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WO2020027046A1 - Composition et article moulé contenant un polymère contenant du fluor - Google Patents

Composition et article moulé contenant un polymère contenant du fluor Download PDF

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Publication number
WO2020027046A1
WO2020027046A1 PCT/JP2019/029642 JP2019029642W WO2020027046A1 WO 2020027046 A1 WO2020027046 A1 WO 2020027046A1 JP 2019029642 W JP2019029642 W JP 2019029642W WO 2020027046 A1 WO2020027046 A1 WO 2020027046A1
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Prior art keywords
group
acid
crosslinking
polymer
fluorine
Prior art date
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PCT/JP2019/029642
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English (en)
Japanese (ja)
Inventor
文宏 上谷
剛 野口
誠一 平野
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority to CN201980049213.4A priority Critical patent/CN112513175B/zh
Priority to US17/265,343 priority patent/US12091537B2/en
Priority to EP19843590.1A priority patent/EP3831876B1/fr
Priority to KR1020217003040A priority patent/KR102470957B1/ko
Priority claimed from JP2019138605A external-priority patent/JP6708290B2/ja
Publication of WO2020027046A1 publication Critical patent/WO2020027046A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers

Definitions

  • the present disclosure relates to compositions and molded articles containing a fluoropolymer.
  • compositions made of fluorine-containing polymers are excellent in heat resistance, chemical resistance, solvent resistance, fuel oil resistance, etc., and are used for molding O-rings, hoses, stem seals, shaft seals, diaphragms, etc. It is widely used for manufacturing goods.
  • a composition for example, in Patent Document 1, a composite particle and a composition containing a fluoropolymer, wherein the composite particle is composed of a polymer and inorganic particles dispersed in the polymer A composition characterized by the following has been proposed.
  • An object of the present disclosure is to provide a composition containing a fluoropolymer and having excellent scorch resistance.
  • Compositions containing monomer units are provided.
  • the acid group-containing monomer unit is preferably an unsaturated carboxylic acid unit.
  • the acid group-containing monomer unit is preferably a methacrylic acid unit. It is preferable that the content of the acid group-containing monomer unit of the polymer is 1 to 100 mol% based on all monomer units.
  • the fluoropolymer is a fluoroelastomer.
  • the inorganic particles are inorganic nitride particles.
  • the composite particles are preferably obtained by polymerizing an acid group-containing monomer in a dispersion in which the inorganic particles are dispersed.
  • the composition is a molding material.
  • the composition of the present disclosure contains a fluoropolymer.
  • a fluorine-containing polymer a fluorine-containing elastomer is preferable because of excellent sealing properties, chemical resistance and heat resistance.
  • the fluorine-containing elastomer is an amorphous fluorine-containing polymer.
  • amorphous refers to a melting peak (differential scanning calorimetry [DSC] (heating rate 10 ° C./min)) or differential thermal analysis [DTA] (heating rate 10 ° C./min) of a fluorine-containing polymer.
  • DSC differential scanning calorimetry
  • DTA differential thermal analysis
  • ⁇ H is 4.5 J / g or less.
  • Fluorine-containing elastomers exhibit elastomer properties when crosslinked. By elastomeric properties is meant the property that allows the polymer to be stretched and retains its original length when the force required to stretch the polymer is no longer applied.
  • the fluoroelastomer may be a partially fluorinated elastomer or a perfluoroelastomer, but it is preferable to use a perfluoroelastomer from the viewpoint of more excellent chemical resistance and heat resistance.
  • a partially fluorinated elastomer is a fluoropolymer containing a fluoromonomer unit and having a perfluoromonomer unit content of less than 90 mol% based on all monomer units, and a glass transition temperature of 20 ° C or lower. And a melting peak ( ⁇ H) of 4.5 J / g or less.
  • a perfluoroelastomer is a fluoropolymer having a perfluoromonomer unit content of 90 mol% or more based on all monomer units, has a glass transition temperature of 20 ° C or less, and has a glass transition temperature of 4.5 J.
  • / G is a fluoropolymer having a magnitude of a melting peak ( ⁇ H) of not more than / g and a polymer having a fluorine atom concentration of 71% by mass or more contained in the fluoropolymer.
  • the concentration of fluorine atoms contained in the fluoropolymer is obtained by calculating the concentration (% by mass) of the fluorine atoms contained in the fluoropolymer from the type and content of each monomer constituting the fluoropolymer. It is.
  • a perfluoromonomer is a monomer having no carbon atom-hydrogen atom bond in the molecule.
  • the perfluoromonomer may be a monomer in which some of the fluorine atoms bonded to the carbon atoms have been replaced with chlorine atoms in addition to carbon atoms and fluorine atoms, and in addition to carbon atoms, nitrogen atoms, oxygen atoms And those having a sulfur atom.
  • the perfluoromonomer is preferably a monomer in which all hydrogen atoms have been replaced with fluorine atoms.
  • the perfluoromonomer does not include a monomer that provides a crosslinking site.
  • Examples of the partially fluorinated elastomer include vinylidene fluoride (VdF) fluorine rubber, tetrafluoroethylene (TFE) / propylene (Pr) fluorine rubber, and tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF) fluorine.
  • VdF vinylidene fluoride
  • TFE tetrafluoroethylene
  • Pr propylene
  • VdF vinylidene fluoride
  • HFP ethylene / hexafluoropropylene
  • HFP ethylene / hexafluoropropylene
  • VdF vinylidene fluoride
  • HFP ethylene / hexafluoropropylene
  • TFE tetrafluoroethylene fluorine Rubber and the like.
  • it is at least one selected from the group consisting of vinylidene fluoride-based fluororubber and tetrafluoroethylene / propylene-based fluororubber.
  • the vinylidene fluoride-based fluororubber is preferably a copolymer comprising 45 to 85 mol% of vinylidenefluoride and 55 to 15 mol% of at least one other monomer copolymerizable with vinylidenefluoride. .
  • Preferred is a copolymer comprising 50 to 80 mol% of vinylidene fluoride and 50 to 20 mol% of at least one other monomer copolymerizable with vinylidene fluoride.
  • the content of each monomer constituting the fluoropolymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis depending on the type of the monomer.
  • Examples of the at least one other monomer copolymerizable with the vinylidene fluoride include TFE, HFP, fluoroalkyl vinyl ether, chlorotrifluoroethylene (CTFE), trifluoroethylene, trifluoropropylene, pentafluoropropylene, and trifluorobutene.
  • Tetrafluoroisobutene, hexafluoroisobutene, vinyl fluoride general formula (1): represented by CH 2 CFCFRf 1 (where Rf 1 is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms)
  • a fluoromonomer represented by the general formula (2): CH 2 CHCH— (CF 2 ) n —X 2 (wherein X 2 is H or F, and n is an integer of 3 to 10).
  • Fluoromonomer monomer that provides a crosslinking site; ethylene, propylene, alkyl vinyl ether It includes non-fluorinated monomers like. 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.
  • CF 2 CF-ORf 3 (Wherein, Rf 3 represents a C 1-8 perfluoroalkyl group).
  • General formula (4): CF 2 CFOCF 2 ORf 4 (In the formula, 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, and 2 to 6 carbon atoms containing 1 to 3 oxygen atoms.
  • CF 2 CFCFO (CF 2 CF (Y 5 ) O) m (CF 2 ) n F
  • Y 5 represents a fluorine atom or a trifluoromethyl group
  • m is an integer of 1 to 4
  • n is an integer of 1 to 4
  • It is preferably at least one kind, and more preferably a fluoromonomer represented by the general formula (3).
  • vinylidene fluoride-based fluorororubber examples include VdF / HFP-based rubber, VdF / HFP / TFE-based rubber, VdF / CTFE-based rubber, VdF / CTFE / TFE-based rubber, and VDF / general formula (1).
  • the VDF / CH 2 CFCFCF 3 rubber is preferably a copolymer composed of VDF 40 to 99.5 mol% and CH 2 CFCFCF 3 0.5 to 60 mol%, and VDF 50 to 85 mol%. And CH 2 CFCFCF 3 , which is more preferably 15 to 50 mol%.
  • the tetrafluoroethylene / propylene-based fluororubber is preferably a copolymer comprising 45 to 70 mol% of tetrafluoroethylene, 55 to 30 mol% of propylene, and 0 to 5 mol% of a fluoromonomer providing a crosslinking site. .
  • the fluorine-containing elastomer may be a perfluoroelastomer.
  • a perfluoroelastomer containing TFE for example, TFE / fluoromonomer copolymer represented by the general formula (3), (4) or (5), and TFE / general formula (3), At least one selected from the group consisting of a fluoromonomer represented by (4) or (5) / a monomer copolymer providing a crosslinking site is preferable.
  • the composition is preferably 45 to 90/10 to 55 (mol%), more preferably 55 to 80/20 to 45, and further preferably 55 to 70 / mol. 30 to 45.
  • the ratio is preferably from 45 to 89.9 / 10 to 54.9 / 0.01 to 4 (mol%), more preferably from 50 to 77.9 / 20-49.9 / 0.1-3.5, more preferably 55-69.8 / 30-44.8 / 0.2-3.
  • the TFE / fluoromonomer copolymer represented by the general formula (3), (4) or (5) having 4 to 12 carbon atoms it is preferably 50 to 90/10 to 50 (mol%), It is more preferably from 60 to 88/12 to 40, and still more preferably from 65 to 85/15 to 35.
  • perfluoroelastomer examples include TFE / fluoromonomer represented by the general formula (5) / monomer copolymer providing a crosslinking site, TFE / fluoromonomer copolymer represented by the general formula (5), TFE / general It is at least one member selected from the group consisting of a fluoromonomer copolymer represented by the formula (3) and a TFE / fluoromonomer represented by the general formula (3) / a monomer copolymer providing a crosslinking site. Is preferred.
  • perfluoroelastomer examples include perfluoroelastomers described in WO 97/24381, JP-B-61-57324, JP-B-4-81608, and JP-B-5-13961. Can be.
  • the monomer that provides a crosslinking site is a monomer having a crosslinkable group (a cure site monomer) that provides a crosslinking site for forming a crosslinking with a crosslinking agent to a fluoropolymer.
  • Z is a straight or branched chain having 1 to 5 carbon atoms which may have an oxygen atom.
  • X 6 is preferably a fluorine atom.
  • Rf 6 and Rf 7 are preferably a perfluoroalkylene group having 1 to 5 carbon atoms.
  • R 6 is preferably a hydrogen atom.
  • X 8 is preferably a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or —CH 2 I.
  • X 9 is preferably a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or —CH 2 OH.
  • the above-mentioned fluorine-containing elastomer preferably has a glass transition temperature of ⁇ 70 ° C. or higher, more preferably ⁇ 60 ° C. or higher, and more preferably ⁇ 50 ° C. or higher, from the viewpoint of excellent compression set resistance at high temperatures. Is more preferred. Further, from the viewpoint of good cold resistance, the temperature is preferably 5 ° C. or lower, more preferably 0 ° C. or lower, and further preferably -3 ° C. or lower.
  • a DSC curve was obtained by raising the temperature of a 10 mg sample at 10 ° C./min, and the glass transition temperature was determined before and after the secondary transition of the DSC curve.
  • the temperature can be obtained as a temperature indicating the midpoint between two intersections of the extension of the line and the tangent at the inflection point of the DSC curve.
  • the fluorine-containing elastomer preferably has a Mooney viscosity ML (1 + 20) at 170 ° C. of 30 or more, more preferably 40 or more, and further preferably 50 or more, from the viewpoint of good heat resistance. Further, from the viewpoint of good workability, it is preferably 150 or less, more preferably 120 or less, and further preferably 110 or less.
  • the fluorine-containing elastomer preferably has a Mooney viscosity ML (1 + 20) at 140 ° C. of 30 or more, more preferably 40 or more, and even more preferably 50 or more. Further, from the viewpoint of good workability, it is preferably 180 or less, more preferably 150 or less, and further preferably 110 or less.
  • the fluorine-containing elastomer preferably has a Mooney viscosity ML (1 + 10) at 100 ° C. of 10 or more, more preferably 20 or more, and further preferably 30 or more from the viewpoint of good heat resistance. Further, from the viewpoint of good workability, it is preferably 120 or less, more preferably 100 or less, and even more preferably 80 or less.
  • the Mooney viscosity can be measured at 170 ° C. or 140 ° C. and 100 ° C. according to JIS K6300 using a Mooney viscometer MV2000E manufactured by ALPHA TECHNOLOGIES.
  • the above-mentioned partially fluorinated elastomer and perfluoroelastomer can be produced by a conventional method, but the molecular weight distribution of the obtained polymer is narrow, the molecular weight can be easily controlled, and an iodine atom or a bromine atom is introduced into a terminal. For this reason, an iodine compound or a bromine compound can be used as a chain transfer agent.
  • Examples of the polymerization method using an iodine compound or a bromine compound include, for example, a method of performing emulsion polymerization in an aqueous medium while applying pressure in the presence of an iodine compound or a bromine compound in a substantially oxygen-free state.
  • iodine transfer polymerization method Representative examples of the iodine compound or bromine compound used include, for example, a compound represented by the following general formula: R 11 I x Br y (Where x and y are each an integer of 0 to 2 and satisfy 1 ⁇ x + y ⁇ 2, and R 11 is a saturated or unsaturated fluorohydrocarbon group having 1 to 16 carbon atoms or chlorofluoro A hydrocarbon group or a hydrocarbon group having 1 to 3 carbon atoms, which may contain an oxygen atom).
  • an iodine compound or a bromine compound an iodine atom or a bromine atom is introduced into the polymer and functions as a crosslinking point.
  • 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-diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodo perfluoro hexadecane, diiodomethane, 1,2-diiodoethane, 1,3-diiodo -n- propane, CF 2 Br 2, BrCF 2 CF 2 Br, CF 3 CFBrCF 2 Br, CFClBr 2, BrCF 2 CFCl
  • 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane are used in view of polymerization reactivity, crosslinking reactivity, availability, and the like. Is preferred.
  • the fluoropolymer is preferably a fluoroelastomer having a cyano group (—CN group) at the terminal and / or side chain of the main chain.
  • Fluorine-containing elastomers having a cyano group (—CN group) at the terminal and / or side chain of the main chain can be crosslinked by forming a triazine ring by cyclization and trimerization of a cyano group, and are excellent in molded articles. Compression set and heat resistance.
  • fluorine-containing elastomer having a cyano group (—CN group) at the terminal and / or side chain of the main chain include perfluoroelastomers and partially fluorinated elastomers.
  • the monomer copolymers providing sites there may be mentioned copolymers in which the monomer providing a crosslinking site is a monomer having a cyano group (—CN group).
  • the content of the monomer unit having a cyano group (—CN group) is represented by the TFE unit and the general formulas (3), (4) and (5) from the viewpoint of good crosslinking properties and heat resistance. It may be 0.1 to 5 mol%, or 0.3 to 3 mol%, based on the total amount with the fluoromonomer unit. Further preferred compositions are as described above.
  • CF 2 CFCF (OCF 2 CF (CF 3 )) m O (CF 2 ) n —CN (Wherein m is an integer of 0 to 5 and n is an integer of 1 to 8), and more preferably CF 2 CFCFOCF 2 CF (CF 3 ) OCF 2 CF 2 CN.
  • perfluoroelastomers can be manufactured by a conventional method.
  • perfluoroelastomers include fluorine rubbers described in WO 97/24381, JP-B-61-57324, JP-B-4-81608, JP-B-5-13961 and the like. Is raised.
  • Examples of the partially fluorinated elastomer having a cyano group (—CN group) at the terminal and / or side chain of the main chain include vinylidene fluoride (VdF) fluororubber, tetrafluoroethylene (TFE) / propylene fluororubber, and tetrafluoroethylene.
  • VdF vinylidene fluoride
  • TFE tetrafluoroethylene
  • propylene fluorororubber propylene fluororubber
  • tetrafluoroethylene tetrafluoroethylene
  • TFE propylene / vinylidene fluoride
  • HFP ethylene / hexafluoroethylene
  • HFP vinylidene fluoride
  • VdF vinylidene fluoride
  • Examples include fluoropropylene (HFP) / tetrafluoroethylene (TFE) -based fluororubber, fluorosilicone-based fluororubber, and fluorophosphazene-based fluororubber, each of which alone or without impairing the effects of the present disclosure. It can be used in any combination in a range.
  • the vinylidene fluoride-based fluororubber is a fluorine-containing copolymer comprising 45 to 85 mol% of vinylidenefluoride and 55 to 15 mol% of at least one other monomer copolymerizable with vinylidenefluoride.
  • it refers to a fluorine-containing copolymer comprising 50 to 80 mol% of vinylidene fluoride and 50 to 20 mol% of at least one other monomer copolymerizable with vinylidene fluoride.
  • TFE polystyrene fluoride
  • CTFE trifluoroethylene
  • HFP trifluoropropylene
  • tetrafluoropropylene pentafluoropropylene
  • trifluorobutene tetrafluoroisobutene
  • fluoromonomers such as perfluoro (alkyl vinyl ether) (PAVE) and vinyl fluoride
  • non-fluorinated monomers such as ethylene, propylene and alkyl vinyl ether.
  • TFE, HFP and perfluoro (alkyl vinyl ether) are preferred.
  • Specific rubbers include VdF-HFP rubber, VdF-HFP-TFE rubber, VdF-CTFE rubber, VdF-CTFE-TFE rubber and the like.
  • the tetrafluoroethylene / propylene-based fluororubber is composed of 45 to 70 mol% of tetrafluoroethylene and 55 to 30 mol% of propylene. Further, the monomer 0 to 5 which provides a crosslinking site is added to the total amount of tetrafluoroethylene and propylene. It refers to a fluorine-containing copolymer containing mol%.
  • Examples of the monomer for providing a crosslinking site include a cyano group-containing monomer described in JP-A-4-505345 and JP-A-5-500070, and a monomer having a cyano group (—CN group) described above. And so on.
  • thermoplastic fluorine rubber composed of an elastomeric fluorine-containing polymer chain segment and a non-elastomeric fluorine-containing polymer chain segment may be used.
  • the composition of the present disclosure further contains composite particles comprising a polymer containing an acid group-containing monomer unit and inorganic particles dispersed in the polymer. That is, in the composite particles, since the inorganic particles are covered with the polymer, the action of the inorganic particles on the crosslinking reaction is controlled. Therefore, the composition of the present disclosure has excellent scorch resistance.
  • the acid group-containing monomer that gives the acid group-containing monomer unit is not particularly limited as long as it has at least one ethylenically unsaturated bond and at least one acid group, but it can further improve scorch resistance. And at least one selected from the group consisting of unsaturated carboxylic acids, unsaturated sulfonic acids, unsaturated phosphonic acids and unsaturated phosphoric acids, and at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated sulfonic acids. One type is more preferred and the unsaturated carboxylic acid is even more preferred.
  • the acid group-containing monomer may form a salt with a cation such as an alkali metal ion, an alkaline earth metal ion, and an ammonium ion.
  • unsaturated carboxylic acids examples include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid, itaconic acid and itaconic acid monoester.
  • CR 11 R 12 CR 13 -R 14 - (COOH) n
  • R 11 to R 13 are the same or different and are each a hydrogen atom or a monovalent hydrocarbon group
  • R 14 is a divalent or trivalent linking group
  • n is 1 or 2.
  • CR 15 R 16 CR 17 -R 18 -Ar-(-COOH) m
  • R 15 to R 17 are the same or different and are each a hydrogen atom or a monovalent hydrocarbon group
  • R 18 is a divalent or trivalent linking group
  • Ar is a divalent or trivalent cyclic aliphatic group. Or an aromatic group, m is 1 or 2.
  • at least one selected from the group consisting of compounds represented by the general formula (11) is more preferable.
  • R 11 to R 13 are the same or different and are preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an aryl group.
  • the carbon number of the alkylene group represented by R 141 is preferably 1 to 10, more preferably 1 to 3.
  • n represents the general formula (11) represents the number of carboxyl groups, in the case of R 14 is divalent is 1, in the case of R 14 is trivalent 2.
  • R 14 and n in the general formula (11) R 14 is preferably a divalent linking group, and n is preferably 1.
  • R 15 to R 17 are the same or different and are preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • the number of carbon atoms of the alkylene group represented by R 181 is preferably from 1 to 10, more preferably from 1 to 3.
  • M in the general formula (12) represents the number of carboxyl groups, and is 1 when Ar is divalent and 2 when Ar is trivalent.
  • the number of carbon atoms of Ar is preferably 6.
  • unsaturated sulfonic acids examples include vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, 2-sulfoethyl acrylate, 2-ethyl sulfo methacrylate, 2-acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid, Allyloxy-2-hydroxypropanesulfonic acid and the like.
  • Examples of the unsaturated phosphonic acid include vinylphosphonic acid, allylphosphonic acid, vinylbenzylphosphonic acid, 1-phenylethenylphosphonic acid, 2-phenylethenylphosphonic acid, 2- (acryloyloxy) ethylphosphonic acid, 2- ( Examples include methacryloyloxy) ethylphosphonic acid, 3- (acryloyloxy) propylphosphonic acid, and 3- (methacryloyloxy) propylphosphonic acid.
  • Examples of the unsaturated phosphoric acid include 2- (acryloyloxy) ethyl phosphate and 2- (methacryloyloxy) ethyl phosphate.
  • the acid group-containing monomer at least one selected from the group consisting of methacrylic acid and vinyl sulfonic acid is preferable, and methacrylic acid is more preferable, because scorch resistance can be further improved.
  • the polymer may be a polymer composed of only the acid group-containing monomer unit, or a polymer containing the acid group-containing monomer unit and another monomer unit other than the acid group-containing monomer unit. Is also good.
  • the polymer may further contain an unsaturated carboxylic acid ester unit.
  • an unsaturated carboxylic acid ester which provides an unsaturated carboxylic acid ester unit, an alkyl acrylate having 1 to 10 carbon atoms in an alkyl group or an alkyl methacrylate having 1 to 10 carbon atoms in an alkyl group is preferable.
  • Examples of the (meth) acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, methyl methacrylate, n-propyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, Examples thereof include alkyl (meth) acrylates such as 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate.
  • “(meth) acrylate” means acrylate or methacrylate.
  • methyl methacrylate is preferable.
  • the content of the acid group-containing monomer unit is preferably from 1 to 100 mol% based on all monomer units, since scorch resistance can be further improved. , More preferably 10 to 100 mol%, and still more preferably 25 to 100 mol%. In this case, the content of the other monomer unit is 99 to 0 mol%, more preferably 90 to 0 mol%, and further preferably 75 to 0 mol%.
  • the content of the acid group-containing monomer unit is preferably from 1 to 99 mol% based on all monomer units from the viewpoint of scorch resistance. And more preferably from 10 to 90 mol%, even more preferably from 25 to 75 mol%. Further, the content of the unsaturated carboxylic acid ester unit is preferably from 99 to 1 mol%, more preferably from 90 to 10 mol%, further preferably from 75 to 25 mol%, based on all monomer units. %.
  • the polymer may further contain a styrene unit.
  • the content of the acid group-containing monomer unit is preferably from 1 to 99 mol%, more preferably from 1 to 99 mol%, from the viewpoint of scorch resistance. Is from 10 to 90 mol%. Further, the content of the styrene unit is preferably from 99 to 1 mol%, more preferably from 90 to 10 mol%, based on all monomer units.
  • the polymer preferably has a number average molecular weight (weight average molecular weight, etc.) of 10,000 to 1,000,000.
  • the molecular weight can be measured by a method using liquid chromatography or a precipitation method.
  • the inorganic particles are preferably inorganic nitride particles.
  • the triazine crosslinking reaction can be advanced by subjecting the cyano group in the fluoroelastomer to a cyclization trimerization reaction.
  • the inorganic particles are not particularly limited, and include inorganic nitride particles such as silicon nitride (Si 3 N 4 ), lithium nitride, titanium nitride, aluminum nitride, boron nitride, vanadium nitride, and zirconium nitride. .
  • silicon nitride particles are preferable because they can supply nano-sized fine particles and do not contain metals and the like that are disliked in the semiconductor manufacturing process.
  • These inorganic nitride particles may be used in combination of two or more.
  • the average particle diameter of the inorganic particles is preferably 1000 nm or less, more preferably 300 nm or less, and further preferably 100 nm or less.
  • the lower limit is not particularly limited, but is preferably 5 nm.
  • the composite particles preferably contain 1 to 80% by mass of the inorganic particles.
  • the content of the inorganic particles is more preferably 10% by mass or more, further preferably 20% by mass or more, particularly preferably 35% by mass or more, and most preferably 50% by mass or more. It is preferably at most 75% by mass, more preferably at most 70% by mass.
  • the average particle size of the composite particles is preferably 0.01 to 100 ⁇ m, more preferably 0.05 ⁇ m or more, further preferably 0.1 ⁇ m or more, more preferably 30 ⁇ m or less, and further preferably It is 15 ⁇ m or less.
  • the average particle diameter is a median diameter determined as a laser diffraction particle size distribution measuring device.
  • the composite particles are preferably obtained by polymerizing at least a monomer containing the acid group-containing monomer in a dispersion in which the inorganic particles are dispersed.
  • the composite particles can be produced by a known method (for example, a method described by Masato Tanaka, “Key Points of Nano / Microcapsule Preparation”, Techno System Publishing Co., Ltd., May 6, 2008).
  • the composite particles are, specifically, a step of dispersing an inorganic particle, a monomer containing at least the acid group-containing monomer, a dispersant and a polymerization initiator in a solvent to obtain a dispersion, and polymerizing the monomer in the dispersion. And obtaining a slurry by collecting the composite particles from the slurry.
  • the above-mentioned unsaturated carboxylic acid ester, styrene, or the like is polymerized with another monomer which gives another monomer unit constituting the above-mentioned polymer. You can also.
  • the mass ratio of the inorganic particles to the monomer is preferably 1/99 to 80/20, more preferably 10/90 or more, and more preferably 75/25 or less. .
  • At least one selected from the group consisting of polyvinylpyrrolidone, saponified polyvinyl alcohol and hydroxypropylcellulose is preferable, and polyvinylpyrrolidone is more preferable.
  • the polymerization initiator at least one selected from the group consisting of an azo compound and a peroxide is preferable, and an azo compound is more preferable.
  • the azo compound include 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobisisobutyronitrile, and 2,2′-azobis (2-methylpropionitrile).
  • the solvent is preferably at least one selected from the group consisting of water, alcohol, benzene and toluene, and more preferably at least one selected from the group consisting of water and alcohol.
  • the alcohol is preferably an alcohol having 1 to 5 carbon atoms, and more preferably 1-butanol, methanol or ethanol.
  • a known means such as ultrasonic waves may be used to disperse each component in the solvent.
  • the polymerization of the above monomers can be started by heating the dispersion above the decomposition temperature of the polymerization initiator.
  • the decomposition temperature is usually from 30 to 120 ° C.
  • the polymerization time is usually 1 to 24 hours.
  • a slurry containing the composite particles and the solvent is generated.
  • Methods for recovering composite particles from a slurry are known. After collection, the composite particles may be dried if desired.
  • the content of the composite particles in the composition of the present disclosure is preferably 0.1 to 30 parts by mass, more preferably 0.3 parts by mass or more, based on 100 parts by mass of the fluoropolymer. It is preferably at least 0.5 part by mass, more preferably at most 10 parts by mass, and even more preferably at most 5 parts by mass.
  • the scorch resistance can be further improved, and the crosslinking reaction can be sufficiently advanced.
  • the crosslinker is not an essential component.
  • the composition may further contain a crosslinking agent.
  • the crosslinking agent include a crosslinking agent used in peroxide crosslinking, polyol crosslinking, polyamine crosslinking, triazine crosslinking, oxazole crosslinking, imidazole crosslinking, and thiazole crosslinking.
  • the fluorine-containing polymer is a fluorine-containing elastomer having a cyano group (—CN group) at a main chain terminal and / or a side chain
  • the crosslinking agent is selected from the group consisting of an oxazole crosslinking agent, an imidazole crosslinking agent, and a thiazole crosslinking agent. Preferably, at least one selected from them is used.
  • the crosslinking agent used in the peroxide crosslinking may be an organic peroxide that can easily generate a peroxy radical in the presence of heat or an oxidation-reduction system.
  • an organic peroxide that can easily generate a peroxy radical in the presence of heat or an oxidation-reduction system.
  • the crosslinking assistant that can be used may be a compound having a reaction activity for a peroxy radical and a polymer radical.
  • triallyl cyanurate triallyl isocyanurate (TAIC), triacrylformal, triallyl trimellitate, N, N'-n-phenylenebismaleimide, dipropagyl terephthalate, diallyl phthalate, tetraallyl Terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1,3,5-tris (2,3,3-trifluoro-2-propenyl) -1,3,5-triazine 2,4, 6-trione), tris (diallylamine) -S-triazine, triallyl phosphite, N, N-diallylacrylamide, 1,6-divinyldodecafluorohexane and the like.
  • TAIC triallyl cyanurate
  • TAIC triallyl isocyanurate
  • triacrylformal triallyl trimellitate
  • N N'-n-phenylenebismaleimide
  • R 21 to R 23 are each independently a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, or a substituted or unsubstituted aryl group, and at least one of R 21 to R 23 is ,
  • a fluorine atom or a group containing a fluorine atom, m is an integer of 1 to 5.
  • m is 2 or more, m R 21 to R 23 are different even if they are the same.
  • the hydrogen atom of the benzene ring may be substituted.
  • R 24 is a single bond, —SO 2 —, —O—, —S—, —CO—, a heteroatom-containing group, a substituted or unsubstituted An alkylene group, a substituted or unsubstituted cycloalkylene group or a substituted or unsubstituted arylene group; m is an integer of 1 to 5.).
  • crosslinking agent used for polyol crosslinking examples include polyhydric alcohol compounds such as bisphenol A and bisphenol AF.
  • crosslinking agent used for the polyamine crosslinking examples include polyamine compounds such as hexamethylenediaminecarbamate, N, N'-dicinnamylidene-1,6-hexanediamine, and 4,4'-bis (aminocyclohexyl) methanecarbamate.
  • crosslinking agent used for triazine crosslinking examples include organotin compounds such as tetraphenyltin and triphenyltin.
  • crosslinking agent used for oxazole crosslinking, imidazole crosslinking, and thiazole crosslinking include, for example, a compound represented by the general formula (30)
  • R 31 is —SO 2 —, —O—, —CO—, an alkylene group having 1 to 6 carbon atoms, a perfluoroalkylene group having 1 to 10 carbon atoms or a single bond, or
  • R 32 and R 33 is —NH 2 and the other is —NHR 34 , —NH 2 , —OH or —SH, and R 34 is a hydrogen atom, a fluorine atom or a monovalent An organic group, and preferably, R 32 is —NH 2 and R 33 is —NHR 34 .
  • R 34 is a hydrogen atom, a fluorine atom or a monovalent An organic group, and preferably, R 32 is —NH 2 and R 33 is —NHR 34 .
  • Preferred specific examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group. Is
  • Bisaminophenol-based crosslinking agent bisaminothiophenol-based crosslinking agent, general formula (31):
  • R 31 is, as described above, R 35 is independently any of the following groups.
  • Rf 31 is a perfluoroalkylene group having 1 to 10 carbon atoms
  • n is an integer of 1 to 10.
  • bisaminophenol-based crosslinking agents bisaminothiophenol-based crosslinking agents, bisdiaminophenyl-based crosslinking agents, and the like have been conventionally used in crosslinking systems having a cyano group as a crosslinking point. It also reacts with the group to form an oxazole ring, thiazole ring, imidazole ring to give a crosslinked product.
  • crosslinking agents include compounds having a plurality of 3-amino-4-hydroxyphenyl groups or 3-amino-4-mercaptophenyl groups, or a compound represented by the general formula (34):
  • R 31 , R 32 and R 33 are as described above), and specifically, for example, 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-ethyl Amino)
  • 2,2-bis [3-amino-4- (N-phenylamino) phenyl] hexafluoropropane is preferred as a crosslinking agent from the viewpoint of heat resistance, steam resistance, amine resistance, and good crosslinking property. Is preferred.
  • the content of the crosslinking agent is preferably 0.05 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the fluoropolymer.
  • the composition may contain a general filler.
  • Examples of the general filler include imide-based fillers having an imide structure such as polyimide, polyamideimide, and polyetherimide, polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, polyetherketone, and polyoxyimide.
  • Organic fillers made of engineering plastics such as benzoate; 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 aluminum fluoride And inorganic fillers such as carbon fluoride, barium sulfate, carbon black, silica, clay and talc.
  • carbon black, aluminum oxide, yttrium oxide, silicon oxide, polyimide, and carbon fluoride are preferred from the viewpoint of the shielding effect of various plasmas.
  • inorganic filler and organic filler may be used alone or in combination of two or more.
  • the amount of the general filler is preferably 0.5 to 100 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the fluoropolymer.
  • compositions of the present disclosure are as follows. That is, a composition comprising a composite particle and a fluorine-containing elastomer having a cyano group (—CN group) at a main chain terminal and / or a side chain, wherein the composite particle is dispersed in a polymer and the polymer.
  • the polymer comprises inorganic nitride particles, and the polymer contains the acid group-containing monomer unit, and contains 0.1 to 30 parts by mass of the composite particles per 100 parts by mass of the fluoroelastomer.
  • a composition As the fluoroelastomer, a perfluoroelastomer is preferable. Further, as the inorganic nitride particles, silicon nitride particles are preferable. Further, as the acid group-containing monomer unit, the above unsaturated carboxylic acid unit is preferable.
  • the above composition can be suitably used as a molding material for obtaining a molded product by cross-linking molding.
  • the composition is a step of obtaining a dispersion by dispersing the inorganic particles, the monomer containing at least the acid group-containing monomer, the dispersant and the polymerization initiator in the solvent, and polymerizing the monomer in the dispersion.
  • the method can include a step of obtaining a slurry by mixing, a step of collecting composite particles from the slurry, and a step of kneading the composite particles and the fluoropolymer.
  • kneading can be carried out using a usual processing machine for polymers, for example, an open roll, a Banbury mixer, a kneader, a closed mixer or the like.
  • the method of obtaining a preformed body using the above composition as a molding material may be a conventional method, and may be a known method such as a method of heating and compressing with a mold, a method of pressing into a heated mold, or a method of extruding with an extruder. Can do it.
  • a molded product can be obtained by performing heat crosslinking with steam or the like after extrusion.
  • a method for obtaining a molded article from the above composition may be an ordinary method. After obtaining a preformed article, a molded article can be obtained in the order of primary crosslinking and finally secondary crosslinking.
  • the primary crosslinking is preferably performed at 150 to 200 ° C. for 5 to 120 minutes, more preferably at 170 to 190 ° C. for 5 to 60 minutes. Any known crosslinking means may be used as the crosslinking means, and examples thereof include press crosslinking.
  • the secondary crosslinking is preferably performed at 180 to 320 ° C. for 2 to 24 hours, more preferably at 190 to 310 ° C. for 5 to 20 hours.
  • the secondary crosslinking may be performed at 250 to 320 ° C. for 2 to 24 hours, or at 280 to 310 ° C. for 5 to 20 hours.
  • a known crosslinking means may be used, and examples thereof include oven crosslinking.
  • the molded article of the present disclosure is obtained from the above composition.
  • the molded product of the present disclosure can be suitably used as a sealing material of a semiconductor manufacturing apparatus that requires particularly heat resistance, particularly a semiconductor manufacturing apparatus that performs high-density plasma irradiation.
  • the sealing material include an O-ring, a square-ring, a gasket, a packing, an oil seal, a bearing seal, and a lip seal.
  • it can be used as various polymer products used in semiconductor manufacturing equipment, for example, diaphragms, tubes, hoses, various rubber rolls, belts and the like. It can also be used as a coating material and a lining material.
  • the semiconductor manufacturing apparatus referred to in the present disclosure is not particularly limited to an apparatus for manufacturing a semiconductor, and is widely used for a semiconductor that requires a high degree of cleanliness, such as an apparatus for manufacturing a liquid crystal panel or a plasma panel. This includes all manufacturing apparatuses used in the field, and examples thereof include the following.
  • etching apparatus Dry etching equipment Plasma etching machine Reactive ion etching machine Reactive ion beam etching machine Sputter etching machine Ion beam etching machine Wet etching equipment Ashing equipment (2) Cleaning system Dry etching cleaning equipment UV / O 3 cleaning machine Ion Beam cleaning device Laser beam cleaning device Plasma cleaning device Gas etching cleaning device Extraction cleaning device Soxhlet extraction cleaning device High-temperature high-pressure extraction cleaning device Microwave extraction cleaning device Supercritical extraction cleaning device (3) Exposure device Stepper coater / developer (4) Polishing device CMP equipment (5) Film formation equipment CVD equipment Sputtering equipment (6) Diffusion / ion implantation equipment Oxidation diffusion equipment Ion implantation equipment
  • the molded product of the present disclosure exhibits excellent performance as a sealing material for, for example, a CVD device, a plasma etching device, a reactive ion etching device, an ashing device, or an excimer laser exposure machine.
  • Preparation Examples 1 to 6 As a reaction tank, a separable flask having a capacity of 1000 ml was used. In a reaction vessel, 15 g of polyvinylpyrrolidone and the monomers shown in Table 1 were dissolved in 790 ml of 1-butanol, and 40 g of silicon nitride particles (average particle diameter: 30 nm) were added.
  • the composite particles were separated from the slurry obtained by the reduced-pressure filtration device, and dried for 15 hours by a dryer set at 75 ° C. Then, it heated at 100 degreeC in inert gas for 2 hours.
  • the obtained composite particles had a structure in which silicon nitride particles were dispersed in a polymer.
  • Ratio of silicon nitride in composite particles Using a thermal mass meter (TG-DTA7200, manufactured by SII Nano Technology Co., Ltd.), change the mass under the conditions of air 200 ml / min, heating rate 10 ° C./min, and temperature range 20 to 600 ° C. It was measured and determined from the residual ratio when the temperature was raised to 600 ° C. Table 1 shows the results.
  • the obtained fluororubber composition was put in an alumina bag, vacuum-packaged, and stored at 40 ° C for the storage period shown in Table 2.
  • a moving die rheometer MDR2000 manufactured by Alpha Technologies vulcanization characteristics were measured at 180 ° C. for 30 minutes, and storage stability was evaluated from a change in ML.
  • ML is a minimum torque value, and this numerical value is an index of fluidity at the time of vulcanization molding. The smaller the value, the better the fluidity, and the greater the scorch due to the crosslinking reaction, the greater the value. Table 2 shows the results.
  • the obtained fluororubber composition was pressed at 180 ° C. for 30 minutes to perform crosslinking, and then subjected to oven crosslinking in an oven at 200 ° C. for 12 hours, 250 ° C. for 3 hours, and 290 ° C. for 3 hours.
  • a test sample of a crosslinked product having a thickness of 2 mm was prepared.
  • the physical properties of the obtained test samples were measured by the following methods.
  • Example 2 A fluororubber composition was prepared in the same manner as in Example 1, except that the composite particles were changed to those obtained in Preparation Example 2. Using the obtained fluororubber composition, storage stability was evaluated in the same manner as in Example 1. Table 2 shows the results. In the same manner as in Example 1, a test sample of a crosslinked product having a thickness of 2 mm was prepared. The physical properties of the obtained test samples were measured in the same manner as in Example 1. Table 3 shows the results.
  • Example 3 A fluororubber composition was prepared in the same manner as in Example 1, except that the composite particles were changed to those obtained in Preparation Example 3. Using the obtained fluororubber composition, storage stability was evaluated in the same manner as in Example 1. Table 2 shows the results. In the same manner as in Example 1, a test sample of a crosslinked product having a thickness of 2 mm was prepared. The physical properties of the obtained test samples were measured in the same manner as in Example 1. Table 3 shows the results.
  • Example 4 A fluororubber composition was prepared in the same manner as in Example 1, except that the composite particles were changed to those obtained in Preparation Example 4. Using the obtained fluororubber composition, storage stability was evaluated in the same manner as in Example 1. Table 2 shows the results. In the same manner as in Example 1, a test sample of a crosslinked product having a thickness of 2 mm was prepared. The physical properties of the obtained test samples were measured in the same manner as in Example 1. Table 3 shows the results.
  • Example 5 A fluororubber composition was prepared in the same manner as in Example 1, except that the composite particles were changed to those obtained in Preparation Example 5. Using the obtained fluororubber composition, storage stability was evaluated in the same manner as in Example 1. Table 2 shows the results. In the same manner as in Example 1, a test sample of a crosslinked product having a thickness of 2 mm was prepared. The physical properties of the obtained test samples were measured in the same manner as in Example 1. Table 3 shows the results.
  • Comparative Example 1 A fluororubber composition was prepared in the same manner as in Example 1, except that the composite particles were changed to those obtained in Preparation Example 6. Using the obtained fluororubber composition, storage stability was evaluated in the same manner as in Example 1. Table 2 shows the results. In the same manner as in Example 1, a test sample of a crosslinked product having a thickness of 2 mm was prepared. The physical properties of the obtained test samples were measured in the same manner as in Example 1. Table 3 shows the results.

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Abstract

L'invention concerne une composition contenant des particules composites et un polymère contenant du fluor, les particules composites comprenant un polymère, et des particules inorganiques dispersées dans le polymère, et le polymère contenant une unité monomère renfermant un groupe acide.
PCT/JP2019/029642 2018-08-03 2019-07-29 Composition et article moulé contenant un polymère contenant du fluor Ceased WO2020027046A1 (fr)

Priority Applications (4)

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CN201980049213.4A CN112513175B (zh) 2018-08-03 2019-07-29 含有含氟聚合物的组合物和成型品
US17/265,343 US12091537B2 (en) 2018-08-03 2019-07-29 Composition and molded article containing fluorine-containing polymer
EP19843590.1A EP3831876B1 (fr) 2018-08-03 2019-07-29 Composition et article moulé contenant un polymère contenant du fluor
KR1020217003040A KR102470957B1 (ko) 2018-08-03 2019-07-29 불소 함유 폴리머를 함유하는 조성물 및 성형품

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