Novel compounds, crosslinking aids, and fluorine-containing polymer compositions

Abstract

To provide novel compounds and novel crosslinking aids. [Solution] General formula: (CH2=CH-CH2)2N-C6H3(R 11 )-Z 11 -C6H3(R 12 )-N(CH2-CH=CH2)2(wherein C6H3 is a benzene ring, R 11 and R 12 These are independently C1 alkyl halogenated compounds, Z 11 The linking group is either a single bond or a divalent linking group. Any hydrogen atom bonded to the benzene ring may be substituted with any substituent. The present invention provides compounds represented by ).

Description

[Technical Field]

[0001] This disclosure relates to novel compounds, crosslinking aids, and fluorine-containing polymer compositions. [Background technology]

[0002] Patent Document 1 contains: a. A fluorinated elastomer gum containing at least 0.05% by weight of cured portions, wherein the cured portions contain at least one of bromine, iodine, nitrile, or a combination thereof, b. A compound of formula I or a salt thereof, wherein formula I is (CH2=CHCH2)2-L 1 -Rf-L 2 -(CH2CH=CH2) n (H) 2-n [In the formula, L 1 is -NSO2- or -NCO-, L 2 A coagent or salt thereof, where n is -SO2N- or -CON-, n is 1 or 2, and Rf is a divalent perfluorocarbon group containing at least one ether bond, A composition containing the following is described. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Special Publication No. 2021-505729 [Overview of the project] [Problems that the invention aims to solve]

[0004] This disclosure aims to provide novel compounds and novel crosslinking aids. [Means for solving the problem]

[0005] According to the present disclosure, a compound represented by general formula (11) is provided. General formula (11):

Chemical formula

Advantages of the Invention

[0006] According to the present disclosure, a novel compound and a novel crosslinking aid can be provided.

Modes for Carrying Out the Invention

[0007] Hereinafter, specific embodiments of the present disclosure will be described in detail, but the present disclosure is not limited to the following embodiments.

[0008] 1. Compound The compound of the present disclosure is a novel compound represented by general formula (11). General formula (11):

Chemical formula

[0009] In the formula, R 11 and R 12 are each independently a halogenated alkyl group having 1 carbon atom. As the halogenated alkyl group having 1 carbon atom, a trifluoromethyl group (-CF3) is preferable. In one embodiment, R 11 and R 12 are both -CF3.

[0010] In the formula, Z 11 Z is a single bond or a divalent linking group. 11 Preferred members include single bonds, -SO2-, -O-, -CO-, alkylene groups having 1 to 3 carbon atoms, or halogenated alkylene groups having 1 to 3 carbon atoms.

[0011] Z 11 Examples of alkylene groups with 1 to 3 carbon atoms include the methylene group (-CH2-), ethylene group, propylene group, and isopropylidene group. 11 As the halogenated alkylene group having 1 to 3 carbon atoms, a fluorinated alkylene group having 1 to 3 carbon atoms is preferred, and a perfluoroalkylene group having 1 to 3 carbon atoms is more preferred, such as -(CF2)2-, -(CF2)-, -(CF2)3-, and -C(CF3)2-.

[0012] Z 11 More preferably, a single bond or a halogenated alkylene group having 1 to 3 carbon atoms is preferred, a single bond or a fluorinated alkylene group having 1 to 3 carbon atoms is even more preferred, and a single bond or -C(CF3)2- is even more preferred.

[0013] In the formula, the hydrogen atom bonded to the benzene ring may be substituted with any substituent. Preferred substituents are C1-C3 alkyl groups or C1-C3 halogenated alkyl groups. In one embodiment, the hydrogen atom bonded to the benzene ring is R 11 and R 12 It is not substituted by any other substituent.

[0014] In one embodiment, the compound of the present disclosure is represented by general formula (11a). General formula (11a): [ka] (In the formula, R 11 , R 12 and Z 11 (As stated above.)

[0015] In general formula (11a), the hydrogen atom bonded to the benzene ring may be substituted with any substituent. Preferred substituents are C1-C3 alkyl groups or C1-C3 alkyl halides. In one embodiment, the hydrogen atom bonded to the benzene ring is not substituted with any substituent.

[0016] In one embodiment, the compound of the present disclosure is represented by formula (12). Formula (12): [ka] (In the formula, the hydrogen atoms bonded to the benzene ring are not substituted by any substituents.)

[0017] The compounds disclosed herein are General formula (11b): [ka] (In the formula, R 11 , R 12 and Z 11 As stated above, the compound shown in ) and General formula (11c): CH2=CH-CH2-X 11 (In the formula, X 11 is a halogen atom. ) and the compound represented by , It can be manufactured by reacting them.

[0018] The above reaction can be carried out in the presence of a base. Examples of bases include alkali metal carbonates such as lithium carbonate, potassium carbonate, and sodium carbonate; and alkali metal hydroxides such as potassium hydroxide and sodium hydroxide.

[0019] The above reaction can be carried out in a solvent. Examples of solvents include aprotic polar solvents such as acetonitrile and acetone.

[0020] The temperature of the above reaction is preferably 40 to 120°C, more preferably 60°C or higher, even more preferably 80°C or higher, and more preferably 110°C or lower.

[0021] The reaction time described above is preferably 1 to 24 hours.

[0022] 2. Crosslinking agent Conventionally, when crosslinking fluorine-containing elastomers by peroxide crosslinking, a technique using crosslinking aids is known. A typical compound used as a crosslinking aid is triallyl isocyanurate (TAIC).

[0023] However, there is a need for a novel crosslinking aid that can produce molded products with even better heat resistance than those obtained by crosslinking fluorine-containing elastomers using triallyl isocyanurate (TAIC).

[0024] The crosslinking aid of this disclosure is a crosslinking aid represented by general formula (21). General formula (21): [ka] (In the formula, Z 21 x is an independent 2-3 valent linking group, x is an independent integer between 1 and 2, and y is an integer between 1 and 2. The hydrogen atoms bonded to the benzene ring may be substituted with any substituent.

[0025] Since the crosslinking aid of this disclosure has the above-described structure, it can be suitably used as a crosslinking aid when crosslinking a fluorine-containing elastomer by peroxide crosslinking. By using the crosslinking aid of this disclosure, it is possible to obtain a molded product with superior heat resistance compared to a molded product obtained by crosslinking a fluorine-containing elastomer by peroxide crosslinking using triallyl isocyanurate (TAIC).

[0026] In the formula, x is Z 21This indicates the number of groups represented by -N-(CH2-CH=CH2)2 that are bonded together. x is an independent integer between 1 and 2, preferably an independent integer of 1.

[0027] In the formula, y is -Z bonded to the benzene ring. 21 This indicates the number of groups represented by -N-(CH2-CH=CH2)2. y is an integer between 1 and 2, preferably 1.

[0028] In the formula, the hydrogen atom bonded to the benzene ring may be substituted with any substituent. Preferred substituents are C1-C3 alkyl groups or C1-C3 halogenated alkyl groups.

[0029] In the formula, Z 21 Z is a linking group that connects a benzene ring to a group represented by -N-(CH2-CH=CH2)2, and has a valency corresponding to the number of x. 21 These are independently divalent to trivalent linking groups, and preferably independently divalent linking groups.

[0030] Z 21 Examples include single bonds; -SO2-; -O-; -CO-; alkylene groups having 1 to 3 carbon atoms; halogenated alkylene groups having 1 to 3 carbon atoms; divalent to trivalent groups having 2 to 50 carbon atoms, which may contain -SO2-, -O-, or -CO- between carbon atoms; and so on. The crosslinking aid is Z 21 When a molecule has linking groups other than single bonds, it has the advantages of becoming more flexible, having a lower melting point, and improving dispersibility.

[0031] Z 21 Preferably, a single bond, [ka] (In the formula, Z 23 is a divalent linking group. The hydrogen atom bonded to the benzene ring may be substituted with any substituent. ) The group represented by [ka] (In the formula, Z 23 is a divalent linking group. X is independently -CH- or -N=. The hydrogen atom bonded to the benzene ring may be substituted with any substituent. ) The group represented by [ka] (In the formula, Z 23 is a divalent linking group. X is independently -CH- or -N=. The hydrogen atom bonded to the benzene ring may be substituted with any substituent. ) The group represented by That is the case.

[0032] In the formula, Z 23 Z is a divalent linking group that attaches to the benzene ring described in general formula (21). 23 Preferably, the crosslinking aid is Z 23 When a molecule has linking groups other than single bonds, it has the advantages of becoming more flexible, having a lower melting point, and improving dispersibility.

[0033] Z 23 Examples of alkylene groups with 1 to 3 carbon atoms include the methylene group (-CH2-), ethylene group, propylene group, and isopropylidene group. 23 As the C1-C3 halogenated alkylene group, a C1-C3 fluorinated alkylene group is preferred, and a C1-C3 perfluoroalkylene group is preferred, such as -(CF2)2-, -(CF2)-, -(CF2)3-, and -C(CF3)2-.

[0034] Z 23 The preferred structures are single bonds, -O-, -CH2-, or -C(CF3)2-.

[0035] In the formula, the hydrogen atom bonded to the benzene ring may be substituted with any substituent. A C1-C3 alkyl group is preferred as the substituent.

[0036] The crosslinking aids of this disclosure are preferably compounds represented by general formula (22), general formula (23), or general formula (24).

[0037] General formula (22): [ka] (In the formula, the hydrogen atom bonded to the benzene ring may be substituted with any substituent.)

[0038] General formula (23): [ka] (In the formula, Z 23 This is a divalent linking group. The hydrogen atoms bonded to the benzene ring may be substituted with any substituent.

[0039] Z in general formula (23) 23 Regarding Z in general formula (21), 21 Z is included in the preferred group 23 It is similar to that.

[0040] General formula (24): [ka] (wherein n is 1 or 2; X is independently -CH- or -N=; hydrogen atoms bonded to the benzene ring and nitrogen-containing six-membered ring may be substituted with any substituent.)

[0041] In general formula (24), it is preferable that all three X are -CH- or all are -N=. Examples of compounds represented by general formula (24) include compounds represented by general formula (24a) and compounds represented by general formula (24b).

[0042] General formula (24a): [ka] (wherein n is 1 or 2. The hydrogen atoms bonded to the benzene ring may be substituted with any substituent.)

[0043] General formula (24b): [ka] (wherein n is 1 or 2. Hydrogen atoms bonded to the benzene ring and triazine ring may be substituted with any substituent.)

[0044] In each formula, the hydrogen atoms bonded to the benzene ring, the nitrogen-containing six-membered ring, and the triazine ring may be substituted with any substituent. Preferred substituents are C1-C3 alkyl groups or C1 halogenated alkyl groups.

[0045] In each formula, it is preferable that at least one of the two carbon atoms located in the ortho position of the benzene ring to which the group represented by -N(CH2-CH=CH2)2 is attached does not have any substituents attached. When using a crosslinking aid having such a configuration, the crosslinking reaction tends to proceed more smoothly compared to when using a crosslinking aid to which substituents are attached to both carbon atoms located in the ortho position of the benzene ring.

[0046] As the crosslinking aid of this disclosure, compounds represented by general formula (23a) are more preferred. General formula (23a): [ka] (In the formula, R 23 and R 24 These independently consist of a hydrogen atom, a C1-C3 alkyl group, or a C1-C1 halogenated alkyl group. Z 23a These are single bonds, -SO2-, -O-, -CO-, alkylene groups with 1 to 3 carbon atoms, or halogenated alkylene groups with 1 to 3 carbon atoms. R 23 and R 24Except for the hydrogen atoms substituted by the substituents, the hydrogen atoms bonded to the benzene ring are not substituted by any substituents.

[0047] In the formula, R 23 and R 24 These are independently a hydrogen atom, a C1-C3 alkyl group, or a C1 C1 halogenated alkyl group.

[0048] A methyl group (-CH3) is preferred as the alkyl group having 1 to 3 carbon atoms. A trifluoromethyl group (-CF3) is preferred as the alkyl halogenated group having 1 carbon atom.

[0049] R 23 and R 24 Preferably, the hydrogen atom, a C1-C3 alkyl group, or a C1 fluorinated alkyl group is preferred, and a hydrogen atom, a methyl group (-CH3), or a trifluoromethyl group (-CF3) is more preferred. Also, R 23 and R 24 Hydrogen atoms or -CF3 are preferred as the element.

[0050] In the formula, Z 23a These are single bonds, -SO2-, -O-, -CO-, alkylene groups with 1 to 3 carbon atoms, or halogenated alkylene groups with 1 to 3 carbon atoms.

[0051] Z 23a Examples of alkylene groups with 1 to 3 carbon atoms include the methylene group (-CH2-), ethylene group, propylene group, and isopropylidene group. 23a As the halogenated alkylene group having 1 to 3 carbon atoms, a fluorinated alkylene group having 1 to 3 carbon atoms is preferred, and a perfluoroalkylene group having 1 to 3 carbon atoms is more preferred, such as -(CF2)2-, -(CF2)-, -(CF2)3-, and -C(CF3)2-.

[0052] Z 23a As for the bond, a single bond, -O-, -CH2-, or -C(CF3)2- is preferred. Also, Z 23a As such, a single bond or -C(CF3)2- is more preferred.

[0053] Also, R 23 , R 24 and Z 23a It is also preferable that at least one of the components contains one or more fluorine atoms. Using a crosslinking aid having such a configuration tends to yield molded articles with even better heat resistance. The crosslinking aid contains R 23 , R 24 and Z 23a As such, by having a fluorine atom or a functional group containing a fluorine atom, for example, when a crosslinking aid is mixed with a fluorine-containing polymer, the affinity between the crosslinking aid and the fluorine-containing polymer is improved, which has the advantage of making mixing easier. Also, if the crosslinking aid is R 23 , R 24 and Z 23a For example, by having a fluorine atom or a functional group containing a fluorine atom, when a molded article is produced by crosslinking a composition containing a crosslinking aid and a fluorine-containing polymer, the electron density of the benzene ring introduced into the crosslinked structure of the molded article decreases, and the oxidation resistance of the molded article is improved. In one embodiment, R 23 and R 24 is a fluorinated alkyl group having 1 carbon atom, such as -CF3, and Z 23a These are single bonds, -SO2-, -O-, -CO-, or alkylene groups with 1 to 3 carbon atoms. In one embodiment, R 23 and R 24 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Z 23a These are fluorinated alkylene groups with 1 to 3 carbon atoms, such as -C(CF3)2-.

[0054] In one embodiment, the crosslinking aid is compound (O-1), compound (O-2), compound (O-6), compound (O-7), compound (O-8), compound (O-9), or compound (O-10). The chemical formulas of these compounds are as described in the examples. Among these crosslinking aids, compound (O-1), compound (O-2), compound (O-6), compound (O-7), compound (O-8), or compound (O-9) are preferred, and compound (O-2) or compound (O-9) are more preferred, as these yield molded articles exhibiting even better heat resistance.

[0055] 3. Composition Furthermore, this disclosure provides compositions containing the above-mentioned crosslinking aid and fluorine-containing polymer.

[0056] The amount of crosslinking aid in the composition is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1.0 part by mass or more, per 100 parts by mass of fluorine-containing polymer, in order to improve the sealing properties of the molded product. Furthermore, the amount of crosslinking aid in the composition is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of fluorine-containing polymer, in order to improve the mechanical properties of the molded product.

[0057] As a fluorine-containing polymer, fluorine-containing elastomers are preferred because they have excellent sealing properties, chemical resistance, and heat resistance.

[0058] In this disclosure, "fluorine-containing elastomer" refers to an amorphous fluorine-containing polymer. "Amorphous" means that the magnitude of the melting peak (ΔH) observed in differential scanning calorimetry (DSC) (heating rate 10°C / min) or differential thermal analysis (DTA) (heating rate 10°C / min) of the fluorine-containing polymer is 4.5 J / g or less. Fluorine-containing elastomers exhibit elastomer properties by crosslinking. Elastomer properties refer to the ability of a polymer to be stretched and to retain its original length when the force required to stretch the polymer is no longer applied.

[0059] The fluorine-containing elastomer may be a partially fluorinated elastomer or a perfluoroelastomer, but it is preferable to use a perfluoroelastomer because it has even better chemical resistance and heat resistance.

[0060] In this disclosure, a partially fluorinated elastomer is a fluorinated polymer containing fluoromonomer units, having a perfluoromonomer unit content of less than 90 mol% relative to the total monomer units, having a glass transition temperature of 20°C or lower, and having a melting peak (ΔH) magnitude of 4.5 J / g or lower.

[0061] In this disclosure, a perfluoroelastomer is a fluorine-containing polymer having a perfluoromonomer unit content of 90 mol% or more, preferably 91 mol% or more, relative to the total monomer units, having a glass transition temperature of 20°C or less, and having a melting peak (ΔH) of 4.5 J / g or less, and further having a fluorine atom concentration of 71% by mass or more, preferably 71.5% by mass or more. In this disclosure, the concentration of fluorine atoms contained in the fluorine-containing polymer is calculated from the types and content of each monomer constituting the fluorine-containing polymer.

[0062] In this disclosure, a perfluoromonomer is a monomer that does not contain carbon-hydrogen atom bonds in its molecule. The perfluoromonomer may be a monomer in which some of the fluorine atoms bonded to the carbon atoms are replaced with chlorine atoms, or it may have nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus atoms, boron atoms, or silicon atoms in addition to carbon atoms. Preferably, the perfluoromonomer is a monomer in which all hydrogen atoms are replaced with fluorine atoms. The perfluoromonomer does not contain monomers that provide crosslinking sites.

[0063] Examples of the partially fluorinated elastomers mentioned above include vinylidene fluoride (VdF)-based fluororubber, tetrafluoroethylene (TFE) / propylene (Pr)-based fluororubber, tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF)-based fluororubber, ethylene / hexafluoropropylene (HFP)-based fluororubber, ethylene / hexafluoropropylene (HFP) / vinylidene fluoride (VdF)-based fluororubber, and ethylene / hexafluoropropylene (HFP) / tetrafluoroethylene (TFE)-based fluororubber. Among these, it is preferable that at least one is selected from the group consisting of vinylidene fluoride-based fluororubber and tetrafluoroethylene / propylene-based fluororubber.

[0064] The above vinylidene fluoride-based fluororubber is preferably a copolymer consisting of 45 to 85 mol% vinylidene fluoride and 55 to 15 mol% of at least one other monomer copolymerizable with vinylidene fluoride. Preferably, it is a copolymer consisting of 50 to 80 mol% vinylidene fluoride and 50 to 20 mol% of at least one other monomer copolymerizable with vinylidene fluoride.

[0065] In this disclosure, the content of each monomer constituting the fluorine-containing polymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis depending on the type of monomer.

[0066] Other monomers copolymerizable with the above vinylidene fluoride include TFE, HFP, fluoroalkyl vinyl ether, chlorotrifluoroethylene (CTFE), trifluoroethylene, trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinyl fluoride, and general formula (1): CH2=CFRf 1 (In the formula, Rf 1 Fluoromers represented by a straight-chain or branched fluoroalkyl group having 1 to 12 carbon atoms, general formula (2): CH2=CH-(CF2) n -X2 (where X 2 is H or F, and n is an integer from 3 to 10.) A fluoromonomer represented by; a monomer that provides a crosslinking site; non-fluorinated monomers such as ethylene, propylene, and alkyl vinyl ether can be mentioned. These can be used alone or in any combination. Among these, it is preferable to use at least one selected from the group consisting of TFE, HFP, fluoroalkyl vinyl ether, and CTFE.

[0067] As the above-mentioned fluoroalkyl vinyl ether, General formula (3): CF2=CF-ORf 3 (where Rf 3 represents a perfluoroalkyl group having 1 to 8 carbon atoms.) A fluoromonomer represented by, General formula (4): CF2=CFOCF2ORf 4 (where Rf 4 is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, a cyclic perfluoroalkyl group having 5 to 6 carbon atoms, or a linear or branched perfluorooxyalkyl group having 2 to 6 carbon atoms containing 1 to 3 oxygen atoms) A fluoromonomer represented by, and, General formula (5): CF2=CFO(CF2CF(Y 5 )O) m (CF2) n F (where Y 5 represents a fluorine atom or a trifluoromethyl group. m is an integer from 1 to 4. n is an integer from 1 to 4.) A fluoromonomer represented by is preferably at least one selected from the group consisting of, and the fluoromonomer represented by general formula (3) is more preferable.

[0068] Specific examples of vinylidene fluoride-based fluororubbers include VdF / HFP rubber, VdF / HFP / TFE rubber, VdF / CTFE rubber, VdF / CTFE / TFE rubber, VDF / fluoromonomer rubber represented by general formula (1), VDF / fluoromonomer / TFE rubber represented by general formula (1), VDF / perfluoro(methyl vinyl ether) [PMVE] rubber, VDF / PMVE / TFE rubber, and VDF / PMVE / TFE / HFP rubber. Among the fluoromonomer rubber represented by VDF / general formula (1), VDF / CH2=CFCF3 rubber is preferred, and among the fluoromonomer / TFE rubber represented by VDF / general formula (1), VDF / TFE / CH2=CFCF3 rubber is preferred.

[0069] The above VDF / CH2=CFCF3 rubber is preferably a copolymer consisting of 40 to 99.5 mol% VDF and 30.5 to 60 mol% CH2=CFCF, and more preferably a copolymer consisting of 50 to 85 mol% VDF and 15 to 50 mol% CH2=CFCF.

[0070] The above-mentioned tetrafluoroethylene / propylene-based fluororubber is preferably a copolymer consisting of 45-70 mol% tetrafluoroethylene, 55-30 mol% propylene, and 0-5 mol% fluoromonomer that provides the crosslinking sites.

[0071] The above-mentioned fluorine-containing elastomer may be a perfluoroelastomer. The above-mentioned perfluoroelastomer is preferably at least one selected from the group consisting of a perfluoroelastomer containing TFE, for example, a TFE / fluoromonomer copolymer represented by general formula (3), (4), or (5), and a fluoromonomer / monomer copolymer that provides a crosslinking site represented by general formula (3), (4), or (5).

[0072] In the case of the TFE / PMVE copolymer, the composition is preferably 45-90 / 10-55 (mol%), more preferably 55-80 / 20-45, and even more preferably 55-70 / 30-45.

[0073] In the case of TFE / PMVE / monomer copolymers that provide crosslinking sites, the preferred values ​​are 45-89.9 / 10-54.9 / 0.01-4 (mol%), more preferably 50-77.9 / 20-49.9 / 0.1-3.5, and even more preferably 55-69.8 / 30-44.8 / 0.2-3.

[0074] In the case of a fluoromonomer copolymer represented by general formula (3), (4), or (5) with 4 to 12 carbon atoms, the ratio is preferably 50 to 90 / 10 to 50 (mol%), more preferably 60 to 88 / 12 to 40, and even more preferably 65 to 85 / 15 to 35.

[0075] In the case of TFE / fluoromonomers represented by general formulas (3), (4), or (5) with 4 to 12 carbon atoms / monomer copolymers that provide crosslinking sites, the preferred values ​​are 50 to 89.9 / 10 to 49.9 / 0.01 to 4 (mol%), more preferably 60 to 87.9 / 12 to 39.9 / 0.1 to 3.5, and even more preferably 65 to 84.8 / 15 to 34.8 / 0.2 to 3. Outside of these compositional ranges, the rubber-elastic properties are lost, and the material tends to become closer in properties to that of a resin.

[0076] The perfluoroelastomer is preferably at least one selected from the group consisting of TFE / fluoromonomer represented by general formula (5) / monomer copolymer that provides a crosslinking site, TFE / fluoromonomer copolymer represented by general formula (5), TFE / fluoromonomer copolymer represented by general formula (3), and TFE / fluoromonomer / monomer copolymer that provides a crosslinking site.

[0077] Examples of the perfluoroelastomer include those described in WO97 / 24381, JP-B-61-57324, JP-B-4-81608, JP-B-5-13961, etc.

[0078] The monomer that provides a crosslinking site is a monomer having a crosslinkable group that provides a crosslinking site for a fluorine-containing polymer to form a crosslink by a crosslinking agent (a cure site monomer).

[0079] Examples of the monomer that provides a crosslinking site include General formula (6): CX 6 2=CX 6 -Rf 6 CHR 6 X 7 (In the formula, X 6 is the same or different and is a hydrogen atom, a fluorine atom, or CH3, and Rf 6 is a fluoroalkylene group, a perfluoroalkylene group, a fluoro(poly)oxyalkylene group, or a perfluoro(poly)oxyalkylene group, and R 6 is a hydrogen atom or CH3, and X 7 is an iodine atom or a bromine atom), a fluoromonomer represented by General formula (7): CX 6 2=CX 6 -Rf 7 X 7 (In the formula, X 6 is the same or different and is a hydrogen atom, a fluorine atom, or CH3, and Rf 7 is a fluoroalkylene group, a perfluoroalkylene group, a fluoro(poly)oxyalkylene group, or a perfluoro(poly)oxyalkylene group, and X 7 is an iodine atom or a bromine atom), a fluoromonomer represented by General formula (8): CF2=CFO(CF2CF(CF3)O) m (CF2) n -X 8 (In the formula, m is an integer of 0 to 5, n is an integer of 1 to 3, and X 8Fluoromers represented by a cyano group, carboxyl group, alkoxycarbonyl group, iodine atom, bromine atom, or -CH2I, General formula (9): CH2=CFCF2O(CF(CF3)CF2O) m (CF(CF3)) n -X 9 (In the formula, m is an integer from 0 to 5, n is an integer from 1 to 3, X 9 Fluoromers represented by a cyano group, carboxyl group, alkoxycarbonyl group, iodine atom, bromine atom, or CH2OH, and General formula (10):CR 10 2=CR 10 -Z-CR 10 =CR 10 2 (In the formula, R 10 Z is either the same or different hydrogen atom or a C1-C5 alkyl group. Z is a linear or branched alkylene group having an oxygen atom, having C1-C18, a cycloalkylene group having C3-C18, a C1-C10 alkylene group or oxyalkylene group that is at least partially fluorinated, or -(Q) p -CF2O-(CF2CF2O) m (CF2O) n -CF2-(Q) p - It is preferable that the monomer is at least one selected from the group consisting of monomers represented by (wherein Q is an alkylene group or an oxyalkylene group, p is 0 or 1, and m / n is 0.2 to 5) and has a molecular weight of 500 to 10000.

[0080] X 6 It is preferably a fluorine atom. Rf 6 and Rf 7 It is preferable that it is a perfluoroalkylene group having 1 to 5 carbon atoms. 6 It is preferably a hydrogen atom. 8It is preferable that this is a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CH2I. 9 It is preferable that the component is a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CH2OH.

[0081] The monomers that provide the crosslinking site are CF2=CFOCF2CF(CF3)OCF2CF2CN, CF2=CFOCF2CF(CF3)OCF2CF2COOH, CF2=CFOCF2CF(CF3)OCF2CF2CH2I, CF2=CFOCF2CF2CH2I, CH2=CFCF2OCF(CF3)CF2OCF(CF3)CN, CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOH, CH2=CFCF2OCF(C It is preferable that F3)CF2OCF(CF3)CH2OH, CH2=CHCF2CF2I, CH2=CH(CF2)2CH=CH2, CH2=CH(CF2)6CH=CH2, and CF2=CFO(CF2)5CN be selected from the group consisting of these, and more preferably that F3)CF2OCF(CF3)CF2CF2CN and CF2=CFOCF2CF2CH2I be selected from the group consisting of these.

[0082] The above fluorine-containing elastomer is preferably such that its glass transition temperature is -40°C or higher, more preferably -20°C or higher, and even more preferably -10°C or higher, in order to have excellent compression set characteristics at high temperatures. Furthermore, in order to have good cold resistance, it is preferably such that its glass transition temperature is 10°C or lower, more preferably 5°C or lower, even more preferably 0°C or lower, and most preferably -3°C or lower.

[0083] The above glass transition temperature can be determined by using a differential scanning calorimeter (Mettler-Toledo, DSC822e) to obtain a DSC curve by heating 10 mg of the sample at 10°C / min, and then finding the temperature at the midpoint of the intersection of the extension of the baseline before and after the second-order transition of the DSC curve and the tangent line at the inflection point of the DSC curve.

[0084] The above-mentioned fluorine-containing elastomer is preferably heat-resistant, and more preferably has a Mooney viscosity ML(1+20) of 30 or higher at 170°C, more preferably 40 or higher, and even more preferably 50 or higher. Furthermore, in terms of good processability, it is preferably 150 or lower, more preferably 120 or lower, and even more preferably 110 or lower.

[0085] The above-mentioned fluorine-containing elastomer is preferably heat-resistant, and more preferably has a Mooney viscosity ML(1+20) of 30 or higher at 140°C, more preferably 40 or higher, and even more preferably 50 or higher. Furthermore, in terms of good processability, it is preferably 180 or lower, more preferably 150 or lower, and even more preferably 110 or lower.

[0086] The above-mentioned fluorine-containing elastomer is preferably heat-resistant, and more preferably has a Mooney viscosity ML(1+10) of 10 or more at 100°C, more preferably 20 or more, and even more preferably 30 or more. Furthermore, in terms of good processability, it is preferably 120 or less, more preferably 100 or less, and even more preferably 80 or less.

[0087] The above Mooney viscosity can be measured using an ALPHA TECHNOLOGIES MV2000E Mooney viscometer at 170°C, 140°C, or 100°C, in accordance with JIS K6300.

[0088] The partially fluorinated elastomers and perfluoroelastomers described above can be produced by conventional methods, but iodine compounds or bromine compounds can also be used as chain transfer agents because they result in a narrow molecular weight distribution of the resulting polymers, allow for easy control of molecular weight, and enable the introduction of iodine or bromine atoms at the terminals. A polymerization method using iodine compounds or bromine compounds includes, for example, emulsion polymerization in an aqueous medium under pressurized conditions in the presence of an iodine or bromine compound, in a substantially oxygen-free environment (iodine transfer polymerization). A typical example of an iodine or bromine compound used is, for example, one with the general formula: R 11 I x Br y (In the formula, x and y are integers from 0 to 2, and satisfy 1 ≤ x + y ≤ 2, R 11 Examples of compounds are those represented by a saturated or unsaturated fluorohydrocarbon group or chlorofluorohydrocarbon group having 1 to 16 carbon atoms, or a hydrocarbon group having 1 to 3 carbon atoms (which may contain an oxygen atom). By using an iodine compound or a bromine compound, an iodine atom or a bromine atom is introduced into the polymer and functions as a crosslinking point.

[0089] Examples of iodine and bromine compounds include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,4-diiodoperfluorobutane, 1,5-diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, diiodomethane, 1,2-diiodoethane, 1,3-diiodo-n-propane, and 1-bromo-4-iodoperfluorobutane. These compounds may be used individually or in combination with each other.

[0090] Among these, 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane are preferred in terms of polymerization reactivity, crosslinking reactivity, and availability.

[0091] As the fluorine-containing polymer, a fluorine-containing elastomer containing an iodine atom or a bromine atom is preferred, and a fluorine-containing elastomer having an iodine atom or a bromine atom at the main chain ends and / or side chains is more preferred.

[0092] As the perfluoroelastomer containing an iodine atom or a bromine atom, at least one selected from the group consisting of a perfluoroelastomer containing monomer units having an iodine atom or a bromine atom, a perfluoroelastomer having an iodine atom or a bromine atom at the main chain terminus, and a perfluoroelastomer having an iodine atom or a bromine atom at the main chain terminus and also containing monomer units having an iodine atom or a bromine atom is preferred.

[0093] Examples of monomers having an iodine atom or a bromine atom include: Formula:CX 4 2=CX 5 R f 2 -X (In the formula, X 4 , X 5 Each of these is independently H, F, or an alkyl group having 1 to 5 carbon atoms, and R f 2 Examples of monomers represented by (where X is a linear or branched alkylene group or oxyalkylene group which may have one or more ether-bonded oxygen atoms, may have an aromatic ring, and may have some or all of its hydrogen atoms substituted with fluorine atoms, and X is an iodine atom or a bromine atom).

[0094] Examples of monomers having an iodine atom or a bromine atom include: Formula:CX 16 2=CX 16 -Rf 16 CHR 16 X (In the formula, X 16 These are, independently, a hydrogen atom, a fluorine atom, or CH3, Rf 16is a fluoroalkylene group, a perfluoroalkylene group, a fluoro(poly)oxyalkylene group or a perfluoro(poly)oxyalkylene group, R 16 Fluoromers represented by a hydrogen atom or CH3, where X is an iodine atom or bromine atom, Formula:CX 16 2=CX 16 -Rf 17 X (In the formula, X 16 These are, independently, a hydrogen atom, a fluorine atom, or CH3, Rf 17 (where X is a fluoroalkylene group, a perfluoroalkylene group, a fluoro(poly)oxyalkylene group, or a perfluoro(poly)oxyalkylene group, and X is an iodine atom or a bromine atom) Formula: CF2 = CFO(CF2CF(CF3)O) m (CF2) n -X Fluoromers represented by the formula (wherein m is an integer from 0 to 5, n is an integer from 1 to 3, and X is an iodine atom, a bromine atom, or -CH2I), Equation: CH2 = CFCF2O(CF(CF3)CF2O) m (CF(CF3)) n -X Examples include monomers represented by the formula (where m is an integer from 0 to 5, n is an integer from 1 to 3, and X is an iodine atom or a bromine atom), which can be used individually or in any combination.

[0095] X 16 It is preferably a fluorine atom. Rf 16 and Rf 17 It is preferable that it is a perfluoroalkylene group having 1 to 5 carbon atoms. 16 It is preferable that it be a hydrogen atom.

[0096] As the monomer having an iodine atom or a bromine atom, at least one selected from the group consisting of CF2=CFOCF2CF(CF3)OCF2CF2CH2I, CF2=CFOCF2CF2CH2I, and CH2=CHCF2CF2I is preferred, with CF2=CFOCF2CF2CH2I being more preferred.

[0097] Perfluoroelastomers having iodine or bromine atoms at the main chain ends can be produced by using an iodine or bromine compound as a chain transfer agent when polymerizing monomers to produce perfluoroelastomers. A polymerization method using an iodine or bromine compound includes, for example, emulsion polymerization in an aqueous medium under pressurized conditions in the presence of an iodine or bromine compound, in a substantially oxygen-free environment (iodine transfer polymerization). A typical example of an iodine or bromine compound used is, for example, one with the general formula: R 21 I x Br y (In the formula, x and y are integers from 0 to 2, and satisfy 1 ≤ x + y ≤ 2, R 21 Examples of compounds represented by a saturated or unsaturated fluorohydrocarbon group or chlorofluorohydrocarbon group having 1 to 16 carbon atoms, or a hydrocarbon group having 1 to 3 carbon atoms (which may contain an oxygen atom).

[0098] Examples of iodine and bromine compounds include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1,5-diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane, diiodomethane, 1,2-diiodoethane, 1,3-diiodo-n-propane, CF2Br2, BrCF2CF2Br, CF3CFBrCF2Br, CFClBr2, and BrCF Examples include 2CFClBr, CFBrClCFClBr, BrCF2CF2CF2Br, BrCF2CFBrOCF3, 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 derivatives of benzene, diiodomonobromo substituted derivatives, and (2-iodoethyl) and (2-bromoethyl) substituted derivatives, and these compounds may be used individually or in combination with each other.

[0099] Among these, 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane are preferred in terms of polymerization reactivity, crosslinking reactivity, and availability.

[0100] The iodine and bromine content of the perfluoroelastomer containing iodine or bromine atoms is preferably 0.001 to 10% by mass, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, and more preferably 5% by mass or less. The iodine and bromine content can be measured by elemental analysis.

[0101] As the perfluoroelastomer containing an iodine atom or a bromine atom, it is preferable to select at least one from the group consisting of perfluoroelastomers containing an iodine atom or a bromine atom containing a TFE unit, for example, a fluoromonomer copolymer represented by general formula (3), (4), or (5), and a fluoromonomer / monomer copolymer having an iodine atom or a bromine atom represented by general formula (3), (4), or (5).

[0102] When the perfluoroelastomer containing iodine or bromine atoms is a TFE / perfluoro(methyl vinyl ether) (PMVE) copolymer, the composition (mol%) of the perfluoroelastomer containing iodine or bromine atoms is preferably 45-90 / 10-55, more preferably 55-80 / 20-45, even more preferably 55-70 / 30-45, and most preferably 56-69.5 / 30.5-44.

[0103] When the perfluoroelastomer containing iodine or bromine atoms is a TFE / PMVE / monomer copolymer having iodine or bromine atoms, the composition (mol%) of the perfluoroelastomer containing iodine or bromine atoms is preferably 45-89.9 / 10-54.9 / 0.01-4, more preferably 55-77.9 / 20-49.9 / 0.01-3.5, even more preferably 55-69.8 / 30-44.8 / 0.03-3.0, and most preferably 55.3-69.5 / 30.3-44.5 / 0.05-2.5.

[0104] When the perfluoroelastomer containing an iodine atom or a bromine atom is a fluoromonomer copolymer represented by general formula (3), (4), or (5) with TFE / 4 to 12 carbon atoms, the composition (mol%) of the perfluoroelastomer containing an iodine atom or a bromine atom is preferably 50 to 90 / 10 to 50, more preferably 60 to 88 / 12 to 40, even more preferably 65 to 85 / 15 to 35, and most preferably 66 to 84 / 16 to 34.

[0105] When a perfluoroelastomer containing an iodine atom or a bromine atom is a TFE / fluoromonomer represented by general formula (3), (4), or (5) with 4 to 12 carbon atoms / monomer copolymer having an iodine atom or a bromine atom, the composition (mol%) of the perfluoroelastomer containing an iodine atom or a bromine atom is preferably 50 to 89.9 / 10 to 49.9 / 0.01 to 4, more preferably 60 to 87.9 / 12 to 39.9 / 0.1 to 3.5, even more preferably 65 to 84.8 / 15 to 34.8 / 0.2 to 3.0, and most preferably 66 to 84.3 / 15.5 to 33.8 / 0.2 to 2.0. Outside of these compositional ranges, the rubber-elastic properties are lost, and the material tends to become closer in properties to that of a resin.

[0106] As the perfluoroelastomer containing an iodine atom or a bromine atom, at least one selected from the group consisting of a fluoromonomer copolymer represented by general formula (3), a fluoromonomer represented by general formula (3) / monomer copolymer having an iodine atom or a bromine atom, a fluoromonomer copolymer represented by general formula (5), and a fluoromonomer copolymer having an iodine atom or a bromine atom represented by general formula (5).

[0107] Perfluoroelastomers containing iodine or bromine atoms are preferably glass transition temperatures of -70°C or higher, more preferably -60°C or higher, and even more preferably -50°C or higher, due to their excellent compression set properties at high temperatures. Furthermore, due to their good cold resistance, the glass transition temperature is preferably 5°C or lower, more preferably 0°C or lower, and even more preferably -3°C or lower.

[0108] The above glass transition temperature can be determined by using a differential scanning calorimeter (Mettler-Toledo, DSC822e) to obtain a DSC curve by heating 10 mg of the sample at 10°C / min, and then finding the temperature at the midpoint of the intersection of the extension of the baseline before and after the second-order transition of the DSC curve and the tangent line at the inflection point of the DSC curve.

[0109] Perfluoroelastomers containing iodine or bromine atoms are preferably heat-resistant, with a Mooney viscosity ML(1+10) at 100°C of 10 or higher, more preferably 20 or higher, and even more preferably 30 or higher. Furthermore, in terms of good processability, the viscosity is preferably 120 or lower, more preferably 100 or lower, and even more preferably 80 or lower.

[0110] The above Mooney viscosity can be measured at 100°C in accordance with JIS K6300 using an ALPHA TECHNOLOGIES MV2000E Mooney viscometer.

[0111] Fluorine-containing polymers can be manufactured by conventional methods.

[0112] The compositions of this disclosure preferably further contain an organic peroxide.

[0113] Examples of organic peroxides include 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butylperoxide (Perbutyl D), t-butylcumylperoxide (Perbutyl C), dicumylperoxide (Permil D, Permil D-40, Permil D-40MB(T)), α,α-bis(t-butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (Perhexa 25B, Perhexa Examples include peroxides (25B-40), 2,5-dimethyl-2,5-di(t-butylperoxy)-hexyn-3 (perhexyn 25B, perhexyn 25B-40), benzoyl peroxide, t-hexyl peroxypivalate (perhexyl PV, perhexyl PV-50E), t-butyl peroxypivalate (perbutyl PV, perbutyl PV-40E), polymer blends of t-butylperoxy-3-methylbenzoate and t-butyl peroxybenzoate (perbutyl ZT), and t-butyl peroxybenzoate (perbutyl Z). Among these, dialkyl types are preferred. Furthermore, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane is particularly preferred. Generally, the type and amount of organic peroxide used are selected considering the amount of active -OO- and the decomposition temperature.

[0114] The content of organic peroxides in the composition is preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1.0 part by mass or more, per 100 parts by mass of fluorine-containing polymer, in terms of facilitating crosslinking, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, in terms of preventing scorching in primary crosslinking processes such as press molding and facilitating molding.

[0115] The compositions of this disclosure may contain fillers.

[0116] Examples of fillers include imide-based fillers having an imide structure such as polyimide, polyamideimide, and polyetherimide; organic fillers made of engineering plastics such as polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, polyetherketone, and polyoxybenzoate; metal oxide fillers such as aluminum oxide, silicon oxide, and yttrium oxide; metal carbides such as silicon carbide and aluminum carbide; metal nitride fillers such as silicon nitride and aluminum nitride; and inorganic fillers such as carbon black, aluminum fluoride, carbon fluoride, barium sulfate, silica, clay, and talc.

[0117] Among these, carbon black, aluminum oxide, yttrium oxide, silicon oxide, silicon carbide, polyimide, and carbon fluoride are preferred in terms of their shielding effect against various plasmas.

[0118] Furthermore, the inorganic fillers and organic fillers mentioned above may be used individually or in combination of two or more types.

[0119] The amount of filler added is preferably 0.5 to 100 parts by mass, more preferably 5 to 50 parts by mass, per 100 parts by mass of the fluorine-containing polymer.

[0120] In fields where high purity and non-contamination are not particularly required, conventional additives that are incorporated into fluorine-containing polymer compositions, such as processing aids, plasticizers, and colorants, may be added as needed.

[0121] The composition may contain an organic basic compound. An example of an organic basic compound is a compound with the formula: CH3(CH2) 17 - NH2 ocdadecylamine; Formula:H2N-C(O)-(CH2) 11 -CH=CH-(CH2)7CH3 elkaamide; Formula: Oleamide of H2N-C(O)-(CH2)7-CH=CH-(CH2)7CH3; Formula: Hexamethylenediamine of the form H2N-(CH2)6-NH2 formula: [ka] Examples include 1,8-diazabicycloundec-7-ene (DBU).

[0122] The compositions of this disclosure can be prepared by mixing the above-mentioned components using conventional polymer processing machinery, such as open rolls, Banbury mixers, and kneaders. Alternatively, they can also be prepared by using a closed-type mixer. The compositions of this disclosure can be suitably used as molding materials for obtaining molded articles by crosslinking.

[0123] 4. Molded products A molded article can be obtained by molding the composition of this disclosure. Furthermore, a molded article can be obtained by molding and crosslinking the composition of this disclosure.

[0124] One method for obtaining molded products from a composition is to first obtain a pre-molded body by molding the composition as a molding material, and then to crosslink the pre-molded body. The method for obtaining a pre-molded body from a composition can be a conventional method, and can be carried out by known methods such as heating and compressing in a mold, press-fitting into a heated mold, or extruding with an extruder. In the case of extruded products such as hoses and electric wires, molded products can be obtained by heating and crosslinking with steam or the like after extrusion.

[0125] The above crosslinking can be carried out in the order of primary crosslinking followed by secondary crosslinking. Primary crosslinking is preferably carried out at 150-250°C for 5-120 minutes, and more preferably at 160-200°C for 5-60 minutes. Any known crosslinking method can be used, such as press crosslinking.

[0126] Secondary crosslinking is preferably carried out at 180-320°C for 2-48 hours, and more preferably at 180-310°C for 5-24 hours. Temperature variations within this temperature range are also possible. Any known crosslinking method can be used, such as oven crosslinking.

[0127] The change in swelling rate of the molded product before and after heat treatment at 300°C for 72 hours is preferably less than 600%, more preferably less than 400%, even more preferably less than 300%, and most preferably less than 250%, in that the cross-linked structure is maintained without collapse. The change in swelling rate of the molded product can be determined by the method described in the examples.

[0128] The molded articles of this disclosure can be suitably used as sealing materials for semiconductor manufacturing equipment that requires particularly high heat resistance, especially for semiconductor manufacturing equipment that undergoes high-density plasma irradiation. Examples of such sealing materials include O-rings, square rings, gaskets, packings, oil seals, bearing seals, lip seals, and the like.

[0129] In addition, it can be used in various polymer products used in semiconductor manufacturing equipment, such as diaphragms, tubes, hoses, various rubber rolls, belts, etc. It can also be used as a coating material and lining material.

[0130] Furthermore, the semiconductor manufacturing equipment referred to in this disclosure is not limited to equipment specifically for manufacturing semiconductors, but broadly includes all manufacturing equipment used in the semiconductor field that requires a high degree of cleanliness, such as equipment for manufacturing liquid crystal panels and plasma panels. Examples include the following:

[0131] (1) Etching apparatus Dry etching equipment Plasma etching equipment Reactive ion etching apparatus Reactive ion beam etching apparatus Sputter etching apparatus Ion beam etching system Wet etching apparatus Ashing device (2) Cleaning equipment Dry etching cleaning equipment UV / O3 cleaning system Ion beam cleaning system Laser beam cleaning device Plasma cleaning device Gas etching cleaning equipment Extraction and washing device Soxhlet extraction and washing apparatus High-temperature, high-pressure extraction and washing apparatus Microwave extraction and washing device Supercritical fluid extraction and washing apparatus (3) Exposure apparatus Stepper Kota Developer (4) Polishing equipment CMP equipment (5) Film deposition equipment CVD equipment Sputtering device (6) Diffusion and ion implantation device Oxidation diffusion device Ion implantation device

[0132] The molded articles of this disclosure exhibit excellent performance as sealing materials for, for example, CVD equipment, plasma etching equipment, reactive ion etching equipment, ashing equipment, or excimer laser exposure machines.

[0133] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims.

[0134] <1> According to the first aspect of this disclosure, A compound represented by general formula (11) is provided. General formula (11): [ka] (In the formula, R 11 and R 12These are independently C1 alkyl halogenated compounds, Z 11 The linking group is either a single bond or a divalent linking group. Any hydrogen atom bonded to the benzene ring may be substituted with any substituent. <2> According to the second aspect of this disclosure, R 11 and R 12 However, all of these provide compounds from the first viewpoint that are -CF3. <3> According to the third aspect of this disclosure, Z 11 However, compounds are provided that are single-bonded or halogenated alkylene groups having 1 to 3 carbon atoms, in a first or second view. <4> According to the fourth aspect of this disclosure, A compound according to any of the first to third aspects represented by formula (12) is provided. Formula (12): [ka] (In the formula, the hydrogen atoms bonded to the benzene ring are not substituted by any substituents.) <5> According to the fifth aspect of this disclosure, A crosslinking aid represented by general formula (21) is provided. General formula (21): [ka] (In the formula, Z 21 x is an independent 2-3 valent linking group, x is an independent integer between 1 and 2, and y is an integer between 1 and 2. The hydrogen atoms bonded to the benzene ring may be substituted with any substituent. <6> According to the sixth aspect of this disclosure, A crosslinking aid according to a fifth aspect, represented by general formula (22), general formula (23), or general formula (24a), is provided. General formula (22): [ka] (In the formula, the hydrogen atom bonded to the benzene ring may be substituted with any substituent.) General formula (23): [ka] (In the formula, Z 23 This is a divalent linking group. The hydrogen atoms bonded to the benzene ring may be substituted with any substituent. General formula (24a): [ka] (wherein n is 1 or 2. The hydrogen atoms bonded to the benzene ring may be substituted with any substituent.) <7> According to the seventh aspect of this disclosure, A crosslinking aid according to the fifth or sixth aspect, represented by general formula (23a), is provided. General formula (23a): [ka] (In the formula, R 23 and R 24 These independently consist of a hydrogen atom, a C1-C3 alkyl group, or a C1-C1 halogenated alkyl group. Z 23a These are single bonds, -SO2-, -O-, -CO-, alkylene groups with 1 to 3 carbon atoms, or halogenated alkylene groups with 1 to 3 carbon atoms. The hydrogen atoms bonded to the benzene ring are not substituted by any substituents. <8> According to the eighth aspect of this disclosure, R 23 , R 24 and Z 23a A crosslinking aid according to a seventh aspect is provided, in which at least one of contains one or more fluorine atoms. <9> According to the ninth aspect of this disclosure, R 23 and R 24 However, a seventh or eighth crosslinking aid is provided, independently of a hydrogen atom or -CF3. <10> According to the tenth aspect of this disclosure, Z 23aHowever, a crosslinking aid is provided that is a single bond or a perfluoroalkylene group having 1 to 3 carbon atoms, in any of the seventh to ninth viewpoints. <11> According to the eleventh aspect of this disclosure, A composition containing a crosslinking aid and a fluorine-containing polymer according to any of the 5th to 10th aspects. <12> According to the 12th aspect of this disclosure, A composition according to an eleventh aspect is provided, wherein the content of the crosslinking aid is 0.1 to 10 parts by mass per 100 parts by mass of the fluorine-containing polymer. <13> According to the 13th aspect of this disclosure, A composition is provided in which the fluorine-containing polymer is a fluorine-containing elastomer, according to an eleventh or twelfth aspect. <14> According to the fourteenth aspect of this disclosure, A composition is provided in which the fluorine-containing polymer contains an iodine atom or a bromine atom, according to any 11th to 13th aspect. <15> According to the 15th aspect of this disclosure, A composition according to any 11th to 13th aspect is provided, further containing an organic peroxide. <16> According to the sixteenth aspect of this disclosure, A composition according to a fifteenth aspect is provided, wherein the content of the organic peroxide is 0.05 to 10 parts by mass per 100 parts by mass of the fluorine-containing polymer. <17> According to the seventeenth aspect of this disclosure, A molded article is provided which is obtained from a composition according to any of the 11th to 16th aspects. [Examples]

[0135] Next, embodiments of the present disclosure will be described with reference to examples, but the present disclosure is not limited to such embodiments.

[0136] Each value in the examples was measured by the following method.

[0137] (Monomer composition) 19It was determined by F-NMR analysis.

[0138] (Iodine content) It was measured by elemental analysis.

[0139] (Mooney viscosity) Using a Mooney viscometer MV2000E manufactured by ALPHA TECHNOLOGIES, it was measured at 100 °C according to JIS K6300.

[0140] (Crosslinking characteristics) For the fluorine-containing elastomer compositions produced in the examples and comparative examples, using an RPA2000 manufactured by ALPHA TECHNOLOGIES, the crosslinking curves at 180 °C (160 °C in Comparative Example 1) were determined, and the minimum storage modulus (ML), maximum storage modulus (MH), and optimum crosslinking time (T90) were determined.

[0141] (Heat resistance test) The samples after crosslinking characteristics evaluation were heated in an electric furnace at 300 °C for 72 hours. The samples after heat treatment and the samples without heat treatment were immersed in a fluorine-containing solvent mainly composed of C4F8Cl2 at room temperature for 72 hours, then taken out, and the volume after immersion was quickly measured. Since the samples swell due to immersion, the volume change before and after immersion was calculated as the swelling ratio as follows. Swelling ratio (%) = ((Volume after immersion) - (Volume before immersion)) / (Volume before immersion) × 100 - 100 Change in swelling ratio (%) = (Swelling ratio after heat treatment) - (Swelling ratio before heat treatment)

[0142] The swelling ratio correlates with the crosslink density, and the higher the crosslink density, the smaller the swelling ratio. When the molecular chains and crosslink points are broken by heat treatment, the crosslink density of the sample after heat treatment decreases compared to the untreated sample, and the swelling ratio increases. Therefore, the smaller the change in the swelling ratio before and after heat treatment, the less the molecular chains and crosslink points are broken at high temperatures, and the better the heat resistance.

[0143] (Compression set (200 °C 72 h)) The compression set rate was measured in accordance with the method described in ASTM D395 or JIS K6262. The O-ring was compressed up to a compression rate of 25% at room temperature using a compression device (the O-ring with a thickness (wire diameter) of 3.5 mm was compressed to a thickness of 2.625 mm).

[0144] Next, the compression device with the compressed O-ring fixed was placed still in an electric furnace, left standing at 200 °C for 72 hours, and then the compression device was taken out of the electric furnace. The O-ring was removed from the compression device, the removed O-ring was placed still in a constant temperature chamber, left standing at 23 °C for 30 minutes, and the thickness (t2) of the O-ring was measured. The compression set was determined by the following formula. Compression set rate (%) = (t0 - t2) / (t0 - t1) × 100 t0: Original thickness of the O-ring (mm) t1: Thickness of the spacer (mm) t2: Thickness of the O-ring after the compression test (mm) In the above test, t0 = 3.5 mm and t1 = 2.625 mm.

[0145] The compression set rate is a value indicating the heat-resistant sealing property of the sealing material. The higher the heat resistance of the sealing material, the smaller the compression set rate. Therefore, the smaller the compression set rate after heat treatment, the higher the heat resistance.

[0146] (Compression set rate (300 °C 24 h → 200 °C 72 h)) The O-ring was left standing in an electric furnace at 300 °C for 24 hours, the heated O-ring was fixed to the compression device, and the compression device with the compressed O-ring fixed was placed still in the electric furnace, left standing at 200 °C for 72 hours, and then the compression device was taken out of the electric furnace. The thickness (t2) of the O-ring was measured and the compression set was determined in the same manner as the measurement method of the above compression set rate (200 °C 72 h), except for this.

[0147] The following materials were used in the examples and comparative examples. Fluorine-containing elastomer: TFE / PMVE / CF2=CFOCF2CF2CH2I copolymer TFE / PMVE / CF2=CFOCF2CF2CH2I (mol%): 67.2 / 32.6 / 0.2 Iodine content: 0.4 mass% Mooney viscosity ML(1+10)(100 °C): 64 MT Carbon: Thermax N-990, manufactured by Cancarb Perhexa (registered trademark) 25B: 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, manufactured by NOF Corporation

[0148] (Crosslinking aid) O-1:

[0149]

Chem.

[0150] O-2:

Chem.

[0151] O-6:

Chem.

[0152] O-7:

Chem.

[0153] O-8:

Chem.

[0154] O-9:

Chem.

Chem.

[0155] Synthesis Example 1 (Synthesis example of compound (O-2)) The following compounds were used in the synthesis example. 2,2'-(bistrifluoromethyl)benzidine: Manufactured by Tokyo Chemical Industry Co., Ltd. Allyl bromide: Manufactured by Tokyo Chemical Industry Co., Ltd. Potassium carbonate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Acetonitrile: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Ethyl acetate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0156] In a 200 mL three-necked flask fitted with a Liebig condenser, thermometer, and septum, 4 g of 2,2'-(bistrifluoromethyl)benzidine, 13.81 g of potassium carbonate, and 50 mL of acetonitrile were added. Allyl bromide (8.45 mL) was added dropwise while stirring at room temperature. After heating and stirring at 100 °C for 10 hours, the mixture was extracted with ethyl acetate and water, and washed with saturated brine. The extract was then concentrated to obtain compound (O-2) in 94% yield. 19 FNMR (CDCl3): -58.7 (s, 6F) 1 HNMR(CDCl3):7.1(d,J=8.4Hz,2H),7.0(s,2H),6.8(d,J=8.4Hz,2H),5.9(m,4H),5.2(m,8H),4.0(d,J=4.4Hz,8H)

[0157] Example 1 A fluorine-containing polymer (100 parts by mass), O-1 (2.15 parts by mass), Perhexa 25B (2 parts by mass), and carbon black (15 parts by mass) were mixed in a fluorine-containing solvent mainly composed of C4F8Cl2 and subjected to ultrasonic treatment for 30 minutes. The fluorine-containing solvent was evaporated at 23°C, and the mixture was kneaded in an open roll to obtain a fluorine-containing elastomer composition. The crosslinking properties of the obtained fluorine-containing elastomer composition were evaluated.

[0158] The obtained fluorine-containing elastomer composition was pressed at 180°C for 30 minutes to crosslink, and then oven-crosslinked in an electric furnace at 250°C for 4 hours to obtain molded articles. The obtained molded articles were subjected to heat resistance tests and compression set measurements. The results are shown in Table 1.

[0159] Examples 2-7 Except for changing the type and amount of crosslinking agent as shown in Table 1, a fluorine-containing elastomer composition and molded article were obtained and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0160] Comparative Example 1 Fluorine-containing polymer (100 parts by mass), TAIC (2 parts by mass), Perhexa 25B (2 parts by mass), and carbon black (15 parts by mass) were mixed in a fluorine-containing solvent mainly composed of C4F8Cl2 and subjected to ultrasonic treatment for 30 minutes. The fluorine-containing solvent was evaporated at 23°C, and the mixture was kneaded in an open roll to obtain a fluorine-containing elastomer composition. The crosslinking properties of the obtained fluorine-containing elastomer composition were evaluated.

[0161] The obtained fluorine-containing elastomer composition was pressed at 160°C for 10 minutes to crosslink, and then oven-crosslinked in an electric furnace at 180°C for 4 hours to obtain molded articles. The obtained molded articles underwent heat resistance testing and compression set measurement. The results are shown in Table 1.

[0162] [Table 1]

[0163] When the molded product prepared in Comparative Example 1 was heated at 300°C for 24 hours, a portion of the surface of the molded product melted.

Claims

1. A compound represented by general formula (11). General formula (11): 【Chemistry 31】 (In the formula, R １１ and R １２ These are, independently, a C1 alkyl halide, Z １１ The linking group is either a single bond or a divalent linking group. Any hydrogen atom bonded to the benzene ring may be substituted with any substituent.

2. R １１ and R １２ However, all of them are -CF ３ The compound according to claim 1.

3. Z １１ The compound according to claim 1 or 2, wherein the compound is a single bond or a halogenated alkylene group having 1 to 3 carbon atoms.

4. The compound according to claim 1 or 2, represented by formula (12). Formula (12): 【Chemistry 32】 (In the formula, the hydrogen atoms bonded to the benzene ring are not substituted by any substituents.)

5. A crosslinking aid represented by general formula (21). General formula (21): 【Transformation 33】 (In the formula, Z ２１ (where x is an independent 2-3 valent linking group, x is an independent integer between 1 and 2, and y is an integer between 1 and 2. The hydrogen atoms bonded to the benzene ring may be substituted with any substituent.)

6. A crosslinking aid according to claim 5, represented by general formula (22), general formula (23), or general formula (24a). General formula (22): 【Transformation 34】 (In the formula, the hydrogen atoms bonded to the benzene ring may be substituted with any substituent.) General formula (23): 【Chemistry 35】 (wherein Z ２３ is a divalent linking group. The hydrogen atom bonded to the benzene ring may be substituted with any substituent.) General formula (24a): 【Transformation 36】 (In the formula, n is 1 or 2. The hydrogen atoms bonded to the benzene ring may be substituted with any substituent.)

7. A crosslinking aid according to claim 5, represented by general formula (23a). General formula (23a): 【Chemistry 37】 (In the formula, R ２３ and R ２４ These independently consist of a hydrogen atom, a C1-C3 alkyl group, or a C1-C1 halogenated alkyl group. Z ２３ａ This is a single bond, -SO ２ These are -, -O-, -CO-, an alkylene group having 1 to 3 carbon atoms, or a halogenated alkylene group having 1 to 3 carbon atoms. The hydrogen atoms bonded to the benzene ring are not substituted by any substituents.

8. R ２３ , R ２４ and Z ２３ａ The crosslinking aid according to claim 7, wherein at least one of contains one or more fluorine atoms.

9. R ２３ and R ２４ However, independently, hydrogen atoms or -CF ３ The crosslinking aid according to claim 7.

10. Z ２３ａ The crosslinking aid according to claim 7, wherein the crosslinking aid is a single bond or a perfluoroalkylene group having 1 to 3 carbon atoms.

11. A composition containing the crosslinking agent and fluorine-containing polymer described in claim 5 or 6.

12. The composition according to claim 11, wherein the amount of the crosslinking aid is 0.1 to 10 parts by mass per 100 parts by mass of the fluorine-containing polymer.

13. The composition according to claim 11, wherein the fluorine-containing polymer is a fluorine-containing elastomer.

14. The composition according to claim 11, wherein the fluorine-containing polymer contains an iodine atom or a bromine atom.

15. The composition according to claim 11, further containing an organic peroxide.

16. The composition according to claim 15, wherein the content of the organic peroxide is 0.05 to 10 parts by mass per 100 parts by mass of the fluorine-containing polymer.

17. A molded article obtained from the composition described in claim 11.

Images