WO2007032310A1 - Fluorinated elastomer, process for production of fluorinated elastomer, and silicon-containing compound - Google Patents

Abstract

Disclosed are a process for production of a fluorinated elastomer which has a residue containing a functional group at the terminus of the backbone and/or the terminus of a side chain; a fluorinated elastomer produced by the process; a curable composition comprising the fluorinated elastomer; a molded article produced by cross-linking the curable composition; and a silicon-containing compound. A process for production of a cross-linkable fluorinated elastomer having a functional group (Y) at the terminus of the backbone and/or the terminus of a side chain, the process comprising the step of performing the cyclization between (A) a fluorinated elastomer having a functional group (Z) at the terminus of the backbone and/or the terminus of a side chain and (B) an organic compound having a functional group (Y) or a segment capable of being converted into the functional group (Y) and a reactive group capable of being cyclized with the functional group (Z).

Description

 Specification

 Fluorine-containing elastomer, method for producing fluorine-containing elastomer, and key compound-containing compound

 Technical field

 [oooi] The present invention relates to a method for producing a crosslinkable fluorine-containing elastomer containing a specific functional group at the main chain end and Z or side chain end, and a fluorine-containing elastomer obtained by the production method. In addition, the present invention relates to a curable composition that also has the power of the fluorine-containing elastomer and a molded product obtained by crosslinking the curable composition. Further, the present invention relates to a key compound-containing compound.

 Background art

 [0002] Fluorine-containing elastomers have excellent chemical resistance, solvent resistance, and heat resistance, and are therefore used in fields such as the automotive industry, semiconductor industry, and chemical industry as sealing materials in harsh environments. It is widely used.

 [0003] However, as the technology advances, the required characteristics become more severe, and in various fields such as the aerospace field, semiconductor manufacturing equipment field, chemical plant field, and automobile industry, better heat resistance and resistance Chemical properties, solvent resistance, and workability are required.

 [0004] In order to reinforce these various properties, a composition containing a fluorine-containing elastomer in which a vinyl group, an aryl group or SiH is introduced at the terminal has been developed. The fluorine-containing elastomer can be cross-linked because a vinyl group, a aryl group or a SiH group is present at the terminal.

 [0005] Specifically, a fluorine-containing elastomer using a fluorine-containing compound in which a double bond is introduced at the terminal via an amide bond or an ether bond is known (for example, see JP-A-5-33). 1372, JP-A-8-67660, JP-A-8-198926 and JP-A-2002-322362). However, since the terminal double bond is introduced via an amide bond or an ether bond, there is a problem that the heat resistance and chemical resistance of the bonded portion are inferior.

[0006] In addition, attempts have been made to improve the heat resistance of the fluorine-containing elastomer by devising a cross-linking system. For example, imidazole-based cross-linking agents and oxazole-based cross-linking agents having excellent heat resistance are proposed. A method of crosslinking with a thiazole-based crosslinking agent is known (for example, see JP-A-2003-231719). However, this method is a method of crosslinking a fluorine-containing elastomer with an imidazole-based crosslinking agent, an oxazole-based crosslinking agent, or a thiazole-based crosslinking agent, and a molded product having excellent heat resistance can be obtained by crosslinking with these crosslinking agents. However, since the functional group is not introduced into one end of the fluorine-containing elastomer via the oxazole ring, imidazole ring or thiazole ring, the elastomer after the introduction of the oxazole ring, imidazole ring or thiazole ring is crosslinked. Can not do it. Disclosure of the invention

 [0007] The present invention provides a method for producing a crosslinkable fluorine-containing elastomer containing specific functional groups at the main chain end and Z or side chain end, and a fluorine-containing elastomer obtained by the production method. Further, the present invention provides a curable composition that makes the best of the fluorine-containing elastomer, and a molded product obtained by crosslinking the curable composition. Furthermore, a silicon-containing compound is provided.

 That is, the present invention relates to a fluorine-containing elastomer (A) containing a functional group Z at the main chain end and Z or side chain end, a reactive group capable of cyclization with the functional group Z, and a functional group Y. Alternatively, a crosslinkable fluorine-containing elastomer having a functional group Y at the main chain end and Z or side chain end, which includes a step of performing a cyclization reaction with the organic compound (B) having a site that can be converted to the functional group Y. It relates to the manufacturing method.

 [0009] The functional group Z is represented by the general formula (1):

 [0010] [Chemical 1]

O

II 1 (1)

 Shi

[Wherein, X ¹ is a chlorine atom, a fluorine atom, OH or OR ¹ , and R ¹ is an organic group having 1 to 10 carbon atoms which may contain an oxygen atom, a hydrogen atom, or a rogen atom. )

 It is preferable that it is group shown by these, or CN.

[0012] The organic compound (B) has the general formula (2):

[0013] [Chemical 2]

[In the formula, one of R 1 and R 2 is —NH, and the other is —NH 2, one NHR, —OH

 twenty two

Or —SH, R ⁴ is a monovalent organic group, and Y ¹ is a monovalent organic group having a functional group Y and a functional group Υ, or one having a site that can be converted to a functional group Υ. Is a valent group. It is preferable that

[0015] Υ ¹ in the general formula (2) are alkenyl groups, Aruke - monovalent organic group having a group, a monovalent organic group having a hydrogen atom bonded to Keimoto atom or the general formula, (3 ):

 [0016] [Chemical 3]

S (3)

 R

(R ⁵ , R ⁶ and R ⁷ are the same or different and each is a hydrogen atom or a monovalent hydrocarbon group which may contain a substituted or unsubstituted oxygen atom, and at least one of them. Is preferably a hydrogen atom or a monovalent organic group represented by a substituted or unsubstituted monovalent hydrocarbon group having an alkenyl group.

 [0018] Further, the present invention provides a general formula (4):

[0019] [Chemical 4]

(In the formula, one of R and R is —NH, and the other is —NH, —NHR, —OH.

 twenty two

Or —SH, R ⁴ is a monovalent organic group, R ⁸ , R ⁹ , R ^{1 (>} are the same force or different, each containing a hydrogen atom or a substituted or unsubstituted oxygen atom. May be monovalent charcoal It is a hydrogen fluoride group. )

 It is related with the silicon containing compound shown by these.

[0021] —SiR ⁸ R ⁹ R ^{1Q in the} general formula (4) is

[0022] [Chemical 5]

C H

 I

— S i-CH = CH ₂ , or

 I

CH ₃

[0023] It is preferable.

[0024] The present invention also relates to a crosslinkable fluorine-containing elastomer having a functional group γ at the main chain end and Z or side chain end, which is obtained by the production method.

 [0025] Further, the present invention provides the general formula (5) at the main chain terminal and the Z or side chain terminal:

[0026] [Chemical 6] CC SII

HH i

(Wherein X ² is — 2—, —NR ¹¹ —, —O—, —S—, R ¹¹ is a monovalent organic group, and Υ ² is an alkyl group, Or a monovalent organic group having an alkenyl group, a monovalent organic group having at least one hydrogen atom bonded to a silicon atom, or the general formula (3):

 [0028] [Chemical 7]

S R (3)

 R

[0029] (R ⁵ , R ⁶ and R ⁷ are the same or different and each is a hydrogen atom or a monovalent hydrocarbon group which may contain a substituted or unsubstituted oxygen atom, and at least one of them. Is a monovalent organic group represented by a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having an alkenyl group. ) And a crosslinkable fluorine-containing elastomer having a functional group Y represented by

[0030] Υ ² in the general formula (5) is

[0031] [Chemical 8]

, Η _? Η

 1 and I Jri, 1 I

 I I

 JH ί ί

[0032] It is preferable.

 [0033] Further, the present invention relates to a curable composition having the fluorinated elastomer, and a molded product obtained by crosslinking the curable composition.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0034] The present invention provides a fluorine-containing elastomer (Α) containing a functional group に at the main chain end and Ζ or side chain end, a functional group Υ or a site that can be converted into the functional group Υ, and the functional group Ζ. Production of a crosslinkable fluorine-containing elastomer having a functional group に at the main chain end and Ζ or side chain end, including a step of performing a cyclization reaction with an organic compound (Β) having a reactive group capable of cyclization reaction It relates to the manufacturing method.

 The fluorine-containing elastomer (エ ラ) used in the present invention is not particularly limited as long as it is a fluorine-containing elastomer containing a functional group に at the main chain end and / or side chain end! Force It is preferable to have functional groups at both ends of the main chain from the viewpoint that it is possible to reduce terminal free chains that cause a reduction in the mechanical strength of the cured product after crosslinking.

 [0036] As the functional group Ζ, an oxazole ring, a thiazole ring, and an imidazole ring can be formed by a cyclization reaction with a reactive group of the organic compound (Β). ):

 [0037] [Chemical 9]

Ο

II (1)

 1

[0038] or a group represented by In the general formula (1), X ¹ is a chlorine atom, a fluorine atom, OH or OR ¹ , and R ¹ is an organic group having 1 to 10 carbon atoms which may contain an oxygen atom or a halogen atom. is there.

 [0040] Specific examples of the organic group having 1 to C0 carbon atoms that may contain an oxygen atom or a halogen atom, preferably an alkyl group, include CH, 1CH, 1CH, and the like.

 3 2 5 3 7

 Among these, the functional group Z is preferably COF because it has excellent reactivity with the organic compound (B) and can be easily introduced.

 [0042] As a method for introducing the functional group Z into the main chain terminal and Z or side chain terminal, a monomer having the functional group Z or a site that can be converted into the functional group Z during the polymerization of the fluorine-containing elastomer (A) A method using a polymerization initiator having a functional group Z or a polymerization initiator having a moiety convertible to the functional group Z, or a terminal of a fluorine-containing elastomer having an iodine atom or a bromine atom at the terminal. The method of converting into the functional group Z is mentioned.

 [0043] Examples of the fluorine-containing elastomer (A) include a fluorine rubber (a), a main chain ether-containing fluorine-containing polymer (b), and a rubber yarn composition having these forces.

[0044] Examples of the fluororubber (a) include non-perfluorofluororubber ( _a1 ) and perfluorofluororubber ( _a- 2). Note that the Pafuruorofutsu containing rubbers, Chi caries its constituent units, refers to the 90 mole _^0/0 or consisting par full O b monomer.

 [0045] Examples of the main chain ether-containing fluorine-containing polymer include non-perfluoropolymer (b-1) and perfluoropolymer (b-2).

[0046] Non-perfluoro fluorine rubber ( _a1 ) includes bi-lidene fluoride (VdF) fluorine rubber, tetrafluoroethylene (TFE) Z propylene fluorine rubber, tetrafluoroethylene (TFE). Z-propylene Z-vinylidene fluoride (VdF) fluorine rubber, ethylene / hexafluoropropylene (HFP) fluorine rubber, ethylene Z-hexafluoropropylene (HFP) Z vinylidene fluoride (VdF) Fluororubber, ethylene Z hexafluoropropylene (HFP) / tetrafluoroethylene (TFE) fluororubber or fluorophosphazene fluororubber, etc., each of which can be used alone or without impairing the effects of the present invention. Any combination can be used within a range.

[0047] The vinylidene fluoride (VdF) fluororubber is preferably represented by the general formula (6). [0048] One (M ¹ ) One (M ² ) — (N ¹ ) One (6)

(In the formula, the structural unit M ¹ is a structural unit derived from berylidene fluoride (m ¹ ), and the structural unit M ² is a structural unit derived from a fluorine-containing ethylenic monomer (m ² ). N ¹ is a repeating unit derived from the monomer (m ¹ ) and the monomer (n ¹ ) that can be copolymerized with the monomer (m ² ). The berylidene fluoride represented by the general formula (6) (VdF) type among the fluorine rubber, structural units of M ¹ and 45 to 85 mole%, 50 to 80 mole of the structural unit M ¹ is properly preferred to preferably those comprising structural units M ^2. 55 to 15 mol% instrument %, 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 .

[0049] As the fluorine-containing ethylenic monomer (m ² ), one or two or more types of monomers can be used. For example, tetrafluoroethylene (TFE), black trifluoroethylene (CTFE) , Trifluoroethylene, hexafluoropropylene (HFP), trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, perfluoro (alkyl butyl ether) (PAVE ), And a force capable of increasing a fluorine-containing monomer such as fluorinated tetrane. Among these, tetrafluoroethylene, hexafluoropropylene, and perfluoro (alkyl butyl ether) are preferable.

[0050] 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 For example, bull ether.

[0051] Further, as the monomer (n ¹ ), a monomer having a crosslinking site, a monomer having a functional group Z, or a monomer giving a site that can be converted to the functional group Z is preferable. .

 [0052] As a monomer having such a crosslinking site, a monomer having a functional group Z, or a monomer giving a site that can be converted to the functional group Z, the general formula (7):

CY ³ = CY ³ -R ¹ CHR ¹² X ³ (7)

 2 f

(In the formula, Y ³ represents a hydrogen atom, a fluorine atom or —CH ³ , a fluoroalkylene group,

3, R ¹ is

 f

Monofluoroalkylene group, fluoropolyoxyalkylene group or perfluoropolyoxyalkylene group, R ¹² is a hydrogen atom or CH, and X ³ is an iodine atom or bromine atom.

 Three

Iodine or bromine-containing monomer represented by formula (8): CF = CFO (CF CF (CF) 0) (CF) —X ⁴ (8)

 2 2 3 m 2 n

(Wherein, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ⁴ is a cyano group, a carboxyl group, an alkoxycarbonyl group, a bromine atom, or an iodine atom) Body, general formula (9): CH = CH (CF) I (9)

 2 2 p

 (Wherein p is an integer of 1 to L0) and the like, and examples thereof include perfluorocarbons as described in JP-B-5-63482 and JP-A-7-316234. Iodine-containing monomers such as (6, 6-dihydro-1 6-oxo 1-hexene) and perfluoro (5 3 3-oxa 1 pentene), CF = CFOCF CF CH described in JP-A-4-217936 I-containing monomers such as I, described in JP-A-4 505341

2 2 2 2

Bromine-containing monomers described in Japanese Patent Laid-Open No. 4-505345, Japanese Patent Laid-Open No. 5-500070 And group-containing monomers. Also, general formulas (10) to (21): CY ⁴ = CY ⁴ (CF) — X ⁵ (10)

 2 2 n

(In the formula, Y ⁴ is a hydrogen atom or a fluorine atom, and n is an integer of 1 to 8)

CF = CFCFR ² — X ⁵ (11)

 2 2 f

 (Where

 [0053] [Chemical 10]

R _f ² tt-^ OCFa ^,-^ OCF (CF ₃ ) τ

[0054] and n is an integer from 0 to 5)

 CF = CFCF (OCF (CF) CF)

 2 2 3 2 m

(OCH CF CF) OCH CF X ⁵ (12)

 2 2 2 n 2 2

 (Where m is an integer from 0 to 5 and n is an integer from 0 to 5)

 CF = CFCF (OCH CF CF)

 2 2 2 2 2 m

(OCF (CF) CF) OCF (CF) X ⁵ (13)

 3 2 n 3

 (Where m is an integer from 0 to 5 and n is an integer from 0 to 5)

CF = CF (OCFCF (CF)) O (CF) —X ⁵ (14)

 2 2 3 m 2 n

(Where m is an integer from 0 to 5 and n is an integer from 1 to 8) CF = CF (OCFCF (CF)) — X ⁵ (15)

 2 2 3 m

 (Where m is an integer from 1 to 5)

CF = CFOCF (CF (CF) OCF) CF (— X ⁵ ) CF (16)

 2 2 3 2 n 3

 (Where n is an integer from 1 to 4)

CF = CFO (CF) OCF (CF) —X ⁵ (17)

 2 2 n 3

 (Where n is an integer from 2 to 5)

CF = CFO (CF) — (CH) — X ⁵ (18)

 2 2 n 6 4

 (Where n is an integer from 1 to 6)

CF = CF (OCF CF (CF)) OCF CF (CF) X ⁵ (19)

 2 2 3 n 2 3

 (Where n is an integer from 1 to 2)

CH = CFCFO (CF (CF) CF O) CF (CF) X ⁵ (20)

 2 2 3 2 n 3

 (Where n is an integer from 0 to 5),

CF = CFO (CF CF (CF) θ) (CF) — X ⁵ (21)

 2 2 3 m 2 n

 (Where m is an integer from 0 to 5 and n is an integer from 1 to 3)

(In the general formulas (10) to (21), X ⁵ is a cyano group (one CN group), a carboxyl group (one COOH group) or an alkoxy carbo group (COOR ¹³ group, R ¹³ has 1 to 10 carbon atoms) And a monomer represented by an alkyl group). These can be used alone or in any combination.

 [0055] Specific examples of such vinylidene fluoride (VdF) fluororubber include VdF-H FP rubber, VdF—HFP—TFE rubber, VdF—CTFE rubber, VdF—CTFE—TFE. Preferred are rubbers.

 [0056] The tetrafluoroethylene (TFE) Z propylene-based fluororubber is preferably represented by the general formula (22).

[0057] One (M ³ ) — (M ⁴ ) — (N ² ) — (22)

(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 single unit. (It is a repeating unit derived from monomer (n ² ) copolymerizable with isomer (m ³ ) and monomer (m ⁴ ))

Tetrafluoroethylene (TFE) Z propylene-based fluororubber represented by the general formula (22) Of these, 40 to 70 mole structural unit M ^{3 _0/0,} the structural unit M ⁴ to 60-30 mol%, including those of preferably 50 to 60 mol of structural units M ³ than good Mashigu _^0/0, the structural unit M ⁴ are those containing from 50 to 40 mole _^0/0. The structural unit N ² is preferably 0 to 40 mol% based on the total amount of the structural unit M ³ and the structural unit M ⁴ ! /.

[0058] As the monomer (n ² ), any monomer can be used as long as it is copolymerizable with the monomer (m ³ ) and the monomer (m ⁴ ). It is preferable that For example, vinylidene fluoride, ethylene and the like.

 [0059] As the perfluoro fluorine rubber (a-2), those represented by the following general formula (23) are preferable.

[0060] One (M ⁵ ) One (M ⁶ ) — (N ³ ) — (23)

(In the formula, structural unit M ⁵ is a structural unit derived from tetrafluoroethylene (m ⁵ ), and structural unit M ⁶ is a structural unit derived from perfluoro (alkyl butyl ether) (m ⁶ ). N ³ is a repeating unit derived from monomer (m ⁵ ) and monomer (n ³ ) copolymerizable with monomer (m ⁶ )

Among the perfluoro fluorine-containing rubbers represented by the general formula (23) (a- 2), the structural unit M ⁵ 5 0 to 90 mole _^0/0, preferably those of the structural unit M ⁶ containing 10 to 50 mol% instrument more preferably structural units M ⁵ 50 to 80 mole _^0/0, which the structural unit M ⁶ comprising 20 to 50 mole _^0/0, more preferably a structural unit M ⁵ 55 to 70 mol%, the structural unit the M ⁶ are those containing 30 to 45 mol%. The structural unit N ^3, based on the total amount of the structural unit M ⁵ and the structural unit M ^6, and more preferably is preferable instrument 0-2 mol% it is 0-5 mol%. If the composition is out of the range, the properties as a rubber elastic body are lost and the properties tend to be close to those of greaves.

[0061] Examples of perfluoro (alkyl butyl ether) (m ⁶ ) include perfluoro (methyl butyl ether) and perfluoro (propyl butyl ether). These may be used alone or in any combination. Can do.

[0062] The monomer (n) may be any monomer as long as it is copolymerizable with the monomer (m ⁵ ) and the monomer (m ⁶ ). Or a monomer having a functional group Z or a monomer that provides a site that can be converted to the functional group Z.

[0063] A monomer having such a crosslinking site, a monomer having a functional group Z, or a functional group Examples of the monomer that provides a site that can be converted to the group z include bi-lidene fluoride, an iodine or bromine-containing monomer represented by the general formula (7), and a single monomer represented by the general formula (8). And monomers represented by the general formula (9), such as those described in JP-B-5-63482 and JP-A-7-316234 !, such as perfluoro (6, 6 dihydro Iodine-containing monomers such as 6 chloro 3 oxa 1 hexene) and perfluoro (5 chloro 3 oxa 1 pentene), CF = CFOCF CF described in JP-A-4217936

 twenty two

Iodine-containing monomers such as CH I, bromine described in JP-A-4-505341

twenty two

 -Containing monomer, a cyano group-containing monomer, a carboxyl group-containing monomer, an alkoxycarbo group-containing monomer as described in JP-A-4-505345 and JP-A-5-500070 Etc. Further, the monomers represented by the above (10) to (21) can be mentioned.

 [0064] These can be used alone or in any combination.

 [0065] Cyano group, carboxyl group, alkoxycarbol group force An oxazole ring, a thiazole ring, and an imidazole ring can be formed by a cyclization reaction with a reactive group possessed by the organic compound (B). Further, when the terminal is an iodine atom or a bromine atom, the fluorine-containing elastomer (A) used in the present invention can also be obtained by using an oxidation reaction or an addition reaction.

 [0066] Specific examples of strong perfluorinated rubber (a-2) include WO 97Z24381 pamphlet, JP-B 61-57324, JP-B 4-81608, JP-B 5-13961, etc. And fluororubber described in the above.

[0067] As the fluororubber ( _a ), a fluorine-containing elastomer having a carboxyl group at the end of the main chain, which uses ammonium persulfate, potassium persulfate, hydrogen peroxide, or the like as a polymerization initiator is preferable. Examples of the fluorine-containing elastomer include fluorine-containing elastomers described in International Publication No. 03/076484 pamphlet and International Publication No. 00/29479 pamphlet.

 [0068] 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 molding can be performed. . The above “normal temperature” means 0 to 50 ° C.

[0069] Specifically, the fluororubber (a) having fluidity at room temperature preferably has a viscosity at room temperature of 0.1 to 2000 Pa's 1 to: LOOOPa's. More preferred. Viscosity If it is less than 0. lPa'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, resulting in a molded product with a complicated shape. Tend to be difficult.

 [0070] Further, it is more preferable that the fluororubber (a) having fluidity at room temperature is preferably 50 to 75 having a mu-1 viscosity of 5 to 100 at room temperature. If the 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. Tend to be difficult to obtain. The Mu-one viscosity is a value obtained by measurement using a Mu-one viscometer MV2000 (manufactured by Monsantone) in accordance with JIS K 6300 (1994).

 [0071] The non-perfluorinated rubber (a-1) and perfluorinated rubber (a

 -2) can be produced by conventional methods.

 [0072] The radical polymerization initiator used for the polymerization may be the same as that conventionally used for the polymerization of the fluorine-containing elastomer. These initiators include organic and inorganic peroxides and azo compounds. Typical initiators include persulfates, peroxide carbonates, peroxyesters, and the like. Preferred initiators include ammonium persulfate (APS). APS can be used alone or in combination with a reducing agent such as sulfite or sulfite.

 [0073] A wide range of emulsifiers can be used as the emulsion polymerization. From the viewpoint of suppressing the chain transfer reaction to the emulsifier molecules during the polymerization, a fluorocarbon chain or a fluoropolyether chain is used. Desirable salts of carboxylic acids having The amount of emulsifier used is preferably about 0.05 to 2% by weight of the added water, and more preferably 0.2 to 1.5% by weight.

 [0074] The monomer mixed gas used in the present invention is the same as that in G. H. Kalb et al., Advances in Chemistry Series., 129, 13 (197

As described in 3), since it has explosive properties, it is necessary to devise measures to prevent the occurrence of sparks and the like as an ignition source in the polymerization apparatus.

[0075] The polymerization pressure can be varied within a wide range. Generally, it is in the range of 0.5-7 MPa. The higher the polymerization pressure, the higher the polymerization rate. From the viewpoint of improving productivity, It is preferably 8 MPa or more.

[0076] Examples of the fluorine-containing non-perfluoropolymer (b-1) containing a main chain ether include polymers of 2,2,3,3-tetrafluorooxetane, and JP-A 64-85218. It is synthesized by the method described in the publication.

[0077] The main chain ether-containing fluorine-containing perfluoropolymer (b-2) includes hexafluoropropylene oxide polymer and 2,2,3,3-tetrafluorooxetane hydrogen. Converted to fluorine, non-fluorinated polyether hydrogen converted to fluorine, using a reaction between perfluoromonomer such as tetrafluoroethylene and oxygen, or reaction between fluorine-containing monomer and oxygen And polymers obtained by perfluorination by fluorination reaction. Hexafluoropropylene oxide polymers can be synthesized by methods such as USP36603 15 and Makromol. Chem. 193, 2211-2219 (1992). The A polymer of 2,2,3,3-tetrafluorooxetane in which hydrogen is converted to fluorine is synthesized by a method described in JP-A No. 64-85218. A polymer obtained by reacting a fluorine-containing monomer with oxygen is synthesized by a method described in JP-A-61-187726 and JP-B-50-28409.

 [0078] Further, in the present invention, it is possible to use a composition having two or more kinds of fluoro rubber as described above.

 [0079] The fluorine-containing elastomer (A) used in the present invention contains a perfluoroalkylene unit and a Z or perfluoropolyether structure because it is excellent in heat resistance and chemical resistance and is easy to synthesize. Specifically, a polymer of hexafluoropropylene oxide and a copolymer of tetrafluoroethylene and perfluoroalkyl butyl ether are preferable. In addition, the main chain ether-containing fluoropolymers are preferred because they are excellent in low-temperature properties, and the main chain ether-containing perfluoropolymers are preferred in terms of excellent low-temperature properties, heat resistance, and chemical resistance.

[0080] The number average molecular weight of the fluorine-containing elastomer (A) used in the present invention is preferably 800 to 500000, more preferably 3000 to 100000, more preferably than force S. If the molecular weight is less than 800, the hardness of the cured product tends to increase and it becomes difficult to form a three-dimensional network structure by crosslinking. There is a tendency, and when it exceeds 500,000, the viscosity tends to be high and the moldability tends to decrease.

[0081] Further, the fluorine-containing elastomer (A) has a number average molecular weight of preferably 800 to 20000, more preferably 900 to 10,000. When the number average molecular weight is within this range, it is possible to obtain a molded article having fluidity at room temperature and a complicated shape. The number average molecular weight is a value determined by size exclusion chromatography (HLC-8020 manufactured by Tosoh Corporation, polystyrene standard).

 In the present invention, the organic compound (B) having a functional group Y or a site that can be converted to the functional group Y and a reactive group capable of undergoing a cyclization reaction with the functional group Z includes a fluorine-containing elastomer (A ) And a cyclization reaction are not particularly limited. The reactive group is preferably a reactive group capable of forming an oxazole ring, thiazole ring, or imidazole ring by cyclization reaction with the functional group Z of the fluorine-containing elastomer (A). .

 [0083] As the organic compound (B), the oxazole ring, thiazole ring, and imidazole ring can be formed by cyclization reaction with the functional group Z, from the general formula (2):

 [0084] [Chemical 11]

[0085] (In the formula, one of R ² and R ³ is —NH, and the other is —NH 2, one NHR ⁴ , —OH

 twenty two

Or —SH, R ⁴ is a monovalent organic group, and Y ¹ is a monovalent organic group having a functional group Y and a functional group Υ, or one having a site that can be converted to a functional group Υ. Is a valent group. ) Upsilon ¹ thing preferred tool formula (2) is found Aruke - group, a monovalent organic group having an alkenyl group, a monovalent organic group having a hydrogen atom bonded to Kei atom, Or general formula (3)

[0086] [Chemical 12]

[0087] (R ⁵ , R ⁶ , R ⁷ are the same force or different, each being a hydrogen atom or a monovalent hydrocarbon group that may contain a substituted or unsubstituted oxygen atom, and at least one of them. Is more preferably a monovalent organic group represented by a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having an alkenyl group.

[0088] Among these, Y ¹ is preferably a group represented by the general formula (3) from the viewpoint of excellent hydrosilylation reaction reactivity and excellent heat resistance at the crosslinking point.

[0089] As the combination of R ² and R ³ , the formed! /, The ring may be selected as appropriate. When it is desired to form an oxazole ring, R ² and R ³ are a combination of —NH and OH. Yes, cheer

 2

When it is desired to form a sol ring, R ² and R ³ are a combination of —NH and SH.

 2

If you want to form a sol ring, R ² and R ³ are both —NH forces, or —NH and —

 twenty two

NHR ⁴ combinations can be selected. Among these, the raw materials of the organic compound (B) can be obtained at low cost, so R ² and R ³ are mixed with —NH and —OH.

 2

 Preferred to form a sazol ring.

[0090] Of these, the combination of -NH and one NHR ⁴

 2

 In combination, it is preferable to form an imidazole ring.

[0091] R ⁴ is a monovalent organic group, and examples of the monovalent organic group include, but are not limited to, an aliphatic hydrocarbon group, a phenyl group, and a benzyl group. Specifically, for example, a lower alkyl group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms such as —CH 2, 1 CH, 1 CH;

3 2 5 3 7

 F, 1 C F, -CH F, -CH CF, — CH C F, etc.

3 2 5 2 2 3 2 2 5

 Fluorine atom-containing lower alkyl group; phenyl group; benzyl group; C F, 1 CH C F, etc.

 Phenyl or benzyl group in which 1 to 5 hydrogen atoms are replaced by fluorine atoms of 6 5 2 6 5; C

 6

1 to 5 hydrogens in CF such as H (CF), 1 CH C H (CF) (n is an integer from 1 to 5)

5-n 3 n 2 6 5-n 3 n 3

 Examples thereof include a phenyl group or a benzyl group in which an atom is substituted. Of these, a phenol group and —CH are preferred because they are particularly excellent in heat resistance, have good crosslinking reactivity, and are relatively easy to synthesize.

 Three

[0092] Examples of the alkyl group for Y ¹ include a bur group, a allyl group, a probe group, an isopropyl group, a butyr group, an isobutenyl group, a hexyl group, a cyclohexyl group, and the like. Number of carbon atoms

2 to 4 alkenyl groups can be mentioned. In addition, a monovalent having a alkenyl group of Y ¹ Examples of the organic group include alkoxyalkyl groups such as a vinyloxycetyl group, an aryloxychetyl group, and a hexyloxypropyl group. Examples of the monovalent organic group having a hydrogen atom bonded to the Y ¹ key atom include dimethylhydrogensilyldimethylsilyl group and dimethylhydrogensilylethyldimethylsilyl group.

[0093] Further, R ⁵ in the general formula (3),

R ⁷ is a hydrogen atom or a monovalent hydrocarbon group which may contain a substituted or unsubstituted oxygen atom, and at least one of them is a hydrogen atom or alkenyl. A substituted or unsubstituted monovalent hydrocarbon group having a group.

 [0094] Examples of the unsubstituted monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.

 [0095] Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, and an octyl group. , Nonyl group, decyl group and the like having 1 to 3 carbon atoms: LO alkyl group, and more representative examples are lower alkyl having 1 to 3 carbon atoms such as methyl group, ethyl group and propyl group. Group: butyl group, tert-butyl group, hexyl group, octyl group.

 [0096] 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 a cyclopentyl group and a cyclopentyl group. A cycloalkyl group having 5 to 6 carbon atoms such as a hexyl group.

 [0097] Examples of the aryl group include aryl groups having 6 to 15 carbon atoms such as phenyl group, tolyl group, xylyl group, naphthyl group, biphenyl group, and the like. Are aryl groups having 6 to 8 carbon atoms, such as a phenol group, a tolyl group, and a xylyl group.

[0098] Examples of the aralkyl group include aralkyl groups having 7 to 7 carbon atoms such as a benzyl group, a phenyl group, a phenylpropyl group, and a methylbenzyl group, and more representative examples thereof. Is a aralkyl group having 7 to 8 carbon atoms, such as a benzyl group or a phenyl group. [0099] Examples of the alkenyl group include carbons such as a vinyl group, a aryl group, a propenyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, and a cyclohexyl group. Examples thereof include alkenyl groups having 2 to 10 atoms, and more representative examples thereof are alkenyl groups having 2 to 4 carbon atoms such as vinyl group, allyl group and butyr group.

 [0100] Further, the substituted monovalent hydrocarbon group includes a (meth) atalylooxypropyl group, and! / ヽ represents at least a part of the hydrogen atoms of the unsubstituted monovalent hydrocarbon group as a fluorine atom. , A chlorine atom, a bromine atom, an iodine atom, a group substituted with a halogen atom such as S--, and representative ones include, for example, a chloromethyl group, a 2-bromoethyl group, a 3-propyl propyl group, 3, 3 , 3-trifluoropropyl group, 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluoro hexyl group and other halogen substituted alkyl groups having 1 to 8 carbon atoms. Such as 3, 3, 3—trifluoropropyl group, 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl group, etc., halogen substitution with 3 to 8 carbon atoms It is an alkyl group.

 [0101] Specifically, as the group represented by the general formula (3),

 [0102] [Chemical 13]

CH _2,

P h P h C C H. C F

 S i C H = C H H S H

 I

CH ₃ CHCH

CH ₂ CH ₂ CF

 S i One C H = C H

 I

C II.

[0103] (Ph represents a phenyl group)

 Among these, the group represented by the general formula (3) is relatively inexpensive, easy to synthesize, and excellent in cross-linking reactivity.

[0104] [Chemical 14] 13

 S i---- rf = C H 2 /

 C H 3 C II 3

[0105] is preferable.

[0106] Y ¹ is an alkenyl group, a monovalent organic group having an alkenyl group, or R ⁵ from the viewpoint of excellent stability of the crosslinking group.

Heat resistance of a molded article of a curable composition comprising a fluorine-containing elastomer preferably represented by the general formula (3) in which at least one of R ⁷ is a substituted or unsubstituted monovalent hydrocarbon group having an alkenyl group In terms of chemical resistance and stability of the cross-linking group,

 [0107] [Chemical 15] 1 "ϊ

― S i— CH = CH ₂

[0108] is preferable.

 [0109] As the organic compound (B), specifically,

[0110] [Chemical 16]

[0111] Among them, among them, as for the strength that raw materials are available and synthesis is easy,

[0112] [Chemical 17]

[0113] is preferable.

 [0114] Further, since the heat resistance and chemical resistance of the molded product of the curable composition that also has the power of fluorine-containing elastomer is excellent,

[0115] [Chemical 18]

[0116] is preferable.

 [0117] Further, as another organic compound (B), since it is inexpensive and easy to synthesize, it contains a monovalent organic group having an alkenyl group, and the j8 position of the amino group and amino group. An aliphatic hydrocarbon compound having a hydroxyl group, an amino group or a mercapto group bonded thereto is preferred. Specifically, because the raw materials are cheap and easy to synthesize,

 [0118] [Chemical 19]

[0119] is preferable.

[0120] Further, as another organic compound (B), it is possible to form a triazine ring by cyclization reaction with the functional group Z. From the general formula (24) (25):

[0122] (Y ⁵ is a monovalent organic group having a alkenyl group or an alkenyl group, a monovalent organic group having a hydrogen atom bonded to a silicon atom, or a compound represented by the general formula (3):

 [0123] [Chemical 21]

[0124] (R ⁵ , R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group which may contain a substituted or unsubstituted oxygen atom, and at least one of them. Is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having an alkenyl group.

It is preferable that it is a compound shown by these. In addition, examples of Y in the formula include the same groups as Y ¹ described above.

 [0125] The addition amount of the organic compound (B) is preferably 1 to 5 moles relative to 1 mole of the functional group Z of the fluorine-containing elastomer (A). It is more preferable. If the addition amount is less than 0.5 mol, there is a tendency that a sufficient crosslinking group cannot be introduced into the fluorine-containing elastomer. Yes.

[0126] The cyclization reaction conditions are not particularly limited as long as they are appropriately selected depending on the types of the fluorine-containing elastomer (A) and the organic compound (B). [0127] In the cyclization reaction, a solvent may be used to increase the reaction rate of the cyclization reaction. As the solvent, it is preferable to use either a fluorine-containing elastomer (A) or an organic compound (B) or a solvent in which both are soluble, and a solvent in which both are soluble is more preferable.

 [0128] The solvent to be used is appropriately selected according to the structures of the fluorine-containing elastomer (A) and the organic compound (B), but the functional group Z of the fluorine-containing elastomer (A) and the organic compound (B) Preferred is a solvent that is not reactive with the amino group, hydroxyl group or mercapto group.

 [0129] The reaction is preferably performed at 50 to 250 ° C for 0.1 to 15 hours.

[0130] In the present invention, examples of the cyclization reaction include the following reactions.

[0131] [Chemical 22]

(Or CN)

[0132] (where X ¹ ,

Same as above, 前 記, ΧΊ—NR OS. )

Examples of the functional group の of the crosslinkable fluorine-containing elastomer of the present invention obtained by the cyclization reaction include Υ ¹ of the organic compound (Β), and are alkenyl groups because they can be cured by a hydrosilylation reaction. Or a monovalent organic group having an alkyl group, a monovalent organic group having at least one hydrogen atom bonded to a silicon atom, or the general formula (3):

[0133] [Chemical 23]

(R ⁵ , R ⁶ , and R ⁷ are the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group that may contain a substituted or unsubstituted oxygen atom, and at least one of them. Is preferably a hydrogen atom or a monovalent organic group represented by a substituted or unsubstituted monovalent hydrocarbon group having an alkenyl group. [0135] Further, as the organic compound (B), a compound having a site that can be converted to the functional group Y is preferable. As the site that can be converted to the functional group Y, iodine or bromine, which is preferably halogen, is particularly preferable because it can be converted by a Grignard reaction or a coupling reaction.

 [0136] Further, the present invention provides the general formula (5):

[0137] [Chemical 24]

[0138] (wherein, X ² is - NH -, - NR ¹¹ -, - O -, - a S-, R ¹¹ is a monovalent organic group, Y ² is, Aruke - group, Or a monovalent organic group having an alkenyl group, a monovalent organic group having at least one hydrogen atom bonded to a silicon atom, or the general formula (3):

 [0139] [Chemical 25]

R ⁶

S 1----■ R ⁶

[0140] (R ⁵ , R ⁶ and R ⁷ are the same force or different, each being a hydrogen atom or a monovalent hydrocarbon group which may contain a substituted or unsubstituted oxygen atom, and at least one of them. Is a monovalent organic group represented by a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having an alkenyl group. )

 And a crosslinkable fluorine-containing elastomer having a functional group Y represented by

[0141] The monovalent organic group of R ¹¹ is not particularly limited as long as it is the monovalent organic group described above.

[0142] In the method of the present invention, an unsaturated group or a -SiH group can be introduced into the main chain terminal and Z or side chain terminal of the fluorine-containing elastomer via a specific ring structure. By using a specific ring structure, it is excellent in heat resistance and chemical resistance, and by cross-linking such a curable composition comprising a fluorine-containing elastomer, a molded product having excellent heat resistance and chemical resistance can be obtained. It can be obtained. [0143] Next, the curable composition of the present invention will be described.

 [0144] The curable composition of the present invention comprises a crosslinkable fluorine-containing elastomer having a functional group Y at the main chain end and Z or side chain end. The inclusion of a compound is preferable from the viewpoint of obtaining a sufficiently crosslinked cured product.

 [0145] Preferred examples of the compound capable of crosslinking reaction include polyfunctional compounds having a plurality of functional groups capable of reacting with the fluorine-containing elastomer in the molecule. 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.

 [0146] Further, in order to sufficiently crosslink the curable yarn and the composition, it is preferable to use a polyfunctional compound corresponding to the cross-linked site of the fluorine-containing elastomer. Hereinafter, the power to give a specific example of the polyfunctional compound The polyfunctional compound may be used alone or in combination of two or more.

 [0147] When the crosslinkable site is an alkenyl group, preferred examples of the polyfunctional compound include a compound having a SiH group and a polyfunctional unsaturated compound.

 —The compound containing a SiH group acts as a crosslinking agent for the fluorine-containing elastomer. The SiH group-containing compound is not particularly limited as long as it has two or more hydrogen atoms bonded to a silicon atom, that is, a hydrosilyl group (SiH group) in one molecule, but the fluorine-containing elastomer is not limited. Considering compatibility with one component, dispersibility, and uniformity after curing, one or more monovalent perfluoroalkyl groups, monovalent perfluoroalkyl groups, divalent perfluoro groups in one molecule Those having a fluoroalkylene group or a divalent perfluoroalkylene group are preferred.

 [0149] Examples of the perfluorooxyalkyl group, the perfluoroalkyl group, the perfluoroalkylene group, and the perfluoroalkylene group include those represented by the following general formula.

 [0150] Monovalent perfluoroalkyl group: C F — (where m is 1

 m 2m + l to 20, preferably an integer of 2 to 10. )

 Divalent perfluoroalkylene group: C F (where m is 1

 m 2m to 20, preferably 2 to 1

It is an integer of 0. )

Monovalent perfluoroalkyl group: [0151] [Chemical 26]

^F — ⁽ ? ^FCF20) “? ^F —

 し 卜 3 し 卜 ■ ¾

F— (CFCF ₂ 0) _n — CF ₂ CF ₂ —

 I

[0152] (where n is an integer of 1 to 5)

 Divalent perfluoroalkylene group:

[0153] [Chemical 27]

-(CFOCF ₂ ) n-(CF20CF) _m -Crs and F3

[0154] (where m is an integer of 1 to 50, n is an integer of 1 to 50, and m + n satisfies 2 to 100).

 -(CF O) One (CF CF O) — CF—

 2 m 2 2 η 2

 (However, m and η are integers of 1 to 50, respectively.)

 Divalent linking groups that connect these perfluoroalkyl groups, perfluoroalkylalkyl groups, perfluoroalkylene groups, or perfluoroalkylene groups with the silicon atoms include alkylene groups, arylenes, and the like. Specifically, a group or a combination thereof, or an ether bond oxygen atom, an amide bond, a carbonyl bond, or the like may be interposed between these groups, —CH 2 CH 1, —CH 2 CH 2 CH 2 — , — CH CH CH Ο

 2 2 2 2 2 2 2 2

CH―, -CH CH CH— NH— CO—, one CH CH CH— N (Ph) —CO— (however

2 2 2 2 2 2 2

 , Ph is a phenol group), — CH CH CH— N (CH) — CO—, — CH CH CH—

 2 2 2 3 2 2 2

Examples thereof include those having 2 to 12 carbon atoms such as O—CO—.

[0155] In addition, the monovalent or divalent fluorine-containing substituent in the compound containing a SiH group, that is, a perfluoroalkyl group, a perfluoroalkylalkyl group, a perfluoroalkylene group, or a perfluorooxy group. Other than monovalent organic groups containing alkylene groups Examples of the monovalent substituent bonded to the silicon atom include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, an octyl group, and a decyl group; An alkenyl group such as a aryl group; an aryl group such as a phenyl group, a tolyl group and a naphthyl group; an aralkyl group such as a benzyl group and a ferroethyl group; and at least some of the hydrogen atoms of these groups are chlorine atoms; Examples thereof include unsubstituted or substituted hydrocarbon groups having 1 to 20 carbon atoms, such as chloromethyl group, chloropropyl group, and cyanoethyl group, which are substituted with a cyano group.

 [0156] As the compound having a SiH group, a compound having a structure that is difficult to be decomposed under acidic or alkaline conditions is used in order to improve chemical resistance such as acid resistance and alkali resistance of the cured product. Also preferred.

 [0157] As a compound having a structure that is difficult to be decomposed under acidic or alkaline conditions, a compound that does not have a Si-O Si bond is preferred, and a compound described in JP-A-2001-354764, or Examples thereof include compounds described in 2002-12597.

 [0158] The compound containing a SiH group may be any of cyclic, chain, three-dimensional network, and combinations thereof. The number of key atoms of the organic key compound is not particularly limited, but is usually about 2 to 60, preferably about 3 to 30.

 [0159] Examples of such organic cage compounds include the following compounds. In the following formulae, Me represents a methyl group, and Ph represents a phenyl group. These compounds can be used alone or in combination of two or more.

[0160] [Chemical 28]

Me

 I.

 CgFi 7CH2C i2oi (OSi— H) 3

 Me

Me

 I

C ₈ F ₁₇ CH ₂ CH ₂ Si (CH ₂ CH ₂ S 卜 H) ₃

 Me

Me Me Me Me

 I I! I

(H_SiO) ₂ S to H ₂ CH ₂ (CF ₂ ) ₆ CH ₂ CH ₂ Si (OS 卜 H) ₂

 Me Me

Me Me

 I I

(H_SiO) ₃ S to H2C H ₂ (CF ₂ ) ₆ CH ₂ CH ₂ Si (OS to H) 3

 Me Me

Me O O Me

I «II I

(H-SiO) ₃ Si (CH ₂ ) 3NHC (CF ₂ CF ₂ 0) _m (CF ₂ 0) _n CF ₂ CNH (CH ₂ ) ₃ Si (OSi-H) 3

Me Me

[0161] (where m is an integer of 1 to 20, average 10 and n is an integer of 1 to 10 and average 6)

[0162] [Chemical 29]

 [0163] [Chemical 30]

 u = 1-200, v = 1-200

[0164] [Chemical 31]

[39 TO]

.6.TC / 900Zdf / X3d 63 οιεMeta · οοζ Ο

TTsiosiQI () 23CH

HI

[0169] and n is an integer of 1 to 30, m is an integer of 1 to 30, and n + m is 2 to 60, average 2 to

Satisfies 50. )

[0170] [Chemical 35]

Ph 0 0 Ph

S— (CH ₂ ) 3— N— C— (CFOCF ₂ ) _n (CF ₂ OCF) _m — C— N— (CH ₂ ) 3— S

 CF3 CF3

 [0171] (However, S is

 [0172] [Chemical 36]

[0173] and n is an integer of 1 to 30, m is an integer of 1 to 30, and n + m is 2 to 60, average 2 to

Satisfies 50. )

[0174] [Chemical 37]

0 Me H Me 0

C ₃ F ₇ OCFCF ₂ OCF— C— N— (CH ₂ ) ₃ — (SiO) _n — (CH ₂ ) ₃ — N— C— CFOCF ₂ CFOC ₃ F ₇ CF ₃ CF ₃ Me CF ₃ CF ₃

[0175] (where n represents an integer of 2 to 60 and an average of 3 to 50)

[0176] [Chemical 38] Ph O

 I II

 N -C-CFOCF2CFOC3F7

 I! i

H (CH ₂ ) ₃ CF ₃ CF ₃

Me ₃ SiO (SiO) _n SiOSiMe ₃

 Me Me

[0177] (However, n represents an integer of 2 to 60 and an average of 3 to 50.)

[0178] [Chemical 39]

H and H and then 3 and 3

Me ₃ SiO (SiO) _n SiOSiMe ₃

 Me Me

[0179] (where n represents an integer of 2 to 60 and an average of 3 to 50)

 In addition, the crosslinking site has a fluorine-containing elastomer which is a monovalent organic group having at least one unsaturated bond, such as a monovalent organic group having at least one alkenyl group or alkenyl group, and the SiH group. In the case of a curable composition comprising a compound, it is preferable to add a hydrosilylation reaction catalyst from the viewpoint of the reactivity of the hydrosilylation reaction.

 [0180] The hydrosilylation reaction catalyst may be any catalyst that promotes the addition reaction (fluorene hydrosilylation reaction) between a fluorine-containing elastomer and a compound having two or more Si H groups in one molecule. Without limitation, for example, an addition reaction catalyst comprising a platinum group element such as a platinum-based catalyst, a palladium-based catalyst, or a rhodium-based catalyst (Group 8 metal catalyst such as Group 8 metal, Group 8 metal complex, Group 8 metal compound, etc. Of these, platinum-based catalysts are preferred because they are relatively easily available.

[0181] The platinum-based catalyst is usually a known one used for addition-curing type curing. For example, a finely divided metal platinum catalyst described in US Pat. No. 2,970,150, US Pat. , 823, 218, a platinum-hydrocarbon complex compound described in U.S. Pat.No. 3,159,601 and U.S. Pat.No. 159,662. A complex compound of salt and platinum acid and olefin described in US Pat. No. 3,516,946, US Examples thereof include complex compounds of platinum and vinylsiloxane described in Japanese Patent No. 3,775,452 and US Pat. No. 3,814,780. More specifically, platinum alone (platinum black); chloroplatinic acid; complex of chloroplatinic acid and olefins such as ethylene; salt 匕 complex of platinic acid and alcohol or bursiloxane; silica, alumina, carbon, etc. Platinum supported on the carrier.

[0182] The palladium-based catalyst is composed of palladium, a palladium compound, chloropalladic acid, and the rhodium-based catalyst is composed of rhodium, a rhodium compound, salted rhodium acid, and the like. For example, RhCl (PPh) , RhCl (CO) (PPh), RhCl (CH), Ru (CO)

 3 3 3 2 2 4 2 3

IrCl (CO) (PPh), Pd (PPh) (Ph represents a phenol group), and the like.

12 3 2 3 4

 [0183] The hydrosilylation reaction catalyst may also be a Lewis acid, cobalt carbo- hydrate, and the like.

 [0184] It is preferable to use a reaction inhibitor. Examples of reaction inhibitors include benzotriazole; acrylonitrile; N, N diallylacetoamide, N, N diallyl benzamide, N, N,, ', Ν, -tetraaryl-ο phthalic acid diamide, Ν, Ν , Ν ', Ν, -Tetralylulu m-phthalic acid diamide, N, N, Ν', Ν, -tetraaryl-ρ-phthalic acid diamide, etc .; ai; phosphorus; nitrogen; aminic compound; Phosphorus compound; Tin; Tin compound; Tetramethyltetravinylcyclotetrasiloxane; Hyde mouth peroxide and other organic peroxides.

 [0185] Examples of the above reaction inhibitor include, for example, 1-Lu 1-hydroxycyclohexane, 2-methyl-3-butyne-2ol, 3,5 dimethyl-1, monohex-3-ol, and phenol. -Acetylene alcohols such as rubutinol, 3-methyl-3-pentene 1-yne, 3,5 dimethyl 1-3 hexene 1-yne, 3-methyl 1-pentene 1-3-ol, US Pat. No. 3,445,420 It may be a compound exemplified as the compound (4) in the specification, or a acetylene compound such as a compound exemplified as the component (2) in JP-B-54-3774.

[0186] When the crosslinkable site has a structure having a -SiH group, it is preferable to use a polyfunctional unsaturated compound. In that case, it is preferable to use the hydrosilylation reaction catalyst in combination. [0187] The addition amount of the crosslinkable fluorine-containing elastomer of the present invention and the compound capable of crosslinking reaction is such that the fluorine-containing compound of the crosslinkable compound is capable of crosslinking with respect to 1 mol of the functional group Y of the crosslinkable fluorine-containing elastomer. The reactive group capable of reacting with the elastomer is preferably 0.2 to 20 mol, and more preferably 0.5 to 10 mol. If the amount is less than 2 mol, there is a tendency that sufficient crosslinking cannot be performed, and if the amount exceeds 20 mol, crosslinking cannot be performed sufficiently.

 [0188] In addition, the curable composition of the present invention can be expected to have a function as a processing aid, and therefore other fluorinated elastomers that are not included in the fluorinated elastomer obtained by the production method of the present invention described above. Including, ok.

 [0189] The curable composition of the present invention includes a reduction in thermal shrinkage at the time of curing, a decrease in the thermal expansion coefficient of the elastic body obtained by curing, thermal stability, weather resistance, chemical resistance, flame retardancy, or A filler may be added for the purpose of improving the mechanical strength and lowering the gas permeability. In this case, examples of the additive include silica such as fumed silica and precipitated silica, quartz powder, glass fiber, carbon, iron oxide, titanium oxide, cerium oxide and other metal oxides, calcium carbonate, magnesium carbonate, and the like. The metal carbonate can be mentioned. Further, if necessary, an appropriate pigment, dye or anti-oxidation agent can be added.

 [0190] Then, the curable composition of the present invention can be prepared by adding usual additives, for example, processing aids, plasticizers, colorants, acids, and the like, which are blended into the curable composition that is fluorinated elastomer as necessary.匕 で き Anti-aging agents, anti-aging agents, ozone degrading agents, UV absorbers, etc. can be added, and one or more conventional cross-linking agents and cross-linking aids different from the above may be added. Each component can be prepared by mixing using an ordinary elastomer processing machine such as an open roll, a Banbury mixer, a kneader or the like. In addition, it can also be prepared by a co-coagulation method such as a method using a closed mixer or a emulsion mixing vessel. 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, calender molding, dip molding, coating, etc. by dissolving in a solvent.

[0191] The crosslinking conditions vary depending on the molding method and the shape of the molded product, but are generally in the range of 100 ° C to 300 ° C for several seconds to 5 hours. In order to stabilize the physical properties of the cross-linked product, You may go on a bridge. Secondary crosslinking conditions are 150 ° C to 300 ° C for 30 minutes to 48 hours.

 [0192] If the fluorine-containing elastomer obtained by the production method of the present invention has a low molecular weight and is fluid at normal temperature, it can be mixed with a planetary mixer or a tabletop mixer. At this time, the temperature may be increased to 50 ° C or higher in order to increase the mixing efficiency.

 [0193] A curable composition having fluidity at room temperature is usually processed with an extrusion gun such as hot melt gun at a temperature of 200 ° C or lower, injection molding or extrusion molding with a LIMS (Liquid Injection Molding System) molding machine, Molding can be performed by pouring into a mold at room temperature to 200 ° C.

 [0194] As a method of crosslinking the curable composition, other methods than the above can be used depending on the type of the crosslinking site.

[0195] The molded article of the present invention can be suitably used in the following fields.

[0196] 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, o (square) rings, packings, sealing materials, tubes Rolls, coatings, linings, gaskets, diaphragms, hoses, adhesives, etc. These include CVD equipment, dry etching equipment, wet etching equipment, oxidation diffusion equipment, sputtering equipment, ashing equipment, cleaning equipment, ion implantation. It can be used for equipment, exhaust equipment, chemical piping, and gas piping. Specifically, as the gate valve O-ring and seal material, the quartz window O-ring and seal material, the chamber O-ring and seal material as the gate O-ring and seal material as the bell jar O-ring and seal O-ring of coupling as seal material, O-ring of pump as seal material, seal material, diaphragm, O-ring of gas control device for semiconductor, O-ring for seal developer as seal material, seal material Wafer for wafer cleaning solution, tube as a wafer material, roll for wafer transfer, resist developer tank, stripping liquid tank lining, coating as wafer cleaning liquid tank lining, coating as plasma etching process, As an insulating layer for electrostatic chuck in ion implantation process, or wet etching Grayed tank lining, can be used as Kotin grayed. In addition, sealing material 'sealing agent, optical fiber's quartz coating Covering materials, insulation, anti-vibration, waterproofing, moisture-proof electronic parts, circuit board potting, coating, adhesive seals, gaskets for magnetic storage devices, modified materials for sealing materials such as epoxies, clean room 'clean equipment Used as sealant.

 [0197] In the automotive field, gaskets, shaft seals, valve stem seals, sealing materials, coatings, pottings, protective agents, adhesives and hoses can be used for engines and peripheral devices, and hoses and sheathing materials are used for AT equipment. 0 (square) rings, tubes, knocks, valve cores, hoses, seals and diaphragms can be used in fuel systems and peripheral devices. Specifically, engine head gasket, metal gasket, oil pan gasket, crankshaft seal, camshaft seal, valve stem seal, hold packing, oil hose, oxygen sensor seal, A TF hose, injector O-ring , Injector packing, Fuel pump O-ring, Diaphragm, Fuel hose, Crankshaft seal, Gear box seal, No. 1 piston seal, Cylinder liner seal, Valve stem seal, Automatic transmission front pump seal, Rear axle Pinion seal, universal joint gasket, speedometer pinion seal, foot brake piston cup, torque transmission O-ring, oil seal, exhaust gas recombustion device seal, bearing seal , EGR tube, twin cap tube, diaphragm for carburetor sensor, anti-vibration rubber (engine mount, exhaust part, etc.), hose for recombustion device, oxygen sensor bush, protective material for pressure sensor, It can be used as an adhesive or the like.

 [0198] In the aircraft field, rocket field, and ship field, there are diaphragms, O (square) rings, valves, tubes, knockers, hoses, sealants, adhesives, etc., which can be used in 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. Screw propeller shaft stern seal, diesel engine valve stem seal

It is used for valve seals of butterfly valves, shaft seals of butterfly valves, and the like.

[0199] In the field of chemicals such as plants, linings, valves, knocks, rolls, hoses, diaphragms, o (square) rings, tubes, sealing materials, chemical-resistant coatings, etc. They can be used in the production process of chemicals such as pharmaceuticals, agricultural chemicals, paints and oils. Specifically, chemical pumps, rheometers, pipe seals, heat exchanger seals, glass cooler packings for sulfuric acid production equipment, pesticide sprayers, seals for pesticide transfer pumps, gas pipe seals, plating solutions Seals, high-temperature vacuum dryer packing, paper belt roller seals, fuel cell seals, wind tunnel joint seals, trichlene-resistant rolls (for textile dyeing), acid-resistant hoses (for concentrated sulfuric acid), gas chromatography, pH It can be used as a packing for a tube connection part of a meter, a chlorine gas transfer hose, a benzene, a rainwater drain hose for a toluene storage tank, an analytical instrument, a seal for a scientific instrument, a tube, a diaphragm, a valve part, and the like.

[0200] In the pharmaceutical field such as pharmaceuticals and cosmetics, it can be used as an additive for cosmetics and the like such as medicine plugs.

 [0201] In the photographic field such as a developing machine, the printing field such as a printing machine, and the coating field such as a painting facility, rolls are listed, which are respectively used for a film developing machine, a tangential film developing machine, a printing roll, and a coating roll. be able to. Specifically, as a developing roll of a film developing machine / coiled film image forming machine, a gravure roll of a printing roll, a guide roll, a gravure roll of a magnetic tape manufacturing coating line of a coating tool, and a magnetic tape manufacturing coating It can be used as a line guide 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 It can be used as a roll, a roll for a printing press, a belt, or the like.

 [0202] Tubes can also be used in the analysis and science machine field.

 [0203] In the field of food plant equipment, linings, valves, knockers, rolls, hoses, diaphragms, ο (square) rings, tubes, sealing materials, belts, adhesives, etc., can be used for food manufacturing processes. it can. Specifically, it can be used as a plate-type heat exchanger seal, a solenoid valve seal of a vending machine, or the like.

 [0204] In the field of nuclear power plant equipment, packing, scissors rings, hoses, sealing materials, diaphragms, nozzles, rolls, tubes, adhesives and the like are listed.

[0205] In the steel field, such as iron plate processing equipment, rolls, etc., are used for iron plate processing rolls, etc. It can be done.

 [0206] 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, Examples include roll blades, belts, adhesives, and coating agents. Specifically, hydraulic seals, lubrication machinery seals, bearing seals, dry cleaning equipment windows, other seals, uranium hexafluoride concentrator seals, cyclotron seal (vacuum) valves, automatic packaging machines It is used for seals, sulfurous acid gas in the air, diaphragms for chlorine gas analysis pumps (pollution measuring devices), printing press rolls, belts, pickling squeeze rolls, and so on.

 [0207] In the electrical field, specifically, it is used as an insulating oil cap for Shinkansen, a ventilator seal for liquid-sealed transformers, a jacket for oil well cables, and the like.

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

 [0209] In the electronic parts field, specifically, heat radiation materials, electromagnetic shielding material materials, modified materials for printed wiring board pre-preda resin such as epoxy, anti-scattering materials for light bulbs, gaskets for computer hard disk drives, etc. Used.

 [0210] There are no particular limitations on what can be used for on-site molding, such as coatings for metal gaskets for automobile engines, gaskets for engine oil pans, rolls for copiers and printers, Architectural sealant, gasket for magnetic recording device, sealant for clean room filter unit, coating agent for printed circuit board, electrical 'electronic component fixing agent, insulation moisture-proof treatment of electrical equipment lead wire terminal, electric furnace, etc. Oven seal, sheathed heater end treatment, microwave window frame seal, CRT edge and neck adhesion, automotive electrical component adhesion, joint seals for kitchens, bathrooms, toilets, etc., liquid crystal, CRT, plasma, etc. Gasket to be applied to the sealing surface using surface coating of display device, anti-reflection film, and application robot FIPG is Lumpur, a coating agent for release paper and the like.

[0211] The curable composition of the present invention makes use of the cleanliness, and is used for gaskets for magnetic recording devices (hard disk drives), semiconductor manufacturing equipment, and wafer storage devices such as wafer storage. It is particularly preferably used as a sealing material for clean equipment such as a sealing material.

 [0212] The curable composition of the present invention utilizes characteristics such as chemical resistance, low gas permeability, and flame retardancy, and is used for fuel cells such as packing used between fuel cell electrodes and pipes around them. It is also particularly suitable for seal materials.

 [0213] Furthermore, the present invention provides a compound of the general formula (4)

 [0214] [Chemical 40]

[0215] (In the formula, one of R 1 and R 2 is —NH, and the other is —NH 2, 1 NHR ′, —OH

 twenty two

Or —SH, R ⁴ is a monovalent organic group, R ⁸ , R ⁹ , R ^{1 (>} are the same force or different, each containing a hydrogen atom or a substituted or unsubstituted oxygen atom. It may be a monovalent hydrocarbon group).

[0216] The silicon-containing compound of the present invention is exemplified by the same compounds as described above as —SiR ⁸ R ⁹ R ^{1Q in} the general formula (4).

[0217] [Chemical 41]

H

 [0218] It is preferable that the fluorine-containing elastomer produced using this compound can be crosslinked by a hydrosilylation reaction.

[0219] The silicon-containing compound of the present invention is synthesized, for example, by the following method.

[0220] After the compound represented by the following general formula (26) was reacted with magnesium to prepare a Grignard reagent, this was reacted with triorganochlorosilane to introduce an organosilyl group, and R ^U , R ¹² Is converted to R ² and R ³ by a deprotection reaction.

[0221] [Chemical 42]

(X ⁶ is a halogen atom, R ″ and R ¹⁵ are groups obtained by converting the hydrogen atoms of R ² and R ³ into protecting groups for the Grignard reaction.)

 As a protective group for the Grignard reaction, any commonly used protecting group may be used.

And a triorganosilyl group.

 Example

 [0223] Next, the present invention will be described with reference to examples. However, the present invention is not limited to only the examples that work.

[0224] Example 1 (Synthesis of Organic Compound (B))

 A 500 ml flask equipped with a Dimroth condenser and dropping funnel was charged with 12 g (500 mmol) of magnesium powder, 200 g of tetrahydrofuran and 0.03 g of iodine under no water, and heated while compound (I):

[0225] [Chemical 43]

[0226] 59.47 g (125 mmol) was added dropwise to prepare a Grignard reagent. After aging at 60 ° C. for 2 hours, 15 g (125 mmol) of butyldimethylchlorosilane was added dropwise. After aging at 60 ° C for 2 hours, purification was performed to obtain compound (Π) in a yield of 65%. Compound (II) was confirmed by ¹ H-NMR and IR analysis. C

[0227] [Chemical 44]

Compound (II) 5. Og was dissolved in 20 ml of methanol, stirred at 50 ° C. for 2 hours, and then purified to obtain Compound (I) (M 192. 33) in a yield of 85%. Compound (III) is ¹ H-NMR, IR, MS

 w

 Confirmed by analysis.

[0229] [Chemical 45]

[0230] Example 2 (Synthesis of organic compound (B))

 A 500 ml flask equipped with a Dimroth condenser and dropping funnel was charged with 12 g (500 mmol) of magnesium powder, 200 g of tetrahydrofuran and 0.03 g of iodine under water-free conditions, while heating compound (IV):

[0231] [Chem 46]

[0232] 50.6 g (125 mmol) was added dropwise to prepare a Grignard reagent. After aging at 60 ° C. for 2 hours, 15 g (125 mmol) of butyldimethylchlorosilane was added dropwise. After aging at 60 ° C for 2 hours, purification was performed to obtain Compound (V) in a yield of 55%. Compound (V) was confirmed by ¹ H-NMR and IR analysis.

[0233] [Chemical 47]

[0234] Compound (V) 5. Og was dissolved in a mixed solution of 20 ml of methanol and 0.2 g of triethylamine, stirred at 50 ° C for 2 hours, and purified to obtain Compound (VI) (M 192. 33). Obtained at a rate of 80%.

 W

Compound (VI) was confirmed by ¹ H-NMR, IR, and MS analysis.

[0235] [Chemical 48]

[0236] Example 3

 In a flask equipped with a stirrer, thermometer and Dimroth condenser, the following formula:

[0237] [Chemical 49]

[0238] (m and n are each independently an integer of 1 to 25, and the average value of m + n is 30.)

Compound (M 5074) 25.4 ₈ (511111101) and the compound (111) obtained in Example 1 2.3 g (12 mmol: 1 mol of functional group of fluorine-containing elastomer (A) 1.2 mol) and 1.21 g (12 mmol) of triethylamine were mixed, heated at 70 ° C. for 2 hours with stirring, and then heated at 180 ° C. for 2 hours.

 [0239] Unreacted compound (III), triethylamine, and triethylamine hydrofluoride are removed by purification, and the following formula:

[0240] [Chemical 50]

 (m and n are independently integers of -25, and the average value of m-卜 n is 30.

Mixed)

The compound (vn) shown by [0241] was obtained. The compound was confirmed by 'H-NMR, ¹⁹ F-NMR and IR analysis.

 [0242] Example 4

 In a flask equipped with a stirrer, thermometer and Dimroth condenser, the following formula:

 [0243] [Chemical 51]

O

II

(CFOCF F O O F _m O----

, ノ I 3 CF

[0244] (m and n are each independently an integer of 1 to 25, and the average value of m + n is 30.)

(M 5074) 25.4 ₈ (511111101) and the compound (¥ 1) obtained in Example 2 2. lg (12 mmol: per 1 mol of functional group of fluorine-containing elastomer (A) 1.2 mol) and 1.21 g (12 mmol) of triethylamine were mixed, heated at 70 ° C. for 2 hours with stirring, and then heated at 180 ° C. for 2 hours.

 [0245] Unreacted compound (VI), triethylamine, and triethylamine hydrofluoric acid salt were removed by purification, and the following formula:

[0246] [Chemical 52]

(in and n are each independently an integer of 1 to 25, and the average value of _λ πι + 11 is 30.

L is

[0247] Compound (VII) shown by the following was obtained. The compound was confirmed by 'H-NMR F-NMR and IR analysis.

 [0248] Example 5

 In a flask equipped with a stirrer, thermometer, and Dimroth condenser, a fluorine-containing elastomer having a carboxyl group at the end of the main chain (tetrafluoroethylene: perfluoromethylvinyl ether composition ratio (mol) = 59.5: 40.5, number average molecular weight 7500) 37.5 g and compound (III) 2.3 g (12 mmol: functional group of fluorine-containing elastomer (A) obtained in Example 1 1.2 mol) with respect to 1 mol, and the mixture was heated at 70 ° C for 2 hours with stirring, and then heated at 180 ° C for 2 hours.

 [0249] Unreacted compound (III) is removed by purification, and the following formula:

[0250] [Chemical 53]

[0251] A fluorine-containing elastomer (IX) having a composition of tetrafluoroethylene and perfluoromethylvinyl ether mixed in force was obtained. The compound was confirmed by —NMR, ¹⁹ F-NMR, IR analysis.

 [0252] Example 6

Instead of the compound (ΠΙ) obtained in Example 1, the compound (VI) obtained in Example 2 was used. The synthesis was performed in the same manner as in Example 5 except that.

[0253] Unreacted compound (VI) is removed by purification, and at the end of the main chain, the following formula:

[0254] [Chemical 54]

[0255] A fluorine-containing elastomer (X) having tetrafluoroethylene and perfluoromethyl vinyl ether having the above-mentioned composition was obtained. The compound was confirmed by Ή-NMR, ¹⁹ F-NMR and IR analysis.

 [0256] Example 7

The fluorine-containing elastomer obtained in Example 3 (number average molecular weight 5390, vinyl group amount 0.03 7 mol / 100 g) 100 parts of fumed silica having a specific surface area of 300 m ² / g treated with hexamethyldisilazane After adding 20 parts and heat-mixing, they were mixed on a three-roll mill. Furthermore, 0.3 parts of 50% toluene solution of ethurcyclohexanol and toluene solution of chloroplatinic acid bisiloxane complex (platinum concentration) 0.5 parts by weight) 0.2 parts, following formula (i):

[0257] [Chemical 55]

[0258] 10.2 parts of the polyfunctional fluorine-containing siloxane represented by the formula (1) is supplied in an amount of 1.2 moles of hydrosilyl group (SiH group) per mole of bur group in the fluorine-containing elastomer. Added and mixed. Next, the obtained mixture was cured at 150 ° C. for 1 hour to obtain a cured product. The resulting cured product was examined for physical properties and chemical resistance. Table the results

Shown in 1 and 2 [0259] Example 8

 Instead of the fluorine-containing hydrogen siloxane of the formula (i) of Example 7, the following formula (ii):

[0260] [Chemical 56]

OH3

C ₈ F ₁₇ CH ₂ CH ₂ Si (CH ₂ CH ₂ SiH) ₃ (1 i)

A composition was prepared in the same manner except that 10.9 parts of the fluorine-containing organosilicon compound represented by [0261] was added, and the physical properties and chemical resistance of the cured product obtained under the same conditions were examined. The results are shown in Tables 1 and 2.

 [0262] Example 9

 Except for using 100 parts of the fluorine-containing polymer obtained in Example 4 (number average molecular weight 5390, bute group weight 0.037 mol ZlOOg) instead of the fluorine-containing elastomer obtained in Example 3 of Example 7. Prepared a composition in the same manner as in Example 7, and examined the physical properties and chemical resistance of the cured product obtained under the same conditions. The results are shown in Tables 1 and 2.

[0263] Example 10

 A composition was prepared in the same manner except that 10.9 parts of a fluorine-containing organosilicon compound of the following formula (ii) was added instead of the fluorine-containing hydrogen siloxane of the formula (i) of Example 9. The cured product was examined for physical properties and chemical resistance. The results are shown in Tables 1 and 2.

[0264] Example 11

 Except for using 142 parts of the fluorine-containing polymer obtained in Example 5 (number average molecular weight 7820, butyl group weight 0.026 mol ZlOOg) instead of the fluorine-containing elastomer obtained in Example 3 of Example 7. Prepared a composition in the same manner as in Example 7, and examined the physical properties and chemical resistance of the cured product obtained under the same conditions. The results are shown in Tables 1 and 2.

[0265] Example 12

A composition was prepared in the same manner except that 10.9 parts of the fluorine-containing organosilicon compound of the above formula (ii) was added instead of the fluorine-containing hydrogen siloxane of the formula (i) of Example 11, and obtained under the same conditions. The hardened materials were examined for physical properties and chemical resistance. The results are shown in Tables 1 and 2. [0266] [Table 1]

Heat resistance 2 0 0 X 7 2 hours

[0267] The results shown in Table 1 indicate that the cured product of the present invention exhibits excellent heat resistance.

[0268] [Table 2] Table 2

 Chemical resistance Dipping Room temperature Surface after 3 days: Condition

[0269] The results shown in Table 2 showed that the cured product of the present invention exhibited excellent chemical resistance.

 Industrial applicability

[0270] In the production method of the present invention, a specific functional group is introduced into the main chain terminal and specific sites at the end of the main chain or the side chain, particularly at the main chain terminal, by a cyclization reaction. It is possible to obtain a functional fluorine-containing elastomer. Further, by cross-linking the curable composition comprising the fluorine-containing elastomer, a molded product having excellent heat resistance and chemical resistance can be obtained.

Claims

 The scope of the claims

 [1] A fluorine-containing elastomer (A) containing a functional group Z at the main chain end and Z or side chain end, and a reactive group capable of cyclization with the functional group Z and converted into the functional group Y or the functional group Y A method for producing a crosslinkable fluorine-containing elastomer having a functional group Y at the main chain terminal and Z or side chain terminal, comprising a step of performing a cyclization reaction with an organic compound (B) having a curable moiety.

 [2] The functional group Z is represented by the general formula (1):

 [Chemical 1]

Shi--.

(In the formula, X ¹ is a chlorine atom, a fluorine atom, —OH or —OR ¹ , and R ¹ is an organic group having 1 to 10 carbon atoms which may contain an oxygen atom or a halogen atom.)

 The method for producing a fluorine-containing elastomer according to claim 1, wherein the group is CN or CN.

 The organic compound (B) has the general formula (2):

 [Chemical 2]

(In the formula, one of R ² and R ³ is —NH, the other is —NH 2, one NHR ⁴ , —OH

 twenty two

Or —SH, R ⁴ is a monovalent organic group, and Y ¹ is a monovalent organic group having a functional group Y and a functional group Υ, or one having a site that can be converted to a functional group Υ. Is a valent group. The method for producing a fluorine-containing elastomer according to claim 1 or claim 2.

Upsilon ¹ in the general formula (2) are alkenyl groups, Aruke - monovalent organic group having a group, monovalent organic group having a hydrogen atom bonded to Keimoto atom or the general formula, (3):

[Chemical 3] R ^D

S i-R ⁶ (3)

R ⁷

(R ⁵ R ⁶ R ⁷ are the same or different and each is a hydrogen atom or a monovalent hydrocarbon group that may contain a substituted or unsubstituted oxygen atom, at least one of which is a hydrogen atom, 4. The method for producing a fluorine-containing elastomer according to claim 3, which is a monovalent organic group represented by a substituted or unsubstituted monovalent hydrocarbon group having an alkenyl group.

General formula (4):

[Chemical 4]

(In the formula, one of, R is —NH, and the other is —NH NHR —OH

 twenty two

Or —SH, R ⁴ is a monovalent organic group, R ⁸ R ⁹ R ^{1 (>} each have the same force or different, and may contain a hydrogen atom or a substituted or unsubstituted oxygen atom. (It is a monovalent hydrocarbon group.)

A silicon-containing compound represented by

SiR ⁸ R ⁹ R ^{1Q in} general formula (4) is

 [Chemical 5]

 1 Γ i.

 ― S i― C H = C H 2, or ― S i― H

 6. The silicon-containing ich compound according to claim 5, which is I I.

A main chain end obtained by the production method according to any one of claims 1 to 4. And a crosslinkable fluorine-containing elastomer having a functional group Y at the end of Z or side chain

 [8] General formula (5) at main chain end and Ζ or side chain end:

 [Chemical 6] CSI,

(In the formula, X ² is — 、 —, —NR ¹¹ —, —O—, —S—, R ¹¹ is a monovalent organic group, and Υ ² is an alkenyl group or an alkenyl group. A monovalent organic group having a monovalent organic group having at least one hydrogen atom bonded to a silicon atom, or a general formula (3):

 [Chemical 7]

― 1 — XV v. 3 /

R ⁷

(R ⁵ , R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group which may contain a substituted or unsubstituted oxygen atom, at least one of which is a hydrogen atom. It is a monovalent organic group represented by a substituted or unsubstituted monovalent hydrocarbon group having an atom or an alkenyl group. )

 A crosslinkable fluorine-containing elastomer having a functional group Y represented by

[9] Y ² in general formula (5) is

 [Chemical 8]

H

C

 9. The crosslinkable fluorine-containing elastomer according to claim 8, which is

[10] The curable composition comprising the fluorine-containing elastomer according to any one of claims 7 to 9. [11] A molded product obtained by crosslinking the curable composition according to claim 10.