WO2020027046A1 - Composition and molded article containing fluorine-containing polymer - Google Patents

Abstract

Provided is a composition containing composite particles and a fluorine-containing polymer, wherein the composite particles comprise a polymer, and inorganic particles dispersed in the polymer, and the polymer contains an acid-group-containing monomer unit.

Description

Composition and molded article containing fluorine-containing polymer

The present disclosure relates to compositions and molded articles containing a fluoropolymer.

Compositions made of fluorine-containing polymers such as fluorine-containing elastomers 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. As such 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.

International Publication No. WO 2016/204272

で は An object of the present disclosure is to provide a composition containing a fluoropolymer and having excellent scorch resistance.

According to the present disclosure, 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, wherein the polymer contains an acid group 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.
Preferably, the fluoropolymer is a fluoroelastomer.
It is preferable that 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.
Preferably, the composition is a molding material.

According to the present disclosure, there is also provided a molded article obtained from the above composition.

According to the present disclosure, it is possible to provide a composition containing a fluoropolymer and having excellent scorch resistance.

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

組成 The composition of the present disclosure contains a fluoropolymer. As the fluorine-containing polymer, a fluorine-containing elastomer is preferable because of excellent sealing properties, chemical resistance and heat resistance.

に お い て In the present disclosure, the fluorine-containing elastomer is an amorphous fluorine-containing polymer. The term "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. ΔH) 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.

In the present disclosure, 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 (ΔH) of 4.5 J / g or less.

In the present disclosure, 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 (ΔH) of not more than / g and a polymer having a fluorine atom concentration of 71% by mass or more contained in the fluoropolymer. In the present disclosure, 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.

に お い て In the present disclosure, 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. Rubber, ethylene / hexafluoropropylene (HFP) fluorine rubber, ethylene / hexafluoropropylene (HFP) / vinylidene fluoride (VdF) fluorine rubber, ethylene / hexafluoropropylene (HFP) / tetrafluoroethylene (TFE) fluorine Rubber and the like. Especially, it is preferable that 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.

に お い て In the present disclosure, 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.

As the above fluoroalkyl vinyl ether,
General formula (3): 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. Which is a linear or branched perfluorooxyalkyl group), and
General formula (5): CF ₂ ＣＦCFO (CF ₂ CF (Y ⁵ ) O) _m (CF ₂ ) _n F
(In the formula, 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).

Specific examples of vinylidene fluoride-based fluororubber are represented by VdF / HFP-based rubber, VdF / HFP / TFE-based rubber, VdF / CTFE-based rubber, VdF / CTFE / TFE-based rubber, and VDF / general formula (1). Fluoromonomer rubber, VDF / fluoromonomer / TFE rubber represented by formula (1), VDF / perfluoro (methyl vinyl ether) [PMVE] rubber, VDF / PMVE / TFE rubber, VDF / PMVE / TFE / HFP rubber and the like. The fluoromonomer rubber represented by the VDF / general formula (1), _VDF / CH 2 = CFCF ₃ based rubber is preferable, as fluoromonomer / TFE type rubber represented by the VDF / general formula (1) VDF / TFE / CH ₂ ＣＦCFCF ₃ rubber is preferred.

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. As the 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.

In the case of the TFE / PMVE copolymer, 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.

In the case of TFE / PMVE / a monomer copolymer providing a crosslinking site, 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.

In the case of 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.

In the case of TFE / fluoromonomer represented by the general formula (3), (4) or (5) having 4 to 12 carbon atoms / monomer copolymer giving a crosslinking site, preferably 50 to 89.9 / 10 to 49.9 / 0.01 to 4 (mol%), more preferably 60 to 87.9 / 12 to 39.9 / 0.1 to 3.5, and even more preferably 65 to 84.8 / mol. 15 to 34.8 / 0.2 to 3.
If the composition is out of the range, the properties of the rubber elastic body are lost, and the properties tend to be close to those of the resin.

Examples of the perfluoroelastomer 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.

Examples of the above perfluoroelastomer include perfluoroelastomers described in WO 97/24381, JP-B-61-57324, JP-B-4-81608, and JP-B-5-13961. Can be.

(4) 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.

As a monomer that provides a crosslinking site,
Formula _{^{(6): CX 6 2 =}} CX 6 -Rf 6 CHR 6 X 7
(Wherein X ⁶ is the same or different, and hydrogen atom, fluorine atom or CH ₃ , Rf ⁶ is a fluoroalkylene group, a perfluoroalkylene group, a fluoro (poly) oxyalkylene group or a perfluoro (poly) oxyalkylene A group, R ⁶ is a hydrogen atom or CH ₃ , and X ⁷ is an iodine atom or a bromine atom),
Formula _{^{(7): CX 6 2 =}} CX 6 -Rf 7 X 7
(In the formula, X ⁶ is the same or different, and a hydrogen atom, a fluorine atom or CH ₃ , Rf ⁷ is a fluoroalkylene group, a perfluoroalkylene group, a fluoro (poly) oxyalkylene group or a perfluoro (poly) oxyalkylene The group, X ⁷ is an iodine atom or a bromine atom);
General formula (8): CF ₂ ＣＦCFO (CF ₂ CF (CF ₃ ) O) _m (CF ₂ ) _n -X ⁸
(Where m is an integer of 0 to 5, n is an integer of 1 to 3, X ⁸ is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or —CH ₂ I). A fluoromonomer represented,
General formula (9): CH ₂ ＣＦCFCF ₂ O (CF (CF ₃ ) CF ₂ O) _m (CF (CF ₃ )) _n -X ⁹
(Wherein, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ⁹ is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or CH ₂ OH). A fluoromonomer, and
General formula (10): CR ¹⁰ ₂ = CR ¹⁰ -Z-CR ¹⁰ = CR ¹⁰ ₂
(Wherein R ¹⁰ is the same or different and is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Z is a straight or branched chain having 1 to 5 carbon atoms which may have an oxygen atom. An alkylene group having 18 carbon atoms, a cycloalkylene group having 3 to 18 carbon atoms, an alkylene group or an oxyalkylene group having 1 to 10 carbon atoms which is at least partially fluorinated, or
-(Q) _p -CF ₂ O- (CF ₂ CF ₂ O) _m (CF ₂ O) _n -CF _2- (Q) _p-
(Wherein Q is an alkylene group or an oxyalkylene group; p is 0 or 1. m / n is 0.2 to 5), and the molecular weight is 500 to 10,000 (per). It is a fluoropolyoxyalkylene group. ) Is preferably at least one selected from the group consisting of monomers represented by the formula:

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.

As monomers for providing a crosslinking site, CF ₂ ＣＦCFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CN, CF ₂ ＣＦCFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOH, CF ₂ ＣＦCFOCF 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 ＣＨCH (CF ₂ ) ₆ CH ＝ CH ₂ , and CF ₂ ＣＦCFO (CF ₂ ) ₅ CN At least one selected from the group consisting of CF ₂ ＣＦCFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CN and CF ₂ ＣＦCFOCF ₂ CF ₂ CH ₂ I More preferred.

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.

Using a differential scanning calorimeter (manufactured by METTLER TOLEDO, DSC822e), 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.

で 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.

In view of good heat resistance, 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). By using an iodine compound or a bromine compound, an iodine atom or a bromine atom is introduced into the polymer and functions as a crosslinking point.

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 CFClBr, CFBrClCFClBr, BrCF 2 CF ₂ CF ₂ Br, BrCF ₂ CFBrOCF ₃ , 1-bromo-2-iodoperfluoroethane, 1-bromo- ₃ -iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo- ₃ -iodoperfluorobutane, 3- Bromo-4-iodoperfluorobutene-1, 2-bromo-4-iodoperfluorobutene-1, monoiodomonobromo-substituted benzene, diiodomonobromo-substituted benzene, and (2-iodoethyl) and (2- (Bromoethyl) -substituted compounds, and these compounds may be used alone or in combination with each other.

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

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.

フ ッ 素 Examples of the 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.

As the perfluoroelastomer having a cyano group (—CN group) at the terminal and / or side chain of the main chain, the above-mentioned TFE / fluoromonomer represented by general formula (3), (4) or (5) / crosslinking Among 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). In this case, 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.

Examples of the monomer having a cyano group (—CN group) include, for example,
^{_{Formula: CY 1 2 = CY 1 (}} CF 2) n -CN
(In the formula, Y ¹ is the same or different, and is a hydrogen atom or a fluorine atom, and n is an integer of 1 to 8.)
Formula: 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 to 5.
Formula: CF ₂ ＣＦCFCF ₂ (OCF (CF ₃ ) CF ₂ ) _m (OCH ₂ CF ₂ CF ₂ ) _n OCH ₂ CF ₂ —CN
(In the formula, m is an integer of 0 to 5, and n is an integer of 0 to 5.)
Formula: CF ₂ ＣＦCFCF ₂ (OCH ₂ CF ₂ CF ₂ ) _m (OCF (CF ₃ ) CF ₂ ) _n OCF (CF ₃ ) -CN
(In the formula, m is an integer of 0 to 5, and n is an integer of 0 to 5.)
Formula: CF ₂ ＣＦCF (OCF ₂ CF (CF ₃ )) _m O (CF ₂ ) _n —CN
(In the formula, m is an integer of 0 to 5, and n is an integer of 1 to 8.)
Formula: CF ₂ = CF (OCF ₂ CF (CF ₃ )) _m -CN
(Where m is an integer of 1 to 5)
Formula: CF ₂ ＣＦCFOCF ₂ (CF (CF ₃ ) OCF ₂ ) _n CF (—CN) CF ₃
(Where n is an integer of 1 to 4)
Formula: CF ₂ ＣＦCFO (CF ₂ ) _n OCF (CF ₃ ) -CN
(Where n is an integer of 2 to 5)
Formula: CF ₂ ＣＦCFO (CF ₂ ) _n — (C ₆ H ₄ ) —CN
(Where n is an integer of 1 to 6)
Formula: CF ₂ ＣＦCF (OCF ₂ CF (CF ₃ )) _n OCF ₂ CF (CF ₃ ) -CN
(Where n is an integer of 1-2)
Formula: CH ₂ ＣＦCFCF ₂ O (CF (CF ₃ ) CF ₂ O) _n CF (CF ₃ ) -CN
(Where n is an integer of 0 to 5),
Formula: CF ₂ ＣＦCFO (CF ₂ CF (CF ₃ ) O) _m (CF ₂ ) _n -CN
(In the formula, m is an integer of 0 to 5, and n is an integer of 1 to 3.)
Formula: CH ₂ ＣＦCFCF ₂ OCF (CF ₃ ) OCF (CF ₃ ) -CN
Formula: CH ₂ ＣＦCFCF ₂ OCH ₂ CF ₂ —CN
Formula: CF ₂ ＣＦCFO (CF ₂ CF (CF ₃ ) O) _m CF ₂ CF (CF ₃ ) -CN
(Where m is an integer of 0 or more)
Formula: CF ₂ ＣＦCFOCF (CF ₃ ) CF ₂ O (CF ₂ ) _n —CN
(Where n is an integer of 1 or more)
Formula: CF ₂ ＣＦCFOCF ₂ OCF ₂ CF (CF ₃ ) OCF ₂ —CN
And these can be used alone or in any combination.

Among the above,
Formula: 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.

(4) Since these monomers have a cyano group, the cyano group undergoes a cyclization trimerization reaction, and triazine crosslinking proceeds.

These perfluoroelastomers can be manufactured by a conventional method.

Specific examples of such 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. (TFE) / propylene / vinylidene fluoride (VdF) fluorine rubber, ethylene / hexafluoroethylene (HFP) fluorine rubber, ethylene / hexafluoropropylene (HFP) / vinylidene fluoride (VdF) fluorine rubber, ethylene / hexa 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. Preferably, 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.

As at least one other monomer copolymerizable with vinylidene fluoride, for example, TFE, CTFE, trifluoroethylene, HFP, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, Examples include fluoromonomers such as 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 them, 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.

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

Also, as the fluorine-containing elastomer, a thermoplastic fluorine rubber composed of an elastomeric fluorine-containing polymer chain segment and a non-elastomeric fluorine-containing polymer chain segment may be used.

組成 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.

Examples of the unsaturated carboxylic acids 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. , Maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitate, undecylenic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl Phthalic acid, 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxypropyl phthalic acid, 2-acryloyloxypropyl hexa Dorofutaru acid, 2-acryloyloxypropyl tetrahydrophthalic acid, methacryloxyethyl trimellitic acid, crotonic acid, N- acryloyl alanine, maleic anhydride, citraconic anhydride, and 4-vinyl benzoate.

Among the unsaturated carboxylic acids, among others,
Formula ^{(11): CR 11 R 12} = CR 13 -R 14 - (COOH) n
(In the formula, 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, and n is 1 or 2.) Compounds, and
General formula (12): CR ¹⁵ R ¹⁶ = CR ¹⁷ -R ¹⁸ -Ar-(-COOH) _m
(Wherein, 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, and Ar is a divalent or trivalent cyclic aliphatic group. Or an aromatic group, m is 1 or 2.), and 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. As R ¹⁴ , a single bond or a compound represented by the formula: — (C ＝ O) _n1 — (O) _n2 —R ¹⁴¹ — (wherein n1 and n2 are the same or different and 0 or 1, and ^R141 is Or an alkylene group in which an oxygen atom may be inserted between carbon-carbon atoms.). The carbon number of the alkylene group represented by R ¹⁴¹ is preferably 1 to 10, more preferably 1 to 3.

Further, 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. As 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. R ¹⁸ is a single bond or a formula: — (C ： O) _m1 — (O) _m2 —R ¹⁸¹ — (O) _m3 — (C ＝ O) _m4 — (wherein, m1 to m4 are The same or different, 0 or 1, and R ¹⁸¹ is an alkylene group in which an oxygen atom may be inserted between 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.

Examples of the unsaturated sulfonic acids 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.

As 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. As the 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. In the present disclosure, “(meth) acrylate” means acrylate or methacrylate.

メ チ ル As the (meth) acrylate, methyl methacrylate is preferable.

In the polymer contained in the composite particles, 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%.

When the polymer further contains an unsaturated carboxylic acid ester unit, 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. When the polymer further contains 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. When the composition contains 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. . Among these, 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.

(4) 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. When the content of the inorganic particles is in the above range, the scorch resistance can be further improved, and the crosslinking reaction can be sufficiently advanced.

The average particle size of the composite particles is preferably 0.01 to 100 μm, more preferably 0.05 μm or more, further preferably 0.1 μm or more, more preferably 30 μm or less, and further preferably It is 15 μm or less. When the average particle size of the composite particles is in the above range, the handleability is excellent and the composite particles can be sufficiently dispersed in the composition. 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.

In the above-mentioned polymerization, in addition to the above-mentioned acid group-containing monomer, in addition to the above-mentioned acid group-containing monomer, 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 (inorganic particles / monomer) is preferably 1/99 to 80/20, more preferably 10/90 or more, and more preferably 75/25 or less. .

と し て As the dispersant, at least one selected from the group consisting of polyvinylpyrrolidone, saponified polyvinyl alcohol and hydroxypropylcellulose is preferable, and polyvinylpyrrolidone is more preferable.

少 な く と も As 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. Examples of the azo compound include 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobisisobutyronitrile, and 2,2′-azobis (2-methylpropionitrile). Can be

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.

公 知 A known means such as ultrasonic waves may be used to disperse each component in the solvent.

重合 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.

と When the polymerization is completed, 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. When the content of the composite particles is in the above range, the scorch resistance can be further improved, and the crosslinking reaction can be sufficiently advanced.

The crosslinker is not an essential component. However, the composition may further contain a crosslinking agent. Examples of the crosslinking agent include a crosslinking agent used in peroxide crosslinking, polyol crosslinking, polyamine crosslinking, triazine crosslinking, oxazole crosslinking, imidazole crosslinking, and thiazole crosslinking. When 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. Specifically, for example, 1,1-bis (t- (Butylperoxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α , Α-bis (t-butylperoxy) -p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t -Butylperoxy) -hexyne-3, benzoyl peroxide, t-butylperoxybenzene, 2,5-dimethyl-2,5-di (benzoylperoxy) Xy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, 1,3-bis (t-butylperoxyisopropyl) benzene, and the like. In general, the type and amount of the organic peroxide are selected in consideration of the amount of active -OO-, the decomposition temperature, and the like.

In this case, the crosslinking assistant that can be used may be a compound having a reaction activity for a peroxy radical and a polymer radical. For example, -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 ), -CH = CF ( Examples thereof include a polyfunctional compound having a functional group such as CF ₃ (“C ₆ H ₅ ” in each formula represents a phenyl group). Specifically, for example, 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.

As a crosslinking agent or a crosslinking assistant used together with a crosslinking agent used in peroxide crosslinking, general formula (21):

(Wherein, 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. When 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.), And a compound having at least one structure represented by the following formula: When m is 1, it is preferable to have two or more of the structures.

As the compound having the structure represented by the general formula (11), a compound represented by the general formula (22):

(Wherein R ²¹ to R ²³ are as described above, p is an integer of 0 to 2, and n is an integer of 2 to 6), and a compound represented by the general formula (23):

(Wherein, R ²¹ to R ²³ are as described above. 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.).

架橋 Examples of the crosslinking agent used for polyol crosslinking include polyhydric alcohol compounds such as bisphenol A and bisphenol AF.

架橋 Examples of the crosslinking agent used for the polyamine crosslinking include polyamine compounds such as hexamethylenediaminecarbamate, N, N'-dicinnamylidene-1,6-hexanediamine, and 4,4'-bis (aminocyclohexyl) methanecarbamate.

架橋 Examples of the crosslinking agent used for triazine crosslinking include organotin compounds such as tetraphenyltin and triphenyltin.

Examples of the crosslinking agent used for oxazole crosslinking, imidazole crosslinking, and thiazole crosslinking include, for example, a compound represented by the general formula (30)

(Wherein, 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

Wherein one of 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 . 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

And so on. These compounds are known as examples of bisdiaminophenyl compounds in Japanese Patent Publication No. 2-59177, JP-A-8-120146, and the like.) 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.)

A bisamidrazone-based crosslinking agent represented by the general formula (32):

(Wherein Rf ³¹ is a perfluoroalkylene group having 1 to 10 carbon atoms), or a general formula (33):

(Wherein, n is an integer of 1 to 10). These 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.

Particularly preferred 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):

(Wherein 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) phenyl] hexafluoropropane, 2,2-bis [3-amino-4- (N-propylamino) phenyl] hexafluoropropane, 2,2-bis [3-amino-4- (N-perfluorophenyl) Amino) phenyl] hexafluoropropane, and 2,2-bis [3-amino-4- (N-benzylamino) phenyl] hexafluoropropane.

Among them, 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.

含有 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.

の Among these, carbon black, aluminum oxide, yttrium oxide, silicon oxide, polyimide, and carbon fluoride are preferred from the viewpoint of the shielding effect of various plasmas.

The above-mentioned 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.

In particular, in fields where high purity and non-staining properties are not required, it is possible to mix ordinary additives, such as fillers, processing aids, plasticizers, and colorants, which are added to the fluoropolymer composition as necessary. Alternatively, one or more conventional cross-linking agents and cross-linking assistants different from those described above may be blended.

特 に Particularly preferred embodiments of the composition 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.

The above-mentioned 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. In the case of an extruded product such as a hose or an electric wire, a molded product can be obtained by performing heat crosslinking with steam or the like after extrusion.

成形 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.

次 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. As the crosslinking means, 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. Examples of the sealing material include an O-ring, a square-ring, a gasket, a packing, an oil seal, a bearing seal, and a lip seal.
In addition, 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.

Note that 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.

(1) 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

成形 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.

Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

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

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.

After stirring 2.0 g of 2,2'-azobis (2-methylpropionitrile) as a polymerization initiator while stirring using a 6-blade inclined paddle, the mixture was heated to 70 ° C. and dispersed for 15 hours. Polymerization was performed.

(5) After the completion of the dispersion polymerization, 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.

複合 The obtained composite particles were evaluated by the following method.

50% diameter (median diameter) of composite particles
The measurement was performed with a laser diffraction particle size distribution analyzer HELOS & RODOS manufactured by Sympatec. Table 1 shows the results.

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.

Example 1
With respect to 100 parts by mass of a fluorine-containing elastomer (TFE / PMVE / cyano group-containing monomer = 59.4 / 40.1 / 0.5 (molar ratio)), the composite particles obtained in Preparation Example 1 were added in an amount of 0.1%. 5 parts by mass, 0.8 part by mass of 4,4 ′-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bis [N1-phenyl-1,2-benzenediamine] as a crosslinking agent A mixture of 23 parts by mass of carbon black (average particle diameter: 0.3 μm) as a filler was kneaded with an open roll to prepare a crosslinkable fluororubber composition.

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. Using 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. In addition, 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.

Normal state physical properties According to JIS K6251, 100% tensile stress (MPa), tensile strength (MPa), elongation (%) and hardness Peak (Shore A) of a test sample having a thickness of 2 mm in a normal state (25 ° C.) were measured. . Table 3 shows the results.

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.

Reference Example 1
Without using composite particles, 100 parts by mass of a fluorine-containing elastomer (TFE / PMVE / cyano group-containing monomer = 59.4 / 40.1 / 0.5 (molar ratio)) was mixed with silicon nitride (average particles). 0.25 parts by mass of a crosslinking agent 4,4 ′-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bis [N1-phenyl-1,2-benzenediamine]. A fluororubber composition was prepared in the same manner as in Example 1, except that 0.8 parts by mass and 23 parts by mass of carbon black (average particle size: 0.3 μm) as a filler were blended. Using the obtained fluororubber composition, a test sample of a crosslinked product having a thickness of 2 mm was prepared in the same manner as in Example 1. The physical properties of the obtained test samples were measured in the same manner as in Example 1. Table 3 shows the results.

From Table 2, it is found that Examples 1 to 5 in which the composite particles obtained using methacrylic acid were blended had a 40 ° C. lower temperature than Comparative Example 1 in which the composite particles obtained without using methacrylic acid were not blended. The increase in ML after the storage test was small, indicating that the scorch stability was improved. Also, from Table 3, there is almost no difference in the physical properties of the crosslinked rubber between Examples 1 to 5 and Reference Example 1. Even when compound particles are blended, excellent physical properties equivalent to those of the conventional crosslinked product can be obtained. I understand.

Claims (9)

1. Composite particles, and a composition containing a fluoropolymer, wherein the composite particles comprise a polymer and inorganic particles dispersed in the polymer,
   A composition wherein the polymer contains an acid group-containing monomer unit.
2. The composition according to claim 1, wherein the acid group-containing monomer unit is an unsaturated carboxylic acid unit.
3. The composition according to claim 1 or 2, wherein the acid group-containing monomer unit is a methacrylic acid unit.
4. (4) The composition according to any one of (1) to (3), wherein the content of the acid group-containing monomer unit in the polymer is 1 to 100 mol% based on all monomer units.
5. 組成 The composition according to any one of claims 1 to 4, wherein the fluoropolymer is a fluoroelastomer.
6. 組成 The composition according to any one of claims 1 to 5, wherein the inorganic particles are inorganic nitride particles.
7. The composition according to any one of claims 1 to 6, wherein the composite particles are obtained by polymerizing an acid group-containing monomer in a dispersion in which the inorganic particles are dispersed.
8. 組成 The composition according to any one of claims 1 to 7, which is a molding material.
9. (8) A molded article obtained from the composition according to any one of (1) to (7).