JP2006233156A - Fluoroelastomer and method for producing fluoroelastomer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a fluoroelastomer containing specified groups on main chain terminals and/or on side-chain terminals, to provide a curable composition comprising the fluoroelastomer, and to provide a molding obtained by crosslinking the curable composition. <P>SOLUTION: The method for producing the fluoroelastomer comprises the step of allowing an amine compound represented by formula (2) and having a base constant Kb of 1×10<SP>-6</SP>or below at 25°C in an aqueous solution to act on a vinylidene-fluoride-based fluoroelastomer having on main chain terminals and/or on side-chain terminals a structure represented by formula (1) [wherein X<SP>1</SP>is a chlorine atom, a fluorine atom, -OH, or -OR<SP>1</SP>(wherein R<SP>1</SP>is a 1 to 10C hydrocarbon group which may contain an oxygen atom or a halogen atom)] to introduce moieties represented by formula (3) into the main chain terminals and/or the side chain terminals. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a fluorine-containing elastomer containing a group having a specific structure at a main chain end and / or a 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, compositions comprising a fluorine-containing elastomer having various groups such as vinyl groups or allyl groups introduced at the terminal and a composition comprising a crosslinking agent have been developed.

  For example, Patent Document 1 discloses a fluorinated amide compound having a main chain composed of perfluoropolyether obtained by reacting a compound having an acid fluoride group at both ends with a secondary amine compound. However, since the main chain structure is a perfluoroelastomer, the compound is expensive, and further, there is a problem that mixing with other crosslinking agents and compounding agents is difficult.

  Patent Document 2 describes a method in which an amine having an unsaturated group is reacted with a vinylidene fluoride-containing fluorine-containing elastomer containing both ester groups at both ends of the main chain to amid. However, in the cited document 2, there is no description about using an amine compound having a specific base constant, and in the examples, since a highly basic amine compound is used, only the methyl ester group is used. However, the main chain may be modified by reacting with a vinylidene fluoride main chain which is weak against a base, and it is difficult to introduce a functional group into a fluorine-containing elastomer under control.

JP-A-8-198926 JP 2001-81131 A

  The present invention provides a method for producing a fluorine-containing elastomer containing a group having a structure 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 provides the general formula (1) at the main chain end and / or the side chain end:

(Wherein X ¹ is a chlorine atom, a fluorine atom, —OH, —OR ¹ (R ¹ is a C 1-10 hydrocarbon group which may contain an oxygen atom or a halogen atom))
General formula (2) in which a base constant Kb in a water solvent is 1 × 10 ⁻⁶ or less is added to a vinylidene fluoride-based fluorine-containing elastomer having a structure represented by:

(In the formula, R ² is a hydrogen atom, or an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group or the aromatic hydrocarbon group includes an oxygen atom, a nitrogen atom, a sulfur atom, (It may contain a silicon atom or a halogen atom, and R ³ is an aliphatic hydrocarbon group or an aromatic hydrocarbon group which may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom or a halogen atom)
Is reacted with an amine compound represented by the general formula (3) at the main chain end and / or the side chain end:

(Wherein R ² and R ³ are the same as above)
The manufacturing method of a fluorine-containing elastomer including the process of introduce | transducing the site | part shown by these.

R ³ in the general formula (2) is preferably an aromatic hydrocarbon group that may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or a halogen atom.

  The present invention also provides a compound represented by the general formula (4):

(In the formula, M is a vinylidene fluoride-based fluorine-containing elastomer, a is an integer of 1 or more, and B is the general formula (5):

(In the formula, R ² is a hydrogen atom, or an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group or the aromatic hydrocarbon group includes an oxygen atom, a nitrogen atom, a sulfur atom, (It may contain a silicon atom or a halogen atom, and R ⁴ is an aromatic hydrocarbon group that may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom or a halogen atom)
It is related with the fluorine-containing elastomer shown by these.

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

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

  In the production method of the present invention, a group having a specific structure can be introduced at a specific site of the main chain and / or side chain, particularly at the end of the main chain, and the introduction position can be controlled. In addition, since the obtained fluorine-containing elastomer can introduce a specific group via an amide bond to the main chain end and / or side chain end, the curable composition comprising the fluorine-containing elastomer can be crosslinked. Thus, a molded product having excellent heat resistance and a 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.

  The present invention provides the general formula (1) at the main chain end and / or the side chain end:

(Wherein X ¹ is a chlorine atom, a fluorine atom, —OH, —OR ¹ (R ¹ is a C 1-10 hydrocarbon group which may contain an oxygen atom or a halogen atom))
General formula (2) in which a base constant Kb in a water solvent is 1 × 10 ⁻⁶ or less is added to a vinylidene fluoride-based fluorine-containing elastomer having a structure represented by:

(In the formula, R ² is a hydrogen atom, or an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group or the aromatic hydrocarbon group includes an oxygen atom, a nitrogen atom, a sulfur atom, (It may contain a silicon atom or a halogen atom, and R ³ is an aliphatic hydrocarbon group or an aromatic hydrocarbon group which may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom or a halogen atom)
Is reacted with an amine compound represented by the general formula (3) at the main chain end and / or the side chain end:

(Wherein R ² and R ³ are the same as above)
The manufacturing method of a fluorine-containing elastomer including the process of introduce | transducing the site | part shown by these.

  The fluorine-containing elastomer used in the present invention has the general formula (1) at the main chain end and / or side chain end:

(Wherein, X ¹ is a chlorine atom, a fluorine atom, —OH, —OR ¹ (R ¹ is a C 1-10 hydrocarbon group which may contain an oxygen atom or a halogen atom)). Any VdF-based fluorine-containing elastomer having a structure may be used.

Among these, X ^{1 in the} general formula (1) is preferably —OH or —OR ¹ because it does not have to be handled under water-free conditions, and chlorine because it is highly reactive in an amidation reaction with an amine compound. An atom and a fluorine atom are preferable.

As a method for introducing the structure represented by the general formula (1) into the VdF-based fluorine-containing elastomer, when X ¹ is —OH or —OR ¹ , a simple compound having a carboxyl group or an alkoxycarbonyl group is used during the fluorine-containing elastomer polymerization. Examples thereof include a method of copolymerizing a monomer and a method of adding a monomer to the iodine terminal of a fluorine-containing elastomer obtained by iodine transfer polymerization as described later.

In addition, when X ¹ is —OH, as described in JP-A-11-269225, a method of introducing a carboxyl group by a method of treating a vinylidene fluoride-containing fluorine-containing elastomer with a base and a peroxide is also available. When X ¹ is —OR ¹ , a method of esterifying terminal —COOH with a corresponding alcohol (R ¹ OH) can also be preferably used.

When X ¹ is a chlorine atom, it can be converted to an acid chloride group by reacting a fluorine-containing elastomer having a carboxyl group with phosphorus pentachloride, phosphorus trichloride, phosphoryl chloride, thionyl chloride, sulfuryl chloride or the like. When X ¹ is a fluorine atom, a method of allowing cyanuric fluoride to act on a fluorine-containing elastomer containing a carboxyl group or a method of causing zinc fluoride or silver fluoride to act on a fluorine-containing elastomer containing an acid chloride group Thus, an acid fluoride group can be obtained.

  Here, the VdF-based fluoroelastomer is not particularly limited as long as it includes a structural unit derived from VdF.

  Examples of the VdF fluorine elastomer include VdF fluorine rubber, tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF) fluorine rubber, and ethylene / hexafluoropropylene (HFP) / vinylidene fluoride (VdF) fluorine rubber. can give.

  As the vinylidene fluoride (VdF) fluororubber, those represented by the following general formula (6) are preferable.

― (M ¹ ) ― (M ² ) ― (N ¹ ) ― (6)
(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 (6) 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 55-15 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 which gives such a crosslinking site, for example, general formula (7):
CY ¹ ₂ = CY ¹ R _f ¹ CHR ⁵ -X ¹ (7)
Wherein Y ¹ is a hydrogen atom, a fluorine atom or —CH ₃ , R _f ¹ is a linear or branched fluoro or perfluoroalkylene group which may have one or more ether type oxygen atoms. Or a fluoro or perfluorooxyalkylene group, or a perfluoropolyoxyalkylene group, R ⁵ is a hydrogen atom or a methyl group, and X ¹ is an iodine atom or a bromine atom), a bromine-containing monomer General formulas (8) to (19):
CY ² ₂ = CY ² (CF ₂ ) _n −X ² (8)
(Wherein Y ² is a hydrogen atom or a fluorine atom, and n is an integer of 1 to 8)
^{_{CF 2 = CFCF 2 R f 2}} -X 2 (9)
(Where R _f ² is

And n is an integer from 0 to 5)
CF ₂ = CFCF ₂ (OCF (CF ₃ ) CF ₂ ) _{m
(OCH 2 CF 2 CF 2)} n OCH 2 CF 2 -X 2 (10)
(In the formula, m is an integer of 0 to 5, and n is an integer of 0 to 5)
CF ₂ = CFCF ₂ (OCH ₂ CF ₂ CF ₂ ) _m
(OCF (CF ₃ ) CF ₂ ) _n OCF (CF ₃ ) -X ² (11)
(In the formula, m is an integer of 0 to 5, and n is an integer of 0 to 5)
_{CF 2 = CF (OCF 2 CF} (CF 3)) m O (CF 2) n -X 2 (12)
(In the formula, m is an integer of 0 to 5, and n is an integer of 1 to 8.)
_{CF 2 = CF (OCF 2 CF} (CF 3)) m -X 2 (13)
(Where m is an integer from 1 to 5)
_{CF 2 = CFOCF 2 (CF (} CF 3) OCF 2) n CF (-X 2) CF 3 (14)
(Where n is an integer from 1 to 4)
_{CF 2 = CFO (CF 2)} n OCF (CF 3) -X 2 (15)
(Where n is an integer from 2 to 5)
_{CF 2 = CFO (CF 2)} n - (C 6 H 4) -X 2 (16)
(Where n is an integer from 1 to 6)
_{CF 2 = CF (OCF 2 CF} (CF 3)) n OCF 2 CF (CF 3) -X 2 (17)
(Where n is an integer from 1 to 2)
_{CH 2 = CFCF 2 O (CF} (CF 3) CF 2 O) n CF (CF 3) -X 2 (18)
(Where n is an integer from 0 to 5),
_{CF 2 = CFO (CF 2 CF} (CF 3) O) m (CF 2) n -X 2 (19)
(In the formula, m is an integer of 0 to 5, and n is an integer of 1 to 3)
(In the general formulas (8) to (19), X ² is a carboxyl group (—COOH group) or an alkoxycarbonyl group (—COOR ¹ group (R ¹ is the same as above)).
A carboxyl group- or alkoxycarbonyl group-containing monomer represented by
Formula (20):
_{CH 2 = CH- (CF 2)} n X 3 (20)
(Where n is an integer from 2 to 8)
_{CF 2 = CFO (CF 2 CF} (CF 3) O) m (CF 2) n -X 3 (21)
(In the formula, m is an integer of 0 to 5, n is an integer of 1 to 3)
(In the general formulas (20) and (21), X ³ is an iodine atom or a bromine atom)
These include iodine-containing monomers, bromine-containing monomers, and the like, and these can be used alone or in any combination.

For example, perfluoro (6,6-dihydro-6-iodo-3-oxa-1-hexene) and perfluoro (5- (5)) described in JP-B-5-63482 and JP-A-7-316234 are disclosed. Iodine-containing monomers such as iodo-3-oxa-1-pentene), iodine-containing monomers such as CF ₂ = CFOCF ₂ CF ₂ CH ₂ I described in JP-A-4-217936, and JP-A-4-505341 Bromine-containing monomers described in JP-A-4-505345, cyano group-containing monomers, carboxyl-group-containing monomers, alkoxy as described in JP-A-4-505345 and JP-A-5-500070 And carbonyl group-containing monomers.

  By copolymerizing the monomers represented by the general formulas (8) to (19), a carboxyl group or an alkoxycarbonyl group can be introduced into the main chain terminal and / or the side chain terminal of the fluorine-containing elastomer. The group can react with an amine compound represented by the general formula (2).

  Specific examples of such VdF fluororubbers include VdF-HFP rubber, VdF-HFP-TFE rubber, VdF-CTFE rubber, VdF-CTFE-TFE rubber, and the like.

  Further, as the fluorine-containing elastomer used in the present invention, in addition to the above-mentioned VdF type fluororubber, TFE / propylene / VdF type fluororubber, ethylene / HFP / VdF type fluororubber, TFE / propylene type fluororubber, ethylene / HFP type Fluororubber, ethylene / HFP / TFE-based fluororubber, fluorosilicone-based fluororubber, or fluorophosphazene-based fluororubber, and the like can be used alone or in any combination as long as the effects of the present invention are not impaired. Can be used.

  As the TFE / propylene fluororubber, those represented by the following general formula (22) are preferable.

― (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 monomer (m ³ ) and repeating unit derived from monomer (n ² ) copolymerizable with monomer (m ⁴ ))

Among the TFE / propylene type fluorine-containing rubbers represented by the general formula (22), the structural unit M ³ 40 to 70 mol%, preferably not containing a structural unit M ⁴ 60 to 30 mol%, more preferably the structural unit M ³ In an amount of 50 to 60 mol% and the structural unit M ⁴ in an amount of 50 to 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.

  Moreover, perfluoro fluororubber represented by the following general formula (23) can be used in combination.

― (M ⁵ ) ― (M ⁶ ) ― (N ³ ) ― (23)
(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 (23), the structural unit M ⁵ 50 to 90 mol%, preferably not containing a structural unit M ⁶ 10 to 50 mol%, more preferably a structural unit M ⁵ 50 80 mol%, which comprises a structural unit M ⁶ 20 to 50 mol%, more preferably a structural unit M ⁵ 55 to 70 mol%, in which the structural unit M ⁶ 30-45 mol%. 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, monomers represented by general formulas (8) to (21), and the like. Perfluoro (6,6-dihydro-6-iodo-3-oxa-1-hexene) and perfluoro (5-iodo-3-oxa-1-pentene) as described in JP-A-7-316234 An iodine-containing monomer such as CF ₂ = CFOCF ₂ CF ₂ CH ₂ I described in JP-A-4-217936, and a bromine-containing monomer described in JP-A-4-505341 Cyano group-containing monomer, carboxyl group-containing monomer, alkoxycarbonyl group-containing, as described in JP-A-4-505345, JP-A-5-500070 Such as the amount thereof and the like. These can be used alone or in any combination.

  Specific examples of such perfluoro fluorine rubber include fluorine described in International Publication No. 97/24381 pamphlet, Japanese Patent Publication No. 61-57324, Japanese Patent Publication No. 4-81608, Japanese Patent Publication No. 5-13961, and the like. For example, rubber.

  As the fluorine-containing elastomer, in addition to those described above, it can also be used as a rubber composition containing thermoplastic fluororubber.

  The fluororubber used in the present invention preferably has a number average molecular weight of 1,000 to 500,000.

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

  Specifically, the fluororubber 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.

  Furthermore, the fluororubber 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 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 fluororubber described above can be produced by a conventional method. However, the resulting polymer has a narrow molecular weight distribution and is easy to control the molecular weight, and from the point that an iodine atom can be introduced at the terminal, A known iodine transfer polymerization method is preferred as a rubber production method. For example, the monomer constituting the fluorine-containing elastomer and, if necessary, the monomer that gives a cross-linking site are stirred under pressure in the presence of an iodine compound, preferably a diiodine compound, substantially in the absence of oxygen. In the presence of a radical initiator, an emulsion polymerization or solution polymerization is carried out in an aqueous medium. As a representative example of the iodine compound to be used, for example, the general formula (24):
R ⁶ I _x Br _y (24)
(Wherein x and y are each an integer of 0 to 2 and satisfy 1 ≦ x + y ≦ 2, and R ⁶ 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 (24) 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 (24) may be 0.0001 to 15% by weight with respect to the total weight of the obtained fluorine-containing elastomer.

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

  As the amine compound used in the present invention, the general formula (2):

Further, the amine compound is a compound having a basic constant Kb of 1 × 10 ⁻⁶ or less in a water solvent at a temperature of 25 ° C.

In the formula, R ² is a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group. The aliphatic hydrocarbon group and the aromatic hydrocarbon group include an oxygen atom, a nitrogen atom, a sulfur atom, silicon An atom and a halogen atom may be included, for example, a hydrogen atom, a C1-C10 saturated aliphatic hydrocarbon group, a C1-C10 alcohol, a C1-C10 unsaturated hydrocarbon group, etc. A methyl group, an ethyl group, an allyl group, a hydroxymethyl group, a hydroxyethyl group, and the like are preferable.

  An aromatic hydrocarbon group may be one in which an aromatic ring structure is formed only with carbon atoms, or an aromatic ring structure is formed from hetero atoms such as carbon atoms, nitrogen atoms, sulfur atoms, oxygen atoms, etc. Further, it may be a short ring structure or a polycyclic structure (condensed ring), and any position in these cyclic structures may be substituted with a substituent.

R ³ is an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group or the aromatic hydrocarbon group may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or a halogen atom. .

R ³ is preferably an aromatic hydrocarbon group that may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or a halogen atom.

Examples of R ³ include an aryl group, a functional group-substituted aryl group, a phenyl group, a functional group-substituted phenyl group, and a phenyl group having a substituent that includes an unsaturated group in the structure.

  As the compound represented by the general formula (2), the general formula (25):

(Wherein R ⁷ , R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, an aromatic group), a functional group-substituted aniline, N-phenyl-3-amino-1-propene, p-aminostyrene, N-methyl-p-aminostyrene,

An amine compound having an unsaturated bond at the terminal, and the general formula (26):

(Wherein, R ¹⁰ is an aliphatic alkyl group having 2 to 5 carbon atoms).

  Examples of N-substituted anilines include N-allyl aniline.

  Examples of the compound represented by the general formula (26) include N-phenylethanolamine, N-phenylpropanolamine, N-phenyl-n-butanolamine and the like.

  Among these, N-substituted aniline is preferable from the viewpoint of easy availability, and N-allylaniline is more preferable.

  A functional group-substituted aniline is preferable and a compound having the following structure is preferable because it is excellent in heat resistance as a crosslinking point and rich in hydrosilylation reaction as a curing reaction.

Base constant Kb of the amine compound used in the present invention, 1 × is 10 ^-6 or less, preferably 1 × 10 ^-7 or less, and more preferably 1 × 10 ^-8 or less. Although it does not specifically limit as a lower limit, It is preferable that it is 1 * 10 < ^-14 > or more. It is preferable for Kb to be in the above range since the reactivity with the vinylidene fluoride moiety in the fluorine-containing elastomer can be suppressed.

  Here, the base constant Kb indicates an equilibrium constant with respect to the dissociation equilibrium of the base, and the smaller the Kb, the weaker the base.

  The addition amount of the amine compound represented by the general formula (2) is preferably 1 to 100 times mol of the content of the moiety represented by the general formula (1) of the fluorine-containing elastomer, and 1 to 50 times mol. More preferably, it is an amount. If the amount is less than 1-fold molar amount, all the ends tend not to be converted, and exceeding 100-fold molar amount only increases the cost of the amine compound and has no merit.

  By adding the amine compound represented by the general formula (2) to the fluorine-containing elastomer having the group represented by the general formula (1) and amidating, the main chain terminal and / or the side chain terminal of the fluorine-containing elastomer are obtained. ,

(Wherein R ² and R ³ are the same as above)
The site | part shown by can be introduce | transduced.

  The method of amidation is not particularly limited, and any method that is usually used may be used. Specifically, for example, the method described in The Chemical Society of Japan, 4th edition, Experimental Chemistry Course 22 pages 137-173, Maruzen Co., Ltd. can be used.

Moreover, when X < ¹ > of General formula (1) is -OH, the method of heating and dehydrating is also possible, However, The method using the condensing agent shown by the said literature is preferable.

  The present invention relates to a fluorine-containing elastomer represented by the following general formula (4).

  In the formula, M is a vinylidene fluoride-based fluorine-containing elastomer, and any vinylidene fluoride-based fluorine-containing elastomer can be suitably used.

  B is the general formula (5):

In the formula, R ² is a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group. The aliphatic hydrocarbon group and the aromatic hydrocarbon group include an oxygen atom, a nitrogen atom, a sulfur atom, silicon An atom or a halogen atom may be contained, and R ⁴ is an aromatic hydrocarbon group which may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom or a halogen atom, and is a functional group-substituted aryl group, particularly a functional group-substituted group A phenyl group is preferable from the viewpoint of excellent heat resistance of the functional group of the fluorine-containing elastomer and easy synthesis.

The aliphatic hydrocarbon group and aromatic hydrocarbon group for R ² are preferably those having 1 to 20 carbon atoms, and the aromatic hydrocarbon group for R ⁴ is one having 1 to 20 carbon atoms. Is preferred.

  a is an integer of 1 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. If the number average molecular weight is less than 500, the crosslinking density tends to be too high when a curing reaction using the main chain ends is performed. If the number average molecular weight exceeds 500,000, the viscosity of the fluorine-containing elastomer is too high to be mixed with the crosslinking agent. Tend to be.

  Next, the curable composition of this invention is demonstrated.

  The curable composition of the present invention is sufficiently crosslinked to contain a compound capable of undergoing a crosslinking reaction with the fluorine-containing elastomer having a site represented by the general formula (5) at the main chain terminal and / or the side chain terminal. This is preferable from the viewpoint of obtaining a cured product.

  Preferred examples of the crosslinkable compound 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.

  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 —OH, preferred examples of the polyfunctional compound include acid anhydrides, polyepoxy compounds, and polyisocyanate compounds.

  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. Examples of the acid anhydride include pyromellitic acid anhydride, tetrahydrofuran-1,2,3,4-tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, and the like. .

  In the case where the crosslinkable site is an unsaturated bond, the polyfunctional compound particularly has two or more Si—H groups because the unsaturated bond can contribute to the three-dimensional network structure by the hydrosilylation reaction. It is preferable that it is a compound which has.

The compound having two or more —SiH groups is usually represented by the general formula (27):
R ¹¹ _b H _c SiO _{(4-bc) / 2} (27)
In the formula, R ¹¹ 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 (27), 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 two or more —SiH groups is preferably an organohydrogenpolysiloxane having 1 to 1000 silicon atoms, more preferably 2 to 300 silicon atoms, and further preferably 4 to 200 silicon atoms in one molecule. Yes, specifically 1,1,3,3-tetramethyldisiloxane, 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5 , 7,9-Pentamethylcyclopentasiloxane, etc .; molecular chain both ends trimethylsiloxy group-blocked methylhydrogen polysiloxane, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain Both ends silanol-blocked methyl hydrogen polysiloxane, both molecular chains End silanol group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, molecular chain both ends dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane, molecular chain both ends dimethyl Hydrogensiloxy-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, comprising R ¹¹ ₂ (H) SiO _1/2 units and SiO _4/2 units, optionally R ¹¹ ₃ SiO _1/2 units, R ¹¹ _Examples thereof include silicone resins containing ₂ SiO _2/2 units, R ¹¹ (H) SiO _2/2 units, (H) SiO _3/2 units or R ¹¹ 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 (28), and a part or all of the methyl groups in the general formula (28) are ethyl, propyl, phenyl And a compound substituted with a trifluoropropyl group.

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

  The trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer having both ends of the molecular chain is a compound represented by the general formula (29), wherein a part or all of the methyl groups in the general formula (29) are ethyl or propyl And compounds substituted with a group, phenyl group, trifluoropropyl group, and the like.

(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.

  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 (30), a part or all of the methyl groups in the general formula (30), And compounds substituted with a group, phenyl group, trifluoropropyl group, and the like.

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

  Examples of the dimethylpolysiloxane blocked with a dimethylhydrogensiloxy group at both ends of the molecular chain include, for example, a compound represented by the general formula (31), a part or all of the methyl groups in the general formula (31), And a compound substituted with a trifluoropropyl group.

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

  Examples of the dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane having both molecular chain terminals include a compound represented by the general formula (32), a part or all of the methyl groups in the general formula (32), an ethyl group, a propyl group, Examples thereof include compounds substituted with a phenyl group, a trifluoropropyl group, and the like.

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

  Examples of the dimethylsiloxane / methylhydrogensiloxane copolymer blocked with dimethylhydrogensiloxy group at both ends of the molecular chain include, for example, a compound represented by the general formula (33), and a part or all of the methyl groups in the general formula (33) are ethyl. And compounds substituted with a group, a propyl group, a phenyl group, a trifluoropropyl group, and the like.

(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 two or more Si-H groups in one molecule is one or more in one molecule. Having a monovalent perfluorooxyalkyl group, a monovalent perfluoroalkyl group, a divalent perfluorooxyalkylene group, or a divalent perfluoroalkylene group, and two or more, preferably three or more Those having Si-H groups are preferred. 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 (34):
C _k F _{2k + 1} − (34)
(Wherein k represents an integer of 1-20, preferably 2-10),
As the divalent perfluoroalkylene group, the general formula (35):
−C _k F _2k − (35)
(Wherein k represents an integer of 1 to 20, preferably 2 to 10),
As the monovalent perfluorooxyalkyl group, the general formula (36) or (37):

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

  As the divalent perfluorooxyalkylene group, the general formula (38):

(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 (39):
_{- (CF 2 O) m -} (CF 2 CF 2 O) n -CF 2 - (39)
(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 two or more —SiH groups in one molecule, that is, a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group, or a perfluorooxy group. Examples of the monovalent substituent bonded to the silicon atom other than the monovalent organic group containing an alkylene group include 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. Alkyl groups such as vinyl groups and 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 Substituted with chlorine atom, cyano group, etc., for example chloromethyl group, chloropropyl group, cyano Unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms such as methyl group and the like.

  The compound having two or more —SiH groups in one molecule 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 two or more —SiH groups in one molecule 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.

(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.)

(Where S is

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. )

(Where S is

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. )

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

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

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

  A curable composition comprising a fluorine-containing elastomer in which the crosslinking site is a C2-C10 hydrocarbon group having at least one unsaturated bond and a compound having two or more Si-H groups in one molecule. In this case, it is preferable to add a hydrosilylation reaction catalyst from the viewpoint of the reactivity of the hydrosilylation reaction.

  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. Is 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.

  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 10 parts by weight, and 0.5 to 5 parts by weight with respect to 100 parts by weight of the fluorine-containing elastomer. It is more preferable that If the amount is less than 0.05 parts by weight, the crosslinking cannot be sufficiently performed. If the amount exceeds 10 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 100 ° C. to 300 ° C. for several seconds to 5 hours. 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 raised to 50 ° C. or higher in order to promote the reaction. 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 Use as a wafer cleaning solution hose, tube, wafer transfer roll, resist developer bath, stripper bath lining, coating, wafer cleaning bath lining, coating or wet etching bath lining, 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, etc.

  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 charged 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.

Reference example 2
7.75 g of the fluorine-containing elastomer obtained in Reference Example 1 was dissolved in 100 g of anhydrous acetonitrile under water-free conditions in a four-necked flask equipped with a reflux condenser, and zinc powder (manufactured by Kishida Chemical Co., Ltd.) ) After adding 0.73 g, the mixture was heated with stirring to reflux acetonitrile for 18 hours.

After removing zinc powder by filtration from the obtained reaction solution, acetonitrile was removed using an evaporator, and then the viscous elastomer precipitated was dissolved in HCFC-141b. This HCFC-141b solution was washed with water four times, then washed twice with a saturated aqueous sodium thiosulfate solution, and dried using anhydrous magnesium sulfate. After removing magnesium sulfate from the HCFC-141b solution by filtration, HCFC-141b was removed using an evaporator and drying under reduced pressure at 120 ° C. to obtain a viscous fluorine-containing elastomer. In the ¹ H-NMR analysis of the elastomer in a heavy acetone solvent, the peak derived from the terminal structure —CF ₂ CH ₂ I observed in Reference Example 1 was not observed, and the terminal unsaturated bond of —CF═CH A complex peak around 5.1 to 5.4 ppm derived from ₂ was observed. In IR measurement, since sharp absorption at 1693 cm ⁻¹ based on C═C stretching of the terminal unsaturated structure was observed, it is considered that the structure of terminal iodine of the fluorine-containing elastomer was converted to a terminal unsaturated structure. The main chain -CH ₂ intensity and fluoroelastomer complex peaks derived from ~CF = CH ₂ - because the ratio of the intensity of the peak derived from was 1:34, the structure of the iodine terminated all terminal It is thought that it was converted to an unsaturated structure.

Reference example 3
In a 300 ml three-necked flask, 2 g of the fluorine-containing elastomer having an unsaturated structure at the end obtained in Reference Example 2 was dissolved in 100 ml of acetone, cooled in an ice bath, and then 0.316 g of potassium permanganate was added. Under stirring, the ice bath was removed and the mixture was stirred at room temperature for 5 hours. The mixture was cooled again in an ice bath, 100 ml of methanol was added dropwise, the ice bath was removed, and the mixture was stirred at room temperature for 1 hour.
When the obtained reaction solution was concentrated with an evaporator, a viscous elastomer was precipitated. Therefore, after redissolving in HCFC-141b, the insoluble matter was filtered. This HCFC-141b solution was washed with dilute hydrochloric acid using a separatory funnel, and then washed with water three times. The solution of this HCFC-141b solution was dried over anhydrous MgSO ₄ , and MgSO ₄ was removed by filtration. Then, HCFC-141b was removed by heat drying under reduced pressure at 120 ° C. to obtain a viscous fluorine-containing elastomer.
In this fluorine-containing elastomer, a complex peak derived from a terminal unsaturated bond observed in the fluorine-containing elastomer obtained in Reference Example 2 was not observed by ¹ H-NMR analysis using heavy acetone. Further, in IR measurement, a large absorption of 1773 cm ⁻¹ derived from the C═O stretching of the terminal carboxylic acid structure was observed, but the sharp absorption of 1693 cm ⁻¹ observed in Reference Example 2 was not observed. The terminal unsaturated structure is considered to have changed to carboxylic acid.

Example 1
Four fluorine-containing elastomers obtained in Reference Example 3 and 1.90 g of N-allylaniline (10-fold molar amount with respect to the unsaturated structure content at the terminal of the fluorine-containing elastomer) were attached to a reflux condenser. The sample was dissolved in 20 g of acetone in a mouth flask and heated with stirring to reflux acetone for 6 hours. Thereafter, acetone was distilled off by heating and heated at 180 ° C. for 6 hours under a nitrogen stream. The obtained fluorine-containing elastomer was dissolved in a small amount of acetone and reprecipitated in dichloromethane. The precipitated fluorine-containing elastomer was heated at 120 ° C. for 12 hours under vacuum.

In the obtained fluorine-containing elastomer, the peak at 1773 cm ⁻¹ derived from C═O stretching of the carboxylic acid structure at the terminal of the fluorine-containing elastomer obtained in Reference Example 3 disappears, and C═O stretching derived from an amide bond is observed. A derived peak was generated.

Moreover, in the analysis by GPC, the peak derived from N-allyl aniline was not observed, but the peak derived from the allyl group and the peak derived from the phenyl group were observed by analysis of ¹ H-NMR using a heavy acetone solvent. It was confirmed that the allyl group was introduced into the fluorine-containing elastomer through an amide bond.

Comparative Example 1
In a four-necked flask equipped with a reflux condenser, 5.0 g of the fluorine-containing elastomer obtained in Reference Example 3 and 0.81 g of allylamine (10-fold mol amount relative to the unsaturated structure content at the terminal of the fluorine-containing elastomer) Acetone was dissolved in 20 g of acetone and refluxed at 20 ° C. for 6 hours with stirring. Thereafter, unreacted allylamine and acetone were distilled off with an evaporator at room temperature. The obtained fluorine-containing elastomer was dissolved in a small amount of acetone and reprecipitated in dichloromethane. The precipitated fluorine-containing elastomer was heated at 120 ° C. for 12 hours under vacuum.

In the obtained fluorine-containing elastomer, the peak at 1773 cm ⁻¹ derived from C═O stretching of the carboxylic acid structure at the terminal of the fluorine-containing elastomer obtained in Reference Example 3 disappeared, but the peak derived from the amide bond did not occur. It was.

Moreover, in the analysis by ¹ H-NMR, an allyl group-derived peak was observed, but the peak intensity was higher than the peak intensity calculated from the amount of terminal carboxylic acid in the fluorine-containing elastomer obtained in Reference Example 3. Therefore, it is considered that allylamine reacted with the main chain portion by reacting with the main chain of the fluorine-containing elastomer.

Claims (6)

At the end of the main chain and / or the end of the side chain, the general formula (1):

(In the formula, X ¹ is a chlorine atom, a fluorine atom, —OH, —OR ¹ (R ¹ is a C 1-10 hydrocarbon group which may contain an oxygen atom or a halogen atom))
General formula (2) in which a base constant Kb in a water solvent is 1 × 10 ⁻⁶ or less is added to a vinylidene fluoride-based fluorine-containing elastomer having a structure represented by:

(In the formula, R ² is a hydrogen atom, or an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group and the aromatic hydrocarbon group include an oxygen atom, a nitrogen atom, a sulfur atom, (It may contain a silicon atom or a halogen atom, and R ³ is an aliphatic hydrocarbon group or an aromatic hydrocarbon group that may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom or a halogen atom)
Is reacted with an amine compound represented by formula (3) at the main chain end and / or side chain end:

(Wherein R ² and R ³ are the same as above)
The manufacturing method of a fluorine-containing elastomer including the process of introduce | transducing the site | part shown by. The method for producing a fluorine-containing elastomer according to claim 1, wherein R ³ in the general formula (2) is an aromatic hydrocarbon group which may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or a halogen atom. General formula (4):

(In the formula, M is a vinylidene fluoride-based fluorine-containing elastomer, a is an integer of 1 or more, and B is the general formula (5):

(In the formula, R ² is a hydrogen atom, or an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group or the aromatic hydrocarbon group includes an oxygen atom, a nitrogen atom, a sulfur atom, (It may contain a silicon atom or a halogen atom, and R ⁴ is an aromatic hydrocarbon group that may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom or a halogen atom)
A fluorine-containing elastomer represented by The fluorine-containing elastomer according to claim 3, which has a number average molecular weight of 500 to 500,000. A curable composition comprising the fluorine-containing elastomer according to claim 3. A molded article obtained by crosslinking the curable composition according to claim 5.