WO2013074412A1 - Fluoropolymer composition - Google Patents

Abstract

A fluoropolymer composition containing a fluoropolymer and a crosslinking agent. The fluoropolymer is an elastomer containing copolymerization units derived from a nitrogen-containing curing site monomer, and the crosslinking agent is a combination of two or more compounds including one or more type of amidine compound and one or more type of bis aminophenol compound.

Description

FLUORQPOLYMBR COMPOSITIO BACKGROUND

Technical Field

The present invention relates to a fiuoropolymer composition containing a combined crossiinking agent.

Related A

Perfliioroelastomers have come into use as sealants in the semiconductor market, for example, due to excellent properties such as heat resistance, chemical resistance, radical resistance, and low outgassmg. In recent years, the semiconductor market has tended to shift toward higher temperatures and cleaner processes.

In Japanese Unexamined Patent Application Publication No. 116-263952 (Patent

Document I ), there is described a fluorine-containing elastomer composition prepared by mixing a bis(aminophenyl) compound with a specific structure as a curing agent into a ternary

copolymer of tetrafluoK>emoxy-(iowe\peri1uoroalkyl substitufed)-eihene, and cyano

group-containing (perfluoro vinyl ether) of a specific structure. In Japanese Unexamined Patent Application Publication No. HS-120 J 46 (Patent Document 2), there is described a

fluorine-containing elastomer composition prepared by mixing bis aminophenyl compound as a curing agent into a ternary copolymer of tetrafluoroethoxy-iJower pertluoroaikyi

subst.tuted)-ethene_; and perfluoro (ocyano alkyl vinyl ether) of a specific structure.

In International Publication No. WQ00 29479 Pamphlet (Patent Documen 3), there is described a fluorine .rubber crossiinking composition containing a fluorine-containing elastomer having carboxy! groups and/or alkoxy carbonyi groups as crossiinking groups at the end of a main chain and/or a branched chain.

In Japanese Unexamined Patent Application Publication No. 2006-502283 (Patent Document 4), there is described a composition which contains (a) a fiuoropolymer containing copoiymerization units derived from a nitrogen-containing curing site monomer; and (b) a curing agent containing amidine; wherein, in some cases, the fiuoropolymer is perfluormated. [Background Documents]

[Patent Documents]

Patent Document 1 : Japanese Unexamined Patent Application Publication No.

H6-263952

Patent Document 2: Japanese Unexamined Patent Application Publication No,

H8-12Q146

Patent Document 3: international Publication No, WO00/29479 Pamphlet

Patent Document 4: Japanese Unexamined Patent Application Publication No.

2006-502283,

[Summary of the Invention]

[Problem to be Solved by the Invention]

However, the present inventors discovered that a molded product (such as a sheet, for example) obtained using a conventional fluoropolymer composition may have crater- like surface detects. The present inventors further discovered that insufficient, curing of the fluoropolymer is one factor contributing to these surface defects.

An object of the present invention is to obtain a fluoropolymer composition capable of providing a molded product in which surface defects are effectively reduced or prevented.

SUMMARY

A first mode of the present invention provides:

a fluoropolymer composition containing a fluoropolymer and a crosslinking agent;

wherein the fluoropolymer is an elastomer containing copolymerizaiion units derived from a nitrogen-containing curing site monomer; and

the crosslinking agent is a combination of two or more compounds including one or more types of amidine compounds and one or more types of bis aminophenol compounds,

[Effect of the Invention]

The present invention provides a fluoropolymer composition, which enables the formation of a molded product w ith few surface defects. DETAILED DESCRIPTION

Details of the embodiments of the present invention will be given hereinafter. Other characteristics, purposes, advantages, and the like of the present invention wil l become clear from the following descriptions and the attached Scope of the Patent Claims.

A first mode of the present invention provides:

a fluoropolymer composition containing a fluoropolymer and a crossiinking agent;

wherein the fluoropolymer is an elastomer containing copolymerr/ation units derived from a nitrogen-containing curing site monomer;, and

the crossiinking agent is a combination of two or more compounds including one or more type of amidine compound and one or more type of bis aminophenol compound.

The fluoropolymer composition of the present invention can form a cured product with high crossiinking density. Such a cured product with a high crossiinking density can be used to form a molded product with few surface defects.

In particular, with the fluoropolymer composition of the present invention, a molded product can be formed so that virtual ly or absolutely no depressions of a size visible to the eye are observed.

in several modes, the fluoropolymer composition may have low compression set properties due to the high crossiinking density thereof.

In the. fluoropolymer composition of several modes, using a combination of an. amidine compound and bis aminophenol compound yields a higher crossiinking density while using the same amount of crossiinking agent in comparison to cases in which an amidine compound and a bis aminophenol compound are respectively used independently, for example.

in several modes, the fluoropolymer composition enables the realization of favorable surface properties while maintaining the advantages resulting from the use of an elastomer containing copoiymerization units derived from a nitrogen-containing curing site monomer (for example, excellent heat resistance and excellent chemical resistance).

In this disclosure, the term "alky!" refers to a straight-chain or branched-chain aliphatic hydrocarbon group. The term "branched-chain" refers to a substance in which one or a plurality of alky I. groups such as methyl, ethyl, propyl, or the like, for example, are attached to a straight alky! chain. An alky! group may be imsubstituted or may be substituted with one or a plurality of halo atoms, eyeloaikyi. or cycSoalkenyl groups, or the like. The term "alkenyl" refers lo an aliphatic hydrocarbon group having a carbon-carbon double bond and may be a straight-chain or branched-chain substance. An alkenyl group may be tmsubstituted or may be substituted with one or a plurality of halo atoms, cyc!oalkyi or cycloalkenyl groups, or the like.

The term "cycloalkyl" refers to a non-aromatic monocyclic or polycyclic ring system containing, for example, approximately 3 to 12 carbon atoms. Examples of cycloalkyl rings include cyclopentyl, cyclofaexyl, and cycioheptyl. This cycloalkyl group may be substituted with one or a plurality of halo atoms, methylene, alkyi, cycloalkyl, heterocyciyl, ara!kyi, heteroaralkyl, aryl heteroaryl, or the like. The term "hetero" refers to oxygen, nitrogen, or sulfur substituted for one or a plurality of carbon atoms.

The term "cycloalkenyl" refers to a non-aromatic monocyclic or polycyclic ring system having a carbon-carbon double bond and containing, for example, approximately 3 to 10 carbon atoms. This cycloalkenyl group may be unsubstiluted or may be substituted with one or a plurality of halo atoms, methylene, alkyi, cycloalkyl, heterocyciyl, aralkyl, heteroaralkyl, aryl or heteroaryl groups, or the like.

The term "aryl" refers to an aromatic carbon ring radical. Examples o aryl groups include phenyl or naphthyl substituted with one or a plurality ofaryl group substituents which may be the same or different in some instances. Here, examples of "aryl group substituents" include hydrogen, alkyi, cycloalkyl, aryl which may be substituted in some instances, heteroaryl which may be substituted in some instances, aralkyl, aralkenyl. aralkynyl, heteroaralkyl, heteroaralkenyl, heteroaralkynyl, hydroxy, hydroxyalkyl alkoxy, aryloxy, aralfcoxy, carboxy, acyl, aro l, halo, nitro, cyano, carboxy, alkoxycarbonyl. aryloxycarbonyl, aralkoxyearbonyl, acylamino, aroylai no, alkylsulfonyl, arylsulfonyL and other known groups.

The term "alkaryl" refers to an aryl-alkyl group, where^'.aryl and alkyi are as described previously. The term "alkenylaryl" refers to an aryl-alkeny! group, where aryl and alkenyl areas described previously.

The descriptions of the chemical groups given above are publicly known in this field, and these descriptions are not intended to alter the generally recognized meanings.

Each component of the iluoropolymer compositio will be further described hereinafter. <Fiu ropolymer>

The fluoropolymer used in the present invention is an elastomer containing

copolymerization units derived from a niirogen-coniai ing curing site monomer (also called a curing elastomer hereafter). Examples of curing elastomers include fluoro !astomer rubbers. A nitrogen-containing curing site monomer is a monomer containing a nitrogen-containing curing site (that is, a structural part which contains nitrogen and participates in curing reactions). Accordingly; the nitrogen-containing curing site gives the curing elastomer curing properties. Examples of nitrogen-containing curing sites include nitrile, imklaie. amidlne, amide, irnide, arnine-oxide groups, and the like, in a preferable mode, the niirogen-coniaining curing site monomer is partially or completely fluorinated.

Examples of useful nitrogen-containing curing site monomers are one or more types selected from nitrik-ecmtaining -fluorinated olefin and nitrite-containing fluorinated vinyl ether. These substances are more preferably peril uorinated. Examples of nitrile-containing fluorinated vinyl ether include, for example. C¾^∞CFO(CF₂)LCN;

CFrCFO CF₂CF(CF₃)Ojq(CF_;0)yCF(CF₃)CN; CF₂=CF[OCF₂CF(CF ]rO{CF₂)_TC ;

CF₂ FO(CF_? OCF(CF₃)CN, and the like, in the formulas, j>2 through 12; q=0 through 4; r~l or 2; y=0 through 6; t~l through 4; and u=2 through 6.

Representative examples of useful nitrogen-containing curing site monomers include CP2=CF0(CF₂)₃0CF(CP )CN, perfiuoroiS-cyano-S-methyl-j^-dioxa-I -octenk and

CF₂-CFO(CF₂)sCN.

The copotymerkation units derived from a nitrogen-containing curing site monomer preferably constitute approximately 0.1 to 5 mo! % or approximately 0.3 to 2 mol % of the total polymer units of the curing elastomer. These ranges are advantageous From the perspective of providing favorable surface properties to the molded product obtained from the fluoropolymer composition of the present invention.

An example of a suitable curing elastomer is an elastomer containing copolymerization units derived from a nitrogen-containing curing site monomer and a main monomer (preferably at least two types of main monomers). Examples of candidate compound suitable for use as main monomers include peril uoroolefms (for example, tetrafluoroethyiene (TFE) and hexafluoropropyiene (HFP)), other perhaiogenated olefins (for example, chlorotrifluoroethylene (CTFE)), and perfluorovinyl ethers (for example, perfluoroalkyl vinyl ether and perfluoroalkoxy vinyl ether). In some instances, a hydrogen-containing monomer such as an olefin (for example, ethylene, propylene, or the like), for example, and a partially fluorinated monomer (for example, vinyl i ene fluoride (VDF)) may also he used,

if the curing elastomer is perhalogenated, it is preferable for the curing elastomer to contain at least approximately 50 mol % of copolymerization units derived from one or a

plurality of types of perhalogenated olefins (for example, TFE and/or CTFE as well as HFP in some instances). The remaining copolymerization units of the curin elastomer (for example, approximately 10 to 50 mol %) may consist of one or a plurality of types of perfiuoro vinyl ether and one or a plurality of types of nitrogen-containing curing site monomers (for example, nitriie-contaming vinyl ether or vmidate-containing vinyl ether). In a more preferable mode, the curing elastomer is perfluorinated.

On the other hand, in a mode in which the curing elastomer is not perhalogenated, the curing e lastomer m ay con tain, for example, approximatel 5 to 90 mol % of copol merization units derived from a perhalogenated olefin, approximately 5 to 90 mol % of copolymerization unit derived from a hydrogen-containing monomer, at most 40 mol % of copolymerization units derived from vinyl ether, and approximately 0, 1 to 5 mol % (more preferably approximately 0.3 to 2 mol %} of copolymerization units deri ved from a nitrogen-containing curing site monomer. in a mode in which the curing elastomer is not perfluorinated,. the curing elastomer may contain, for example, approximately 5 to 90 mol % of copolymerization units derived from TFE. CTFE. and/or HFP, approximately 5 to 90 mo! % of copolymerization units derived from VDF, ethylene, and/or propylene, at most 40 mol % of copolymerization units derived from vinyl ether, and approximately 0.1 to 5 mol % (more preferably approximately 0.3 to 2 mol %) of

copolymerization units derived from a nitrogen-containing curing site monomer.

A suitable example of a perhalogenated: olefin is a perfluorinated olefin, and a

particularly suitable example is a perfluorinated olefin expressed by the formula Cp₂=CF-Rf

(wherein R_f is fluorine or a€; ·_¾ perf!iioroalkyl).

A suitable example of a hydrogen-containing olefin is a hydrogen containing C₂-C olefin in which less than 1/2 or less than 1 /4 of the hydrogen atoms in the molecule have been replaced with fluorine or have not been fluorinated. However, in several embodiments,

copolymerization units derived from an olefin that has not been fluorinated are not contained i the curing elastomer. A suitable example of a hydrogen-containing olefin is an olefin expressed by the formula CX?=CX-R (wherein each X is independently hydrogen, fluorine, or chlorine, and R is hydrogen, fluorine, a C s-C ₁₂ alkyl, or C j -€₃ alkyl). Suitable examples of these olefins are partially fluorinaled monomers (for example, vinyiidene fluoride) and hydrogen-containing monomers (for example, a-olefins (for example, ethylene, propylene, butene, pentene, hexene, or the like) or the like).

Two or more types of the respective raw materials described above may be used in combination.

Examples of perfluoro vinyl ethers include CP ₂=€FOCF_3i CF2-CFOCF₂CF2OCF3, CF-rCFOCFaCFiCFaOCFs, CF₂-CFOCF₂CF₂CF_3? CF₂= FOCF₂CF(CF₃)OCF₂CF₂CF₃, and CF2^!SCFOCF₂CF(CF3)OCF₂CF(CF₃)OCF₂CF₂CF₃.

In a preferable mode, the curing elastomer is a copolymer of a perfluoroo!efin, a perfluorovmyl ether, and a nitrogen-containing curing site monomer. In this copolymer, a suitable example of a nitrogen-containing curing site monomer is one o more types selected from nitrite-containing fluorinaled olefins and nitri^'le-containing fluorinated vinyl ethers.

In a more preferable mode, the curing elastomer is a copolymer of tetrailuoroethykne (TFE), at least one type of eriluoroalkyl vinyl ether, and a nitrogen-containing curing site monomer (preferably, at least one type selected from nitrite-containing fluorinated olefins and nitrite-containing, fluorinated vinyl ethers}.

In a particularly preferable mode, the curing elastomer is a ternary copolymer of tetrafluoroethylene (TFE), perf!uoromethyl vinyl ether (PMVE), and

Cl¾=CFO(CF₃)_iCN^'(MV5CN).

In these copolymers, the copo!ymerized perfliioro vinyl ether units (preferably

perfliioroalkyi vinyl ether units, and more preferably PMVE units) preferably constitute approximately i to 60 mo! % and more preferably constitute approximately 10 to 40 mol % of all of the copolymerization units of the curing elastomer.

The curing elastomer may be one type of elastomer or a blended product of two or more types of elastomers. n the case of a blended product, each elastomer contains

copolymerization units derived from nitrogen-containing curing site monomers such as those described above. For example, two or more types of elastomers containing reactive sites enabling a suitable combination with the cross-linking agent used may be blended. Additional fluoropolymers)

in addition to the curing elastomer described above, the fluoropoiymer composition may contain one or a plurality of types of additional fluoropolymers that do not contain

copolymerization units derived from a nitrogen-containing curing site monomer. The additional fluor olymers may be single polymers or copolymers. The additional

tluoropoiyraers may be blended with the curing elastomer.

Ail of the substances described above as copolymerizaiion units which may be contained in the curing elastomer except nitrogen-containing curing site monomers can be used as examples of polymerization units of the additional fluoropolymers. For example,

polytetrafluoroethylene (PI^'F^'E) and tetrafiuoroethylene-perfluoroviny! ether (PFA) are useful

For e am le the fluoropoiymer composition can be provided with a desired property by combining an additional fluoropoiymer with an additional curing agent, which can be used as desired, other than the ami dine compound and the bis aroinopheool compound used as a

crossli king agent in the present invention. For example, the chemical stability of the fluoropoiymer composition can be improved by combining an additional fluoropoiymer suitable for peroxide curing and a peroxide curing agent. Using such an additional fluoropoiymer and an additional curing agent enables a balance between the thermal stability and chemical stability of the resulting blended product and also yields economic effects.

If an additional fluoropoiymer is used, the mass percentage of the curing elastomer is preferably at least approximately 25 mass % or at least approximately 50 mass % of the total of the curing elastomer and the additional fluoropoiymer (also called the fluoropoiymer component hereafter) contained in the fluoropoiymer composition. In this ease, a fluoropoiymer

composition, which yields a molded product having excellent surface properties, is obtained, in several modes, the fluoropoiymer component contained in the fluoropoiymer composition consists of only a curing elastomer.

The curing elastomer and a desired additional fluoropoiymer can be prepared using a publicly known method. For example, the polymerization process can be implemented by subjecting a monomer to tree-radical polymerization by means of aqueous emulsion

polymerization or solution polymerization in an organic solvent. When preparing a blended product of two or more types of fluoropolymers, two or more types of fluoropoiymer latex, for example, are blended at a selected ratio, coagulated, and then dried. In the curing elastomer and the desired additional fluoropoiymer, the types and amounts of end groups are not absolute. For example, the polymer may contain an S03^' end group generated by an .APS/sulfite. The polymer may also contain a COO^" end group generated by an APS polymerization initiator. The polymer may also contain a "neutral" end group - for example, an end group generated by using a fluorosulfinate polymerization initiator or an organic peroxide. The number of end groups can be dramatically reduced by using a desired chain transfer agent. The presence of end groups of strong polarity such as SO₃ ^", for example, can be minimized as desired for the purpose of improving processability, for example. In addition, the amount of COO^" or other unstable end groups may also be reduced as desired by post-treatment (for example, decarboxylation, post- i uori nation, or the like).

The curing elastomer and/or the desired additional fluoropoiymer may contain curing sites other than nitrogen-containing curing sites. These may contain halogens so as to allow participation in peroxid curing reactions. Halogens may be introduced at intermediate and/or end positions of a fluoropoiymer chain. Halogens are typically bromine or iodine.

Copolymerization is a preferable method for introducing halogens at an intermediate position of a polymer chain in the .tl^' oropolymef component, When this method is used, an appropriate fluorination curing site monomer such as a bromo- or iodo-fluoroolefin or a bromo- or iodo-lluoro vinyl ether, for example, is used as a copolymerization component. Examples of bromo- or iodo-fiuoroolefins include bromodiiluoroethyiene, bromotrifluoroethyleiie, iodotrifluoroethy!ene, 1 -bromo-2,2-difluoroeth lene, 4-bromo«3 ,3,4,4-tetraTiuorobiitene- 1 , and the like. Examples of bromo- or iodo-tluorovinyl ethers include RrCFsOCF-CI^,

BrCF₂CF₂0CF=CF_2! BrCF₂CF₂CF₂OCF F₂, CF₃CF(Br}CF₂OCF-CF₂, and the like. Further, bromo- or iodo-oiefms, which have not been Ouorinated such as vinylbromide,

4-bromo-l-butene, and the like, may also be used.

in general, the amount of the curing sites introduced at the side chain position of the polymer in the fluoropoiymer component is preferably approximately 0.05 to 5 mo! % and more preferably approximately 0.1 to 2 mol % of the total polymerization units,

The curing sites may be located at the ends of a polymer chain of the fluoropoiymer component. For example, a halogen may be introduced at the end position using a chain transfer agent or a polymerization initiator. Typically, a curing site is introduced at the end position by introducing an appropriate chain transfer agent into a reaction medium or deriving the site from an appropriate polymerization i nitiator at the time of polymer preparation.

An example of a useful chai n transfer agent is a compound expressed by the formula fZx (wherein R_f is a substituted or un substituted C ~C_\i fhioroalkyl radical which may be perf!uormated, Z is Br or Ϊ, and x is 1 or 2). Specific examples containing bromine include ί _?Br_:. Br(CF₂)iBr,

C¾CF(Br)CF₂Br_? and the like.

An example of a useful polymerization initiator is a compound expressed by

Na0₂S(CF₂)nX (wherein X is Br or 1 and n is 1 to 10).

The amount of curing sites introduced at the end position of the polymer of the fluoropoiymer component is typically approximately 0.05 to 5 mol % and more preferably approximately 0.1 to 2 mol % of the total polymerization units.

Combinations of two or more types of curing sites are also useful in the present invention. For example, a useful fluoropoiymer is one that contains halogens capable of participating in peroxide curing reaction along with a nitrogen-containing curing site such as a nitriie

group-containing curing site, for example. The total amount of curing sites is typically approximately 0.1 to 5 mol % and preferably approximately 0.3 to 2 mol % of the total polymerization units.

Effective amounts of the erosslinking agent used in the present invention and the desired additional curing agent can be used as a curing agent to crosslink the curing elastomer and the desired additional fluoropoiymer. If the amount of the curing agent is too small, the

erosslinking o the fluoropoiymer component -will not progress sufficiently, and as a result, the desired, physical properties may not be achieved and/or the erosslinking rate may be lower than expected, if the amount of the curing agent is too large, the fluoropoiymer component may not be crosslinked as expected and/or erosslinking may occur more quickly than according to the expected manufacturing conditions. The amount of the curing agent required may be affected by the selection of the specific components of the composition. For example, depending on the type and/or amount of the selected filler, it may be possible to promote or suppress curing in comparison to the same composition to which a filler is not added, so it i necessary to adjust the amount of the curing agent appropriately, but this is known to people having ordinary skill in the art. The type and amount of the curing agent that is used are influenced by the composition of the fluoropoiymer component. For example, when a blended product of a nitrile

group-containing tluoropolymer and an additional fluoropoiymer not containing a nitrile curing site is used, an effective amount of a first selected curing agent is used to crosslink the tluoropolylmer having copolymerization units derived from a nitrile group-containing monomer, and an effective amount of a second selec ted curing agent is concurrently used to crosslink the additional fluoropoiymer. ^'The first and second selected curing agents may respectively be one type or combinations of two or more types of curing compounds. In addition, the first and second selected curing agents may he the same or different compositions. That is, at least one type out of a plurality of types of curing agents should have the effect of crosslinking at least one type of polymer.

<Amidme compounds

The amidine compound used in the present invention can function as a crosslinking agent. An amidine compound may typically be one type or a combination of two or more types se lected from a group including mono-amidines. bis-amidines, tris-amidines, tetra-amidines, and salts thereof. One preferable mode of a amidine compound is one typ or a combination of two or more types selected from a group including mono-amines, bis-amidines. and salts thereof from the perspective of availability and practicality. Here, when a mono-amidine is used, a compound having a structure capable of functioning as a crosslinking agent such as a

mono-amidine salt, for example, is selected.

In a preferable mode, the amidine compound has at least one C-Q-C bond. An amidine compound having at least one C-O-C bond is advantageou from the perspective of providing the molded product with particularly favorable surface properties and, in several modes, further providing favorable compression set properties.

The amidine compound may contain hetero atoms such as oxygen, sulfur, phosphorus, or nitrogen present outside the amidine groups, for example.

in a particularly preferable mode, the amidine compound is a .mono-amidine having at least one C-O-C bond. In a preferable mode, the mono-amidine may have alkyl groups, alken l groups, aryl groups, or alkaryl groups having from 1 to approximately 15 carbon atoms. These may be straight-chain or branched-chain substances. These substances may be unsuhstituted substituted (for example, fluorinated; in particular, perfiuorinated).

In a preferable mode, a preferable amidine compound is expressed by the following general formula (2);

[Formula I ]

(wherei

R¹ is a hydrogen atom; or an aikyl group, alkenyl group, aryl group, alkaryl group, or alkenyl aryl group;

R is a hydrogen atom; or an aikyl group, alkenyl group, aryl group, .alkaryl group, or a!kenyl aryl group; or (R²}2 forms a group expressed by H ^{f fi"!}A, where '^'· A is an anion:

Y is a single bond or a monovalent, to quadrivalent group;

n is an integer of 1 to 4, wherein if n is 1 , (R")₂ forms a group expressed by iV^A and R^s and K² may be the same or different, when a plurality of components are present in the molecule).

The aikyl group described above may have 1 to approximately 15, 1 to approximately 10, or 1 to approximately 8 carbon atoms. The alkenyl group described above may have approximately 2 to 15, approximately 2 to 10, or approximately 2 to 6 carbon atoms. The aryl group described above may have approximately 6 to 15 or approximately 6 to 12 carbon atoms.

In a preferable mode, R' is hydrogen and R^ is l¾ ^)WA.

The anion expressed by may be an inorganic anion or an organic anion. In a preferable mode, ^WA contains a Ci anion, a Br anion, an I anion, or a COO anion. A preferable example of ^WA is an anion selected from a group including COO, S0₃, SO2, SO2NIT PO3, CH₂OPQ¾ (CH₂0)₂P0_2; QHkA OS0₃, N(S0₂)R\ N(S0₂)S0₂R\ and C(S0₂)RS02R' (wherein R and R^! are respectively independently an aikyl group, alkenyl group, aryl group, alkaryl group, or alkenyl aryl group, and these may be unsubstituted or partially or completely fluorinated).

in a preferable mode, ^WA has an aikyl group having 1 to approximately 12 carbon atoms. In a preferable mode, ^i→A has an ether bond.

in a preferable mode, ^WA is a halogenated carboxylie acid anion, particularly a

fluorocarboxylic acid anion, and more preferably a periluoroearboxylie acid anion.

in a preferable mode, A is expressed

(wherein k is Ϊ to approximaiely 10).

In another preferable mode, ¾ is expressed by CF₃(CF₂)jCOG^("} (wherein j is 1 to approximately 15, 1 to approximately 8, o 1 to approximately 3),

In a preferable mode, A is an acetic acid anion, a fluorinated acetic acid anion, or a triiluoroacetic acid anion.

Regarding Y, if n described above is 1 (that is, a ono-amidine), Y is a monovalent organic group, for example, if n is 2 (that is. a di-amidine), V is a single bond, -0~, -S-, or a bivalent organic group, for example. If n is 3 (thai is, a tri- ami dine), Y is a irivalent organic group, for example, if n is 4 (that is, a tetra-amidine), Y is N^w or quadrivalent organic group, for example. These monovalent to quadrivalent organic groups may respectively contain hydrocarbon groups having 1 to. approximately i 5 carbon atoms, for example. The

hydrocarbon groups may be unsubstituteci or substituted (for example, halogcnated; particularly, fluorinated; more- articularly, perfiuorinated) and ma he straight-chain or branehed-chain groups.. Y preferably has at least one C-O-C bond.

A preferable example is a m-ono-amidinc compound in which n is I and Y is a group expressed by R³OR.⁴- (wherein R^j is a peril uoroalkyl group having 1 to approximately 3 carbon atoms, and R⁴ is a perfluoroalkyl group having 1 to approximately 3 carbon atoms). These amidine compounds are advantageous from the perspective that the compounds are extremely easy to acquire and the perspective that the compounds are considered to have favorable crossltnking reactivity.

Another preferable example is a di-amidine compound in which n is 2 and Y is a group expressed by -( 'O ⁶)^- (wherein R ^' and R⁶ are respectively independently a perfluoroafkyfene group having 1 to appro imately 3 carbon atoms and m is an integer from 1 to 3). These amidine compounds are advantageous from the perspective that the -compounds are extremely easy to acquire and the perspective that the compounds are considered to have favorable crosslinking reactivity. Modes in which any two or more of the preferable modes described above with regard to each of R\ R , Y, n, and -^"-A in the general formula (2) are also included in this disclosure.

A preferable example among these modes is a mono-amidine compound in which ¹ is a hydrogen atom, (R²)₂ is j¾^{l+ w}A, ^WA is a trif!uoroacetic acid anion, and Y is a CF3OCF₂CIV group. This amidine compound is expressed by the following formula (3):

[Formula 2]

Another preferable example is a di-amidivte compound in. which R is a hydrogen atom,

(R¾ is Hj - ^)l"iA_; ^{( "}'A is an acetic acid anion, and Y is a ~(CF₂OCF2) group. This amidine compound is expressed by the foilowing formula (4):

I Formula 3]

CHsCOOM

The amidine compound itself may be introduced into the fluoropoiymer composition, or the amidine compound m ay be genera ted at the time of use by typically introducing the raw material or prec ursor of the amidine compound as a mixture. An example of the raw material or precursor of the amidine compound is a mixture of a compound expressed by the follo wing formula (5) when an amidine compound expressed by the formula (3) described above is used: [Formula 4]

mixed with CF₃COOH (trifluoroacetic acid).

The amoun of the amidine compound used per 100 parts by mass of the curing elastomer in the fluoropoiymer composition is preferably at least approximately 0.5 parts by mass from, the perspective of achieving a particularly favorable crosslinking densit and preferably at most approximately 1.5 parts by mass from the perspective of avoiding residual unreacted curing agent in the molded product and the perspective of economic superiority.

<Bis aminophenol eompound>

The bis aminophenol compound can function as a crosslinking agent in the fluoropolymer composition of the present invention. By using a bis aminophenol compound as a crosslinking agent in combination with the amidine compound as described above, it is possible to provide a higher crossl nking density than when the amidine compound and the bis aminophenol compound are respectively used alone, for example.

In a preferable mode, the bis aminophenol compound is expressed by the following genera! formula (1):

[Formula 5]

(wherein

Z Z², Z\ and Z^'! are respectively independently an -NH₂ group or an -OH group, one of Z¹ or 2? is an >NH₂ group while the other is an -OH group, and one of Z/¹ or Z⁴ is an -Nf¾ group while the other is an -OH group; and

1? is a single bond or a bivalent group selected from a group comprising -0-, -CO-, -S 2-, and perfluoroa!kyiene groups with a carbon number of 1 to 3).

In a preferable mode, Z* is a perfluoroalkylene group with a carbon number of 1 to 3 from the perspective of providing the resulting molded product with particularly favorable surface properties.

in a preferable mode, the bis phenol compound is

2,2-dianiino-4,4^,-(perfluorop-Opane-2,2-diyl) from the perspective that the compound is

extremely easy to acquire and the perspective that the compound is considered to have favorable erossitnkina reactivity.

in another preferable mode, the bis aminophenol compound is

bis(3«amino-4-hydroxyphenyl)sulfone from the perspective that the compound is extremely easy to acquire and the perspective that the compound, is considered to have favorable crosslinking reactivity.

The amount of the bis aminophenol compound used per 100 parts by mass of the curing elastomer in the fluoropolymer composition is preferably at least approximateiv 0.1 parts by mass from the perspective of achieving a particularly favorable crosslinking density and

preferably at most approximately 1.0 parts by mass from the perspective of avoiding residual unreached curing agent in the molded product and the perspective of economic superiority.

In a particularly preferable mode, the fluoropolymer composition contains approximately 0.5 to 1.5 parts by mass of an amidine compound and approximately 0.1 to 1.0 parts by mass of a bis aminophenol compound per 100 parts by mas of the curing elastomer. Such a composition is particularly advantageous from the perspective of providing a molded product with few surface defects by realizing a favorable crosslinking density.

<Other components-'

In addition to the above, the fluoropolymer composition may arbitrarily contain one or more types of the following components, for example.

(Additional curing agents)

The properties of the fluoropolymer composition may be altered by using additional curing agents in addition to the crosslinking agents described above. Examples of additional curing agents include bis-amidoximes, ammonium salts, organic compounds (compounds containing arsenic, antimony, or tin, for example), ammonia-generating compounds, and peroxide curing agents. An example of an additional curing agent is a compound expressed by the general formula CH₂=CH _fCiM¾ (wherein R_f is a C Ca straight-chain or branched chain alkylene, cycloaikylene, or oxyalkylene which is at least partially fluorinated). In the formula described above, one or a plurality of H atoms may be substituted with halogen atoms such as fluorine atoms, for example. Similarly, a polymer containing a lateral group of€Hr=CHRr ( wherein R_f is as defined above) and a polymer in which one or a plurality of H atoms in the formula are substituted with halogen atoms such as fluorine atoms, for example, are also useful as additional curing agents in the present invention. A desired adjuvant, which is typically used for curable fiuoropolymer compositions may also be incorporated into the fluoropolymer composition. For example, a substance which is often blended into fluoropolymer compositions as a part of a curing agent system is a

crosslinking aid (also sometimes called a co-curing agent), and this can work together with the peroxide curing agent to provide effective curing. Accordingly, these crosslinking aids are particularly useful when combined with the peroxide curing agent, it is typically preferable to use a crosslinking auxiliary agent in an amount between approximately 0.1 and 10 parts by mass (phr) or approximately 1 to 5 parts by mass (phr) with respect to a total of 100 parts by mass of the curing elastomer and the desired additional fiuoropoiymer.

For example, additives such as tillers (for example, carbon black, fluoropolymer fillers, and the like), stabilizers, plasticizers, lubricants, and processing aids ordinarily used in the compounding of a fluoropolymer composition and the like may be incorporated into the fluoropolymer composition. However, i is desirable for these additives to he sufficiently stable under the target usage conditions.

For example, the low-temperature performance can be improved by incorporating perfluoropolyether into the composition.

In addition, carbon black may be used in order to achieve a balance in the performance of the fiuoropoiymer composition - for example, the modulus, tensile strength, elongation, hardness, wear resistance, conductivity, processabilk , and the like. Suitable examples include MX blacks (medium thermal blacks) of the part numbers N-991 , N-9 0, N-908, and N-907;

FEFN-550; furnace black with a large particle size, and the like. Whe carbon black is used, the amount used is preferably approximately 1 to 70 parts by mass (phr) with respect to a total of 100 parts by mas of the curing elastomer and the additional fluoropolymer. This range is particularly suitable when using furnace black with a large particle size.

One type or a plurality of acid receptors may be incorporated into the fluoropolymer composition. However, in cases in which the presence of extractabie metal compounds is not desirable (in semiconductor applications, for example), the use of inorganic acid receptors should be kept to a minimum and preferably forgone entirely. Examples of typically used acid receptors include zinc oxide, calcium hydroxide, calcium carbonate,, magnesium oxide, silicon dioxide (silica), and the like. These compounds are typicall used to bind to HF or other acids. These acids can be generated at high temperatures, which may be encountered in the curing process when forming a molded product using the fluoropolymer composition or at the temperatures observed when exhibiting the functions of the fluoropolymer composition.

<Curing of the fluoropolymer composition]^'

The fluoropolymer composition of the present invention is useful in the manufacture of molded products such as O-rings, gaskets, tubes, sheets, films, sealing materials, and the like, for example. Such molded products can be manufactured with conventionally known methods. Typically, these products can be manufactured by compounding the ingredients of the

fluoropolymer composition and molding the resulting blend under increased pressure, curing the resulting product, and then further subjecting the cured product to a post-curing cycle. For example, a curable composition of a formulation, which does not use inorganic acid receptors is particularly suited to applications such as sealing materials and gaskets for manufacturing semiconductor elements and sealing materials for high-temperature parts of automobile applications.

The fluoropolymer composition can be prepared by compounding the ingredients - that is, the curing elastomer, the desired additional fluoropolymer, crossHnking agents, and various desired components (for example, one or a plurality of additional curing agents, one or a plurality of desired adjuvants used in an ordinary rubber processing device, and various other additives). More specifically, the ingredients of the fluoropolymer composition can be sufficiently mixed (that is, compounded) by adding prescribed amounts of crossHnking agents and other desired additives to the fluoropolymer component as are ordinaril used and using a desired genera rubber mixing device. An example of such a device is a sealed mixer (for example, a Banbury mixer), a roll mill, or another desired simple mixing device, it is desirable for the mixing temperature at the time of mixing to be set so as to not exceed approximately 120°C. During mixing, it is preferable to uniformly disperse the other components into the fluoropolymer.

Next, the mixture is extruded (for example, when forming a shape such as a film, tube, or hose) or processed and molded with a mold (for example, when forming a shape such as a sheet or an O-ring).

The molding or pressurized curing of the compounded mix ture is ordinarily performed under an appropriate pressure for a desi red amount of time at a temperature sufficient for curing the mixture. The temperature is typically approximately 95°C to 230°C and preferably approximately 150°C to 205^CC, and the time is approximately 1 minute to 15 hours and typicall approximately 5 minutes to 30 minutes. A pressure of approximatel 700 kPa to 2 L000 kPa is ordinarily applied to the mixture placed in a mold. The mold may be baked after first being coated with a release agent.

Next, the mixture molded in this way or the pressure-cured product is ordinarily post-cured over time in a heating furnace at a temperature sufficient to complete curing. This temperature is ordinarily approximately 150°C to 300°C and typically approximately 230°C, while the time is approximately 2 to 5.0 hours or longer, but the time typicall increases as the cross-sectional thickness of the product increases. For a product with a certain thickness, the temperature at the time of post-curing is ordinarily increased gradually irom the lower limit temperature to the target maximum temperature. The maximum temperature used is preferably approximately 300°C, and this temperature is maintained for approximately four or more hours. Any residual volatile components are ordinarily discharged irom the composition, which is completely crosslinked or cured as a result of this post-curing process. An example of a suitable post-curing cycle is to use six-stage processing conditions to expose the product to heat in a nitrogen atmosphere. First, the product is heated from 25°C to 200°C over the course of 6 hours, the product is then held at 200°C for 16 hours, and then the product is then heated from 200°C to 250*0 over the course of 2 hours. Next, the product is kept at 250°€ for 8 hours and is then heated from 250°C to 3G0°C over the course of 2 hours. Next, Che product is kept at 300°C for 16 hours. Finally, the heating of the furnace is interrupted, for example, and the product i returned to ambient temperature.

[Working Examples]

Working Examples of the present invention will be further described hereinafter.

Unless specifically stated otherwise, the displayed results were obtained using the following test method. The test results are shown in the table below,

<Mooney scorch (T5 and T35)>

The Mooney scorch time was evaluated in compliance with J1S Κ63ΌΟ-1 2001.

<Curing rheology properties (Monsanto ODR)>

The curing rheology properties - specifically, ML, MH, Ts2, TelO, TcSO, and Tc90 - were measured as indices of crosslinki g properties. Uncured composition samples were tested in compliance with J !S 6300-2 ^'2001 using a model R- 100 Monsanto rheometer. Both the minimum torque (ML) obtained during a prescribed period of time, as well as the highest torque (MH) for cases where a flat part or maximum torque could not be not obtained, were measured. Further, the time required to reach the 2-unii high torque from ML ("Ts2"), the time required for the torque to reach a value equal to ML+0.1 (MH-MI.) ("Tcl "), the time required for the torque to reach a value equal to ML+Q.5 (MH-MI.) ("Tc50"), and the time required for the torque to reach a value equal to ML+0.9 (MH-ML) ("Tc90") were measured.

Similarly, after the uncured composition samples were respectively stored for 7 days and 30 days at room temperature (approximately 25°C}, ML, MH, Ts2, TclO, TeSO, and Te90 were measured with the same method as that described above ("after 7 days" and "after 30 days" in the table).

<Curing conditions>

Pressurized curing: Unless specifically stated otherwise, sample sheets of a size of 150x150x2.0 mm for measuring physical properties were prepared by pressurizing the sheet for 30 minutes at a pressure -of approximately 20 megapascal (MPa) and a temperature of 165°C,

Post-curing: The pressure-cured sample sheets were further exposed to heat in a nitrogen atmosphere. Specifically, this entails step curing in which the following steps are performed sequentially: 1) heating from room temperature to 150°C over the course of 1 hour, .2) maintenance for 7 hours at. 1 50°C, 3) heating from I 50°C to 300^CC over the course of 2 hours, 4) maintenance for 4 hours at 30Q°C, and 5) cooling from 300°C to room temperature over the course of 2 hours. In this manner, these samples were used in tests after first being returned to the ambient temperature.

<Duro A hardness>

The Duro A hardness was measured in accordance with J1S 6253 2006 using a type A-2 shore durometer.

<Breaking tensile strength, breaking elongation, and modulus at 100% elongatior>>

The breaking tensile strength, breaking elongation, and modulus at 100% elongation were measured in accordance with ASTM D412 2006 for samples cut out using an ASTM die D from the sheets, which were pressure-cured and post-cured under the conditions described above. The units used in the report of the results were percentage and MPa. <Compression sei properties"*

O-ring samples (half of #2140-rtngs) which were pressure-cured and post-cured under the conditions described above were measured in accordance with JIS K6262 2006 at the

temperatures and times shown in the table. The results are reported as percentages with respect to the original compression deformation (taken as 25%).

<Surface appearance>

The sheets, which were pressure-cured and posl-cured under the conditions described above were observed visually, and sheets with no irregularities on the surface were evaluated as "favorable^", whereas sheets demonstrating irregularities were evaluated as ''poor".

[Working Examples 1 through 13 and Comparative Examples 1 through 3]

in Working Examples 1 through 3 and Comparative Example 1 , the properties of perfiuoroelastomer compositions for which the content of BOAP, which, is a bis aminophenol compound, was respectively 0 plu\ 0.2 pfar, 0.3 phr, or 0.4 phr were evaluated. In Working Examples 4 through 13 and Comparative Examples 2 and 3, the properties- of perfiuoroelastomer compositions consisting of various ingredients were evaluated.

The ingredients shown in- the Table were mixed using a roll mill 6 inches in diameter to obtain uncured composition samples. Various tests were performed on the composition samples and samples formed by pressure-curing and post-curing the composition samples under the conditions described above. The test results are shown in Tables 1 through 3.

[ingredients]

Fluoropolymers.

Fluoropolymer A

A ternary copolymer obtained by copolymerizing 65.7 mo! % of tetrafluoroethylene (TFE), 33.0 mo! % of perfluoromethy! vinyl ether (FMVE), and 1.3 moi % of a nitriie group-containing curing site monomer

polymerization.

Fluoropolymer B

A ternary copolymer obtained by copolymerizing 64.8 mo! % of tetrafluoroethylene (TFE), 33.0 mol. % of perfluoromethy ivinyl ether (P.MVE), and 2.2 mol % of a nitriie group-containing curing site monomer (CF₂~CFO(CF₂)₅CN) by emulsion polymerization. Amidine compounds

Amidine compound A

f 1 ,1 ,2,2 etrafluoro^2-(trifluororaethoxy)ethyl]amidinium trifluoroacelate (available from the 3M Corporation},

Amidine compound B

Perfluoroadiponitrile bis amidine di peril ^'uoromethoxy propionate

(CH30C]¾CF2COO-NHj^÷(NH-)C(CF₂)4C(=NH)Nl'b ^' OOCCF₂CF₂OCF₃): synthesized by the method described below.

Amidine compound C

Periluoroteiraethyiene oxide dinifrile bis amidine diacetate

(CH₃COO^* H ^' l -)C(CF₂0CF_i}_iC -NH)NH3^+'OOCCiI₃);. synthesized by the method described below.

Bis ammophenol compounds

Bis aminophenoi compound A

BOAP (2,2^>-di¾iuno-4,4'-(perfluoropropane-2,2.-di !)diphenol}; available from the Aldrich Corporation.

Bis aminophenoi compound B

Bis(3-amino-4~ ydroxypheny.l)sulfone; available from the Aldrich Corporation.

Filler

T Carbon; available from the CanC rb Corporation.

Synthesis of amidine compound B - perfluoroadiponiirile bis amidine

diperfluoromethoxy propionate

(A) First, perfiuoroadiponitjrik bis amidine (NH2( H=C(CF₂) C(-NH)NH2) was synthesized.

Methanol (188 g, 5,9 mol) was placed in a 4 L plastic flask containing a magnetic stirrer, and perfluoroadipoyi fluoride (454 g, 1.5 mol) (available from the 3M Company) was added thereto over the course of 1 hour. The hydrofluoric acid by-product was processed using a caustic scrubber. Water was added, and perftuoroadipate (446 g, 1 ,4 mol) was then isolated by evaporating the lower fluorochemical product phase. Perftuoroadipate (446 g, 1 .4 mol), which was dissolved in methanol and placed in a 2 L flask equipped with a mechanical stirrer, was reacted with an excessive amount of ammonia (54 g, 3.2 mol), whereby perfluoroadipoylaraide (385 g, i ,3 l after vacuum drying} was obtained. Pyridine (508 g, 6,4 mol) and then anhydrous trifluoroacetic acid (674 g. 3.2 mol) (available from Aldrich) were reacted at -10°C in a dimethyl forrnamide solution of perfiuoroadipoiyamide (385 g, 1 ,3 mol) placed in a 3 L flask equipped with a mechanical stirrer. Water was added, and periluoroadi onitrile (235 g, 0,9 mol) with a boiling point of 64°C was then isolated by evaporating the lower fluorochemical product phase. When perfluoroadiponitrile ( 108 g, 0.4 mol) dissolved in diethyl ether was placed in a 1 L flask equipped with a mechanical stirrer and reacted with ammonia ( 17 g, 1.0 mol) at -I CC, perfluoroadiponitrile bis amidine ( 1 12 g, 0,9 mol) was obtained, but the melting point alter vacumn. drying was 132°C, and the structure of the compound was confirmed by fluorine and proton NMR.

(B) Next, perfluoroadiponitrile bis amidine (26 g, 0.1 ml) prepared as described above and dissolved in methanol was placed in a 100 mL ilask containing a magnetic stirrer, and perfiuorornemoxy propionic acid (46 g, 0.2 mol) prepared by hydrolyzing perfiuorornemoxy propionyl fluoride as described in the pamphlet of International Publication No. WOO 1/461 1 s dripped into the solution. The solution was vacuum-dried, and perfluoroadiponitrile bis amidine diperfiuororaethoxy propionate (59 g, 0,8 mol) was isolated. The structure of the compound was confirmed by fluorine and proton NMR.

Synthesis of amidine compound C - Perflirarotetraethylene oxide dinitrile bis amidine diacetate

(C) Tetraethylene glycol diacetate was directly fluorinated as described in the specification of US Patent No. 5,488,142, and perfluorotetraethylene oxide dimethyl ester was isolated. Next, bis amide was first synthesized by reacting the compound with ammonia in accordance with the synthesis procedure described in (A) above, and bis nitriie was formed by dehydration. Next, the compound was reacted with ammonia to obtain fluorochemical bis mudmc,

(D) Next, when acetic acid was dripped into this fluorochemical bis amidine as described in (B) above, perfluorotetraethylene oxide dinitrile bis amidine diacetate was obtained. [Table 1] _____ _ _„ _ _„

Comparative Working Working Working Example 1 Example Example Example

Formulation (parts by mass)

Fluoro pol mers

Ternary copolymer of 64.8 mo)¾ of 77Έ, 33. D

moI% ofPMVE, and 2.2 mol% of CF,-CFO(CF,)_s

Amide compounds

K ! ,2,2-ietr¾ft^joiO-2-(trifl orornethoxy)ethy!^'j

am id i n i urn tr i fiuo roa e e t ate

Bis a mi no phenol compounds

2,2'-diamino-4,4'-(pertooropropane-'2_J2-diy{)dfphenol

Filler

MX Carbon

Monsanto ODR

Test conditions 30 min 30 min 30 min 30 min

(I65°C) (!65^:C) (165^:C) t.165 C)

ML <JNm) 16.99 17.31 19.01 17.00 MH (d m) 74.94 98.48 99.05 96.95 M-ML (dNm) 57.95 SI.17 80.04 79.95 Ts2 (min) 1.39 U6 1.44 1.14 Tc!O (min) 1.67 1.53 i.8^'3 1.50 Tc5G (min) 2.94 3.17 3.49 3.06 T 90 (min) 6.16 17.19 18.24 17.65 Cured product properties

Duro A hardness 74 76 77 7 100^'% modulus (MPa) 12.1 15.1 15.7 1 .5 Breaking tensile strength (MPa.) 21 24.3 25.0 24.5 Breaking longation (^'%) 140 140 140 130 Compression, set (%) for 70 hours at 250°C 12 8 7 7 Compression set (%) for 70 hours at 300°C 12. 11 10

Surface appearance Poor Favorable Favorable Favorabli

[Table 2]

Comparative Working Working Working

Example 1 Example 1 Example 2 Example 3

Moonev scorch ML

( 121 °C)

T5 10.09 8.49 8.06 7.99

T35 20.84 15.18 14.01 13.52

Monsanto ODR

Test conditions 30 min 30 min 30 min 30 mirs

( 165°C) ( ! 65^;T) ( 165°C) (i 65°C)

Initial composition

NL (dNm) 16.99 17.31 19.01 17.00

MH (dNm) 74.94 98.48 99.05 96.95 H-ML (dNm) 57.95 81 .17 80.04 79.95

T2 (min) 1.39 i . 16 1.44 1.14

TclO (min) 1 ,67 1.53 1.83 1.50

Tc50 (rain) 2.94 3.17 3.49 3.06

Tc90 (min) 6.16 17.19 18.24 17.65

Composition after ? days

ML (dNm.) 15.96 17.74 1 56 18.04

MH (dNm) 92.77 93.1 95.1 97.32

MH-ML (dN m) 76.81 75.36 76.55 79.28

T2 (min) 1.23 1.15 1.23 1 . 12

TclO (min) 1.61 1 .48 1.57 3 .45

Tc50 (min) 3.30 2.91 3.03 2.88

Tc90 (min) 17,37 16.48 16.86 17.06

Composition after 30 days

ML (dNm) 16.40 18.32 20.23 1 .07

MH (dNm) 94.91 97,72 101.17 102.73

MH-ML (dNm) 78.51 79.40 80.94 83.66

Ts2 (min) 1.24 1 .1 1 .48 1.19

Tc 10 (min) 1 .61 1.53 L86 1.55

Tc50 (min) 3.28 3,38 3.01

Tc90 (mm) 17.77 18.48 18.55 18.12.

li able 3] cMupitfaiiye Working Comparative- Working Woitifig Working Wori ing Working Waking Wortcifig Working Worki fc^'xampie 2 f tar ple 4 example 3 Example 5 E am le 6 E ample ? Example s Example 9 Example ) Example 11 Example 12 Exampl

Formti!ation (parts by roiiss)

Fiuoropolymers

A Ternary copolymer of 65.7 r»oi¾ 100 100

οΠΤΕ, 33.0, ma\% ofPMVE and

Ϊ .3 ma of CF,=CFO(CF₂)₅CM

Ternary' copolymer of 64. S mo\% 100 100 100 100 100 !OO 100 100 ! OO 100 of TFE, 33.0 mol% of P VE, and

2.2 tnol% of CF₂ ^«CFO(CFi)_sCN

Arotdine compounds

A [i.l,2,2-tetrafuoro-2- L i u i. i i . i

( tri fuororn ethoxy ¾ th 1] am id 11 J m

trifuoro acetate

B perfluttfodiponitrite bis aojidine 0.5

diper 11 uorome: hoxy prop ionate

C Perfhtorotetraetbylene oxide 0.5

dinitrife bis arokline

peril uorote t ra et yk ne oxl dc

Bis aminophenof compounds

A 2,2'-di3mjno-4., ' 0.3 0.3 0.3 0.3 0.1 0.5 2

-(perfltJoropropany-2,2- diyl)

diphenol

8 Bis(3 -amfno~4-hydroxypbeny I)

siiSfone

Filler

MT Carbon 20 20 20 20 20 20 20 20

Monsa to ODR

Test conditions 30 min 30 mtn 30 min 30 min 30 min 30 min 30 min 30 min 30 min 30 min 30 min 30

(ίό.5 V) (165 :) ( (>< ·(.·} (165 ¾) (165 Ό (165 °C) (165 °C) (165 (165 (165 °C) (165 °C) (165

ML (dNm) 13.64 19.32 17.7 19,71 18.60 28.44 18,47 20.17 19.40 20,48 21.97 15. mi (dNm) 63.99 514.61 87.07 97.23 91.79 103.57 74.64 108.41 97.59 104.00 Π1.75 72. MH~ML (d m) 50.35 95.19 69.28 77.52 73.19 75.13 56.17 88.24 78.19 83.52 89.78 56. Ts2 (rum) 1.57 1.0? 1.19 1.11 2.13 8.91 1.1S 1,23 1.20 1.08 QM 1.4 Tc 30 (mm) 1.91 1.43 1.51 1.43 3.21 1.19 1.45 LSI 1.55 1.41 1.31 1.7 Tc50 (min) 4.02 2.90 3.16 2.92 7.36 2.60 3.42 3.46 3.20 2.88 2.72 3.6 Te90 (min) 16.12 17.66 18.76 18.09 17.21 12.60 17.65 19.57 18.47 18.27 18.50 16. Cured product properties

Duro A hardness 71 73 78 80 80 80 79 79 79 78 78 79 Breaking tensile strength ί Pa) 20.9 20.4 24.0 21.4 19,4 22.1 22,4 24.0 22,3 22,7 21.5 22. Breaking elongation (%} 220 190 150 120 100 100 130 130 130 1.20 90 13 Compression set (%) for 70 hours 18 15 13 1 11 Π 11 8 5 8 8 9 at 250'^:'C

Poor FavorPoor FavorPixir Favor- Favor- Favor- Favor- Favor- Favor- Fav

Surface properties

able able able able able able able able abl

[Field of Industrial Application]

The fluoropoiymer composition of the present invention can be suitably applied to the formation of various molded products such as sheets, films, hoses, gaskets, O-rings, and the like, for example.

Claims

Claims What is claimed is:

1. A fluoropoiymer composition comprising a fluoropoiymer and a crosslinking agent;

wherein the fiuoropolymer is an elastomer containing copolymerization units derived from a nitrogen-containing curing site monomer; and

the crosslinking agent is a combination of two or more compounds including one or more type of amidine compound and one or more type of bis aminophenol compound,

2. The fluoropoiymer composition of claim L wherein the nitrogen-containing, curing site monomer is one or more type selected from nitrite-containing fluorinated olefins and nitrite-containing fluorinated vinyl ethers; and

the fiuoropolymer is a copolymer of a perfiuoroolefm, a perfluorovinyl ether, and a nitrogen-containing curing site monomer,

3. The fluoropoiymer composition of claim 1 or 2, wherein the amidine compound is. one type or a combination of two or more types selected From a group comprising mono-amidines, bis-amidines, and salts thereof.

4. The fluoropoiymer composition, of any one of claims 1 through 3, wherein the bis aminophenol compound is expressed by the following general formula ( 1 ):

[Formula 1 ]

(wherein

Z^f , Z², Ζ and Z⁴ are respectively independently an -NHj group or a -OH group, one of Z or Z^" is an -N% group while the other is an -OH group, and one of / or Z is an -N¾ group while the other is an -OH group; and

Z⁵ is a single bond or a bivalent group selected from a group comprising -0-, -CO- _j -SO?-, and perfluoroaikvlene groups with a carbon number of 1 to 3),

5. The fhioropoiymer composition of any one of claims 1 through 4, further comprising from 0.5 to 1.5 parts by mass of the amidine compound and from 0.1 to 1.0 parts by mass of the bis aminophenpl compound per 1 0 parts by weight of the fiuoropolymer.