JP2013216915A - Crosslinkable composition including fluorine-containing elastomer and crosslinked rubber molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crosslinkable composition having a low glass transition temperature and exhibiting excellent amine resistance and including an amorphous fluorine-containing elastomer, and to provide a crosslinked rubber molded composition formed by crosslinking the composition.SOLUTION: A crosslinkable composition includes an amorphous fluorine-containing elastomer and an crosslinking agent. The amorphous fluorine-containing elastomer is a copolymer including only fluorine-containing monomers including vinylidene fluoride and a monomer shown by a general formula (1) CH=CFR(wherein Rf is a linear or branched 1-12C fluoroalkyl group), wherein the molar ratio of the vinylidene fluoride/fluorine-containing monomer units is 87/13 to 22/78, and the glass transition temperature is ≤25°C.

Description

The present invention relates to a crosslinkable composition containing a fluorine-containing elastomer and a crosslinked rubber molded article.

Fluorine-containing elastomers (fluorine rubbers) containing VdF as an essential constituent monomer such as vinylidene fluoride (VdF) / hexafluoropropylene (HFP) copolymer and VdF / HFP / tetrafluoroethylene (TFE) copolymer are outstanding. Various parts in fields that require harsh use conditions such as exposure to high temperatures and various chemicals due to their excellent heat resistance, chemical resistance, and oil resistance, such as the automotive industry, aircraft industry, and semiconductor industry It is used as a material.

In addition, several other polymers having VdF as a structural unit are known. In Patent Documents 1 and 2, VdF and 2,3,3,3-tetrafluoropropene are copolymerized to obtain a polymer. It is described.

U.S. Pat. No. 2,970,988 US Patent Application Publication No. 2008/0153978

However, Patent Documents 1 and 2 do not describe amorphous fluorine-containing elastomers.

The present invention provides a crosslinkable composition having a low glass transition temperature, excellent amine resistance, and containing an amorphous fluorine-containing elastomer, and a crosslinked rubber molded product obtained by crosslinking the composition. It is to be an issue.

The inventors of the present invention have a vinylidene fluoride unit and the following general formula (1):
CH ₂ = CFR _f (1)
(Wherein R _f is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms) and the polymer having a specific composition ratio is a non-crystalline polymer. Not only was it found to be an elastomer, it was also found to have an extremely low glass transition temperature and excellent amine resistance. And it discovered that the crosslinkable composition containing such a fluorine-containing elastomer and a crosslinking agent, and the crosslinked rubber molding obtained by bridge | crosslinking the said composition can be used suitably in a various industrial field, this invention. It came to complete.

That is, the present invention relates to vinylidene fluoride and the following general formula (1):
CH ₂ = CFR _f (1)
(Wherein R _f is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms), and is a copolymer comprising only a fluorine-containing monomer represented by vinylidene fluoride units / fluorine-containing Amorphous fluorine-containing elastomer (hereinafter, also referred to as “first fluorine-containing elastomer”) having a monomer unit molar ratio of 87/13 to 22/78 and a glass transition temperature of 25 ° C. or lower. And a crosslinkable composition (hereinafter also referred to as “first crosslinkable composition”).

The first fluorine-containing elastomer preferably has a vinylidene fluoride unit / fluorine monomer unit molar ratio of 82/18 to 60/40.

The present invention relates to vinylidene fluoride, the following general formula (1):
CH ₂ = CFR _f (1)
(Wherein, R _f is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms), copolymerized with vinylidene fluoride and the above fluorine-containing monomer It is a copolymer consisting only of other possible monomers, the molar ratio of vinylidene fluoride units / fluorinated monomer units is 85/15 to 20/80, and the other monomer units are all single units. An amorphous fluorine-containing elastomer (hereinafter, also referred to as “second fluorine-containing elastomer”) having a glass transition temperature of 25 ° C. or less, and a crosslinking agent. It also relates to a crosslinkable composition (hereinafter, also referred to as “second crosslinkable composition”).

The second fluorine-containing elastomer preferably has a vinylidene fluoride unit / fluorine monomer unit molar ratio of 85/15 to 50/50.

In the first or second fluorine-containing elastomer, the fluorine-containing monomer is preferably 2,3,3,3-tetrafluoropropene.

A crosslinked rubber molded product obtained by crosslinking the first or second crosslinkable composition is also one aspect of the present invention.

The present invention also provides vinylidene fluoride, the following general formula (1):
CH ₂ = CFR _f (1)
(Wherein, R _f is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms), copolymerized with vinylidene fluoride and the above fluorine-containing monomer It is a copolymer comprising other possible monomers, the molar ratio of vinylidene fluoride units / fluorinated monomer units is 85/15 to 20/80, and the other monomer units are all in a single amount. 0 to 50 mol% of the body unit, the glass transition temperature is 25 ° C or lower, has at least one of iodine atom and bromine atom, and the total content thereof is 0.001 to 10 wt%, It is also a crosslinkable composition (hereinafter also referred to as “third crosslinkable composition”) containing a crystalline fluorine-containing elastomer (hereinafter also referred to as “third fluorine-containing elastomer”) and a crosslinking agent. .

The third fluorine-containing elastomer is vinylidene fluoride and the following general formula (1):
CH ₂ = CFR _f (1)
(Wherein R _f is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms), and is a copolymer comprising only a fluorine-containing monomer represented by vinylidene fluoride units / fluorine-containing It is preferable that the molar ratio of the monomer units is 80/20 to 20/80.

The third fluorine-containing elastomer has a vinylidene fluoride unit / fluorine monomer unit molar ratio of 85/15 to 50/50, and the other monomer units are 1 to 50 mol of the total monomer units. % Is also preferred.

In the third fluorine-containing elastomer, the fluorine-containing monomer is preferably 2,3,3,3-tetrafluoropropene.

The third crosslinkable composition preferably contains an organic peroxide as a crosslinker.

A cross-linked rubber molded product obtained by cross-linking the third cross-linkable composition is also one aspect of the present invention.

The fluorine-containing elastomer in the present invention has good rubber elasticity and is excellent in cold resistance and amine resistance. The fluorine-containing elastomer in the present invention has a fluorine-containing monomer content represented by the formula (1) and a hexafluoropropylene content as compared with a vinylidene fluoride (VdF) / hexafluoropropylene (HFP) copolymer. When the amount is the same in molar ratio, the glass transition temperature (Tg) is low. The crosslinkable composition of the present invention containing such a fluorine-containing elastomer and a crosslinking agent, and the crosslinked rubber molded article of the present invention obtained by crosslinking the composition can be suitably used in various industrial fields. .

VdF obtained in Examples 2 to 5 / copolymer of fluorine-containing monomer represented by formula (1) and VdF / HFP copolymer obtained in Comparative Examples 5 to 8 are represented by formula (1). It is a graph which shows the glass transition temperature with respect to the molar composition of the fluorine-containing monomer or HFP represented by these.

The first, second and third fluorine-containing elastomers are composed of vinylidene fluoride units and the following general formula (1):
CH ₂ = CFR _f (1)
(In the formula, R _f is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms.) And a fluorine-containing monomer unit represented by a specific composition ratio. And exhibits a very low glass transition temperature. Moreover, it is excellent in crosslinkability, and furthermore, the fluorine-containing elastomer containing the fluorine-containing monomer unit represented by the general formula (1) is difficult to dehydrofluoride and has excellent amine resistance.

In this specification, “amorphous” means that the magnitude of the melting peak (ΔH) appearing in DSC measurement (temperature rising temperature 10 ° C./min) is 2.0 J / g or less.

The first, second and third fluorine-containing elastomers can have a glass transition temperature of 25 ° C. or lower, can be 0 ° C. or lower, and can be −20 ° C. or lower. It is. Since the fluorine-containing elastomer in the present invention exhibits an extremely low glass transition temperature as described above, it is excellent in cold resistance.

The glass transition temperature is obtained by using a differential scanning calorimeter (Mettler Toledo, DSC822e) to obtain a DSC curve by raising the temperature of 10 mg of the sample at 10 ° C./min. It can be determined as the temperature indicating the intersection of the extended line and the tangent at the inflection point of the DSC curve.

The first fluorine-containing elastomer is a copolymer composed only of vinylidene fluoride and a fluorine-containing monomer represented by the formula (1). The fluorine-containing single unit represented by the vinylidene fluoride unit / formula (1) The molar ratio of the monomer units is 87/13 to 22/78. The first fluorine-containing elastomer is a copolymer containing only monomer units derived from vinylidene fluoride and the fluorine-containing monomer represented by the formula (1).

In the first fluorine-containing elastomer, the molar ratio of the vinylidene fluoride unit / the fluorine-containing monomer unit represented by the formula (1) is preferably 82/18 to 60/40.

The second fluorine-containing elastomer is copolymerizable with vinylidene fluoride, the fluorine-containing monomer represented by the formula (1), and the vinylidene fluoride and the fluorine-containing monomer represented by the formula (1). It is a copolymer consisting only of other monomers, and the molar ratio of vinylidene fluoride units / fluorinated monomer units represented by the formula (1) is 85/15 to 20/80. A monomer unit is 1-50 mol% of all the monomer units.

In the second fluorine-containing elastomer, the molar ratio of the vinylidene fluoride unit / the fluorine-containing monomer unit represented by the formula (1) is preferably 85/15 to 50/50. More preferably, it is 85 / 15-60 / 40.

In the second fluorine-containing elastomer, the other monomer units are preferably 1 to 40 mol% of the total monomer units.

In the first or second fluoroelastomer, the fluorine-containing monomer of the formula (1), the monomer is preferably located in the fluoroalkyl group R _f is a straight chain, R _f is a straight-chain A monomer that is a perfluoroalkyl group is more preferred. R _f preferably has 1 to 6 carbon atoms.

As the fluorine-containing monomer represented by the above formula (1), CH ₂ = CFCF ₃ , CH ₂ = CFCF ₂ CF ₃ , CH ₂ = CFCF ₂ CF ₂ CF ₃ , CH ₂ = CFCF ₂ CF ₂ CF ₂ Examples thereof include CF ₃ , and among them, 2,3,3,3-tetrafluoropropene represented by CH ₂ ═CFCF ₃ is preferable.

The other monomer is not particularly limited as long as it is a monomer copolymerizable with vinylidene fluoride and the fluorine-containing monomer represented by the formula (1), one or more monomers May be used.

In the second fluorine-containing elastomer, other monomers are tetrafluoroethylene [TFE], hexafluoropropylene, perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), chlorotrifluoro. It is preferably at least one selected from the group consisting of ethylene, trifluoroethylene, hexafluoroisobutene, vinyl fluoride, ethylene, propylene, alkyl vinyl ether, and a monomer that provides a crosslinking site. More preferably, it is TFE. It is also a preferable form that only TFE is used.

In the second fluorine-containing elastomer, examples of the monomer that gives the crosslinking site include a general formula:
CX ¹ ₂ = CX ¹ -R _f ¹ CHR ¹ X ²
Wherein X ¹ is a hydrogen atom, a fluorine atom or —CH ₃ , R _f ¹ is a fluoroalkylene group, a perfluoroalkylene group, a fluoro (poly) oxyalkylene group or a perfluoro (poly) oxyalkylene group, R ¹ is a hydrogen atom or —CH ₃ , and X ² is an iodine atom or a bromine atom.) An iodine or bromine-containing monomer represented by the general formula:
_{CF 2 = CFO (CF 2 CF} (CF 3) O) m (CF 2) n -X 3
(Wherein, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ³ is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, or a bromine atom). Body, general formula:
_{CH 2 = CFCF 2 O (CF} (CF 3) CF 2 O) m (CF (CF 3)) n -X 4
(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, an iodine atom, a bromine atom, or —CH ₂ OH). Monomers represented.

Among _{them, CF 2 = CFOCF 2 CF (} CF 3) OCF 2 CF 2 CN, CF 2 = CFOCF 2 CF (CF 3) OCF 2 CF 2 COOH, CF 2 = CFOCF 2 CF 2 CH 2 I, CF 2 = CFOCF _{2 CF (CF 3) OCF 2} CF 2 CH 2 I, CH 2 = CFCF 2 OCF (CF 3) CF 2 OCF (CF 3) CN, CH 2 = CFCF 2 OCF (CF 3) CF 2 OCF (CF 3) It is preferably at least one selected from the group consisting of COOH and CH ₂ ═CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ OH.
As the monomer that gives the crosslinking site, CF ₂ = CFOCF ₂ CF ₂ CH ₂ I can improve the crosslinking density and improve the compression set in the crosslinking using peroxide. Particularly preferred.

The third fluorine-containing elastomer is vinylidene fluoride, the following general formula (1):
CH ₂ = CFR _f (1)
(Wherein, R _f is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms), copolymerized with vinylidene fluoride and the above fluorine-containing monomer It is a copolymer comprising other possible monomers, the molar ratio of vinylidene fluoride units / fluorinated monomer units is 85/15 to 20/80, and the other monomer units are all in a single amount. It is 0-50 mol% of a body unit, a glass transition temperature is 25 degrees C or less, has at least one of an iodine atom and a bromine atom, and the sum total of the content is 0.001-10 weight%.

The third fluorine-containing elastomer is vinylidene fluoride and the following general formula (1):
CH ₂ = CFR _f (1)
(Wherein R _f is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms), a copolymer consisting of only a fluorine-containing monomer represented by the formula, or vinylidene fluoride, the following general formula (1):
CH ₂ = CFR _f (1)
(Wherein, R _f is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms), copolymerized with vinylidene fluoride and the above fluorine-containing monomer A copolymer consisting only of other possible monomers is preferred.
In this case, the third fluorine-containing elastomer is substantially a vinylidene fluoride and a copolymer consisting only of the fluorine-containing monomer represented by the formula (1), or substantially vinylidene fluoride, a formula A copolymer comprising only the fluorine-containing monomer represented by (1) and the above-mentioned other monomers, but produced using a reactive emulsifier within a range not impairing the effects of the present invention. It may be. Moreover, the I terminal etc. which originate in a chain transfer agent may be included.

The third fluorine-containing elastomer is vinylidene fluoride and the following general formula (1):
CH ₂ = CFR _f (1)
(Wherein R _f is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms), and is a copolymer comprising only a fluorine-containing monomer represented by vinylidene fluoride units / fluorine The molar ratio of monomer units is more preferably 80/20 to 20/80.

The third fluorine-containing elastomer has a vinylidene fluoride unit / fluorine-containing monomer unit molar ratio of 85/15 to 50/50, and the other monomer units are 1 to 1 of all monomer units. It is also preferable that it is 50 mol%.

In the third fluorine-containing elastomer, the fluorine-containing monomer is preferably 2,3,3,3-tetrafluoropropene.

The content of each monomer unit is a value measured by NMR method.

A 3rd fluorine-containing elastomer has at least one of an iodine atom and a bromine atom, and the sum total of the content is 0.001 to 10 weight%. The total content of iodine atoms and bromine atoms is preferably 0.01 to 5% by weight, and more preferably 0.1 to 5% by weight. The iodine content was measured by mixing 5 mg of Na ₂ SO ₃ with 12 mg of sample (fluorinated elastomer), and mixing Na ₂ CO ₃ and K ₂ CO ₃ in a 1: 1 ratio (weight ratio) with 20 ml of pure water. It is possible to measure using an Shimadzu 20A ion chromatograph after 30 mg of the absorbing solution dissolved in a quartz combustion flask, burned in oxygen and allowed to stand for 30 minutes. As the calibration curve, a KI standard solution, one containing 0.5 ppm of iodine ions or one containing 1.0 ppm can be used.

The bonding position of the iodine atom and the bromine atom may be the terminal of the main chain or the terminal of the side chain of the fluorine-containing elastomer, and may be both. In such a fluorine-containing elastomer, the iodine terminal or bromine terminal serves as a crosslinking point (crosslinking site), and a crosslinked fluorine-containing elastomer having a high crosslinking density can be obtained, and peroxide crosslinking can be performed more easily. become.

The third fluorine-containing elastomer is produced by using iodine or a bromine-containing monomer as a monomer for providing a crosslinking site, using a bromine compound or an iodine compound as a polymerization initiator or a chain transfer agent, and the like. Can do.

In the third fluorine-containing elastomer, the fluorine-containing monomer represented by the formula (1) is preferably a monomer in which R _f is a linear fluoroalkyl group, and R _f is a linear perfluoroalkyl. A monomer as a group is more preferable. R _f preferably has 1 to 6 carbon atoms.

As the fluorine-containing monomer represented by the above formula (1), CH ₂ = CFCF ₃ , CH ₂ = CFCF ₂ CF ₃ , CH ₂ = CFCF ₂ CF ₂ CF ₃ , CH ₂ = CFCF ₂ CF ₂ CF ₂ Examples thereof include CF ₃ , and among them, 2,3,3,3-tetrafluoropropene represented by CH ₂ ═CFCF ₃ is preferable.

In the third fluorine-containing elastomer, the other monomers are vinylidene fluoride and a monomer copolymerizable with the fluorine-containing monomer represented by the formula (1) (however, a monomer that gives a crosslinking site) Is not particularly limited, and one or more monomers may be used.

Other monomers include tetrafluoroethylene [TFE], hexafluoropropylene, perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), chlorotrifluoroethylene, trifluoroethylene, hexafluoro It is preferably at least one selected from the group consisting of isobutene, vinyl fluoride, ethylene, propylene, and alkyl vinyl ether. The other monomer is also preferably TFE. It is also a preferable form that only TFE is used. In the third fluorine-containing elastomer, the other monomer is preferably 0 to 50 mol% of the total monomer units. More preferably, it is 1-50 mol%.

In the third fluorine-containing elastomer, examples of the monomer that gives a crosslinking site include, for example, the general formula:
CX ¹ ₂ = CX ¹ -R _f ¹ CHR ¹ X ²
Wherein X ¹ is a hydrogen atom, a fluorine atom or —CH ₃ , R _f ¹ is a fluoroalkylene group, a perfluoroalkylene group, a fluoro (poly) oxyalkylene group or a perfluoro (poly) oxyalkylene group, R ¹ is a hydrogen atom or —CH ₃ , and X ² is an iodine atom or a bromine atom.) An iodine or bromine-containing monomer represented by the general formula:
CX ¹ ₂ = CX ¹ -R _f ¹ X ²
Wherein X ¹ is a hydrogen atom, a fluorine atom or —CH ₃ , R _f ¹ is a fluoroalkylene group, a perfluoroalkylene group, a fluoro (poly) oxyalkylene group or a perfluoro (poly) oxyalkylene group, X ² is an iodine or bromine-containing monomer represented by an iodine atom or a bromine atom (preferably, general formula: CH ₂ ═CH (CF ₂ ) _n I (n is an integer of 2 to 8) .) Iodine-containing monomer represented by the general formula:
_{CF 2 = CFO (CF 2 CF} (CF 3) O) m (CF 2) n -X 3
(Wherein, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ³ is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, or a bromine atom). Body, general formula:
_{CH 2 = CFCF 2 O (CF} (CF 3) CF 2 O) m (CF (CF 3)) n -X 4
(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, an iodine atom, a bromine atom, or —CH ₂ OH). Monomer, general formula:
^{CR 2 R 3 = CR 4 -Z} -CR 5 = CR 6 R 7
(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Z is linear or branched. An alkylene group having 1 to 18 carbon atoms, a cycloalkylene group having 3 to 18 carbon atoms, an alkylene or oxyalkylene group having 1 to 10 carbon atoms that is at least partially fluorinated Or
_{- (Q) p -CF 2 O-} (CF 2 CF 2 O) m (CF 2 O) n -CF 2 - (Q) p -
(Wherein Q is an alkylene or oxyalkylene group, p is 0 or 1, m / n is 0.2 to 5), and the molecular weight is 500 to 10,000 (per) fluoro. It is a polyoxyalkylene group. ) And the like.

General formula above:
^{CR 2 R 3 = CR 4 -Z} -CR 5 = CR 6 R 7
In The compound represented by, for _{example, CH 2 = CH- (CF 2} ) 2 -CH = CH 2, CH 2 = CH- (CF 2) 4 -CH = CH 2, CH 2 = CH- (CF 2 ₆ -CH = CH ₂ , the following formula:
^{_{CH 2 = CH-Z 1 -CH}} = CH 2
(In the formula, Z ¹ is a fluoropolyoxyalkylene group represented by —CH ₂ OCH ₂ —CF ₂ O— (CF ₂ CF ₂ O) _m1 (CF ₂ O) _n1 —CF ₂ —CH ₂ OCH ₂ —). M1 / n1 is 0.5 and the molecular weight is 2000.).

Examples of the monomer giving a crosslinking _{site, CF 2 = CFOCF 2 CF (} CF 3) OCF 2 CF 2 CN, CF 2 = CFOCF 2 CF (CF 3) OCF 2 CF 2 COOH, CF 2 = CFOCF 2 CF (CF _{3) OCF 2 CF 2 CH 2} I, CF 2 = CFOCF 2 CF 2 CH 2 I, CH 2 = CFCF 2 OCF (CF 3) CF 2 OCF (CF 3) CN, CH 2 = CFCF 2 OCF (CF 3) _{CF 2 OCF (CF 3) COOH} , CH 2 = CFCF 2 OCF (CF 3) CF 2 OCF (CF 3) CH 2 OH, _{and, CH 2 = CHCF 2 CF 2} I, CH 2 = CH (CF 2) 2 One of the preferred embodiments is at least one selected from the group consisting of CH═CH ₂ .
As the monomer that gives the crosslinking site, CF ₂ = CFOCF ₂ CF ₂ CH ₂ I can improve the crosslinking density and improve the compression set in the crosslinking using peroxide. Particularly preferred.

Monomers that give cross-linking sites may also be represented, for example, by the general formula:
CX ¹ ₂ = CX ¹ -R _f ¹ CHR ¹ X ²
Wherein X ¹ is a hydrogen atom, fluorine atom or —CH ₃ , R _f ¹ is a fluoroalkylene group, perfluoroalkylene group, fluoropolyoxyalkylene group or perfluoropolyoxyalkylene group, and R ¹ is hydrogen atoms or _-CH 3, ^{X 2} is an iodine atom or a bromine atom)
Iodine or bromine-containing monomer represented by the general formula:
CX ¹ ₂ = CX ¹ -R _f ¹ X ²
(In the formula, X ¹ is a hydrogen atom, a fluorine atom or —CH ₃ , R _f ¹ is a fluoroalkylene group, a perfluoroalkylene group, a fluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group, and X ² is iodine. Atom or bromine atom)
An iodine- or bromine-containing monomer represented by (preferably an iodine-containing monomer represented by CH ₂ ═CH (CF ₂ ) _n I (n is an integer of 2 to 8)), a general formula:
_{CF 2 = CFO (CF 2 CF} (CF 3) O) m (CF 2) n -X 5
(In the formula, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ⁵ is an iodine atom or a bromine atom)
And a monomer represented by the general formula:
_{CH 2 = CFCF 2 O (CF} (CF 3) CF 2 O) m (CF (CF 3)) n -X 5
(In the formula, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ⁵ is an iodine atom or a bromine atom)
It is also a preferred embodiment that the monomer is at least one monomer selected from the group consisting of: The third fluorine-containing elastomer can be produced by using such an iodine or bromine-containing monomer as the other monomer.

The monomer that gives a cross-linked site is preferably 0.01 to 10 mol%, more preferably 0.01 to 2 mol% of all monomer units.

The first, second and third fluorine-containing elastomers can be produced by a general radical polymerization method. The polymerization form may be any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, but is preferably emulsion polymerization because it is industrially easy to implement.

In the above polymerization, a polymerization initiator, a chain transfer agent, a surfactant, and a solvent can be used, and conventionally known ones can be used.

In the polymerization of the first, second or third fluorine-containing elastomer, an oil-soluble radical polymerization initiator or a water-soluble radical initiator can be used as a polymerization initiator.

The oil-soluble radical polymerization initiator may be a known oil-soluble peroxide, for example, dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and disec-butylperoxydicarbonate, t-butylperoxy Peroxyesters such as isobutyrate and t-butyl peroxypivalate, dialkyl peroxides such as di-t-butyl peroxide, and di (ω-hydro-dodecafluoroheptanoyl) peroxide, di (Ω-hydro-tetradecafluoroheptanoyl) peroxide, di (ω-hydro-hexadecafluorononanoyl) peroxide, di (perfluorobutyryl) peroxide, di (perfluarparyl) peroxide, di (perfluoro) Hexanoyl) Oxide, di (perfluoroheptanoyl) peroxide, di (perfluorooctanoyl) peroxide, di (perfluorononanoyl) peroxide, di (ω-chloro-hexafluorobutyryl) peroxide, di (ω- Chloro-decafluorohexanoyl) peroxide, di (ω-chloro-tetradecafluorooctanoyl) peroxide, ω-hydro-dodecafluoroheptanoyl-ω-hydrohexadecafluorononanoyl-peroxide, ω-chloro- Hexafluorobutyryl-ω-chloro-decafluorohexanoyl-peroxide, ω-hydrododecafluoroheptanoyl-perfluorobutyryl-peroxide, di (dichloropentafluorobutanoyl) peroxide, di (trichlorooctaf Olohexanoyl) peroxide, di (tetrachloroundecafluorooctanoyl) peroxide, di (pentachlorotetradecafluorodecanoyl) peroxide, di (undecachlorodotriacontafluorodocosanoyl) peroxide di [perfluoro ( Or fluorochloro) acyl] peroxides.

The water-soluble radical polymerization initiator may be a known water-soluble peroxide, for example, ammonium salts such as persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, percarbonate, potassium salts, sodium salts. , T-butyl permaleate, t-butyl hydroperoxide and the like. A reducing agent such as sulfites and sulfites may also be included, and the amount used may be 0.1 to 20 times that of the peroxide.

The addition amount of the radical polymerization initiator is not particularly limited, but an amount that does not significantly reduce the polymerization rate (for example, several ppm to water concentration) or more in the initial stage of polymerization, sequentially, or continuously. And then add. The upper limit is a range in which the heat of polymerization reaction can be removed from the surface of the apparatus.

As the surfactant, a nonionic surfactant, an anionic surfactant, a cationic surfactant or the like can be used, and a linear or branched fluorine-containing anion having 4 to 20 carbon atoms such as ammonium perfluorooctanoate. A surfactant is preferred. The addition amount (with respect to polymerization water) is preferably 10 to 5000 ppm. More preferably, it is 50-5000 ppm.
Moreover, a reactive emulsifier can be used as a surfactant. The reactive emulsifier is not particularly limited as long as it is a compound having at least one unsaturated bond and one or more hydrophilic groups. For example, CH ₂ = CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COONH ₄ , CH _{2 = CFCF 2 CF (CF 3} ) OCF 2 CF 2 COONH 4, CF 2 = CFOCF 2 CF (CF 3) OCF (CF 3) COONH 4 and the like. The addition amount (with respect to polymerization water) is preferably 10 to 5000 ppm. More preferably, it is 50-5000 ppm.

As the solvent, a solvent having no chain transfer property is preferable. In the case of solution polymerization, dichloropentafluoropropane (R-225) is exemplified. In the case of emulsion polymerization and suspension polymerization, water, a mixture of water and a water-soluble organic solvent, or water and a water-insoluble organic solvent. A mixture.

In the polymerization of the first and second fluorine-containing elastomers, examples of the chain transfer agent include esters such as dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, butyl acetate, dimethyl succinate, isopentane, Examples include methane, ethane, propane, isopropanol, acetone, various mercaptans, carbon tetrachloride, and cyclohexane.

A bromine compound or iodine compound may be used as the chain transfer agent. Examples of the polymerization method using a bromine compound or iodine compound include a method in which emulsion polymerization is carried out in an aqueous medium under pressure in the presence of a bromine compound or iodine compound in a substantially oxygen-free state. (Iodine transfer polymerization method). Representative examples of bromine compounds or iodine compounds to be used include, for example, the general formula:
R ² I _x Br _y
(Wherein x and y are each an integer of 0 to 2 and satisfy 1 ≦ x + y ≦ 2, and R ² 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). By using a bromine compound or an iodine compound, iodine or bromine is introduced into the polymer and functions as a crosslinking point.

Examples of the iodine compound include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 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-diiodoperfluorohexadecane , 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 CFBrO F _3, 1-bromo-2-iodoperfluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, 3-bromo -4-iodoperfluorobutene-1, 2-bromo-4-iodoperfluorobutene-1, monoiodomonobromo and diiodomonobromo substituents of benzene, and (2-iodoethyl) and (2-bromoethyl) ) Substituents, etc., and these compounds may be used alone or in combination with each other.

Among these, 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane are used from the viewpoint of polymerization reactivity, crosslinking reactivity, availability, and the like. Is preferred.

In the polymerization of the third fluorine-containing elastomer, it is preferable to use a bromine compound or an iodine compound as a chain transfer agent. Examples of the polymerization method using a bromine compound or iodine compound include a method in which emulsion polymerization is carried out in an aqueous medium under pressure in the presence of a bromine compound or iodine compound in a substantially oxygen-free state. (Iodine transfer polymerization method). Representative examples of bromine compounds or iodine compounds to be used include, for example, the general formula:
R ² I _x Br _y
(Wherein x and y are each an integer of 0 to 2 and satisfy 1 ≦ x + y ≦ 2, and R ² 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). By using a bromine compound or an iodine compound, iodine or bromine is introduced into the polymer and functions as a crosslinking point.

Examples of the iodine compound include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 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-diiodoperfluorohexadecane , 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 CFBrO F _3, 1-bromo-2-iodoperfluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, 3-bromo -4-iodoperfluorobutene-1, 2-bromo-4-iodoperfluorobutene-1, monoiodomonobromo and diiodomonobromo substituents of benzene, and (2-iodoethyl) and (2-bromoethyl) ) Substituents, etc., and these compounds may be used alone or in combination with each other.

Among these, 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane are used from the viewpoint of polymerization reactivity, crosslinking reactivity, availability, and the like. Is preferred.

In the polymerization of the third fluorine-containing elastomer, as the chain transfer agent, for example, esters such as dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, butyl acetate, dimethyl succinate, isopentane, methane, ethane Propane, isopropanol, acetone, various mercaptans, carbon tetrachloride, cyclohexane and the like can also be used.

In the polymerization of the first, second and third fluorine-containing elastomers, the polymerization temperature, the polymerization pressure, and the polymerization time vary depending on the type of the solvent and the polymerization initiator, but are -15 to 150 ° C, atmospheric pressure to 6.5 MPa, It may be 1 to 24 hours. In particular, when an oil-soluble radical polymerization initiator containing a fluorine atom is used as a polymerization initiator in solution polymerization, the polymerization temperature is preferably −15 to 50 ° C., more preferably 10 to 35 ° C. In the case of using an oil-soluble radical polymerization initiator containing a fluorine atom in emulsion polymerization and suspension polymerization, the polymerization temperature is preferably 30 to 95 ° C. When a water-soluble radical polymerization initiator is used as the polymerization initiator, the polymerization temperature is preferably 0 to 100 ° C, and more preferably 10 to 95 ° C.
The polymerization pressure is preferably 1.0 MPa or more, more preferably 2.0 MPa or more, because the value of compression set of the vulcanized molded article becomes good, and the polymerization rate increases and productivity is improved. 3.0 MPa or more is more preferable, and 4.5 MPa or more is most preferable.

The first, second or third fluorine-containing elastomer may be in any form such as an aqueous dispersion or a powder.
In the case of emulsion polymerization, the fluorine-containing elastomer powder can be obtained by coagulating the dispersion after polymerization, washing with water, dehydrating, and drying. The coagulation can be performed by adding an inorganic salt such as aluminum sulfate or an inorganic acid, applying a mechanical shear force, or freezing the dispersion. In the case of suspension polymerization, it can be obtained by recovering from the dispersion after polymerization and drying. In the case of solution polymerization, it can be obtained by drying a solution containing a fluorine-containing elastomer as it is, or it can also be obtained by purifying by adding a poor solvent dropwise.

The first, second or third fluorine-containing elastomer preferably has a number average molecular weight (Mn) of 7000 to 500,000, and the weight average molecular weight (Mw) is suitable for sealing materials. It is preferably 10,000 to 1,000,000, and Mw / Mn is preferably 1.3 to 4.0.

The number average molecular weight (Mn), the weight average molecular weight (Mw), and Mw / Mn are values measured by the GPC method.

The first, second or third fluorine-containing elastomer preferably has a Mooney viscosity (ML1 + 10 (100 ° C.)) at 100 ° C. of 2 or more, preferably 5 or more from the viewpoint of good moldability. It is more preferable. Similarly, it is preferably 200 or less, more preferably 150 or less, and even more preferably 100 or less, from the viewpoint of good moldability. Mooney viscosity is a value measured according to ASTM-D1646 and JIS K6300.

In addition, as a fluorine-containing elastomer in this invention, 1 type may be used and 2 or more types may be used. In particular, two types of fluorine-containing elastomers having different molecular structures may be used in combination. As a form using together two kinds of fluorine-containing elastomers having different molecular structures, a form using two kinds of first fluorine-containing elastomers having different molecular structures, a form using two kinds of second fluorine-containing elastomers having different molecular structures, A form using two kinds of third fluorine-containing elastomers having different molecular structures, a form using one kind of first fluorine-containing elastomer and one kind of second fluorine-containing elastomer, one kind of first fluorine-containing elastomer and a third kind Examples include a mode in which one type of fluorine-containing elastomer is used in combination, and a mode in which one type of second fluorine-containing elastomer and one type of third fluorine-containing elastomer are used in combination.

As described above, when two types of fluorine-containing elastomer are used in combination as the fluorine-containing elastomer in the present invention, one type is a branched fluorine-containing elastomer and the other type is a linear fluorine-containing elastomer. preferable. More preferably, one type described in International Publication No. 2009/119409 has a crosslinking site capable of peroxide crosslinking (A), and the number average molecular weight is in the range of 1,000 to 300,000. A branched fluorine-containing elastomer having a Mark-Houwint gradient a of less than 0.6 when the absolute weight molecular weight and the intrinsic viscosity are plotted on a Mark-Houwint plot in which the horizontal axis is the absolute weight molecular weight and the vertical axis is the intrinsic viscosity. And the other is (B) a mark having a number average molecular weight in the range of 1,000 to 250,000, an absolute weight molecular weight and an intrinsic viscosity, the horizontal axis representing the absolute weight molecular weight and the vertical axis representing the intrinsic viscosity— A form that is a linear fluorine-containing elastomer having a Mark-Hawin gradient a of 0.6 or more when plotted in a Hawin plot, or one type is A) an ethylenically unsaturated compound containing at least one fluoroolefin represented by the general formula:
CY ¹ ₂ = CY ² R _f ¹ X ¹
(Wherein Y ¹ and Y ² are fluorine atoms, hydrogen atoms or —CH ₃ ; R _f ¹ may have an etheric oxygen atom, and part or all of the hydrogen atoms are substituted with fluorine atoms. A linear or branched fluorine-containing alkylene group; X ¹ is an iodine atom or a bromine atom), and when the compound represented by the above general formula is copolymerized, A branched fluorine-containing elastomer obtained by a production method starting at a time when 0 to 10% by mass of the total amount of ethylenically unsaturated compounds added to the system is added. (B) Produced in a Mark-Houwin plot where the number average molecular weight is in the range of 1,000-250,000 and the absolute weight molecular weight and intrinsic viscosity are absolute weight molecular weight and the vertical axis is intrinsic viscosity. Mark when bets - Hawin gradient a is in the form a straight-chain fluorine-containing elastomer is 0.6 or more.
Thus, as the fluorine-containing elastomer in the present invention, one type is the second or third fluorine-containing elastomer, has a crosslinking site capable of peroxide crosslinking, and has a number average molecular weight of 1,000 to 300, When the absolute weight molecular weight and the intrinsic viscosity are plotted in a Mark-Houwin plot in which the abscissa is the absolute weight molecular weight and the ordinate is the intrinsic viscosity, the mark-Hawin gradient a is less than 0.6. An ethylenically unsaturated compound which is a branched fluorine-containing elastomer or contains at least one fluoroolefin, and a general formula:
CY ¹ ₂ = CY ² R _f ¹ X ¹
(Wherein Y ¹ and Y ² are fluorine atoms, hydrogen atoms or —CH ₃ ; R _f ¹ may have an etheric oxygen atom, and part or all of the hydrogen atoms are substituted with fluorine atoms. A linear or branched fluorine-containing alkylene group; X ¹ is an iodine atom or a bromine atom), and when the compound represented by the above general formula is copolymerized, A branched fluorine-containing elastomer obtained by a production method starting at a time when 0 to 10% by mass of the total amount of ethylenically unsaturated compounds added to the system is added. A first, second or third fluorine-containing elastomer having a number average molecular weight in the range of 1,000 to 250,000, and an absolute weight molecular weight and an intrinsic viscosity, the horizontal axis is the absolute weight molecular weight and the vertical axis is A chromatic viscosity Mark - Ha mark when plotted Wynn Plot - form Hawin gradient a is a straight chain type fluorine-containing elastomer is 0.6 or more is also preferable.

The present invention is a crosslinkable composition excellent in crosslinkability, characterized by comprising the first, second or third fluorine-containing elastomer and a crosslinking agent.

The amount of the crosslinking agent is 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the fluorine-containing elastomer. If the crosslinking agent is less than 0.01 parts by mass, the degree of crosslinking is insufficient, so the performance of the fluorine-containing molded product tends to be impaired. In addition to being long, it tends to be economically undesirable.

The crosslinking agent is not particularly limited as long as it is a crosslinking agent usually used in polyamine crosslinking, polyol crosslinking, and peroxide crosslinking, but at least one selected from the group consisting of polyamine compounds, polyhydroxy compounds, and organic peroxides. Preferably it is a seed.

Examples of the polyamine compound include hexamethylenediamine carbamate, N, N′-dicinnamylidene-1,6-hexamethylenediamine, 4,4′-bis (aminocyclohexyl) methanecarbamate, and the like. Among these, N, N′-dicinnamylidene-1,6-hexamethylenediamine is preferable.

As the polyhydroxy compound, a polyhydroxy aromatic compound is preferably used from the viewpoint of excellent heat resistance.

The polyhydroxy aromatic compound is not particularly limited. For example, 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 2,2-bis (4-hydroxyphenyl) perfluoropropane. (Hereinafter referred to as bisphenol AF), resorcin, 1,3-dihydroxybenzene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4,4′-dihydroxydiphenyl, 4,4 ′ -Dihydroxystilbene, 2,6-dihydroxyanthracene, hydroquinone, catechol, 2,2-bis (4-hydroxyphenyl) butane (hereinafter referred to as bisphenol B), 4,4-bis (4-hydroxyphenyl) valeric acid, 2 , 2-Bis (4-hydroxyphenyl) Tetrafluorodichloropropane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl ketone, tri (4-hydroxyphenyl) methane, 3,3 ′, 5,5′-tetrachlorobisphenol A, 3,3 Examples include ', 5,5'-tetrabromobisphenol A. These polyhydroxy aromatic compounds may be an alkali metal salt, an alkaline earth metal salt or the like, but when the copolymer is coagulated using an acid, it is preferable not to use the metal salt.

When the crosslinking agent is a polyhydroxy compound, the crosslinking composition of the present invention preferably contains a crosslinking accelerator. The crosslinking accelerator promotes the formation of an intramolecular double bond in the dehydrofluorination reaction of the fluorine-containing elastomer main chain and the addition of a polyhydroxy compound to the generated double bond.

Examples of the crosslinking accelerator include onium compounds. Among onium compounds, ammonium compounds such as quaternary ammonium salts, phosphonium compounds such as quaternary phosphonium salts, oxonium compounds, sulfonium compounds, cyclic amines, and 1 It is preferably at least one selected from the group consisting of functional amine compounds, and more preferably at least one selected from the group consisting of quaternary ammonium salts and quaternary phosphonium salts.

The quaternary ammonium salt is not particularly limited. For example, 8-methyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 8-methyl-1,8-diazabicyclo [5. 4.0] -7-undecenium iodide, 8-methyl-1,8-diazabicyclo [5.4.0] -7-undecenium hydroxide, 8-methyl-1,8-diazabicyclo [5]. 4.0] -7-undecenium methyl sulfate, 8-ethyl-1,8-diazabicyclo [5.4.0] -7-undecenium bromide, 8-propyl-1,8-diazabicyclo [5 4.0] -7-undecenium bromide, 8-dodecyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 8-dodecyl-1,8-diazabicyclo 5,4,0] -7-undecenium hydroxide, 8-eicosyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 8-tetracosyl-1,8-diazabicyclo [ 5.4.0] -7-undecenium chloride, 8-benzyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride (hereinafter referred to as DBU-B), 8-benzyl -1,8-diazabicyclo [5.4.0] -7-undecenium hydroxide, 8-phenethyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 8- ( 3-phenylpropyl) -1,8-diazabicyclo [5.4.0] -7-undecenium chloride and the like. Among these, DBU-B is preferable from the viewpoint of excellent crosslinkability and physical properties of the molded product.

The quaternary phosphonium salt is not particularly limited. For example, tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride (hereinafter referred to as BTPPC), benzyltributylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl. Examples thereof include -2-methoxypropylphosphonium chloride, benzylphenyl (dimethylamino) phosphonium chloride, and among these, benzyltriphenylphosphonium chloride (BTPPC) is preferable from the viewpoint of excellent crosslinkability and physical properties of the molded product.

Further, as a crosslinking accelerator, a quaternary ammonium salt, a solid solution of a quaternary phosphonium salt and bisphenol AF, or a chlorine-free crosslinking accelerator disclosed in JP-A-11-147891 can also be used.

It is preferable that the compounding quantity of a crosslinking accelerator is 0.01-8 mass parts with respect to 100 mass parts of fluorine-containing elastomers, More preferably, it is 0.02-5 mass parts. When the crosslinking accelerator is less than 0.01 parts by mass, the crosslinking of the fluorine-containing elastomer does not proceed sufficiently, and the heat resistance and oil resistance of the resulting molded product tend to decrease, and when the amount exceeds 8 parts by mass. The moldability of the crosslinkable composition tends to decrease.

The organic peroxide may be an organic peroxide that can easily generate radicals in the presence of heat or a redox system. For example, 1,1-bis (t-butylperoxy) -3,5, 5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α-bis (t-butylperoxide Oxy) -p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3 Benzoyl peroxide, t-butylperoxybenzene, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, t-butylperoxide -Oxybenzoate can be listed. Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3 are preferable.

When the crosslinking agent is an organic peroxide, the crosslinkable composition of the present invention preferably contains a crosslinking aid. Examples of the crosslinking aid include triallyl cyanurate, trimethallyl isocyanurate, triallyl isocyanurate (TAIC), triacryl formal, triallyl trimellitate, N, N′-m-phenylenebismaleimide, dipropargyl. Terephthalate, diallyl phthalate, tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1,3,5-tris (2,3,3-trifluoro-2-propenyl) -1,3, 5-triazine-2,4,6-trione), tris (diallylamine) -S-triazine, triallyl phosphite, N, N-diallylacrylamide, 1,6-divinyldodecafluorohexane, hexaallylphosphoramide, N , N, N ', N'-teto Allylphthalamide, N, N, N ′, N′-tetraallylmalonamide, trivinylisocyanurate, 2,4,6-trivinylmethyltrisiloxane, tri (5-norbornene-2-methylene) cyanurate, triallyl Examples include phosphite. Among these, triallyl isocyanurate (TAIC) is preferable from the viewpoint of excellent crosslinkability and physical properties of the molded product.

The compounding quantity of a crosslinking adjuvant is 0.01-10 mass parts with respect to 100 mass parts of fluorine-containing elastomers, Preferably it is 0.1-5.0 mass parts. If the crosslinking aid is less than 0.01 parts by mass, the crosslinking time tends to be unpractical, and if it exceeds 10 parts by mass, the crosslinking time becomes excessively fast and the molded article is permanently compressed. There is also a tendency for distortion to decrease.

Crosslinking may be appropriately determined depending on the type of the crosslinking agent used, but is usually fired at a temperature of 150 to 300 ° C. for 1 minute to 24 hours. Moreover, it can bridge | crosslink under normal pressure, pressurization, pressure reduction, and also in the air.

The cross-linking method is not particularly limited, and a steam cross-linking method, a pressure forming method, a normal method in which a cross-linking reaction is started by heating can be employed, and a radiation cross-linking method at normal temperature and pressure may be used.

After performing the first crosslinking treatment (referred to as primary crosslinking), a post-treatment step called secondary crosslinking may be performed.

Polyamine crosslinking using a polyamine compound as a crosslinking agent can be carried out in the same manner as before. For example, the fluorine-containing elastomer in the present invention and a crosslinking agent, if necessary, a crosslinking accelerator, and other additives that can be mixed as appropriate, are roll-kneaded and pressed into a mold for primary crosslinking, followed by secondary crosslinking. How to do. In general, the conditions for the primary crosslinking are adopted from the range of a temperature of 100 to 200 ° C., a time of 5 to 120 minutes and a pressure of about 2 to 10 MPa, and the conditions of the secondary crosslinking are a temperature of 150 to 300 ° C. and a time of 30 minutes to 30 minutes. It is adopted from the time range.

Polyol crosslinking using a polyhydroxy compound as a crosslinking agent can be carried out in the same manner as before. For example, the fluorine-containing elastomer in the present invention and a crosslinking agent, if necessary, a crosslinking accelerator, and other additives that can be mixed as appropriate, are roll-kneaded and pressed into a mold for primary crosslinking, followed by secondary crosslinking. How to do. For the kneading, an internal mixer, a Banbury mixer or the like can be preferably used. In general, primary crosslinking can be performed at 2 to 10 MPa at 100 to 200 ° C. for 5 to 60 minutes, and secondary crosslinking can be performed at 150 to 300 ° C. for 30 minutes to 30 hours.

Peroxide crosslinking using an organic peroxide as a crosslinking agent can be carried out in the same manner as before. For example, the fluorine-containing elastomer in the present invention and a crosslinking agent, if necessary, a crosslinking accelerator, and other additives that can be mixed as appropriate, are roll-kneaded and pressed into a mold for primary crosslinking, followed by secondary crosslinking. How to do. In general, primary crosslinking can be performed at 2 to 10 MPa at 100 to 200 ° C. for 5 to 60 minutes, and secondary crosslinking can be performed at 150 to 300 ° C. for 30 minutes to 30 hours.

Since the 3rd crosslinkable composition of this invention has a 3rd fluorine-containing elastomer which has at least one of an iodine atom and a bromine atom, and the total of the content is 0.001 to 10 weight%, The terminal or bromine terminal becomes a crosslinking point (crosslinking site), and the crosslinking density can be further increased.

The third crosslinkable composition of the present invention more preferably contains an organic peroxide as a crosslinker. The third fluorine-containing elastomer has at least one of iodine atom and bromine atom, and the total content thereof is 0.001 to 10% by weight. Can be performed more easily. Examples of the organic peroxide include those described above, among which 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5-dimethyl-2,5-di (t- Preferably, it is at least one compound of (butylperoxy) -hexyne-3. In addition, the third crosslinkable composition of the present invention preferably contains a crosslinking aid, and examples of the crosslinking aid include those described above. Among them, triallyl is preferred because of its excellent crosslinkability and physical properties of the molded product. Isocyanurate (TAIC) is preferred.

In the third crosslinkable composition of the present invention, the amount of the crosslinking aid is 0.01 to 10 parts by mass, preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the fluorine-containing elastomer. It is. If the crosslinking aid is less than 0.01 parts by mass, the crosslinking time tends to be unpractical, and if it exceeds 10 parts by mass, the crosslinking time becomes excessively fast and the molded article is permanently compressed. There is also a tendency for distortion to decrease.

In the third crosslinkable composition of the present invention, the crosslinking condition may be appropriately determined depending on the kind of the crosslinking agent used, but is usually baked at a temperature of 150 to 300 ° C. for 1 minute to 24 hours. Moreover, it can bridge | crosslink under normal pressure, pressurization, pressure reduction, and also in the air.

It is preferable that the 3rd crosslinkable composition of this invention contains an organic peroxide as a crosslinking agent, and bridge | crosslinks by peroxide bridge | crosslinking. Peroxide crosslinking using an organic peroxide as a crosslinking agent can be carried out in the same manner as before. For example, a third fluorine-containing elastomer and a crosslinking agent, if necessary, a crosslinking accelerator, and other additives that can be mixed as appropriate, are roll-kneaded and pressed into a mold for primary crosslinking, followed by secondary crosslinking. How to do. In general, primary crosslinking can be performed at 2 to 10 MPa at 100 to 200 ° C. for 5 to 60 minutes, and secondary crosslinking can be performed at 150 to 300 ° C. for 30 minutes to 30 hours.

The first, second or third crosslinkable composition of the present invention preferably also contains a filler. Fillers include metal oxides such as calcium oxide, titanium oxide, and aluminum oxide; metal hydroxides such as magnesium hydroxide, aluminum hydroxide, and calcium hydroxide; magnesium carbonate, aluminum carbonate, calcium carbonate, barium carbonate, etc. Carbonates; silicates such as magnesium silicate, calcium silicate, sodium silicate, and aluminum silicate; sulfates such as aluminum sulfate, calcium sulfate, and barium sulfate; synthetic hydrotalcite, molybdenum disulfide, iron sulfide, sulfide Metal sulfides such as copper; diatomaceous earth, asbestos, lithopone (zinc sulfide / barium sulfide), graphite, carbon black, carbon fluoride, calcium fluoride, coke, quartz fine powder, zinc white, talc, mica powder, wax Lastite, carbon fiber, aramid fiber Various whiskers, glass fiber, organic reinforcing agents, organic fillers, polytetrafluoroethylene, mica, silica, Celite, clay and the like.

The first, second or third crosslinkable composition of the present invention preferably contains a plasticizer. Examples of the plasticizer include dioctyl phthalic acid and pentaerythritol.

The first, second or third crosslinkable composition of the present invention preferably also contains a processing aid, which includes higher fatty acids such as stearic acid, oleic acid, palmitic acid, lauric acid; stearic acid Higher fatty acid salts such as sodium and zinc stearate; higher fatty acid amides such as stearic acid amide and oleic acid amide; higher fatty acid esters such as ethyl oleate, higher aliphatic amines such as stearylamine and oleylamine; carnauba wax, ceresin wax, etc. Petroleum-based waxes; Polyglycols such as ethylene glycol, glycerin and diethylene glycol; Aliphatic hydrocarbons such as petroleum jelly and paraffin; Silicone oils, silicone polymers, low molecular weight polyethylene, phthalates, phosphates, rosin, (Hallowe Reduction) dialkylamine, surfactants, sulfone compounds, fluorine-based aids, and the like.

The first, second or third crosslinkable composition of the present invention comprises an acid acceptor, a release agent, a pigment, a flame retardant, a lubricant, a light stabilizer, a weathering stabilizer, an antistatic agent, an ultraviolet absorber, an oxidation agent. An inhibitor, a foaming agent, a fragrance, an oil, a softening agent, and the like may be included as long as the effects of the present invention are not affected.

The first, second or third crosslinkable composition of the present invention may contain a solvent. When the fluorine-containing elastomer is dissolved in a solvent, it can be used as a paint. Examples of the solvent include ketone solvents and ester solvents.

The 1st, 2nd, or 3rd crosslinkable composition of this invention may contain the other polymer different from the fluorine-containing elastomer in this invention. Examples of the other polymer include nitrile rubber, acrylic rubber, epichlorohydrin rubber, fluorosilicone rubber, silicone rubber, fluorine-containing thermoplastic elastomer, and polyvinylidene fluoride.

The first, second, or third cross-linking composition of the present invention is prepared by kneading at least the first, second, or third fluorine-containing elastomer, the cross-linking agent, and the above-described cross-linking accelerator as required. It is preferable that it is obtained.

For the kneading, an open roll, a Banbury mixer, a pressure kneader, an extruder or the like can be used, but an extruder such as a pressure kneader or a twin screw extruder can be used in that a high shear force can be applied. preferable.

The present invention is a crosslinked rubber molded product obtained by crosslinking the first, second or third crosslinkable composition.

The crosslinked rubber molded product of the present invention can be produced by molding the first, second or third crosslinkable composition, and crosslinking the resulting molded product, or simultaneously performing molding and crosslinking. Can also be manufactured. Moreover, it can also be obtained as a coating film by coating and crosslinking the crosslinkable composition.

The molding method is not particularly limited, and examples thereof include compression molding, extrusion molding, transfer molding, and injection molding.

The crosslinked rubber molded article of the present invention has excellent heat resistance, oil resistance, amine resistance, chemical resistance and cold resistance, and slides in contact with other materials, or seals other materials and substances. It is generally used for the purpose of stopping, sealing, vibration-proofing and sound-proofing, and can be used as various parts in various fields such as automobile industry, aircraft industry, and semiconductor industry.
Fields used include, for example, semiconductor-related fields, automotive fields, aircraft fields, space / rocket fields, ship fields, chemical fields such as chemical plants, pharmaceutical fields such as pharmaceuticals, photographic fields such as developing machines, printing machines, etc. Printing field, painting field such as coating equipment, analysis equipment, analysis / physical machinery field such as instruments, food equipment field including food plant equipment and household goods, beverage food production equipment field, pharmaceutical production equipment field, medical parts field, chemical Chemical transportation equipment field, nuclear plant equipment field, steel field such as iron plate processing equipment, general industrial field, electrical field, fuel cell field, electronic parts field, optical equipment parts field, space equipment parts field, petrochemical plant equipment field Oil, gas and other energy resource exploration equipment parts field, oil refining field, oil transportation equipment parts field.

Examples of usage forms of the crosslinked rubber molded product of the present invention include, for example, a ring, packing, gasket, diaphragm, oil seal, bearing seal, lip seal, plunger seal, door seal, lip and face seal, gas delivery plate seal, and wafer support. Examples include various sealing materials such as seals and barrel seals, and packing. As a sealing material, it can be used for applications requiring heat resistance, solvent resistance, chemical resistance and non-adhesiveness.
Also used as tubes, hoses, rolls, various rubber rolls, flexible joints, rubber plates, coatings, belts, dampers, valves, valve seats, valve discs, chemical-resistant coating materials, laminating materials, lining materials, etc. it can.
The cross-sectional shapes of the ring, packing, and seal may be various shapes. Specifically, for example, the ring, the packing, and the seal may have a square shape, an O shape, a ferrule shape, a D shape, Different shapes such as L, T, V, X, Y may be used.

In the semiconductor related field, for example, semiconductor manufacturing apparatus, liquid crystal panel manufacturing apparatus, plasma panel manufacturing apparatus, plasma display panel manufacturing apparatus, plasma address liquid crystal panel manufacturing apparatus, organic EL panel manufacturing apparatus, field emission display panel manufacturing apparatus, solar It can be used for a battery substrate manufacturing apparatus, a semiconductor transfer apparatus, and the like. Examples of such an apparatus include a gas control apparatus such as a CVD apparatus and a semiconductor gas control apparatus, a dry etching apparatus, a wet etching apparatus, a plasma etching apparatus, a reactive ion etching apparatus, a reactive ion beam etching apparatus, and a sputter etching. Apparatus, ion beam etching apparatus, oxidation diffusion apparatus, sputtering apparatus, ashing apparatus, plasma ashing apparatus, cleaning apparatus, ion implantation apparatus, plasma CVD apparatus, exhaust apparatus, exposure apparatus, polishing apparatus, film forming apparatus, dry etching cleaning apparatus, UV / O ₃ cleaning device, ion beam cleaning device, laser beam cleaning device, plasma cleaning device, gas etching cleaning device, extraction cleaning device, Soxhlet extraction cleaning device, high temperature high pressure extraction cleaning device, microwave extraction cleaning device, supercritical extraction Cleaning equipment Equipment, cleaning equipment using hydrofluoric acid, hydrochloric acid, sulfuric acid, ozone water, stepper, coater / developer, CMP equipment, excimer laser exposure machine, chemical piping, gas piping, NF ₃ plasma treatment, O ₂ plasma treatment, fluorine plasma treatment Such as plasma processing equipment, heat treatment film forming equipment, wafer transfer equipment, wafer cleaning equipment, silicon wafer cleaning equipment, silicon wafer processing equipment, equipment used in LP-CVD processes, equipment used in lamp annealing processes, reflow Examples include an apparatus used in the process.

Specific usage forms in the semiconductor-related field include, for example, gate valves, quartz windows, chambers, chamber lits, gates, bell jars, couplings, pump O-rings, gaskets, and other various sealing materials; resist developers and strips Various sealing materials such as O-rings for liquids, hoses and tubes; linings and coatings for resist developer tanks, stripping liquid tanks, wafer cleaning liquid tanks, wet etching tanks; pump diaphragms; rolls for wafer transfer; for wafer cleaning liquids Hose tube; Clean equipment sealant for clean equipment such as clean rooms; Sealing material for storage equipment for storing semiconductor manufacturing equipment and wafers; Diaphragm for transferring chemicals used in semiconductor manufacturing processes Can be mentioned.

In the automotive field, the engine body, main motion system, valve system, lubrication / cooling system, fuel system, intake / exhaust system, drive system transmission system, chassis steering system, brake system, basic electrical components, control It can be used for electrical components such as system electrical components and equipment electrical components. Note that the automobile field includes a motorcycle.
In the engine body and its peripheral devices as described above, the molded product of the present invention can be used for various sealing materials that are required to have heat resistance, oil resistance, fuel oil resistance, engine cooling antifreeze resistance, and steam resistance. Examples of such seal materials include seals such as gaskets, shaft seals, valve stem seals, and non-contact type or contact type packings such as self-seal packing, piston rings, split ring type packings, mechanical seals, and oil seals. In addition to types, bellows, diaphragms, hoses, tubes, electric wires, cushioning materials, anti-vibration materials, and various sealing materials used for belt AT devices.

Specific usage forms in the above fuel system include fuel injectors, cold start injectors, fuel line quick connectors, sender flange quick connectors, fuel pumps, fuel tank quick connectors, gasoline mixing pumps, gasoline pumps, fuel O-rings used for tube bodies, fuel tube connectors, injectors, etc .; expiratory manifolds, fuel filters, pressure regulators, canisters, fuel tank caps, fuel pumps, fuel tanks, fuel tank sender units, fuel Used in injection devices, high-pressure fuel pumps, fuel line connector systems, pump timing control valves, suction control valves, solenoid subassemblies, fuel cut valves, etc. Seal, canister, purge, solenoid, valve seal, onboard, refueling, vapor, recovery (ORVR) valve seal, oil seal for fuel pump, fuel sender seal, fuel tank rollover valve seal, filler seal, Injector seal, filler cap seal, filler cap valve seal; fuel hose, fuel supply hose, fuel return hose, vapor (evaporation) hose, vent (breather) hose, filler hose, filler neck hose, hose in fuel tank (in Tank hoses), carburetor control hoses, fuel inlet hoses, fuel breather hoses and other hoses; gas filters used in fuel filters, fuel line connector systems, etc. Flange gaskets used for fuel tanks, carburetors, etc .; Line materials such as steam recovery lines, fuel feed lines, vapor / ORVR lines; canisters, ORVR, fuel pumps, fuel tank pressure sensors, gasoline pumps, carburetor sensors, combined air control Diaphragms used in equipment (CAC), pulsation dampers, canisters, auto cocks, etc., pressure regulator diaphragms for fuel injection devices; valves for fuel pumps, carburetor needle valves, rollover check valves, check valves; Breather), tubes used in fuel tanks; tank packings for fuel tanks, packing for accelerating pump pistons for carburetors; fuel sender anti-vibration parts for fuel tanks O-ring and diaphragm to control fuel pressure; accelerator pump cup; in-tank fuel pump mount; fuel injector injector cushion ring; injector seal ring; carburetor needle valve core valve; carburetor acceleration pump Examples include a piston; a valve seat of a composite air control device (CAC); a fuel tank main body; a seal part for a solenoid valve.

Specific usage forms in the brake system include: a diaphragm used for a master back, a hydraulic brake hose air brake, a brake chamber of an air brake; a hose used for a brake hose, a brake oil hose, a vacuum brake hose, etc .; an oil seal Various sealing materials such as O-ring, packing, brake piston seal, etc .; Master valve atmospheric valve, vacuum valve, brake valve check valve; Master cylinder piston cup (rubber cup), brake cup; Hydraulic brake Master cylinders and vacuum boosters, hydraulic brake wheel cylinder boots, anti-lock brake system (ABS) O-rings and grommets.

Specific usage forms of the basic electrical component include an insulator and sheath of an electric wire (harness), a tube of a harness exterior component, a grommet for a connector, and the like.
Specific usage forms in control system electrical components include coating materials for various sensor wires.
Specific use forms in the above-mentioned electrical equipment parts include car air conditioner O-rings, packing, cooler hoses, high pressure air conditioner hoses, air conditioner hoses, gaskets for electronic throttle units, plug plugs for direct ignition, diaphragms for distributors, etc. Is mentioned. It can also be used for bonding electrical components.

Specific usage forms in the intake / exhaust system include packing used for intake manifolds, exhaust manifolds, etc., throttle body packing of throttles; EGR (exhaust gas recirculation), pressure control (BPT), wastegate, turbo waist Diaphragms used for gates, actuators, variable turbine geometry (VTG) turbo actuators, exhaust purification valves, etc .; EGR (exhaust recirculation) control hoses, emission control hoses, turbocharger turbo oil hoses (supply), turbo Oil hose (return), turbo air hose, intercooler hose, turbocharger hose, hose connected to compressor of turbo engine equipped with intercooler, exhaust Hose such as air hose, air intake hose, turbo hose, DPF (diesel particulate filter) sensor hose; air duct or turbo air duct; intake manifold gasket; EGR seal material, AB valve afterburn prevention valve seat, (turbocharger etc. And a seal member used for groove parts such as a rocker cover and an air suction manifold used in an automobile engine.

In addition, in exhaust gas control parts, seals used for steam recovery canisters, catalytic converters, exhaust gas sensors, oxygen sensors, etc., and steam recovery and steam canister solenoid armature seals; used as intake manifold gaskets, etc. Can do.
Further, in parts related to a diesel engine, it can be used as an O-ring seal for a direct injection injector, a rotary pump seal, a control diaphragm, a fuel hose, an EGR, a priming pump, a boost compensator diaphragm, and the like. It can also be used for O-rings, sealing materials, hoses, tubes, diaphragms used in urea SCR systems, urea water tank bodies of urea SCR systems, and urea water tank sealing materials.

Specific usage forms in the transmission system include transmission-related bearing seals, oil seals, O-rings, packings, torque converter hoses, and the like.
Examples include a mission oil seal, an AT mission oil hose, an ATF hose, an O-ring, and packings.
Transmissions include AT (automatic transmission), MT (manual transmission), CVT (continuously variable transmission), DCT (dual clutch transmission), and the like.
In addition to oil seals, gaskets, O-rings and packings for manual or automatic transmissions, oil seals, gaskets, O-rings and packings for continuously variable transmissions (belt type or toroidal type), ATF linear solenoids Packing, oil hose for manual transmission, ATF hose for automatic transmission, CVTF hose for continuous transmission (belt type or toroidal type), and the like.
Specific usage forms in the steering system include a power steering oil hose and a high pressure power steering hose.

Examples of forms used in the engine body of automobile engines include cylinder head gaskets, cylinder head cover gaskets, oil pan packings, gaskets such as general gaskets, seals such as O-rings, packings, timing belt cover gaskets, and control hoses. These include hoses, anti-vibration rubber for engine mounts, control valve diaphragms, and camshaft oil seals.
In a main motion system of an automobile engine, it can be used for a shaft seal such as a crankshaft seal and a camshaft seal.
In a valve system of an automobile engine, it can be used for a valve stem oil seal of an engine valve, a valve seat of a butterfly valve, and the like.
In automotive engine lubrication and cooling systems, engine oil cooler hoses, oil return hoses, seal gaskets, water hoses around radiators, radiator seals, radiator gaskets, radiator O-rings, vacuum pumps In addition to a vacuum pump oil hose, etc., it can be used for a radiator hose, a radiator tank, an oil pressure diaphragm, a fan coupling seal, and the like.

Thus, specific examples of use in the automotive field include engine head gaskets, oil pan gaskets, manifold packings, oxygen sensor seals, oxygen sensor bushings, nitrogen oxide (NOx) sensor seals, and nitrogen oxide (NOx). Sensor bushing, sulfur oxide sensor seal, temperature sensor seal, temperature sensor bush, diesel particle filter sensor seal, diesel particle filter sensor bush, injector O-ring, injector packing, fuel pump O-ring and diaphragm, gearbox Seal, power piston seal, cylinder liner seal, valve stem seal, static valve stem seal, dynamic valve stem seal, automatic Speed pump front pump seal, rear axle pinion seal, universal joint gasket, speedometer pinion seal, foot brake piston cup, torque transmission device O-ring and oil seal, exhaust gas recombustion device seal and bearing seal, Recombustion device hose, carburetor sensor diaphragm, anti-vibration rubber (engine mount, exhaust, muffler hanger, suspension bush, center bearing, strut bumper rubber, etc.), suspension anti-vibration rubber (strut mount, bush, etc.), Drive system anti-vibration rubber (damper, etc.), fuel hose, EGR tube and hose, twin cab tube, carburetor needle valve core valve, carburetor flange gasket, oil hose Oil cooler hose, ATF hose, cylinder head gasket, water pump seal, gear box seal, needle valve tip, motorcycle reed valve lead, automotive engine oil seal, gasoline hose gun seal, car air conditioner seal, engine intercooler Rubber hoses, seals for fuel line connector systems, CAC valves, needle tips, engine wires, filler hoses, car air conditioner O-rings, intake gaskets, fuel tank materials, distributor diaphragms, water hoses , Clutch hose, PS hose, AT hose, master back hose, heater hose, air conditioner hose, ventilation hose, oy Filler cap, PS rack seal, rack & pinion boot, CVJ boot, ball joint dust cover, strut dust cover, weather strip, glass run, center unit packing, body sight welt, bumper rubber, door latch, dash insulator, high tension cord, Flat belts, poly V belts, timing belts, toothed belts, V-ribbed belts, tires, wiper blades, diaphragms and plungers for LPG car regulators, diaphragms and valves for CNG car regulators, DME compatible rubber parts, diaphragms and boots for auto tensioners , Idle speed control diaphragms and valves, Auto speed control actuators, Negative pressure pump diaphragms and valves Kkubarubu and plunger, O. P. S. Diaphragms and O-rings, gasoline pressure relief valves, engine cylinder sleeve O-rings and gaskets, wet cylinder sleeve O-rings and gaskets, differential gear seals and gaskets (gear oil seals and gaskets), power steering devices Seals and gaskets (PSF seals and gaskets), shock absorber seals and gaskets (SAF seals and gaskets), constant velocity joint seals and gaskets, wheel bearing seals and gaskets, metal gasket coating agents, caliper seals, Examples include boots, wheel bearing seals, and bladders used for vulcanization molding of tires.

In the aircraft field, space / rocket field, and ship field, the fuel system and the lubricating oil system can be used.
In the aircraft field, for example, various aircraft seal parts, various aircraft parts for aircraft engine oil applications, jet engine valve stem seals, gaskets and O-rings, rotating shaft seals, hydraulic equipment gaskets, firewall seals, etc. They can be used as fuel supply hoses, gaskets, O-rings, aircraft cables, oil seals, shaft seals, and the like.

In the space and rocket field, for example, as lip seals, diaphragms, O-rings for spacecraft, jet engines, missiles, etc., O-rings for oil for gas turbine engines, anti-vibration stand pads for missile ground control, etc. Can be used.
In the marine field, for example, screw propeller shaft stern seals, diesel engine intake and exhaust valve stem seals, butterfly valve valve seals, butterfly valve valve seats and shaft seals, butterfly valve shaft seals, stern tube seals , Fuel hoses, gaskets, engine O-rings, marine cables, marine oil seals, marine shaft seals, and the like.

In the chemical field such as the above chemical plant and in the pharmaceutical field such as pharmaceuticals, it should be used in processes that require a high degree of chemical resistance, for example, processes for manufacturing chemicals such as pharmaceuticals, agricultural chemicals, paints, and resins. Can do.
Specific usage forms in the chemical field and chemical field include chemical equipment, chemical pumps and flow meters, chemical pipes, heat exchangers, agricultural chemical sprayers, agricultural chemical transfer pumps, gas piping, fuel cells, Analytical instruments and physics and chemistry instruments (for example, analytical instruments and instrument column fittings), exhaust gas desulfurization fittings, seals used in nitric acid plants, power plant turbines, etc., seals used in medical sterilization processes, Seals for plating solutions, roller seals for papermaking belts, joint seals for wind tunnels; chemical devices such as reactors and stirrers, analytical instruments and instruments, chemical pumps, pump housings, valves, tachometers, etc. O-ring for mechanical seal, O-ring for compressor sealing; high-temperature vacuum dryer, gas chromatography and p Packing used for tube connection parts of meters, glass cooler packing of sulfuric acid production equipment; Diaphragms used for diaphragm pumps, analytical instruments and physics and chemistry instruments; Gaskets used for analytical instruments and instruments; Analytical instruments and instruments Ferrules used in the field; valve seats; U cups; linings used in chemical equipment, gasoline tanks, wind tunnels, etc., corrosion resistant linings in anodized processing tanks; coating of masking jigs for plating; Parts; Expansion joints of flue gas desulfurization plants; Acid-resistant hoses for concentrated sulfuric acid, chlorine gas transfer hoses, oil-resistant hoses, rainwater drain hoses for benzene and toluene storage tanks; chemical-resistant tubes used for analytical instruments and physics and chemistry instruments Medical tube; anti-trick for textile dyeing Down roll and dyeing roll; pharmaceutical Kusurisen; rubber stopper for medical, chemical bottle, chemical tank, bags, drug containers; Resistant acid, and the like protection gloves and boots, etc. solvent.

In the photographic field such as the developing machine, the printing field such as a printing machine, and the coating field such as a coating facility, it can be used as a roll, a belt, a seal, a valve part, etc. of a dry copying machine.
Specific usage forms in the photographic field, printing field, and painting field include a surface layer of a transfer roll of a copying machine, a cleaning blade of a copying machine, a belt of a copying machine; for OA equipment such as a copying machine, a printer, and a facsimile machine. Rolls (for example, fixing rolls, pressure rolls, pressure rolls, etc.), belts; rolls for PPC copiers, roll blades, belts; rolls for film developing machines and X-ray film developing machines; printing rolls for printing machines , Scrapers, tubes, valve parts, belts; printer ink tubes, rolls, belts; coating, painting equipment coating rolls, scrapers, tubes, valve parts; development rolls, gravure rolls, guide rolls, magnetic tape production coating lines Guide rolls, gravure rolls for magnetic tape production coating lines, coating lows And the like.

In the field of food equipment including the above-mentioned food plant equipment and household goods, it can be used for food production processes, food transporters or food reservoirs.
Specific uses in the food equipment field include plate heat exchanger seals, vending machine solenoid valve seals, jar pot packing, sanitary pipe packing, pressure cooker packing, water heater seals, heat exchange. Gaskets for equipment, diaphragms and packing for food processing equipment, rubber materials for food processing equipment (for example, heat exchanger gaskets, diaphragms, O-rings and other seals, piping, hoses, sanitary packing, valve packing, when filling And packing for use as a joint between a mouth such as a bottle and a filler. Moreover, packing, a gasket, a tube, a diaphragm, a hose, a joint sleeve etc. which are used for products, such as alcoholic beverages and soft drinks, a filling apparatus, a food sterilization apparatus, a brewing apparatus, a water heater, various automatic food vending machines, etc. are mentioned.

In the nuclear plant equipment field, it can be used as a check valve, a pressure reducing valve, a seal of a uranium hexafluoride concentrator, etc. around the reactor.

Specific usage forms in the general industrial field include: sealing materials for hydraulic equipment such as machine tools, construction machines, hydraulic machines; seals and bearing seals for hydraulic and lubrication machines; sealing materials used for mandrels, etc .; dry cleaning equipment Seals used for windows, etc .; cyclotron seals, (vacuum) valve seals, proton accelerator seals, automatic packaging machine seals, pump diaphragms and snakes for sulfur dioxide and chlorine gas analyzers (pollution measuring instruments) in the air Pump lining, printing press rolls and belts, transport belts (conveyor belts), pickling rolls for pickling iron plates, robot cables, solvent rolling rolls such as aluminum rolling lines, coupler O-rings, acid-resistant cushioning materials , Dust seals and lip rubber on sliding parts of cutting machines, garbage incinerators Basket, friction materials, metal or a surface modifier for rubbers, and the like dressing. Also, gaskets and sealants for equipment used in the papermaking process, sealants for clean room filter units, sealants for construction, protective coatings for concrete and cement, glass cloth impregnated materials, polyolefin processing aids, polyethylene molding It can also be used as a property improving additive, a fuel container such as a small generator or a lawn mower, a pre-coated metal obtained by subjecting a metal plate to a primer treatment, and the like. In addition, it can be impregnated into a woven fabric and baked to be used as a sheet and a belt.

Specific examples of usage in the steel field include iron plate processing rolls for iron plate processing equipment.

Specific usage forms in the electrical field include: Shinkansen insulating oil caps, liquid-sealed transformer benching seals, transformer seals, oil well cable jackets, electric furnace oven oven seals, microwave oven window frames, etc. Used for sealing, sealing materials used when bonding CRT wedges and necks, halogen lamp sealing materials, electrical component fixing agents, sheathing heater end treatment sealing materials, electrical equipment lead wire terminals Sealing materials that can be used. Also used for coating materials such as oil and heat resistant wires, high heat resistant wires, chemical resistant wires, high insulating wires, high voltage transmission lines, cables, wires used in geothermal power generation equipment, wires used around automobile engines, etc. You can also. It can also be used for oil seals and shaft seals for vehicle cables. Furthermore, electrical insulating materials (for example, insulating spacers for various electrical equipment, insulating tapes used for cable joints and terminals, materials used for heat-shrinkable tubes, etc.) It can also be used for electronic equipment materials (for example, lead wire materials for motors, wire materials around high-temperature furnaces). Moreover, it can be used also for the sealing layer and protective film (back sheet) of a solar cell.

In the above fuel cell field, sealing materials between electrodes, electrode-separators, piping seals, packings, separators for hydrogen, oxygen, produced water, etc., in polymer electrolyte fuel cells, phosphate fuel cells, etc. It can be used as such.

In the electronic component field, it can be used as a heat radiating material, an electromagnetic shielding material, a gasket for a computer hard disk drive (magnetic recording device), and the like. In addition, buffer rubber (crash stopper) for hard disk drives, binder for electrode active materials for nickel hydride secondary batteries, binder for active materials for lithium ion batteries, polymer electrolyte for lithium secondary batteries, binder for positive electrodes for alkaline storage batteries, EL element (electroluminescent element) binder, capacitor electrode active material binder, sealant, sealing agent, optical fiber quartz coating, optical fiber coating film and sheets, electronic parts, circuit board potting And coating and adhesive seals, electronic component fixing agents, epoxy and other sealant modifiers, printed circuit board coating agents, epoxy and other printed wiring board prepreg resin modifiers, light bulbs and other anti-scattering materials, computer gaskets , Large computer cooling hose, secondary battery, Packing such as gaskets and O- ring for a lithium secondary battery, a sealing layer covering one or both surfaces of the outer surface of the organic EL structure, the connector is also used as such a damper.

In the chemical transport equipment field, it can be used as a safety valve or a shipping valve for trucks, trailers, tank trucks, ships, etc.

In the field of parts for exploring and mining energy resources such as oil and gas, they are used as various sealing materials used in the mining of oil and natural gas, boots for electrical connectors used in oil wells, and the like.
Specific uses in the energy resource search and mining equipment parts field include drill bit seals, pressure adjustment diaphragms, horizontal drilling motor (stator) seals, stator bearing (shaft) seals, and blowout prevention devices (BOP). Sealing material, sealing material used for rotation blowout prevention device (pipe wiper), sealing material used for MWD (real-time excavation information detection system), gas-liquid connector, logging used for logging equipment (logging equipment) Tool seals (for example, O-rings, seals, packing, gas-liquid connectors, boots, etc.), inflatable packers and completion packers, packer seals used in them, seals and packings used in cementing devices, perforators (perforators) ) Seals, seals used for mud pumps, packing, motor lining, underground detector covers, U cups, composition seating cups, rotating seals, laminated elastomeric bearings, flow control seals, sand control seals, safety valves Seals, hydraulic fracturing equipment (fracturing equipment) seals, linear packer and linear hanger seals and packing, wellhead seals and packing, chalk and valve seals and packing, LWD (logging during logging), Diaphragms used in oil exploration and oil drilling applications (for example, diaphragms for supplying lubricating oil such as oil drilling pits), gate valves, electronic boots, drill gun seal elements, and the like.

In addition, joint seals for kitchens, bathrooms, toilets, etc .; outdoor tent pulling cloth; seals for printing materials; rubber heat hoses for gas heat pumps, refractory rubber hoses; agricultural films, linings, weatherproof covers; It can also be used for tanks such as laminated steel plates used in the above.

Furthermore, it can be used as an article combined with a metal such as aluminum. Examples of such usage include door seals, gate valves, pendulum valves, and solenoid tips, as well as metal rubber parts combined with metals such as piston seals, diaphragms, and metal gaskets combined with metals.
It can also be used for rubber parts, brake shoes, brake pads, etc. in bicycles.

Moreover, a belt is mentioned as one of the forms of the crosslinked rubber molded product of this invention. Such a belt is also one aspect of the present invention.
The following are illustrated as said belt. Power transmission belts (including flat belts, V-belts, V-ribbed belts, toothed belts, etc.) and conveyor belts (conveyor belts), such as parts around the engine of agricultural machinery, machine tools, industrial machinery, etc. Flat belts used in slabs; conveyor belts for transporting loose and granular materials such as coal, crushed stone, earth and sand, ore, and wood chips in a high-temperature environment; conveyor belts used in steelworks such as blast furnaces; precision Conveyor belts in applications exposed to high temperatures in equipment assembly factories, food factories, etc .; agricultural machinery, general equipment (eg, OA equipment, printing machines, commercial dryers, etc.), V belts for automobiles, etc. V-ribbed belts; Transmission belts for conveyor robots; Toothed belts for food machines and machine tools; Used in automobiles, OA equipment, medical devices, printing machines, etc. Such as a toothed belt to be like.
In particular, a timing belt is typical as a toothed belt for automobiles.

The belt of the present invention may have a single layer structure or a multilayer structure.
In the case of a multilayer structure, the belt of the present invention may be composed of a layer obtained by crosslinking the crosslinkable composition of the present invention and a layer made of another material.
In the multilayer belt, examples of the layer made of another material include a layer made of other rubber, a layer made of a thermoplastic resin, various fiber reinforcing layers, a canvas, and a metal foil layer.

The crosslinked rubber molded product of the present invention can also be used for industrial vibration-proof pads, vibration-proof mats, railway slab mats, pads, automobile vibration-proof rubbers, and the like. Anti-vibration rubbers for automobiles include anti-vibration rubbers for engine mount, motor mount, member mount, strut mount, bush, damper, muffler hanger, and center bearing.

Other usage forms include joint members such as flexible joints and expansion joints, boots, grommets, and the like. If it is a ship field, a marine pump etc. will be mentioned, for example.
A joint member is a joint used for piping and piping equipment. It prevents vibration and noise generated from the piping system, absorbs expansion and contraction due to temperature changes and pressure changes, absorbs dimensional fluctuations, earthquakes, and subsidence. It is used for applications such as mitigating and preventing the effects of
Flexible joints and expansion joints are preferably used as complex shaped molded bodies for shipbuilding piping, mechanical piping such as pumps and compressors, chemical plant piping, electrical piping, civil engineering / water supply piping, automobiles, etc. it can.
Boots include, for example, constant velocity joint boots, dust covers, rack and pinion steering boots, pin boots, piston boots and other automobile boots, agricultural machinery boots, industrial vehicle boots, building machinery boots, hydraulic machinery boots, empty It can be preferably used as a compact shaped article such as various industrial boots such as pressure machine boots, centralized lubricator boots, liquid transfer boots, fire fighting boots and various liquefied gas transfer boots.

The crosslinked rubber molded product of the present invention can be used for diaphragms for filter presses, diaphragms for blowers, diaphragms for water supply, diaphragms for liquid storage tanks, diaphragms for pressure switches, diaphragms for accumulators, diaphragms for air springs such as suspensions, etc. .

By adding the crosslinked rubber molded product of the present invention to rubber or resin, it is possible to obtain an anti-slip agent for obtaining a molded product or a coating film that is difficult to slip in an environment wet with water such as rain, snow, ice or sweat.

Further, the crosslinked rubber molded product of the present invention is, for example, a cushion for hot press molding when manufacturing a decorative plywood, a printed board, an electrical insulating board, a hard polyvinyl chloride laminated board, etc. made of melamine resin, phenol resin, epoxy resin or the like. It can also be used as a material.

The crosslinked rubber molded article of the present invention can also contribute to impermeability of various supports such as weapon-related sealing gaskets and protective clothing against contact with invasive chemical agents.

Lubricating oils (engine oil, mission oil, gear oil, etc.) containing amine additives (especially amine additives used as antioxidants and detergent dispersants) used in automobiles, ships and other transportation systems O-Ring, V-Ring, X-Ring, Packing, Gasket, Diaphragm, Oil Seal, Bearing Seal, Lip Seal used for sealing and sealing oil, fuel oil and grease (especially urea grease) Can be used for plunger seals, door seals, lip and face seals, gas delivery plate seals, wafer support seals, barrel seals and other various sealing materials, etc., tube, hose, various rubber rolls, coatings, belts, valve discs It can also be used as such. It can also be used as a laminating material and a lining material.

Coating materials for heat and oil resistant wires used for lead wires of sensors that detect the oil temperature and / or oil pressure when contacting with the oil and / or engine oil of an internal combustion engine such as an automobile, as well as for automatic transmissions and engines It can also be used in a high temperature oil atmosphere such as in an oil pan.

In addition, the crosslinked rubber molded product of the present invention may be used with a vulcanized film formed thereon. Specifically, non-adhesive oil-resistant rolls for copiers, weather strips for weathering and anti-icing, infusion rubber stoppers, vial rubber stoppers, mold release agents, non-adhesive light transport belts, anti-adhesion coatings on automobile engine mount play gaskets, Applications include synthetic fiber coating, bolt members or joints having a thin packing coating layer, and the like.

In addition, about the automotive-related parts use of the crosslinked rubber molding of this invention, the parts use of the motorcycle of the same structure is also included.
Examples of the fuel for the automobile include light oil, gasoline, diesel engine fuel (including biodiesel fuel), and the like.

The crosslinkable composition of the present invention can be used as various parts in various industrial fields, in addition to being crosslinked and used as a crosslinked rubber molded product. Then, next, the use of the crosslinkable composition of this invention is demonstrated.
The crosslinkable composition of the present invention comprises a surface modifying material such as metal, rubber, plastic, and glass; a sealing material that requires heat resistance, chemical resistance, oil resistance, and non-adhesiveness, such as a metal gasket and oil seal; Coating materials: Non-adhesive coating materials such as rolls for OA equipment, belts for OA equipment, or bleed barriers; Can be used for impregnation of woven fabric sheets and belts and application by baking.
The crosslinkable composition of the present invention can be used as a sealing material, lining, or sealant having a complicated shape by a usual usage by increasing the viscosity and concentration, and by reducing the viscosity to a thin film of several microns. It can be used to form a film, and can be used to apply pre-coated metal, O-rings, diaphragms, and reed valves by setting the viscosity to medium.
Further, it can also be used for coating woven fabrics and paper sheet transport rolls or belts, printing belts, chemical resistant tubes, chemical stoppers, fuel hoses, and the like.

Article base materials to be coated with the crosslinkable composition of the present invention include metals such as iron, stainless steel, copper, aluminum and brass; glass products such as glass plates, woven fabrics and nonwoven fabrics of glass fibers; polypropylene, polyoxy Molded and coated products of general-purpose and heat-resistant resins such as methylene, polyimide, polyamideimide, polysulfone, polyethersulfone, polyetheretherketone; general-purpose rubber such as SBR, butyl rubber, NBR, EPDM, and silicone rubber, fluorine rubber Heat-resistant rubber moldings and coatings such as; natural and synthetic fiber woven and non-woven fabrics; and the like can be used.
The coating formed from the crosslinkable composition of the present invention can be used in fields where heat resistance, solvent resistance, lubricity, and non-adhesiveness are required. Specific applications include copying machines, printers, and facsimiles. Rolls for OA equipment such as fixing rolls, pressure rolls and conveying belts; sheets and belts; O-rings, diaphragms, chemical resistant tubes, fuel hoses, valve seals, chemical plant gaskets, engine gaskets, etc. Can be mentioned.

The crosslinkable composition of the present invention can also be dissolved in a solvent and used as a paint or an adhesive. Moreover, it can be used as a coating material as an emulsified dispersion (latex).
The above composition is a surface treatment agent for structures composed of various materials, sealing materials for pipes, linings, metals, ceramics, glass, stones, concrete, plastics, rubber, wood, paper, fibers, and other inorganic and organic substrates. Used as etc.
The said composition can be apply | coated to a base material etc. by dispenser system coating or screen printing coating.

The crosslinkable composition of the present invention may be used as a coating composition for casting films or dipping substrates such as fabrics, plastics, metals, or elastomers.
In particular, the crosslinkable composition of the present invention is in the form of latex in the form of coated fabrics, protective gloves, impregnated fibers, O-ring coatings, fuel system quick connect O-ring coatings, fuel system seal coatings, fuel tank rollovers. Manufacture valve diaphragm coating, fuel tank pressure sensor diaphragm coating, oil filter and fuel filter seal coating, fuel tank sender seal and sender head fitting seal coating, copier fuser roll coating, and polymer coating composition May be used for
They are useful for coating silicone rubber, nitrile rubber, and other elastomers. For the purpose of increasing both the permeation resistance and chemical resistance of the base elastomer as well as its thermal stability, they are also useful for coating parts made from such elastomers. Other applications include coatings for heat exchangers, expansion joints, bats, tanks, fans, flue ducts and other conduits, and storage structures such as concrete storage structures. The composition may be applied to the exposed cross section of the multilayer part structure, for example in a hose structure and a method of manufacturing a diaphragm. Sealing members at joints and joints often consist of a hard material, and the crosslinkable composition of the present invention has an improved frictional interface, increased dimensions with reduced trace leakage along the sealing surface. Provide an interference fit. The latex enhances seal durability in various automotive system applications.
They can also be used in the manufacture of power steering systems, fuel systems, air conditioning systems, and any joint where hoses and tubes are connected to other parts. A further utility of the composition is in repairing manufacturing defects (and damage due to use) in multilayer rubber structures such as three-layer fuel hoses. The composition is also useful for the application of thin steel sheets that can be formed or embossed before or after the paint is applied. For example, multiple layers of coated steel can be assembled to create a gasket between two rigid metal members. The sealing effect is obtained by applying the crosslinkable composition of the present invention between the layers. This process reduces the bolt force and strain of the assembled parts, while engine head gaskets and exhaust manifold gaskets for the purpose of providing better fuel economy and low emissions due to low cracks, deflection, and hole strain Can be used to manufacture.

The crosslinkable composition of the present invention includes, in addition, a coating agent; a base material-integrated gasket formed by dispenser molding on a base material containing an inorganic material such as a metal or ceramic; It can also be used as a multilayer product formed by coating a material.

Next, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

Each physical property was measured by the following methods.

[Copolymer composition]
Measured by NMR method.
Measuring device: VNMRS400 manufactured by Varian
Resonance frequency: 376.04 (Sfrq)
Pulse wave: 30 ° (pw = 6.8)

[Glass transition temperature (Tg)]
Using a differential scanning calorimeter (manufactured by METTLER TOLEDO, DSC822e), a DSC curve was obtained by heating 10 mg of the sample at 10 ° C./min, an extension of the baseline before and after the secondary transition of the DSC curve, The temperature indicating the intersection with the tangent at the inflection point of the DSC curve was defined as the glass transition temperature.

[Heat of fusion]
Using a differential scanning calorimeter (Mettler Toledo Co., Ltd., DSC822e), a 10 mg sample was heated at 10 ° C./min to obtain a DSC curve, which was melted from the size of the melting peak (ΔH) appearing in the DSC curve. The heat was calculated.

[Number average molecular weight (Mn), weight average molecular weight (Mw)]
Based on the results measured by the GPC method, the molecular weight was calculated based on standard polystyrene.
GPC device: TOSOH HLC-8020
Column: 2 Shodex GPC806M, 1 each of GPC801, 802 Developing solvent: Tetrahydrofuran [THF]
Sample concentration: 0.1% by mass
Measurement temperature: 35 ° C

Example 1
A 100 ml stainless steel (SUS) autoclave was charged with 40 ml of dichloropentafluoropropane (R-225), cooled to dry ice temperature, and di- (2,2,3,3,4,4,5,5,6, (6,7,7-dodecafluoroheptanoyl) Perfluorohexane solution containing 8.20% by weight of 9.20 g perfluorohexane solution was quickly charged, this was cooled to dry ice temperature and purged with nitrogen, then 2,3,3,3-tetra 12.4 g of fluoropropene (hereinafter sometimes abbreviated as 1234yf or simply yf) and 7.1 g of VdF were charged, and the mixture was shaken at 25 ° C. for 5.3 hours using a shaker. The obtained colorless and transparent solution was dried to obtain 2.5 g of a colorless and transparent polymer. The resulting polymer contained 1234yf and VdF in a molar ratio of 77/23. The Tg of the resulting polymer was determined to be 24.6 ° C. by DSC. Also, no melting peak was confirmed. Mn was 7190, weight average molecular weight (Mw) was 10500, and Mw / Mn was 1.5.

Example 2
A 100 ml stainless steel (SUS) autoclave was charged with 40 ml of dichloropentafluoropropane (R-225), cooled to dry ice temperature, and di- (2,2,3,3,4,4,5,5,6, (6,7,7-dodecafluoroheptanoyl) Perfluorohexane solution containing 8.20% by weight of 9.20 g perfluorohexane solution was quickly charged, this was cooled to dry ice temperature and purged with nitrogen, then 2,3,3,3-tetra 5.0 g of fluoropropene (hereinafter sometimes abbreviated as 1234yf or simply yf) and 11.0 g of VdF were charged, and the mixture was shaken at 25 ° C. for 5.2 hours using a shaker. The obtained colorless and transparent solution was dried to obtain 3.5 g of a colorless and transparent polymer. The resulting polymer contained 1234yf and VdF in a molar ratio of 51/49. The Tg of the resulting polymer was determined to be 7.0 ° C. by DSC. Also, no melting peak was confirmed. Mn was 10300, the weight average molecular weight (Mw) was 16000, and Mw / Mn was 1.5.

Example 3
A 100 ml stainless steel (SUS) autoclave was charged with 40 ml of dichloropentafluoropropane (R-225), cooled to dry ice temperature, and di- (2,2,3,3,4,4,5,5,6, (6,7,7-dodecafluoroheptanoyl) Perfluorohexane solution containing 8.20% by weight of 9.20 g perfluorohexane solution was quickly charged, this was cooled to dry ice temperature and purged with nitrogen, then 2,3,3,3-tetra 2.7 g of fluoropropene (hereinafter sometimes abbreviated as 1234yf or simply yf) and 12.6 g of VdF were charged, and the mixture was shaken at 25 ° C. for 5.1 hours using a shaker. The obtained colorless and transparent solution was dried to obtain 3.5 g of a colorless and transparent polymer. The resulting polymer contained 1234yf and VdF in a molar ratio of 38/62. The Tg of the resulting polymer was determined to be −5.2 ° C. by DSC. Also, no melting peak was confirmed. Mn was 9200, Mw was 16000, and Mw / Mn was 1.5.

Example 4
A 100 ml stainless steel (SUS) autoclave was charged with 40 ml of dichloropentafluoropropane (R-225), cooled to dry ice temperature, and di- (2,2,3,3,4,4,5,5,6, (6,7,7-dodecafluoroheptanoyl) Perfluorohexane solution containing 8 wt% of 9.18 g was quickly charged, and this was cooled to dry ice temperature and purged with nitrogen, then 2,3,3,3-tetra 1.3 g of fluoropropene (hereinafter sometimes abbreviated as 1234yf or simply yf) and 13.2 g of VdF were charged, and the mixture was shaken at 25 ° C. for 1.2 hours using a shaker. The resulting colorless and transparent solution was dried to obtain 0.9 g of a colorless and transparent polymer. The resulting polymer contained 1234yf and VdF in a molar ratio of 28/72. The Tg of the resulting polymer was determined to be -16.6 ° C by DSC. Also, no melting peak was confirmed. Mn was 7400, Mw was 12000, and Mw / Mn was 1.7.

Example 5
A 100 ml stainless steel (SUS) autoclave was charged with 40 ml of dichloropentafluoropropane (R-225), cooled to dry ice temperature, and di- (2,2,3,3,4,4,5,5,6, 6,7,7-dodecafluoroheptanoyl) perfluorohexane solution containing 8 wt% of peroxide was quickly charged, and this was cooled to dry ice temperature and purged with nitrogen, then 2,3,3,3-tetra 0.8 g of fluoropropene (hereinafter sometimes abbreviated as 1234yf or simply yf) and 13.4 g of VdF were charged, and the mixture was shaken at 25 ° C. for 2.0 hours using a shaker. The obtained colorless and transparent solution was dried to obtain 1.0 g of a colorless and transparent polymer. The resulting polymer contained 1234yf and VdF in a molar ratio of 29/71. The Tg of the resulting polymer was determined to be -14.8 ° C by DSC. Also, no melting peak was confirmed. Mn was 31000, Mw was 47000, and Mw / Mn was 1.5.

Comparative Example 1
A 100 ml stainless steel (SUS) autoclave was charged with 40 ml of dichloropentafluoropropane (R-225), cooled to dry ice temperature, and di- (2,2,3,3,4,4,5,5,6, (6,7,7-dodecafluoroheptanoyl) Perfluorohexane solution containing 8.20% by weight of 9.20 g perfluorohexane solution was quickly charged, this was cooled to dry ice temperature and purged with nitrogen, then 2,3,3,3-tetra 17.6 g of fluoropropene (hereinafter sometimes abbreviated as 1234yf or simply yf) and 4.0 g of VdF were charged, and the mixture was shaken at 25 ° C. for 5.1 hours using a shaker. The obtained colorless and transparent solution was dried to obtain 2.8 g of a colorless and transparent polymer. The obtained polymer contained 1234yf and VdF in a molar ratio of 87/13. The Tg of the resulting polymer was determined to be 32.4 ° C. by DSC. Also, no melting peak was confirmed. Mn was 7000, Mw was 10200, and Mw / Mn was 1.5.

Comparative Example 2
A 100 ml stainless steel (SUS) autoclave was charged with 40 ml of dichloropentafluoropropane (R-225), cooled to dry ice temperature, and di- (2,2,3,3,4,4,5,5,6, 6,7,7-dodecafluoroheptanoyl) perfluorohexane solution containing 8 wt% of peroxide was quickly charged, and this was cooled to dry ice temperature and purged with nitrogen, then 2,3,3,3-tetra 0.5 g of fluoropropene (hereinafter sometimes abbreviated as 1234yf or simply yf) and 13.6 g of VdF were charged, and the mixture was shaken at 25 ° C. for 1.6 hours using a shaker. The obtained colorless and transparent solution was dried to obtain 2.1 g of a colorless and transparent polymer. The resulting polymer contained 1234yf and VdF in a molar ratio of 4/96. The Tg of the obtained polymer could not be confirmed. Also, no melting peak was confirmed. Mn was 14700, Mw was 25300, and Mw / Mn was 1.7.

Comparative Example 3
A 100 ml stainless steel (SUS) autoclave was charged with 40 ml of dichloropentafluoropropane (R-225), cooled to dry ice temperature, and di- (2,2,3,3,4,4,5,5,6, 6,7,7-dodecafluoroheptanoyl) perfluorohexane solution containing 8 wt% of peroxide was quickly charged, and this was cooled to dry ice temperature and purged with nitrogen, then 2,3,3,3-tetra 0.6 g of fluoropropene (hereinafter sometimes abbreviated as 1234yf or simply yf) and 13.4 g of VdF were charged, and the mixture was shaken at 25 ° C. for 1.0 hour using a shaker. The obtained colorless and transparent solution was dried to obtain 0.3 g of a colorless and transparent polymer. The resulting polymer contained 1234yf and VdF in a molar ratio of 13/87. The Tg of the resulting polymer was determined to be −23.5 ° C. by DSC. A melting peak with a heat of fusion of 15 J / g was observed at around 96 ° C. Mn was 13800, Mw was 26300, and Mw / Mn was 1.9.

Example 6
A 100 ml stainless steel (SUS) autoclave was charged with 40 ml of dichloropentafluoropropane (R-225), cooled to dry ice temperature, and di- (2,2,3,3,4,4,5,5,6, 6,7,7-dodecafluoroheptanoyl) perfluorohexane solution containing 8 wt% of peroxide was quickly charged, and this was cooled to dry ice temperature and purged with nitrogen, then 2,3,3,3-tetra 1.6 g of fluoropropene (hereinafter sometimes abbreviated as 1234yf or simply yf), 3.7 g of TFE and 11.1 g of VdF were charged, and the mixture was shaken at 25 ° C. for 3.0 hours using a shaker. . The obtained colorless and transparent solution was dried to obtain 4.5 g of a colorless and transparent polymer. The resulting polymer contained 1234yf, VdF and TFE in a molar ratio of 23/59/18. The Tg of the resulting polymer was determined to be −11.3 ° C. by DSC. Also, no melting peak was confirmed. Mn was 58000, Mw was 91000, and Mw / Mn was 1.6.

Example 7
A 100 ml stainless steel (SUS) autoclave was charged with 40 ml of dichloropentafluoropropane (R-225), cooled to dry ice temperature, and di- (2,2,3,3,4,4,5,5,6, 6,7,7-dodecafluoroheptanoyl) perfluorohexane solution containing 8 wt% of peroxide was quickly charged, cooled to dry ice temperature and purged with nitrogen, then 2,3,3,3-tetra 1.0 g of fluoropropene (hereinafter sometimes abbreviated as 1234yf or simply yf), 7.9 g of TFE, and 8.0 g of VdF were charged, and the mixture was shaken at 25 ° C. for 2.0 hours using a shaker. . The resulting colorless and transparent solution was dried to obtain 1.6 g of a colorless and transparent polymer. The resulting polymer contained 1234yf, VdF and TFE in a molar ratio of 21/55/24. The Tg of the resulting polymer was determined to be −7.5 ° C. by DSC. A melting peak with a heat of fusion of 1.6 J / g was observed near 50 ° C. Mn was 84000, Mw was 120,000, and Mw / Mn was 1.4.

Example 8
A 100 ml stainless steel (SUS) autoclave was charged with 40 ml of dichloropentafluoropropane (R-225), cooled to dry ice temperature, and di- (2,2,3,3,4,4,5,5,6, 6,7,7-dodecafluoroheptanoyl) perfluorohexane solution containing 8 wt% of peroxide was quickly charged, cooled to dry ice temperature and purged with nitrogen, and then 2,3,3,3-tetra 0.2 g of fluoropropene (hereinafter sometimes abbreviated as 1234yf or simply yf), 1.0 g of TFE and 13.0 g of VdF were charged, and the mixture was shaken at 25 ° C. for 2.0 hours using a shaker. . The obtained colorless and transparent solution was dried to obtain 1.5 g of a colorless and transparent polymer. The resulting polymer contained 1234yf, VdF and TFE in a molar ratio of 27/68/5. The Tg of the resulting polymer was determined to be −12.3 ° C. by DSC. Also, no melting peak was confirmed. Mn was 29000, Mw was 47000, and Mw / Mn was 1.6.

Example 9
A 100 ml stainless steel (SUS) autoclave was charged with 40 ml of dichloropentafluoropropane (R-225), cooled to dry ice temperature, and di- (2,2,3,3,4,4,5,5,6, 6,7,7-dodecafluoroheptanoyl) perfluorohexane solution containing 8 wt% of peroxide was quickly charged, and this was cooled to dry ice temperature and purged with nitrogen, then 2,3,3,3-tetra 1.0 g of fluoropropene (hereinafter sometimes abbreviated as 1234yf or simply yf), 1.8 g of TFE and 12.0 g of VdF were charged, and the mixture was shaken at 25 ° C. for 1.0 hour using a shaker. . The colorless and transparent solution obtained was dried to obtain 0.6 g of a colorless and transparent polymer. The resulting polymer contained 1234yf, VdF and TFE in a molar ratio of 17/70/13. The Tg of the resulting polymer was determined to be −20.5 ° C. by DSC. Also, no melting peak was confirmed. Mn was 30000, Mw was 49000, and Mw / Mn was 1.6.

Example 10
A 100 ml stainless steel (SUS) autoclave was charged with 40 ml of dichloropentafluoropropane (R-225), cooled to dry ice temperature, and di- (2,2,3,3,4,4,5,5,6, 6,7,7-dodecafluoroheptanoyl) perfluorohexane solution containing 8 wt% of peroxide was quickly charged, and this was cooled to dry ice temperature and purged with nitrogen, then 2,3,3,3-tetra 3.4 g of fluoropropene (hereinafter sometimes abbreviated as 1234yf or simply yf), 3.4 g of TFE, and 9.7 g of VdF were charged, and the mixture was shaken at 25 ° C. for 0.5 hours using a shaker. . The obtained colorless and transparent solution was dried to obtain 0.2 g of a colorless and transparent polymer. The resulting polymer contained 1234yf, VdF and TFE in a molar ratio of 39/50/11. The Tg of the resulting polymer was determined to be 2.8 ° C. by DSC. Also, no melting peak was confirmed. Mn was 16,800, Mw was 31000, and Mw / Mn was 1.9.

Comparative Example 4
A 100 ml stainless steel (SUS) autoclave was charged with 40 ml of dichloropentafluoropropane (R-225), cooled to dry ice temperature, and di- (2,2,3,3,4,4,5,5,6, 6,7,7-dodecafluoroheptanoyl) perfluorohexane solution containing 8 wt% of peroxide was quickly charged, and this was cooled to dry ice temperature and purged with nitrogen, then 2,3,3,3-tetra A shaker was charged with 0.3 g of fluoropropene (hereinafter sometimes abbreviated as 1234yf or simply yf), 4.0 g of tetrafluoroethylene (hereinafter abbreviated as TFE) and 11.0 g of VdF. And shaken at 25 ° C. for 1.0 hour. The resulting colorless and transparent solution was dried to obtain 1.1 g of a colorless and transparent polymer. The resulting polymer contained 1234yf, VdF and TFE in a molar ratio of 9/64/27. The Tg of the resulting polymer was determined to be −15.9 ° C. by DSC. A melting peak with a heat of fusion of 7.4 J / g was observed at around 92 ° C. Mn was 26600, Mw was 57200, and Mw / Mn was 2.2.

Comparative Example 5
A 100 ml stainless steel (SUS) autoclave was charged with 40 ml of dichloropentafluoropropane (R-225), cooled to dry ice temperature, and di- (2,2,3,3,4,4,5,5,6, (6,7,7-dodecafluoroheptanoyl) Perfluorohexane solution containing 8 wt% of peroxide was quickly charged, and this was cooled to dry ice temperature and purged with nitrogen, then hexafluoropropene (hereinafter abbreviated as HFP). 23.0 g and VdF 4.0 g were charged, and shaken at 25 ° C. for 8.7 hours using a shaker. The resulting colorless and transparent solution was dried to obtain 1.6 g of a colorless and transparent polymer. The resulting polymer contained HFP and VdF in a molar ratio of 69/31. The Tg of the resulting polymer was determined to be −3.8 ° C. by DSC. Also, no melting peak was confirmed. Mn was 10900, Mw was 17000, and Mw / Mn was 1.6.

Comparative Example 6
A 100 ml stainless steel (SUS) autoclave was charged with 40 ml of dichloropentafluoropropane (R-225), cooled to dry ice temperature, and di- (2,2,3,3,4,4,5,5,6, (6,7,7-dodecafluoroheptanoyl) Perfluorohexane solution containing 8 wt% of peroxide was quickly charged with 1.55 g, cooled to dry ice temperature and purged with nitrogen, then hexafluoropropene (hereinafter abbreviated as HFP). 27.3 g and VdF 2.0 g, and shaken at 25 ° C. for 6.5 hours using a shaker. The resulting colorless and transparent solution was dried to obtain 1.1 g of a colorless and transparent polymer. The resulting polymer contained HFP and VdF in a molar ratio of 68/32. The Tg of the resulting polymer was determined to be −3.0 ° C. by DSC. Also, no melting peak was confirmed. Mn was 7700, Mw was 12000, and Mw / Mn was 1.6.

Comparative Example 7
A 100 ml stainless steel (SUS) autoclave was charged with 40 ml of dichloropentafluoropropane (R-225), cooled to dry ice temperature, and di- (2,2,3,3,4,4,5,5,6, (6,7,7-dodecafluoroheptanoyl) Perfluorohexane solution containing 8 wt% of peroxide was quickly charged with 1.54 g, cooled to dry ice temperature, and purged with nitrogen, then 30.1 g of HFP and 1 VdF. .4 g was charged and shaken at 25 ° C. for 7.4 hours using a shaker. The resulting colorless and transparent solution was dried to obtain 1.6 g of a colorless and transparent polymer. The resulting polymer contained HFP and VdF in a molar ratio of 68/32. The Tg of the resulting polymer was determined to be -1.7 ° C by DSC. Also, no melting peak was confirmed. Mn was 9900, Mw was 1500, and Mw / Mn was 1.5.

Comparative Example 8
A 100 ml stainless steel (SUS) autoclave was charged with 40 ml of dichloropentafluoropropane (R-225), cooled to dry ice temperature, and di- (2,2,3,3,4,4,5,5,6, (6,7,7-dodecafluoroheptanoyl) Perfluorohexane solution 1.49 g containing 8 wt% of peroxide was quickly charged, and this was cooled to dry ice temperature and purged with nitrogen, then 18.5 g of HFP and 6 VdF. .2 g was charged and shaken at 25 ° C. for 2.1 hours using a shaker. The obtained colorless and transparent solution was dried to obtain 1.2 g of a colorless and transparent polymer. The resulting polymer contained HFP and VdF in a molar ratio of 76/24. The Tg of the resulting polymer was determined to be -13.6 ° C by DSC. Also, no melting peak was confirmed. Mn was 12000, Mw was 21000, and Mw / Mn was 1.7.

As shown in FIG. 1, the VdF / 2,3,3,3-tetrafluoropropene copolymer obtained in Examples 2 to 5 is more than the VdF / HFP copolymer obtained in Comparative Examples 5 to 8. It was also found that the glass transition temperature was low.

Reference example 1
In a 500 ml stainless steel autoclave, add 250 ml of pure water and 1.55 g of ammonium perfluorooctanoate, purge with nitrogen, slightly pressurize with 1234yf, adjust the temperature to 80 ° C while stirring at 600 rpm, and further add 1234yf with pressure Press-fitting to 0.29 MPa and further press-fitting VdF to 0.72 MPa. A solution prepared by dissolving 0.1 g of ammonium persulfate in 4 ml of pure water was press-fitted with nitrogen. When the pressure dropped by 0.04 MPa after the reaction for 6.5 hours, the gas in the autoclave was released and cooled to recover the dispersion. The solid content of the dispersion was 2.1 wt%. Nitric acid was added to the dispersion and coagulated to obtain about 2 g of copolymer. According to NMR, the molar ratio was 1234yf / VdF = 50/50. The glass transition temperature of this copolymer was 0.1 ° C.

Example 11
In a 3 L stainless steel autoclave, put 1500 ml of pure water, 15.03 g of ammonium perfluorooctanoate, 1.4297 g of 1,4-diiodoperfluorobutane, purge with nitrogen, make slight pressurization with 1234yf, and stir at 600 rpm The temperature was adjusted to 80 ° C., and 1234yf was further press-fitted to 1.21 MPa, and a mixed liquid monomer having a molar ratio of VdF to 1234yf of 69/31 was press-fitted to 1.47 MPa. A solution obtained by dissolving 0.0243 g of ammonium persulfate in 4 ml of pure water was press-fitted with nitrogen. When the pressure dropped to 1.42 MPa, the pressure was increased to 1.47 MPa with a continuous monomer. This was repeated, and after 222 g of continuous monomer was charged for 6.68 hours, the gas in the autoclave was released and cooled to recover 1730.6 g of dispersion. On the way, ammonium persulfate was appropriately added. The solid content of the dispersion was 13.3 wt% (polymer amount 230.3 g). The dispersion was coagulated with nitric acid and dried to obtain 224.41 g of polymer. The resulting polymer contained 1234yf and VdF in a molar ratio of 31/69. The Tg of the resulting polymer was determined to be -16.6 ° C by DSC. Moreover, the heat of fusion was not recognized in the second run. The number average molecular weight (Mn) was 69837, the weight average molecular weight (Mw) was 169549, Mw / Mn was 2.4, and the fluorine content was 62.6% by weight. The iodine content was 0.23% by weight. The iodine content was measured by mixing 5 mg of Na ₂ SO ₃ with 12 mg of the sample (the obtained polymer), and mixing Na ₂ CO ₃ and K ₂ CO ₃ in a 1: 1 ratio (weight ratio) with 20 ml of pure water. Can be measured using an Shimadzu 20A ion chromatograph after being burned in oxygen in a quartz flask and allowed to stand for 30 minutes. The calibration curve was measured using a KI standard solution, one containing 0.5 ppm iodine ion and one containing 1.0 ppm.

Using the polymer (yf polymer) obtained in Example 11, a crosslinkable composition 1 having the composition shown in Table 1 below was produced. Moreover, comparative crosslinkable compositions 1 to 3 were produced with the compositions shown in Table 1 below.

As the crosslinkable composition, an 8-inch open roll was used, and each raw rubber and additives were mixed in a necessary amount in a usual manner.

The compounds in Table 1 are as follows.
VdF / HFP copolymer (VdF / HFP = 78/22 mol%)
VdF / HFP / TFE copolymer (VdF / HFP / TFE = 50/30/20 mol%)
TFE / Pr copolymer (TFE / Pr = 55/45 mol%)
MT Carbon (trade name: Thermax N990, manufactured by Can Carb)
Taic (trade name: TAIC, manufactured by Nippon Kasei Co., Ltd.)
Perhexa 25B (manufactured by NOF Corporation)
Perbutyl P (manufactured by NOF Corporation)

Table 2 shows the VdF content, fluorine content, iodine content, and glass transition temperature of the polymer, VdF / HFP copolymer, VdF / HFP / TFE copolymer, and TFE / Pr copolymer of Example 11 above. (Tg), Mooney viscosity (ML1 + 10 (100 ° C.)). The Mooney viscosity was measured under the following conditions.
<Mooney viscosity>
Measured according to ASTM-D1646 and JIS K6300.
Measuring instrument: MV2000E rotor manufactured by ALPHA TECHNOLOGIES Inc .: 2 rpm
Measurement temperature: 100 ° C

Crosslinking (vulcanization) characteristics were examined using the crosslinkable composition produced by the above method. The cross-linking characteristics were measured according to JIS K6300-2, using the curast meter type II (manufactured by JSR Corporation) with the minimum torque (ML), maximum torque (MH), induction time (t10) and optimum vulcanization time (t90). Was measured. The results are shown in Table 3 below.

Next, an amine resistance test is performed on the molded product in which each crosslinkable composition is cross-linked, and 100% modulus (M100), tensile break strength (Tb), tensile break elongation (Eb) after the test, Hardness (Hs [Shore A, peak]) was measured. Moreover, (DELTA) V (volume swelling rate) was calculated | required. Table 4 shows the initial characteristics before the amine resistance test. Each measurement condition is as follows.
ΔV is the rate of change of volume after the sample piece is immersed under a predetermined condition (representing the degree of swelling). When the original volume of the sample piece is Vo and the volume after the test is V, ΔV = It is represented by (V−Vo) / Vo × 100. The volume is calculated from the weight in air and the weight in water.

100% Modulus (M100)
It measured according to JIS K6251.

Tensile strength at break (Tb)
It measured according to JIS K6251.

Tensile elongation at break (Eb)
It measured according to JIS K6251.

Hardness (Hs [Shore A, peak])
It was measured with a durometer type A according to JIS K6253 (peak value and after 1 s).

Specific density was determined by measuring the density according to JIS K6268.

Amine resistance test A molded product obtained by crosslinking each crosslinkable composition was subjected to an immersion test at 175 ° C for 185 hours using Toyota Standard Oil (manufactured by Toyota Corporation, SJ OIL Toyota genuine oil SJ 10W-30). Went.
100% modulus, Tb, Eb, Hs (Shore A, peak) and volume swelling ratio (ΔV) after the immersion test are measured on the molded product obtained by crosslinking each crosslinkable composition, and the value before the measurement is measured. The change rate is shown in Table 5.

Example 12
In a 3 L stainless steel autoclave, 1500 ml of pure water, 1.2001 g of CH ₂ = CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COONH ₄ 50% aqueous solution, and C ₅ F ₁₁ COONH ₄ 50% aqueous solution 6000 g The atmosphere was replaced with nitrogen, slightly pressurized with VdF, adjusted to 80 ° C. with stirring at 600 rpm, VdF was press-fitted to 1.20 MPa, and the molar ratio of VdF to 1234yf was 78.2 / 21.8. The mixed solution monomer was pressed into 1.46 MPa. A solution obtained by dissolving 0.078 g of ammonium persulfate in 2 ml of pure water was press-fitted with nitrogen. On the way, ammonium persulfate was added appropriately. When the pressure dropped to 1.42 MPa, the pressure was increased to 1.47 MPa with a continuous monomer. This was repeated, and after about 20 minutes, when 12.7 g of a continuous monomer was charged, 2.067 g of 1,4-diiodoperfluorobutane and 2 g of pushing water were injected with nitrogen. Further, after about 9.6 hours, when 532 g of continuous monomer was charged, the gas in the autoclave was released and cooled to recover 2051 g of the dispersion. The solid content of the dispersion was 26.75 wt% (polymer amount 548.6 g). Aluminum sulfate was added to this dispersion for coagulation and drying to obtain 538.5 g of polymer. The resulting polymer contained 1234yf and VdF in a molar ratio of 21.4 / 78.6. The Tg of the resulting polymer was determined to be -13.2 ° C by DSC. Moreover, the heat of fusion was not recognized in the second run. The number average molecular weight (Mn) was 118344, the weight average molecular weight (Mw) was 215556, and Mw / Mn was 1.821. The iodine content was 0.17% by weight. The iodine content was measured by mixing 5 mg of Na ₂ SO ₃ with 12 mg of the sample (the obtained polymer), and mixing Na ₂ CO ₃ and K ₂ CO ₃ in a 1: 1 ratio (weight ratio) with 20 ml of pure water. Can be measured using an Shimadzu 20A ion chromatograph after being burned in oxygen in a quartz flask and allowed to stand for 30 minutes. The calibration curve was measured using a KI standard solution, one containing 0.5 ppm iodine ion and one containing 1.0 ppm.

Using the polymer (yf polymer) obtained in Example 12, a crosslinkable composition 2 having the composition shown in Table 6 below was produced.

As the crosslinkable composition, an 8-inch open roll was used, and each raw rubber and additives were mixed in a necessary amount in a usual manner.

The compounds in Table 6 are as follows.
MT Carbon (trade name: Thermax N990, manufactured by Can Carb)
Taic (trade name: TAIC, manufactured by Nippon Kasei Co., Ltd.)
Perhexa 25B (manufactured by NOF Corporation)

Table 7 shows the VdF content, iodine content, glass transition temperature (Tg), and Mooney viscosity (ML1 + 10 (100 ° C.)) of the polymer of Example 12. The Mooney viscosity was measured under the following conditions.
<Mooney viscosity>
Measured according to ASTM-D1646 and JIS K6300.
Measuring instrument: MV2000E rotor manufactured by ALPHA TECHNOLOGIES Inc .: 2 rpm
Measurement temperature: 100 ° C

Crosslinking (vulcanization) characteristics were examined using the crosslinkable composition produced by the above method. The cross-linking characteristics were measured according to JIS K6300-2, using the curast meter type II (manufactured by JSR Corporation) with the minimum torque (ML), maximum torque (MH), induction time (t10) and optimum vulcanization time (t90). Was measured. The results are shown in Table 8 below.

Example 13
In a 3 L stainless steel autoclave, 1500 ml of pure water, 1.2045 g of 50% aqueous solution of CH ₂ = CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COONH ₄ and 6.0044 g of C ₅ F ₁₁ COONH ₄ 50% aqueous solution Then, the atmosphere was replaced with nitrogen, slightly pressurized with VdF, adjusted to 80 ° C. while stirring at 600 rpm, and VdF was pressed into 1.21 MPa. Further, the molar ratio of VdF to 1234yf was 79.6 / 20.4. The mixed solution monomer was press-fitted to 1.47 MPa. A solution obtained by dissolving 0.0566 g of ammonium persulfate in 2 ml of pure water was press-fitted with nitrogen. When the pressure dropped to 1.42 MPa, the pressure was increased to 1.47 MPa with a continuous monomer. This was repeated, and after about 20 minutes, when 14 g of the continuous monomer was charged, 2.0616 g of 1,4-diiodoperfluorobutane and 2 g of pushing water were injected with nitrogen. Furthermore, after about 7.4 hours, when 533 g of continuous monomer was charged, the gas in the autoclave was released and cooled to recover 2065 g of the dispersion. On the way, ammonium persulfate was added appropriately. The solid content of the dispersion was 26.48 wt% (polymer amount 546.8 g). Aluminum sulfate was added to this dispersion to coagulate and dried to obtain 536.4 g of polymer. The resulting polymer contained 1234yf and VdF in a molar ratio of 20.2 / 79.8. The Tg of the resulting polymer was determined to be -14.5 ° C by DSC. Moreover, the heat of fusion was not recognized in the second run. The number average molecular weight (Mn) was 112839, the weight average molecular weight (Mw) was 243273, and Mw / Mn was 2.156. The iodine content was 0.14% by weight. The iodine content was measured by mixing 5 mg of Na ₂ SO ₃ with 12 mg of the sample (the obtained polymer), and mixing Na ₂ CO ₃ and K ₂ CO ₃ in a 1: 1 ratio (weight ratio) with 20 ml of pure water. Can be measured using an Shimadzu 20A ion chromatograph after being burned in oxygen in a quartz flask and allowed to stand for 30 minutes. The calibration curve was measured using a KI standard solution, one containing 0.5 ppm iodine ion and one containing 1.0 ppm.

Using the polymer (yf polymer) obtained in Example 13, a crosslinkable composition 3 having the composition shown in Table 9 below was produced.

As the crosslinkable composition, an 8-inch open roll was used, and each raw rubber and additives were mixed in a necessary amount in a usual manner.

The compounds in Table 9 are as follows.
MT Carbon (trade name: Thermax N990, manufactured by Can Carb)
Taic (trade name: TAIC, manufactured by Nippon Kasei Co., Ltd.)
Perhexa 25B (manufactured by NOF Corporation)

Table 10 shows the VdF content, iodine content, glass transition temperature (Tg), and Mooney viscosity (ML1 + 10 (100 ° C.)) of the polymer of Example 13. The Mooney viscosity was measured under the following conditions.
<Mooney viscosity>
Measured according to ASTM-D1646 and JIS K6300.
Measuring instrument: MV2000E rotor manufactured by ALPHA TECHNOLOGIES Inc .: 2 rpm
Measurement temperature: 100 ° C

Using the crosslinkable composition produced by the above method, the physical properties of the crosslinkable composition were examined. The crosslinking (vulcanization) method is shown in Table 11 below.

Amine resistance test Each molded product obtained by crosslinking each crosslinkable composition was subjected to a 1 hour immersion test at room temperature using 100% dicyclohexylamine and 100% trimethylamine, and then each crosslinkable composition was crosslinked. The volume swelling rate (ΔV) was measured for the molded article.
ΔV is the rate of change of volume after the sample piece is immersed under a predetermined condition (representing the degree of swelling). When the original volume of the sample piece is Vo and the volume after the test is V, ΔV = It is represented by (V−Vo) / Vo × 100. The volume is calculated from the weight in air and the weight in water.
As a result, ΔV = 12% for the crosslinkable composition 3 immersed in 100% dicyclohexylamine, ΔV = 31% for the comparative crosslinkable composition 2, and ΔV = 26% for the comparative crosslinkable composition 3. The crosslinkable composition 3 immersed in 100% trimethylamine had ΔV = 1%, and the comparative crosslinkable composition 2 had ΔV = 24%.

The molded product obtained by crosslinking the crosslinkable composition 3 is subjected to an amine resistance test. After the test, 100% modulus (M100), tensile breaking strength (Tb), tensile breaking elongation (Eb), hardness (Hs [ Shore A, peak]). The specific gravity was determined in the same manner as described above. Moreover, (DELTA) V (volume swelling rate) was calculated | required. Table 12 shows the initial characteristics before the amine resistance test. Each measurement condition is as follows.
ΔV is the rate of change of volume after the sample piece is immersed under a predetermined condition (representing the degree of swelling). When the original volume of the sample piece is Vo and the volume after the test is V, ΔV = It is represented by (V−Vo) / Vo × 100. The volume is calculated from the weight in air and the weight in water.

100% Modulus (M100)
It measured according to JIS K6251.

Tensile strength at break (Tb)
It measured according to JIS K6251.

Tensile elongation at break (Eb)
It measured according to JIS K6251.

Hardness (Hs [Shore A, peak])
It was measured with a durometer type A according to JIS K6253 (peak value and after 1 s).

Specific density was determined by measuring the density according to JIS K6268.

For a molded article obtained by crosslinking the amine resistance test crosslinking composition 3, Ford 75W-140 Gear Oil (WSP-M2C192-A) (6% additive Friction Modifier (EST-M2C118-A)) An immersion test was conducted at 150 ° C. for 1000 hours.
100% modulus, Tb, Eb, Hs (Shore A, peak) and volume swell ratio (ΔV) after the immersion test are measured for the molded product obtained by crosslinking the crosslinkable composition 3, and the value before the measurement is measured. The change rate is shown in Table 13.

Amine resistance test The molded article obtained by crosslinking the crosslinkable composition 3 was subjected to a dipping test at 150 ° C for 500 hours using Dexron LS 75W-90 Gear Oil.
100% modulus, Tb, Eb, Hs (Shore A, peak) and volume swell ratio (ΔV) after the immersion test are measured for the molded product obtained by crosslinking the crosslinkable composition 3, and the value before the measurement is measured. The change rate is shown in Table 14.

Amine resistance test A molded article obtained by crosslinking the crosslinkable composition 3 was subjected to an immersion test at 150 ° C. for 1500 hours using Generation 3 LubeOil.
100% modulus, Tb, Eb, Hs (Shore A, peak) and volume swell ratio (ΔV) after the immersion test are measured for the molded product obtained by crosslinking the crosslinkable composition 3, and the value before the measurement is measured. The change rate is shown in Table 15.

Example 14
In a 138 L stainless steel autoclave, pure water 69 L, CH ₂ = CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COONH ₄ 50% aqueous solution 55.2 g, C ₅ F ₁₁ COONH ₄ 50% aqueous solution 276 g, After substituting with nitrogen, the internal pressure was evacuated, slightly pressurized with VdF, the temperature inside the autoclave was adjusted to 80 ° C. while stirring at 150 rpm, VdF was press-fitted to 1.34 MPa, and the molar ratio of VdF to 1234yf was , 76.2 / 23.8 mixed solution monomer was injected to 1.62 MPa. A solution obtained by dissolving 2.76 g of ammonium persulfate in 50 ml of pure water was press-fitted with nitrogen. As the polymerization progressed and the pressure decreased, a continuous monomer was charged so as to maintain a pressure of 1.57 MPa. When 610 g of this continuous monomer was charged, 116.24 g of 1,4-diiodoperfluorobutane and 50 g of pushing water were injected with nitrogen. The charging of the continuous monomer was repeated, and after 8.43 hours, 24.43 kg of the continuous monomer was charged, the gas in the autoclave was discharged, and the emulsion was cooled to recover 94.87 kg of the emulsified dispersion. On the way, a solution prepared by dissolving 1.38 g of ammonium persulfate in 50 ml of pure water every 3 hours from the start of polymerization was added by press-fitting with nitrogen. The solid content of the dispersion was 26.1 wt% (polymer amount 25.0 kg). The resulting polymer contained 1234yf and VdF in a molar ratio of 23.1 / 76.9. The Tg of the obtained polymer was determined to be -13.0 ° C by DSC. In addition, the heat of fusion was not observed in either the first run or the second run.

Using the polymer obtained in Example 14, a crosslinkable composition 4 having the composition shown in Table 16 below was produced.

As the crosslinkable composition, an 8-inch open roll was used, and each raw rubber and additives were mixed in a necessary amount in a usual manner.

The compounds in Table 16 are as follows.
MT Carbon (trade name: Thermax N990, manufactured by Can Carb)
Taic (trade name: TAIC, manufactured by Nippon Kasei Co., Ltd.)
Perhexa 25B (manufactured by NOF Corporation)

The Mooney viscosity (ML1 + 10 (100 ° C.)) of the polymer of Example 14 was 45.1. (ML1 + 10 (121 ° C.)) was 23.3.
<Mooney viscosity>
Measured according to ASTM-D1646 and JIS K6300.
Measuring equipment: MV2000E type manufactured by ALPHA TECHNOLOGIES
Rotor speed: 2rpm
Measurement temperature: 100 ° C, 121 ° C

Using the crosslinkable composition produced by the above method, the physical properties of the crosslinkable composition were examined. The crosslinking method is shown in Table 17 below, and various physical properties are shown in Table 18 below. Regarding the compression set test, the compression set after elapse of 200 ° C. × 70 hours was measured in accordance with JIS K6262 for a fluororubber molded product molded into a P-24 O-ring.

Example 15
In a 138 L stainless steel autoclave, pure water 69 L, CH ₂ = CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COONH ₄ 50% aqueous solution 55.2 g, C ₅ F ₁₁ COONH ₄ 50% aqueous solution 276 g, After substituting with nitrogen, the internal pressure was evacuated, slightly pressurized with VdF, the temperature inside the autoclave was adjusted to 80 ° C. while stirring at 150 rpm, VdF was press-fitted to 1.34 MPa, and the molar ratio of VdF to 1234yf was , 76.2 / 23.8 mixed solution monomer was injected to 1.62 MPa. A solution obtained by dissolving 2.76 g of ammonium persulfate in 50 ml of pure water was press-fitted with nitrogen. As the polymerization progressed and the pressure decreased, a continuous monomer was charged so as to maintain a pressure of 1.57 MPa. When 610 g of this continuous monomer was charged, 78.67 g of 1,4-diiodoperfluorobutane and 50 g of pushing water were injected with nitrogen. The continuous monomer charge was repeated, and after 7.42 hours, 24.43 kg of the continuous monomer was charged, the gas in the autoclave was released and cooled to recover 94.37 kg of the emulsified dispersion. In the middle of the polymerization, a solution obtained by dissolving 1.38 g of ammonium persulfate in 50 ml of pure water every 3 hours was injected with nitrogen and added. The solid content of the dispersion was 26.6 wt% (polymer amount 24.9 kg). The resulting polymer contained 1234yf and VdF in a molar ratio of 23.1 / 76.9. The Tg of the obtained polymer was determined to be -13.0 ° C by DSC. In addition, the heat of fusion was not observed in either the first run or the second run.

Using the polymer obtained in Example 15, a crosslinkable composition 5 having the composition shown in Table 19 below was produced.

As the crosslinkable composition, an 8-inch open roll was used, and each raw rubber and additives were mixed in a necessary amount in a usual manner.

The compounds in Table 19 are as follows.
MT Carbon (trade name: Thermax N990, manufactured by Can Carb)
Taic (trade name: TAIC, manufactured by Nippon Kasei Co., Ltd.)
Perhexa 25B (manufactured by NOF Corporation)

The Mooney viscosity (ML1 + 10 (100 ° C.)) of the polymer of Example 15 was 85.2. (ML1 + 10 (121 ° C.)) was 52.7.
<Mooney viscosity>
Measured according to ASTM-D1646 and JIS K6300.
Measuring equipment: MV2000E type manufactured by ALPHA TECHNOLOGIES
Rotor speed: 2rpm
Measurement temperature: 100 ° C, 121 ° C

Using the crosslinkable composition produced by the above method, the physical properties of the crosslinkable composition were examined. The crosslinking method is shown in Table 20 below, and various physical properties are shown in Table 21 below. Regarding the compression set test, the compression set after elapse of 200 ° C. × 70 hours was measured in accordance with JIS K6262 for a fluororubber molded product molded into a P-24 O-ring.

Example 16
3L stainless steel autoclave of pure water _{1500ml, CH 2 = CFCF 2 OCF} (CF 3) CF 2 OCF (CF 3) COONH 4 50% aqueous 1.20 _g, the C ₅ F 11 COONH ₄ 50% aqueous solution of 6.00g After substituting with nitrogen, the internal pressure was evacuated, the temperature inside the autoclave was adjusted to 80 ° C. with stirring at 600 rpm, and a mixed liquid monomer having a molar ratio of VdF to 1234yf of 76.2 / 23.8 was 6. Press-fitted to 10 MPa. A solution obtained by dissolving 0.02 g of ammonium persulfate in 2 ml of pure water was press-fitted with nitrogen. As the polymerization proceeds and the pressure decreases, a monomer mixed with a molar ratio of VdF and 1234yf of 76.2 / 23.8 is continuously charged by a pump so as to maintain a pressure of 6.10 MPa. It was. When 14 g of this continuous monomer was charged, 2.06 g of 1,4-diiodoperfluorobutane and 2 g of pushing water were injected with nitrogen. Further, after about 1.4 hours, when 406 g of the continuous monomer was charged, the gas in the autoclave was released and cooled to recover 2012 g of the emulsified dispersion. The solid content of the dispersion was 26.1 wt% (polymer amount 525 g). Under stirring, an aqueous aluminum sulfate solution was added to the dispersion to cause coagulation, followed by drying to obtain 505 g of a polymer. The resulting polymer contained 1234yf and VdF in a molar ratio of 23.0 / 77.0.

Using the polymer obtained in Example 16, a crosslinkable composition 6 having the composition shown in Table 22 below was produced.

As the crosslinkable composition, an 8-inch open roll was used, and each raw rubber and additives were mixed in a necessary amount in a usual manner.

The compounds in Table 22 are as follows.
MT Carbon (trade name: Thermax N990, manufactured by Can Carb)
Taic (trade name: TAIC, manufactured by Nippon Kasei Co., Ltd.)
Perhexa 25B (manufactured by NOF Corporation)

The Mooney viscosity (ML1 + 10 (100 ° C.)) of the polymer of Example 16 was 80.2. (ML1 + 10 (121 ° C.)) was 48.3.
<Mooney viscosity>
Measured according to ASTM-D1646 and JIS K6300.
Measuring equipment: MV2000E type manufactured by ALPHA TECHNOLOGIES
Rotor speed: 2rpm
Measurement temperature: 100 ° C, 121 ° C

The crosslinkable composition produced by the above method was subjected to crosslink molding by heat compression molding, and the obtained molded article was subjected to oven crosslinking in an electric furnace to produce a molded article of P-24 standard O-ring. The crosslinking conditions were 160 ° C. × 10 minutes for heat compression molding and 180 ° C. × 4 hours for oven crosslinking.

Compression set test P-24 The compression set after elapse of 200 ° C. × 70 hours was measured in accordance with JIS K6262 for a fluororubber molded product molded into an O-ring.
The compression set value of the molded product obtained in Example 15 was 31%, and the compression set value of the molded product obtained in Example 16 was 24%. The compression set was improved by polymerization under high pressure.

The crosslinkable composition of the present invention containing a fluorine-containing elastomer and a crosslinking agent, and crosslinked rubber molded products obtained by crosslinking the composition are various in various industrial fields such as the automobile industry, aircraft industry, and semiconductor industry. It can be suitably used as a component.

Claims (4)

Vinylidene fluoride and the following general formula (1):
CH ₂ = CFR _f (1)
(In the formula, R _f is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms.)
Is a copolymer consisting only of a fluorine-containing monomer represented by
The molar ratio of vinylidene fluoride unit / fluorinated monomer unit is 87/13 to 22/78,
A crosslinkable composition comprising an amorphous fluorine-containing elastomer having a glass transition temperature of 25 ° C. or lower and a crosslinking agent. Vinylidene fluoride, the following general formula (1):
CH ₂ = CFR _f (1)
(In the formula, R _f is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms.)
And a copolymer consisting only of vinylidene fluoride and other monomers copolymerizable with the fluorine-containing monomer,
The molar ratio of vinylidene fluoride unit / fluorinated monomer unit is 85/15 to 20/80,
The other monomer units are 1 to 50 mol% of the total monomer units,
A crosslinkable composition comprising an amorphous fluorine-containing elastomer having a glass transition temperature of 25 ° C. or lower and a crosslinking agent. Vinylidene fluoride, the following general formula (1):
CH ₂ = CFR _f (1)
(In the formula, R _f is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms.)
And a copolymer consisting of vinylidene fluoride and other monomers copolymerizable with the fluorine-containing monomer,
The molar ratio of vinylidene fluoride unit / fluorinated monomer unit is 85/15 to 20/80,
The other monomer units are 0 to 50 mol% of the total monomer units,
The glass transition temperature is 25 ° C. or lower,
A crosslinkable composition comprising an amorphous fluorine-containing elastomer having at least one of an iodine atom and a bromine atom and a total content of 0.001 to 10% by weight and a crosslinking agent object. A crosslinked rubber molded product obtained by crosslinking the crosslinkable composition according to claim 1, 2 or 3.

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