and t is 2 or 3.)
It is a bivalent linear perfluoropolyether group shown by these. ] The fluorine-containing organohydrogenpolysiloxane of component (B) is one or more monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group, or divalent in one molecule. The method of suppressing foaming at the time of hermetic hardening of the fluoropolyether rubber cured product according to any one of claims 8 to 10, which has a perfluorooxyalkylene group. The fluoropolyether rubber according to any one of claims 8 to 11, wherein the fluorine-containing organohydrogenpolysiloxane of component (B) is one or more selected from the group of compounds represented by the following formulae. A method for suppressing foaming during hermetically curing a cured product.

The photoactive hydrosilylation reaction catalyst of component (C) is (η ^Five The fluoropolyether rubber curing according to any one of claims 8 to 12, which is a -cyclopentadienyl) tri (σ-alkyl) platinum (IV) complex compound and / or a β-diketonatoplatinum (II) complex compound. A method for suppressing foaming during the sealing and curing of an object. 14. The cured fluoropolyether rubber product according to claim 8, wherein the photocurable fluoropolyether rubber composition further contains a reaction control agent for hydrosilylation reaction as component (E). A method of suppressing foaming during hermetic cure. (A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and a linear perfluoropolyether structure in the main chain: 100 parts by mass;
(B) Fluorinated organohydrogenpolysiloxane having two or more hydrogen atoms (Si-H groups) directly bonded to silicon atoms in one molecule and a fluorine content of 40% by mass or more: (A) The amount that the Si-H group in the component (B) is 0.5 to 3 mol with respect to 1 mol of the alkenyl group in the component,
(C) Photoactive hydrosilylation reaction catalyst: (A) 0.1 to 500 ppm in terms of metal atom with respect to the mass of the component, and
(D) BET specific surface area is 50 m ² / G hydrophobic silica powder: 0.5-30 parts by mass
A rubber adhesive comprising a photocurable fluoropolyether rubber composition containing The fluorine-containing organohydrogenpolysiloxane of the component (B) is an amount such that the Si—H group in the component (B) is 0.5 to 3 mol per mol of the alkenyl group in the component (A) (A The rubber-based adhesive according to claim 15, which can be uniformly and transparently dispersed in the component (A) when mixed with the component. The rubber adhesive according to claim 15 or 16, wherein the component (A) is a linear polyfluoro compound represented by the following formula (1).
    CH ₂ = CH- (X) _a -Rf ¹ -(X ') _a -CH = CH ₂           (1)
[In the formula (1), X represents —CH ₂ -, -CH ₂ O-, -CH ₂ OCH ₂ -Or -Y-NR ¹ -CO- [where Y is -CH ₂ -, -Si (CH _Three ) ₂ CH ₂ CH ₂ CH ₂ -, -Si (CH _Three ) (CH = CH ₂ ) CH ₂ CH ₂ CH ₂ -, -Si (CH = CH ₂ ) ₂ CH ₂ CH ₂ CH ₂ -Or the following structural formula (Z)

(In formula (Z), R ^Three , R ^Four Are each independently -CH _Three Or -CH = CH ₂ It is. )
An o-, m- or p-silylphenylene group represented by ¹ Is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group. X ′ is —CH ₂ -, -OCH ₂ -, -CH ₂ OCH ₂ -Or -CO-NR ² -Y '-[where Y' is -CH ₂ -, -CH ₂ CH ₂ CH ₂ Si (CH _Three ) ₂ -, -CH ₂ CH ₂ CH ₂ Si (CH _Three ) (CH = CH ₂ )-, -CH ₂ CH ₂ CH ₂ Si (CH = CH ₂ ) ₂ -Or the following structural formula (Z ')

(In the formula (Z ′), R ^{3 ’} , R ^Four' Are each independently -CH _Three Or -CH = CH ₂ It is. )
An o-, m- or p-silylphenylene group represented by ² Is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group. ]. a is independently 0 or 1. Rf ¹ Is the following formula (i) or (ii)

(In formula (i), p and q are each 0 or an integer of 1-150, and the average of the sum of p and q is 2-200. R is an integer of 0-6, t is 2 or 3)

(In formula (ii), u is an integer of 1 to 200, v is an integer of 1 to 50, and t is 2 or 3.)
It is a bivalent linear perfluoropolyether group shown by these. ] The fluorine-containing organohydrogenpolysiloxane of component (B) is one or more monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group, or divalent in one molecule. The rubber-based adhesive according to any one of claims 15 to 17, which has a perfluorooxyalkylene group. The rubber-based adhesive according to any one of claims 15 to 18, wherein the fluorine-containing organohydrogenpolysiloxane as the component (B) is one or more selected from the group of compounds represented by the following formula.

The photoactive hydrosilylation reaction catalyst of component (C) is (η ^Five The rubber-based adhesive according to any one of claims 15 to 19, which is a -cyclopentadienyl) tri (σ-alkyl) platinum (IV) complex compound and / or a β-diketonatoplatinum (II) complex compound. 21. The rubber-based adhesive according to any one of claims 15 to 20, further comprising a hydrosilylation reaction control agent as component (E). The rubber adhesive according to any one of claims 15 to 21, which is photocured to bond two substrates together.