JP2019094430A - Fluororubber molded body and composition - Google Patents

Abstract

To provide a fluororubber molded body having low hardness and excellent amine resistance and to provide a composition.SOLUTION: A fluororubber molded body is produced by crosslinking a composition containing a fluorine-containing copolymer. The fluororubber molded body has a hardness of IRHD in accordance with JIS K6253-2:2012 of 50 or less and has a volume change rate of 20% or less in an immersion test in diethanolamine at 120°C for 72 hours.SELECTED DRAWING: None

Description

The present invention relates to a fluororubber molded article and a composition.

Fluorine-containing polymers are characterized by their excellent heat resistance, chemical resistance, oil resistance, etc., and in areas where severe use conditions such as high temperature and exposure to various chemicals are required, such as automotive industry, aircraft industry, semiconductor industry etc. Used as a material for various parts in the field of

For example, Patent Documents 1 to 6 provide a fluorine-containing rubber material having excellent performance even to a heat-resistant engine oil containing an amine-based additive and the like and further having low temperature characteristics. By copolymerizing a monomer containing iodine or bromine, vinylidene fluoride and hexafluoropropylene to a fluorine-containing rubber obtained by copolymerizing vinylidene fluoride, tetrafluoroethylene and propylene for the purpose The fluorine-containing rubber composition which mix | blended fluorine-containing rubber etc. which are obtained is proposed.

Japanese Patent Application Laid-Open No. 6-306243 Japanese Patent Application Laid-Open No. 6-306244 Japanese Patent Application Laid-Open No. 6-306245 JP-A-6-322214 JP, 2013-216915, A JP-A-6-116464

An object of the present invention is to provide a fluororubber molded article and a composition which have low hardness and excellent amine resistance.

The present invention is a fluororubber molded article obtained by crosslinking a composition containing a fluorocopolymer,
The fluororubber molded article is characterized in that the hardness of IRHD in JIS K6253-2: 2012 is 50 or less, and the volume change rate in an immersion test in diethanolamine at 120 ° C. for 72 hours is 20% or less. It is a fluorine rubber molded body.

In the fluororubber molded article, the composition preferably further contains a crosslinking agent.

The fluorine-containing rubber molded product is a fluorine-containing copolymer which can be vulcanized with peroxide.
The composition preferably contains 0.1 to 3.0 parts by mass of the polyfunctional co-crosslinking agent and 0.3 to 3.0 parts by mass of the organic peroxide based on 100 parts by mass of the fluorine-containing copolymer. .

In the fluororubber molded article, the composition preferably contains 0.1 to 10 parts by mass of perfluoropolyether based on 100 parts by mass of the fluorocopolymer.

In the fluororubber molded article, the composition preferably contains 0.1 to 10 parts by mass of silicone oil with respect to 100 parts by mass of the fluorocopolymer.

In the fluorine rubber molded article, the fluorine-containing copolymer has a glass transition temperature of 25 ° C. or less
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)
It is preferable that it is a copolymer which consists of a fluorine-containing monomer (1) represented by these.

In the fluorine rubber molded article, the fluorine-containing polymer 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)
And a copolymer comprising the fluorine-containing monomer (1) represented by and other monomers copolymerizable therewith, wherein the molar ratio of vinylidene fluoride unit / fluorine-containing monomer (1) unit is It is preferable that it is 85/15-20/80, and another monomer unit is 0-50 mol% of all the monomer units.

The present invention provides a fluororubber molded article having an IRHD hardness of 50 or less according to JIS K6253-2: 2012 after crosslinking, and a volume change of 20% or less in a dipamine test in diethanolamine at 120 ° C for 72 hours. A composition that can be obtained,
The composition has a glass transition temperature of 25 ° C. or less
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)
It is a composition containing the fluorine-containing copolymer which consists of a fluorine-containing monomer (1) represented by these.

The composition may contain 0.1 to 6.0 parts by mass of the polyfunctional co-crosslinking agent and 0.3 to 5.0 parts by mass of the organic peroxide with respect to 100 parts by mass of the fluorine-containing copolymer. preferable.

The present invention is a composition containing a fluorine-containing copolymer, a crosslinking agent and a perfluoropolyether,
The fluorine-containing copolymer has a glass transition temperature of 25 ° C. or less
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 comprising the fluorine-containing monomer (1) represented by
It is a composition containing 0.1 to 10 parts by mass of the perfluoropolyether relative to 100 parts by mass of the fluorine-containing copolymer.

The present invention is also a composition comprising a fluorine-containing copolymer, a crosslinking agent and a silicone oil,
The fluorine-containing copolymer has a glass transition temperature of 25 ° C. or less
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 comprising the fluorine-containing monomer (1) represented by
It is a composition containing 0.1 to 10 parts by mass of the silicone oil with respect to 100 parts by mass of the fluorine-containing copolymer.

According to the present invention, it is possible to provide a fluorine rubber molded article and a composition which have low hardness and excellent amine resistance.

[Fluorinated rubber molded product (after crosslinking)]
The present invention is a fluororubber molded article (after crosslinking) obtained by crosslinking a composition containing a fluorocopolymer, and the fluororubber molded article (after crosslinking) is IRHD of JIS K6253-2: 2012. The fluororubber molded article is characterized by having a hardness of 50 or less, and a volume change rate in an immersion test in diethanolamine at 120.degree. C. for 72 hours being 20% or less.

Although fluororubbers having an amine property are used in various applications, fluororubbers usually have high hardness, and it is generally difficult to provide a molded article of low hardness. Low hardness molded articles are very useful because of their flexibility. Conventional low-hardness fluororubber molded articles have no amine resistance. In addition, the low-hardness foamed rubber molded product of low hardness has a problem that the swelling after immersion in liquid chemicals is large and the mechanical strength is also inferior.

The inventors of the present invention conducted intensive studies, and in particular, a fluororubber molded article (after crosslinking) obtained by crosslinking a composition containing a fluorocopolymer, and the fluororubber molded article was measured according to JIS K6253- The fluororubber molded article (after crosslinking) is characterized in that the hardness of IRHD of 2: 2012 is 50 or less and the volume change rate in the immersion test in diethanolamine at 120 ° C. for 72 hours is 20% or less. The inventors have found that they have low hardness, excellent flexibility, excellent amine resistance, and good mechanical properties, and have reached the present invention.

The fluororubber molded product (after crosslinking) has an IRHD hardness of 50 or less according to JIS K6253-2: 2012. The hardness of the IRHD is desirably as small as possible from the viewpoint of obtaining a material with good flexibility, for example, 48 or less is preferable, and 46 or less is more preferable. The lower limit is not particularly limited, but is preferably 20 or more, more preferably 30 or more, and particularly preferably 40 or more from the viewpoint of the mechanical strength of the molded body.
According to the hardness and shape of the fluororubber molded product (after crosslinking), the above IRHD hardness measurement method is based on M method, CM method, N method, CN method, L method and CL method described in JIS K6253-2: 2012. You can choose from

In addition, another method of measuring the hardness of a fluororubber molded product (after crosslinking) is a method of measuring a measurement time of 3 seconds of a type A durometer according to JIS K6253-3: 2012, and a material having good flexibility is obtained. From the viewpoint, the type A durometer hardness is preferably 50 or less, more preferably 48 or less, and even more preferably 46 or less. The lower limit is not particularly limited, but is preferably 20 or more, more preferably 30 or more, and particularly preferably 40 or more from the viewpoint of the mechanical strength of the molded body.

The fluororubber molded product (after crosslinking) has a volume change of not more than 20% in an immersion test in diethanolamine at 120 ° C. for 72 hours. When it is 20% or less, it has good amine resistance. From the viewpoint of amine resistance, the volume change rate is desirably small, for example, preferably 15% or less, and more preferably 11% or less. The lower limit is not particularly limited.

The fluororubber molded product (after crosslinking) is obtained by crosslinking a composition containing a fluorine-containing copolymer and a crosslinking agent, and each component (fluorine-containing copolymer, crosslinking agent) used in the composition , Fillers, co-agents, other additives, etc.) in consideration of technical common knowledge of those skilled in the art, by the selection of materials capable of adjusting the hardness and the amine resistance, adjustment of the compounding amount, the above-mentioned hardness and volume change It is possible to produce a molded body having a rate.

For example, in a composition for producing a fluororubber molded product, (1) Amine-resistant fluororubber such as a fluorocopolymer described later, a crosslinking agent and a crosslinking aid are used, and a filler such as carbon black is used for hardness. (2) A method of adding an appropriate amount of perfluoropolyether while using the amine-resistant fluororubber, a crosslinking agent and a crosslinking assistant, (3) the amine-resistant fluororubber, a crosslinking agent And the said hardness and volume change rate can be provided by the method etc. of adding a suitable amount of silicone oils while using a crosslinking adjuvant.

The fluororubber molded article is obtained by crosslinking a composition containing a fluorocopolymer and a crosslinking agent, and the composition will be described below.

The above composition has a glass transition temperature of 25 ° C. or less from the viewpoint of low hardness, amine resistance and mechanical properties,
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)
It is preferable to contain the fluorine-containing copolymer which consists of a fluorine-containing monomer (1) represented by these.

The fluorine-containing copolymer 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)
It is a copolymer containing the polymerization unit based on fluorine-containing monomer (1) represented by these.

The said fluorine-containing copolymer exhibits extremely low glass transition temperature by having the said specific structure. Further, the fluorine-containing copolymer containing the fluorine-containing monomer (1) unit represented by the above general formula (1) is difficult to be dehydrofluorinated, and is excellent in amine resistance, oil resistance and low temperature resistance. It also has a fast cure rate and good processability. Furthermore, it is excellent in steam resistance.
The fluorine-containing copolymer is preferably a fluorine-containing elastomer, and preferably an amorphous polymer.

The fluorine-containing copolymer has a glass transition temperature of 25 ° C. or less. Moreover, it can also be 0 degrees C or less. -5 degrees C or less is preferable, and -10 degrees C or less of the said glass transition temperature is more preferable. Furthermore, it is also possible to make it -20 degrees C or less. The above-mentioned fluorine-containing copolymer exhibits a very low glass transition temperature as described above, and therefore is excellent also in low temperature characteristics (cold resistance).
The glass transition temperature is obtained by cooling to −75 ° C. using a differential scanning calorimeter (X-DSC 823 e manufactured by Hitachi Techno-Science Corporation), and then a temperature of 10 mg of the sample is raised at 20 ° C./min to obtain a DSC curve. The temperature which shows the intersection of the extension line of the baseline before and behind the quadratic transition of a DSC curve, and the tangent in the inflexion point of a DSC curve was made into glass transition temperature.

A fluorine-containing monomer represented by the above-mentioned general formula (1) from the viewpoint of imparting low hardness to the obtained molded article and excellent in amine resistance, mechanical properties, fuel oil resistance and low temperature resistance, 1) is preferably a monomer in which Rf is a linear fluoroalkyl group, more preferably a monomer in which Rf is a linear perfluoroalkyl group. It is preferable that carbon number of Rf is 1-6. Examples of the fluorine-containing monomer (1) represented by the general 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 CF ₃ and the like, among _them, is preferably a 2,3,3,3-tetrafluoropropene represented by CH 2 = CFCF _3.

The fluorine-containing copolymer may further contain a polymerization unit based on vinylidene fluoride and another monomer other than the fluorine-containing monomer (1) represented by the formula (1).
The other monomer is not particularly limited as long as it is a monomer copolymerizable with the vinylidene fluoride and the fluorine-containing monomer (1) represented by the formula (1), and one or more kinds thereof Of monomers may be used.

The other monomers mentioned above are tetrafluoroethylene [TFE], hexafluoropropylene, perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), chlorotrifluoroethylene, trifluoroethylene, hexa It is preferable that it is at least one selected from the group consisting of fluoroisobutene, vinyl fluoride, ethylene, propylene, alkyl vinyl ether, and a monomer that provides a crosslinking site, and tetrafluoroethylene, hexafluoropropylene, perfluoro ( Methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), chlorotrifluoroethylene, trifluoroethylene, hexafluoroisobutene, fluorinated Cycloalkenyl, ethylene, alkyl vinyl ether, and, more preferably at least one selected from the group consisting of monomer giving a crosslinking site. More preferably, it is TFE. It is also one of the preferable forms that it is only TFE.

In the above-mentioned fluorine-containing copolymer, as a monomer which gives the above-mentioned bridge part, for example, general formula:
CX ¹ ₂ = CX ¹ -Rf 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)) or 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 are listed.

Among them, CF ₂ CCFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CN, CF ₂ CCFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOH, CF ₂ CCFOCF ₂ CF ₂ CH ₂ I, CF ₂ CCFOCF _{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) COOH, and is _preferably at least one selected from the group consisting of _{CH 2 = CFCF 2 OCF (CF} 3) CF 2 OCF (CF 3) CH 2 OH.
As a monomer for providing the above-mentioned crosslinking site, CF ₂ CCFOCF ₂ CF ₂ CH ₂ I can improve the crosslink density in the crosslinking using a peroxide, and can make the compression set good, Particularly preferred.
In addition, in the copolymer (III) described later, a monomer exemplified as a monomer providing a crosslinking site can also be suitably used.

The fluorine-containing copolymer preferably has a molar ratio of 87/13 to 20/80 of a vinylidene fluoride unit / a fluorine-containing monomer (1) unit represented by the formula (1). The molar ratio of the vinylidene fluoride unit / the fluorine-containing monomer (1) unit represented by the formula (1) is preferably 22/78 or more, more preferably 50/50 or more, 60 / More preferably, it is 40 or more. Moreover, it is preferable that it is 0-50 mol% of another monomer unit, and it is more preferable that it is 1-40 mol%.

It is preferable that the said fluorine-containing copolymer is a copolymer which consists of a vinylidene fluoride, the fluorine-containing monomer (1) represented by General formula (1), and the polymer unit based on another monomer.

The fluorine-containing copolymer may have at least one of an iodine atom and a bromine atom. In that case, it is preferable that the sum total of content of an iodine atom and a bromine atom is 0.001 to 10 weight%.

The above-mentioned fluorine-containing copolymer is a vinylidene fluoride and a fluorine-containing monomer, since it has low vulcanization properties, low hardness to the obtained molded product, and excellent amine resistance, mechanical properties, fuel oil resistance and low temperature resistance. Copolymer (I) comprising vinyl monomer (1), wherein the molar ratio of vinylidene fluoride unit / fluorinated monomer (1) unit is 87/13 to 22/78, vinylidene fluoride, fluorine-containing unit amount Body (1) and other monomers copolymerizable with vinylidene fluoride and fluorine-containing monomer (1), and the molar ratio of vinylidene fluoride unit / fluorine-containing monomer (1) unit is Copolymer (II) having 85/15 to 20/80, and the other monomer units being 1 to 50 mol% of the total monomer units, and vinylidene fluoride, fluorine-containing monomer (1 ), As well as vinylidene full And other monomers copolymerizable with the monomer (1), and the molar ratio of vinylidene fluoride unit / monomer (1) unit is 85/15 to 20/80, And other monomer units are 0 to 50 mol% of all monomer units, and have at least one of an iodine atom and a bromine atom, and the total content thereof is 0.001 to 10% by weight. It is preferable that it is at least 1 sort (s) selected from the group which consists of a polymer (III).

The copolymer (I) is composed of vinylidene fluoride and the fluorine-containing monomer (1) represented by the formula (1), and the fluorine-containing monomer represented by vinylidene fluoride unit / formula (1) (1) The molar ratio of units is 87/13 to 22/78.
The above copolymer (I) has a vinylidene fluoride unit / formula from the viewpoint of imparting low hardness to the resulting molded article and being excellent in amine resistance, mechanical properties, fuel oil resistance and low temperature resistance. It is preferable that the molar ratio of the fluorine-containing monomer (1) unit represented by (1) is 82/18-60/40.

The copolymer (II) is a vinylidene fluoride, a fluorine-containing monomer (1) represented by the formula (1), and a vinylidene fluoride and a fluorine-containing monomer represented by the formula (1) 1) A copolymer comprising polymerized units based on other monomers copolymerizable with 1), wherein the molar ratio of vinylidene fluoride unit / fluorinated monomer (1) unit represented by formula (1) is 85/15 to 20/80, and the other monomer units are 1 to 50% by mole of the total monomer units.
The copolymer (II) has a fluorine content represented by vinylidene fluoride unit / formula (1) because of excellent vulcanization characteristics and amine resistance, fuel oil resistance and low temperature resistance of the resulting molded article. It is preferable that the molar ratio of a monomer (1) unit is 85/15-50/50. More preferably, it is 85/15 to 60/40.

The copolymer (II) is another monomer unit because it has low vulcanization properties, low hardness to the resulting molded article, and excellent amine resistance, mechanical properties, fuel oil resistance and low temperature resistance. Is preferably 1 to 40 mol% of the total monomer units. As the other monomer, those described above are suitable.

The above copolymer (III) is vinylidene fluoride, which is represented by the following general formula (1):
CH ₂ = CFR f (1)
(Wherein R f represents a linear or branched fluoroalkyl group having 1 to 12 carbon atoms), a fluorine-containing monomer (1), and a vinylidene fluoride and the above-mentioned fluorine-containing monomer ( 1) a copolymer comprising a polymerization unit based on another monomer copolymerizable with 1), wherein the molar ratio of vinylidene fluoride unit / fluorinated monomer (1) unit is 85/15 to 20/80 Other monomer units are 0 to 50 mol% of all monomer units, and have at least one of an iodine atom and a bromine atom, and the total content thereof is 0.001 to 10% by weight .

The copolymer (III) 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 comprising polymerized units based on the fluorine-containing monomer (1), or vinylidene fluoro Ride, the following general formula (1):
CH ₂ = CFR f (1)
(Wherein R f represents a linear or branched fluoroalkyl group having 1 to 12 carbon atoms), a fluorine-containing monomer (1), and a vinylidene fluoride and the above-mentioned fluorine-containing monomer ( It is preferable that it is a copolymer which consists of a polymerization unit based on other monomers copolymerizable with 1).
In this case, the copolymer (III) is a copolymer substantially consisting of vinylidene fluoride and a polymer unit based on the fluorine-containing monomer (1) represented by the formula (1), or substantially The copolymer is composed of vinylidene fluoride, the fluorine-containing monomer (1) represented by the formula (1), and a polymerization unit based on the other monomer, but the It may be manufactured using an organic emulsifier. Moreover, I terminal etc. which originate in a chain transfer agent may be included.

The copolymer (III) 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), which is a copolymer comprising polymerized units based on the fluorinated monomer (1) represented by vinylidene fluoro It is more preferable that the molar ratio of a ride unit / fluorine-containing monomer (1) unit is 80/20-20/80.

Further, the copolymer (III) has a molar ratio of vinylidene fluoride unit / fluorinated monomer (1) unit of 85/15 to 50/50, and the other monomer units are all monomers. It is also preferable that it is 1 to 50 mol% of the unit.

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

The copolymer (III) has at least one of an iodine atom and a bromine atom, and the total content thereof is 0.001 to 10% by weight. It is preferable that it is 0.01 to 5 weight%, and, as for the sum total of content of an iodine atom and a bromine atom, it is more preferable that it is 0.1 to 5 weight%. Moreover, it is more preferable that the said copolymer (III) has an iodine atom from the point of a vulcanization | cure characteristic.
The iodine content was determined by mixing 12 mg of sample (fluorinated polymer) with 5 mg of Na ₂ SO ₃ and mixing 20 ml of pure water with Na ₂ CO ₃ and K ₂ CO ₃ at a ratio of 1 to 1 (weight ratio) The absorption liquid in which 30 mg is dissolved is burned in oxygen in a quartz combustion flask, and after standing for 30 minutes, it can be measured using Shimadzu 20A ion chromatograph. The calibration curve may be KI standard solution, one containing 0.5 ppm of iodine ion, or one containing 1.0 ppm.

The bonding position of the iodine atom and the bromine atom may be at the end of the main chain of the copolymer (III) or at the end of the side chain, or both of them. In such a copolymer, the iodine end or bromine end becomes a crosslinking point (crosslinking site), a crosslinked fluorine-containing polymer having a high crosslinking density can be obtained, and peroxide crosslinking can be more easily performed. become.

The copolymer (III) is produced by using iodine or bromine-containing monomer as a monomer giving a crosslinking site, using a bromine compound or iodine compound as a polymerization initiator or chain transfer agent, etc. be able to.

In the above-mentioned copolymer (III), other monomers are particularly limited as long as they are monomers copolymerizable with vinylidene fluoride and fluorine-containing monomer (1) represented by formula (1). Alternatively, one or more monomers may be used.

The other monomer in the above-mentioned copolymer (III) is preferably 0 to 50% by mole of all monomer units. More preferably, it is 1 to 50 mol%.

In the above-mentioned copolymer (III), as a monomer which provides a crosslinking site, for example,
CX ¹ ₂ = CX ¹ -Rf 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)) or an iodine- or bromine-containing monomer represented by the general formula:
CX ¹ ₂ = CX ¹ -Rf ¹ X ²
(Wherein, X ¹ represents a hydrogen atom, a fluorine atom or -CH ₃ , and R f ¹ represents a fluoroalkylene group, a perfluoroalkylene group, a fluoro (poly) oxyalkylene group or a perfluoro (poly) oxyalkylene group, X ² Is an iodine atom or a bromine atom.) An iodine- or bromine-containing monomer (preferably, a general formula: CH ₂ CHCH (CF ₂ ) _n I (n is an integer of 2 to 8) represented by Iodine-containing monomer represented by), 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; 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 each is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Z is a linear or branched group) Alkylene group having 1 to 18 carbon atoms, cycloalkylene group having 3 to 18 carbon atoms, alkylene or oxyalkylene group having 1 to 10 carbon atoms which 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 -
(In the formula, Q is an alkylene or oxyalkylene group; p is 0 or 1; m / n is 0.2 to 5); and (per) fluoro having a molecular weight of 500 to 10,000 It is a polyoxyalkylene group. And the like.

Above general formula:
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
(Wherein, Z ¹ represents a fluoropolyoxyalkylene group represented by —CH ₂ OCH ₂ —CF ₂ O— (CF ₂ CF ₂ O) _{m 1} (CF ₂ O) _{n 1} —CF ₂ —CH ₂ OCH ₂ — And m1 / n1 is 0.5, and the molecular weight is 2000.) and the like.

As a monomer which provides a crosslinking site, CF ₂ CCFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CN, CF ₂ CCFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOH, CF ₂ CCFOCF 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 it is one of the preferred embodiments is at least one selected from the group consisting of CH = CH _2.
As a monomer for providing the above-mentioned crosslinking site, CF ₂ CCFOCF ₂ CF ₂ CH ₂ I can improve the crosslink density in the crosslinking using a peroxide, and can make the compression set good, Particularly preferred.

As a monomer which provides a crosslinking site, for example, a compound of the general formula:
CX ¹ ₂ = CX ¹ -Rf 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 fluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group, and R ¹ is a hydrogen atom Or -CH ₃ , X ² is an iodine atom or a bromine atom)
Or iodine- or bromine-containing monomers represented by the general formula:
CX ¹ ₂ = CX ¹ -Rf 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 fluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group, and X ² is an iodine atom Or bromine atom)
Or a bromine-containing monomer (preferably an iodine-containing monomer represented by CH ₂ CHCH (CF ₂ ) _n I (n is an integer of 2 to 8) represented by the general formula:
CF ₂ = CFO (CF ₂ CF (CF ₃ ) O) _m (CF ₂ ) _n −X ⁵
(Wherein, 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)
Monomer represented by and the general formula:
_{CH 2 = CFCF 2 O (CF} (CF 3) CF 2 O) m (CF (CF 3)) n -X 5
(Wherein, 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 one of the preferred embodiments that it is at least one monomer selected from the group consisting of monomers represented by Copolymer (III) can also be produced by using such an iodine or bromine containing monomer as the other monomer.

In the copolymer (III), the monomer giving a crosslinking site is preferably 0.01 to 10 mol%, and more preferably 0.01 to 2 mol%, of all monomer units.

The above-mentioned fluorine-containing copolymer is copolymer (III) because of its vulcanizing properties and the low hardness imparted to the resulting molded article, and its excellent amine resistance, fuel oil resistance and low temperature resistance. preferable.

The above-mentioned fluorine-containing copolymer is excellent in vulcanization characteristics and bending fatigue resistance, tear strength, amine resistance, mechanical properties, fuel oil resistance and low temperature resistance of the obtained molded article, so the Mooney at 121 ° C. The viscosity (ML _{1 + 10} (121 ° C.)) is preferably 2 or more, and more preferably 15 or more. Moreover, it is preferable that it is 200 or less, it is more preferable that it is 150 or less, and it is further more preferable that it is 100 or less from the point that molding processability is good similarly. The Mooney viscosity is a value measured in accordance with ASTM-D1646 and JIS K6300-1: 2013.

The fluorine-containing copolymer preferably has a number average molecular weight (Mn) of 7,000 to 500,000, and a weight average molecular weight (Mw) of 10,000 to 1,000,000, since the fluorine-containing copolymer is excellent in sealability, and Mw / Mn Is preferably 1.3 to 4.0.
The said number average molecular weight (Mn), weight average molecular weight (Mw), and Mw / Mn are values measured by GPC method.

The above-mentioned fluorine-containing copolymer can be manufactured by a general radical polymerization method. The polymerization form may be any form of bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization, but is preferably emulsion polymerization because industrial implementation is easy.

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

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

The oil-soluble radical polymerization initiator may be a known oil-soluble peroxide, for example, dialkylperoxy carbonates such as diisopropyl peroxy dicarbonate, di sec-butyl peroxy dicarbonate, etc., t-butyl peroxy Peroxy esters such as isobutyrate, t-butylperoxypivalate, and dialkyl peroxides such as di-t-butyl peroxide; di (ω-hydro-dodecafluoroheptanoyl) peroxide; (Ω-hydro-tetradecafluoroheptanoyl) peroxide, di (ω-hydro-hexadecafluorononanoyl) peroxide, di (perfluorobutyryl) peroxide, di (perflupareryl) 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-clo-decafluorohexanoyl peroxide, ω-hydrododecafluoroheptanoyl-perfluorobutyryl peroxide, di (dichloropentafluorobutanoyl) peroxide, di (trichlorooctafluoro) Orohexanoyl) peroxide, di (tetrachloroundecafluorooctanoyl) peroxide, di (pentachlorotetradecafluorodecanoyl) peroxide, di (undecachlorodotriacontafluorodocosanoyl) peroxide di [perfluoro ( And fluorochloro) acyl] peroxides and the like.

The water-soluble radical polymerization initiator may be a known water-soluble peroxide, for example, persulfate, perborate, perchlorate, perphosphate, ammonium salt such as percarbonate, potassium salt, sodium salt , 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 the amount of peroxide.

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

As surfactant, nonionic surfactant, anionic surfactant, cationic surfactant etc. can be used, and C4-C20 linear chains, such as ammonium perfluoro octanoate and ammonium perfluoro hexanoate Alternatively, a branched fluorinated anionic surfactant is preferred. The addition amount (relative to polymerization water) is preferably 10 to 5000 ppm. More preferably, it is 50 to 5000 ppm.
Also, reactive emulsifiers can be used as surfactants. The reactive emulsifier is not particularly limited as long as it is a compound having one or more unsaturated bonds and one or more hydrophilic groups, for example, CH ₂ CFCFCF 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 (relative to polymerization water) is preferably 10 to 5000 ppm. More preferably, it is 50 to 5000 ppm.

The solvent is preferably a solvent having no chain transferability. In the case of solution polymerization, dichloropentafluoropropane (R-225) is exemplified, and 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 The mixture is mentioned.

In the polymerization of the copolymers (I) and (II), examples of the chain transfer agent include esters such as dimethyl malonate, diethyl malonate, methyl acetate, methyl acetate, ethyl acetate, butyl acetate and dimethyl succinate; Isopentane, methane, ethane, propane, 2-propanol, acetone, various mercaptans, carbon tetrachloride, cyclohexane and the like.

A bromine compound or an iodine compound may be used as a chain transfer agent. As a polymerization method carried out using a bromine compound or an iodine compound, for example, a method of carrying out an emulsion polymerization in an aqueous medium under pressure in the presence of a bromine compound or an iodine compound substantially in the absence of oxygen can be mentioned. (Iodine transfer polymerization method). As a representative example of the bromine compound or iodine compound to be used, for example, general formula:
R ² I _x Br _y
(Wherein, x and y each represent an integer of 0 to 2 and satisfy 1 ≦ x + y ≦ 2, and R ² represents a saturated or unsaturated fluorohydrocarbon group having 1 to 16 carbon atoms or chlorofluorocarbon) And a compound represented by the group consisting of 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, and 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-substituted benzene, diiodomonobromo-substituted, and (2-iodoethyl) and (2-bromoethyl) And the like, 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 in view of polymerization reactivity, crosslinking reactivity, availability and the like. Is preferred.

In the polymerization of the copolymer (III), it is preferable to use a bromine compound or an iodine compound as a chain transfer agent. As a polymerization method carried out using a bromine compound or an iodine compound, for example, a method of carrying out an emulsion polymerization in an aqueous medium under pressure in the presence of a bromine compound or an iodine compound substantially in the absence of oxygen can be mentioned. (Iodine transfer polymerization method). As a representative example of the bromine compound or iodine compound to be used, for example, general formula:
R ² I _x Br _y
(Wherein, x and y each represent an integer of 0 to 2 and satisfy 1 ≦ x + y ≦ 2, and R ² represents a saturated or unsaturated fluorohydrocarbon group having 1 to 16 carbon atoms or chlorofluorocarbon) And a compound represented by the group consisting of 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, and 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-substituted benzene, diiodomonobromo-substituted, and (2-iodoethyl) and (2-bromoethyl) And the like, 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 in view of polymerization reactivity, crosslinking reactivity, availability and the like. Is preferred.

In the polymerization of the copolymer (III), examples of the chain transfer agent include esters such as dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, butyl acetate, dimethyl succinate, isopentane, methane, It is also possible to use ethane, propane, 2-propanol, acetone, various mercaptans, carbon tetrachloride, cyclohexane and the like.

In the polymerization of the fluorine-containing copolymer, 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, and 1 to 24 hours. You may In particular, when using an oil-soluble radical polymerization initiator containing a fluorine atom as a polymerization initiator in solution polymerization, the polymerization temperature is preferably −15 to 50 ° C., and more preferably 10 to 35 ° C. When an oil-soluble radical polymerization initiator containing a fluorine atom is used in the 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 the compression set of the molded article is good, and the polymerization rate is increased to improve the productivity. 0 MPa or more is more preferable, and 4.5 MPa or more is the most preferable.

The fluorine-containing copolymer may be in any form such as an aqueous dispersion, powder or the like.
The powder of the fluorine-containing copolymer can be obtained by coagulating a dispersion after polymerization, washing with water, dehydrating and drying in the case of emulsion polymerization. The coagulation can be carried out by adding an inorganic salt such as aluminum sulfate or inorganic acid, applying 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 the solution containing the fluorine-containing polymer as it is, or can be obtained by purifying the poor solvent dropwise.

As said fluorine-containing copolymer, 1 type may be used and 2 or more types may be used. In particular, it may be a form in which two types of copolymers having different molecular structures are used in combination.
As a form using two kinds of copolymers having different molecular structures in combination, a form using two kinds of copolymers (I) having different molecular structures, a form using two kinds of copolymers (II) having different molecular structures, Form using two kinds of copolymers (III) different in molecular structure, form using one kind of copolymer (I) and one kind of copolymer (II) in combination, one kind of copolymer (I) and An embodiment in which one type of copolymer (III) is used in combination, and an embodiment in which one type of copolymer (II) and one type of copolymer (III) are used in combination are mentioned.

As described above, in the case where two types of copolymers are used in combination as the above-mentioned fluorine-containing copolymer, one type is a branched fluorine-containing polymer and the other type is a linear fluorine-containing polymer Is preferred. More preferably, one type has (A) peroxide-crosslinkable crosslinking sites and has a number average molecular weight in the range of 1,000 to 300,000, as described in WO 2009/119409. And a branched fluorine-containing weight having a Mark-Houwink gradient a of less than 0.6 when the horizontal axis is the absolute weight molecular weight and the vertical axis is the intrinsic viscosity, and the absolute weight molecular weight and the intrinsic viscosity are plotted on the Mark-Hawin plot. And the other is (B) a number average molecular weight in the range of 1,000 to 250,000, and a mark having an absolute weight molecular weight and an intrinsic viscosity, the horizontal axis being an absolute weight molecular weight and the vertical axis being an intrinsic viscosity -The form of a linear fluorine-containing polymer having a Mark-Houwink gradient a of 0.6 or more when plotted on the Hawin plot, or one type is less (A) An ethylenically unsaturated compound containing one fluoroolefin with the general formula:
CY ¹ ₂ = CY ² Rf ² X ²
(Wherein, Y ¹ and Y ^{2 each} represents a fluorine atom, a hydrogen atom or —CH ₃ ; Rf ² may have an etheric oxygen atom, and some or all of the hydrogen atoms may be substituted with a fluorine atom; In copolymerizing a linear or branched fluorine-containing alkylene group; a compound represented by X ² is an iodine atom or a bromine atom), addition of the compound represented by the above general formula is carried out after addition of a polymerization initiator. It is a branched fluorine-containing polymer obtained by the manufacturing method characterized by starting at the time of 0 to 10% by mass addition of the total addition amount of the ethylenically unsaturated compound added to the inside, and the other type is (B) The number average molecular weight was in the range of 1,000 to 250,000, and the absolute weight molecular weight and the intrinsic viscosity were plotted on the Mark-Houwin plot in which the abscissa represents the absolute weight molecular weight and the ordinate represents the intrinsic viscosity It is a form which is a linear fluorine-containing polymer whose time mark-Hawin gradient a is 0.6 or more.
Thus, when two or more polymers are used as the fluorine-containing copolymer, one of them is the copolymer (II) or the copolymer (III), and has a crosslinking site which can be peroxide-crosslinked. , When the number average molecular weight is in the range of 1,000 to 300,000, and the absolute weight molecular weight and the intrinsic viscosity are plotted on the Mark-Houwin plot where the abscissa is the absolute weight molecular weight and the ordinate is the intrinsic viscosity An ethylenically unsaturated compound which is a branched fluoropolymer having a Hawin gradient a of less than 0.6 or which comprises at least one fluoroolefin, and a compound of the general formula:
CY ¹ ₂ = CY ² Rf ² X ²
(Wherein, Y ¹ and Y ^{2 each} represents a fluorine atom, a hydrogen atom or —CH ₃ ; Rf ² may have an etheric oxygen atom, and some or all of the hydrogen atoms may be substituted with a fluorine atom; In copolymerizing a linear or branched fluorine-containing alkylene group; a compound represented by X ² is an iodine atom or a bromine atom), addition of the compound represented by the above general formula is carried out after addition of a polymerization initiator. It is a branched fluorine-containing polymer obtained by the manufacturing method characterized by starting at the time of 0 to 10% by mass addition of the total addition amount of the ethylenically unsaturated compound added to the inside, and the other type is a co-type Polymer (I), copolymer (II) or copolymer (III), wherein the number average molecular weight is in the range of 1,000 to 250,000, and the absolute weight molecular weight and the intrinsic viscosity are plotted on the horizontal axis Absolute weight molecular weight In a preferred embodiment, the linear fluorine-containing polymer has a Mark-Houwink gradient a of 0.6 or more when plotted on the Mark-Houwink plot, the vertical axis of which is the intrinsic viscosity.

Still other fluorine-containing copolymers include ethylene / tetrafluoroethylene / perfluoroalkyl vinyl ether copolymers such as Viton ETP manufactured by The Chemours Company, AFLAS 100 grade, 150 grade, 200 grade and 300 grade by Asahi Glass Co., Ltd. And tetrafluoroethylene / propylene copolymers and tetrafluoroethylene / propylene / vinylidene fluoride copolymers, such as Solvay S. et al. A. Copolymers having amine resistance such as vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene / perfluoroalkyl vinyl ether / ethylene copolymer such as Tecnoflon BR9151 and BR9152 manufactured by Co., Ltd. can be mentioned.

Among the above-mentioned fluorine-containing copolymers, the above-mentioned fluorine-containing copolymers are preferable from the viewpoint of obtaining good amine resistance while imparting low hardness, and the above-mentioned copolymers (I) and (II), (III) is more preferable, and the copolymer (III) is particularly preferable.

The composition preferably contains a crosslinking agent. In the above composition, the compounding amount of the crosslinking agent is usually 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 copolymer. If the amount of the crosslinking agent is less than 0.01 parts by mass, the degree of crosslinking is insufficient, and the performance of the resulting molded article tends to be impaired. If it is more than 10 parts by mass, the crosslinking density becomes too high. In addition to being long, it is economically unpreferable.

The crosslinking agent is not particularly limited as long as it is a crosslinking agent usually used for polyamine crosslinking, polyol crosslinking and peroxide crosslinking (organic peroxide crosslinking), and it comprises a polyamine compound, a polyhydroxy compound and an organic peroxide. At least one selected from the group is preferred, and organic peroxides are particularly preferred.

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

As a polyhydroxy compound, a polyhydroxy aromatic compound is suitably used from the point which is excellent in 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-bis (4-hydroxyphenyl) Tetrafluorodichloropropane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl ketone, tri (4-hydroxyphenyl) methane, 3,3 ′, 5,5′-tetrachlorobisphenol A, 3,3 And 5,5'-tetrabromobisphenol A and the like. These polyhydroxy aromatic compounds may be alkali metal salts, alkaline earth metal salts and the like, but when coagulating a fluorine-containing copolymer using an acid, the above metal salts may not be used. preferable.

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

Examples of the crosslinking accelerator include onium compounds, and among onium compounds, ammonium compounds such as quaternary ammonium salts, phosphonium compounds such as quaternary phosphonium salts, oxonium compounds, sulfonium compounds, cyclic amines, 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] 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 in terms of excellent crosslinkability and physical properties of molded articles obtained from the above composition.

Further, the quaternary phosphonium salt is not particularly limited. For example, tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride (hereinafter referred to as BTPPC), benzyltrimethylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl -2-methoxypropyl phosphonium chloride, benzylphenyl (dimethylamino) phosphonium chloride and the like, and among these, benzyl triphenyl phosphonium chloride from the viewpoint of excellent crosslinkability and physical properties of molded articles obtained from the above composition. (BTPPC) is preferred.

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

The compounding amount of the crosslinking accelerator is preferably 0.01 to 8 parts by mass, and more preferably 0.02 to 5 parts by mass with respect to 100 parts by mass of the fluorocopolymer. If the crosslinking accelerator is less than 0.01 parts by mass, crosslinking of the fluorine-containing polymer does not proceed sufficiently, and the performance of the resulting molded article tends to be impaired. If it is more than 8 parts by mass, the above composition Molding processability tends to decrease.

The organic peroxide may be any organic peroxide which can easily generate a radical 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-butylperoxide, t-butylcumylperoxide, dicumylperoxide, 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 -We can mention oxy benzoate and the like. Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3 are preferable.

In the case of peroxide crosslinking, in the above composition, the compounding amount of the organic peroxide is usually 0.3 to 5.0 parts by mass with respect to 100 parts by mass of the fluorine-containing copolymer. The lower limit is preferably 0.4 parts by mass or more. The upper limit is preferably 3.0 parts by mass or less, more preferably 2.5 parts by mass or less, and still more preferably 2.0 parts by mass or less. If the amount is less than 0.3 parts by mass, the degree of crosslinking will be insufficient, so the performance of the resulting molded article tends to be impaired. If it exceeds 5.0 parts by mass, the processability at the time of kneading will be inferior and In addition to being prone to cause molding defects due to an increase in gas generated by the decomposition of the organic peroxide, it is economically unpreferable. When the organic peroxide is blended in the above composition, it may be impregnated with an inert inorganic powder or the like.

When the crosslinking agent is an organic peroxide, the composition preferably contains a crosslinking aid. Examples of the crosslinking assistant include triallyl cyanurate, trimethallyl isocyanurate, triallyl isocyanurate (TAIC), triacrylic formal, triallyl trimellitate, N, N'-m-phenylenebismaleimide, and dipropargyl. Terephthalate, diallyl phthalate, tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallylisocyanurate (1,3,5-tris (2,3,3-trifluoro-2-propenyl) -1,3,7 5-triazine-2,4,6-trione), tris (diallylamine) -S-triazine, triallyl phosphite, N, N-diallylacrylamide, 1,6-divinyldodecafluorohexane, hexaallyl phosphoramide, N , N, N ', N'-Tet Allylphthalamide, N, N, N ', N'-tetraallylmalonamide, trivinylisocyanurate, 2,4,6-trivinylmethyltrisiloxane, tri (5-norbornene-2-methylene) cyanurate, triallyl Mention may be made of polyfunctional co-crosslinking agents such as phosphites. Among these, triallyl isocyanurate (TAIC) and trimethallyl isocyanurate are preferable from the viewpoint of excellent crosslinkability and physical properties of molded articles obtained from the above composition.

The compounding quantity of a crosslinking adjuvant (polyfunctional co-crosslinking agent) is 0.1-6.0 mass parts with respect to 100 mass parts of fluorine-containing copolymers. The lower limit is preferably 0.3 parts by mass or more, more preferably 0.4 parts by mass or more. The upper limit is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, and still more preferably 2.0 parts by mass or less. When the amount of the crosslinking assistant is less than 0.1 parts by mass, the strength of the resulting molded article tends to be so low that it can not be practically used. If it exceeds 6.0 parts by mass, the hardness of the resulting molded article tends to be high.

Polyamine crosslinking using a polyamine compound as a crosslinking agent can be carried out in a conventional manner. For example, the above composition is manufactured by kneading the fluorine-containing copolymer and the crosslinking agent, if necessary, the crosslinking accelerator, and the other additives which can be suitably mixed, with a roll or the like to produce the above composition, and the composition is used as a mold. Method of primary crosslinking and then secondary crosslinking if necessary. After pre-forming the composition by extrusion, etc., heat and pressure are applied using steam etc. in a closed vessel such as a vulcanized can. By carrying out the method, primary crosslinking and then secondary crosslinking, if necessary, may be mentioned. For kneading, an open roll, a kneader, an internal mixer, a Banbury mixer and the like can preferably be used. In general, the conditions for primary crosslinking are adopted at a temperature of 130 to 230 ° C., for a time of 5 to 120 minutes, from a pressure range of about 0.2 to 15 MPa, and the conditions for secondary crosslinking are at a temperature of 150 to 300 ° C., for 10 minutes of time. It is adopted from the range of about-48 hours.

Polyol crosslinking using polyhydroxy compounds as crosslinking agents can be carried out in a conventional manner. For example, the above composition is manufactured by kneading the fluorine-containing copolymer and the crosslinking agent, if necessary, the crosslinking accelerator, and the other additives which can be suitably mixed, with a roll or the like to produce the above composition, and the composition is used as a mold. Method of primary crosslinking and then secondary crosslinking if necessary. After pre-forming the composition by extrusion, etc., heat and pressure are applied using steam etc. in a closed vessel such as a vulcanized can. By carrying out the method, primary crosslinking and then secondary crosslinking, if necessary, may be mentioned. For kneading, an open roll, a kneader, an internal mixer, a Banbury mixer and the like can preferably be used. In general, primary crosslinking can be performed at 0.2 to 15 MPa and 130 to 230 ° C. for 5 to 60 minutes, and secondary crosslinking can be performed at 150 to 300 ° C. for 10 minutes to 48 hours.

Peroxide crosslinking, using organic peroxides as crosslinking agents, can be carried out in a conventional manner. For example, the above composition is manufactured by kneading the fluorine-containing copolymer and a crosslinking agent, if necessary, a crosslinking assistant (crosslinking accelerator), and further, other additives which can be mixed as appropriate, etc. The material is put into a mold and pressurized, primary crosslinking is performed, and then, if necessary, secondary crosslinking is performed, and the composition is subjected to preforming such as extrusion, and then steam or the like is used in a closed container such as a vulcanized can. Primary cross-linking may be carried out by heating and pressing, followed by secondary cross-linking if necessary. For kneading, an open roll, a kneader, an internal mixer, a Banbury mixer and the like can preferably be used. In general, primary crosslinking can be performed at 0.2 to 15 MPa and 130 to 230 ° C. for 5 to 60 minutes, and secondary crosslinking can be performed at 150 to 300 ° C. for 10 minutes to 48 hours.

When the fluorine-containing copolymer is the copolymer (III), it has at least one of an iodine atom and a bromine atom, and the total content thereof is 0.001 to 10% by mass, so iodine end or bromine end Is the crosslinking point (crosslinking site), and the crosslinking density can be further increased.

When the fluorine-containing copolymer is the copolymer (III), the composition more preferably contains an organic peroxide as a crosslinking agent. The compounding amount of the organic peroxide is usually 0.3 to 5.0 parts by mass, preferably 0.3 to 2.5 parts by mass, more preferably 0 based on 100 parts by mass of the fluorine-containing copolymer. .4 to 2.0 parts by mass. If the amount is less than 0.3 parts by mass, the degree of crosslinking will be insufficient, so the performance of the resulting molded article tends to be impaired. If it exceeds 5.0 parts by mass, the processability at the time of kneading will be inferior and In addition to being prone to cause molding defects due to an increase in gas generated by the decomposition of the organic peroxide, it is economically unpreferable. When the organic peroxide is blended in the above composition, it may be impregnated with an inert inorganic powder such as silica or diatomaceous earth.

Since the said copolymer (III) has at least one of an iodine atom and a bromine atom, and the sum total of the content is 0.001 to 10% by mass, peroxide crosslinking is achieved by including an organic peroxide. It will be possible to do 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. The composition preferably contains a crosslinking aid, and the above-mentioned crosslinking aid includes those mentioned above. Among them, triallyl isocyanurate (TAIC) is preferred from the viewpoint of excellent crosslinkability and physical properties of molded articles. .

When the fluorine-containing copolymer is the copolymer (III), the compounding amount of the crosslinking assistant (polyfunctional co-crosslinking agent) in the above composition is 0.1 to 0.1 parts by mass with respect to 100 parts by mass of the fluorine-containing copolymer. It is 6.0 parts by mass. The lower limit is preferably 0.3 parts by mass or more, more preferably 0.4 parts by mass or more. The upper limit is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, and still more preferably 2.0 parts by mass or less. When the amount of the crosslinking assistant is less than 0.1 parts by mass, the strength of the resulting molded article tends to be so low that it can not be practically used. If it exceeds 6.0 parts by mass, the hardness of the resulting molded article tends to be too high. Moreover, when mix | blending a crosslinking adjuvant in the said composition, you may be made to impregnate with inactive inorganic powders, such as a silica and diatomaceous earth.

When the fluorine-containing copolymer is the copolymer (III), the crosslinking conditions of the above composition may be appropriately determined depending on the kind of the crosslinking agent used, etc., but usually at a temperature of 130 to 230 ° C. Baking for 60 minutes (primary crosslinking). In addition, crosslinking can be performed under normal pressure, increased pressure, reduced pressure, and also in air. Then, if necessary, secondary crosslinking may be performed at 150 to 300 ° C. for 10 minutes to 48 hours.

When the fluorine-containing copolymer is the copolymer (III), it is preferable that the composition contains an organic peroxide as a crosslinking agent and is crosslinked by peroxide crosslinking. Peroxide crosslinking, using organic peroxides as crosslinking agents, can be carried out in a conventional manner. For example, the above composition is manufactured by roll-kneading the copolymer (III) and the crosslinking agent, if necessary, the crosslinking aid, and other additives which can be mixed as appropriate, and the composition is put into a mold. By applying pressure, primary crosslinking, and then secondary crosslinking if necessary, after pre-forming of the composition by extrusion, etc., heat and pressure are applied using steam or the like in a closed container such as a vulcanized can. A method of primary crosslinking and then secondary crosslinking if necessary may be mentioned. In general, primary crosslinking can be performed at 0.2 to 15 MPa and 130 to 230 ° C. for 5 to 60 minutes, and secondary crosslinking can be performed at 150 to 300 ° C. for 10 minutes to 48 hours.

It is also preferred that the composition comprises a filler. As the filler, conventionally known inorganic fillers, organic fillers and the like can be used. Specifically, metal oxides such as magnesium oxide, calcium oxide, titanium oxide and aluminum oxide; metal hydroxides such as magnesium hydroxide, aluminum hydroxide and calcium hydroxide; magnesium carbonate, aluminum carbonate, calcium carbonate and carbonate Carbonates such as barium; silicates such as magnesium silicate, calcium silicate, sodium silicate and aluminum silicate; sulfates such as aluminum sulfate, calcium sulfate and barium sulfate; molybdenum disulfide, iron sulfide, copper sulfide etc. Metal sulfides; Synthetic hydrotalcite, diatomaceous earth, asbestos, lithopone (zinc sulfide / barium sulfide), graphite, carbon black, carbon fluoride, calcium fluoride, coke, fine quartz powder, zinc flower, talc, mica Powder, wollastonite, carbon fiber Aramid fiber, various whiskers, glass fiber, organic reinforcing agents, organic fillers, polytetrafluoroethylene, mica, silica, Celite, clay and the like. Among them, carbon and silica are preferable because excellent physical properties can be obtained even when the molded body has low hardness, and among carbon, MT carbon is more preferable.

In the above composition, it is preferable that the blending amount of the filler be appropriately adjusted because the hardness and physical properties of the molded product differ depending on the kind of the filler even in the same blending amount. It is preferably 0 to 18.0 parts by mass, more preferably 0 to 15.0 parts by mass, more preferably 1.0 to 10.0 parts by mass, further preferably 2 with respect to 100 parts by mass of the fluorine-containing copolymer. It is from 0 to 8.0 parts by mass. If it exceeds 18.0 parts by mass, the hardness tends to be high. When the above-mentioned organic peroxide and the above-mentioned cross-linking coagent are compounded into the composition, when the above-mentioned inert inorganic powder is impregnated, the compounding amount of the inert inorganic powder is the same as the compounding amount of the above-mentioned filler. included.

The above composition preferably contains a perfluoropolyether from the viewpoint that good amine resistance can be obtained while imparting low hardness, and further that the releasability is improved without deteriorating the amine property. .

The perfluoropolyether comprises a perfluoropolyether structure.

As said perfluoropolyether, the compound represented by the following general formula (I) is mentioned.
R ^1- (OC ₄ F ₈ ) _r- (OC ₃ F ₆ ) _a- (OC ₂ F ₄ ) _b- (OCF ₂ ) _c- R ² (I)
In the formula, R ¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms, and preferably, it may be substituted by one or more fluorine atoms It is a C1-C3 alkyl group. Preferably, the alkyl group optionally substituted by one or more fluorine atoms is a fluoroalkyl group in which the terminal carbon atom is CF ₂ H- and all other carbon atoms are fully substituted by fluorine. Or a perfluoroalkyl group, more preferably a perfluoroalkyl group.
R ² represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms, preferably substituted by one or more fluorine atoms It is a C1-C3 alkyl group which may be. Preferably, the alkyl group optionally substituted by one or more fluorine atoms is a fluoroalkyl group in which the terminal carbon atom is CF ₂ H- and all other carbon atoms are fully substituted by fluorine. Or a perfluoroalkyl group, more preferably a perfluoroalkyl group.
a, b, c and r each represent the number of repeating units of four types of perfluoropolyethers constituting the main skeleton of the polymer, and are each independently an integer of 0 or more and 300 or less, and a, b, c And the sum of r is at least 1, preferably 1 to 100. The order in which each repeating unit enclosed in parentheses with the subscripts a, b, c or r is present is arbitrary in the formula. Among these repeating _{units, - (OC 4 F 8)} - _{is, - (OCF 2 CF 2 CF} 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2) -, - (OCF 2 CF (CF _{3) CF 2) -, -} (OCF 2 CF 2 CF (CF 3)) -, - (OC (CF 3) 2 CF 2) -, - (OCF 2 C (CF 3) 2) -, - (OCF (CF ₃ ) CF (CF ₃ ) —, — (OCF (C ₂ F ₅ ) CF ₂ ) — and — (OCF ₂ CF (C ₂ F ₅ )) —, which may be any of _{(OCF 2 CF 2 CF 2 CF} 2) - a. - _{(OC 3} F 6) - _{is, - (OCF 2 CF 2 CF} 2) -, - (OCF (CF 3) CF 2) - and _{- (OCF 2 CF (CF 3} )) - be any of well, preferably _{- (OCF 2 CF 2 CF 2} ) - a. - _(OC 2 _{F 4)} - is, - _{(OCF 2} CF 2) - and _{- (OCF (CF 3))} - but may be any of, preferably - _{(OCF 2} CF 2) - a.

As commercially available perfluoropolyethers, trade names Demnum (made by Daikin Industries, Ltd.), fomblin (made by Solvay Specialty Polymers Japan), Barierta (made by NOK Kruber), Klitex (made by DuPont), etc. It can be mentioned.

The perfluoropolyether preferably has an average molecular weight of 1,000 to 30,000.
The average molecular weight can be measured by gel permeation chromatography (GPC).

In the above composition, the blending amount of perfluoropolyether is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, more preferably 100 parts by mass of the fluorocopolymer. It is 1 to 7 parts by mass. If the amount is less than 0.1 parts by mass, good releasability tends not to be obtained. If it exceeds 10 parts by mass, the mechanical strength of the fluororubber tends to decrease.

The above composition preferably contains a silicone oil from the viewpoint that good amine resistance can be obtained while imparting low hardness, and further that the releasability is improved without deteriorating the amine property.

Examples of the silicone oil include unmodified silicone oil, and modified silicone oil having a functional group in the molecular structure, such as at the molecular chain end or in the molecular chain, and examples of the functional group include linear alkyl groups and branched alkyl groups. Groups, cyclic alkyl groups, alkenyl groups, aryl groups, aralkyl groups and other aromatic groups and ring-opened groups thereof, epoxy groups, carbinol groups, carboxyl groups, polyether groups and the like.

As silicone oil, specifically, as dimethyl silicone oil, SH200 (made by Toray Dow Corning Co., Ltd.), KF-96, KF-965 (made by Shin-Etsu Chemical Co., Ltd.), SH510 (as methylphenyl silicone oil) Toray Dow Corning Co., Ltd.), KF-50, KF-54 (Shin-Etsu Chemical Co., Ltd.), cyclic dimethyl silicone oil, KF-995 (Shin-Etsu Chemical Co., Ltd.), aralkyl-modified silicone oil, KF -410 (manufactured by Shin-Etsu Chemical Co., Ltd.), long-chain alkyl-modified silicone oil as KF-412, KF-413, X-22-2322 (manufactured by Shin-Etsu Chemical Co., Ltd.), as fluoroalkyl-modified silicone oil as FS1265 ( Toray Dow Corning Co., Ltd.), X-2 -821 (manufactured by Shin-Etsu Chemical Co., Ltd.), as an epoxy-modified silicone oil, SF8411, BY16-839 (manufactured by Toray Dow Corning Co., Ltd.), KF-1001, KF-102, KF-105, X-22-169B, X-22-173DX (made by Shin-Etsu Chemical Co., Ltd.), and as a carbinol modified silicone oil, SF8427, SF8428 (made by Toray Dow Corning Co., Ltd.), X-22-4015, X-22-170 DX (Shin-Etsu Chemical Co., Ltd.) Made as Inc., as carboxyl modified silicone oil, BY-16-880 (made by Toray Dow Corning Co., Ltd.), X-22-3701E, X-22-162C (made by Shin-Etsu Chemical Co., Ltd.), polyether modified silicone As oil, SF8410, SH8700 (Toray ・ Dauko Training Ltd.), KF-6123, KF-6012, X-22-4515 (but manufactured by Shin-Etsu Chemical Co., Ltd.), but is not limited thereto. Among these, at least one type may be arbitrarily selected, and two or more types may be mixed and used. Further, a silicone oil compound in which a silica oil or the like is blended with a silicone oil as a base oil, or a silicone grease in which a thickening agent such as metal soap is blended can be used. As silicone grease compounds, KS-62F, G-777 (manufactured by Shin-Etsu Chemical Co., Ltd.), Trefil F-202, Trefil Z-6598, Trefil Z-6898 (manufactured by Toray Dow Corning Corp.), Straktor WS280 ( S & S Japan Co., Ltd. product etc. are mentioned, G-420, G-501 (made by Shin-Etsu Chemical Co., Ltd.) etc. are mentioned as silicone grease.

In the above composition, the compounding amount of the silicone oil is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8.0 parts by mass, still more preferably 100 parts by mass of the fluorocopolymer. It is 1.0 to 5.0 parts by mass. If the amount is less than 0.1 parts by mass, good releasability tends not to be obtained. If it exceeds 10 parts by mass, the mechanical strength of the fluororubber tends to decrease.

The kinematic viscosity of the silicone oil is, from the viewpoints of kneading processability, difficulty in bleeding out from the molded article after crosslinking, and mechanical properties of the molded article after crosslinking, the kinematic viscosity at 25 ° C. is 1 to 10,000,000 mm ² / The range of s is preferable, the range of 20 to 100,000 mm ² / s is more preferable, and the range of 30 to 10,000 mm ² / s is further preferable.
The kinematic viscosity is a value measured using a Ubbelode viscometer according to JIS K 8803: 2011.

It is also preferred that the composition comprises a plasticizer. Examples of the plasticizer include dioctyl phthalic acid and pentaerythritol.

It is also preferred that the composition comprises a processing aid. Processing aids include higher fatty acids such as stearic acid, oleic acid, palmitic acid and lauric acid; higher fatty acid salts such as sodium stearate and zinc stearate; higher fatty acid amides such as stearic acid amide and oleic acid amide; oleic acid Higher fatty acid esters such as ethyl, higher aliphatic amines such as stearylamine, oleylamine; waxes derived from animals and plants such as carnauba wax; waxes derived from minerals such as ceresin wax; petroleum waxes such as paraffin wax; petroleum based waxes such as paraffin wax; Aliphatic hydrocarbons such as petrolatum and paraffin; silicone oils, silicone polymers, low molecular weight polyethylene, phthalates, phosphates, rosin, (halogen ) Dialkylamine, surfactants, sulfone compounds, fluorine-based aids, and the like.

The above composition comprises an acid acceptor, a mold release agent, a pigment, a flame retardant, a lubricant, a light stabilizer, a weathering stabilizer, an antistatic agent, an ultraviolet absorber, an antioxidant, a foaming agent, a fragrance, an oil, and a softener Etc. may be included in the range which does not affect the effect.

The composition may contain a solvent. When the fluorine-containing copolymer is dissolved in a solvent, it can be used as a paint. Examples of the solvent include ketone solvents and ester solvents.

The composition may contain other polymers different from the fluorine-containing copolymer. Other polymers include nitrile rubber, acrylic rubber, epichlorohydrin rubber, silicone rubber, ethylene propylene diene rubber and the like.

The content of the fluorine-containing copolymer in the composition is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and 75% by mass or more Is particularly preferred.

The composition is preferably obtained by kneading at least a fluorine-containing copolymer, and optionally, the above-mentioned crosslinking agent, crosslinking accelerator and the like.

Although an open roll, a Banbury mixer, a pressure kneader, an extruder, etc. can be used for the said kneading | mixing, It is preferable to use an open roll, a Banbury mixer, or a pressure kneader from the point which can apply high shear force.

The fluorine-containing rubber molded article can be obtained by crosslinking the above-mentioned composition containing the fluorine-containing copolymer.
The shaped body is preferably obtained by crosslinking and shaping the above composition. The molded article can be produced by molding the above composition and crosslinking the obtained molded article, or can be produced by simultaneously carrying out molding and crosslinking.

The crosslinking may be appropriately determined depending on the kind of the crosslinking agent to be used, but usually, it is fired at a temperature of 130 to 300 ° C. for 1 minute to 48 hours. In addition, crosslinking can be performed under normal pressure, increased pressure, reduced pressure, and also in air.

The crosslinking method is not particularly limited, and a conventional method in which a crosslinking reaction is initiated by steam crosslinking, pressure molding, heating, or the like may be employed, and radiation crosslinking at normal temperature and pressure may be employed.

After the initial crosslinking treatment (referred to as primary crosslinking), a post-treatment step called secondary crosslinking may be applied. In general, primary crosslinking can be performed at 0.2 to 15 MPa and 130 to 230 ° C. for 3 to 180 minutes, and secondary crosslinking can be performed at 150 to 300 ° C. for 10 minutes to 48 hours.

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

The fluororubber molded article has low hardness, excellent flexibility, and excellent amine resistance. Moreover, it is excellent in low temperature characteristics, and is hard to be cured even at low temperatures. Furthermore, the fuel resistance is excellent.

The fluororubber molded product has excellent amine resistance, fuel oil resistance, vulcanization characteristics and low temperature characteristics while having low hardness and excellent flexibility, and slides in contact with other materials. It is generally used in parts intended to seal and seal other materials and substances, as well as vibration and soundproofing, and can be used as various parts in various fields such as automobile industry, aircraft industry and semiconductor industry.
The fields to be used include, for example, semiconductor related fields, automobile fields, aircraft fields, space / rocket fields, ship fields, chemical fields such as chemical plants, medicine fields such as pharmaceuticals, photography fields such as developing machines, printing machines etc. Printing field, painting field such as painting equipment, analytical instrument, analytical / physical chemical machine field such as instrument, food equipment field including food plant equipment and household goods, beverage food production field, pharmaceutical production field, medical parts field, chemistry Chemical transportation equipment field, Nuclear power plant equipment field, Steel field such as iron plate processing equipment, General industrial field, Electricity field, Fuel cell field, Electronic parts field, Optical parts field, Space equipment field, Petrochemical plant field And energy resources such as oil and gas, etc., mining equipment parts, oil refining, oil transportation parts and the like.

Examples of usage of the fluorine rubber molded body include rings, packings, gaskets, diaphragms, oil seals, bearing seals, lip seals, plunger seals, door seals, lip and face seals, gas delivery plate seals, wafer support seals, Examples include various sealing materials such as barrel seals and packings. The sealing material can be used in applications where heat resistance, solvent resistance, chemical resistance and non-adhesiveness are required.
Also used as tubes, hoses, rolls, various rubber rolls, flexible joints, rubber plates, coatings, belts, dampers, valves, valve seats, valve bodies for valves, chemical-resistant coating materials, laminating materials, lining materials, etc. it can.
The cross-sectional shape of the ring, the packing, and the seal may be various shapes. Specifically, for example, the shape may be a square, an O-shape, a hem-rule or the like, a D-shape, It may have an irregular shape such as L, T, V, X, or Y.

In the above semiconductor related field, for example, semiconductor manufacturing apparatus, liquid crystal panel manufacturing apparatus, plasma panel manufacturing apparatus, plasma display panel manufacturing apparatus, plasma addressed 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. As such an apparatus, for example, CVD apparatus, gas control apparatus such as gas control apparatus for semiconductor, dry etching apparatus, wet etching apparatus, plasma etching apparatus, reactive ion etching apparatus, reactive ion beam etching apparatus, sputter etching Apparatus, ion beam etching apparatus, oxidation diffusion apparatus, oxidation 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 equipment Soxhlet extractive cleaning machine, high temperature and high pressure extractive cleaning machine, microwave extraction cleaning device, supercritical extraction Washing equipment , Cleaning equipment using hydrofluoric acid, hydrochloric acid, sulfuric acid, ozone water, etc., stepper, coater / developer, CMP apparatus, excimer laser exposure machine, chemical piping, gas piping, NF ₃ plasma processing, O ₂ plasma processing, fluorine plasma processing , Etc., thermal processing film forming equipment, wafer transfer equipment, wafer cleaning equipment, silicon wafer cleaning equipment, silicon wafer processing equipment, equipment used for LP-CVD process, equipment used for lamp annealing process, reflow The apparatus used for a process etc. are mentioned.

Specific usage modes in the semiconductor related field include, for example, various sealing materials such as gate valves, quartz windows, chambers, chamber lit, gates, bell jars, couplings, pump O-rings and gaskets; resist developer and peeling Various sealing materials such as O-rings for liquids, hoses and tubes; resist developer tank, stripping liquid tank, wafer cleaning liquid tank, lining and coating of wet etching tank; diaphragm of pump; roll for wafer conveyance; Sealing materials for clean equipment such as clean equipment and sealants for clean equipment; Sealing materials for storage for storing devices such as semiconductor manufacturing equipment and wafers; Diaphragms for chemical solution transfer used in the process of manufacturing semiconductors It can be mentioned.

In the above automobile 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 electric parts, control It can be used for electrical components such as system electrical components and equipment electrical components. The above-mentioned field of automobiles also includes motorcycles.
In the above-mentioned engine body and its peripheral devices, the above-mentioned fluororubber molded body can be used for various sealing materials which are required to have heat resistance, oil resistance, fuel oil resistance, antifreeze liquid resistance for engine cooling, and steam resistance. Such sealing materials include, for example, seals such as gaskets, shaft seals, valve stem seals, etc., self seal packings, piston rings, split ring type packings, mechanical seals, non-contact type such as oil seals, etc. In addition to packings, bellows, diaphragms, hoses, tubes, electric wires, shock absorbing materials, anti-vibration materials, and various sealing materials used in a belt AT device can be mentioned.

The fuel injector, cold start injector, fuel line quick connector, sender flange quick connector, fuel pump, fuel tank quick connector, gasoline mixing pump, gasoline pump Tube body of tube, connector of fuel tube, O-ring used for injector etc .; Exhalation system manifold, fuel filter, pressure control valve, canister, cap of fuel tank, fuel pump, fuel tank, sender unit of fuel tank, fuel Used for injectors, 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 (evaporo) 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 for fuel filters, fuel line connector systems, etc. Flange gaskets used in castings, carburetors, etc .; Line materials such as steam recovery lines, fuel feed lines, vapor / ORVR lines, etc. Canisters, ORVRs, fuel pumps, fuel tank pressure sensors, gasoline pumps, carburetor sensors, combined air control Equipment (CAC), pulsation dampers, diaphragms for canisters, autococks, etc., pressure regulator diaphragms of fuel injection devices; valves for fuel pumps, carburetor needle valves, roll over check valves, check valves, etc .; Breather), tube used in fuel tank; tank packing such as fuel tank, packing of acceleration pump piston of carburetor, fuel sender anti-vibration parts for fuel tank O-rings and diaphragms to control fuel pressure; accelerator pump cups; in-tank fuel pump mounts; injector cushion rings for fuel injectors; injector seal rings; carburetor needle valve core valves; carburetor acceleration pumps Piston; valve seat of complex air control device (CAC); fuel tank main body; seal part for solenoid valve etc.

As a concrete usage form in the above-mentioned brake system, a diaphragm used for a master back, a hydraulic brake hose air brake, a brake chamber of an air brake, etc .; a hose used for a brake hose, a brake oil hose, a vacuum brake hose etc .; Various sealing materials such as O-rings, packings, brake piston seals, etc .; Atmospheric valves and vacuum valves for master back; check valves for brake valves; piston cups (rubber cups) for master cylinder; brake cups; hydraulic brakes Master cylinders and vacuum boosters, boots for hydraulic brake wheel cylinders, O-rings and grommets for antilock brake systems (ABS).

Specific examples of use of the basic electrical component include an insulator or sheath of a wire (harness), a tube of a harness external component, a grommet for a connector, and the like.
Specific examples of usage in control system electrical components include coating materials for various sensor wires.
As specific usages of the above-mentioned electric parts, O-rings of car air conditioners, packings, cooler hoses, high pressure air conditioner hoses, air conditioner hoses, gaskets for electronic throttle units, plug boots for direct ignition, diaphragms for distributors, etc. Can be mentioned. It can also be used to bond electrical components.

As specific usage modes in the above intake and exhaust systems, packings used for intake manifolds, exhaust manifolds, etc., throttle body packings for throttles; EGR (exhaust gas recirculation), pressure control (BPT), waist gate, turbo waist Gates, actuators, diaphragms used in variable turbine geometry (VTG) turbo actuators, exhaust purification valves, etc .; EGR (exhaust gas recirculation) control hoses, emission control hoses, turbocharger turbo oil hose (supply), turbo Hose connected with oil hose (return), turbo air hose, intercooler hose, turbocharger hose, turbo engine compressor with intercooler, exhaust Hoses such as air hoses, air intake hoses, turbo hoses, DPF (diesel particulate collection filter) sensor hoses; air ducts and turbo air ducts; intake manifold gaskets; EGR sealing materials, AB valve afterburn preventing valve seats, (turbochargers, etc. ) Turbine shaft seals and seal members used for groove parts such as rocker covers and air intake manifolds used in automobile engines.

In addition, in exhaust gas control parts, seals used for steam recovery canisters, catalytic converters, exhaust gas sensors, oxygen sensors, etc., seals of steam recovery and steam canister solenoid armatures; used as intake manifold gaskets etc. Can.
Further, in parts relating 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, EGR, a priming pump, a diaphragm of a boost compensator, and the like. In addition, it can be used for O-rings, sealing materials, hoses, tubes, diaphragms, gaskets, pipes used in urea SCR systems, pipes for urea SCR systems, and sealing materials for urea aqueous tanks. .

Specific use modes in the transmission system include transmission-related bearing seals, oil seals, O-rings, packings, torque converter hoses and the like.
A mission oil seal, a transmission oil hose of AT, an ATF hose, an O-ring, packings, etc. are also mentioned.
The transmissions include AT (automatic transmission), MT (manual transmission), CVT (continuously variable transmission), DCT (dual clutch transmission) and the like.
In addition, oil seals for manual or automatic transmissions, gaskets, O-rings, packings, oil seals for continuously variable transmissions (belt type or toroidal type), gaskets, O-rings, packings, ATF linear solenoids Packings, oil hoses for manual transmissions, ATF hoses for automatic transmissions, and CVTF hoses for continuously variable transmissions (belt type or toroidal type).
As a specific use form in a steering system, a power steering oil hose, a high pressure power steering hose, etc. are mentioned.

As a form used in an engine body of an automobile engine, for example, cylinder head gasket, cylinder head cover gasket, oil pan packing, gasket such as general gasket, O-ring, packing, seal such as timing belt cover gasket, control hose etc. Hoses, anti-vibration rubbers for engine mounts, control valve diaphragms, camshaft oil seals, etc. may be mentioned.
In the main motion system of an automobile engine, it can be used for shaft seals such as crankshaft seals and camshaft seals.
In a valve system of an automobile engine, it can be used as a valve stem oil seal of an engine valve, a valve seat of a butterfly valve or the like.
In automobile 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, etc. In addition to vacuum pump oil hoses, it can be used for radiator hoses, radiator tanks, diaphragms for oil pressure, fan coupling seals, etc.

Thus, as an example of a specific example of use in the automotive field, engine head gaskets, oil pan gaskets, manifold packings, seals for oxygen sensors, oxygen sensor bushes, seals for nitrogen oxide (NOx) sensors, nitrogen oxide (NOx) Sensor bush, seal for sulfur oxide sensor, seal for temperature sensor, temperature sensor bush, seal for diesel particle filter sensor, diesel particle filter sensor bush, injector O-ring, injector packing, fuel pump O-ring or diaphragm, gearbox Seal, power piston packing, cylinder liner seal, valve stem seal, static valve stem seal, dynamic valve stem seal, automatic Speed pump front pump seal, rear axle and pinion seal, universal joint gasket, speedometer pinion seal, foot brake piston cup, torque transmission O-ring and oil seal, exhaust gas reburner seal and bearing seal, Hose for re-combustion device, sensor diaphragm for carburetor, anti-vibration rubber (engine mount, exhaust part, muffler hanger, suspension bush, center bearing, strut bumper rubber, etc.), anti-vibration rubber for suspension (strut mount, bush etc.), Drive system anti-vibration rubber (damper etc.), fuel hose, EGR tube and hose, twin cab tube, needle valve core valve of carburetor, flange gasket of carburetor, oil hose Oil cooler hose, ATF hose, cylinder head gasket, water pump seal, gearbox seal, needle valve tip, reed valve lead for motorcycle, oil seal for automobile engine, seal for gasoline hose gun, seal for car air conditioner, engine intercooler Rubber hoses, seals of fuel line connector systems, CAC valves, needle tips, engine cables, 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 Rufiller cap, PS rack seal, rack & pinion boots, CVJ boots, 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, rubber parts for DME, diaphragms and boots for auto tensioners , Idle speed control diaphragm and valve, auto speed control actuator, negative pressure pump diaphragm and 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 device 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 coatings, caliper seals, Examples thereof include boots, wheel bearing seals, and bladders used for vulcanization molding of tires.

In the above-mentioned aircraft field, space / rocket field, and ship field, it can be used particularly for a fuel system and a lubricating oil system.
In the above-mentioned aircraft field, for example, various seal parts for aircraft, various parts for aircraft for engine oil application, jet engine valve stem seals, gaskets, O-rings, rotating shaft seals, gaskets for hydraulic equipment, firewall seals It can be used as a fuel supply hose, a gasket, an O-ring, an aircraft cable, an oil seal, a shaft seal or the like.

In the space and rocket field, for example, lip seals for spacecraft, jet engines, missiles etc., diaphragms, O-rings, O-rings for oil resistant to gas turbine engines, vibration isolation pads for missile ground control etc. It can be used.
In the marine field, for example, propeller shaft stern seals for screws, valve stem seals for intake and exhaust of diesel engines, valve seals for butterfly valves, valve seats and shaft seals for butterfly valves, shaft seals for butterfly valves, stern tube seals And fuel hoses, gaskets, O-rings for engines, cables for ships, oil seals for ships, shaft seals for ships and the like.

In the chemical products field such as the above-mentioned chemical plant etc., and in the pharmaceutical fields such as pharmaceuticals, it is used in the process where high chemical resistance is required, for example, the process of producing chemical products such as pharmaceuticals, agricultural chemicals, paints, resins etc Can.
Specific modes of use in the above-mentioned chemical products field and chemical field include chemical devices, chemical pumps and flow meters, chemical pipes, heat exchangers, agrochemical sprayers, agrochemical transfer pumps, gas pipes, fuel cells, Seals used in analytical equipment and physicochemical equipment (for example, columns and fittings of analytical equipment and instruments, etc.), shrink joints of exhaust gas desulfurization equipment, nitric acid plants, power plant turbines, etc., seals used in medical sterilization processes, Seals for plating solutions, Coro seals for belts for papermaking, joint seals for wind tunnels; Chemical devices such as reactors and stirrers, O-rings used in analytical instruments and instruments, chemical pumps, pump housings, valves, tachometers, etc. Mechanical seal O-rings, O-rings for compressor sealing; High temperature vacuum dryer, gas chromatography or p Packings used for tube joints of meters, glass cooler packings for sulfuric acid production equipment; Diaphragm pumps, diaphragms used for analytical instruments and physicochemical instruments etc. Gaskets used for analytical instruments and instruments; Analytical instruments and instruments Valve rings; U-cups; linings used in chemical equipment, gasoline tanks, wind tunnels, etc .; corrosion resistant linings for anodizing tanks; coatings for plating jigs; valves for analytical and physicochemical equipment Parts; Expansion joints of exhaust gas desulfurization plant; Acid resistant hose to concentrated sulfuric acid etc., chlorine gas transfer hose, oil resistant hose, rainwater drain hose for benzene and toluene storage tank; Chemical resistant tube used for analytical equipment and physicochemical equipment etc. Medical tubing; anti-trik 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 field of photography such as developing machines and the like, the field of printing such as printing machines, and the field of painting such as coating equipment, it can be used as rolls, belts, seals and valve parts of dry copiers.
As specific usage forms in the above-mentioned photography field, printing field and painting field, surface layer of transfer roll of copying machine, cleaning blade of copying machine, belt of copying machine; for OA equipment such as copying machine, printer, facsimile etc. Rolls (for example, fixing rolls, pressure rolls, pressure rolls, etc.), belts; rolls of PPC copying machines, roll blades, belts; rolls of film developing machines, rolls of X-ray film developing machines; printing rolls of printing machines , Scrapers, tubes, valve parts, belts; printer ink tubes, rolls, belts; coating, painting equipment paint rolls, scrapers, tubes, valve parts; developing rolls, gravure rolls, guide rolls, magnetic tape production coating line Guide Roll, Gravure Roll for Magnetic Tape Production Coating Line, Coating Row And the like.

In the field of food equipment including the above-mentioned food plant equipment and household products, it can be used for food production processes, food transporters or food reservoirs.
As specific usage modes in the above food equipment field, seal of plate type heat exchanger, solenoid valve seal of vending machine, packing of jar pot, sanitary pipe packing, packing of pressure cooker, water heater seal, heat exchange Gaskets for food processing equipment, diaphragms and packings for food processing equipment, rubber materials for food processing equipment (eg heat exchanger gaskets, various seals such as diaphragms and O-rings, piping, hoses, sanitary packings, valve packings, etc. And packings used as a joint between the mouth of the bottle and the filler. In addition, packings, gaskets, tubes, diaphragms, hoses, joint sleeves, and the like used in products such as liquors and soft drinks, filling devices, food sterilization devices, brewing devices, brewing devices, water heaters, various automatic food vending machines, etc.

In the above-mentioned nuclear power plant equipment field, it can be used as a check valve or a pressure reducing valve around a nuclear reactor, a seal of a uranium hexafluoride enrichment apparatus, or the like.

Specific usage modes in the above-mentioned general industrial fields are sealing materials for hydraulic machines such as machine tools, construction machines, hydraulic machines, etc .; seals for hydraulic and lubricating machines and bearing seals; sealing materials used for mandrels etc; dry cleaning equipment Seals used for windows, etc .; Cyclotron seals and (vacuum) valve seals, seals of proton accelerators, seals of automatic packaging machines, diaphragms of pumps for sulfur dioxide and chlorine gas analyzers (pollution measuring instruments) in air, snakes Pump linings, rolls and belts of printing machines, conveyor belts (conveyor belts), squeeze rolls for pickling such as iron plates, cables for robots, solvent squeeze rolls such as aluminum rolling lines, coupler O-rings, acid-resistant cushioning materials , Dust seal and lip rubber of sliding part of cutting machine, garbage incinerator Basket, friction materials, metal or a surface modifier for rubbers, and the like dressing. In addition, gaskets and sealing materials for equipment used in papermaking processes, sealing agents for clean room filter units, sealing agents for construction, protective coatings such as 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 precoated 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.

As a specific usage form in the said steel field | area, the iron plate processing roll of an iron plate processing installation, etc. are mentioned.

Specific use forms in the above-mentioned electric field include insulating oil caps for Shinkansen, venting seals for liquid-filled transformers, transformer seals, oil well cable jackets, oven oven seals such as electric furnaces, microwave oven window frames Seals, sealing materials used when bonding CRT wedges and necks, sealing materials for halogen lamps, fixing agents for electrical parts, sealing materials for end treatment of sheathed heaters, insulation of lead wires for electrical equipment, and insulation treatment Sealing materials and the like. In addition, it should be used for covering materials such as oil resistant / heat resistant electric wire, high heat resistant electric wire, chemical resistant electric wire, high insulating electric wire, high voltage transmission line, cable, electric wire used for geothermal power generation equipment, electric wire used around automobile engine You can also. It can also be used as an oil seal or shaft seal of a cable for a vehicle. Furthermore, electrical insulating materials (eg, materials used for insulating spacers of various electric devices, insulating tapes used for cable joints or ends, heat-shrinkable tubes, etc.), electricity used in high temperature atmosphere, It can also be used for electronic device materials (for example, lead wire materials for motors, wire materials around high-temperature furnaces). Moreover, it can use also for the sealing layer and protective film (back sheet) of a solar cell.

In the above-mentioned fuel cell field, the sealing material between electrodes, between the electrode and the separator, and the seal or packing of piping such as hydrogen, oxygen, generated water, etc. in a polymer electrolyte fuel cell, a phosphate type fuel cell, etc. It can be used as etc.

In the above-mentioned electronic component field, it can be used as a heat sink material, an electromagnetic wave shield material, a gasket for a hard disk drive (magnetic recording device) of a computer, or the like. In addition, buffer rubber (crash stopper) of hard disk drive, binder of electrode active material of nickel hydrogen secondary battery, binder of active material of lithium ion battery, polymer electrolyte of lithium secondary battery, binder of positive electrode of alkaline storage battery, Binders for EL devices (electroluminescent devices), binders for electrode active materials of capacitors, sealants, sealing agents, quartz covering materials for optical fibers, films and sheets such as optical fiber covering materials, CMOS electronic circuits, transistors, integration Circuits, organic transistors, light emitting elements, actuators, memories, sensors, coils, capacitors, electronic components such as resistors, potting and coating of circuit boards and adhesive seals, fixing agents for electronic components, modifiers for sealants such as epoxy, Coating agent for printed circuit board, d Dexts of printed wiring board prepreg resin such as resin, shatterproof materials such as light bulbs, gaskets for computers, large computer cooling hoses, secondary batteries, especially gaskets for lithium secondary batteries, packings such as O-rings, organic EL It is also used as a sealing layer, a connector, a damper, etc. which cover one side or both sides of the outer surface of a structure.

In the above-mentioned field of chemical transport equipment, it can be used for safety valves and loading valves of trucks, trailers, tank lorries, ships and the like.

In the above-mentioned field of energy resource search and mining equipment parts such as oil and gas, it is used as various sealing materials used in mining of oil, natural gas and the like, boots of electrical connectors used in oil wells and the like.
As a specific usage form in the above-mentioned energy resource search and mining equipment parts field, it is used for a drill bit seal, a pressure control diaphragm, a seal of a horizontal drilling motor (stator), a stator bearing (shaft) seal, and a blowout prevention device (BOP) Seal material, seal material used for rotational blowout prevention device (pipe wiper), seal material used for MWD (real time drilling information detection system), air / liquid connector, logging used for logging equipment (logging equipment) Tool seals (eg, O-rings, seals, packings, gas-liquid connectors, boots, etc.), expansion type packers and completion packers, packers seals used therefor, seals, packings, and perforations used in cementing devices Used in Seals, seals and packings used in mud pumps, motor linings, underground hearing instrument covers, U-cups, composition seating cups, rotary seals, laminated elastic bearings, flow control seals, sand control seals, safety valves Seal, seal of hydraulic fracturing device (fracturing equipment), seal and packing of linear packer and linear hanger, seal and packing of well head, seal and packing of choke and valve, seal material for LWD (during drilling), Examples include diaphragms used in oil exploration and oil drilling applications (eg, diaphragms for lubricating oil supply such as oil drilling pits), gate valves, electronic boots, and sealing elements of drilling guns.

Seals for kitchens, bathrooms, washrooms, etc .; outdoor tent pulls; seals for seals; rubber hoses for gas heat pumps, fluorocarbon rubber hoses; films for agricultural use, linings, weatherproof covers, etc. It can also be used for tanks such as laminated steel plates used in

Furthermore, it is also possible to use as an article combined with a metal such as aluminum. Examples of such usage include a door seal, a gate valve, a pendulum valve, a tip of a solenoid, a piston seal or a diaphragm coupled to a metal, and a metal rubber component coupled to a metal such as a metal gasket.
In addition, it can be used for rubber parts in bicycles, brake shoes, brake pads and the like.

Further, the fluororubber molded article can be applied to a belt.
The following are illustrated as the said belt. Power transmission belts (including flat belts, V-belts, V-ribbed belts, toothed belts, etc.), transport belts (conveyor belts), various high-temperature parts such as agricultural machinery, machine tools, engines of industrial machines, etc. Conveyor belts for transporting loose materials and granular materials such as coal, crushed stone, earth and sand, ores, wood chips under high temperature environment; Conveyor belts used in steelworks such as blast furnaces; Precision Conveyor belts for applications exposed to high-temperature environments in equipment assembly plants, food plants, etc .; Agricultural machines, general equipment (eg, OA equipment, printing machines, industrial dryers, etc.), V-belts for automobiles, etc. V-ribbed belts; Transmission belts for transfer robots; Toothed belts such as food machines and transmission belts for machine tools; Used for automobiles, OA equipment, medical equipment, printing machines, etc. Such as a toothed belt to be like.
In particular, a timing belt is typical as a toothed belt for a motor vehicle.

The belt may have a single layer structure or a multilayer structure.
In the case of a multilayer structure, the belt may be composed of a layer obtained by crosslinking the composition and a layer composed of other materials.
In the belt of multilayer structure, layers made of other materials include layers made of other rubbers, layers made of thermoplastic resin, various fiber reinforced layers, canvas, metal foil layers and the like.

The fluorine rubber molded product can also be used for industrial vibration proofing pads, vibration proofing mats, railway slab mats, pads, vibration proofing rubbers for automobiles, and the like. As anti-vibration rubbers for automobiles, anti-vibration rubbers for engine mounts, motor mounts, member mounts, strut mounts, bushes, dampers, muffler hangers, center bearings, etc. may be mentioned.

In addition, as other usage forms, flexible joints, joint members such as expansion joints, boots, grommets and the like can be mentioned. If it is a ship field, a marine pump etc. will be mentioned, for example.
The joint member is a joint used for piping and piping equipment, prevents vibration and noise generated from piping system, absorption of expansion and displacement due to temperature change, pressure change, absorption of dimensional fluctuation, earthquake, ground settlement Used for applications such as mitigation and prevention of the effects of
Flexible joints and expansion joints are preferably used as complex shape moldings for shipbuilding piping, for mechanical piping such as pumps and compressors, for chemical plant piping, for electrical piping, for civil engineering / water piping, for automobiles, etc. it can.
Boots include, for example, constant velocity joint boots, dust covers, rack and pinion steering boots, pin boots, boots for automobiles such as piston boots, boots for agricultural machines, boots for industrial vehicles, boots for construction machines, boots for hydraulic machines, empty It can be preferably used as a complex-shaped molded product such as various industrial boots such as boots for pressure machines, boots for intensive lubricating machines, boots for liquid transfer, boots for fire fighting, and boots for transferring liquefied gas.

The fluororubber molded article can be used also for a filter press diaphragm, a blower diaphragm, a water supply diaphragm, a liquid storage tank diaphragm, a pressure switch diaphragm, an accumulator diaphragm, an air spring diaphragm such as a suspension, and the like.

By adding the above-mentioned fluororubber molded body to rubber or resin, an anti-slip agent can be obtained to obtain a molded article or a coating film which is not slippery in an environment wet with water such as rain, snow, ice and sweat.

Further, the fluororubber molded product is, for example, as a cushioning material for hot press molding when producing decorative plywood made of melamine resin, phenol resin, epoxy resin or the like, a printed circuit board, an electric insulating plate, a rigid polyvinyl chloride laminate, etc. Can also be used.

The fluororubber molded body can also contribute to the impermeability of various supports such as a weapon-related sealing gasket and a protective garment against contact with an invasive chemical agent.

In addition, lubricating oils (engine oils, mission oils, gear oils, etc.) containing amine additives (especially antioxidants, amine additives used as detergents and dispersants) used for transportation such as automobiles and ships. And O (corner) used to seal and seal fuel oil and grease (especially urea grease), V-ring, X-ring, packing, gasket, diaphragm, oil seal, bearing seal, lip seal 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., and valve bodies of tubes, hoses, various rubber rolls, coatings, belts, valves It can also be used as Moreover, it can also be used as a laminating material and a lining material.

Coating materials for heat and oil resistant electric wires used for lead wires of sensors that contact transmission oil and / or engine oil of internal combustion engines such as automobiles and detect the oil temperature and / or oil pressure, automatic transmissions and engines It is also possible to use in a high temperature oil atmosphere such as in an oil pan.

In addition, there may be a case where a vulcanized film is formed on the fluororubber molded body. Specifically, non-adhesive oil-resistant rolls for copiers, weather strips for anti-icing, rubber stoppers for infusion, vial rubber stoppers, mold release agents, non-adhesive light transfer belts, anti-adhesive coatings for pre-gaskets of automobile engine mounts, Applications include coating of synthetic fibers, bolted members or joints with thin packing layers.

The application of the fluororubber molded article to automobile-related parts also includes the application of parts of a motorcycle having a similar structure.
Further, as fuels in the above-mentioned automobile-related matters, there are diesel fuel, gasoline, fuel for diesel engine (including biodiesel fuel) and the like.

The fluororubber molded article can also be used as a rolling bearing seal member.

As said rolling bearing, a ball bearing, a roller bearing, a bearing unit, a linear bearing etc. are mentioned.

As a ball bearing, a radial ball bearing, a thrust ball bearing, a thrust angular contact ball bearing etc. are mentioned.

As said radial ball bearing, a deep groove ball bearing, an angular contact ball bearing, a four-point contact ball bearing, a self-aligning ball bearing etc. are mentioned.
The deep groove ball bearings are used, for example, in electric motors, home electric appliances, office automation equipment, and the like.
The above-mentioned angular contact ball bearings include single-row angular contact ball bearings, combined angular contact ball bearings, double-row angular contact ball bearings, etc. The single-row angular contact ball bearings are motors, household electrical appliances, OA equipment, etc. In addition, it is used for hydraulic pumps, vertical pumps, etc. to which an axial load is applied. The combination angular contact ball bearing is used as a main spindle, a grinding spindle, etc. of a machine tool that requires improvement in shaft rotational accuracy and rigidity improvement. Double-row angular contact ball bearings are used, for example, in electromagnetic clutches for automobile air conditioners.
The above-mentioned four-point contact ball bearing is used for a reduction gear or the like in which axial load from both directions is applied and the space of the bearing width can not be enlarged.
The above-described self-aligning ball bearing is used for a portion where alignment between the shaft and the housing is difficult, a transmission shaft in which the shaft is flexible, and the like.

The above thrust ball bearings include single type thrust ball bearings and double thrust ball bearings, which can be applied to conventionally known applications in which these ball bearings are used.
The above-described thrust angular contact ball bearing is used in combination with a double-row cylindrical roller bearing as an axial load receiver for a main shaft of a machine tool.

As said roller bearing, a radial roller bearing, a thrust roller bearing, etc. are mentioned.

Examples of the radial roller bearings include cylindrical roller bearings, needle roller bearings, tapered roller bearings, and self-aligning roller bearings.
The cylindrical roller bearing is used for a general machine, a machine tool, an electric motor, a reduction gear, a railway axle, an aircraft and the like.
Needle roller bearings are used in general machines, automobiles, motors and the like.
Tapered roller bearings are used in machine tools, automobile and railway axles, rolling machines, reduction gears, and the like.
Spherical roller bearings are used in general machines, rolling mills, paper machines, axles and the like.

The thrust roller bearings include thrust cylindrical roller bearings, thrust needle roller bearings, thrust tapered roller bearings, thrust self-aligning roller bearings and the like.
Thrust cylindrical roller bearings are used in machine tools, general machines and the like.
Thrust needle roller bearings are used in automobiles, pumps, general machines and the like.
Thrust tapered roller bearings are used in general machines, rolling mills and the like.
Thrust spherical roller bearings are used in cranes, extruders, general machines and the like.

Among the applications to which the above-mentioned fluororubber molded article is applied, it can be suitably used particularly for tubes and diaphragms from the viewpoint of low hardness, excellent flexibility, and excellent amine resistance.

〔Composition〕
The present invention is also a fluororubber molded article having a IRHD hardness of 50 or less according to JIS K6253-2: 2012 after crosslinking and having a volume change of 20% or less in an immersion test in diethanolamine at 120 ° C for 72 hours. A composition capable of obtaining
The composition has a glass transition temperature of 25 ° C. or less
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)
It relates to the composition containing the fluorine-containing copolymer which consists of a fluorine-containing monomer (1) represented by these.

It is possible to obtain a fluororubber molded article having an IRHD hardness of 50 or less according to JIS K6253-2: 2012 after crosslinking and having a volume change rate of 20% or less in an immersion test in diethanolamine at 120 ° C for 72 hours. The use of the above composition gives a fluororubber molded product having such physical properties, and as a result, it has low hardness and excellent flexibility, and is also excellent in amine resistance, and also obtains good mechanical properties. Can. Examples of the composition include those described above in the section of the fluororubber molded article, and the above-mentioned effects are exhibited.

The present invention further comprises (1) the fluorine-containing copolymer, the polyfunctional co-crosslinking agent, and the organic peroxide, and the polyfunctional co-crosslinking agent per 100 parts by mass of the fluorine-containing copolymer. 0.1 to 3 parts by mass, the above composition containing 0.3 to 3 parts by mass of the organic peroxide, (2) the fluorine-containing copolymer, the crosslinking agent, and the perfluoropolyether, and The composition containing 0.1 to 10 parts by mass of the perfluoropolyether with respect to 100 parts by mass of the fluorine-containing copolymer, (3) containing the fluorocopolymer, the crosslinking agent, and silicone oil And the composition containing 0.1 to 10 parts by mass of the silicone oil with respect to 100 parts by mass of the fluorine-containing copolymer.

By using these compositions, good amine resistance and mechanical properties can be obtained while imparting low hardness and excellent flexibility. The above compositions of (1) to (3) are as described above in the section of the fluororubber molded article, and thereby the above-described effects are exhibited.

The above composition can be used as various parts in various industrial fields in addition to being crosslinked and used as a molded article. Then, the use of the said composition is demonstrated next.
The above composition is a surface modifier such as metal, rubber, plastic, glass, etc .; a sealing material and a covering material such as a metal gasket and an oil seal which are required to have heat resistance, chemical resistance, oil resistance and non-adhesiveness; Non-adhesive coatings such as equipment rolls and belts for office automation equipment, or bleed barriers; can be used for impregnating woven sheets and belts, coating by baking, etc.
The above composition can be used as a sealing material, lining, sealant of complicated shape by high viscosity and high concentration by usual usage, and for formation of a thin film of several microns by lowering viscosity. It can be used, and it can be used for application of a precoat metal, O-ring, a diaphragm, and a reed valve by making it a medium viscosity.
Furthermore, it can be used for coating of transport rolls or belts for woven fabrics and paper sheets, belts for printing, chemical resistant tubes, stoppers, fuel hoses and the like.

The article substrate coated with the above composition includes metals such as iron, stainless steel, copper, aluminum, and brass; glass products such as glass plate, woven fabric and non-woven fabric of glass fiber; polypropylene, polyoxymethylene, polyimide, Molded articles and coatings of general-purpose and heat-resistant resins such as polyamideimide, polysulfone, polyether sulfone and polyetheretherketone; general-purpose rubbers such as SBR, butyl rubber, NBR and EPDM, and heat resistances such as silicone rubber and fluororubber Molded articles and coatings of rubber; woven and non-woven fabrics of natural fibers and synthetic fibers; and the like can be used.
The coating formed from the above composition can be used in the field where heat resistance, solvent resistance, lubricity and non-adhesiveness are required, and as a specific application, it is an OA device such as a copying machine, printer, facsimile etc. Rolls (for example, fixing rolls, pressure rolls) and conveying belts; sheets and belts; O-rings, diaphragms, chemical resistant tubes, fuel hoses, valve seals, gaskets for chemical plants, engine gaskets and the like.

The above composition can also be dissolved in a solvent and used as a paint or an adhesive. In addition, it can be used as a coating as an emulsified dispersion (latex).
The composition is a surface treatment agent for a structure comprising various devices, sealing materials such as piping, linings, metals, ceramics, glass, stone, concrete, plastics, rubber, wood, paper, inorganic materials such as paper, fibers, and organic substrates Used as etc.
The composition can be applied to a substrate or the like by dispenser coating or screen printing coating.

The above composition may be used as a coating composition to cast a film or to immerse a substrate such as a fabric, plastic, metal or elastomer.
In particular, the above composition is in the form of a latex, coated fabric, protective gloves, impregnated fiber, O-ring coating, fuel system quick connect O-ring coating, fuel system sealing coating, fuel tank roll over valve diaphragm coating , Used as a coating for fuel tank pressure sensor diaphragm, a coating for oil filter and fuel filter seal, a coating for fuel tank sender seal and sender head fitting seal, a coating for copier fuser roll, and a polymer paint composition May be
They are useful for the coating of silicone rubbers, nitrile rubbers, and other elastomers. They are also useful for the coating of parts made from such elastomers, for the purpose of enhancing both the permeation resistance and the chemical resistance of the substrate elastomer as well as its thermal stability. Other applications include heat exchangers, expansion joints, butts, tanks, fans, flue ducts and other conduits, and coatings for 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 method of manufacturing a hose structure and a diaphragm. Sealing members at joints and joints are often made of hard material and the above mentioned composition has an improved frictional interface, an enhanced dimensional interference fit with reduced traces of leakage along the sealing surface. provide. 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 connections where hoses and tubes are connected to other parts. A further utility of the above composition is in the repair of 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 plates that can be formed or embossed before or after the paint is applied. For example, multiple layers of coated steel can be assembled to make a gasket between two rigid metal members. The sealing effect is obtained by applying the composition between the layers. This process reduces the bolting force and strain of assembled parts while engine head gaskets and exhaust manifold gaskets for the purpose of providing good fuel savings and low emissions due to low cracking, deflection and hole strain Can be used to make

In addition, the composition may be coated on a substrate; an integrated substrate gasket formed by dispenser molding on a substrate containing an inorganic material such as metal or ceramic; packings; on a substrate containing an inorganic material such as metal or ceramic Can also be used as multi-layered products.

The composition is also suitable as a wiring material for light and bendable electronic devices, and can be used for known electronic components. Electronic components such as CMOS electronic circuits, transistors, integrated circuits, organic transistors, light emitting elements, actuators, memories, sensors, coils, capacitors, resistors, and the like can be given. By using this, it is possible to obtain flexible electronic devices such as solar cells, various displays, sensors, actuators, electronic artificial skin, sheet type scanners, Braille displays, wireless power transmission sheets and the like.

Among the application applications of the above-mentioned composition, from the viewpoint of low hardness and excellent amine resistance, it can be suitably used particularly for tubes and diaphragms.

Next, the present invention will be described by way of examples, but the present invention is not limited to only these examples.

Each numerical value of the example was measured by the following method.

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

<Glass transition temperature (Tg)>
After cooling to −75 ° C. using a differential scanning calorimeter (X-DSC 823e, manufactured by Hitachi Techno-Science Corporation), a 10 mg sample is heated at 20 ° C./min to obtain a DSC curve, and a second-order DSC curve The temperature at which the extension of the baseline before and after transition and the tangent at the inflection point of the DSC curve is taken as the glass transition temperature.

<Iodine content measurement>
12 mg of sample mixed with 5 mg of Na ₂ SO ₃ and 30 mg of mixed solution of Na ₂ CO ₃ and K ₂ CO ₃ mixed with 20 ml of pure water in a ratio of 1 to 1 (mass ratio) Medium, after burning in oxygen and leaving for 30 minutes, it can measure using Shimadzu 20A ion chromatograph. The calibration curve was measured using KI standard solution, one containing 0.5 ppm of iodine ion and one containing 1.0 ppm.

<Mooney viscosity>
Mooney viscosity was measured according to ASTM-D1646 and JIS K6300-1: 2013 (measurement temperature: 121 ° C. or 100 ° C., L-shaped rotor).

<Vulcanization characteristics>
Using the compositions obtained in Examples and Comparative Examples, the optimum vulcanization time (T90) was measured according to JIS K 6300-2: 2001 using RUBBER PROCESS ANALYLY ANALYZER RPA 2000 (manufactured by ALPHA TECHNOLOGIES) (temperature 170). ° C).

<Tensile strength and elongation at break>
Test speed 500 mm / min, dumbbell No. 6 shape according to JIS K6251: 2010, using Tylon RTG-1310 manufactured by A & D Co., Ltd., using molded articles having a thickness of 2 mm obtained in Examples and Comparative Examples. Tensile strength (Tb) and elongation at break (Eb) were measured under conditions of a test temperature of 23 ° C.

<Hardness (Type A Durometer)>
The hardness of 3 seconds of measurement time was measured with a type A durometer according to K6253-3: 2012 using what piled up three sheets of molded objects of thickness 2 mm obtained by an example and a comparative example with K6253-3: 2012.

<Hardness (IRHD)>
The hardness of the IRHDM method was measured in accordance with K6253-2: 2012 using the molded articles having a thickness of 2 mm obtained in Examples and Comparative Examples.

<Specific gravity (S.G.)>
The density was measured and determined in accordance with JIS K6268.

<Amine resistance test>
A test piece (30 × 30 × 2 (mm)) cut out from the molded body of 2 mm in thickness obtained in Examples and Comparative Examples was subjected to a soaking test at 120 ° C. for 72 hours using diethanolamine. The volume change rate (ΔV) after the immersion test was measured. ΔV is a rate of change in volume (representing the degree of swelling) after immersing the sample piece under predetermined conditions, and when the original volume of the sample piece is Vo and the volume after the test is V, ΔV ( %) = (V-Vo) / Vo * 100. Volume is calculated from the weight in air and the weight in water.

Releasability
The composition obtained in Examples and Comparative Examples was press-crosslinked at 170 ° C. for 10 minutes using a sheet mold of 120 mm × 150 mm × 2 mm thickness, and the release property when peeling the obtained crosslinked sheet from the mold Was rated in 5 steps.
5: Very good, the seat is lifted.
4: The sheet can be peeled off without resistance.
3: The corner portion of the sheet is hard to peel off, but the central portion can be easily peeled off.
2: It is possible to peel off the sheet, but it is totally sticky.
1: It can not be stuck and the sheet can not be removed.

Each material of Table 1 used by the Example and the comparative example is shown below.
(Fluorinated copolymer)
Fluorinated copolymer 1: Peroxide vulcanizable copolymer of vinylidene fluoride / 2,3,3,3-tetrafluoropropene = 77/23 (molar ratio) prepared by iodine transfer polymerization (121 ° C. Mooney viscosity ML _{1 + 10} : 60, glass transition temperature: -13 ° C, iodine content: 0.14% by mass)
Fluorine-containing copolymer 2: peroxide-vulcanizable copolymer of vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene = 50/30/20 (molar ratio) prepared by iodine transfer polymerization (Moony viscosity at 100 ° C. ML _{1 + 10} : 50, glass transition temperature: -6 ° C, iodine content: 0.23% by mass)
Fluorinated copolymer 3: Peroxide vulcanizable copolymer of vinylidene fluoride / tetrafluoroethylene / perfluoro (methyl vinyl ether) = 72/8/20 (molar ratio) prepared by iodine transfer polymerization (100 ° C. Mooney viscosity ML _{1 + 10} : 65, glass transition temperature: -31 ° C, iodine content: 0.30 mass%)

(Carbon black)
Carbon black: MT carbon (N ₂ SA = 8 m ² / g, DBP oil absorption = 43 ml / 100 g).

(Crosslinking agent)
Perhexa 25B-40 (trade name): 40% impregnation of inorganic powder with 2,5-dimethyl-2,5-di (t-butylperoxy) hexane 2,5-dimethyl-2,5-di (T-butylperoxy) hexane

(Crosslinking accelerator (Crosslinking assistant))
Tyck M60 (trade name): 60% impregnated with triallyl isocyanurate in diatomaceous earth triallyl isocyanurate

(Additive)
Perfluoropolyether: average molecular weight: 8,400, structural _{formula; F- (CF 2 CF 2 CF} 2 O) n -C 2 F 5 polyether Silicone oil kinematic viscosity 2000 mm ² / s (temperature 25 ° C.) Dimethylpolysiloxane liquid rubber 1: Daiel G-101 (manufactured by Daikin Industries, Ltd.)

Examples 1 to 4 and Comparative Examples 1 to 4
Each composition (crosslinkable composition) of the composition shown in Table 1 was prepared. Each composition was compounded in an amount as shown in Table 1 using an 8-inch oven roll and each fluorocopolymer and various additives, and mixed in a usual manner. The vulcanization properties of the resulting composition were investigated. The results are shown in Table 1.
Each composition was crosslinked (press crosslinking: 170 ° C. × 10 minutes) to obtain a molded body. The obtained molded product was used to evaluate tensile strength, elongation at break, hardness (type A durometer), hardness (IRHD), specific gravity, and amine resistance test. The results are shown in Table 1.
Moreover, mold release property was evaluated using each obtained composition. The results are shown in Table 1.

Claims (11)

It is a fluororubber molded article obtained by crosslinking a composition containing a fluorocopolymer,
The fluororubber molded article is characterized in that the hardness of IRHD in JIS K6253-2: 2012 is 50 or less, and the volume change rate in an immersion test in diethanolamine at 120 ° C. for 72 hours is 20% or less. Fluorine rubber moldings. The fluororubber molded article according to claim 1, wherein the composition further comprises a crosslinking agent. The fluorine-containing copolymer is peroxide-vulcanizable.
The composition contains 0.1 to 3.0 parts by mass of a polyfunctional co-crosslinking agent and 0.3 to 3.0 parts by mass of an organic peroxide with respect to 100 parts by mass of the fluorine-containing copolymer. Or the fluorine rubber molded object as described in 2. The fluororubber molded article according to any one of claims 1 to 3, wherein the composition contains 0.1 to 10 parts by mass of perfluoropolyether with respect to 100 parts by mass of the fluorine-containing copolymer. The fluororubber molded article according to any one of claims 1 to 4, wherein the composition contains 0.1 to 10 parts by mass of silicone oil with respect to 100 parts by mass of the fluorocopolymer. The fluorine-containing copolymer has a glass transition temperature of 25 ° C. or less
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)
The fluororubber molded article according to any one of claims 1 to 5, which is a copolymer comprising the fluorine-containing monomer (1) represented by The fluorine-containing polymer 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)
And a copolymer comprising the fluorine-containing monomer (1) represented by and other monomers copolymerizable therewith, wherein the molar ratio of vinylidene fluoride unit / fluorine-containing monomer (1) unit is The fluororubber molded article according to claim 6, which is 85/15 to 20/80, and the other monomer units are 0 to 50 mol% of the total monomer units. It is possible to obtain a fluororubber molded article having an IRHD hardness of 50 or less according to JIS K6253-2: 2012 after crosslinking and having a volume change rate of 20% or less in an immersion test in diethanolamine at 120 ° C for 72 hours. Composition, and
The composition has a glass transition temperature of 25 ° C. or less
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)
The composition containing the fluorine-containing copolymer which consists of a fluorine-containing monomer (1) represented by these. The composition according to claim 8, which contains 0.1 to 6.0 parts by mass of the polyfunctional co-crosslinking agent and 0.3 to 5.0 parts by mass of the organic peroxide based on 100 parts by mass of the fluorine-containing copolymer. object. A composition comprising a fluorine-containing copolymer, a crosslinking agent and a perfluoropolyether,
The fluorine-containing copolymer has a glass transition temperature of 25 ° C. or less
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 comprising the fluorine-containing monomer (1) represented by
The composition containing 0.1-10 mass parts of said perfluoropolyethers with respect to 100 mass parts of said fluorine-containing copolymers. A composition comprising a fluorine-containing copolymer, a crosslinking agent and a silicone oil,
The fluorine-containing copolymer has a glass transition temperature of 25 ° C. or less
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 comprising the fluorine-containing monomer (1) represented by
The composition containing 0.1-10 mass parts of said silicone oils with respect to 100 mass parts of said fluorine-containing copolymers.