Fluororubber crosslinking composition and molded article

Abstract

Provided is a fluororubber crosslinking composition containing a fluororubber (a) and a crosslinking agent (b), the crosslinking agent (b) being a compound represented by general formula (b1) or the like.

Description

TECHNICAL FIELD

[0001] The present application relates to a fluororubber crosslinking composition and a molded article. BACKGROUND

[0002] In Patent Literature 1, as an essential component in a final curable composition, an aromatic polyhydroxy compound capable of functioning as a crosslinking agent or an auxiliary curing agent for a fluorinated elastomer is described. One of the most useful aromatic polyphenols is a bisphenol compound known as bisphenol AF as hexafluoroisopropylidene-bis(4-hydroxyphenyl).

[0003] Patent Literature 2 describes a composition comprising a fluorocarbon elastomer rubber, a fluorinated aliphatic sulfonamide as a curing agent therefor, and a second curing agent selected from the group consisting of a polyhydroxy compound, a polyamine compound, and derivatives thereof.

[0004] Patent Literature 3 describes a composition comprising a fluorocarbon elastomer rubber and a vulcanizing agent therefor, the composition being characterized in that the vulcanizing agent is a composition comprising one or a mixture of aromatic compounds having a hydroxyl group directly bonded to an aromatic ring-carbon atom and an oxyallyl group.

[0005] Patent Literature 4 describes a fluororubber vulcanization composition containing (a) a fluorine-containing elastomer, (b) one or two or more selected from the group consisting of a divalent metal oxide, a divalent metal hydroxide, and a mixture of these metal oxides or metal hydroxides with a metal salt of a weak acid, (c) a polyhydroxy aromatic compound, and (d) a specific vulcanization accelerator.

[0006] PRIOR ART DOCUMENTS

[0007] PATENT LITERATURE

[0008] Patent Literature 1: Japanese Patent Publication No. 64-418

[0009] Patent Literature 2: Japanese Patent Laid-Open No. 60-215042

[0010] Patent Literature 3: Japanese Patent Laid-Open No. 59-105046

[0011] Patent Literature 4: Japanese Patent Laid-Open No. 63-268757 SUMMARY

[0012] PROBLEMS TO BE SOLVED BY THE INVENTION

[0013] An object of the present application is to provide a fluororubber crosslinking composition containing a compound not containing a fluorine atom as a crosslinking agent, which can provide a molded article having balanced tensile strength and elongation.

[0014] Means for solving the problem

[0015] According to the present application, there is provided a fluororubber crosslinking composition containing a fluororubber (a) and a crosslinking agent (b), the crosslinking agent (b) being at least one selected from the group consisting of a compound (b1) represented by the general formula (b1), a compound (b2) represented by the general formula (b2), a compound (b3) represented by the general formula (b3), and a salt of any one of these compounds with an alkali metal, an alkaline earth metal or an onium compound.

[0016] [Chemical Formula 1]

[0017]

[0018] (In the formula (b1), the hydrogen atoms bonded to the two benzene rings can be substituted with an alkyl group having 1 to 6 carbon atoms not containing a halogen atom.)

[0019] [Chemical Formula 2]

[0020]

[0021] (In the formula (b2), the hydrogen atoms bonded to the two benzene rings can be substituted with an alkyl group having 1 to 6 carbon atoms not containing a halogen atom.)

[0022] [Chemical Formula 3]

[0023]

[0024] (In the formula (b3), the hydrogen atoms bonded to the coumarin ring can be substituted with an arbitrary substituent not containing a halogen atom.)

[0025] Effects of the Invention

[0026] According to the present application, it is possible to provide a fluororubber crosslinking composition containing a compound not containing a fluorine atom as a crosslinking agent, and to obtain a molded product which has both a tensile strength and an elongation in balance. DETAILED DESCRIPTION

[0027] Hereinafter, a specific embodiment of the present application will be described in detail, but the present application is not limited to the following embodiment.

[0028] The fluororubber crosslinking composition of the present application contains a fluororubber (a) and a crosslinking agent (b).

[0029] In the past, a molded product of fluororubber has been obtained by using a cross-linkable composition containing bisphenol AF as a cross-linking agent. However, if bisphenol AF adheres to equipment used for metering or composition preparation, since bisphenol AF is a compound containing a fluorine atom, in order to clean bisphenol AF adhering to the equipment and to treat the resulting substance, a dedicated incineration device or the like is required, and there is a considerable burden in terms of cost. Furthermore, while a molded product of fluororubber preferably has both excellent tensile strength and elongation, in the case where an existing compound not containing a fluorine atom is used as a cross-linking agent, it has been found that it is difficult to obtain a molded product that has both tensile strength and elongation in balance. Therefore, it is desirable to use a compound not containing a fluorine atom as a cross-linking agent, which enables a molded product having both tensile strength and elongation in balance to be obtained.

[0030] The fluororubber cross-linking composition of the present application contains a compound having the structure described below as a cross-linking agent. These compounds are easy to handle since they do not contain a fluorine atom. Furthermore, the fluororubber cross-linking composition of the present application is able to provide a molded product having both tensile strength and elongation in balance, despite containing a compound not containing a fluorine atom as a cross-linking agent.

[0031] Hereinafter, each component of the fluororubber cross-linking composition of the present application will be described.

[0032] (a) Fluororubber

[0033] As the fluororubber used in the present application, a fluororubber capable of polyol cross-linking is preferred. The fluororubber capable of polyol cross-linking is a fluororubber having a site capable of polyol cross-linking. In the present application, fluororubber refers to an amorphous fluorine-containing polymer. "Amorphous" refers to the fact that the size of the melting peak (ΔH) appearing in differential scanning calorimetry [DSC] (temperature increase rate: 20°C / min) or differential thermal analysis [DTA] (temperature increase rate: 20°C / min) of the fluorine-containing polymer is 4.5 J / g or less. The fluororubber exhibits elastomer properties by being cross-linked. Elastomer properties refer to the ability to stretch the polymer and to maintain its original length when the force required to stretch the polymer has not been applied.

[0034] As the site capable of polyol cross-linking, sites having a vinylidene fluoride (VdF) unit or the like can be given. Among these, a fluororubber containing a VdF unit is preferred since it is easy to exert the effects brought about by the use of the cross-linking agent (b).

[0035] As the fluororubber having a site capable of polyol cross-linking, non-perfluorinated fluororubber, fluororubber having a main chain containing -CH2- (methylene), or the like can be given. The fluororubber having a site capable of polyol cross-linking can be, for example, a fluororubber having a main chain containing -CH2- (methylene) and a VdF unit.

[0036] A vinylidene fluoride (VDF) elastomer substantially having no polar end group described in Japanese Patent Application Laid-Open No. 2003-277563;

[0037] A vinylidene fluoride base fluorine elastomer containing a repeating unit from vinylidene fluoride (VDF) and at least one additional repeating unit from a (per)fluorinated monomer described in Japanese Patent Application Laid-Open No. 2018-527449;

[0038] A cured fluorine elastomer of 100 parts (phr) having a small amount of fluorine of less than 67% by weight, containing 40 to 68% by weight of vinylidene fluoride (VDF) units and 20 to 50% by weight of hexafluoropropylene (HFP) units in a manner that the total becomes 100, optionally containing one or more than two comonomers having unsaturated ethylene described in Japanese Patent Application Laid-Open No. Hei 7-316377; and the like.

[0039] As the fluorine rubber having a site capable of polyol crosslinking, a VdF-based fluorine rubber or the like can be given. As the VdF-based fluorine rubber, a tetrafluoroethylene (TFE) / propylene / VdF-based fluorine rubber, an ethylene / hexafluoropropylene (HFP) / VdF-based fluorine rubber, a VdF / HFP-based fluorine rubber, a VdF / TFE / HFP-based fluorine rubber, or the like can be given. These fluorine rubbers having a site capable of polyol crosslinking can be used alone, respectively, or in any combination within a range not impairing the effects of the present application.

[0040] As the VdF-based fluorine rubber, a substance represented by the following general formula (1) is preferable.

[0041] -(M 1 )-(M 2 )-(N 1 )- (1)

[0042] (In the formula, a structural unit M 1 is a structural unit from vinylidene fluoride (m 1 ), a structural unit M 2 is a structural unit from a fluorine-containing olefinic monomer (m 2 ), and a structural unit N 1 is a repeating unit from a monomer (n 1 ) capable of copolymerization with the monomer (m 2 ) and the monomer (m 1 ).)

[0043] In the VdF-based fluorine rubber represented by the general formula (1), it is preferable to contain 30 to 85 mol% of the structural unit M 1 , 55 to 15 mol% of the structural unit M 2 , and more preferably the structural unit M 150 to 80 mole % of structural unit M 2 50 to 20 mole % of structural unit N 1 with respect to the total amount of structural unit M 1 and structural unit M 2 is preferably 0 to 20 mole %.

[0044] As the fluorine-containing olefinic monomer (m 2 ), one or two or more kinds of monomers can be used, and examples thereof include TFE, chlorotrifluoroethylene (CTFE), trifluoroethylene, HFP, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutylene, tetrafluoroisobutylene, perfluoro(alkyl vinyl ether) (PAVE), a fluorine-containing monomer represented by general formula (2) :

[0045] CF2=CFO(Rf 1 O) q (Rf 2 O) r Rf 3 (2)

[0046] (in the formula, Rf 1 and Rf 2 each independently represent a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms, Rf 3 represents a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, and q and r each independently represent an integer of 0 to 6 (where 0 < q + r ≤ 6 is satisfied), a fluorine-containing monomer represented by general formula (3) :

[0047] CHX 11 =CX 12 Rf 4 (3)

[0048] (in the formula, one of X 11 and X 12 is H and the other is F, and Rf 4 represents a linear or branched fluoroalkyl group having 1 to 12 carbon atoms), a fluorine-containing monomer such as fluoroethylene, and among these, TFE, HFP, and PAVE are preferred.

[0049] As the monomer (n 1 ), any monomer can be used as long as it is copolymerizable with the monomer (m 1 ) and the monomer (m 2 ), and examples thereof include ethylene, propylene, an alkyl vinyl ether, a monomer that provides a crosslinking site, a diene compound, and the like. These can be used individually or in any combination.

[0050] As such a monomer that provides a crosslinking site, a monomer represented by general formula (4) can be given:

[0051] CY1 2 = CY 1 -Rf 5 CHR 1 X 1 (4)

[0052] (where Y) 1 Independently a hydrogen atom, a fluorine atom, or -CH3, Rf 5 It is a fluoroalkylene, perfluoroalkylene, fluoropolyoxyalkylene, or perfluoropolyoxyalkylene, R 1 For hydrogen atoms or -CH3, X 1 Monomers containing iodine or bromine (e.g., iodine or bromine atoms), general formula (5):

[0053] CF2 = CFO(CF2CF(CF3)O) m (CF2) n -X 2 (5)

[0054] (In the formula, m is an integer from 0 to 5, n is an integer from 1 to 3, X) 2 Monomers represented by cyano, carboxyl, alkoxycarbonyl, bromine, and iodine atoms, and general formula (6):

[0055] CH2=CH(CF2) p I (6)

[0056] (Where p is an integer from 1 to 10) Examples of monomers include, for instance, perfluorinated monomers such as perfluorinated (6,6-dihydro-6-iodo-3-oxa-1-hexene) and perfluorinated (5-iodo-3-oxa-1-pentene) as described in Japanese Patent Application Publication No. 5-63482 and No. 7-316234, and CF2=CFOCF2 as described in Japanese Patent Application Publication No. 4-217936. Iodine-containing monomers such as CF2CH2I, iodine-containing monomers such as 4-iodo-3,3,4,4-tetrafluoro-1-butene as described in Japanese Patent Application Publication No. 61-55138, bromine-containing monomers as described in Japanese Patent Application Publication No. 4-505341, and cyano-containing, carboxyl-containing, and alkoxycarbonyl-containing monomers as described in Japanese Patent Application Publication Nos. 4-505345 and 5-500070, etc. These can be used individually or in any combination.

[0057] Alternatively, the diene compound described in Japanese Patent Application Publication No. 8-12726 may be used as the diene compound.

[0058] As the above-mentioned VdF-based fluororubber, specifically, VdF / HFP-based rubber, VdF / HFP / TFE-based rubber, VdF / TFE / PAVE-based fluororubber, VdF / CTFE-based rubber, VdF / CTFE / TFE-based rubber, and the like can be mentioned.

[0059] Among these, as the fluororubber capable of being crosslinked with a polyol, a fluororubber composed of VdF and at least one other fluorine-containing monomer is preferable, at least one rubber selected from the group consisting of VdF / HFP-based fluororubber, VdF / TFE / HFP-based fluororubber, and VdF / TFE / PAVE-based fluororubber is particularly preferable, and at least one rubber selected from the group consisting of VdF / HFP-based fluororubber and VdF / TFE / HFP-based fluororubber is more preferable.

[0060] The fluororubber preferably has a Mooney viscosity (ML1+10 (121°C)) at 121°C of 1 or more, more preferably 3 or more, further preferably 5 or more, and particularly preferably 10 or more. In addition, it is preferably 200 or less, more preferably 170 or less, further preferably 150 or less, more further preferably 130 or less, and particularly preferably 100 or less. The Mooney viscosity is measured in accordance with ASTM D1646-15 and JIS K6300-1:2013.

[0061] The fluororubber preferably has a fluorine content of 50 to 75 mass%. More preferably, it has a fluorine content of 60 to 73 mass%, and further preferably 63 to 72 mass%. The fluorine content is calculated from the composition ratio of the monomer units constituting the fluororubber.

[0062] The fluororubber preferably has a glass transition temperature of -50 to 0°C. The glass transition temperature can be obtained by using a differential scanning calorimeter to obtain a DSC curve by raising a 10-mg sample at 20°C / minute, and taking the temperature at which the intersection of the extended line of the baseline before and after the secondary phase transition of the DSC curve and the tangent line at the inflection point of the DSC curve as the glass transition temperature.

[0063] The fluororubber described above can be produced by a conventional method.

[0064] (b) Crosslinking agent

[0065] The fluororubber crosslinking composition of the present application contains a crosslinking agent. The crosslinking agent used in the present application is at least one selected from the group consisting of a compound (b1) represented by general formula (b1), a compound (b2) represented by general formula (b2), a compound (b3) represented by general formula (b3), and a salt of any one of these compounds with an alkali metal, an alkaline earth metal, or an onium compound.

[0066] [Chemical Formula 4]

[0067]

[0068] (In formula (bl), the hydrogen atoms bonded to the two benzene rings can be replaced with alkyl groups having 1 to 6 carbon atoms not containing a halogen atom.)

[0069] [Chemical Formula 5]

[0070]

[0071] (In formula (b2), the hydrogen atoms bonded to the two benzene rings can be replaced with alkyl groups having 1 to 6 carbon atoms not containing a halogen atom.)

[0072] [Chemical Formula 6]

[0073]

[0074] (In formula (b3), the hydrogen atom bonded to the benzene ring can be replaced with any substituent not containing a halogen atom.)

[0075] In general formula (bl), the hydrogen atoms bonded to the two benzene rings can be replaced with alkyl groups having 1 to 6 carbon atoms not containing a halogen atom. Therefore, the compound (bl) does not contain a fluorine atom.

[0076] As the compound (bl), 2,2'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl are preferred, and 2,2'-dihydroxybiphenyl is more preferred.

[0077] In general formula (b2), the hydrogen atoms bonded to the two benzene rings can be replaced with alkyl groups having 1 to 6 carbon atoms not containing a halogen atom. Therefore, the compound (b2) does not contain a fluorine atom. The compound (b2) can be a compound (b2) (except for the compound (bl)), or a compound (b2) (except for 2,3'-dihydroxybiphenyl).

[0078] As the compound (b2), 3,3'-dihydroxybiphenyl is preferred.

[0079] The compound (b3) has a coumarin skeleton, one hydroxyl group bonded to any one of the carbon atoms constituting the benzene ring in the coumarin skeleton, and one hydroxyl group bonded to the 4-position of the 2-pyrone ring (4-position of the coumarin ring) in the coumarin skeleton. The hydroxyl group bonded to the benzene ring in the coumarin skeleton can be bonded to any one of the carbon atoms to which the substitutable hydrogen atoms of the carbon atoms constituting the benzene ring are bonded.

[0080] In General Formula (b3), the hydrogen atom bonded to the coumarin ring which is not substituted with a hydroxyl group can be substituted with a hydroxyl group, a halogen atom, and a substituent other than a group containing a halogen atom, or can not be substituted. As the substituent, there is no particular limitation as long as it is a substituent not containing a halogen atom, and examples include a cyano group, an alkyl group having 1 to 10 carbon atoms, and the like. The substituent is a substituent not containing a fluorine atom, a group containing a fluorine atom, and the like, and thus the compound (b3) does not contain a fluorine atom.

[0081] As the compound (b3), 4,7-dihydroxycoumarin is preferable.

[0082] As the crosslinking agent (b), a compound (b1) or a compound (b2) is preferable.

[0083] Further, as the compounds (b1) to (b3), 2,2'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 2,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,5-dihydroxycoumarin, 4,6-dihydroxycoumarin, 4,7-dihydroxycoumarin, 4,8-dihydroxycoumarin are preferable, 2,2'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 4,6-dihydroxycoumarin, 4,7-dihydroxycoumarin are more preferable, 2,2'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 4,7-dihydroxycoumarin are further preferable, 2,2'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 4,7-dihydroxycoumarin are particularly preferable, and 2,2'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl are especially preferable.

[0084] The crosslinking agent can be a salt of the compound (b1) with an alkali metal, a salt of the compound (b1) with an alkaline earth metal, a salt of the compound (b1) with an onium compound, a salt of the compound (b2) with an alkali metal, a salt of the compound (b2) with an alkaline earth metal, a salt of the compound (b2) with an onium compound, a salt of the compound (b3) with an alkali metal, a salt of the compound (b3) with an alkaline earth metal, or a salt of the compound (b3) with an onium compound. Of these salts, a salt of the compound (b1) with an onium compound, a salt of the compound (b2) with an onium compound, or a salt of the compound (b3) with an onium compound is preferable. The salt of the above-mentioned compound with an onium compound is an onium salt composed of an anion part from the above-mentioned compound and a cation part from the onium compound. By using the onium salt as the crosslinking agent (b), the onium salt not only functions as a crosslinking agent but also functions as a crosslinking accelerator.

[0085] The compound (b1), the salt of the compound (b1) with an alkali metal, the salt of the compound (b1) with an alkaline earth metal, the salt of the compound (b1) with an onium compound, the compound (b2), the salt of the compound (b2) with an alkali metal, the salt of the compound (b2) with an alkaline earth metal, the salt of the compound (b2) with an onium compound, the compound (b3), the salt of the compound (b3) with an alkali metal, the salt of the compound (b3) with an alkaline earth metal, and the salt of the compound (b3) with an onium compound can be used alone or in combination.

[0086] The salt of the compound (b1) with an onium compound, the salt of the compound (b2) with an onium compound, or the salt of the compound (b3) with an onium compound is obtained by reacting any one of the compounds (b1) to (b3) with a basic substance such as sodium hydroxide or with metallic sodium in water or an organic solvent, and further reacting with an onium compound such as benzyltriphenylphosphonium chloride, and distilling off water or the organic solvent. Alternatively, the solution of the reaction product can be filtered or the reaction product can be washed with water, an organic solvent, or the like, as needed, to remove a by-product such as sodium chloride.

[0087] As the alkali metal, Na or K is preferred. As the alkaline earth metal, Ca or Mg is preferred.

[0088] As the onium salt, for example, an ammonium salt, a phosphonium salt, a sulfonium salt, or the like can be given.

[0089] As the onium compound constituting the onium salt, an ammonium compound, a phosphonium compound, a sulfonium compound, or the like can be given. In the present application, the onium compound does not contain a fluorine atom.

[0090] As the onium compound constituting the onium salt, an ammonium compound, a phosphonium compound, a sulfonium compound, or the like can be given. In the present application, the onium compound does not contain a fluorine atom.

[0091] The crosslinking agent can be used in combination with other compounds. As the mixture containing the crosslinking agent, for example, a mixture of the crosslinking agent and a crosslinking accelerator, a mixture of the crosslinking agent and a compound capable of dissolving the crosslinking agent, or the like can be given. As the mixture of the crosslinking agent and the crosslinking accelerator, a mixture of any one of the compounds (b1) to (b3) and a quaternary phosphonium salt, or a mixture of any one of the compounds (b1) to (b3) and a quaternary ammonium salt is preferred, a mixture of any one of the compounds (b1) to (b3) and a quaternary phosphonium salt is more preferred, and a mixture of any one of the compounds (b1) to (b3) and benzyltriphenylphosphonium chloride is further preferred.

[0092] The content of the cross-linking agent is preferably 1.0 mmol to 50 mmol, more preferably 2.0 mmol or more, further preferably 4.0 mmol or more, more preferably 30 mmol or less, further preferably 20 mmol or less, particularly preferably 15 mmol or less, relative to 100 parts by mass of the fluororubber, in order to obtain a cross-linking reaction in the cross-linking step that proceeds at an appropriate rate and a molded product having sufficient tensile strength, elongation at break, and compression set characteristics at high temperatures, and a moderate hardness.

[0093] (c) a cross-linking accelerator

[0094] The fluororubber cross-linking composition of the present application preferably contains a cross-linking accelerator. If a cross-linking accelerator is used, the cross-linking reaction can be accelerated by promoting the formation of intramolecular double bonds in the dehydrofluorination reaction of the fluororubber main chain. In the case where at least one compound selected from the group consisting of any one of compounds (b1) to (b3) and a salt of any one of compounds (b1) to (b3) with an alkali metal or an alkaline earth metal is used as the cross-linking agent, it is preferable to use a cross-linking accelerator together with the cross-linking agent. Even in the case where an onium salt is used as the cross-linking agent, a cross-linking accelerator can be used together with the cross-linking agent, but it is not necessarily required. The amount of the cross-linking accelerator can be appropriately adjusted depending on the cross-linking conditions and the physical properties of the molded product. If the amount of the cross-linking accelerator is increased, the cross-linking reaction becomes faster or the cross-linking can be performed at a lower temperature, but the compression set characteristics tend to deteriorate. In contrast, if the amount of the cross-linking accelerator is decreased, the cross-linking reaction becomes slower, but the compression set characteristics tend to improve.

[0095] As the cross-linking accelerator of the polyol cross-linking system, an onium compound (excluding a salt of any one of compounds (b1) to (b3) and an onium compound) is generally used. There is no particular limitation on the onium compound, and examples thereof include ammonium salts such as quaternary ammonium salts, phosphonium salts such as quaternary phosphonium salts, and sulfonium salts. Among these, quaternary ammonium salts and quaternary phosphonium salts are preferable.

[0096] As the quaternary ammonium salt, there are no particular limitations, and examples that can be given include 8-methyl-1,8-diazabicyclo[5,4,0]-7-undecene chloride, 8-methyl-1,8-diazabicyclo[5,4,0]-7-undecene iodide, 8-methyl-1,8-diazabicyclo[5,4,0]-7-undecene hydroxide, 8-methyl-1,8-diazabicyclo[5,4,0]-7-undecene methyl sulfate, 8-ethyl-1,8-diazabicyclo[5,4,0]-7-undecene bromide, 8-propyl-1,8-diazabicyclo[5,4,0]-7-undecene bromide, 8-dodecyl-1,8-diazabicyclo[5,4,0]-7-undecene chloride, 8-dodecyl-1,8-diazabicyclo[5,4,0]-7-undecene hydroxide, 8-icosyl-1,8-diazabicyclo[5,4,0]-7-undecene chloride, 8-tetracosyl-1,8-diazabicyclo[5,4,0]-7-undecene chloride, 8-benzyl-1,8-diazabicyclo[5,4,0]-7-undecene chloride (hereinafter referred to as DBU-B), 8-benzyl-1,8-diazabicyclo[5,4,0]-7-undecene hydroxide, 8-phenethyl-1,8-diazabicyclo[5,4,0]-7-undecene chloride, 8-(3-phenylpropyl)-1,8-diazabicyclo[5,4,0]-7-undecene chloride, benzyldimethyloctadecylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, benzyltritylammonium chloride, benzytriethylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrabutylammonium hydroxide, and the like. Among these, from the aspects of crosslinkability and the properties of the crosslinked product, DBU-B or benzyldimethyloctadecylammonium chloride is preferable.

[0097] In addition, as the quaternary phosphonium salt, there are no particular limitations, and examples that can be given include tetrabutylphosphonium chloride, benzyltritylphosphonium chloride (hereinafter referred to as BTPPC), benzytrimethylphosphonium chloride, benzytributylphosphonium chloride, tributylallylphosphonium chloride, tributyl-2-methoxypropylphosphonium chloride, benzyphenyl(dimethylamino)phosphonium chloride, and the like, among which, from the aspects of crosslinkability and the properties of the crosslinked product, benzyltritylphosphonium chloride (BTPPC) is preferable.

[0098] The content of the cross-linking accelerator is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 3 parts by mass, further preferably 0.1 to 1 part by mass, particularly preferably 0.3 to 0.8 parts by mass, relative to 100 parts by mass of the fluororubber, in order to obtain a molded product in which the cross-linking reaction proceeds at an appropriate rate and the compression set characteristics at high temperatures are more excellent. Note that, in the case where the cross-linking agent is a salt of any one of compounds (b1) to (b3) and an onium compound, the content of the above cross-linking accelerator is a value including the mass of the cationic portion of the cross-linking agent (i.e., the cation from the onium compound).

[0099] (d) acid acceptor

[0100] The fluororubber cross-linking composition of the present application can further contain an acid acceptor. By containing an acid acceptor, the cross-linking reaction of the fluororubber cross-linking composition proceeds more smoothly, and the compression set characteristics at high temperatures are further improved.

[0101] As the acid acceptor, for example, metal oxides such as magnesium oxide, calcium oxide, bismuth oxide, and zinc oxide; metal hydroxides such as calcium hydroxide; alkali metal silicates described in Japanese Patent Application Publication No. 2011-522921; metal salts of weak acids described in Japanese Patent Application Publication No. 2003-277563; and the like can be given. As the metal salts of weak acids, carbonates, benzoates, oxalates, and phosphites of Ca, Sr, Ba, Na, and K can be given.

[0102] As the acid acceptor, at least one selected from the group consisting of metal oxides, metal hydroxides, alkali metal silicates, metal salts of weak acids, and hydrotalcites is preferred, more preferably a hydrate of sodium metasilicate, calcium hydroxide, magnesium oxide, bismuth oxide, and hydrotalcite, further preferably calcium hydroxide and magnesium oxide, in order to obtain a molded product in which the compression set characteristics at high temperatures are more excellent. In addition, in the case where the obtained molded product needs to have good water resistance, acid resistance, or resistance to organic acid esters including those of biodiesel engines, at least one selected from the group consisting of bismuth oxide and hydrotalcite is preferred as the acid acceptor.

[0103] The content of the acid acceptor in the fluororubber cross-linking composition is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, further preferably 1 to 30 parts by mass, particularly preferably 1 to 20 parts by mass, relative to 100 parts by mass of the fluororubber, in order to obtain a molded product in which the compression set characteristics at high temperatures are more excellent.

[0104] If the content of the acid acceptor is increased, there is a tendency that the water resistance, acid resistance, and organic acid ester resistance including that of a biodiesel engine of the resulting molded article decrease. On the other hand, if the content of the acid acceptor is decreased, the crosslinking speed decreases, and there is a tendency that the mechanical properties decrease due to the decrease in crosslinking density. Therefore, the content of the acid acceptor can be selected depending on the use of the resulting molded article. In addition, in the case where the acid acceptor other than calcium hydroxide is contained, by reducing the content of calcium hydroxide to 0 to 1.5 parts by mass or the like and adjusting the content of the other acid acceptor, the crosslinking density can be adjusted, and a molded article having more excellent compression set characteristics at high temperatures can be obtained.

[0105] (e) Other Components

[0106] The fluororubber crosslinking composition can be compounded with various additives such as a filler (carbon black, bituminous coal, barium sulfate, diatomaceous earth, baked clay, talc, wollastonite, carbon nanotube, etc.), a processing aid (wax, etc.), a plasticizer, a colorant, a stabilizer, an adhesion agent (benzofuran resin, benzofuran-indene resin, etc.), a releasing agent, an electrically conductive agent, a thermally conductive agent, a surface non-adhesion agent, a softness-improving agent, a heat resistance-improving agent, a flame retardant, a foaming agent, the antioxidant described in International Publication No. 2012 / 023485, and the like, which are generally compounded into the fluororubber crosslinking composition as needed, and one or two or more kinds of common crosslinking agents or crosslinking accelerators other than the above-described substances can be compounded. Among them, as the carbon black, thermal carbon black, furnace carbon black are preferred, and MT carbon black, FT carbon black, SRF carbon black are more preferred. If a carbon black or a carbon black having a large particle diameter such as FT carbon black is compounded, a molded article having excellent compression set characteristics can be obtained, and if a carbon black having a fine particle diameter is compounded, a molded article having excellent strength and elongation can be obtained. By compounding different grades together, a balance of the above-described characteristics can be achieved.

[0107] As the filler other than carbon black, barium sulfate and wollastonite are preferred.

[0108] As the processing aid, there is no particular limitation, and aliphatic amines such as stearylamine, fatty acid esters such as stearate or sebacate, fatty acid amides such as stearic acid amide, long-chain alkyl alcohol, natural wax, polyethylene wax, phosphoric acid esters such as trimesyl phosphate, silicone processing aids, and the like can be compounded, and when two or more kinds are compounded as needed in an appropriate amount, sometimes the balance between the mold releasability at molding and the properties of the molded article becomes good.

[0109] As the content of the filler such as carbon black, there is no particular limitation, and relative to 100 parts by mass of the fluororubber, it is preferably 0 to 300 parts by mass, more preferably 1 part by mass to 150 parts by mass, further preferably 2 parts by mass to 100 parts by mass, and particularly preferably 2 parts by mass to 75 parts by mass.

[0110] The content of the processing aid such as wax is preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass, and particularly preferably 0 to 2 parts by mass, relative to 100 parts by mass of the fluororubber. If the processing aid, plasticizer, and release agent are used, there is a tendency that the mechanical properties and the sealing properties of the obtained molded product decrease, and thus it is necessary to adjust the contents within a range permitted by the properties of the target molded product to be obtained.

[0111] The fluororubber crosslinking composition can contain a dialkyl sulfone compound. By containing the dialkyl sulfone compound, the crosslinking efficiency of the fluororubber crosslinking composition is improved, the crosslinking speed is accelerated, or the compression set properties are further improved, and the flowability of the rubber base material is improved. As the dialkyl sulfone compound, dimethyl sulfone, diethyl sulfone, dibutyl sulfone, methyl ethyl sulfone, diphenyl sulfone, and sulfolane can be given. Among them, sulfolane is preferable from the viewpoints of crosslinking efficiency and compression set properties, and the viewpoint of appropriate boiling point. The content of the dialkyl sulfone compound is preferably 0 to 10 parts by mass, further preferably 0 to 5 parts by mass, and particularly preferably 0 to 3 parts by mass, relative to 100 parts by mass of the fluororubber. In the case where the fluororubber crosslinking composition of the present application contains a dialkyl sulfone compound, the lower limit of the content of the dialkyl sulfone compound can be, for example, 0.1 parts by mass or more, relative to 100 parts by mass of the fluororubber.

[0112] Since the balance of the crosslinking speed, the flowability of the rubber base material at the time of molding, the mold releasability at the time of molding, and the mechanical properties of the molded product is good, the above-described dialkyl sulfone compound and the above-described processing aid can be simultaneously compounded.

[0113] The fluororubber crosslinking composition is obtained by mixing the fluororubber (a), the crosslinking agent (b), the crosslinking accelerator (c), the acid acceptor (d), the other components (e), and the like using a rubber mixing device generally used. As the rubber mixing device, a roll, a kneader, a Banbury mixer, an internal mixer, a twin-screw extruder, and the like can be used.

[0114] In addition, in order to uniformly disperse each component in the rubber, the following method can be used: the fluororubber (a), the crosslinking agent (b), and the crosslinking accelerator (c) are simultaneously mixed by melting at a high temperature of 100°C to 200°C using a closed-type mixing device such as a kneader, and then the acid acceptor (d), the other components (e), and the like are mixed at a lower temperature than the above.

[0115] Further, after the fluororubber (a), the crosslinking agent (b), the crosslinking accelerator (c), the acid acceptor (d), the other components (e), and the like are mixed, the dispersibility is further improved by mixing again after standing at room temperature for 12 hours or more.

[0116] < Molded Product >

[0117] The molded article of the present application can be obtained by crosslinking the fluororubber with the crosslinking composition. In addition, the molded article of the present application can be obtained by molding and crosslinking the crosslinking composition for fluororubber. The crosslinking composition for fluororubber can be molded by a publicly known method. As the method and conditions of molding and crosslinking, those known in the molding and crosslinking employed can be used. The order of molding and crosslinking is not limited, and crosslinking can be performed after molding, molding can be performed after crosslinking, or molding and crosslinking can be performed simultaneously.

[0118] As the molding method, for example, compression molding, injection molding, injection molding, extrusion molding, molding using a rotocure, and the like can be mentioned, but are not limited thereto. As the crosslinking method, a steam crosslinking method, a crosslinking method using heat, a radiation crosslinking method, and the like can be used, of which a steam crosslinking method and a crosslinking method using heat are preferred. As non-limiting specific crosslinking conditions, the temperature is usually in the range of 140°C to 250°C, and the crosslinking time is usually in the range of 1 minute to 24 hours, and is appropriately determined according to the type of the crosslinking agent (b), the crosslinking accelerator (c), the acid acceptor (d), and the like.

[0119] In addition, by heating the obtained molded article using an oven or the like, the mechanical properties such as tensile strength, heat resistance, and compression set properties at high temperatures can be improved. As non-limiting specific crosslinking conditions, the temperature is usually in the range of 140°C to 300°C, and the crosslinking time is usually in the range of 30 minutes to 72 hours, and is appropriately determined according to the type of the crosslinking agent (b), the crosslinking accelerator (c), the acid acceptor (d), and the like.

[0120] The molded article of the present application is excellent in heat resistance, oil resistance, chemical resistance, softness, and the like, and further excellent in compression set properties at high temperatures. Therefore, the molded article of the present application is usually used in portions for the purpose of sliding contact with other materials, packaging and sealing of other materials and substances, vibration and sound proofing, and can be used as various components in various fields such as the automobile industry, the aircraft industry, the semiconductor industry, and the like.

[0121] As the field used, there can be cited, for example, a semiconductor-related field, an automobile field, an aircraft field, a space rocket field, a ship field, a chemical field such as a chemical plant, a pharmaceutical field such as a pharmaceutical product, a photographic field such as a developing machine, a printing field such as a printing machine, a coating field such as a coating apparatus, an analysis and physical chemistry machine field such as an analysis apparatus and a meter, a food equipment field including a food plant apparatus and a household article, a beverage food manufacturing apparatus field, a pharmaceutical manufacturing apparatus field, a medical component field, a chemical product transfer apparatus field, an atomic power plant apparatus field, a steel field such as a steel plate processing apparatus, a general industrial field, an electrical field, a fuel cell field, an electronic component field, an optical apparatus component field, a space apparatus component field, a petroleum chemical plant apparatus field, an energy exploration and extraction apparatus component field such as petroleum, natural gas, and the like, a petroleum refining field, a petroleum transport apparatus component field, and the like.

[0122] As the use form of the molded product, there can be cited, for example, various sealing materials or gaskets such as a ring, a gasket, a packing, a diaphragm, an oil seal device, a bearing seal, a lip seal, a plunger seal, a door seal, a lip and end face seal, a gas delivery plate seal, a wafer support seal, a cylinder seal, and the like. As the sealing material, it can be used for applications requiring heat resistance, solvent resistance, chemical resistance, and non-adhesion.

[0123] In addition, it can also be used as a tube, a hose, a roll, various rubber rolls, a flexible joint, a rubber plate, a coating, a belt, a damper, a valve, a valve seat, a valve body of a valve, a chemical resistant coating material, a laminated material, a lining material, and the like.

[0124] The cross-sectional shape of the above-mentioned ring, gasket, and seal can be various shapes, and specifically, it can be, for example, a quadrangle, an O shape, a collar, and the like, and can also be a D shape, an L shape, a T shape, a V shape, an X shape, a Y shape, and the like.

[0125] In the above-mentioned semiconductor-related fields, it can be used in, for example, semiconductor manufacturing apparatuses, liquid crystal panel manufacturing apparatuses, plasma panel manufacturing apparatuses, plasma display panel manufacturing apparatuses, plasma-addressing liquid crystal panel manufacturing apparatuses, organic EL panel manufacturing apparatuses, field emission display panel manufacturing apparatuses, solar cell substrate manufacturing apparatuses, semiconductor transfer apparatuses, and the like. As such apparatuses, for example, CVD apparatuses, gas control apparatuses such as semiconductor gas control apparatuses, dry etching apparatuses, wet etching apparatuses, plasma etching apparatuses, reactive ion etching apparatuses, reactive ion beam etching apparatuses, sputtering etching apparatuses, ion beam etching apparatuses, oxidation diffusion apparatuses, sputtering apparatuses, ashing apparatuses, plasma ashing apparatuses, cleaning apparatuses, ion implantation apparatuses, plasma CVD apparatuses, exhaust apparatuses, exposure apparatuses, polishing apparatuses, film forming apparatuses, dry etching cleaning apparatuses, UV / O3 cleaning apparatuses, ion beam cleaning apparatuses, laser beam cleaning apparatuses, plasma cleaning apparatuses, gas etching cleaning apparatuses, Soxhlet extraction cleaning apparatuses, high-temperature high-pressure extraction cleaning apparatuses, microwave extraction cleaning apparatuses, supercritical extraction cleaning apparatuses, cleaning apparatuses using hydrofluoric acid, hydrochloric acid, sulfuric acid, ozone water, and the like, lithography machines, coating and developing equipment, CMP apparatuses, excimer laser exposure machines, reagent piping, gas piping, apparatuses for plasma treatment of NF3, O2, fluorine, and the like, heat treatment film forming apparatuses, wafer transfer equipment, wafer cleaning apparatuses, silicon wafer cleaning apparatuses, silicon wafer processing apparatuses, apparatuses used in LP-CVD processes, apparatuses used in lamp annealing processes, apparatuses used in reflow processes, and the like.

[0126] As specific usage forms in the semiconductor-related fields, for example, various sealing materials such as O-rings or gaskets for gate valves, quartz windows, chambers, chamber covers, gates, bell jars, connectors, pumps, and the like; various sealing materials such as O-rings for resist developer or stripping liquid, hoses, or tubes; liners or coatings for resist developer tanks, stripping liquid tanks, wafer cleaning liquid tanks, and wet etching tanks; diaphragms for pumps; rollers for wafer transfer; hoses for wafer cleaning liquid; sealing materials for clean equipment such as clean room sealing agents; sealing materials for storage libraries that store semiconductor manufacturing apparatuses or devices such as wafers; and diaphragms for reagent delivery used in processes for manufacturing semiconductors can be given.

[0127] In the above-mentioned automobile fields, it can be used in, for example, engine main bodies, main motion systems, valve operating systems, lubrication and cooling systems, fuel systems, intake and exhaust systems, transmission systems of drive systems, steering systems of chassis, brake systems, or electric components such as basic electric components, control system electric components, equipment electric components, and the like of drive systems. Note that the above-mentioned automobile fields also include automatic two-wheeled vehicles.

[0128] In the engine main body or its peripheral device described above, the molded article can be used in various sealing materials required to have heat resistance, oil resistance, fuel oil resistance, engine cooling antifreeze resistance, vapor resistance, and as such sealing materials, sealing members such as gaskets, shaft seal devices, valve stem seals, or non-contact or contact type sealing members such as self-sealing seals, piston rings, open ring-shaped sealing gaskets, mechanical seals, oil seal devices, bellows, diaphragms, hoses, tubes, and various sealing materials used in AT devices, cushioning materials, shock absorbers, and the like can be mentioned.

[0129] As specific usage modes in the fuel system described above, O-rings used in fuel injectors, cold start injectors, quick connectors for fuel lines, sender flange quick connectors, fuel pumps, fuel tank quick connectors, gasoline blending pumps, gasoline pumps, tube bodies of fuel lines, connectors for fuel lines, injectors, and the like; sealing members used in breather system manifolds, fuel filters, pressure regulating valves, canisters, covers of fuel tanks, fuel pumps, fuel tanks, sending units of fuel tanks, fuel injection devices, fuel high-pressure pumps, fuel line connection systems, pump timing control valves, suction control valves, solenoid valve subassemblies, fuel shut-off valves, and the like; canister solenoid valve sealing members, on-board refueling vapor recovery (ORVR) valve sealing members, oil seal devices for fuel pumps, fuel transfer sealing members, fuel tank roll-over valve sealing members, packing sealing members, injector sealing members, filler cap sealing members, filler cap valve sealing members; hoses such as fuel hoses, fuel supply hoses, fuel return hoses, vapor hoses, vent (ventilation) hoses, filler hoses, filler neck hoses, hoses inside fuel tanks (in-tank hoses), control hoses of carburetors, fuel inlet hoses, fuel breather hoses, and the like; gaskets used in fuel filters, fuel line connection systems, and the like, or flange gaskets used in carburetors and the like; piping materials of vapor recovery lines, fuel feed lines, oil gas ORVR lines, and the like; diaphragms used in canisters, ORVRs, fuel pumps, fuel tank pressure sensors, gasoline pumps, sensors of carburetors, composite air control devices (CACs), pulsation dampers, canisters, automatic valves, and the like, or pressure regulator diaphragms of fuel injection devices; valves for fuel pumps, carburetor needle valves, roll-over check valves, check valve types; tubes used in fuel tanks; can sealing gaskets of fuel tanks and the like, sealing gaskets of accelerator pump pistons of carburetors; fuel transfer shock absorbing members for fuel tanks; O-rings and diaphragms for controlling fuel pressure; accelerator pump cups; in-tank fuel pump mounts; injector gaskets of fuel injection devices; injector sealing rings; needle valve cores of carburetors; accelerator pump pistons of carburetors; valve seats of composite air control devices (CACs); fuel tank bodies; sealing members for solenoid valves, and the like can be mentioned.

[0130] As specific examples of the above-mentioned brake device system, there are diaphragms used in vacuum boosters, oil pressure brake hoses, air brake devices, brake device chambers of air brake devices, etc.; hoses used in brake device hoses, brake device oil hoses, vacuum brake device hoses, etc.; various sealing materials such as oil seal devices, O-rings, gaskets, brake device piston seals, etc.; atmospheric valves or vacuum valves for vacuum boosters, check valves for brake device valves; piston cups (rubber sealing cups) for master cylinders, brake device sealing cups; protective covers for master cylinders of oil pressure brake devices or vacuum boosters, wheel cylinders of oil pressure brake devices, O-rings or grommets for anti-lock brake systems (ABS), etc.

[0131] As specific examples of the above-mentioned basic electrical components, there are insulators or sheaths for electric wires (electrical wiring), tubes for electrical wiring outer members, grommets for connectors, etc.

[0132] As specific examples of the above-mentioned control system electrical components, there are coating materials for various sensor wires, etc.

[0133] As specific examples of the above-mentioned equipment electrical components, there are O-rings, gaskets, cooler hoses, high-pressure air conditioner hoses, air conditioner hoses, gaskets for electronic throttle valve units, plug protective covers for direct ignition, diaphragms for power distributors, etc. In addition, they can be used in the bonding of electrical components.

[0134] As specific examples of the above-mentioned intake and exhaust systems, there are gaskets used in intake manifolds, exhaust manifolds, etc., throttle valve gaskets; diaphragms used in EGR (exhaust gas recirculation), BPT (boost pressure turbine), exhaust valves, turbo exhaust valves, actuators, turbo actuators for variable geometry turbines (VTG), exhaust purification valves, etc.; hoses such as control hoses for EGR (exhaust gas recirculation), exhaust control hoses, turbine oil hoses (supply) for turbochargers, turbine oil hoses (return) for turbochargers, turbo air hoses, internal cooler hoses, turbocharger hoses, hoses for connecting turbo engines with compressors provided with internal coolers, exhaust gas hoses, intake hoses, turbo hoses, DPF (diesel particulate filter) sensor hoses, etc.; air pipes or turbo air pipes; intake manifold gaskets; sealing materials for EGR, anti-afterburn valve seats for AB valves, turbo shaft seals for turbochargers, etc., sealing members used in groove members such as rocker covers or air intake manifolds used in engines of automobiles, etc.

[0135] Further, in exhaust gas control components, they can be used as sealing members used in vapor recovery tanks, catalytic converters, exhaust gas sensors, oxygen sensors, etc., or sealing members for electromagnetic valve armatures of vapor recovery and vapor tanks; intake system manifold gaskets, etc.

[0136] In addition, in the diesel engine-related components, O-ring seals for direct injection injectors, rotary pump seals, control diaphragms, fuel hoses, EGR, priming pumps, boost compensators, diaphragms can be used. In addition, O-rings, sealing materials, hoses, tubes, diaphragms, gasket materials, pipes, or urea water tank bodies of urea SCR systems, and sealing materials of urea water tanks, etc. used in urea SCR systems can also be used.

[0137] As a specific use form in the above transmission device system, transmission device-related bearing seals, oil seal devices, O-rings, sealing gaskets, torque converter hoses, etc. can be cited. Gearbox oil seal devices, ATF hoses for AT gearboxes, ATF hoses, O-rings, sealing gaskets, etc. can also be cited.

[0138] Note that, in the transmission device, AT (automatic transmission), MT (manual transmission), CVT (continuously variable transmission), DCT (dual clutch transmission), etc. are included.

[0139] In addition, oil seal devices, gaskets, O-rings, sealing gaskets for manual or automatic transmissions, or oil seal devices, gaskets, O-rings, sealing gaskets for continuously variable transmissions (belt or ring type), and sealing gaskets for ATF linear solenoid valves, oil hoses for manual transmissions, ATF hoses for automatic transmissions, CVTF hoses for continuously variable transmissions (belt or ring type), etc. can also be cited.

[0140] As a specific use form in the steering system, power steering oil hoses, high-pressure power steering hoses, etc. can be cited.

[0141] As a form used in the engine body of an automobile engine, for example, cylinder head gaskets, cylinder head cover gaskets, oil pan sealing gaskets, gaskets such as general gaskets, O-rings, sealing gaskets, sealing members such as timing belt cover gaskets, hoses such as control hoses, engine mounts, shock-absorbing rubbers, control valve diaphragms, camshaft oil seal devices, etc. can be cited.

[0142] In the main motion system of an automobile engine, shaft seal devices such as crankshaft seals, camshaft oil seals, etc. can be used.

[0143] In the valve operating system of an automobile engine, valve stem oil seal devices for engine valves, valve seats for butterfly valves, etc. can be used.

[0144] In the lubrication and cooling system of automobile engines, oil cooler hoses, return hoses, sealing gaskets, water hoses around radiators, radiator seals, radiator gaskets, radiator O-rings, vacuum pump oil hoses for vacuum pumps, as well as radiator hoses, radiator water tanks, hydraulic diaphragms, fan connection seals, etc.

[0145] Thus, as a specific example used in the automotive field, examples include engine mount gaskets, oil pan gaskets, manifold gaskets, oxygen sensor seals, oxygen sensor bushings, and nitrogen oxide (NOx) gaskets. x Sensor seals, nitrogen oxides (NOx) x) sensor bushings, sealings for sulfur oxide sensors, sealings for temperature sensors, temperature sensor bushings, sealings for diesel particulate filter sensors, diesel particulate filter sensor bushings, injector O-rings, injector gaskets, O-rings or diaphragms for fuel pumps, gear box sealings, power piston gaskets, sealings for cylinder liners, sealings for valve stems, static valve stem sealings, dynamic valve stem sealings, front pump sealings for automatic transmissions, rear axle pinion sealings, gaskets for universal joints, pinion sealings for tachometers, piston cups for foot brakes, O-rings or oil seal devices for torque transfer devices, sealings or bearing sealings for exhaust gas recirculation devices, hoses for recirculation devices, diaphragms for carburetors, shock absorbing rubbers (engine mounts, exhaust sections, muffler hangers, suspension bushings, center bearings, support rubber bumpers, etc.), shock absorbing rubbers for suspensions (support rod assemblies, bushings, etc.), shock absorbing rubbers for drive systems (dampers, etc.), fuel hoses, tubes or hoses for EGR, dual carburetor tubes, spool valves for carburetors, flange gaskets for carburetors, oil hoses, oil cooler hoses, ATF hoses, cylinder head gaskets, water pump sealings, gear box sealings, needle valve pieces, reed valves for motorcycles, oil seal devices for automobile engines, sealings for gasoline hose guns, sealings for automobile air conditioners, rubber hoses for engine intercoolers, sealings for fuel line connector systems, CAC valves, needle pieces, engine surrounding wires, fueling hoses, automobile air conditioner O-rings, air intake gaskets, fuel tank materials, diaphragms for electrical distributors, water hoses, clutch hoses, PS hoses, AT hoses, vacuum booster hoses, heater hoses, air conditioning hoses, ventilation hoses, fuel filler caps, PS rack sealings, rack and pinion protective covers, CVJ protective covers, ball joint dust covers, strut dust covers, weather strips, glass runners, center unit gaskets, body side gaskets, bumper rubbers, door locks, instrument panel insulators, high tension wires, flat belts, multi-V belts, synchronous toothed belts, toothed belts, V multi-ribbed belts, tires, windshield wiper blades, diaphragms or plungers for LPG automobile regulators, diaphragms or valves for CNG automobile regulators, DME corresponding rubber parts, self-tensioning diaphragms or protective covers, idle speed control diaphragms or valves, automatic speed control actuators, diaphragms for negative pressure pumps, check valves or plungers, diaphragms or O-rings for O.P.S., gasoline pressure relief valves, O-rings or gaskets for engine cylinder liners, O-rings or gaskets for wet cylinder liners, sealings or gaskets for differential gears (gear oil sealings or gaskets), sealings or gaskets for power steering devices (PSF sealings or gaskets), sealings or gaskets for shock absorbers (SAF sealings or gaskets), sealings or gaskets for constant velocity joints, sealings or gaskets for wheel bearings, coating agents for metal gaskets, caliper sealings, protective covers, wheel bearing sealings, capsules used in the vulcanization of tires, etc.

[0146] In the above-mentioned aircraft field, aerospace / rocket field, and ship field, it is particularly useful for fuel systems, lubricating oil systems.

[0147] In the above-mentioned aircraft field, it is useful as, for example, various sealing members for aircraft, various members for aircraft for oil use, jet engine valve stem seals, gaskets or O-rings, rotary shaft seals, gaskets for oil pressure equipment, fire wall seals, fuel supply hoses, gaskets or O-rings, cables for aircraft, oil seal devices or shaft seal devices, and the like.

[0148] In the above-mentioned aerospace / rocket field, it is useful as, for example, lip seals, diaphragms, O-rings, or O-rings for gas turbine engine oil, shock mount pads for missile ground control, and the like for spacecraft, jet engines, missiles, and the like.

[0149] In addition, in the above-mentioned ship field, it is useful as, for example, drive shaft stern seal for propellers, valve stem seals for air intake and exhaust of diesel engines, valve seals for butterfly valves, valve seats and shaft seals for butterfly valves, shaft seals for butterfly valves, stern tube seals, fuel hoses, gaskets, O-rings for engines, cables for ships, oil seal devices for ships, shaft seal devices for ships, and the like.

[0150] In the above-mentioned chemical plant and the like chemical field, and the pharmaceutical and the like pharmaceutical field, it is useful in processes requiring high chemical resistance, such as manufacturing processes for chemicals such as pharmaceuticals, pesticides, paints, resins, and the like.

[0151] As specific use forms in the above-mentioned chemical field and pharmaceutical field, there can be mentioned seals used in chemical apparatus, pumps or flowmeters for chemical agents, piping for chemical agents, heat exchangers, pesticide spraying machines, pesticide delivery pumps, gas piping, fuel cells, analytical instruments or physicochemical instruments (for example, analytical instruments, column of a meter class, fittings, etc.), pinch joints of flue gas desulfurization devices, seals used in nitric acid plants, power plant turbines, and the like, seals used in sterilization processes for medical use, seals for electroplating solutions, seals for pulley wheels for papermaking, joint seals for wind tunnels; O-rings used in chemical apparatus such as reaction machines, stirrers, and the like, analytical instruments or meters, chemical pumps, pump casings, valves, rotary meters, and the like, O-rings for mechanical seals, O-rings for seals of compressors; gaskets used in high-temperature vacuum dryers, tube joints of gas chromatographs or pH meters, and the like, gaskets for glass coolers of sulfuric acid manufacturing devices; diaphragms used in diaphragm pumps, analytical instruments or physicochemical instruments, and the like; gaskets used in analytical instruments or meters; bushings (metallic ferrules) used in analytical instruments or meters; valve seats; U-seals; liners used in chemical apparatus, gasoline tanks, wind tunnels, and the like, corrosion-resistant liners for acid-resistant aluminum processing tanks; coatings for masking jigs for plating; valve parts of analytical instruments or physicochemical instruments; expansion joints of flue gas desulfurization plants; acid-resistant hoses for concentrated sulfuric acid and the like, chlorine gas delivery hoses, oil-resistant hoses, rainwater drainage hoses for benzene or toluene tanks; chemical-resistant pipes or medical pipes used in analytical instruments or physicochemical instruments, and the like; trichloroethylene-resistant rollers or dyeing rollers for fiber dyeing; medicinal suppositories; rubber stoppers for medical use; liquid medicine bottles, liquid medicine tanks, bags, medicine containers; protective equipment such as gloves or boots for strong acid resistance, solvent resistance, and the like.

[0152] In the above-mentioned photographic field of developing machines and the like, the printing field of printing machines and the like, and the coating field of coating equipment and the like, they can be used as rollers, belts, seals, valve parts, and the like of dry copiers.

[0153] As specific use forms in the above-mentioned photographic field, printing field, and coating field, there can be mentioned surface layers of transfer rollers of copiers, cleaning blades of copiers, belts; rollers (for example, fixing rollers, pressure contact rollers, pressure rollers, and the like) and belts for OA equipment such as copiers, printers, facsimile machines, and the like; rollers, roller blades, belts of PPC copiers; rollers of film developing machines, X-ray film developing machines; printing rollers, doctor blades, tubes, valve parts, belts of printing machines; ink tubes, rollers, belts of printers; coating rollers, doctor blades, tubes, valve parts of coating and coating equipment; developing rollers, gravure rollers, guide rollers, guide rollers of magnetic tape manufacturing coating production lines, gravure rollers of magnetic tape manufacturing coating production lines, coating rollers, and the like.

[0154] In the above-mentioned food equipment field including food plant equipment and household goods, they can be used in food manufacturing processes, for food conveyors, or for food storage.

[0155] As a specific use form in the above-mentioned food equipment field, there can be mentioned a seal for a plate heat exchanger, a seal for a solenoid valve of a vending machine, a gasket for a can or a bottle, a gasket for a sewer pipe, a gasket for a pressure cooker, a seal for a water heater, a gasket for a heat exchanger, a diaphragm or a gasket for a food processing device, a rubber material for a food processing machine (e.g., various seals such as a heat exchanger gasket, a diaphragm, an O-ring, a pipe, a hose, a sanitary gasket, a valve gasket, a filling gasket used as a joint between a mouth of a bottle or the like and a filler at the time of filling), and the like. In addition, there can be mentioned a gasket, a gasket, a pipe, a diaphragm, a hose, a joint sleeve, and the like used in a product such as wine, chilled water, and the like, a filling device, a food sterilization device, a brewing device, a water heater, various automatic food vending machines, and the like.

[0156] In the above-mentioned nuclear power plant equipment field, there can be mentioned a check valve, a pressure reducing valve, a seal for a uranium hexafluoride concentration device, and the like used in the vicinity of a nuclear reactor.

[0157] As a specific use form in the above-mentioned general industrial field, there can be mentioned a seal material for a machine tool, a construction machine, an oil hydraulic machine, and the like; a seal or a bearing seal for an oil hydraulic machine, a lubricating machine, and the like; a seal material used in a mandrel and the like; a seal used in a window and the like of a dry cleaning machine; a seal or a (vacuum) valve seal for a particle cyclotron, a seal for a proton accelerator, a seal for an automatic packaging machine, a diaphragm for a pump used in a sulfur dioxide or chlorine gas analyzer (a public nuisance measuring device), a snake pump liner, a roller or a belt for a printing machine, a belt (a conveyor belt) for conveyance, an extrusion roller for pickling of a sheet metal, a cable for a robot, a solvent extrusion roller for an aluminum calender line, an O-ring for a coupler, an acid-resistant buffer material, a dustproof seal or a lip rubber for a sliding portion of a cutting machine, a gasket for a garbage incineration machine containing moisture, a friction material, a surface modifier for metal or rubber, a coating material, and the like. In addition, there can be used as a gasket or a seal material for a device used in a papermaking process, a sealant for a filter unit for a clean room, a sealant for construction, a protective coating agent for concrete or cement and the like, a glass cloth impregnation material, a processing aid for polyolefin, a moldability improving additive for polyethylene, a fuel container for a small power generator or a lawn mower, and the like, a pre-coated metal obtained by performing a primer treatment on a metal sheet, and the like. Further, it can be impregnated into a woven fabric and sintered to be used as a sheet and a belt.

[0158] As a specific use form in the above-mentioned steel field, there can be mentioned a sheet metal processing roller and the like for a sheet metal processing device.

[0159] As a specific use form in the above-mentioned electrical field, there can be mentioned an insulating oil cover for a new Shinkansen, a ventilation seal for a liquid-sealed transformer, a seal for a transformer, a jacket for an oil well cable, a seal for an oven such as an electric furnace, a window frame seal for a microwave oven, a sealing material used when bonding a wedge and a groove of a CRT, a sealing material for a halogen lamp, a fixing agent for an electrical component, a sealing material for end processing of a sheath heater, a sealing material used in insulation and moisture-proof processing of an electrical equipment lead terminal, and the like. In addition, it can also be used as a coating material for an oil-resistant and heat-resistant electric wire, a highly heat-resistant electric wire, a chemical-resistant electric wire, a highly insulating electric wire, a high-voltage power transmission wire, a cable, an electric wire used in a geothermal power generation device, an electric wire used in the periphery of an automobile engine, and the like. It can also be used as an oil seal device or a shaft seal device for a vehicle cable. Furthermore, it can also be used as an electrical insulating material (for example, an insulating tape used in insulation for various electrical equipment, a joint or a terminal portion of a cable, a material used in a heat-shrinkable tube, and the like), an electrical and electronic equipment material used in a high-temperature atmosphere (for example, a lead wire material for a motor, an electric wire material for the periphery of a high-heat furnace). In addition, it can also be used as a sealing layer or a protective film (back sheet) for a solar cell.

[0160] In the above-mentioned fuel cell field, it can be used as a sealing material between electrodes, between an electrode and a separator, a seal or a gasket for a pipe for hydrogen, oxygen, generated water, and the like, a separator, and the like in a solid polymer fuel cell, a phosphate fuel cell, and the like.

[0161] In the above-mentioned electronic component field, it can be used as a raw material for a heat dissipation material, a raw material for an electromagnetic wave shielding material, a gasket for a hard disk drive (magnetic recording device) of a computer, and the like. In addition, it can also be used as a cushion rubber (collision damper) for a hard disk drive, a binder for an electrode active material of a nickel-hydrogen secondary battery, a binder for an active material of a lithium ion battery, a polymer electrolyte for a lithium secondary battery, a binder for a positive electrode of an alkaline storage battery, a binder for an EL element (electroluminescent element), a binder for an electrode active material of a condenser, a packaging agent, a sealing agent, a coating material for quartz of an optical fiber, a film or sheet for an optical fiber coating material, a CMOS electronic circuit, a transistor, an integrated circuit, an organic transistor, a light-emitting element, an actuator, a memory, a sensor, a coil, a capacitor, a resistor, and the like electronic component, potting, coating, or adhesive sealing for a circuit board, a fixing agent for an electronic component, a modifier for a packaging agent such as an epoxy resin, a coating agent for a printed board, a modifier for a printed circuit board prepreg resin such as an epoxy resin, a flying material for a light bulb, a gasket for a computer, a large computer cooling hose, a gasket or an O-ring and the like sealing gasket for a secondary battery, particularly a lithium secondary battery, a sealing layer for covering a single surface or both surfaces of an outer surface of an organic EL structure, a connector, a damper, and the like.

[0162] In the field of the above-mentioned chemical medicine delivery apparatus, it can be used for a safety valve or a shipping valve, etc. for a truck, a trailer, a tanker, a ship, etc.

[0163] In the field of the above-mentioned energy exploration and production equipment components, it is used as a variety of sealing materials used in the exploration of oil, natural gas, etc., a protective cover for an electrical connector used in an oil well, etc.

[0164] As a specific use form in the field of the above-mentioned energy exploration and production equipment components, there can be mentioned a drill bit seal, a pressure regulating diaphragm, a seal for a horizontal excavating motor (stator), a seal for a stator bearing (shaft), a sealing material used in a blowout preventer (BOP), a sealing material used in a rotary blowout preventer (drill pipe mud saver), a sealing material or a gas-liquid connector used in an MWD (real-time excavation information acquisition system), a logging tool seal (for example, an O-ring, a seal, a gasket, a gas-liquid connector, a protective cover, etc.) used in a logging device (logging equipment), an inflatable packer or a completion packer and a packer seal used therein, a seal or a gasket used in a cementing device, a seal used in a perforator (perforating device), a seal, a gasket or a motor liner used in a mud pump, an underground detector cover, a U-seal cup, a composite mounting seal cup, a rotary seal, a laminated elastomeric bearing, a flow control seal, a sand volume control seal, a safety valve seal, a hydraulic fracturing device (fracturing equipment) seal, a liner packer or a liner hanger seal or gasket, a wellhead seal or gasket, a gas check valve or valve seal or gasket, a sealing material for LWD (logging while drilling), a diaphragm used in oil exploration / oil drilling (for example, a lubricating oil supply diaphragm for an oil drilling fluid tank, etc.), a gate valve, an electronic protective cover, a seal element for a perforating gun, etc.

[0165] Further, it can be used for a joint sealant for a kitchen, a bathroom, a washroom, etc.; a tent adhesive for an outdoor tent; a seal for a seal material for a stamp; a rubber hose for a gas heat pump, a Freon-resistant rubber hose; a film, a liner, a weather-resistant cover for agricultural use; a can for a laminated steel sheet, etc. used in the field of construction or home appliances, etc.

[0166] Further, it can be used as an article combined with a metal such as aluminum. As such a use form, there can be mentioned, for example, a door seal, a gate valve, a swing valve, an electromagnetic valve tip, and a piston seal or a diaphragm combined with a metal, a metal rubber member combined with a metal, etc.

[0167] In addition, it can be used for a rubber member, a brake pad, a brake block, etc. in a bicycle.

[0168] In addition, the molded article can be applied to a belt.

[0169] As a belt, the following belts can be exemplified. As a power transmission belt (including flat belts, V-belts, V-ribbed belts, toothed belts, etc.), a conveyor belt (conveyor belt), the following can be exemplified: flat belts for various high-temperature parts around engines for agricultural machines, machine tools, industrial machines, etc.; conveyor belts for conveying loose or granular materials such as coal, gravel, sand, ores, wood chips, etc. in high-temperature environments; conveyor belts used in steelworks such as blast furnaces; conveyor belts for use in applications exposed to high-temperature environments in precision equipment assembly plants, food plants, etc.; V-belts or V-ribbed belts for agricultural machines, general equipment (for example, OA equipment, printing machines, business drying machines, etc.), automobiles, etc.; drive belts for conveyor robots; toothed belts for food machines, machine tools, etc.; toothed belts used in automobiles, OA equipment, medical equipment, printing machines, etc.

[0170] In particular, as a toothed belt for automobiles, a synchronous toothed belt is representative.

[0171] The above-described belt can be a single-layer structure or a multi-layer structure.

[0172] In the case of a multi-layer structure, the above-described belt can be composed of a layer obtained by crosslinking a fluororubber crosslinking composition and a layer formed of another material.

[0173] In a belt of a multi-layer structure, as a layer formed of another material, a layer formed of another rubber or a layer formed of a thermoplastic resin, various fiber-reinforced layers, a canvas, a metal foil layer, etc. can be exemplified.

[0174] The molded product can also be used for industrial vibration-damping mats, vibration-damping mats, railway slab mats, mats, automobile vibration-damping rubbers, etc. As an automobile vibration-damping rubber, a vibration-damping rubber for engine mounts, motor mounts, component mounts, support rod mounts, bushings, dampers, muffler hangers, center bearings, etc. can be exemplified.

[0175] In addition, as other use forms, connection members for flexible joints, expansion joints, etc., protective covers, grommets, etc. can be exemplified. In the field of ships, for example, a marine pump, etc. can be exemplified.

[0176] The connection member refers to a joint used in piping and piping equipment and can be used for the following purposes: preventing vibration and noise generated by a piping system; absorbing expansion or displacement due to temperature changes, pressure changes; absorbing dimensional variations; mitigating or preventing the effects of earthquakes, ground subsidence; etc.

[0177] The flexible joint, the expansion joint can be preferably used as a complex shape molded product for, for example, shipbuilding piping, mechanical piping such as pumps or compressors, chemical equipment piping, electrical piping, civil engineering / waterway piping, automobiles, etc.

[0178] The protective cover can preferably be used as a complex shape molded product such as a protective cover for a constant velocity universal joint, a dust cover, a rack and pinion operating protective cover, a bolt protective cover, a piston protective cover, and the like for automobiles, a protective cover for agricultural machines, a protective cover for industrial vehicles, a protective cover for construction machines, a protective cover for oil pressure machines, a protective cover for air pressure machines, a protective cover for centralized lubrication machines, a protective cover for liquid delivery, a protective cover for fire fighting, a protective cover for various liquefied gas delivery, and the like.

[0179] The molded product can also be used as a diaphragm for a filter press, a diaphragm for a blower, a diaphragm for water supply, a diaphragm for a liquid storage tank, a diaphragm for a pressure switch, a diaphragm for an air spring for a hanger, and the like.

[0180] By adding the molded product to rubber or resin, an antislip agent can be obtained, which can provide a molded product or a coated film that does not easily slip in an environment wetted with water such as rain, snow, ice, or sweat.

[0181] In addition, the molded product can also be used as a cushioning material for hot press molding when manufacturing decorative plywood, a printed substrate, an electrically insulating board, a rigid polyvinyl chloride laminate, and the like using melamine resin, phenol resin, epoxy resin, and the like.

[0182] The molded product also contributes to the prevention of permeation of various support bodies such as a sealing gasket for weapons, a protective clothing for protection against contact with aggressive chemical agents, and the like.

[0183] In addition, it can be used as a covering material for a heat-resistant and oil-resistant electric wire used in a lead wire for a sensor that detects the oil temperature and / or the oil pressure of a transmission oil and / or an engine oil of an internal combustion engine of an automobile or the like, and the like, in a high-temperature oil gas atmosphere in an oil pan of an automatic transmission or an engine, and the like, and as a pipe, a hose, various rubber rollers, a coating, a belt, a valve body of a valve, and the like for lubricating oil (engine oil, transmission oil, gear oil, and the like) containing an amine-based additive (particularly, an amine-based additive used as an antioxidant, a cleaning dispersant) used for sealing and packaging in a transportation device such as an automobile, a ship, and the like, fuel oil, grease (particularly, urea-based grease), various sealing materials such as an O-ring, a V-ring, an X-ring, a sealing gasket, a gasket, a diaphragm, an oil seal device, a bearing seal, a lip seal, a plunger seal, a door seal, a lip and end face seal, a gas transfer plate seal, a wafer support seal, a roller seal, and the like.

[0184] It can also be used as a laminating material, a lining material.

[0185] Further, sometimes a vulcanized coating film is formed on a molded product to be used. Specifically, there can be mentioned a non-adhesive oil-resistant roller for a copying machine, a weather-resistant de-icing weather strip, a rubber stopper for an infusion, a rubber stopper for a medicine vial, an anti-adhesive agent, a non-adhesive light conveyor belt, an anti-adhesive coating film for a flat gasket of an automobile engine support, a coating process for synthetic fibers, a bolt member or a joint having a gasket coating thin layer, and the like.

[0186] Note that, as to the automobile-related component use of the molded product, the component use of a motorized two-wheeled vehicle of the same structure is also included.

[0187] Further, as the fuel in the above automobile-related, there can be mentioned light oil, gasoline, diesel engine fuel (including bio-diesel fuel), and the like.

[0188] The molded product can also be used for a seal for a rolling bearing.

[0189] As the rolling bearing, there can be mentioned a ball bearing, a roller bearing, a bearing unit, a linear bearing, and the like.

[0190] As the ball bearing, there can be mentioned a radial ball bearing, a thrust ball bearing, a thrust-thrust ball bearing, and the like.

[0191] As the radial ball bearing, there can be mentioned a deep groove ball bearing, a radial ball bearing, a four-point contact ball bearing, an automatic aligning ball bearing, and the like.

[0192] The deep groove ball bearing is used, for example, for a motor, a household electric appliance, an OA device, and the like.

[0193] The radial ball bearing can be mentioned a single-row radial ball bearing, a combined radial ball bearing, a multi-row radial ball bearing, and the like. The single-row radial ball bearing is used for a motor, a household electric appliance, an OA device, and the like, an oil hydraulic pump, a vertical pump, and the like, to which an axial load is applied in addition to a radial load. The combined radial ball bearing is used for a spindle of a machine tool, a grinding shaft, and the like, which require an improvement in rotational accuracy of a shaft or an improvement in rigidity. The multi-row radial ball bearing is used for an electromagnetic clutch for an air conditioner of an automobile, and the like.

[0194] The four-point contact ball bearing is used for a speed reducer, and the like, to which an axial load is applied from two directions and a large bearing width space cannot be obtained.

[0195] The automatic aligning ball bearing is used for a position where aligning of a shaft with a housing is difficult or a transmission shaft where a shaft is easily bent, and the like.

[0196] The thrust ball bearing includes a one-way thrust ball bearing, a multi-way thrust ball bearing, and can be used for the existing known uses using these ball bearings.

[0197] The thrust-thrust ball bearing is used in combination with a multi-row cylindrical roller bearing as an axial load support of a spindle of a machine tool.

[0198] As the above-mentioned roller bearing, a radial roller bearing, a thrust roller bearing, and the like can be given.

[0199] As the above-mentioned radial roller bearing, a cylindrical roller bearing, a needle roller bearing, a tapered roller bearing, and a self-aligning roller bearing can be given.

[0200] The above-mentioned cylindrical roller bearing is used for general machinery, machine tools, electric motors, speed reducers, railway axles, airplanes, and the like.

[0201] The needle roller bearing is used for general machinery, automobiles, electric motors, and the like.

[0202] The tapered roller bearing is used for machine tools, automobile and railway axles, rolling mills, speed reducers, and the like.

[0203] The self-aligning roller bearing is used for general machinery, rolling mills, papermaking machinery, axles, and the like.

[0204] As the above-mentioned thrust roller bearing, a thrust cylindrical roller bearing, a thrust needle roller bearing, a thrust tapered roller bearing, a thrust self-aligning roller bearing, and the like can be given.

[0205] The thrust cylindrical roller bearing is used for machine tools, general machinery, and the like.

[0206] The thrust needle roller bearing is used for automobiles, pumps, general machinery, and the like.

[0207] The thrust tapered roller bearing is used for general machinery, rolling mills, and the like.

[0208] The thrust self-aligning roller bearing is used for cranes, extruders, general machinery, and the like.

[0209] The fluororubber crosslinking composition can be used as a surface modification material for metals, rubbers, plastics, glass, and the like; a sealing material and a coating material that require heat resistance, chemical resistance, oil resistance, non-adhesion, such as a metal gasket, an oil seal device, and the like; a non-adhesive coating material, or an exudation barrier for OA equipment rollers, OA equipment belts, and the like; or a coating on a woven fabric sheet and a belt by infiltration and sintering.

[0210] The fluororubber crosslinking composition can be used as a surface modification material for metals, rubbers, plastics, glass, and the like; a sealing material and a coating material that require heat resistance, chemical resistance, oil resistance, non-adhesion, such as a metal gasket, an oil seal device, and the like; a non-adhesive coating material, or an exudation barrier for OA equipment rollers, OA equipment belts, and the like; or a coating on a woven fabric sheet and a belt by infiltration and sintering.

[0211] The fluororubber crosslinking composition can be used as a sealing material, a liner, a sealant for a complex shape by using a general usage by being high in viscosity and high in concentration; can be used for forming a thin film of several micrometers by being low in viscosity; and can be used for coating a pre-coated metal, an O-ring, a diaphragm, a reed valve by being moderate in viscosity.

[0212] Further, it can be used for coating of a transfer roll or belt for woven fabric or paper, a printing belt, a chemical resistant tube, a suppository, a fuel hose, and the like.

[0213] As the article substrate to be coated with the fluororubber crosslinking composition, there can be used metals such as iron, stainless steel, copper, aluminum, brass, and the like; glass products such as glass plates, woven fabrics and nonwoven fabrics of glass fibers, and the like; molded products and coated articles of general-purpose and heat-resistant resins such as polypropylene, polyoxymethylene, polyimide, polyamide-imide, polysulfone, polyethersulfone, polyether ether ketone, and the like; molded products and coated articles of general-purpose rubbers such as SBR, butyl rubber, NBR, EPDM, and the like, and heat-resistant rubbers such as silicone rubber, fluororubber, and the like; woven fabrics and nonwoven fabrics of natural fibers and synthetic fibers; and the like.

[0214] The coated article formed from the fluororubber crosslinking composition can be used in fields requiring heat resistance, solvent resistance, lubricity, non-adhesion, and the like, and as specific applications, there can be mentioned rollers (e.g., fixing rollers, pressure contact rollers) and transfer belts for OA equipment such as copying machines, printers, facsimile machines, and the like; sheets and belts; O-rings, diaphragms, chemical resistant tubes, fuel hoses, valve seals, gaskets for chemical equipment, engine gaskets, and the like.

[0215] The fluororubber crosslinking composition can also be dissolved in a solvent and used as a coating material, an adhesive. Alternatively, it can be prepared as an emulsion dispersion (emulsion) and used as a coating material.

[0216] The fluororubber crosslinking composition is used as a sealing material or a lining for various devices, piping, and the like, a surface treatment agent for structures formed from inorganic and organic substrates such as metals, ceramics, glass, stone, concrete, plastics, rubber, wood, paper, fibers, and the like, and the like.

[0217] The fluororubber crosslinking composition can be applied to a substrate or the like by a dispenser method, a screen printing method, and the like.

[0218] The fluororubber crosslinking composition can also be used as a coating composition for casting a film, or for impregnating a substrate such as a fabric, a plastic, a metal, or an elastomer.

[0219] In particular, the fluororubber crosslinking composition can be used in the form of an emulsion for manufacturing a coated fabric, a protective glove, an impregnated fiber, an O-ring coated article, a fuel system quick connect O-ring coated article, a fuel system seal coated article, a fuel tank roll-over valve diaphragm coated article, a fuel tank pressure sensor diaphragm coated article, an oil and fuel filter seal coated article, a fuel tank sender seal and sender head assembly seal coated article, a copying machine fixing mechanism roller coated article, and a polymer coating composition.

[0220] They are useful in the coating of silicone rubbers, nitrile rubbers, and other elastomers. They are also useful in the coating of parts made from such elastomers, to improve both the permeation resistance and chemical resistance of the base elastomer, as well as its thermal stability. Other uses include the coating of heat exchangers, expansion joints, tanks, drums, blowers, flues and other ducts, and containment structures, such as concrete containment structures. The fluoroelastomer crosslinking composition can be coated, for example, on the exposed cross-section of a multi-layered part structure in the manufacture of hose structures and diaphragms. Sealing parts in joints and junctions are often formed from hard materials, and the fluoroelastomer crosslinking composition can provide improved interference fit with reduced micro-leakage along the modified frictional interface, sealing surface. Its emulsion can improve the durability of seals in various automotive system applications.

[0221] They can also be used in the manufacture of power steering systems, fuel systems, air conditioning systems, and any junctions of hoses and tubes to other parts. Further usefulness of the fluoroelastomer crosslinking composition is in the repair of manufacturing defects (and use-induced damage) in multi-layered rubber structures such as 3-layer fuel hoses. The fluoroelastomer crosslinking composition is formed before or after the coating of the paint, or is also useful for the coating of thin steel sheets that can be embossed. For example, multiple layers of coated steel can be assembled to form a gasket between 2 rigid metal parts. The sealing effect can be obtained by coating the fluoroelastomer crosslinking composition between its layers. In this process, the fluoroelastomer crosslinking composition can be used to make head gaskets and exhaust manifold gaskets in order to reduce the bolt force and strain of the assembled parts, and to provide good fuel economy and low emissions through low cracking, flexing, and hole strain.

[0222] The fluoroelastomer crosslinking composition can also be used as a coating agent; a substrate-integrated gasket, a sealant, etc. formed by dispensing machine molding on a substrate containing an inorganic material such as metal, ceramic, etc.; a multi-layered article formed by coating on a substrate containing an inorganic material such as metal, ceramic, etc.

[0223] The fluoroelastomer crosslinking composition is also suitable as a wiring material for lightweight and bendable electronic devices, and can be used for known electronic parts. Electronic parts that can be cited include CMOS electronic circuits, transistors, integrated circuits, organic transistors, light-emitting elements, actuators, memories, sensors, coils, capacitors, resistors, etc. By using the fluoroelastomer crosslinking composition, flexible electronic devices such as solar cells, various displays, sensors, actuators, electronic artificial skin, sheet-fed type scanners, Braille displays, wireless power transmission sheets, etc. can be obtained.

[0224] The embodiments have been described above, but it is understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

[0225] According to the present application, there is provided a fluororubber crosslinking composition containing a fluororubber (a) and a crosslinking agent (b), the crosslinking agent (b) being at least one selected from the group consisting of a compound (bl) represented by general formula (bl), a compound (b2) represented by general formula (b2), a compound (b3) represented by general formula (b3), and a salt of any one of these compounds with an alkali metal, an alkaline earth metal or an onium compound.

[0226] [Chem. 7]

[0227]

[0228] (In formula (bl), the hydrogen atoms bonded to the two benzene rings can be replaced with alkyl groups having 1 to 6 carbon atoms not containing halogen atoms.)

[0229] [Chem. 8]

[0230]

[0231] (In formula (b2), the hydrogen atoms bonded to the two benzene rings can be replaced with alkyl groups having 1 to 6 carbon atoms not containing halogen atoms.)

[0232] [Chem. 9]

[0233]

[0234] (In formula (b3), the hydrogen atoms bonded to the coumarin ring can be replaced with any substituents not containing halogen atoms.)

[0235] The crosslinking agent (b) is preferably at least one selected from the group consisting of a compound (bl) represented by general formula (bl), a compound (b2) represented by general formula (b2), and a salt of any one of these compounds with an alkali metal, an alkaline earth metal or an onium compound.

[0236] The crosslinking agent (b) is preferably at least one selected from the group consisting of a compound represented by the following formula, and a salt of any one of these compounds with an alkali metal, an alkaline earth metal or an onium compound.

[0237] [Chem. 10]

[0238]

[0239] The crosslinking agent (b) is preferably at least one selected from the group consisting of a compound represented by the following formula, and a salt of any one of these compounds with an alkali metal, an alkaline earth metal or an onium compound.

[0240] [Chem. 11]

[0241]

[0242] Fluororubber (a) preferably contains vinylidene fluoride units.

[0243] The content of crosslinking agent (b) is preferably 1.0 mmol to 50 mmol relative to 100 parts by weight of fluororubber (a).

[0244] Preferably, it also contains a crosslinking accelerator (c), the content of which is 0.1 to 10 parts by weight relative to 100 parts by weight of fluororubber (a).

[0245] Preferably, it also contains an acid acceptor (d), which is at least one selected from the group consisting of metal oxides, metal hydroxides, alkali metal silicates, metal salts of weak acids, and hydrotalcite.

[0246] Preferably, it also contains an acid acceptor (d), the content of which is 0.1 to 50 parts by weight relative to 100 parts by weight of fluororubber (a).

[0247] In addition, according to the present invention, a molded article obtained from the above-described fluororubber crosslinking composition is provided.

[0248] Example

[0249] Next, embodiments will be given to illustrate the implementation of the present invention, but the present invention is not limited to the embodiments described.

[0250] The values ​​in the examples were measured using the following methods.

[0251] <Monomer Composition of Fluororubber>

[0252] use 19 The measurements were performed using F-NMR (Bruker AC300P model).

[0253] Fluorine content

[0254] By utilization 19 The composition of fluororubber, determined by F-NMR, was calculated.

[0255] Mooney viscosity

[0256] The measurements were performed according to ASTM D1646-15 and JIS K6300-1:2013. The measurement temperature was 121℃.

[0257] Glass transition temperature (Tg)

[0258] Using a differential scanning calorimeter (DSC822e manufactured by Mettler Toredo or X-DSC7000 manufactured by Hitachi High-Tech Science), a 10 mg sample was heated at 20 °C / min to obtain a DSC curve. The temperature at which the extended line representing the second-order phase transition of the DSC curve intersects the tangent at the inflection point of the DSC curve is taken as the glass transition temperature.

[0259] <Heat of Melting>

[0260] Using a differential scanning calorimeter (DSC822e manufactured by Mettler Toredo or X-DSC7000 manufactured by Hitachi High-Tech Science), a 10 mg sample was heated at 20 °C / min to obtain a DSC curve. The heat of fusion was calculated from the magnitude of the melting peak (ΔH) that appeared in the DSC curve.

[0261] <Cross-linking characteristics (maximum torque (MH), optimal cross-linking time (T90))>

[0262] For the fluororubber crosslinking composition, the crosslinking curve was determined using a vulcanizing tester (MDRH2030 manufactured by M&K) during the first crosslinking, at the temperatures listed in Tables 1 and 2. The maximum torque (MH) and the optimal crosslinking time (T90) were determined from the change in torque.

[0263] <Tensile strength and elongation at break>

[0264] Dumbbell-shaped test pieces were prepared using a 2 mm thick cross-linked sheet. Using the obtained test pieces and a tensile testing machine (Tensilon RTG-1310, A&D Corporation), the tensile strength at 23°C and elongation at break were determined according to JIS K6251:2010 at a speed of 500 mm / min, in accordance with JIS K6251:2010.

[0265] The following materials are used in the examples and comparative examples.

[0266] Fluororubber A:

[0267] Molar ratio of vinylidene fluoride / hexafluoropropylene: 78 / 22

[0268] Fluorine content: 66%

[0269] Mooney viscosity (ML1+10 (121℃)): 43

[0270] Glass transition temperature: -18℃

[0271] Heat of fusion: Not confirmed in the second round

[0272] MT carbon (N2SA: 8 ml / 100 g, DBP: 43 ml / 100 g) 2 / g, DBP: 43 ml / 100 g)

[0273] Calcium hydroxide

[0274] Magnesium oxide

[0275] Crosslinking accelerator A: mixture of benzyl dimethyl octadecyl ammonium chloride 91 mass% and isopropyl alcohol 9 mass%

[0276] Crosslinking agent-A: 2,2'-dihydroxydiphenyl

[0277] [Chemical 12]

[0278]

[0279] Crosslinking agent-B: 4,4'-dihydroxydiphenyl

[0280] Crosslinking agent-C: resorcinol

[0281] Crosslinking agent-D: p-benzoguaicol

[0282] Crosslinking agent-E: bisphenol A

[0283] Crosslinking agent-F: 1,6-dihydroxynaphthalene

[0284] Crosslinking agent-G: 4,7-dihydroxycoumarin

[0285] [Chemical 13]

[0286]

[0287] Crosslinking agent-H: 3,3'-dihydroxydiphenyl

[0288] [Chemical 14]

[0289]

[0290] Crosslinking agent-I: 4,4'-dihydroxybenzophenone

[0291] Examples 1 to 3 and Comparative Examples 1 to 11

[0292] Each component was mixed according to the formulations of Tables 1 and 2, and kneaded on an open mill to prepare a fluororubber crosslinking composition. The maximum torque (MH) and optimum crosslinking time (T90) of the obtained fluororubber crosslinking composition are shown in Tables 1 and 2. Next, the fluororubber crosslinking composition was crosslinked by primary crosslinking (press crosslinking) under the conditions described in Tables 1 and 2 and secondary crosslinking (heat crosslinking) under the conditions described in Tables 1 and 2 to obtain a crosslinked sheet (thickness 2 mm). The evaluation results of the obtained crosslinked sheet are shown in Tables 1 and 2.

[0293] [table 1]

[0294]

[0295] [table 2]

[0296]

Claims

1. A composition for crosslinking fluororubber, comprising fluororubber (a) and a crosslinking agent (b), wherein the crosslinking agent (b) is at least one selected from the group consisting of a compound (b1) of general formula (b1), a compound (b2) of general formula (b2), a compound (b3) of general formula (b3), and any one of these compounds combined with a salt of an alkali metal, an alkaline earth metal, or an onium compound. [Chemistry 15] In formula (b1), the hydrogen atoms bonded to the two benzene rings can be replaced by alkyl groups with 1 to 6 carbon atoms that do not contain halogen atoms. [Chemistry 16] In formula (b2), the hydrogen atoms bonded to the two benzene rings can be replaced by alkyl groups with 1 to 6 carbon atoms that do not contain halogen atoms. [Chemistry 17] 。 2. The composition for crosslinking fluororubber as described in claim 1, wherein, The crosslinking agent (b) is selected from at least one of the following groups: compound (b1) represented by general formula (b1), compound (b2) represented by general formula (b2), and any of these compounds combined with a salt of an alkali metal, an alkaline earth metal, or an onium compound.

3. The composition for crosslinking fluororubber as described in claim 1, wherein, The crosslinking agent (b) is at least one of the following: a compound selected from the group consisting of any one of these compounds and a salt of an alkali metal, alkaline earth metal, or onium compound. [Chemistry 18] 。 4. The composition for crosslinking fluororubber as described in claim 1, wherein, The crosslinking agent (b) is at least one of the following: a compound selected from the group consisting of any one of these compounds and a salt of an alkali metal, alkaline earth metal, or onium compound. [Chemistry 19] 。 5. The composition for crosslinking fluororubber according to any one of claims 1 to 4, wherein, Fluororubber (a) contains vinylidene fluoride units.

6. The composition for crosslinking fluororubber according to any one of claims 1 to 4, wherein, The content of crosslinking agent (b) is 1.0 mmol to 50 mmol per 100 parts by weight of fluororubber (a).

7. The fluororubber crosslinking composition according to any one of claims 1 to 4, further comprising a crosslinking accelerator (c), wherein the content of the crosslinking accelerator (c) is 0.1 to 10 parts by weight relative to 100 parts by weight of fluororubber (a).

8. The fluororubber crosslinking composition according to any one of claims 1 to 4, further comprising an acid acceptor (d), wherein the acid acceptor (d) is at least one selected from the group consisting of metal oxides, metal hydroxides, alkali metal silicates, metal salts of weak acids, and hydrotalcite.

9. The fluororubber crosslinking composition according to any one of claims 1 to 4, further comprising an acid acceptor (d), wherein the content of the acid acceptor (d) is 0.1 to 50 parts by weight relative to 100 parts by weight of fluororubber (a).

10. A molded article obtained from any one of the fluororubber crosslinking compositions according to claims 1 to 9.

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