JP4997707B2 - Fluorine-containing elastomer and method for producing fluorine-containing elastomer - Google Patents

Description

  The present invention relates to a method for producing a fluorine-containing elastomer containing a group having an unsaturated bond at the main chain end and / or side chain end. The present invention also relates to a curable composition comprising the fluorine-containing elastomer and a molded product obtained by crosslinking the curable composition.

  Fluorine-containing elastomers are widely used in fields such as the automobile industry, semiconductor industry, and chemical industry as sealing materials in harsh environments because they exhibit excellent chemical resistance, solvent resistance, and heat resistance. .

  However, with the advancement of technology, the required characteristics become more severe, and in various fields such as aerospace field, semiconductor manufacturing equipment field, chemical plant field, automobile industry, etc., superior heat resistance, chemical resistance, solvent resistance And processability are required.

  In order to reinforce these various properties, a composition comprising a fluorine-containing elastomer having a vinyl group or an allyl group introduced at the terminal and a composition comprising a crosslinking agent have been developed.

  For example, Patent Document 1 discloses a chemically connectable mixture of a fluoroelastomer having a lateral olefin double bond and a silicon oligomer, a silicon elastomer, or a Si-H group-containing fluorosilicone elastomer. However, the fluoroelastomer having side olefinic double bonds is obtained by copolymerizing a small amount of monomers containing at least two olefinic double bonds, such as alkenyl isocyanurate, alkenyl cyanurate and / or non-conjugated dienes. In this method, since it is difficult to control the introduction position of the double bond, it is not possible to obtain a fluoroelastomer having an olefin double bond introduced at the end of the main chain.

  Therefore, development of a method for economically and simply introducing a site having an unsaturated bond at the terminal of the fluorine-containing elastomer is eagerly desired.

JP-A-6-192524

  The present invention provides a method for producing a fluorine-containing elastomer containing a group having an unsaturated bond at the main chain end and / or side chain end. Moreover, the curable composition which consists of this fluorine-containing elastomer, and the molded article obtained by bridge | crosslinking this curable composition are provided.

  That is, the present invention relates to a fluorine-containing elastomer containing iodine or bromine at the main chain terminal and / or side chain terminal, with the general formula (1):

（式中、Ｒ¹は、同じかまたは異なり、一般式（２）：

Wherein R ¹ are the same or different and are represented by the general formula (2):

（式中、Ｘ¹、Ｘ²、Ｘ³は同じかまたは異なり、水素原子、フッ素原子、−ＣＹ¹ ₃（Ｙ¹は同じかまたは異なりフッ素原子または水素原子である）であり、Ｚは、水素原子、フッ素原子、塩素原子、硫黄原子、窒素原子、ケイ素原子、リン原子を含んでも良い炭素数１〜２０のｎ価の有機基であり、ｎは２〜７の整数である）
で示される化合物を付加させて主鎖末端および／または側鎖末端に一般式（３）：

Wherein X ¹ , X ² and X ³ are the same or different and are a hydrogen atom, a fluorine atom or —CY ¹ ₃ (Y ¹ is the same or different, a fluorine atom or a hydrogen atom), and Z is A hydrogen atom, a fluorine atom, a chlorine atom, a sulfur atom, a nitrogen atom, a silicon atom, or a phosphorus atom, and an n-valent organic group having 1 to 20 carbon atoms, where n is an integer of 2 to 7)
The compound represented by general formula (3) is added to the main chain terminal and / or the side chain terminal:

または、一般式（４）：

Or, general formula (4):

（式中Ｒ¹、Ｘ¹、Ｘ²、Ｘ³、Ｚ、ｎは前記と同様であり、Ｙ²はヨウ素原子、臭素原子または水素原子である）
で示される部位を導入する工程を含む含フッ素エラストマーの製造方法に関する。

(Wherein R ¹ , X ¹ , X ² , X ³ , Z and n are the same as above, and Y ² is an iodine atom, a bromine atom or a hydrogen atom)
The manufacturing method of a fluorine-containing elastomer including the process of introduce | transducing the site | part shown by these.

  Furthermore, the general formula (5)

（式中、Ｒ²は同じかまたは異なり、置換または非置換の１価の炭化水素基、Ｘ⁴は同じかまたは異なり、加水分解性基、ｂは１〜３の整数）
で示されるオルガノハイドロジェンシランと触媒の存在下に反応させて、
前記一般式（３）または（４）で示される部位を、一般式（６）：
−ＳｉＲ² _3-bＸ⁴ _b （６）
で示される加水分解性シリル基を有する構造に変換する工程を含むことが好ましい。

(Wherein R ² is the same or different and is a substituted or unsubstituted monovalent hydrocarbon group, X ⁴ is the same or different, a hydrolyzable group, b is an integer of 1 to 3)
In the presence of a catalyst with an organohydrogensilane represented by
The site represented by the general formula (3) or (4) is represented by the general formula (6):
-SiR ² _3-b X ⁴ _b (6)
It is preferable to include the process of converting into the structure which has a hydrolyzable silyl group shown by these.

  Further, the structure represented by the general formula (3) or (4) is reacted with an organosilicon compound having two or more —SiH groups in one molecule in the presence of a catalyst. It is preferable to include the step of converting into

  The present invention also provides a compound represented by the general formula (7):

（式中、Ｍはテトラフルオロエチレンおよび／またはビニリデンフルオライドからなる重合体であり、ａは１以上の整数であり、Ｂは一般式（３）：

(In the formula, M is a polymer composed of tetrafluoroethylene and / or vinylidene fluoride, a is an integer of 1 or more, and B is the general formula (3):

または、一般式（４）：

Or, general formula (4):

（式中、Ｒ¹は、同じかまたは異なり、一般式（２）：

Wherein R ¹ are the same or different and are represented by the general formula (2):

（式中、Ｘ¹、Ｘ²、Ｘ³は同じかまたは異なり、水素原子、フッ素原子、−ＣＹ¹ ₃（Ｙ¹は同じかまたは異なりフッ素原子または水素原子である）、Ｘ¹、Ｘ²、Ｘ³は前記と同様であり、Ｙ²はヨウ素原子、臭素原子または水素原子であり、Ｚは、水素原子、フッ素原子、塩素原子、窒素原子、硫黄原子、ケイ素原子、リン原子を含んでも良い炭素数１〜２０のｎ価の有機基であり、ｎは２〜７の整数である）で示される含フッ素エラストマーに関する。

Wherein X ¹ , X ² and X ³ are the same or different and are a hydrogen atom, a fluorine atom, —CY ¹ ₃ (Y ¹ is the same or different, a fluorine atom or a hydrogen atom), X ¹ , X ² X ³ is the same as above, Y ² is an iodine atom, a bromine atom or a hydrogen atom, and Z may contain a hydrogen atom, a fluorine atom, a chlorine atom, a nitrogen atom, a sulfur atom, a silicon atom or a phosphorus atom. It is a good n-valent organic group having 1 to 20 carbon atoms, and n is an integer of 2 to 7).

  The fluorine-containing elastomer is preferably a vinylidene fluoride-based fluororubber.

The present invention provides the general formula (6):
-SiR ² _3-b X ⁴ _b (6)
(Wherein R ² is the same or different and is a substituted or unsubstituted monovalent hydrocarbon group, X ⁴ is the same or different, a hydrolyzable group, b is an integer of 1 to 3)
The fluorine-containing elastomer which consists of a vinylidene fluoride type fluororubber containing the site | part which has a hydrolyzable silyl group shown by these.

  The number average molecular weight is preferably 500 to 500,000.

  Furthermore, the present invention relates to a curable composition comprising a fluorine-containing elastomer and a molded product obtained by crosslinking the curable composition.

In the production method of the present invention, an unsaturated group can be introduced into a specific part of the main chain and / or side chain, particularly at the end of the main chain, and the introduction position can be controlled. Moreover, since the obtained fluorine-containing elastomer can introduce a group having an unsaturated bond at the main chain terminal and / or side chain terminal, by crosslinking the curable composition comprising the fluorine-containing elastomer, A molded product having excellent heat resistance and small compression set (CS) can be obtained. Moreover, the curable composition comprising the fluorine-containing elastomer is excellent in processability and can form a molded product having a complicated shape. Moreover, since this fluorine-containing elastomer has a highly reactive unsaturated group, it is also possible to convert the unsaturated group and introduce a different functional group.

  The present invention relates to a fluorine-containing elastomer containing iodine or bromine at the main chain terminal and / or side chain terminal, with the general formula (1):

（式中、Ｒ¹は、同じかまたは異なり、一般式（２）：

Wherein R ¹ are the same or different and are represented by the general formula (2):

（式中、Ｘ¹、Ｘ²、Ｘ³は同じかまたは異なり、水素原子、フッ素原子、−ＣＹ¹ ₃（Ｙ¹は同じかまたは異なりフッ素原子または水素原子である）であり、Ｚは、水素原子、フッ素原子、塩素原子、硫黄原子、窒素原子、ケイ素原子、リン原子を含んでも良い炭素数１〜２０のｎ価の有機基であり、ｎは２〜７の整数である）
で示される化合物を付加させて主鎖末端および／または側鎖末端に一般式（３）：

Wherein X ¹ , X ² and X ³ are the same or different and are a hydrogen atom, a fluorine atom or —CY ¹ ₃ (Y ¹ is the same or different, a fluorine atom or a hydrogen atom), and Z is A hydrogen atom, a fluorine atom, a chlorine atom, a sulfur atom, a nitrogen atom, a silicon atom, or a phosphorus atom, and an n-valent organic group having 1 to 20 carbon atoms, where n is an integer of 2 to 7)
The compound represented by general formula (3) is added to the main chain terminal and / or the side chain terminal:

または、一般式（４）：

Or, general formula (4):

（式中Ｒ¹、Ｘ¹、Ｘ²、Ｘ³、Ｚ、ｎは前記と同様であり、Ｙ²はヨウ素原子、臭素原子または水素原子である）
で示される部位を導入する工程を含む含フッ素エラストマーの製造方法に関する。

(Wherein R ¹ , X ¹ , X ² , X ³ , Z and n are the same as above, and Y ² is an iodine atom, a bromine atom or a hydrogen atom)
The manufacturing method of a fluorine-containing elastomer including the process of introduce | transducing the site | part shown by these.

X ¹ , X ² and X ³ in the general formula (2) are the same or different and are a hydrogen atom, a fluorine atom or —CY ¹ ₃ (Y ¹ is the same or different and is a fluorine atom or a hydrogen atom). However, among these, a fluorine atom and —CF ₃ are preferable from the viewpoint of excellent heat resistance of the group having an unsaturated bond to be introduced, and from the viewpoint of excellent reactivity of the curing reaction by hydrosilylation reaction using the unsaturated bond. , A hydrogen atom, and —CH ₃ are preferable.

  Z is an n-valent organic group having 1 to 20 carbon atoms. Moreover, a hydrogen atom, a fluorine atom, a chlorine atom, a nitrogen atom, a sulfur atom, a silicon atom, or a phosphorus atom may be included.

  n is an integer of 2 to 7, preferably an integer of 2 to 5, more preferably an integer of 2 to 3, and further preferably 2. When n is 1, the moiety represented by the general formula (3) or (4) cannot be introduced into the terminal of the fluorine-containing elastomer, and when it exceeds 7, the main chain terminal and / or the side chain terminal When added, the fluorine-containing elastomer tends to gel.

  Specifically, as Z,

などをあげることができる。

Etc.

  Examples of the compound represented by the general formula (1) include triallyl cyanurate, triallyl isocyanurate (TAIC), tris (diallylamine) -s-triazine, triallyl phosphite, N, N-diallyl-acrylamide, N , N, N ′, N′-tetraallyl-malonamide, trivinyl isocyanurate, 2,4,6-trivinyl-methyltrisiloxane, N, N′-bisallylbicyclo-oct-7-ene-disuccinimide (BOSA) Diallyl isocyanurate, diallyldimethylsilane, 1,3-divinyltetramethyldisiloxane, N, N-diallyl-2,2,2-trifluoroacetamide, trimethacryl isocyanate, triallyl formal, triallyl trimellitate, N N′-m-phenylene bismaleimide, di Propagyl terephthalate, diallyl phthalate, tetraallyl terephthalate amide, triallyl phosphate, N, N'-diallyl urea, N, N-diallyl-acetamide, general formula (8):

（式中、Ｘ⁵はそれぞれ同じかまたは異なり、水素原子、塩素原子、フッ素原子、炭素数１〜３のアルキル基またはパーフルオロアルキル基であり、ｍは２〜２０の整数であり、４〜１２の整数であることが好ましく、４〜８の整数であることがより好ましい)
で示されるトリアジンのトリオレフィン、一般式（９）：

(Wherein X ⁵ is the same or different and is a hydrogen atom, a chlorine atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms or a perfluoroalkyl group, m is an integer of 2 to 20, It is preferably an integer of 12 and more preferably an integer of 4 to 8)
A triolefin of a triazine represented by the general formula (9):

（式中、Ｘ⁶は、水素原子または炭素数１〜１０のフッ素原子を含んでいてもよい炭化水素基である）
で示される化合物、一般式（１０）：

(Wherein X ⁶ is a hydrogen atom or a hydrocarbon group optionally containing a fluorine atom having 1 to 10 carbon atoms)
A compound represented by the general formula (10):

（式中、Ｘ⁷は、それぞれ同じかまたは異なり、水素原子、塩素原子、フッ素原子、炭素数１〜３のアルキル基またはパーフルオロアルキル基であり、ｍは２〜２０の整数であり、４〜１２の整数であることが好ましく、４〜８の整数であることがより好ましい）で示されるトリアジンのビスオレフィン、

(Wherein X ⁷ is the same or different and is a hydrogen atom, a chlorine atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms or a perfluoroalkyl group, m is an integer of 2 to 20, An integer of ˜12, more preferably an integer of 4˜8).

などがあげられる。

Etc.

  Among these, as the compound represented by the general formula (1), a compound of n = 2 is preferable from the viewpoint of preventing gelation of the fluorine-containing elastomer upon introduction by addition reaction. In addition, diallyl isocyanurate, N, N′-diallyl urea, and isocyanuric acid diallyl methyl ester are preferred from the viewpoint of heat resistance at the crosslinking point. On the other hand, in order to prevent an increase in the viscosity of the fluorine-containing elastomer due to aggregation of crosslinking points, a compound that does not generate a hydrogen bond, for example, a compound that does not have a structure of -C (= O) NH- is preferable. 3-divinyltetramethyldisiloxane, N, N-diallyl-2,2,2-trifluoroacetamide, N, N-diallyl-acetamide, isocyanuric acid diallylmethyl ester,

が好ましい。

Is preferred.

  In the production method of the present invention, the compound represented by the general formula (1) is added to a fluorine-containing elastomer containing iodine or bromine at the main chain end and / or the side chain end, thereby obtaining the general formula (3):

または、一般式（４）：

Or, general formula (4):

（式中Ｒ¹、Ｘ¹、Ｘ²、Ｘ³、Ｚ、ｎは前記と同様であり、Ｙ²はヨウ素原子、臭素原子または水素原子である）
で示される不飽和結合を有する部位へ経済的にかつ簡便に変換することが可能となる。

(Wherein R ¹ , X ¹ , X ² , X ³ , Z and n are the same as above, and Y ² is an iodine atom, a bromine atom or a hydrogen atom)
It is possible to economically and easily convert to the site having an unsaturated bond represented by

  Moreover, in the method of this invention, the group which has an unsaturated group can be introduce | transduced through the specific structure to the principal chain terminal and / or side chain terminal of a fluorine-containing elastomer. In this introduction, since an unsaturated group can be introduced in a one-step reaction, an unsaturated group can be easily introduced, and by changing the structure of Z, desired characteristics derived from the structure of Z can be obtained. It can be introduced into the elastomer. By crosslinking such a curable composition comprising a fluorine-containing elastomer, a molded product having excellent heat resistance and a small compression set (CS) can be obtained.

  The fluorine-containing elastomer used in the present invention is not particularly limited as long as it is a fluorine-containing elastomer containing iodine or bromine at the main chain terminal and / or side chain terminal.

  As a method of introducing iodine or bromine into the main chain end and / or side chain end, a method of copolymerizing a monomer having iodine or bromine at the time of polymerization of the fluorine-containing elastomer, or polymerization by iodine transfer polymerization as described later. And how to do it.

  Examples of the fluorine-containing elastomer include fluororubber (a), thermoplastic fluororubber (b), and rubber compositions composed of these fluororubbers. Among these, fluororubber (a) is preferable.

  Examples of the fluororubber (a) include non-perfluorofluororubber (a-1) and perfluorofluororubber (a-2). In addition, perfluoro fluororubber means the thing which 90 mol% or more consists of a perfluoro monomer among the structural units.

  Non-perfluoro fluororubber (a-1) includes vinylidene fluoride (VdF) fluororubber, tetrafluoroethylene (TFE) / propylene fluororubber, tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF). Fluorine rubber, ethylene / hexafluoropropylene (HFP) fluorine rubber, ethylene / hexafluoropropylene (HFP) / vinylidene fluoride (VdF) fluorine rubber, ethylene / hexafluoropropylene (HFP) / tetrafluoroethylene (TFE) Fluororubbers, fluorosilicone fluororubbers, fluorophosphazene fluororubbers, etc., and these can be used alone or in any combination as long as the effects of the present invention are not impaired. Two isopropylidene fluoride (VdF) type fluorine-containing rubbers, it is preferable to use a tetrafluoroethylene (TFE) / propylene fluorine rubber.

  As the vinylidene fluoride (VdF) -based fluororubber, those represented by the following general formula (11) are preferable.

^{- (M 1) - (M} 2) - (N 1) - (11)
(In the formula, the structural unit M ¹ is a structural unit derived from vinylidene fluoride (m ¹ ), the structural unit M ² is a structural unit derived from a fluorine-containing ethylenic monomer (m ² ), and the structural unit N ¹ Is a repeating unit derived from the monomer (m ¹ ) and the monomer (n ¹ ) copolymerizable with the monomer (m ² )
Formula (11) Among the vinylidene fluoride (VdF) fluorine rubber represented by the structural unit M ¹ 45 to 85 mol%, preferably not containing a structural unit M ² from 55 to 15 mol%, more preferably structure The unit M ¹ is 50 to 80 mol%, and the structural unit M ² is 50 to 20 mol%. The structural unit N ¹ is preferably 0 to 10 mol% with respect to the total amount of the structural unit M ¹ and the structural unit M ² .

As the fluorine-containing ethylenic monomer (m ² ), one or more monomers can be used. For example, tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), trifluoroethylene, hexafluoro Fluorine-containing monomers such as propylene (HFP), trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, perfluoro (alkyl vinyl ether) (PAVE), and vinyl fluoride can be mentioned. Of these, tetrafluoroethylene, hexafluoropropylene, and perfluoro (alkyl vinyl ether) are preferable.

The monomer (n ¹ ) may be any monomer as long as it is copolymerizable with the monomer (m ¹ ) and the monomer (m ² ). For example, ethylene, propylene, alkyl vinyl ether, etc. can give.

The monomer (n ¹ ) is preferably a monomer that gives a cross-linked site.

As a monomer that gives such a crosslinking site, the general formula (12):
CY ³ ₂ = CY ³ −R _f ¹ CHR ³ X ⁸ (12)
Wherein Y ³ is a hydrogen atom, a fluorine atom or —CH ₃ , R _f ¹ is a fluoroalkylene group, a perfluoroalkylene group, a fluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group, and R ³ is a hydrogen atom Atom or —CH ₃ , X ⁸ is an iodine atom or a bromine atom), or an iodine or bromine-containing monomer represented by the general formula (13):
_{CF 2 = CFO (CF 2 CF} (CF 3) O) m (CF 2) n -X 9 (13)
(Wherein, m is an integer of 0 to 5, n is an integer of 1 to 3, X ⁹ is a cyano group, a carboxyl group, an alkoxycarbonyl group, a bromine atom, an iodine atom), General formula (14):
CH ₂ = CH (CF ₂ ) _p I (14)
(Wherein p is an integer of 1 to 10) and the like, and examples thereof include perfluoro (described in JP-B-5-63482 and JP-A-7-316234). Iodine-containing monomers such as 6,6-dihydro-6-iodo-3-oxa-1-hexene) and perfluoro (5-iodo-3-oxa-1-pentene), described in JP-A-4-217936 Iodine-containing monomers such as CF ₂ = CFOCF ₂ CF ₂ CH ₂ I, bromine-containing monomers described in JP-A-4-505341, JP-A-4-505345, JP-A-5-500070 And cyano group-containing monomers, carboxyl group-containing monomers, alkoxycarbonyl group-containing monomers, and the like as described in Japanese Patent Publication. These can be used alone or in any combination.

  Specific examples of such vinylidene fluoride (VdF) -based fluororubber include VdF-HFP rubber, VdF-HFP-TFE rubber, VdF-CTFE rubber, VdF-CTFE-TFE rubber, and the like. It is done.

As the tetrafluoroethylene (TFE) / propylene-based fluororubber, those represented by the following general formula (15) are preferable.
^{- (M 3) - (M} 4) - (N 2) - (15)
(In the formula, the structural unit M ³ is a structural unit derived from tetrafluoroethylene (m ³ ), the structural unit M ⁴ is a structural unit derived from propylene (m ⁴ ), and the structural unit N ² is a monomer (m ³ ) and repeating unit derived from monomer (n ² ) copolymerizable with monomer (m ⁴ ))

Formula Among tetrafluoroethylene (TFE) / propylene fluorine rubber represented by (15), the structural unit M ³ 40 to 70 mol%, preferably not containing a structural unit M ⁴ 60 to 30 mol%, more preferably it is a structural unit M ³ 50-60 mol%, in which the structural unit M ⁴ 50-40 mol%. The structural unit N ² is preferably 0 to 40 mol% with respect to the total amount of the structural unit M ³ and the structural unit M ⁴ .

The monomer (n ² ) may be any monomer that can be copolymerized with the monomer (m ³ ) and the monomer (m ⁴ ). Is preferred. Examples thereof include vinylidene fluoride and ethylene.

As perfluoro fluororubber (a-2), what is represented by following General formula (16) is preferable.
^{- (M 5) - (M} 6) - (N 3) - (16)
(In the formula, structural unit M ⁵ is a structural unit derived from tetrafluoroethylene (m ⁵ ), structural unit M ⁶ is a structural unit derived from perfluoro (alkyl vinyl ether) (m ⁶ ), and structural unit N ³ is (It is a repeating unit derived from the monomer (m ³ ) and the monomer (n ³ ) copolymerizable with the monomer (m ⁶ ))

Among the perfluoro fluorine-containing rubbers represented by the general formula (16) (a-2) , the structural unit M ⁵ 50 to 90 mol%, preferably not containing a structural unit M ⁶ 10 to 50 mol%, more preferably structure unit M ⁵ 50 to 80 mol%, which comprises a structural unit M ⁶ 20 to 50 mol%, more preferably a structural unit M ⁵ 55 to 70 mol%, the structural unit M ⁶ 30-45 mole% containing It is a waste. The structural unit N ³ is preferably 0 to 5 mol%, more preferably 0 to 2 mol%, based on the total amount of the structural unit M ⁵ and the structural unit M ⁶ . When the composition is out of the range, the properties as a rubber elastic body are lost, and the properties tend to be similar to those of a resin.

Examples of perfluoro (alkyl vinyl ether) (m ⁶ ) include perfluoro (methyl vinyl ether) and perfluoro (propyl vinyl ether), and these can be used alone or in any combination.

The monomer (n ³ ) may be any monomer as long as it is copolymerizable with the monomer (m ⁵ ) and the monomer (m ⁶ ). preferable.

Examples of the monomer that gives such a crosslinking site include vinylidene fluoride, an iodine or bromine-containing monomer represented by the general formula (12), a monomer represented by the general formula (13), and a general formula (14) and the like, and examples thereof include perfluoro (6,6-dihydro-6-iodo as described in JP-B-5-63482 and JP-A-7-316234. Iodine-containing monomers such as -3-oxa-1-hexene) and perfluoro (5-iodo-3-oxa-1-pentene), CF ₂ = CFOCF ₂ CF ₂ CH described in JP-A-4-217936 iodine-containing monomers such as ₂ I, bromine-containing monomers disclosed in JP-a-4-505341, JP-a-4-505345 and JP-are described in JP-a-5-500070 Cyano group-containing monomers such carboxyl group-containing monomers, and alkoxycarbonyl group-containing monomers and the like. These can be used alone or in any combination.

  With the iodine atom and bromine atom, the compound represented by the general formula (1) can undergo an addition reaction. In addition, a vinyl group, an iodine atom, a bromine atom, a cyano group, a carboxyl group, and an alkoxycarbonyl group can function as a crosslinking point.

  Specific examples of such perfluoro fluororubber (a-2) include International Publication No. 97/24381, Japanese Patent Publication No. 61-57324, Japanese Patent Publication No. 4-81608, Japanese Patent Publication No. 5-13961, and the like. Examples thereof include fluororubber described.

  The fluororubber (a) preferably has a number average molecular weight of 1,000 to 500,000.

  On the other hand, it is preferable that the fluororubber (a) has fluidity at room temperature in that a molded product having a complicated shape can be easily obtained and on-site construction molds can be formed. The above “normal temperature” means 0 to 50 ° C.

  Specifically, the fluororubber (a) having fluidity at room temperature preferably has a viscosity at room temperature of 0.1 to 2000 Pa · s, and more preferably 1 to 1000 Pa · s. If the viscosity is less than 0.1 Pa · s, the polymer chain tends to be too short to be crosslinked, and if it exceeds 2000 Pa · s, it may not have fluidity at room temperature, and the molded product has a complicated shape. Tend to be difficult to obtain.

  Further, the fluororubber (a) having fluidity at room temperature preferably has a Mooney viscosity at room temperature of 5 to 100, and more preferably 50 to 75. If the Mooney viscosity is less than 5, the polymer chain tends to be too short to be crosslinked, and if it exceeds 100, it may not have fluidity at room temperature and it is difficult to obtain a molded product having a complicated shape. Tend to be. The Mooney viscosity is a value obtained by measurement using a Mooney viscometer MV2000 (manufactured by Monsanto) in accordance with JIS K 6300 (1994).

  And as for the fluororubber (a) which has fluidity at normal temperature, it is preferable that a number average molecular weight is 500-20000, and it is more preferable that it is 900-10000. If the number average molecular weight is less than 500, it tends to be difficult to form a three-dimensional network structure by crosslinking, and if it exceeds 20000, it may not have fluidity at room temperature, and a molded product having a complicated shape is obtained. Tend to be difficult. The number average molecular weight is a value determined by size exclusion chromatography (HLC-8020 manufactured by Tosoh Corporation, polystyrene standard).

The non-perfluorofluororubber (a-1) and the perfluorofluororubber (a-2) described above can be produced by a conventional method, but the obtained polymer has a narrow molecular weight distribution and the molecular weight can be easily controlled. From the point that iodine atoms can be introduced into the terminal, a known iodine transfer polymerization method is preferred as a method for producing fluororubber. For example, radical initiation in the absence of oxygen, preferably in the presence of an iodine compound, preferably a diiodine compound, while stirring the ethylenic monomer and, if necessary, a monomer that provides a crosslinking site under pressure. Examples of the method include emulsion polymerization or aqueous solution polymerization in an aqueous medium in the presence of an agent. As a representative example of the iodine compound to be used, for example, the general formula (17):
R ⁴ I _x Br _y (17)
(Wherein x and y are each an integer of 0 to 2 and satisfy 1 ≦ x + y ≦ 2, and R ⁴ is a saturated or unsaturated fluorohydrocarbon group having 1 to 16 carbon atoms or chlorofluoro A hydrocarbon group, or a hydrocarbon group having 1 to 3 carbon atoms, which may contain an oxygen atom). An iodine atom or a bromine atom is introduced into the terminal of the fluorine-containing elastomer obtained using such an iodine compound.

Examples of the compound represented by the general formula (17) include 1,3-diiodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1,5. -Diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluoro hexadecane, diiodomethane, 1,2-diiodoethane, 1,3-diiodo -n- _{propane, CF 2 Br 2, BrCF 2} CF 2 Br, CF 3 CFBrCF 2 Br, CFClBr 2, BrCF 2 CFClBr, CFBrClCFClBr, BrCF 2 CF 2 _{CF 2 Br, BrCF 2 CFBrOCF 3} , 1- bromo-2-iodo -Fluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, 3-bromo-4-iodoperfluorobutene-1, 2- Bromo-4-iodoperfluorobutene-1, benzene monoiodomonobromo-substituted, diiodo-substituted, (2-iodoethyl) and (2-bromoethyl) -substituted, etc. They may be used or may be used in combination with each other.

  Among these, 1,4-diiodoperfluorobutane, diiodomethane, and the like are preferable from the viewpoints of polymerization reactivity, crosslinking reactivity, availability, and the like.

  The radical polymerization initiator used in the present invention may be the same as that conventionally used for the polymerization of fluorine-containing elastomers. These initiators include organic and inorganic peroxides and azo compounds. Typical initiators include persulfates, carbonate peroxides, peroxide esters and the like, and a preferred initiator is ammonium persulfate (APS). APS may be used alone or in combination with a reducing agent such as sulfites and sulfites.

  A wide range of emulsifiers can be used as the emulsion polymerization. From the viewpoint of suppressing the chain transfer reaction to the emulsifier molecule that occurs during the polymerization, the carboxylic acid having a fluorocarbon chain or a fluoropolyether chain is used. Salts are desirable. The amount of the emulsifier used is preferably about 0.05 to 2% by weight, more preferably 0.2 to 1.5% by weight, of the added water.

  The monomer mixed gas used in the present invention is explosive as described in GH Kalb et al., Advances in Chemistry Series., 129, 13 (1973). Therefore, it is necessary to devise a polymerization apparatus so as not to generate a spark or the like as an ignition source.

  The polymerization pressure can be varied within a wide range. Generally, it is the range of 0.5-7MPa. The higher the polymerization pressure, the higher the polymerization rate. Therefore, from the viewpoint of improving productivity, the polymerization pressure is preferably 0.8 MPa or more.

  The amount of the compound represented by the general formula (17) may be appropriately changed in order to adjust the molecular weight of the fluorine-containing elastomer, but is 0.0001 to 15% by weight of the total weight of the fluorine-containing elastomer to be obtained. %.

  Furthermore, in the present invention, a composition comprising the fluororubber as described above can also be used.

  The method for adding the compound represented by the general formula (1) to the fluorine-containing elastomer containing iodine or bromine at the main chain terminal and / or the side chain terminal is not particularly limited, and the fluorine-containing elastomer, general formula ( Optimum conditions may be selected as appropriate depending on the type of the compound, solvent and the like shown in 1), but the reaction is preferably carried out at 50 to 250 ° C. for 0.1 to 20 hours.

  The amount of the compound represented by the general formula (1) is preferably 1.2 to 20 times the molar amount relative to the iodine or bromine content of the fluorine-containing elastomer, preferably 2 to 10 times the molar amount. More preferably. If the amount of the compound represented by the general formula (1) is less than 1.2 times the molar amount, the compound represented by the general formula (1) tends to be insufficiently introduced, and exceeds the 20 times molar amount. And only the cost for introducing the compound represented by the general formula (1) increases, and there is no merit.

  Moreover, as a solvent used for the addition reaction, a solvent having a structure that hardly causes radical chain is preferable because side reactions can be suppressed, and a solvent that dissolves rubber is more preferable in order to increase the reaction rate.

  As the solvent having a structure that hardly causes radical chain, a solvent having a structure that does not have a hydrogen atom that is easily extracted by a radical reaction is preferable.

  Specifically, alcohols are preferable from the viewpoint of rubber solubility and radical stability, and nitriles, ketones, esters, ethers, and chlorofluorocarbon solvents are preferable from the viewpoint of rubber solubility and radical stability. Nitriles and chlorofluorocarbon solvents are more preferable.

  As the alcohols, alcohols having 15 or less carbon atoms are preferable and alcohols having 7 or less carbon atoms are more preferable from the viewpoint of rubber solubility and radical stability. Specific examples include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, phenol, and the like. Among these, methanol is preferable from the viewpoint of rubber solubility.

  Nitriles are preferably those having 10 or less carbon atoms, more preferably those having 8 or less carbon atoms, from the viewpoint of rubber solubility and radical stability. Specific examples include acetonitrile, ethyl cyanide, butyronitrile, butyl cyanide, and benzonitrile. Among these, acetonitrile is preferable because of its high rubber solubility.

  The ketones are preferably those having 10 or less carbon atoms, more preferably those having 6 or less carbon atoms, from the viewpoint of rubber solubility and radical stability. Specific examples include acetone, dimethyl ketone, methyl ethyl ketone, diethyl ketone, and cyclohexanone.

  Esters are preferably those having 10 or less carbon atoms, more preferably those having 6 or less carbon atoms, from the viewpoint of rubber solubility and radical stability. Specific examples include methyl acetate, ethyl acetate, butyl acetate, propyl acetate and the like.

  The ethers are preferably those having 10 or less carbon atoms, more preferably those having 6 or less carbon atoms, from the viewpoint of rubber solubility and radical stability. Specific examples include tetrahydrofuran, monoglyme, diglyme, and tetraglyme.

As the chlorofluorocarbon solvent, those having 10 or less carbon atoms are preferable and those having 6 or less carbon atoms are more preferable from the viewpoint of rubber solubility and radical stability. Specifically, a mixture of CF ₃ CF ₂ CHCl ₂ and CClF ₂ CF ₂ CHClF (Asahi Glass AK-225, manufactured by Asahi Glass Co., Ltd.) or CH ₃ CFCl ₂ (HCFC-141b, manufactured by Daikin Industries, Ltd.) Can be given.

  The addition amount of the solvent is not particularly limited, but is preferably 500 to 5000 parts by weight with respect to 100 parts by weight of the fluorine-containing elastomer.

  Further, in the present invention, an oxidizing agent is allowed to act on the fluorine-containing elastomer having the site represented by the general formula (3) or (4) at the main chain end and / or the side chain end, so that the general formula (3) or A step of converting the site represented by the formula (4) into a structure containing —COOH may be included.

  The oxidizing agent is not particularly limited. For example, any oxidizing agent described in, for example, the Chemical Society of Japan, 5th edition, Experimental Chemistry Course Vol. 17, 2004 Maruzen Co., Ltd. can be used. Specifically, hypochlorite, chromic acid, manganese compound, osmium tetroxide, ruthenium tetroxide, copper compound, palladium compound, iron compound, vanadium compound, metal oxide, oxygen, ozone, etc. are preferable, chromic acid Permanganate, activated manganese dioxide, manganese (III) salt, osmium tetroxide, and ruthenium tetroxide are more preferred.

  As addition amount of an oxidizing agent, it is preferable that it is 1-50 times mole amount of content of the site | part shown by general formula (3) or (4) of a fluorine-containing elastomer, and it should be 2-50 times mole amount. Is more preferable, and from the viewpoint of high conversion efficiency to -COOH, the molar amount is more preferably 5 to 20 times. If the amount is less than 1 times the molar amount, the oxidation reaction tends not to proceed sufficiently. If the amount exceeds 50 times the molar amount, only the cost of the oxidizing agent is increased and there is no merit.

  As reaction conditions, optimal conditions may be selected as appropriate depending on the type of fluorine-containing elastomer, oxidizing agent, solvent, etc., but it is preferable to react at room temperature to 100 ° C. for 1 to 20 hours.

  In the present invention, the fluorine-containing elastomer having the moiety represented by the general formula (3) or (4) at the main chain terminal and / or the side chain terminal is represented by the following general formula (5):

（式中、Ｒ²は同じかまたは異なり、置換または非置換の１価の炭化水素基、Ｘ⁴は同じかまたは異なり、加水分解性基、ｂは１〜３の整数）
で示されるオルガノハイドロジェンシランと触媒の存在下に反応させ、前記一般式（３）または（４）で示される部位を、一般式（６）：
−ＳｉＲ² _3-bＸ⁴ _b （６）
で示される加水分解性シリル基を有する構造に変換する工程を含むこともできる。なお、このようにして得られる含フッ素エラストマーのうち、主鎖末端に一般式（６）で示される部位を有するビニリデンフルオライド系フッ素ゴムは新規物質である。

(Wherein R ² is the same or different and is a substituted or unsubstituted monovalent hydrocarbon group, X ⁴ is the same or different, a hydrolyzable group, b is an integer of 1 to 3)
And a site represented by the general formula (3) or (4) is reacted with an organohydrogensilane represented by the general formula (6):
-SiR ² _3-b X ⁴ _b (6)
The process of converting into the structure which has a hydrolyzable silyl group shown by these can also be included. Among the fluorine-containing elastomers thus obtained, vinylidene fluoride-based fluororubber having a site represented by the general formula (6) at the main chain terminal is a novel substance.

R ² in the general formulas (5) and (6) is the same or different and is a substituted or unsubstituted monovalent hydrocarbon group. Examples of the unsubstituted monovalent hydrocarbon group include an alkyl group, Examples thereof include a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, and a (meth) acryloyloxypropyl group.

  Examples of the alkyl group include 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, nonyl group, decyl group. Examples thereof include alkyl groups having 1 to 10 carbon atoms such as groups, and more representative examples include lower alkyl groups having 1 to 3 carbon atoms such as methyl group, ethyl group and propyl group; butyl group, tert- A butyl group, a hexyl group, and an octyl group.

  Examples of the cycloalkyl group include cycloalkyl groups having 3 to 8 carbon atoms such as cyclopentyl, cyclohexyl and cycloheptyl, and more representative examples include 5 to 5 carbon atoms such as cyclopentyl group and cyclohexyl group. 6 cycloalkyl groups.

  Examples of the aryl group include aryl groups having 6 to 15 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenylyl group, and more representative examples include a phenyl group, a tolyl group, 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 representative examples include a benzyl group and a phenylethyl group. An aralkyl group having 7 to 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, cyclohexenyl group, and the like. A typical example is an alkenyl group having 2 to 4 carbon atoms such as a vinyl group, an allyl group, or a butenyl group.

  The substituted monovalent hydrocarbon group is a group in which at least part of the hydrogen atoms of the unsubstituted monovalent hydrocarbon group is substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. And typical ones include, for example, chloromethyl group, 2-bromoethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, 3,3,4,4,5,5,6, Examples thereof include halogen-substituted alkyl groups having 1 to 8 carbon atoms such as 6,6-nonafluorohexyl group, and more representative examples include 3,3,3-trifluoropropyl group, 3,3,4,4, and the like. , 5, 5, 6, 6, 6-nonafluorohexyl group and the like, a halogen-substituted alkyl group having 3 to 8 carbon atoms.

X ⁴ in the general formulas (5) and (6) is the same or different and is a hydrolyzable group. Examples of the hydrolyzable group include halogens such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Atoms; groups represented by the following general formulas (18) to (23), and the like.

（式中、Ｒ⁵およびＲ⁶はそれぞれ水素原子または置換または非置換の１価炭化水素基である）
前記、置換または非置換の１価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基等のアルキル基、代表的なものとしてはメチル基、エチル基、プロピル基、イソブチル基等の炭素原子数が１〜４のアルキル基；シクロヘキシル基等の炭素原子数が３〜６のシクロアルキル基；ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、イソブテニル基等のアルケニル基、代表的なものとしてはビニル基、イソプロペニル基等の炭素原子数が２〜４のアルケニル基；フェニル基等のアリール基；あるいはこれらの基の水素原子が部分的にアルコキシ基などで置換された基、例えば、メトキシメチル基、メトキシエチル基、エトキシメチル基、エトキシエチル基等のアルコキシ置換アルキル基などがあげられる。

(Wherein R ⁵ and R ⁶ are each a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group)
Examples of the substituted or unsubstituted monovalent hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group, and representative examples include a methyl group and an ethyl group. Alkyl group having 1 to 4 carbon atoms such as propyl group and isobutyl group; cycloalkyl group having 3 to 6 carbon atoms such as cyclohexyl group; vinyl group, allyl group, propenyl group, isopropenyl group and butenyl group Alkenyl groups such as isobutenyl groups, typically, alkenyl groups having 2 to 4 carbon atoms such as vinyl groups and isopropenyl groups; aryl groups such as phenyl groups; or the hydrogen atoms of these groups are partially A group substituted with an alkoxy group, for example, an alkoxy such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, and an ethoxyethyl group. And substituted alkyl groups, and the like.

  B in general formula (5) and (6) is an integer of 1-3.

  Examples of the catalyst include platinum group metal catalysts known as catalysts used in hydrosilylation reactions, such as chloroplatinic acid, alcohol-modified chloroplatinic acid (see US Pat. No. 3,220,972), chlorination. A complex of platinum acid and olefin (see US Pat. Nos. 3,159,601, 3,159,662, and 3,775,452), platinum black, palladium, etc. Examples thereof include those supported on a carrier such as alumina, silica, carbon, rhodium-olefin complex, chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst), and the like. Of these, the complex type is preferably used by dissolving in an organic solvent such as alcohol, ketone or ether. The amount of catalyst used may be a so-called catalyst amount.

  In the present invention, the fluorine-containing elastomer having the moiety represented by the general formula (3) or (4) at the main chain terminal and / or the side chain terminal is also an organic compound having two or more —SiH groups in the molecule. By reacting the silicon compound in the presence of a catalyst and carrying out an addition reaction (hydrosilylation reaction), the site represented by the general formula (3) or (4) at the main chain end and / or the side chain end is represented by —Si—. A step of converting to a structure having an H group can also be included.

  The organosilicon compound having two or more —SiH groups in one molecule is represented by the following formulas (24) and (25):

（式中、Ｒ⁷、Ｒ⁸、Ｒ⁹は同一又は異種の１価の有機基または水素原子であり、ｂは１〜３の整数であり、ｃ、ｄは０〜３の整数である。ただし、ｃ＋ｄ≠０である。）
で示されるものがあげられ、具体的には、

(In formula, R < ⁷ >, R < ⁸ >, R < ⁹ > is the same or different monovalent organic group or a hydrogen atom, b is an integer of 1-3, c, d is an integer of 0-3. However, c + d ≠ 0.)
In particular,

などをあげることができる。

Etc.

  When the organosilicon compound having two or more —SiH groups in one molecule is subjected to an addition reaction in the presence of a catalyst, the organosilicon compound having —SiH groups is preferably used in an excess amount.

  The above addition reaction is carried out in the presence of an addition reaction catalyst. As this addition reaction catalyst, a known catalyst can be used in the same manner as the catalyst used in the step of converting to the hydrolyzable silyl group. .

  The present invention also relates to a fluorine-containing elastomer represented by the following general formula (7).

式中、Ｍはテトラフルオロエチレンおよび／またはビニリデンフルオライドからなる重合体であり、前記した含フッ素エラストマーであれば好適に用いることができる。

In the formula, M is a polymer comprising tetrafluoroethylene and / or vinylidene fluoride, and any of the above-described fluorine-containing elastomers can be suitably used.

  B is the general formula (3):

または、一般式（４）：

Or, general formula (4):

で示される部位である。

It is a site | part shown by.

R ¹ , X ¹ , X ² , X ³ , Z, Y ² and n are the same as described above, a is an integer of 1 or more, and preferably an integer of 2 or more.

  Moreover, it is preferable that the number average molecular weights of a fluorine-containing elastomer are 500-500000, and it is more preferable that it is 3000-500000. When the number average molecular weight is less than 500, the crosslinking density tends to be excessively increased when a terminal-based curing reaction is performed. When the number average molecular weight exceeds 500,000, the viscosity of the fluorine-containing elastomer is too high and mixing with the crosslinking agent becomes difficult. Tend.

  Next, the curable composition of this invention is demonstrated.

  It is sufficient that the curable composition of the present invention contains a compound capable of undergoing a crosslinking reaction with a fluorine-containing elastomer having a site represented by the general formula (3) or (4) at the main chain terminal and / or the side chain terminal. It is preferable from the viewpoint of obtaining a cured product crosslinked in the same manner.

  As the compound capable of crosslinking reaction, a polyfunctional compound having a plurality of functional groups capable of reacting with the fluorine-containing elastomer in the molecule is preferably exemplified. As the polyfunctional compound, it is preferable to use a polyfunctional compound having at least 2 functional groups per molecule and, if necessary, 3 or more from the viewpoint of sufficient crosslinking.

Moreover, in order for a curable composition to fully bridge | crosslink, it is preferable to use the polyfunctional compound according to the crosslinked part which the said fluorine-containing elastomer has. Hereinafter, although the specific example of this polyfunctional compound is given, this polyfunctional compound may use 1 type (s) or 2 or more types.
When the crosslinkable site is a hydrocarbon group having 2 to 10 carbon atoms having at least one unsaturated bond, examples of the polyfunctional compound include a compound having a —SiH group and a polyfunctional unsaturated compound.

The compound having a -SiH group is generally represented by the general formula (26):
R ¹⁰ _b H _c SiO _{(4-bc) / 2} (26)
(Wherein R ¹⁰ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, excluding an aliphatic unsaturated bond). Examples of such a monovalent hydrocarbon group include an alkyl group substituted with a halogen such as a trifluoropropyl group, an alkyl group, and a phenyl group. Among these, a methyl group, an ethyl group, a propyl group, a phenyl group, and a trifluoropropyl group are preferable, and a methyl group and a phenyl group are particularly preferable.

  In the general formula (26), b is preferably 0 ≦ b <3, more preferably 0.6 <b <2.2, and further preferably 1.5 ≦ b ≦ 2. , C is preferably 0 <c ≦ 3, more preferably 0.002 ≦ c <2, and still more preferably 0.01 ≦ c ≦ 1. Further, b + c is preferably 0 <b + c ≦ 3, and more preferably 1.5 <b + c ≦ 2.7.

The compound having the -SiH group is an organohydrogenpolysiloxane having preferably 2 to 1000, more preferably 2 to 300, and still more preferably 4 to 200 silicon atoms in one molecule. 1,1,3,3-tetramethyldisiloxane, 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9 Siloxane oligomers such as pentamethylcyclopentasiloxane; molecular chain both ends trimethylsiloxy group blocked methylhydrogen polysiloxane, molecular chain both ends trimethylsiloxy group blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends silanol group Capped methylhydrogenpolysiloxane, silanols at both ends of the molecular chain Dimethyl-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, dimethylhydrogensiloxy-blocked dimethylpolysiloxane at both ends of molecular chain, dimethylhydrogensiloxy-blocked methylhydrogenpolysiloxane at both ends of molecular chain, dimethylhydro at both ends of molecular chain Gensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, comprising R ¹⁰ ₂ (H) SiO _1/2 units and SiO _4/2 units, optionally R ¹⁰ ₃ SiO _1/2 units, R ¹⁰ _{2 Examples} thereof include silicone resins containing SiO _2/2 units, R ¹⁰ (H) SiO _2/2 units, (H) SiO _3/2 units or R ¹⁰ SiO _3/2 units.

  Examples of the methyl hydrogen polysiloxane blocked with trimethylsiloxy groups at both ends of the molecular chain include, for example, a compound represented by the general formula (27), and a part or all of the methyl groups in the general formula (27) are an ethyl group, a propyl group, and a phenyl group. And a compound substituted with a trifluoropropyl group.

（式中、ｄは、２以上の整数を表す。）

(In the formula, d represents an integer of 2 or more.)

  As the dimethylsiloxane / methylhydrogensiloxane copolymer blocked with trimethylsiloxy groups at both molecular chain ends, a compound represented by the general formula (28), a part or all of the methyl groups in the general formula (28) is ethyl group, propyl And compounds substituted with a group, phenyl group, trifluoropropyl group, and the like.

（式中、ｅは、１以上の整数を表し、ｆは、２以上の整数を表す。）

(In the formula, e represents an integer of 1 or more, and f represents an integer of 2 or more.)

  Examples of the silanol group-blocked methyl hydrogen polysiloxane having both molecular chain ends include, for example, a compound represented by the following formula, and in the following formula, part or all of the methyl group is an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group, etc. Examples thereof include substituted compounds.

分子鎖両末端シラノール基封鎖ジメチルシロキサン／メチルハイドロジェンシロキサン共重合体としては、たとえば一般式（２９）で表される化合物、一般式（２９）においてメチル基の一部または全部をエチル基、プロピル基、フェニル基、トリフルオロプロピル基などで置換した化合物などがあげられる。

Examples of the dimethylsiloxane / methylhydrogensiloxane copolymer blocked with silanol groups at both ends of the molecular chain include, for example, a compound represented by the general formula (29), wherein a part or all of the methyl groups in the general formula (29) are ethyl group, propyl And compounds substituted with a group, phenyl group, trifluoropropyl group, and the like.

（式中、ｅは、１以上の整数を表し、ｆは、２以上の整数を表す。）

(In the formula, e represents an integer of 1 or more, and f represents an integer of 2 or more.)

  Examples of dimethylpolysiloxane blocked with a dimethylhydrogensiloxy group blocked at both ends of the molecular chain include, for example, a compound represented by the general formula (30), wherein a part or all of the methyl groups in the general formula (30) are ethyl, propyl, phenyl And a compound substituted with a trifluoropropyl group.

（式中、ｅは、１以上の整数を表す。）

(In the formula, e represents an integer of 1 or more.)

  Examples of the dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane having both molecular chain ends include, for example, a compound represented by the general formula (31), a part or all of the methyl groups in the general formula (31), an ethyl group, a propyl group, Examples thereof include compounds substituted with a phenyl group, a trifluoropropyl group, and the like.

（式中、ｅは、１以上の整数を表す。）

(In the formula, e represents an integer of 1 or more.)

  As the dimethylsiloxane / methylhydrogensiloxane copolymer blocked with dimethylhydrogensiloxy group at both ends of the molecular chain, for example, a compound represented by the general formula (32), a part or all of the methyl groups in the general formula (32) is ethyl And compounds substituted with a group, a propyl group, a phenyl group, a trifluoropropyl group, and the like.

（式中、ｇおよびｈは、それぞれ、１以上の整数を表す。）
このような化合物は、公知の方法により製造することができ、たとえばオクタメチルシクロテトラシロキサンおよび／もしくはテトラメチルシクロテトラシロキサンと、末端基となり得るトリオルガノシリル基またはジオルガノハイドロジェンシロキシ基を含む化合物とを、硫酸、トリフルオロメタンスルホン酸、メタンスルホン酸などの触媒の存在下、−１０〜４０℃程度の温度で平衡化させることによって容易に得ることができる。上記トリオルガノシリル基を含む化合物としては、たとえばヘキサメチルジシロキサンなどがあげられ、上記ジオルガノハイドロジェンシロキシ基を含む化合物としては、たとえば１，３−ジハイドロ−１，１，３，３−テトラメチルジシロキサンなどがあげられる。

(In the formula, g and h each represent an integer of 1 or more.)
Such a compound can be produced by a known method, for example, a compound containing octamethylcyclotetrasiloxane and / or tetramethylcyclotetrasiloxane and a triorganosilyl group or diorganohydrogensiloxy group which can be a terminal group. Can be easily obtained by equilibrating at a temperature of about −10 to 40 ° C. in the presence of a catalyst such as sulfuric acid, trifluoromethanesulfonic acid or methanesulfonic acid. Examples of the compound containing a triorganosilyl group include hexamethyldisiloxane, and examples of the compound containing a diorganohydrogensiloxy group include 1,3-dihydro-1,1,3,3-tetra. Examples thereof include methyldisiloxane.

  In consideration of compatibility with the fluorine-containing elastomer of the present invention, dispersibility, and uniformity after crosslinking, the compound having the Si-H group is one or more monovalent perfluorooxyalkyl per molecule. Having a group, a monovalent perfluoroalkyl group, a divalent perfluorooxyalkylene group or a divalent perfluoroalkylene group, and having two or more, preferably three or more Si-H groups preferable. Examples of the perfluorooxyalkyl group, perfluoroalkyl group, perfluorooxyalkylene group, and perfluoroalkylene group include those represented by the following general formula.

As the monovalent perfluoroalkyl group, the general formula (33):
C _k F _{2k + 1} − (33)
(Wherein k represents an integer of 1-20, preferably 2-10),
As the divalent perfluoroalkylene group, the general formula (34):
−C _k F _2k − (34)
(Wherein k represents an integer of 1 to 20, preferably 2 to 10),
As the monovalent perfluorooxyalkyl group, the general formula (35) or (36):

（式中、ｎは、１〜５の整数を表す。）

(In the formula, n represents an integer of 1 to 5.)

  As the divalent perfluorooxyalkylene group, the general formula (37):

（式中、ｍは、１〜５０の整数を表し、ｎは、１〜５０の整数を表す。ｍ＋ｎは、２〜１００を満足する。）、または一般式（３８）：
−（ＣＦ₂Ｏ）_m−（ＣＦ₂ＣＦ₂Ｏ）_n−ＣＦ₂− （３８）
（式中、ｍおよびｎは、それぞれ、１〜５０の整数を表す。）

(In the formula, m represents an integer of 1 to 50, n represents an integer of 1 to 50, m + n satisfies 2 to 100), or General Formula (38):
_{- (CF 2 O) m -} (CF 2 CF 2 O) n -CF 2 - (38)
(In the formula, m and n each represent an integer of 1 to 50.)

As the divalent linking group for connecting the perfluoroalkyl group, perfluorooxyalkyl group, perfluoroalkylene group or perfluorooxyalkylene group and a silicon atom, an alkylene group, an arylene group, an alkylene group and an arylene group are combined. A group in which an ether bond oxygen atom, an amide bond, a carbonyl bond or the like is interposed in these groups, for example, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —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-, ( wherein, Ph represents a phenyl group.) Examples thereof include those having 2 to 12 carbon atoms such as —CH ₂ CH ₂ CH ₂ —N (CH ₃ ) —CO— and —CH ₂ CH ₂ CH ₂ —O—CO—.

  In addition, the monovalent or divalent fluorine-containing substituent in the compound having the —SiH group, that is, a monovalent containing a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group or a perfluorooxyalkylene group. Examples of monovalent substituents bonded to silicon atoms other than organic groups include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl and decyl groups; vinyl groups, Alkenyl groups such as allyl groups; aryl groups such as phenyl groups, tolyl groups, and naphthyl groups; aralkyl groups such as benzyl groups and phenylethyl groups; at least some of the hydrogen atoms of these groups are substituted with chlorine atoms, cyano groups, and the like For example, chloromethyl group, chloropropyl group, cyanoethyl group, etc. Unsubstituted or substituted hydrocarbon group having 20 and the like.

  The compound having a -SiH group may be any of cyclic, chain, three-dimensional network, or a combination thereof. The number of silicon atoms in the compound having two or more —SiH groups in one molecule is not particularly limited, but is usually 2 to 60, preferably 3 to 60, and more preferably 3 to 30.

  Examples of the compound having a -SiH group include the following compounds. In the following formulae, Me represents a methyl group and Ph represents a phenyl group. In addition, these compounds can be used individually by 1 type or in combination of 2 or more types.

（式中、ｍは、１〜２０、平均１０の整数を表し、ｎは、１〜１０、平均６の整数を表す。）

(In the formula, m represents an integer of 1 to 20 and an average of 10, and n represents an integer of 1 to 10 and an average of 6.)

（式中、Ｓは、

(Where S is

を表し、ｎは、１〜３０の整数を表し、ｍは、１〜３０の整数を表す。ｎ＋ｍは、２〜６０、平均２〜５０を満足する。）

N represents an integer of 1 to 30, and m represents an integer of 1 to 30. n + m satisfies 2 to 60 and an average of 2 to 50. )

（式中、Ｓは、

(Where S is

を表し、ｎは、１〜３０の整数を表し、ｍは、１〜３０の整数を表す。ｎ＋ｍは、２〜６０、平均２〜５０を満足する。）

N represents an integer of 1 to 30, and m represents an integer of 1 to 30. n + m satisfies 2 to 60 and an average of 2 to 50. )

（式中、ｎは、２〜６０、平均３〜５０の整数を表す。）

(In the formula, n represents an integer of 2 to 60 and an average of 3 to 50.)

（式中、ｎは、２〜６０、平均３〜５０の整数を表す。）

(In the formula, n represents an integer of 2 to 60 and an average of 3 to 50.)

（式中、ｎは、２〜６０、平均３〜５０の整数を表す。）
また、架橋部位が、不飽和結合を少なくとも１つ有する炭素数２〜１０の炭化水素基である含フッ素エラストマーと上記Ｓｉ−Ｈ基を有する化合物からなる硬化性組成物の場合、ヒドロシリル化反応の反応性の点から、ヒドロシリル化反応触媒を加えることが好ましい。

(In the formula, n represents an integer of 2 to 60 and an average of 3 to 50.)
In the case where the crosslinking site is a curable composition comprising a fluorine-containing elastomer which is a hydrocarbon group having 2 to 10 carbon atoms having at least one unsaturated bond and the compound having the Si-H group, hydrosilylation reaction From the viewpoint of reactivity, it is preferable to add a hydrosilylation reaction catalyst.

  The hydrosilylation reaction catalyst is not particularly limited as long as it promotes an addition reaction (alkene hydrosilylation reaction) between a fluorine-containing elastomer and a compound having two or more Si-H groups in one molecule. An addition reaction catalyst (group 8 metal catalyst such as group 8 metal, group 8 metal complex, group 8 metal compound, etc.) of platinum group elements such as platinum catalyst, palladium catalyst, rhodium catalyst, etc. Among them, a platinum-based catalyst is preferable because it is relatively easy to obtain.

  The platinum-based catalyst may be a known one that is usually used for addition-curing type curing, such as a finely powdered platinum metal catalyst described in US Pat. No. 2,970,150, US Pat. No. 2,823, No. 218, chloroplatinic acid catalyst, platinum and hydrocarbon complex compounds described in US Pat. No. 3,159,601 and US Pat. No. 159,662, US Pat. Complexes of chloroplatinic acid and olefins described in US Pat. No. 516,946, platinum and vinylsiloxane described in US Pat. No. 3,775,452 and US Pat. No. 3,814,780 And the complex compounds. More specifically, platinum alone (platinum black); chloroplatinic acid; a complex of chloroplatinic acid and an olefin such as ethylene; a complex of chloroplatinic acid and an alcohol or vinylsiloxane; a carrier such as silica, alumina or carbon For example, platinum supported thereon.

The palladium-based catalyst is composed of palladium, palladium compound, chloropalladic acid, and the rhodium-based catalyst is composed of rhodium, rhodium compound, rhodium chloride, and the like. For example, RhCl (PPh ₃ ) ₃ , RhCl (CO ) (PPh ₃ ) ₂ , RhCl (C ₂ H ₄ ) ₂ , Ru ₃ (CO) ₁₂ , IrCl (CO) (PPh ₃ ) ₂ , Pd (PPh ₃ ) ₄ (Ph represents a phenyl group), etc. Can be given.

  The hydrosilylation reaction catalyst may also be a Lewis acid, cobalt carbonyl, or the like.

  Moreover, it is preferable to use a reaction inhibitor. Examples of the reaction inhibitor include benzotriazole; acrylonitrile; N, N-diallylacetamide, N, N-diallylbenzamide, N, N, N ′, N′-tetraallyl-o-phthalic acid diamide, N, N, N. Amide compounds such as ', N'-tetraallyl-m-phthalic acid diamide, N, N, N', N'-tetraallyl-p-phthalic acid diamide; sulfur; phosphorus; nitrogen; amine compound; sulfur compound; Tin; tin compound; tetramethyltetravinylcyclotetrasiloxane; and organic peroxides such as hydroperoxide.

  Examples of the reaction inhibitor include 1-ethynyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and phenylbutynol. Of acetylene alcohol, 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, 3-methyl-1-penten-3-ol, US Pat. No. 3,445,420 It may be an acetylene compound such as a compound exemplified as the compound (4) in the specification and a compound exemplified as the component (d) in JP-B-54-3774.

  Further, when the crosslinking site is a -COOH group (for example, when the site represented by the general formula (3) or (4) is converted to a structure containing -COOH as described above), the polyfunctional compound is Preferred examples include polyaminophenol compounds, polyaminothiophenol compounds, polyamine compounds, polyisocyanate compounds, and polyepoxy compounds.

  Examples of the polyamine compound include polyamines such as hexamethylenediamine, triethylenetetramine, and triethylenediamine; combined use of a polyamine salt and a guanidine derivative.

  Examples of the polyisocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and the like. The polyisocyanate compound may be a block type capable of selecting a prepolymer and a crosslinking temperature.

  Examples of the polyepoxy compound include novolak type, bisphenol A type, and bisphenol AF type. The polyepoxy compound may be a prepolymer.

  In addition, when the crosslinking site is a hydrocarbon group having 2 to 10 carbon atoms having at least one unsaturated bond, the unsaturated bond can contribute to the three-dimensional network structure by hydrosilylation reaction. Especially as a compound, it is preferable that it is a compound which has a 2 or more Si-H group.

  As the polyaminophenol compound, polyaminothiophenol compound, and polyamine compound, the general formula (39):

（式中、Ｘ¹⁰は−ＯＨ、−ＳＨ、−ＮＨ₂、−ＮＨＲ¹¹であり、Ｒ¹¹は炭素数１〜１０の炭化水素基、ｎは２〜５の整数である）で示される化合物があげられる。

(Wherein X ¹⁰ is —OH, —SH, —NH ₂ , —NHR ¹¹ , R ¹¹ is a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 to 5). Can be given.

And -SiR ² _3-b X ⁴ _b (R ² is the same or different, a substituted or unsubstituted monovalent hydrocarbon group, X ⁴ is the same or different at the main chain end and / or the immediate chain end; A hydrolyzable group, b is an integer of 1 to 3), and when the crosslinkable site is a hydrolyzable silyl group, two or more hydrolyzable silyl groups Since dehydration condensation with water in the atmosphere causes crosslinking to proceed, a crosslinking agent is not always necessary, but if necessary, condensation catalysts such as organotin esters, organotitanate esters, tetramethylguanidylpropyltrimethoxysilane, etc. , Methyltrimethoxysilane, methyltripropenoxysilane, vinyltributanoximesilane, storage stabilizer such as methyltriacetoxysilane, etc., in one molecule described in JP-A-9-137027 A combination of an organic compound having at least one carbonyl group (for example, acetone) and a compound having at least one primary amino group in one molecule (for example, ethylamine), and an organic compound having at least one carbonyl group in one molecule Adding a deep-curing improver such as a combination of (for example, acetone) and a compound (for example, maleic acid) having at least one proton in one molecule and an acid dissociation constant (pka) in water of 2 or less. Is preferred.

  In addition, when the crosslinkable site has a structure having a —SiH group (for example, when the site represented by the general formula (3) or (4) is converted into a structure containing —SiH as described above), It is preferable to use a polyfunctional unsaturated compound. In that case, it is preferable to use together the catalyst or organic peroxide used for the process of converting into the said hydrolysable silyl group.

  The amount of the compound capable of undergoing a crosslinking reaction with the crosslinking site of the fluorine-containing elastomer of the present invention is preferably 0.05 to 30 parts by weight, and 0.5 to 20 parts by weight with respect to 100 parts by weight of the fluorine-containing elastomer. It is more preferable that If it is less than 0.05 part by weight, there is a tendency that the crosslinking cannot be carried out sufficiently. If it exceeds 30 parts by weight, the crosslinking reaction tends to proceed only to an extent corresponding to the amount added.

  In the curable composition of the present invention, an acid acceptor may be added in advance in order to accelerate the reaction. Examples of the acid acceptor include metal oxides such as magnesium oxide, calcium oxide, silicon oxide, aluminum oxide, and lead oxide; metal hydroxides such as magnesium hydroxide, calcium hydroxide, and aluminum hydroxide; synthetic hydrotalcite, etc. Can be used. It is preferable that the usage-amount of an acid acceptor is 1-30 weight part with respect to 100 weight part of fluorine-containing elastomers.

  In addition, the curable composition of the present invention may also contain other fluorine-containing elastomers that are not included in the fluorine-containing elastomer obtained by the production method of the present invention described above, from the viewpoint that a function as a processing aid can be expected. Good.

  The curable composition of the present invention is a conventional additive blended in the curable composition comprising a fluorine-containing elastomer as necessary, for example, a filler, a processing aid, a plasticizer, a colorant, an antioxidant. , Anti-aging agents, ozone degrading agents, ultraviolet absorbers and the like can be blended, and one or more conventional crosslinking agents and crosslinking aids different from those mentioned above may be blended, It can prepare by mixing using a normal elastomer processing machine, for example, an open roll, a Banbury mixer, a kneader. In addition, it can be prepared by a method using a closed mixer or a method of co-coagulation from emulsion mixing. The curable composition thus obtained is crosslinked and molded according to a conventional method. That is, it is molded by compression molding, injection molding, extrusion molding, calendar molding, dip molding, coating, etc. by dissolving in a solvent.

  The crosslinking conditions vary depending on the molding method and the shape of the molded product, but are generally in the range of several seconds to 5 hours at 100 ° C to 300 ° C. Further, secondary crosslinking may be performed in order to stabilize the physical properties of the crosslinked product. The secondary crosslinking conditions are 150 ° C. to 300 ° C. and about 30 minutes to 48 hours.

  Moreover, what is necessary is just to mix with a planetary mixer or a tabletop mixer, when the fluorine-containing elastomer obtained by the manufacturing method of this invention is low molecular weight and has fluidity | liquidity at normal temperature. At this time, the temperature may be increased to 50 ° C. or higher in order to increase the mixing efficiency. Furthermore, the curable composition is preferably reacted at a temperature of 50 ° C. or higher for 3 hours or longer.

  The curable composition having fluidity at room temperature is usually processed at a temperature of 200 ° C. or less by an extrusion gun such as a hot melt gun, injection molding or extrusion molding by a LIMS (Liquid Injection Molding System) molding machine, room temperature to 200 ° C. The molding performed by pouring into a mold can be performed.

  As a method for crosslinking the curable composition, a method other than the above can be used depending on the type of the crosslinking site.

  The molded article of the present invention can be suitably used in the following fields.

  In semiconductor-related fields such as semiconductor manufacturing equipment, liquid crystal panel manufacturing equipment, plasma panel manufacturing equipment, plasma addressed liquid crystal panels, field emission display panels, solar cell substrates, etc., O (square) rings, packing, sealing materials, tubes, rolls, coatings Linings, gaskets, diaphragms, hoses, etc. These include CVD equipment, dry etching equipment, wet etching equipment, oxidation diffusion equipment, sputtering equipment, ashing equipment, cleaning equipment, ion implantation equipment, exhaust equipment, chemical piping, gas Can be used for piping. Specifically, as a gate valve O-ring, seal material, quartz window O-ring, seal material, chamber O-ring, seal material, gate O-ring, seal material, bell jar O-ring, seal material As an O-ring for a coupling, as a sealing material, as an O-ring for a pump, as a sealing material, as a diaphragm, as an O-ring for a semiconductor gas control device, as a sealing material, as an O-ring for a resist developer, as a stripping solution, as a sealing material As a wafer cleaning solution hose and tube, as a wafer transfer roll, as a resist developer bath, a stripping solution bath lining, as a coating, as a wafer cleaning bath lining, as a coating or as a wet etching bath lining, as a coating Can do. In addition, sealing materials and sealants, optical fiber quartz coatings, electronic parts for insulation, vibration proofing, waterproofing and moisture proofing, circuit board potting, coating, adhesive sealing, gaskets for magnetic storage devices, epoxies, etc. Used as a sealing material modifier, sealant for clean rooms and clean facilities, etc.

  In the automotive field, gaskets, shaft seals, valve stem seals, sealing materials and hoses can be used for engines and peripheral devices, hoses and sealing materials can be used for AT devices, O (square) rings, tubes, packings. The valve core material, hose, sealing material and diaphragm can be used for fuel systems and peripheral devices. Specifically, engine head gasket, metal gasket, oil pan gasket, crankshaft seal, camshaft seal, valve stem seal, manifold packing, oil hose, oxygen sensor seal, ATF hose, injector O-ring, injector packing, fuel Pump O-ring, diaphragm, fuel hose, crankshaft seal, gear box seal, power piston seal, cylinder liner seal, valve stem seal, automatic transmission front pump seal, rear axle pinion seal, universal joint gasket, speed Meter pinion seal, foot brake piston cup, torque transmission O-ring, oil seal, exhaust gas reburner seal, bearing Lumpur, EGR tubes, Tsuinkyabu tube, the sensor diaphragm of the carburetor, rubber vibration isolator (engine mount, exhaust part, etc.), afterburners hoses, can be used as an oxygen sensor bush.

  In the aircraft field, the rocket field, and the marine field, there are diaphragms, O (square) rings, valves, tubes, packings, hoses, sealing materials, and the like, which can be used for fuel systems. Specifically, in the aircraft field, it is used for jet engine valve steal seals, fuel supply hoses, gaskets and O-rings, rotating shaft seals, hydraulic equipment gaskets, firewall seals, etc. Used for propeller shaft stern seal, diesel engine intake / exhaust valve stem seal, butterfly valve seal, butterfly valve shaft seal, etc.

  In the field of chemical products such as plants, linings, valves, packing, rolls, hoses, diaphragms, O (square) rings, tubes, sealing materials, chemical-resistant coatings, etc., these are pharmaceuticals, agricultural chemicals, paints, resins, etc. It can be used in chemical manufacturing processes. Specifically, chemical pumps, rheometers, pipe seals, heat exchanger seals, glass cooler packing for sulfuric acid production equipment, pesticide sprayers, pesticide transfer pump seals, gas pipe seals, plating solutions Seals, packing for high-temperature vacuum dryers, roller seals for papermaking belts, fuel cell seals, wind tunnel joint seals, rolls for trichrene (for fiber dyeing), acid-resistant hoses (for concentrated sulfuric acid), gas chromatography, pH meter It can be used as packing for tube joints, chlorine gas transfer hoses, benzene, rainwater drain hoses for toluene storage tanks, seals for analytical instruments, physics and chemistry instruments, tubes, diaphragms, valve parts, and the like.

  In the pharmaceutical field such as pharmaceuticals, it can be used as a medicine stopper.

  In the photographic field such as a developing machine, the printing field such as a printing machine, and the coating field such as a coating facility, there are rolls and the like, which can be used for a film developing machine, an X-ray film developing machine, a printing roll and a coating roll, respectively. Specifically, as a developing roll of a film developing machine / X-ray film developing machine, a gravure roll of a printing roll, a guide roll, a gravure roll of a magnetic tape manufacturing coating line of a coating roll, a guide of a magnetic tape manufacturing coating line It can be used as a roll, various coating rolls, and the like. Furthermore, dry copying machine seals, printing equipment printing rolls, scrapers, tubes, valve parts, coating, coating equipment coating rolls, scrapers, tubes, valve parts, printer ink tubes, rolls, belts, dry copying machine belts , Rolls, printing press rolls, belts, and the like.

  Tubes can also be used in the field of analysis and physics and chemistry.

  In the field of food plant equipment, linings, valves, packings, rolls, hoses, diaphragms, O (square) rings, tubes, sealing materials, belts and the like can be mentioned and used in food production processes. Specifically, it can be used as a seal for a plate heat exchanger, a solenoid valve seal for a vending machine, or the like.

  In the field of nuclear plant equipment, packing, O-rings, hoses, sealing materials, diaphragms, valves, rolls, tubes and the like can be mentioned.

  In the steel field such as iron plate processing equipment, rolls and the like can be mentioned, and they can be used for iron plate processing rolls and the like.

  In general industrial fields, packing, O-rings, hoses, sealing materials, diaphragms, valves, rolls, tubes, linings, mandrels, electric wires, flexible joints, belts, rubber plates, weather strips, rolls for PPC copiers, roll blades, belts Etc. Specifically, hydraulic, lubrication machinery seals, bearing seals, dry cleaning equipment windows, other seals, uranium hexafluoride concentrator seals, cyclotron seals (vacuum) valves, automatic packaging machine seals, air It is used for diaphragms (pollution measuring devices) for analysis of sulfurous acid gas and chlorine gas in the inside, rolls for printing presses, belts, pickling rolls for pickling.

  In the electric field, specifically, it is used as an insulating oil cap for Shinkansen, a bench seal for a liquid seal transformer, a jacket for an oil well cable, and the like.

  In the fuel cell field, specifically, it is used as a sealing material between electrodes and separators, a seal for hydrogen / oxygen / product water piping, and the like.

  Specifically, in the field of electronic components, it is used as a heat radiation material, an electromagnetic shielding material, a modified material of a printed wiring board prepreg resin such as epoxy, an anti-scattering material such as a light bulb, and a gasket of a hard disk drive of a computer.

  There are no particular limitations on what can be used for on-site molding, such as metal gasket coatings for automobile engines, engine oil pan gaskets, copier / printer rolls, architectural sealants, Gaskets for magnetic recording devices, sealants for filter units for clean rooms, coating agents for printed boards, fixing agents for electrical and electronic components, insulation and moisture-proof treatment of electrical equipment lead wire terminals, oven seals for electric furnaces, sheathed heaters Examples include end treatment, microwave window frame seals, adhesion of CRT wedges and necks, adhesion of automotive electrical components, joint seals for kitchens, bathrooms, washrooms, and the like.

  The curable composition of the present invention is particularly suitable for a sealing material for clean equipment such as a gasket for a magnetic recording device (hard disk drive), a sealing material for a device storage such as a semiconductor manufacturing apparatus or a wafer, etc., taking advantage of cleanliness. Used.

  The curable composition of the present invention utilizes characteristics such as chemical resistance, low gas permeability, flame retardancy, etc., and seals for fuel cells such as packing used between fuel cell electrode electrodes and surrounding pipes, etc. Also particularly preferably used.

  Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.

Reference example 1
(Polymerization of fluorine-containing elastomer)
A polymerization tank having an internal volume of 3.0 liters having a magnetic induction stirrer was supplied with 1.47 L of pure water and 30 g of an aqueous 10% by weight ammonium perfluorooctanoate solution. After sufficiently replacing the system with nitrogen gas and then reducing the pressure, the internal temperature was raised to 80 ° C., HFP was charged to an internal pressure of 0.73 MPa, and VdF was charged to 1.5 MPa. Under stirring, 0.114 g of ammonium persulfate (APS) was dissolved in 8.1 g of water and charged to initiate polymerization. The polymerization pressure was set to 1.5 MPa, and VdF / HFP mixed monomer (78/22 (mol%)) was continuously supplied to compensate for the pressure drop during polymerization, and 300 g of monomer was put into the tank until the polymerization was completed. Supplied. In the middle, when 7 g of the VdF / HFP mixed monomer was supplied, 22.7 g of octafluoro-1,4-diiodobutane and 0.114 g of APS were dissolved in 8.1 g of water 3 hours and 6 hours after the start of polymerization, respectively. Additional aqueous solution was charged. The reaction time was 10 hours and 1 minute. The weight of the obtained emulsion was 1851 g, and the polymer concentration was 17.7% by weight.

This emulsion was coagulated with an aluminum sulfate aqueous solution and then washed with warm water to obtain a viscous fluorine-containing elastomer. The copolymer composition ratio of the obtained fluorine-containing elastomer was VdF / HFP = 77.5 / 22.5 (mol%) as measured by ¹⁹ F-NMR. The molecular weight in terms of polystyrene as analyzed by GPC was a weight average molecular weight of 10760 and a number average molecular weight of 8600. Further, in the analysis of ¹ H-NMR with a heavy acetone solvent, peaks of 3.97, 3.91, 3.85, 3.78 ppm derived from the terminal structure —CF ₂ CH ₂ I were observed. The ratio between the intensity of this peak and the intensity of the peak (2.7 to 3.4 ppm) derived from the main chain —CH ₂ — of the fluorine-containing elastomer was 1:34.

Example 1
A solution prepared by dissolving 23.3 g of the fluorine-containing elastomer obtained in Reference Example 1 in 120 g of acetonitrile and 2,5-dimethyl-2,5-di (t-butylperoxyhexane) (trade name: Perhexa 25B Nippon Oil & Fats 0.974 g, diallyl isocyanurate 7.01 g (5 times the molar amount with respect to the iodine content of the fluorinated elastomer) in an SUS pressure-resistant autoclave with an internal volume of 0.3 liter having a magnetic induction stirrer. The system was sufficiently replaced with nitrogen gas at −30 ° C., and then pressurized to 0.1 MPa with nitrogen gas.

  Under stirring, the internal temperature was heated at 150 ° C. for 6 hours. Once cooled to room temperature, 0.451 g of 2,5-dimethyl-2,5-di (t-butylperoxyhexane) was additionally charged. Thereafter, the reaction was further completed by heating at an internal temperature of 150 ° C. for 6 hours.

  In order to purify the fluorine-containing elastomer in the reaction solution, the obtained reaction solution was concentrated, redissolved in a small amount of acetone, and dropped into concentrated hydrochloric acid to reprecipitate the fluorine-containing elastomer. The obtained fluorine-containing elastomer was washed with water and dried by heating at 120 ° C. under reduced pressure.

It was confirmed from the analysis of ¹ H-NMR with a heavy acetone solvent that the allyl group derived from diallyl isocyanurate was introduced into the fluorine-containing elastomer after drying. The peak derived from an allyl group is 5.8 to 6.0 ppm (1H) 5.1 to 5.3 ppm (2H) 4.3 to 4.5 ppm (2H), and the main chain —CH ₂ — of the fluorine-containing elastomer. The peak derived from is 2.7 to 3.4 ppm (74H).

  Moreover, although the molecular weight of polystyrene conversion by analysis by GPC was the weight average molecular weight 13650 and the number average molecular weight 9080, the peak derived from the diallyl isocyanurate or the oligomer of diallyl isocyanurate was not observed.

Example 2
A solution prepared by dissolving 25.6 g of the fluorine-containing elastomer obtained in Reference Example 1 in 120 g of acetonitrile and 2,5-dimethyl-2,5-di (t-butylperoxyhexane) (trade name: Perhexa 25B Nippon Oil & Fats (Made by Co., Ltd.) 1.07 g, diallyldimethylsilane 5.17 g (5 times mole amount with respect to the iodine content of the fluorinated elastomer) in a 0.3 liter SUS pressure-resistant autoclave having a magnetic induction stirrer The inside of the system was sufficiently replaced with nitrogen gas at −30 ° C., and then pressurized to 0.1 MPa with nitrogen gas. Under stirring, the internal temperature was raised to 150 ° C. and heated for 6 hours to complete the reaction.

  In order to purify the fluorine-containing elastomer in the reaction solution, the obtained reaction solution was concentrated, redissolved in a small amount of acetone, and dropped into hexane to reprecipitate the fluorine-containing elastomer. The obtained fluorine-containing elastomer was heat-dried at 90 ° C. under vacuum.

It was confirmed from the analysis of ¹ H-NMR with a heavy acetone solvent that the allyl group derived from diallyldimethylsilane was introduced into the fluorine-containing elastomer after drying. The peak derived from the allyl group is 5.7 to 6.0 ppm (1H) 5.0 to 5.2 ppm (2H), and the peak derived from the main chain —CH ₂ — of the fluorine-containing elastomer is 2.7 to 3.4 ppm (67H).

  Moreover, although the molecular weight of polystyrene conversion by analysis by GPC was the weight average molecular weight 13640 and the number average molecular weight 9920, the peak derived from the oligomer of diallyl dimethylsilane or the diallyl dimethylsilane was not observed.

Example 3
0.115 g of the fluorine-containing elastomer obtained in Example 1 and a dimethyl-methylhydrogenpolysiloxane (25-30% methylhydrosiloxane)-(dimethylsiloxane) copolymer (trade name: HMS-301) as a crosslinking agent , Amax Co., Ltd. GELEST, INC. 0.0195 g (molecular weight 1900-2000) dissolved in 1.0 g of acetone, 0.011 g of toluene solution of platinum catalyst having a platinum concentration of 0.06% (OMG Precious) Metals Japan Co., Ltd. Pt-VTSC-12.0VTS (solution diluted 200 times with toluene) was added to prepare a solution mixed at room temperature. This solution was heated on a glass petri dish at 50 ° C. to evaporate acetone as a solvent, and then further heated at 100 ° C. for 1 hour. As a result, there was no viscosity but an elastic sheet-like cured body was obtained. . Further, since this cured product was insoluble in acetone, the curing reaction is considered to have progressed.

Example 4
10 g of the fluorine-containing elastomer obtained in Example 1 was dissolved in 100 g of anhydrous tetrahydrofuran under water-free conditions in a four-necked flask equipped with a reflux condenser, and the temperature of the flask content reached 80 ° C. while stirring. So that it was heated in an oil bath. Next, 1.0 g of a 2% solution of chloroplatinic acid in isopropyl alcohol was added to the flask, and then 0.4 g of trimethoxysilane was dropped from the dropping funnel to carry out the reaction. After completion of the dropwise addition, heating and refluxing were continued at 80 ° C. for 5 hours, and then tetrahydrofuran and unreacted trimethoxysilane were removed by heating under reduced pressure. In the ¹ H-NMR analysis of the obtained polymer, no peak derived from the allyl group of the fluorine-containing elastomer of Example 1 was observed, and a peak derived from the trimethoxysilyl group was observed near 3.5 ppm. It is thought that hydrolyzed silyl groups were introduced into the elastomer.

Example 5
0.1 g of the fluorine-containing elastomer obtained in Example 4 was dissolved in 1 g of acetone and applied on a glass plate. Acetone was removed by air drying, heated at 100 ° C. for 5 hours, and then allowed to stand at room temperature for 24 hours. When the glass plate was observed, an adhesive film was formed that was not sticky, but this film was formed. Since it did not dissolve even when immersed in acetone, it is considered that the curing reaction proceeded due to the hydrolyzed silyl group.

Claims (8)

A fluorine-containing elastomer containing iodine or bromine at the main chain terminal and / or side chain terminal is represented by the general formula (1):

Wherein R ¹ is the same or different and is represented by the general formula (2):

Wherein X ¹ , X ² , X ³ are the same or different and are a hydrogen atom, a fluorine atom, —CY ¹ ₃ (Y ¹ is the same or different, a fluorine atom or a hydrogen atom), and Z is ,

An organic group selected from the group consisting of: n is 2 or 3)
The compound represented by general formula (3) is added to the main chain terminal and / or the side chain terminal:

Or, general formula (4):

(Wherein R ¹ , X ¹ , X ² , X ³ , Z and n are the same as above, and Y ² is an iodine atom, a bromine atom or a hydrogen atom)
The manufacturing method of a fluorine-containing elastomer including the process of introduce | transducing the site | part shown by. Furthermore, the general formula (5)

(Wherein R ² is the same or different, a substituted or unsubstituted monovalent hydrocarbon group, X ⁴ is the same or different, a hydrolyzable group, b is an integer of 1 to 3)
In the presence of a catalyst with an organohydrogensilane represented by
The site represented by the general formula (3) or (4) is represented by the general formula (6):
-SiR ² _3-b X ⁴ _b (6)
The manufacturing method of the fluorine-containing elastomer of Claim 1 including the process converted into the structure which has a hydrolyzable silyl group shown by these. Further, the structure represented by the general formula (3) or (4) is reacted with an organosilicon compound having two or more —SiH groups in one molecule in the presence of a catalyst. The method for producing a fluorine-containing elastomer according to claim 1, comprising a step of converting into a fluorine-containing elastomer. General formula (7):

(In the formula, M is a polymer composed of tetrafluoroethylene and / or vinylidene fluoride, a is an integer of 1 or more, and B is the general formula (3):

Or, general formula (4):

Wherein R ¹ is the same or different and is represented by the general formula (2):

(Wherein X ¹ , X ² and X ³ are the same or different and are a hydrogen atom, a fluorine atom or —CY ¹ ₃ (Y ¹ is the same or different and is a fluorine atom or a hydrogen atom)), X ¹ , X ² and X ³ are the same as above, Y ² is an iodine atom, a bromine atom or a hydrogen atom, and Z is

A fluorine-containing elastomer represented by the following formula: n is an organic group selected from the group consisting of: The fluorine-containing elastomer according to claim 4, wherein the fluorine-containing elastomer is a vinylidene fluoride-based fluorine rubber. Claim 4 or 5 fluorine-containing elastomer according a number average molecular weight of 500 to 500,000. A curable composition comprising the fluorine-containing elastomer according to claim 4, 5 or 6 . A molded article obtained by crosslinking the curable composition according to claim 7 .