COMPOSITION WITH FLUORINE-CONTAINING POLYMER AND LINKED ARTICLE

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a composition comprising a fluorine-containing polymer and to a crosslinked product.BACKGROUND ART

[0002] Since a composition comprising a fluorine-containing polymer such as a fluorine-containing elastomer is excellent in heat resistance, chemical resistance, solvent resistance, fuel oil resistance and the like, it is widely used for producing a molded article such as O-rings, hoses, stem seals, shaft seals, and diaphragms. As such a composition, for example, WO 00 / 078871 proposes a crosslinkable elastomer composition comprising a crosslinkable elastomer component and silicon oxide fine particles, wherein the silicon oxide fine particles have ≤ 100 × 10 19< hydroxyl groups / g on the surface thereof and have an average particle size of ≤ 0.5 µm.SUMMARY OF THE INVENTIONPROBLEM TO BE SOLVED BY THE INVENTION

[0003] It is an object of the present disclosure to provide a novel composition containing a specific silicon oxide.MEANS FOR SOLVING THE PROBLEM

[0004] The present invention provides a composition comprising a fluorine-containing polymer which is a fluorine-containing elastomer, and 0.1-50 parts by mass per 100 parts by mass of the fluorine-containing polymer of a silicon oxide of the formula SiO x wherein 0 < x < 2.

[0005] According to the present disclosure, there is also provided Also, the invention provides (i) a crosslinked product obtained by crosslinking the above composition and (ii) the use of this crosslinked product as a sealing material.

[0006] Preferred embodiments of the invention are as defined in the appended dependent claims and / or in the following detailed description.EFFECTS OF INVENTION

[0007] According to the present invention, it is possible to provide a novel composition containing a specific silicon oxide.DESCRIPTION OF EMBODIMENTS

[0008] Hereinafter, specific embodiments of the present invention will be described in detail.

[0009] A composition of the present invention (also "the present composition" hereinafter) contains a fluorine-containing elastomer and a silicon oxide of the formula SiO x , where 0 < x < 2. The present composition can adsorb oxygen in the air by containing the above-mentioned silicon oxide. Therefore, by using the present composition for producing a crosslinked product such as a sealing material of an apparatus including a sealed space such as a semiconductor manufacturing apparatus, oxygen in the sealed space can be adsorbed to reduce the oxygen concentration in the sealed space, and oxygen can be prevented from entering the sealed space from the outside. Furthermore, the present composition contains a fluorine-containing polymer, and thus it is possible to obtain a crosslinked product having excellent heat resistance and plasma resistance.

[0010] The silicon oxide is an oxide containing a silicon atom. The silicon oxide of the formula SiO x where 0 < x < 2 is a compound having a compositional feature deviated from stoichiometric compositional features, and may be referred to as a non-stoichiometric compound.

[0011] The constituent ratio of Si in the silicon oxide as the filler (Si / (Si + O)), as specified by X-ray photoelectron spectroscopy (ESCA) of the silicon oxide, is preferably 35-90 atom%, more preferably ≥ 37 atom%, further preferably ≥ 39 atom%, more preferably ≤ 80 atom%, and further preferably ≤ 70 atom%.

[0012] The constituent ratio of Si in the silicon oxide (Si / (Si + O)) can be calculated by the following method using a value obtained by X-ray photoelectron spectroscopy (ESCA) of the silicon oxide. Constituent ratio Si / Si + O = A / B A: Peak area value of Si element B: Total value of peak area values of Si element and O element

[0013] The particle size of the silicon oxide is preferably < 200 µm, more preferably 5-100 nm. The particle size of the silicon oxide can be determined by converting the specific surface area measured by measuring the specific surface area of the silicon oxide into the particle size.

[0014] The silicon oxide is preferably produced by a thermal plasma method, and more preferably obtained by supplying silicon powder to a thermal plasma flame. By supplying silicon powder to the thermal plasma flame, the supplied silicon powder is subjected to thermal plasma treatment to form silicon oxide. The compositional feature of the silicon powder is adjusted according to the desired compositional feature of the silicon oxide. The thermal plasma flame is preferably derived from at least one gas selected from hydrogen, nitrogen, helium, and argon, and more preferably derived from a mixed gas of hydrogen and argon. The temperature of the thermal plasma flame is, for example, 2000-3000°C. The pressure of the thermal plasma treatment is preferably atmospheric pressure or less. The silicon powder can be supplied to the thermal plasma flame by using, for example, argon gas as a carrier gas.

[0015] The silicon oxide can be produced, for example, by a method for producing silicon oxide particles comprising a step of preparing a stoichiometric silicon oxide powder and at least one powder of a silicon powder, a powder of a compound of an element other than oxygen and silicon, and a powder of a non-stoichiometric silicon oxide, and a step of supplying the stoichiometric silicon oxide powder and the at least one powder which is prepared into a thermal plasma flame. Examples of such a production method include the production method described in JP-A-2014-144884.

[0016] In the production method, the powder such as silicon powder acts as a reducing agent to the stoichiometric silicon oxide powder, and the stoichiometric silicon oxide powder is partially reduced by the thermal plasma flame to become the above-described silicon oxide. Oxygen generated by the reduction of the stoichiometric silicon oxide powder is bonded to the silicon element of the silicon powder to form the above-described silicon oxide, but since oxygen sufficient to form the stoichiometric silicon oxide is not obtained as there is no oxygen not supplied from the outside, the above-described silicon oxide is formed. In this manner, the above-described silicon oxide particles are considered to be formed from any of the stoichiometric silicon oxide powder and the powder such as silicon powder.

[0017] The content of the silicon oxide in the present composition is 0.1-50 parts by mass (pbm), preferably ≥ 0.5 pbm, further preferably ≥ 1.0 pbm, particularly preferably ≥ 5 pbm, and further preferably ≤ 30 pbm, particularly preferably ≤ 25 pbm, with respect to 100 pbm of the fluorine-containing elastomer.

[0018] For the present composition, a rate of weight increase when a temperature of a crosslinked product obtained by crosslinking the composition is increased from normal temperature to 400°C at a rate of 10°C / min by heating the crosslinked product in air is preferably ≥ 0.1%. The rate of weight increase of the present composition is preferably ≥ 0.2%, more preferably ≥ 0.3%. Since a larger rate of weight increase is preferred, the upper limit is not limited, but the fluorine-containing elastomer contained in the present composition has excellent heat resistance and hardly increases in weight upon heating. Therefore, the rate of weight increase in the range that can be easily realized and can sufficiently enjoy the excellent properties of the fluorine-containing elastomer is usually ≤ 2%, and preferably ≤ 1%.

[0019] The rate of weight increase of the crosslinked product can be determined by the following method. A composition containing a fluorine-containing elastomer is crosslinked by a known method, and a sample having a thickness of 2 mm is produced from the obtained crosslinked product. About 10 mg of the sample is heated in an air atmosphere to increase the temperature of the sample from normal temperature to ≥ 400°C at a rate of 10°C / min, and the weight at the time when the temperature reaches 400°C is measured using a simultaneous thermogravimetry / differential thermal analyzer. Next, the initial weight is subtracted from the weight at the time when the temperature reaches 400°C to calculate the weight increase at the time when the temperature reaches 400°C. Then, as the rate of weight increase, the proportion (%) of the weight increase amount at the time when the temperature reaches 400°C with respect to the initial weight is calculated.

[0020] Herein, the weight of the sample measured at normal temperature is used as a reference for calculating the rate of weight increase, and the sample is heated from normal temperature to 400°C for measuring the weight of the sample when the temperature reaches 400°C. In the present disclosure, the normal temperature may be a temperature in the range of 10-40°C. The temperature range of 10-40°C does not significantly affect the calculated value.

[0021] The fluorine-containing elastomer has excellent heat resistance, and usually does not oxidize or decompose even when heated to the above temperature, so that the weight of the crosslinked product does not usually change. However, the crosslinked product obtained from the present composition has a feature that the weight is increased upon heating in the air, and this feature provides a surprising effect that oxygen in the air can be adsorbed.

[0022] The rate of weight increase of the composition can be adjusted, for example, by adjusting the content of the silicon oxide.

[0023] The present composition contains a fluorine-containing elastomer. The fluorine-containing elastomer has excellent sealability, chemical resistance and heat resistance.

[0024] Herein, the fluorine-containing elastomer is an amorphous fluorine-containing polymer. "Amorphous" refers to a state in which the melting peak (ΔH) that appears in differential scanning calorimetry [DSC] (temperature-increasing rate 10 °C / min) or differential thermal analysis [DTA] (temperature-increasing rate 10 °C / min) of the fluorine-containing elastomer is 4.5 J / g or less. Fluorine-containing elastomers exhibit elastomeric characteristics through cross-linking. "Elastomeric characteristics" means characteristics that allow the polymer to be stretched and to retain its original length when the force required to stretch the polymer is no longer applied.

[0025] The fluorine-containing elastomer may be a partially fluorinated elastomer or a perfluoroelastomer, but it is preferable to use a perfluoroelastomer from the viewpoint of having even better chemical resistance and heat resistance.

[0026] Herein, the partially fluorinated elastomer is a fluorine-containing polymer that includes a fluoromonomer unit, has a perfluoromonomer unit content of < 90 mol% with respect to all the polymerization units, has a glass transition temperature of ≤ 20°C, and has a melting peak (ΔH) of ≤ 4.5 J / g.

[0027] Herein, the perfluoroelastomer is a fluorine-containing polymer that has a perfluoromonomer unit content with respect to all the polymerization units of ≥ 90 mol%, has a glass transition temperature of ≤ 20°C, and has a melting peak (ΔH) of ≤ 4.5 J / g, and further, has a fluorine atom concentration in the fluorine-containing polymer of ≥ 71 mass%. The fluorine atom concentration in the fluorine-containing polymer is determined by calculating the concentration (% by mass) of the fluorine atoms included in the fluorine-containing polymer from the type and content of each monomer constituting the fluorine-containing polymer.

[0028] The perfluoromonomer is a monomer that does not include a carbon atom-hydrogen atom bond in the molecule. The perfluoromonomer may be a monomer in which, in addition to carbon atoms and fluorine atoms, some of the fluorine atoms bonded to carbon atoms are replaced with chlorine atoms, and may have, other than carbon atoms, a nitrogen atom, an oxygen atom, and a sulfur atom. The perfluoromonomer is preferably a monomer in which all the hydrogen atoms are replaced with fluorine atoms. A monomer that provides a crosslinking site does not fall within the scope of the perfluoromonomer.

[0029] Examples of the partially fluorinated elastomer include vinylidene fluoride(VdF)-based fluoroelastomers, tetrafluoroethylene (TFE) / propylene(Pr)-based fluoroelastomers, TFE / Pr / VdF-based fluoroelastomers, ethylene(Et) / hexafluoropropylene(HFP)-based fluoroelastomers, Et / HFP / VdF-based fluoroelastomers, and Et / HFP / TFE-based fluoroelastomers. Among these, at least one selected from VdF-based fluoroelastomers and TFE / Pr-based fluoroelastomers is preferable.

[0030] The VdF-based fluoroelastomer is preferably a copolymer comprising 45-85 mol% of VdF and 55-15 mol% of at least one other monomer copolymerizable with VdF, preferably 50-80 mol% of VdF and 50-20 mol% of at least one other monomer copolymerizable with VdF.

[0031] 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 according to the type of monomer.

[0032] Examples of the at least one other monomer copolymerizable with VdF include TFE, HFP, fluoroalkyl vinyl ether, chlorotrifluoroethylene (CTFE), trifluoroethylene, trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinyl fluoride, a fluoromonomer of the formula CHX 11< =CX 11< Rf 11< (11) wherein of two X 11< , one is H and the other is F, and Rf 11< is linear or branched C 1-12 -fluoroalkyl, and a fluoromonomer of the formula CH 2 =CH-(CF 2 ) n -X 12< (12) wherein X 12< is H or F, and n is an integer of 3-10; a monomer that provides a crosslinking site; and a non-fluorinated monomer such as ethylene, propylene, and alkyl vinyl ether. These can be used alone or in any combination. Among these, it is preferable to use at least one selected from TFE, HFP, fluoroalkyl vinyl ether and CTFE.

[0033] The fluoroalkyl vinyl ether is preferably at least one selected from fluoromonomers of the formulae (13)-(15):         CF 2 =CF-ORf 13<      (13) wherein Rf 13< is C 1-8 -perfluoroalkyl;         CF 2 =CFOCF 2 ORf 14<      (14) wherein Rf 14< is linear or branched C 1-6 -perfluoroalkyl, a cyclic C 5-6 -perfluoroalkyl, or linear or branched C 2-6 -perfluorooxyalkyl including 1-3 oxygen atoms; and         CF 2 =CFO(CF 2 CF(Y 15< )O) m (CF 2 ) n F     (15) wherein Y 15< is F or trifluoromethyl, m is an integer of 1-4, and n is an integer of 1-4.

[0034] More preferably, the fluoroalkyl vinyl ether is a fluoromonomer of formula (13).

[0035] Specific examples of the VdF-based fluoroelastomer include a VdF / HFP-based rubber, a VdF / HFP / TFE-based rubber, VdF / CTFE-based rubber, a VdF / CTFE / TFE-based rubber, a VdF / fluoromonomer (11)-based rubber, a VdF / fluoromonomer (11) / TFE-based rubber, a VdF / perfluoro(methyl vinyl ether) [PMVE]-based rubber, a VdF / PMVE / TFE-based rubber, and a VdF / PMVE / TFE / HFP-based rubber. The VdF / fluoromonomer (11)-based rubber is preferably a VdF / CH 2 =CFCF 3 -based rubber, and the VdF / fluoromonomer (11) / TFE-based rubber is preferably VdF / TFE / CH 2 =CFCF 3 -based rubber.

[0036] The VdF / CH 2 =CFCF 3 -based rubber is preferably a copolymer comprising 40-99.5 mol% of VdF and 0.5-60 mol% of CH 2 =CFCF 3 , and more preferably 50-85 mol% of VdF and 15-50 mol% of CH 2 =CFCF 3 .

[0037] The TFE / Pr-based fluoroelastomer is preferably a copolymer comprising 45-70 mol% of TFE, 55-30 mol% of Pr, and 0-5 mol% of fluoromonomer that provides a crosslinking site.

[0038] The fluorine-containing elastomer may be a perfluoroelastomer. Examples of the perfluoroelastomer include at least one selected from a perfluoroelastomer including TFE, for example, a copolymer of TFE / fluoromonomer (13), (14) or (15), and a copolymer of TFE / fluoromonomer (13), (14) or (15) / monomer providing a crosslinking site.

[0039] In the case of a TFE / PMVE copolymer, the compositional features thereof are preferably 45-90 / 10-55 (mol%), more preferably 55-80 / 20-45, and further preferably 55-70 / 30-45.

[0040] In the case of a copolymer of TFE / PMVE / monomer that provides a crosslinking site, the compositional features thereof are preferably 45-89.9 / 10-54.9 / 0.01-4 (mol%), more preferably 55-77.9 / 20-49.9 / 0.1-3.5, and further preferably 55-69.8 / 30-44.8 / 0.2-3.

[0041] In the case of a copolymer of TFE / fluoromonomer (13), (14) or (15) having 4-12 carbon atoms, the compositional features thereof are preferably 50-90 / 10-50 (mol%), more preferably 60-88 / 12-40, and further preferably 65-85 / 15-35.

[0042] In the case of a copolymer of TFE / fluoromonomer (13), (14) or (15) having 4-12 carbon atoms / monomer that provides a crosslinking site, the compositional features thereof are preferably 50-89.9 / 10-49.9 / 0.01-4 (mol%), more preferably 60-87.9 / 12-39.9 / 0.1-3.5, and further preferably 65-84.8 / 15-34.8 / 0.2-3.

[0043] If the compositional features of these copolymers are beyond these ranges, their nature as a rubber elastic body is lost, and the copolymer tends to have a nature close to that of a resin.

[0044] Examples of the perfluoroelastomer include at least one selected from a copolymer of TFE / fluoromonomer formula (15) / monomer that provides a crosslinking site, a copolymer of TFE / fluoromonomer (15), a copolymer of TFE / fluoromonomer (13), and a copolymer of TFE / fluoromonomer (13) / monomer that provides a crosslinking site.

[0045] Examples of the perfluoroelastomer may include the perfluoroelastomers described in e.g. WO 97 / 24381, JP-B-1986-57324, JP-B-1992-81608 and JP-B-1993-13961.

[0046] The monomer that provides a crosslinking site is a monomer (cure site monomer) having a crosslinkable group that provides the fluorine-containing polymer with a crosslinking site for forming a crosslink by a cross-linking agent.

[0047] Examples of the monomer that provides a crosslinking site include monomers of formula (16):         CX 4< 2 =CX 5< R f 2< X 6< wherein X 4< and X 5< are each independently H, F, or C 1-5 -alkyl, R f 2< is linear or branched alkylene or oxyalkylene which may have one or more ether-bonding oxygen atoms, which may have an aromatic ring, and in which a part or all of its hydrogen atoms may be replaced with F, and X 6< is I, Br, , nitrile, carboxyl, alkoxycarbonyl, hydroxyl, vinyl, azide, sulfonyl azide, carbonyl azide, or alkyne. The alkyne group may be ethynyl.

[0048] The monomer that provides a crosslinking site is preferably, from among the following, at least one selected from the monomers of the following formulae (17)-(21):         CX 16< 2 =CX 16< -Rf 16< CHR 16< X 17<      (17) wherein each X 16< is independently H, F or CH 3 , Rf 16< is fluoroalkylene, perfluoroalkylene, fluoro(poly)oxyalkylene, or perfluoro (poly) oxyalkylene, R 16< is H or CH 3 , and X 17< is I or Br;         CX 16< 2 =CX 16< -Rf 17< X 17<      (18) wherein each X 16< is independently H, F or CH 3 , Rf 17< is fluoroalkylene, perfluoroalkylene, fluoro(poly)oxyalkylene, or perfluoro(poly)oxyalkylene, and X 17< is I or Br;         CF 2 =CFO(CF 2 CF(CF 3 )O) m (CF 2 ) n -X 18<      (19) wherein m is an integer of 0-5, n is an integer of 1-3, and X 18< is cyano, azide, sulfonyl azide, carbonyl azide, carboxyl, alkoxycarbonyl, alkyne, I, Br, or -CH 2 I;         CH 2 =CFCF 2 O(CF(CF 3 )CF 2 O) m (CF(CF 3 )) n -X 19<      (20) wherein m is an integer of 0-5, n is an integer of 1-3, and X 19< is cyano, carboxyl, alkoxycarbonyl, I, Br, or -CH 2 OH; and         CR 20< 2 =CR 20< -Z-CR 20< =CR 20< 2      (21) wherein each R 20< is independently H or C 1-5 -alkyl, and Z is linear or branched C 1-18 -alkylene which may have an oxygen atom, C 3-18 -cycloalkylene, an C 1-10 -alkylene or -oxyalkylene which is at least partially fluorinated, or a (per)fluoropolyoxyalkylene group having a molecular weight of 500-10,000 and represented by         -(Q) p -CF 2 O-(CF 2 CF 2 O) m (CF 2 O) n --CF 2 -(Q) p - wherein Q is alkylene or oxyalkylene, P is 0 or 1, and m / n is 0.2-5.

[0049] X 16< is preferably F. Rf 16< and Rf 17< are preferably C 1-5 -perfluoroalkylene. R 16< is preferably H. X 18< is preferably cyano, alkoxycarbonyl, I, Br, or -CH 2 I. X 19< is preferably cyano, alkoxycarbonyl, I, Br, or -CH 2 OH.

[0050] The monomer that provides the crosslinking site is preferably at least one selected from CF 2 =CFOCF 2 CF(CF 3 )OCF 2 CF 2 CN, CF 2 =CFOCF 2 CF(CF 3 )OCF 2 CF 2 COOH, CF 2 =CFOCF 2 CF(CF 3 )OCF 2 CF 2 CH 2 I, CF 2 =CFOCF 2 CF 2 CH 2 I, CH 2 =CFCF 2 OCF(CF 3 )CF 2 OCF(CF 3 )CN, CH 2 =CFCF 2 OCF(CF 3 )CF 2 OCF(CF 3 )COOH, CH 2 =CFCF 2 OCF(CF 3 )CF 2 OCF(CF 3 )CH 2 OH, CH 2 =CHCF 2 CF 2 I, CH 2 =CH(CF 2 ) 2 CH=CH 2 , CH 2 =CH(CF 2 ) 6 CH=CH 2 , and CF 2 =CFO(CF 2 ) 5 CN 2 , and more preferably at least one selected from the group consisting of CF 2 =CFOCF 2 CF(CF 3 )OCF 2 CF 2 CN and CF 2 =CFOCF 2 CF 2 CH 2 I.

[0051] From the viewpoint of excellent compression set at high temperature, the fluorine-containing elastomer has a glass transition temperature of preferably -70°C or higher, more preferably -60°C or higher, and further preferably -50°C or higher. Further, from the viewpoint of good low-temperature resistance, the fluorine-containing elastomer has a glass transition temperature of preferably 5°C or lower, more preferably ≤ 0°C, and further preferably -3°C or lower.

[0052] The glass transition temperature is determined as follows: using a differential scanning calorimeter (DSC822e, manufactured by Mettler Toledo), a DSC curve is obtained by heating 10 mg of a sample at 10 °C / min; and the temperature is read at the intermediate point of two intersections between each of the extension lines of the baselines before and after the secondary transition of the DSC curve and the tangent line at the inflection point of the DSC curve.

[0053] From the viewpoint of good heat resistance, the fluorine-containing elastomer has a Mooney viscosity ML (1+20) at 170°C of preferably ≥ 30, more preferably ≥ 40, and further preferably ≥ 50. Further, from the viewpoint of good processibility, the fluorine-containing elastomer has a Mooney viscosity ML of preferably ≤ 150, more preferably ≤ 120, and further preferably ≤ 110.

[0054] From the viewpoint of good heat resistance, the fluorine-containing elastomer has a Mooney viscosity ML (1+20) at 140°C of preferably ≥ 30, more preferably ≥ 40, and further preferably ≥ 50. Further, from the viewpoint of good processability, the fluorine-containing elastomer has a Mooney viscosity ML of preferably ≤ 180, more preferably ≤ 150, and further preferably ≤ 110.

[0055] From the viewpoint of good heat resistance, the fluorine-containing elastomer has a Mooney viscosity ML (1+10) at 100°C of preferably ≥ 10, more preferably ≥ 20, and further preferably ≥ 30. Further, from the viewpoint of good processability, the fluorine-containing elastomer has a Mooney viscosity ML of preferably ≤ 120, more preferably ≤ 100, and further preferably ≤ 80.

[0056] The Mooney viscosity can be measured at 170°C, 140°C, or 100°C according to JIS K6300 by using a Mooney viscometer MV2000E manufactured by ALPHA TECHNOLOGIES.

[0057] The above-described partially fluorinated elastomer and perfluoroelastomer can be produced by a conventional method. However, from the viewpoint of a narrow molecular weight distribution of the obtained polymer, easy control of the molecular weight, and being able to introduce an iodine atom or a bromine atom to a terminal, an iodine compound or a bromine compound can also be used as a chain transfer agent. Examples of a polymerization method performed using an iodine compound or a bromine compound include a method in which emulsion polymerization is carried out in an aqueous medium under pressure in the presence of the iodine compound or the bromine compound in a substantially oxygen-free state (iodine transfer polymerization method). Typical examples of the iodine compound or bromine compound to be used include, for example, a compound of the formula:         R 21< I x Br y wherein x and y are each an integer of 0-2 and satisfy 1 ≤ x + y ≤ 2; and R 21< is a saturated or unsaturated C 1-16 -fluorohydrocarbon or - chlorofluorocarbon group or a C 1-3 -hydrocarbon group, 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 to function as a cross-linking point.

[0058] Examples of the iodine compound and the bromine compound include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1,5-diode-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodineperfluorohexadecane, 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 CFBrOF 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, a monoiodomonobromo-substituted benzene, a diiodomonobromo-substituted benzene, and a (2-iodoethyl)-substituted benzene and a (2-bromoethyl)-substituted benzene. These compounds can be used alone or in combination together.

[0059] Among these, it is preferable to use 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, or 2-iodoperfluoropropane from the viewpoint of polymerization reactivity, cross-linking reactivity and availability.

[0060] The above-described fluorine-containing polymer preferably has a cyano group. In particular, when a cage-type silsesquioxane is used as a cross-linking agent, the fluorine-containing polymer preferably has a cyano group. When the fluorine-containing polymer has a cyano group, the cage-type silsesquioxane acts as a cross-linking agent in a more suitable manner, and further, a crosslinked product having excellent heat resistance can be obtained.

[0061] The fluorine-containing polymer having a cyano group is a fluorine-containing elastomer having a cyano group (-CN group) at a main chain terminal and / or in a side chain.

[0062] Examples of the fluorine-containing elastomer having a cyano group (-CN group) at a terminal of the main chain and / or in a side chain include a perfluoroelastomer and a partially fluorinated elastomer.

[0063] Examples of the perfluoroelastomer having a cyano group (-CN group) at a terminal of the main chain and / or in a side chain include copolymers in which the monomer that provides a crosslinking site is a monomer having a cyano group (-CN group) among the above-described copolymers of TFE / fluoromonomer (13), (14) or (15) / monomer that provides a crosslinking site. In this case, the content of the monomer unit having a cyano group (-CN group) may be 0.1-5 mol% with respect to the total amount of the TFE units and the fluoromonomer units of formula (13), (14) or (15), from the viewpoint of good crosslinking characteristics and heat resistance, and may even be 0.3-3 mol%. Even more preferable compositional features are as described above.

[0064] Further, examples of the monomer having a cyano group (-CN group) include monomers of the following formulas:         CY 1< 2 =CY 1< (CF 2 ) n -CN wherein each Y 1< is independently H or F, and n is an integer of 1-8;         CF 2 =CFCF 2 Rf 8< -CN wherein Rf 8< is -(OCF 2 ) n - or -(OCF(CF 3 )) n -, and n is an integer of 0-5;         CF 2 =CFCF 2 (OCF(CF 3 )CF 2 ) m (OCH 2 CF 2 CF 2 ) n OCH 2 CF 2 -CN wherein m is an integer of 0-5, and n is an integer of 0-5;         CF 2 =CFCF 2 (OCH 2 CF 2 CF 2 ) m (OCF(CF 3 )CF 2 ) n OCF(CF 3 )-CN wherein m is an integer of 0-5, and n is an integer of 0-5;         CF 2 =CF(OCF 2 CF(CF 3 )) m O(CF 2 ) n -CN wherein m is an integer of 0-5, and n is an integer of 1-8;         CF 2 =CF(OCF 2 CF(CF 3 )) m -CN wherein m is an integer of 1-5;         CF 2 =CFOCF 2 (CF(CF 3 )OCF 2 ) n CF(-CN)CF 3 wherein n is an integer of 1-4;         CF 2 =CFO(CF 2 ) n OCF(CF 3 )-CN wherein n is an integer of 2-5;         CF 2 =CFO(CF 2 ) n -(C 6 H 4 )-CN wherein n is an integer of 1-6;         CF 2 =CF(OCF 2 CF(CF 3 )) n OCF 2 CF(CF 3 )-CN wherein n is an integer of 1-2;         CH 2 =CFCF 2 O(CF(CF 3 )CF 2 O) n CF(CF 3 )-CN wherein n is an integer of 0-5;         CF 2 =CFO(CF 2 CF(CF 3 )O) n ,(CF 2 ) n -CN wherein m is an integer of 0-5, and n is an integer of 1-3;         CH 2 =CFCF 2 OCF(CF 3 )OCF(CF 3 )-CN;         CH 2 =CFCF 2 OCH 2 CF 2 -CN;         CF 2 =CFO(CF 2 CF(CF 3 )O) m CF 2 CF(CF 3 )-CN wherein m is an integer of ≥ 0;         CF 2 =CFOCF(CF 3 )CF 2 O(CF 2 ) n -CN wherein n is an integer of ≥ 1; and         CF 2 =CFOCF 2 OCF 2 CF(CF 3 )OCF 2 -CN.

[0065] These monomers can be used alone or in any combination.

[0066] Among the above, a monomer of the Formula CF 2 =CF(OCF 2 CF(CF 3 )) m O(CF 2 ) n -CN wherein m is an integer of 0-5, n is an integer of 1-8; and CF 2 =CFOCF 2 CF(CF 3 )OCF 2 CF 2 CN is more preferable.

[0067] These perfluoroelastomers can be produced by a conventional method.

[0068] Specific examples of the perfluoroelastomer may include the fluoroelastomers described in e.g. WO 97 / 24381, JP-B-1988-57324, JP-B-1992-81608 and JP-B-1993-13961.

[0069] Examples of the partially fluorinated elastomer having a cyano group (-CN) at a terminal of the main chain and / or in a side chain include VdF-based fluoroelastomers, TFE / Pr-based fluoroelastomers, TFE / Pr / VdF-based fluoroelastomers, Et / HFP-based fluoroelastomers, Et / HFP / VdF-based fluoroelastomers, Et / HFP / TFE-based fluoroelastomers, fluorinesilicone-based fluoroelastomers, and fluorophosphazene fluoroelastomers. These can each be used alone, or in any combination as long as the effects of the present disclosure are not impaired.

[0070] The VdF-based fluoroelastomer is a fluorine-containing copolymer comprising 45-85 mol% of VdF and 55-15 mol% of at least one other monomer copolymerizable with VdF, preferably 50-80 mol% of VdF and 50-20 mol% of at least one other monomer copolymerizable with VdF.

[0071] Examples of the at least one other monomer copolymerizable with vinylidene fluoride include a fluoromonomer such as TFE, CTFE, trifluoroethylene, HFP, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, perfluoro(alkyl vinyl ether) (PAVE), and vinyl fluoride, and non-fluorinated monomers such as ethylene, propylene and alkyl vinyl ether. These can be used alone or in any combination. Among these, TFE, HFP, and perfluoro(alkyl vinyl ether) are preferable.

[0072] Specific examples of the rubber include VdF-HFP-based rubber, VdF-HFP-TFE-based rubber, VdF-CTFE-based rubber, and VdF-CTFE-TFE-based rubber.

[0073] These partially fluorinated elastomers can be produced by a conventional method.

[0074] Further, as the fluorine-containing elastomer, a thermoplastic fluoroelastomer comprising an elastomeric fluorine-containing polymer chain segment and a non-elastomeric fluorine-containing polymer chain segment may be used.

[0075] The present composition preferably further contains a cross-linking agent. Examples of the cross-linking agent include cross-linking agents used in peroxide cross-linking, polyol cross-linking, polyamine cross-linking, triazine cross-linking, oxazole cross-linking, imidazole cross-linking, and thiazole cross-linking. When the fluorine-containing polymer is a fluorine-containing elastomer having a cyano group (-CN group) at a terminal of a main chain and / or in a side chain, the cross-linking agent is preferably at least one selected from an oxazole cross-linking agent, an imidazole cross-linking agent, and a thiazole cross-linking agent.

[0076] The cross-linking agent used for peroxide crosslinking may be any organic peroxide that can easily generate a peroxy radical in the presence of heat or a redox system. Specific examples include 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide (Perbutyl D), t-butylcumyl peroxide (Perbutyl C), dicumyl peroxide (Percumyl D, Percumyl D-40, Percumyl D-40 MB(T)), α,α-bis(t-butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (Perhexa 25B, Perhexa 25B-40), 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 (Perhexyne 25B, Perhexyne 25B-40), benzoyl peroxide, t-butylperoxybenzene, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane (Perhexa 25Z), t-butylperoxy maleate (t-butyl MA), t-butylperoxyisopropyl carbonate (Perbutyl I-75), methyl ethyl ketone peroxide (Permek D (DR), Permek H (HR, HY), Permek N (NR, NY), Permek S (SR), Permek F (FR), Permek G (GR, GY)), cyclohexanone peroxide (Perhexa H), acetylacetone peroxide (Percure AH, AL), 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane (Perhexa TMH), 1,1-di(t-hexylperoxy)cyclohexane (Perhexa HC), 1,1-di(t-butylperoxy)-2-methyl cyclohexane (Perhexa MC), 1,1-di(t-butylperoxy)cyclohexane (Perhexa C-80(S), Perhexa C-75(EB), Perhexa C(C), Perhexa C-40, Perhexa C-40 MB(S)), 2,2-di(t-butylperoxy)butane (Perhexa 22), butyl 4,4-di-(t-butylperoxy) pentanoate (Perhexa V, Perhexa V-40(F)), 2,2-di(4,4-di-(t-butylperoxy) cyclohexyl) propane (Pertetra A), p-menthane hydroperoxide (Permentha H), diisopropylbenzene hydroperoxide (Percumyl P), 1,1,3,3-tetramethylbutyl hydroperoxide (Perocta H), cumene hydroperoxide (Percumyl H-80), t-butyl hydroperoxide (Perbutyl H-69), di(2-t-butylperoxyisopropyl)benzene (Perbutyl P, Perbutyl P-40, Peroxymon F-40, Perbutyl P-40 MB(K)), di-t-hexyl peroxide (Perhexyl D), diisobutyryl peroxide (Peroyl IB), di(3,5,5-trimethylhexanoyl) peroxide (Peroyl 355(S)), dilauroyl peroxide (Peroyl L), disuccinic peroxide (Peroyl SA), a mixture of di-(3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, and dibenzoyl peroxide (Nyper BMT-K40, Nyper BMT-M), dibenzoyl peroxide (Nyper BW, Nyper BO, Nyper FF, Nyper BS, Nyper E, Nyper NS), di (4-methylbenzoyl) peroxide (Nyper PMB), di-n-propyl peroxydicarbonate (Peroyl NPP-50M), diisopropyl peroxydicarbonate (Peroyl IPP-50, Peroyl IPP-27), di (4-t-butylcyclohexyl) peroxydicarbonate (Peroyl TCP), di (2-ethylhexyl) peroxydicarbonate (Peroyl OPP), di-sec-butylperoxydicarbonate (Peroyl SBP), cumyl peroxyneodecanoate (Percumyl ND, Percumyl ND-50E), 1,1,3,3-tetramethylbutylperoxyneodecanoate (Perocta ND, Perocta ND-50E), t-hexyl peroxyneodecanoate (Perhexyl ND, Perhexyl ND-50E), t-butylperoxyneodecanoate (Perbutyl ND, Perbutyl ND-50E), t-butylperoxy neoheptanoate (Perbutyl NHP), t-hexylperoxy pivalate (Perhexyl PV, Perhexyl PV-50E), t-butylperoxy pivalate (Perbutyl PV, Perbutyl PV-40E), 1,1,3,3-tetramethylbutylperoxy-2-ethyl hexanoate (Perocta O), 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane (Perhexa 25 O), t-hexyl peroxy-2-ethyl hexanoate (Perhexyl O, Percure HO(N)), t-butylperoxy-2-ethyl hexanoate (Perbutyl O, Percure O), t-hexyl peroxyisopropyl monocarbonate (Perhexyl I), t-butylperoxy-3,5,5-trimethyl hexanoate (Perbutyl 355), t-butylperoxy laurate (Perbutyl L), t-butylperoxy-2-ethylhexyl monocarbonate (Perbutyl E), t-hexyl peroxybenzoate (Perhexyl Z), t-butyl peroxyacetate (Perbutyl A), a mixture of t-butylperoxy-3-methyl benzoate and t-butylperoxy benzoate (Perbutyl ZT), t-butylperoxy benzoate (Perbutyl Z), t-butylperoxyallyl monocarbonate (peromer AC), 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone (BTTB-25), and 2,3-dimethyl-2,3-diphenylbutane (Nofmer BC-90). Preferred among these are dialkyl-type organic peroxides, and particularly preferred is 2,5-dimethyl-2,5-di(t-butylperoxy) hexane. Usually, the type and amount of the organic peroxide are selected in consideration of e.g. the amount of active -O-O- and the decomposition temperature.

[0077] Further, the cross-linking aid that can be used for peroxide crosslinking may be a compound having a reactivity with a peroxy radical and a polymer radical. Examples thereof include polyfunctional compounds having a functional group such as -CH=CH 2 , -CH 2 CH=CH 2 , -CF=CF 2 , -C(CF 3 )=CF 2 , -C(CH 3 )=CF 2 , -CF=CF(CF 3 ), -CF=CF(CH 3 ), -C(C 6 H 5 )=CF 2 , -CF=CF(C 6 H 5 ), -CH=CF 2 , -CF=CHF, -C(CF 3 )=CHF, -CF=CH(CF 3 ), and -CH=CF(CF 3 ) wherein "C 6 H 5 " represents a phenyl radical. Specific examples thereof include triallyl cyanurate, triallyl isocyanurate (TAIC), triacryl formal, triallyl trimerite, N,N'-n-phenylene bismaleimide, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1,3,5-tris(2,3,3-trifluoro-2-propenyl)-1,3,5-triazine 2,4,6-trione), tris(diallylamine)-S-triazine, triallyl phosphite, N,N-diallylacrylamide, and 1,6-divinyldodecafluorohexane.

[0078] Further, examples of a cross-linking aid used together with the peroxide cross-linking agent include a compound of formula (31): wherein each of the six R 31< is independently H, halogen, or an optionally halogenated C 1-5 -group in which an ether bond may be inserted, and Z 31< is optionally halogenated linear or branched alkylene or cycloalkylene, or (per)fluoropolyoxyalkylene, each of which has 1-18 carbon atoms and optionally contains a hetero atom.

[0079] Examples of the compound of formula (31) include the compounds of formulae (32)-(34): wherein j is an integer of 2-10, preferably 4-8, and each of the four R 32< is independently H, F, C 1-5 -alkyl or C 1-5 -(per) fluoroalkyl, wherein each Y 31< is independently F, Cl, or H, each Y 32< is independently F, Cl, H, or OR 33< , where R 33< is branched or linear alkyl that may be partially, substantially, or completely fluorinated or chlorinated, Z 33< is an optionally fluorinated divalent C 2-10 -group in which an ether bond may be inserted, preferably Z 33< is -(CF 2 ) m - in which m is an integer of 3-5, and the compound of formula (33) is preferably F 2 C=CF-O-(CF 2 ) 5 -O-CF=CF 2 ), wherein Y 31< , Y 32< , and Z 33< are as defined above, and each R 34< is independently H, F, C 1-5 -alkyl or C 1-5 - (per) fluoroalkyl.

[0080] Examples of the cross-linking agent, or cross-linking aid used together with the peroxide cross-linking agent, include compounds having at least one structure offormula (35): wherein R 35< -R 37< are each independently H, F, alkyl, fluoroalkyl, or optionally substituted aryl, and at least one of R 35< -R 37< is F or a group containing F; m is an integer of 1-5; when m is ≥ 2, m-number of R 35< -R 37< may be the same or different with each other; and the H atoms of the benzene ring may be substituted. When m is 1, it is preferable to have two or more of the structures.

[0081] Examples of the compound of formula (36) include compounds of the formulae (36) and (37): wherein R 35< -R 37< are as defined above; p is an integer of 0-2; and n is an integer of 2-6, wherein R 35< -R 37< are as defined above, R 38< is a single bond, - SO 2 -, -O-, -S-, -CO-, a heteroatom-containing group, or alkylene, cycloalkylene arylene, each optionally substituted, m is an integer of 1-5, and a part or all of these groups may be fluorinated.

[0082] The heteroatom-containing group is not limited as long as it is a divalent group containing a heteroatom. Examples of the heteroatom include O, N, S, B and P.

[0083] Examples of the cross-linking agent used for polyol crosslinking include polyhydric alcohol compounds such as bisphenol A and bisphenol AF.

[0084] Examples of the cross-linking agent used for polyamine crosslinking include polyamine compounds such as hexamethylenediamine carbamate, N,N'-dicinenamiridene-1,6-hexanediamine, and 4,4'-bis(aminocyclohexyl)methane carbamate.

[0085] Examples of the cross-linking agent used for triazine crosslinking include organic tin compounds such as tetraphenyltin and triphenyltin.

[0086] Examples of the cross-linking agents used for oxazole crosslinking, imidazole crosslinking, and thiazole crosslinking include a bisdiaminophenyl-based cross-linking agent, a bis-aminophenol-based cross-linking agent, and a bis-aminothiophenol-based cross-linking agent of formula (41): wherein R 41< is -SO 2 -, -O-, -CO-, an alkylene group having 1-6 carbon atoms, a perfluoroalkylene group having 1-10 carbon atoms, a single bond, or a group one of R 42< and R 43< is -NH 2 and the other is -NHR 44< , -NH 2 , -OH, or -SH, R 44< is H, F, or a monovalent organic group, preferably R 42< is -NH 2 and R 43< is -NHR 44< ; preferred specific examples of the C 1-6 -alkylene group include methylene, ethylene, propylene, butylene, pentylene, and hexylene, and examples of the C 1-10 -perfluoroalkylene group include -C(CF 3 ) 2 -:

[0087] These compounds are known as examples of bisdiaminophenyl compounds in e.g. JP-B-1990-59177 and JP-A-1996-120146; a bisamidrazone-based cross-linking agent of formula (42): R 41< is as defined above, and each R 45< is independently any one of the following groups: an amidrazone-based cross-linking agent of formula (43): wherein Rf 41< is C 1-10 -perfluoroalkylene; and a bisamidoxime-based cross-linking agent of formula (44): wherein n is an integer of 1-10, a compound of the formula HN=CR 45< R 46< (45), wherein R 45< is H, NH 2 , or NHR 47< , R 46< is Ph, SO 2 H, NR 48< R 49< , 2-pyridine, or CH 2 CONH 2 , R 47< is Ph, NH 2 , or CN, R 48< is H, NHPh, CH 2 CONH 2 , or linear or branched C 1-8 -alkyl, and R 49< is Ph, COOC(CH 3 ) 3 , NH 2 , CH 2 COOH, CSNH 2 , CNHNH 3 +< Cl -< , p-phenyl CN, or COPh.

[0088] These bisaminophenol-based cross-linking agents, bisaminothiophenol-based cross-linking agents, and bisdiaminophenyl-based cross-linking agents have conventionally been used in crosslinking systems that use a cyano group as a crosslinking point, but these agents also react with a carboxyl group and an alkoxycarbonyl group to form an oxazole ring, a thiazole ring, and an imidazole ring to provide a crosslinked product.

[0089] Further, examples of the cross-linking agent include a cross-linking agent of the formula X 41< -(CH 2 ) n -R 50< -(CH 2 ) m -X 41< (46), wherein each X 41< is independently alkyne, nitrile, or Y 41< P N 3 , wherein Y 41< is SO, SO 2 , C 6 H 4 , or CO, and p is 0 or 1, n and m are independently integers of 1-4, and R 50< is selected from i) C 3-10 -fluoroalkylene, ii) a C 3-10 -fluoralkoxylene, iii) substituted arylene, iv) an oligomer including a copolymerization unit of VdF and perfluoro(methylvinylether), v) an oligomer including a copolymerization unit of VdF and HFP, vi) an oligomer including a copolymerization unit of TFE and perfluoro(methylvinylether), and vii) an oligomer including a copolymerization unit of TFE and a hydrocarbon olefin.

[0090] This cross-linking agent is preferably used together with a fluorine-containing elastomer having a nitrile group, an azide group, a sulfonyl azide group, a carbonyl azide group, or an alkyne group. For example, the nitrile group of the fluorine-containing elastomer reacts with the azide group of the cross-linking agent to form a tetrazole ring to provide a crosslinked product.

[0091] Examples of a particularly preferred cross-linking agent include a compound having a plurality of 3-amino-4-hydroxyphenyl groups or 3-amino-4-mercaptophenyl groups, or a compound of formula (47): wherein R 41< , R 42< , and R 43< are as defined above. Specifically, examples include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (generic name: bis(aminophenol)AF), 2,2-bis(3-amino-4-mercaptophenyl)hexafluoropropane, tetraaminobenzene, bis-3,4-diaminophenylmethane, bis-3,4-diaminophenyl ether, 2,2-bis(3,4-diaminophenyl)hexafluoropropane, 2,2-bis[3-amino-4-(N-phenylamino)phenyl]hexafluoropropane, 2,2-bis[3-amino-4-(N-methylamino)phenyl]hexafluoropropane, 2,2-bis[3-amino-4-(N-ethylamino)phenyl]hexafluoropropane, 2,2-bis[3-amino-4-(N-propylamino)phenyl]hexafluoropropane, 2,2-bis[3-amino-4-(N-perfluorophenylamino)phenyl]hexafluoropropane, and 2,2-bis[3-amino-4-(N-benzylamino)phenyl]hexafluoropropane.

[0092] Among these, from the viewpoints of heat resistance, steam resistance, amine resistance, and good crosslinkability, the cross-linking agent is preferably 2,2-bis[3-amino-4-(N-phenylamino)phenyl]hexafluoropropane.

[0093] The content of the cross-linking agent is, with respect to 100 pbm of the fluorine-containing elastomer, preferably 0.05-10 pbm, and more preferably 0.5-5 pbm.

[0094] The composition may contain a filler (provided that the above-described silicon oxide is excluded).

[0095] Examples of the filler other than the silicon oxide include an imide-based filler having an imide structure such as polyimide, polyamideimide, and polyetherimide, an organic filler made of engineering plastic such as polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyether ether ketone, polyether ketone, and polyoxybenzoate, a metal oxide filler such as aluminum oxide (Al 2 O 3 ), silicon oxide (SiO 2 ), and yttrium oxide, a metal carbide such as silicon carbide and aluminum carbide, a metal nitride filler such as silicon nitride and aluminum nitride, an inorganic filler such as aluminum fluoride, carbon fluoride, barium sulfate, carbon black, silica, clay, and talc.

[0096] Among these, carbon black, aluminum oxide (Al 2 O 3 ), silicon oxide (SiO 2 ), yttrium oxide, silicon nitride, silicon carbide, polyimide, and carbon fluoride are preferable from the viewpoint of a shield effect against various plasmas.

[0097] Further, the inorganic filler and organic filler may be used alone or blended in a combination of two or more thereof.

[0098] The amount of the filler other than the silicon oxide to be blended is preferably 0.5-100 pbm, and more preferably 5-50 pbm, with respect to 100 pbm of the fluorine-containing elastomer.

[0099] Especially in fields not requiring high purity and non-contamination properties, an ordinary additive that is blended in the fluorine-containing polymer composition, such as a processing aid, a plasticizer, and a colorant, can optionally be blended. One or more common cross-linking agents and cross-linking aids different from those described above may also be blended.

[0100] The composition may contain an organic basic compound. Examples of the organic basic compound include an octadecylamine of formula: CH 3 (CH 2 ) 17 -NH 2 ; an erucamide of formula: H 2 N-C(O)- (CH 2 ) 11 -CH=CH-(CH 2 ) 7 CH 3; an oleamide of formula: H 2 N-C(O)-(CH 2 ) 7 -CH=CH-(CH 2 ) 7 CH 3 ; a hexamethylenediamine of formula: H 2 N-(CH 2 ) 6 -NH 2 ; and a 1,8-diazabicycloundec-7-en (DBU) of formula:

[0101] The composition can be prepared by mixing each of the above-described components by using an ordinary polymer processing machine, for example, an open roll, a Banbury mixer, or a kneader. In addition, the fluorine-containing elastomer composition can also be prepared by a method using a closed mixer.

[0102] The composition can be suitably used as a crosslinkable composition for obtaining a crosslinked product by crosslinking.

[0103] The present crosslinked product can be obtained by crosslinking the above-described composition. The composition for obtaining a crosslinked product preferably contains a cross-linking agent. The present crosslinked product can adsorb oxygen in the air. Therefore, by using the present crosslinked product as a sealing material or the like of an apparatus including a sealed space such as a semiconductor manufacturing apparatus, oxygen in the sealed space can be adsorbed to reduce the oxygen concentration in the sealed space, and oxygen can be prevented from entering the sealed space from the outside. Furthermore, the present crosslinked product contains a fluorine-containing polymer, and is thus also excellent in heat resistance and plasma resistance.

[0104] The ability of the crosslinked product to adsorb oxygen can be confirmed, for example, by a method for confirming the weight increase of the crosslinked product when the crosslinked product is heated in air. The fluorine-containing polymer contained in the crosslinked product has excellent heat resistance, and the weight hardly increases upon heating. Therefore, the present composition, which increase in weight upon heating in air, is a novel composition.

[0105] The above-described crosslinking can be performed in the order of primary crosslinking and secondary crosslinking. The primary crosslinking is preferably carried out at 150-200°C for 5-120 minutes, and more preferably at 160-190°C for 5-60 minutes. As the crosslinking means, known crosslinking means may be used, and examples thereof include press-crosslinking.

[0106] The secondary crosslinking is preferably carried out at 170-320°C for 2-24 hours, and more preferably at 180-310°C for 5-20 hours. As the crosslinking means, known crosslinking means may be used, and examples thereof include oven crosslinking. Further, by crosslinking in an inert gas such as nitrogen gas, the oxygen adsorption capacity of the obtained crosslinked product can be further improved.

[0107] The crosslinked product (molded article) may be obtained by molding the composition to obtain a preform, and then crosslinking the preform. The method for obtaining the preform by using the composition may be an ordinary method, and is performed by a known method such as a method of heating and compressing in a mold, a method of press-fitting into a heated mold, and a method of extruding with an extruder. In the case of an extruded product such as a hose and an electric wire, the crosslinked product can be obtained, for example, by heating and crosslinking with steam after extrusion.

[0108] The present crosslinked product can be suitably used as a sealing material for a semiconductor fabrication apparatus that particularly requires heat resistance, and particularly a semiconductor fabrication apparatus in which high-density plasma irradiation is performed. Examples of the sealing material include O-rings, square-rings, gasket, packing, oil seals, bearing seals, and lip seals.

[0109] In addition, the present molded article can also be used as various polymer products used in semiconductor fabrication apparatus, such as diaphragms, tubes, hoses, various rubber rolls, and belts. Further, the molded article of the present disclosure can also be used as a coating material and a lining material.

[0110] As referred to herein, the "semiconductor fabrication apparatus" is not limited to an apparatus for fabricating semiconductors, and widely includes general fabrication apparatus used in the semiconductor field requiring a high level of cleanliness, such as apparatus for manufacturing liquid crystal panels and plasma panels. Examples thereof include the following.

[0111] (1) Etching apparatus Dry etching apparatus Plasma etching apparatus Reactive ion etching apparatus Reactive ion beam etching apparatus Sputter etching apparatus Ion beam etching apparatus Wet etching apparatus Ashing apparatus (2) Cleaning apparatus dry etching cleaning apparatus UV / O 3 cleaning apparatus Ion beam cleaning apparatus Laser beam cleaning apparatus Plasma cleaning apparatus Gas etching cleaning apparatus Extraction and cleaning apparatus Soxhlet extraction cleaning apparatus High-temperature high-pressure extraction cleaning apparatus Microwave extraction cleaning apparatus Supercritical extraction cleaning apparatus (3) Exposure apparatus Stepper Coater / developer (4) Polishing apparatus CMP apparatus (5) Film formation apparatus CVD apparatus Sputtering apparatus (6) Diffusion / ion implantation apparatus Oxidation diffusion apparatus Ion implantation apparatus

[0112] The present crosslinked product exhibits excellent performance as a sealing material for, for example, a CVD apparatus, a plasma etching apparatus, a reactive ion etching apparatus, an ashing apparatus, and an excimer laser exposure machine.EXAMPLES

[0113] Next, embodiments of the present disclosure will be described with reference to examples.

[0114] The numerical values in the examples were measured by the following methods.<Monomer unit compositional feature of fluorine-containing elastomer>

[0115] The monomer unit compositional feature was measured 19< F-NMR analysis was carried out.<Mooney viscosity of fluorine-containing elastomer>

[0116] The Mooney viscosity was measured at 170°C according to JIS K6300 by using a Mooney viscometer MV2000E manufactured by ALPHA TECHNOLOGIES.<Rate of weight increase>

[0117] A test sample having a thickness of 2 mm was used to produce a sample for measuring rate of weight increase of 10 mg. The weight change of the sample was measured using a simultaneous thermogravimetry / differential thermal analyzer (TG / DTA7200 manufactured by SII NanoTechnology Inc.) under the conditions of air 200 ml / min, temperature-increasing rate of 10°C / min, and normal temperature to 600°C. A TG curve was drawn on a graph in which the vertical axis represents the weight change ratio (%) and the horizontal axis represents the temperature (°C), and the weight increase at the time when the temperature reached 400°C was shown as a percentage with respect to the initial weight. A rate of weight increase of > 0% means that the sample has adsorbed oxygen. In addition, a larger rate of weight increase means a larger oxygen adsorption of the sample.<Ordinary-state properties>

[0118] In accordance with JIS K6251, 100% tensile stress (MPa), tensile strength (MPa), elongation (%), and hardness Peak (Shore A) at ordinary state (25°C) of a test sample having a thickness of 2 mm were measured.Production Example (production of silicon oxide)

[0119] A mixed powder of SiO 2 powder and Si powder was used as the raw material powder. Silicon oxide particles represented by formula: SiO x where 0 < x < 2 were produced by generating a thermal plasma flame using hydrogen gas and argon gas as plasma gas, using argon gas as carrier gas, and supplying mixed powder to the thermal plasma flame.

[0120] The obtained particles were analyzed for the compositional feature of the elements constituting the particles with an X-ray photoelectron analyzer ESCA-3400 manufactured by Shimadzu Corporation. As a result, the constituent ratio of silicon and oxygen was 41 atomic% of silicon and 59 atomic% of oxygen.

[0121] The specific surface area of the obtained particles was measured using the BELSOAP-mini II specific surface area-pore distribution measuring apparatus manufactured by BEL JAPAN, INC., and the particle size of the obtained particles was converted from the specific surface area, and as a result, the particle size of the obtained particles was 22 nm.Example 1

[0122] A crosslinkable composition was prepared by kneading with an open roll 100 pbm of a fluorine-containing elastomer (TFE / PMVE / CF 2 =CFOCF 2 CF(CF 3 )OCF 2 CF 2 CN = 59.3 / 39.9 / 0.8 (mol%), Mooney Viscosity (ML (1+20) (170°C)) = 80), 10 pbm of the silicon oxide obtained in Production Example, and 0.8 pbm of 4,4'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[N1-phenyl-1,2-benzenediamine] as a cross-linking agent.

[0123] The obtained crosslinkable composition was pressed at 180°C for 30 minutes to perform cross-linking, and further crosslinked in an oven at 290°C for 18 hours in a nitrogen environment to produce a test sample of a crosslinked product having a thickness of 2 mm.

[0124] Ordinary-state properties of the obtained crosslinked product were measured by the above method. The results are shown in Table 1.

[0125] Furthermore, the weight change of the test sample of the obtained crosslinked product was measured by the above-mentioned method. As a result, the rate of weight increase was 0.18% when the temperature reached 400°C.Example 2

[0126] A crosslinkable composition was prepared in the same manner as in Example 1 except that the content of the silicon oxide was changed to 20 pbm with respect to 100 pbm of the fluorine-containing elastomer, and a test sample of a crosslinked product having a thickness of 2 mm was produced. The results of the same evaluation are shown in Table 1. The rate of weight increase when the temperature reached 400°C was 0.51%.[Table 1]

[0127] Table 1Example 1Example 2Non-stoichiometric silicon oxideConstituent ratio of Si (atom%)4141Content (parts by mass)1020Crosslinked product100% tensile stress (MPa)3.69.9Tensile strength (MPa)10.220.4Elongation (%)201216Hardness Peak (Shore A)7588

Claims

1. A composition comprising - a fluorine-containing polymer which is a fluorine-containing elastomer, and - 0.1-50 parts by mass per 100 parts by mass of the fluorine-containing polymer of a silicon oxide of the formula SiOx wherein 0 < x < 2.

2. The composition of claim 1, wherein the constituent ratio (Si / (Si+O)) of Si in the silicon oxide, determined by X-ray photoelectron spectroscopy (ESCA), is 35-90 atom%.

3. The composition of claim 1 or 2, wherein the rate of weight increase is ≥ 0.1% when a crosslinked product obtained by crosslinking the composition is heated in air from normal temperature to 400°C at a rate of 10°C / min, wherein the rate of weight increase is determined according to the method of the description.

4. The composition of any of claims 1-3, further comprising a cross-linking agent.

5. A crosslinked product obtained by crosslinking the composition of any of claims 1-4.

6. The use of the crosslinked product of claim 5 as a sealing material.