WO2022210042A1 - フッ素ゴム架橋用組成物、成形品およびシール材 - Google Patents
フッ素ゴム架橋用組成物、成形品およびシール材 Download PDFInfo
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- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
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- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C09K2003/1034—Materials or components characterised by specific properties
- C09K2003/1053—Elastomeric materials
Definitions
- the present disclosure relates to fluororubber cross-linking compositions, molded articles, and sealing materials.
- Patent Document 1 describes an aromatic polyhydroxy compound that can act as a cross-linking agent or co-curing agent for fluorinated elastomers as an essential component in the final curable composition.
- One of the most useful aromatic polyphenols is the bisphenol compound hexafluoroisopropylidene-bis(4-hydroxybenzene) known as bisphenol AF.
- Patent Document 2 describes a composition comprising a fluorocarbon elastomer gum, a fluoroaliphatic sulfonamide as a curing agent therefor, and a second curing agent selected from the group consisting of polyhydroxy compounds, polyamine compounds, and derivatives thereof. It is
- Patent Document 3 discloses a composition comprising a fluorocarbon elastomer gum and a vulcanizing agent thereof, wherein the vulcanizing agent comprises one or a mixture of aromatic compounds having hydroxy and oxyallyl groups directly bonded to aromatic ring-carbon atoms.
- the composition is described as being a composition comprising:
- Patent Document 4 discloses (a) a fluorine-containing elastomer, (b) a divalent metal oxide, a divalent metal hydroxide, and a mixture of these metal oxides or metal hydroxides and a metal salt of a weak acid.
- a fluororubber vulcanizing composition is described which contains one or more substances selected from the group, (c) a polyhydroxyaromatic compound, and (d) a specified vulcanization accelerator.
- Patent Document 5 describes a polyol-vulcanized fluororubber composition obtained by blending a hydrotalcite-related compound with a polyol-vulcanized fluororubber.
- the present disclosure provides a fluororubber cross-linking composition that contains a compound that does not contain a fluorine atom as a cross-linking agent and is capable of obtaining a molded article that exhibits excellent compression set properties at high temperatures and excellent heat resistance. With the goal.
- a polyol-crosslinkable fluorororubber (a) and a cross-linking agent (b) are contained, and the cross-linking agent (b) is a compound represented by the following general formula (b1), Compounds shown, and at least one selected from the group consisting of salts of any of these compounds with alkali metals, alkaline earth metals or onium compounds.
- n and n independently represent an integer of 1 to 5.
- the hydrogen atoms bonded to the two benzene rings are optional substituents (however, hydroxy group, sulfanyl group, amino group, acid group, halogen atom and groups containing halogen atoms) may be substituted.)
- p represents an integer of 0 to 3 and q represents an integer of 1 to 4.
- the hydrogen atoms bonded to the two benzene rings are optional substituents (however, hydroxy group, sulfanyl group, amino group , acid groups, halogen atoms and groups containing halogen atoms)).
- the fluororubber (a) preferably contains vinylidene fluoride units.
- the content of the cross-linking agent (b) is preferably 1.0 to 50 mmol with respect to 100 parts by mass of the fluororubber (a).
- the fluororubber cross-linking composition of the present disclosure preferably further contains a cross-linking accelerator (c).
- the fluororubber cross-linking composition of the present disclosure preferably further contains an alkaline earth metal oxide (d).
- the fluororubber cross-linking composition of the present disclosure preferably further contains an acid acceptor (e).
- the fluororubber crosslinking composition of the present disclosure is a group consisting of metal oxides (excluding oxides of alkaline earth metals), metal hydroxides, alkali metal silicates, metal salts of weak acids and hydrotalcite It is preferable to further contain at least one more selected acid acceptor (e).
- the fluororubber cross-linking composition of the present disclosure preferably further contains 1 to 10 parts by mass of hydrotalcite and 2.5 to 8 parts by mass of magnesium oxide with respect to 100 parts by mass of the fluororubber (a). .
- the fluororubber cross-linking composition of the present disclosure preferably does not contain calcium hydroxide.
- the fluororubber cross-linking composition of the present disclosure preferably further contains a carboxylic acid ester processing aid (f).
- the fluororubber crosslinking composition of the present disclosure preferably contains a dialkylsulfone compound (g).
- the crosslinking agent (b) is 4,4'-biphenol, 2,6-dihydroxyanthraquinone, 2,7-dihydroxyanthraquinone, and any of these compounds and an alkali metal , an alkaline earth metal or a salt with an onium compound.
- a molded article or sealing material obtained from the fluororubber cross-linking composition is provided.
- a fluororubber cross-linking composition that contains a fluorine atom-free compound as a cross-linking agent and that can provide molded articles that exhibit excellent compression set properties at high temperatures and excellent heat resistance. can do.
- the fluororubber cross-linking composition of the present disclosure contains a polyol-crosslinkable fluororubber (a) and a cross-linking agent (b).
- the fluororubber cross-linking composition of the present disclosure contains a compound having a structure described later as a cross-linking agent. These compounds are easy to handle because they do not contain fluorine atoms. Furthermore, the molded article obtained from the fluororubber cross-linking composition of the present disclosure has excellent compression set properties at high temperatures, and even when the molded article is exposed to high temperatures, the tensile strength does not easily change. It also has excellent heat resistance.
- the polyol-crosslinkable fluororubber used in the present disclosure is a fluororubber having a polyol-crosslinkable site.
- fluororubber is an amorphous fluoropolymer.
- Amorphous means a melting peak ( ⁇ H ) is 4.5 J/g or less.
- Fluororubber exhibits elastomeric properties by cross-linking. By elastomeric properties is meant the property of being able to stretch a polymer and retain its original length when the force required to stretch the polymer is no longer applied.
- a site having a vinylidene fluoride (VdF) unit can be given as a site that can be crosslinked with a polyol.
- a fluororubber containing a VdF unit is preferable because the effect of using the cross-linking agent (b) is likely to be exhibited.
- a fluororubber having a polyol-crosslinkable site is, for example, A vinylidene fluoride (VDF)-based fluoroelastomer substantially free of polar terminal groups described in JP-A-2003-277563; A vinylidene fluoride-based fluoroelastomer containing repeating units derived from vinylidene fluoride (VDF) and at least one additional (per)fluorinated monomer described in JP-T-2018-527449, 40 to 68% by weight of vinylidene fluoride (VDF) units and 20 to 50% by weight of hexafluoropropylene (HFP) units having a small amount of fluorine of less than 67% by weight as described in JP-A-7-316377 and optionally one or more comonomers having ethylene unsaturation, such as 100 parts (phr) of the cured fluoroelastomer.
- VDF vinylidene fluoride
- HFP hexafluor
- fluororubber having a polyol-crosslinkable site examples include non-perfluororubber and fluororubber containing —CH 2 — (methylene group) in the main chain.
- fluororubbers having polyol-crosslinkable sites examples include VdF-based fluororubbers and rubbers having polyol-crosslinkable functional sites such as double bonds in side chains and/or main chains.
- the VdF-based fluororubber includes tetrafluoroethylene (TFE)/propylene/VdF-based fluororubber, ethylene/hexafluoropropylene (HFP)/VdF-based fluororubber, VdF/HFP-based fluororubber, and VdF/TFE/HFP-based fluororubber. etc.
- TFE tetrafluoroethylene
- HFP ethylene/hexafluoropropylene
- HFP ethylene/hexafluoropropylene
- VdF/HFP-based fluororubber VdF/HFP-based fluororubber
- VdF/TFE/HFP-based fluororubber etc.
- VdF-based fluororubber one represented by the following general formula (1) is preferable.
- structural unit M 1 is a structural unit derived from vinylidene fluoride (m 1 )
- structural unit M 2 is a structural unit derived from a fluorine-containing ethylenic monomer (m 2 )
- structural unit N 1 is a repeating unit derived from a monomer (n 1 ) copolymerizable with the monomer (m 1 ) and the monomer (m 2 )
- VdF-based fluororubbers represented by the general formula ( 1 ) those containing 30 to 85 mol% of the structural unit M1 and 55 to 15 mol% of the structural unit M2 are preferable, and more preferably the structural unit M1. 50-80 mol %, structural unit M 2 50-20 mol %.
- Structural unit N 1 is preferably 0 to 20 mol % relative to the total amount of structural unit M 1 and structural unit M 2 .
- the monomer (n 1 ) may be any monomer as long as it can be copolymerized with the monomer (m 1 ) and the monomer (m 2 ).
- Site-providing monomers, bisolefin compounds, and the like can be mentioned. Each of these can be used alone or in any combination.
- CY 1 2 CY 1 -Rf 5 CHR 1 X 1 (4)
- Y 1 is independently a hydrogen atom, a fluorine atom or —CH 3
- Rf 5 is a fluoroalkylene group, a perfluoroalkylene group, a fluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group
- R 1 is , a hydrogen atom or —CH 3
- X 1 is an iodine atom or a bromine atom
- CF 2 CFO(CF 2 CF(CF 3 )O) m (CF 2 ) n ⁇ X 2 (5)
- m is an integer of 0 to 5
- n is an integer of 1 to 3
- X 2 is a cyano group, a carboxyl group, an al
- Iodine-containing monomers such as 6,6-dihydro-6-iodo-3-oxa-1-hexene) and perfluoro (5-iodo-3-oxa-1-pentene), described in JP-A-4-217936 CF 2 ⁇ CFOCF 2 CF 2 CH 2 I and other iodine-containing monomers such as 4-iodo-3,3,4,4-tetrafluoro-1-butene described in JP-A-61-55138
- Such iodine-containing monomers, bromine-containing monomers described in JP-A-4-505341, JP-A-4-505345, cyano group as described in JP-A-5-500070 Containing monomers, carboxyl group-containing monomers, alkoxycarbonyl group-containing monomers and the like can be mentioned. Each of these can be used alone or in any combination.
- bisolefin compound those described in JP-A-8-12726 can be used.
- the VdF-based fluorororubber is preferably a VdF/HFP-based rubber, a VdF/HFP/TFE-based rubber, a VdF/TFE/PAVE-based fluororubber, a VdF/CTFE-based rubber, or a VdF/CTFE/TFE-based rubber. can give.
- the fluorororubber that can be crosslinked with a polyol is preferably a fluororubber composed of VdF and at least one other fluorine-containing monomer. It is preferably at least one rubber selected from the group consisting of rubber and VdF/TFE/PAVE fluororubber, and from the group consisting of VdF/HFP fluororubber and VdF/TFE/HFP fluororubber. More preferably, at least one rubber is selected.
- the fluororubber has a Mooney viscosity (ML1+10 (121°C)) at 121°C of preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, and preferably 10 or more. Especially preferred. Also, it is preferably 200 or less, more preferably 170 or less, even more preferably 150 or less, even more preferably 130 or less, and particularly preferably 100 or less. Mooney viscosity is measured according to ASTM D1646-15 and JIS K6300-1:2013.
- the fluororubber preferably has a fluorine content of 50 to 75% by mass. More preferably 60 to 73 mass %, still more preferably 63 to 72 mass %.
- the fluorine content is obtained by calculation from the composition ratio of the monomer units constituting the fluororubber.
- the fluororubber preferably has a glass transition temperature of -50 to 0°C.
- a DSC curve was obtained by heating 10 mg of a sample at a rate of 20°C/min using a differential scanning calorimeter. The temperature at which the point of intersection with the tangent line at the point of inflection can be determined as the glass transition temperature.
- the fluororubber described above can be produced by a conventional method.
- the fluororubber cross-linking composition of the present disclosure contains a cross-linking agent.
- the cross-linking agent is a compound represented by the following general formula (b1), a compound represented by the following general formula (b2), a salt of any of these compounds with an alkali metal, or a salt of any of these compounds with an alkaline earth metal. It is at least one selected from the group consisting of salts and salts of any of these compounds with an onium compound.
- n and n independently represent an integer of 1 to 5.
- the hydrogen atoms bonded to the two benzene rings are optional substituents (however, hydroxy group, sulfanyl group, amino group, acid group, halogen atom and groups containing halogen atoms) may be substituted.)
- p represents an integer of 0 to 3 and q represents an integer of 1 to 4.
- the hydrogen atoms bonded to the two benzene rings are optional substituents (however, hydroxy group, sulfanyl group, amino group , acid groups, halogen atoms and groups containing halogen atoms)).
- m and n represent the number of hydroxy groups respectively bonded to two benzene rings.
- Each of m and n is preferably an integer of 1 to 2, more preferably 1, from the standpoint of good cross-linking properties, tensile strength and compression set properties of molded articles.
- hydrogen atoms not substituted by hydroxy groups are hydroxy groups, sulfanyl groups, amino groups, acid groups, halogen atoms and halogen atoms. It may or may not be substituted with other substituents other than the containing group.
- substituents include a cyano group and an alkyl group having 1 to 10 carbon atoms.
- the substituent is a substituent that does not contain a halogen atom, such as a fluorine atom or a group containing a fluorine atom. Therefore, the compound represented by general formula (b1) does not contain a fluorine atom.
- An acid group is a group having a hydrogen atom that can be ionized as a proton.
- acid groups also include acid bases in which the hydrogen atoms are replaced by other atoms (eg, alkali metal atoms, etc.).
- Typical examples of acid groups include a carboxy group, a sulfo group, a sulfino group, a phosphoric acid group, a phosphonic acid group, acid bases thereof, and the like.
- Compounds represented by the general formula (b1) include 4,4'-biphenol, 2,2'-biphenol, 2,3'-biphenol, 2,4'-biphenol, 3,3'-biphenol, 3,4 '-biphenol and the like. Among them, 4,4'-biphenol is particularly preferred because of its easy availability.
- the compound represented by general formula (b2) has an anthraquinone skeleton and a hydroxy group bonded to the 6-position of the anthraquinone skeleton.
- the compound represented by the general formula (b2) further has at least one hydroxy group in addition to the hydroxy group bonded to the 2-position of the anthraquinone skeleton, and this hydroxy group is bonded to the 2-position of the anthraquinone skeleton. It is bonded to the other benzene ring different from the benzene ring to which the hydroxy group is bonded.
- p and q represent the number of hydroxy groups respectively bonded to the two benzene rings.
- p is an integer from 0 to 3;
- q is an integer from 1 to 4;
- the above p is preferably an integer of 0 to 1, more preferably 0.
- the above q is preferably an integer of 1 to 2, more preferably 1.
- a molded product having a hydroxyl group at the 2-position of the anthraquinone skeleton and a hydroxyl group at the 6- or 7-position has good mechanical properties and high-temperature compression set characteristics. is particularly preferable from the point of being obtained.
- the hydrogen atoms not substituted by hydroxy groups are hydroxy groups, sulfanyl groups, amino groups, acid groups, halogen atoms and halogen atoms. It may or may not be substituted with other substituents other than the containing group.
- substituents include a cyano group and an alkyl group having 1 to 10 carbon atoms.
- the substituent is a substituent that does not contain a halogen atom such as a fluorine atom or a group containing a fluorine atom, and therefore the compound represented by the general formula (b2) does not contain a fluorine atom.
- Examples of compounds represented by general formula (b2) include 2,6-dihydroxyanthraquinone and 2,7-dihydroxyanthraquinone.
- the cross-linking agent includes a salt of the compound represented by the general formula (b1) and an alkali metal, a salt of the compound represented by the general formula (b1) and an alkaline earth metal, and a compound represented by the general formula (b1) and an onium compound.
- the salt of the compound and the onium compound is an onium salt composed of an anion portion derived from the compound and a cation portion derived from the onium compound.
- the onium salt acts not only as a cross-linking agent but also as a cross-linking accelerator.
- the cross-linking agent is 4,4′-biphenol, a salt of 4,4′-biphenol and alkali metal, alkaline earth metal or onium compound, 2,6-dihydroxyanthraquinone, 2,6-dihydroxyanthraquinone and alkali Forming obtained is a salt with a metal, alkaline earth metal or onium compound, 2,7-dihydroxyanthraquinone, or a salt of 2,7-dihydroxyanthraquinone with an alkali metal, alkaline earth metal or onium compound It is preferable from the viewpoint of mechanical physical properties of the body and compression set characteristics.
- 4,4'-biphenol, a salt of 4,4'-biphenol and an onium compound 2,6-dihydroxyanthraquinone, a salt of 2,6-dihydroxyanthraquinone and an onium compound, 2,7-dihydroxyanthraquinone, or 2
- a salt of ,7-dihydroxyanthraquinone and an onium compound is more preferable, and 2,6-dihydroxyanthraquinone, a salt of 2,6-dihydroxyanthraquinone and an onium compound, 2,7-dihydroxyanthraquinone, or 2,7- Salts of dihydroxyanthraquinone and onium compounds are particularly preferred.
- the compound represented by the general formula (b1), the salt of the compound represented by the general formula (b1) and an alkali metal, the salt of the compound represented by the general formula (b1) and an alkaline earth metal, the general formula (b1) A salt of the compound represented by the general formula (b2) and an onium compound, a compound represented by the general formula (b2), a salt of the compound represented by the general formula (b2) and an alkali metal, a compound represented by the general formula (b2) and an alkaline earth metal A salt of and a salt of the compound represented by the general formula (b2) and an onium compound can be used alone or in combination.
- the salt of the compound represented by the general formula (b1) and the onium compound or the salt of the compound represented by the general formula (b2) and the onium compound is the compound represented by the general formula (b1) in water or an organic solvent.
- the compound represented by the general formula (b2) is reacted with an alkaline substance such as sodium hydroxide or with metallic sodium in an organic solvent, and then further reacted with an onium compound such as benzyltriphenylphosphonium chloride, It is obtained by distilling off water or an organic solvent.
- the solution of the reaction product may be filtered, or the reaction product may be washed with water or an organic solvent to remove by-products such as sodium chloride.
- Na or K is preferable as the alkali metal.
- Ca or Mg is preferred as the alkaline earth metal.
- Onium salts include, for example, ammonium salts, phosphonium salts, and sulfonium salts.
- onium compounds that constitute onium salts include ammonium compounds, phosphonium compounds, and sulfonium compounds. In the present disclosure, the onium compounds do not contain fluorine atoms.
- an ammonium compound and a phosphonium compound are preferable, a phosphonium compound is more preferable, a quaternary phosphonium compound is more preferable, and benzyltriphenylphosphonium is particularly preferable.
- ammonium compound quaternary ammonium compounds are preferable, and 8-benzyl-1,8-diazabicyclo[5,4,0]-7-undecenium and benzyldimethyloctadecylammonium are more preferable.
- the cross-linking agent can be used by mixing with other compounds.
- Mixtures containing a cross-linking agent include, for example, a mixture such as a solid solution of a cross-linking agent and a cross-linking accelerator, and a mixture of a cross-linking agent and a compound capable of dissolving it.
- the compound represented by the general formula (b1) or a mixture of the compound represented by the general formula (b2) and a quaternary phosphonium salt, or the compound represented by the general formula (b1) A mixture of a compound represented by the general formula (b2) and a quaternary ammonium salt is preferable, and a compound represented by the general formula (b1) or a compound represented by the general formula (b2) and a quaternary phosphonium salt and more preferably a mixture of the compound represented by the general formula (b1) or the compound represented by the general formula (b2) and benzyltriphenylphosphonium chloride.
- the content of the cross-linking agent is such that the cross-linking reaction in the cross-linking step proceeds at an appropriate rate, and a molded article having sufficient tensile strength, elongation at break, compression set properties at high temperatures, and moderate hardness is obtained. Therefore, it is preferably 1.0 to 50 mmol, more preferably 2.0 mmol or more, still more preferably 4.0 mmol or more, and more preferably 100 parts by mass of the polyol-crosslinkable fluororubber. is 30 mmol or less, more preferably 20 mmol or less, and particularly preferably 15 mmol or less.
- the fluororubber cross-linking composition of the present disclosure may further contain a cross-linking accelerator.
- a cross-linking accelerator can accelerate the cross-linking reaction by promoting the formation of intramolecular double bonds in the dehydrofluoric acid reaction of the fluororubber main chain.
- the compound represented by the general formula (b1) or the compound represented by the general formula (b2) is used as the cross-linking agent, it is preferable to use a cross-linking accelerator together with the cross-linking agent. Even when an onium salt is used as a cross-linking agent, a cross-linking accelerator can be used together with the cross-linking agent, but is not necessarily used.
- the amount of the cross-linking accelerator can be appropriately adjusted depending on the cross-linking conditions and physical properties of the molded product. If the amount of the crosslinking accelerator is increased, the crosslinking reaction can be accelerated or the crosslinking can be performed at a lower temperature, but the compression set property tends to be deteriorated. Conversely, if the amount of the cross-linking accelerator is reduced, the cross-linking reaction will slow down, but the compression set tends to improve.
- an onium salt (excluding a salt of the compound represented by the general formula (b1) and the onium compound and a salt of the compound represented by the general formula (b2) and the onium compound) is used.
- the onium salt is not particularly limited and includes, for example, ammonium salts such as quaternary ammonium salts, phosphonium salts such as quaternary phosphonium salts, and sulfonium salts. Phosphonium salts are preferred.
- the quaternary ammonium salt is not particularly limited. 4,0]-7-undecenium iodide, 8-methyl-1,8-diazabicyclo[5,4,0]-7-undecenium hydroxide, 8-methyl-1,8-diazabicyclo[5 ,4,0]-7-undecenium methyl sulfate, 8-ethyl-1,8-diazabicyclo[5,4,0]-7-undecenium bromide, 8-propyl-1,8-diazabicyclo[5 ,4,0]-7-undecenium bromide, 8-dodecyl-1,8-diazabicyclo[5,4,0]-7-undecenium chloride, 8-dodecyl-1,8-diazabicyclo[5,4 ,0]-7-undecenium hydroxide, 8-eicosyl-1,8-diazabicyclo[5,4,0]-7-undecenium chloride, 8-t
- the quaternary phosphonium salt is not particularly limited, and examples thereof include tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride (hereinafter referred to as BTPPC), benzyltrimethylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl -2-Methoxypropylphosphonium chloride, benzylphenyl(dimethylamino)phosphonium chloride and the like can be mentioned, and among these, benzyltriphenylphosphonium chloride (BTPPC) is preferred from the viewpoint of crosslinkability and physical properties of the crosslinked product.
- BTPPC benzyltriphenylphosphonium chloride
- the content of the cross-linking accelerator is 100 parts by mass per 100 parts by mass of polyol-crosslinkable fluororubber, because the cross-linking reaction proceeds at an appropriate rate and a molded article with even better compression set characteristics at high temperatures can be obtained. , preferably 0.1 to 10 parts by mass, more preferably 0.2 parts by mass or more, still more preferably 0.3 parts by mass or more, more preferably 1.0 parts by mass or less, More preferably, it is 0.8 parts by mass or less.
- the content of the cross-linking accelerator is a value including the mass of the cationic portion of the cross-linking agent (that is, the cation derived from the onium compound).
- the fluororubber cross-linking composition preferably further contains an alkaline earth metal oxide.
- Magnesium oxide is preferable as the oxide of the alkaline earth metal, since a molded article with even better compression set characteristics at high temperatures can be obtained.
- the content of alkaline earth metal oxides such as magnesium oxide is such that polyol-crosslinkable fluorine can be obtained, since it is possible to obtain molded articles with even better compression set characteristics at high temperatures. It is preferably 0.1 to 20 parts by mass, more preferably 1.0 parts by mass or more, still more preferably 2.5 parts by mass or more, and particularly preferably 3.0 parts by mass with respect to 100 parts by mass of rubber. parts or more, more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less.
- the fluororubber cross-linking composition of the present disclosure may further contain an acid acceptor. By containing the acid acceptor, the cross-linking reaction of the fluororubber cross-linking composition becomes smoother It progresses, and the compression set property at high temperature is further improved.
- acid acceptors include metal oxides such as bismuth oxide and zinc oxide (excluding oxides of alkaline earth metals), metal hydroxides such as calcium hydroxide, hydrotalcite, sodium metasilicate, and the like.
- metal oxides such as bismuth oxide and zinc oxide (excluding oxides of alkaline earth metals)
- metal hydroxides such as calcium hydroxide, hydrotalcite, sodium metasilicate, and the like.
- Weak acid metal salts include Ca, Sr, Ba, Na, and K carbonates, benzoates, oxalates, phosphites, and the like.
- metal oxides excluding oxides of alkaline earth metals
- metal hydroxides excluding oxides of alkaline earth metals
- alkali metal silicates etc.
- At least one selected from the group consisting of salts, metal salts of weak acids and hydrotalcite is preferable, and sodium metasilicate hydrate, calcium hydroxide, bismuth oxide and hydrotalcite are more preferable, and calcium hydroxide and hydrotalcite are more preferable.
- Talcites are more preferred, and hydrotalcites are particularly preferred.
- the hydrotalcite is not particularly limited, but hydrotalcites described in International Publication No. 2019/098062 can be used. Specifically, the general formula: [(M 1 2+ ) 1 ⁇ x M 3+ x (OH) 2 ] x+ [A n ⁇ x/n ⁇ mH 2 O] x ⁇ (wherein M 1 2+ is a divalent metal ion, M 3+ is a trivalent metal ion, A n- is an n-valent anion, and x is a number that satisfies 0 ⁇ x ⁇ 0.5. and m is a number that satisfies 0 ⁇ m.) from the standpoint of easy availability. Hydrotalcite may be a natural product or a synthetic product.
- M 1 2+ represents a divalent metal ion such as Mg 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ or Zn 2+ .
- Mg 2+ and/or Zn 2+ are preferred because they are readily available.
- M 3+ represents a trivalent metal ion such as Al 3+ , Fe 3+ , Cr 3+ , Co 3+ or In 3+ .
- Al 3+ is preferable because of its easy availability.
- a n- denotes an n-valent anion such as OH ⁇ , F ⁇ , Cl ⁇ , Br ⁇ , NO 3 ⁇ , CO 3 2 ⁇ , SO 4 2 ⁇ , Fe(CN) 6 3 ⁇ , CH 3 COO ⁇ , oxalate ions or salicate ions can be mentioned.
- CO 3 2- is preferable because of its easy availability.
- M 1 2+ is Mg 2+ and/or Zn 2+
- M 3+ is Al 3+
- a n- is CO 3 2- .
- x is a number that satisfies 0 ⁇ x ⁇ 0.5, preferably a number that satisfies 0.2 ⁇ x ⁇ 0.4, more preferably a number that satisfies 0.2 ⁇ x ⁇ 0.33 preferable.
- m is a number that satisfies 0 ⁇ m, and preferably a number that satisfies 0 ⁇ m ⁇ 1.
- Hydrotalcite is a non - stoichiometric compound represented by the above formula .
- OH) 13CO3.mH2O ( 0 ⁇ m ) Mg4Al2 ( OH) 12CO3.3.5H2O , Mg4.3Al2 ( OH ) 12.6CO3.mH2O ( 0 ⁇ m) , Mg5Al2 ( OH) 14CO3.4H2O , Mg3Al2 ( OH) 10CO3.1.7H2O , and Mg3ZnAl2 ( OH ) 12CO3 .
- At least one compound selected from the group consisting of mH 2 O (0 ⁇ m) is preferred, such as Mg 6 Al 2 (OH) 16 CO 3.4H 2 O, Mg 4.5 Al 2 (OH) 13 CO 3 . 3.5H2O , Mg4.3Al2 ( OH) 12.6CO3.mH2O ( 0 ⁇ m), and Mg3ZnAl2 ( OH) 12CO3.mH2O ( 0 ⁇ m) At least one compound selected from the group consisting of is more preferred.
- the acid acceptor may be selected from the group consisting of bismuth oxide and hydrotalcite. At least one selected is preferred.
- the content of the acid acceptor such as hydrotalcite is 100 masses of polyol-crosslinkable fluororubber, since molded articles with even better compression set characteristics at high temperatures can be obtained. parts, preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, still more preferably 1 to 20 parts by mass, and particularly preferably 1 to 10 parts by mass.
- the content of the acid acceptor increases, the water resistance, acid resistance, and resistance to organic acid esters including biodiesel of the resulting molded product tend to decrease. decreases, and mechanical properties tend to decrease due to a decrease in crosslink density. Therefore, the content of the acid acceptor can be selected depending on the use of the resulting molded product. Further, when the fluororubber cross-linking composition contains an acid acceptor other than calcium hydroxide, the content of calcium hydroxide is 0 to 1.5 parts by mass with respect to 100 parts by mass of the polyol-crosslinkable fluororubber. is preferred, 0 to 1.0 parts by mass is more preferred, and 0 part by mass is even more preferred.
- the fluororubber cross-linking composition does not contain calcium hydroxide.
- Preferred combinations of acid acceptor (e) and alkaline earth metal oxide (d) include adequate cross-linking speed, high temperature compression set properties of the resulting molded article, water resistance, acid resistance and biodiesel. It is a combination of hydrotalcite and magnesium oxide because it has good organic acid ester resistance.
- the fluororubber cross-linking composition may further contain 1 to 10 parts by mass of hydrotalcite and 2.5 to 8 parts by mass of magnesium oxide with respect to 100 parts by mass of polyol-crosslinkable fluororubber.
- the content of calcium hydroxide is preferably 0 to 3 parts by mass, more preferably 0 to 1 part by mass, and even more preferably 0 part by mass. That is, it is particularly preferable that the fluororubber cross-linking composition does not contain calcium hydroxide.
- the fluororubber crosslinking composition may contain a carboxylic acid ester-based processing aid.
- processing aids are added for the purpose of improving workability during kneading or improving mold releasability during molding.
- it often affects the cross-linking reaction and tends to deteriorate the physical properties of the resulting molded product, especially the compression set at high temperatures.
- the cross-linking agent (c) when the cross-linking agent (c) is blended, when the carboxylic acid ester processing aid (f) is blended, the effect on the cross-linking reaction is small and the physical properties of the resulting molded product are impaired. In addition, the processability during kneading is improved, or the mold releasability during molding is improved.
- the carboxylic acid ester-based processing aid (f) preferably has a melting point or softening point of 120° C. or lower, more preferably 110° C. or lower, even more preferably 100° C. or lower, and 90° C. or lower. It is particularly preferred to have
- the carboxylic acid ester-based processing aid (f) may be a synthetic carboxylic acid ester, a carboxylic acid ester synthesized from a carboxylic acid or alcohol derived from a natural product, or a natural wax containing a carboxylic acid ester.
- the carboxylic acid-derived moieties and/or alcohol-derived moieties may be saturated or unsaturated.
- the carboxylic acid-derived portion and/or the alcohol-derived portion may be aliphatic or may contain an aromatic ring.
- the carboxylic acid ester-based processing aid (f) may have a plurality of carboxylic acid ester structures in the molecule, and the alcohol-derived moiety may be monovalent or polyvalent.
- carboxylic acid esters and esters synthesized from natural carboxylic acids or alcohols as raw materials are not particularly limited, but stearate, palmitate, oleate, laurate, 2- Ethylhexanoate, myristate, sebacate, glycerin fatty acid ester, sorbitan fatty acid ester, phthalate, trimellitate, adipate, propylene glycol fatty acid ester, and carboxylic acid ester of polyethylene glycol.
- stearyl stearate 2-ethylhexyl stearate, isotridecyl stearate, myristyl myristate, dibutyl sebacate, and di(2-ethylhexyl) sebacate.
- Examples of natural waxes containing carboxylic acid esters include carnauba wax, candelilla wax, beeswax, and rice bran wax.
- carboxylic acid ester-based processing aid (f) may be the processing aid described in JP-A-10-502955.
- stearyl stearate, dibutyl sebacate, di(2-ethylhexyl) sebacate and carnauba wax are preferred, and carnauba wax is particularly preferred.
- carnauba wax is particularly preferred.
- the balance between mold releasability during molding and the physical properties of the molded product may be improved.
- the content of the carboxylic acid ester-based processing aid (f) is preferably 0 to 10 parts by mass, more preferably 0 to 3 parts by mass, with respect to 100 parts by mass of the polyol-crosslinkable fluororubber. It is preferably from 0 to 1.5 parts by mass, and particularly preferably from 0.1 to 1 part by mass.
- the carboxylic acid ester processing aid (f) is used, the resulting molded product tends to have poor mechanical properties and sealability. is obtained.
- the fluororubber cross-linking composition may contain a dialkylsulfone compound.
- a dialkyl sulfone compound By containing a dialkyl sulfone compound, the cross-linking efficiency of the fluororubber cross-linking composition is increased, the cross-linking speed is increased, the compression set property is further improved, and the fluidity of the rubber fabric is improved.
- the dialkylsulfone compound (g) includes dimethylsulfone, diethylsulfone, dibutylsulfone, methylethylsulfone, diphenylsulfone, sulfolane and the like. Of these, sulfolane is preferred from the viewpoint of crosslinking efficiency and compression set properties, and because it has a suitable boiling point.
- the content of the dialkylsulfone compound (g) is preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass, more preferably 0 to 100 parts by mass of the polyol-crosslinkable fluororubber. It is more preferably 3 parts by mass, and particularly preferably 0.1 to 1 part by mass.
- the lower limit of the content of the dialkylsulfone compound (g) is, for example, relative to 100 parts by mass of the polyol-crosslinkable fluororubber. and may be 0.1 parts by mass or more.
- a dialkyl sulfone compound ( g) and the carboxylic acid ester processing aid (f) may be blended together.
- the total amount of the dialkylsulfone compound (g) and the carboxylic acid ester-based processing aid (f) to be blended is preferably 3 parts by mass or less with respect to 100 parts by mass of the polyol-crosslinkable fluororubber.
- the fluororubber cross-linking composition may optionally contain conventional additives blended in the fluororubber cross-linking composition, such as fillers (carbon black, bituminous coal, barium sulfate, diatomaceous earth, calcined clay, talc, wollastonite, carbon nanotubes, etc.), processing aids (excluding carboxylic acid ester processing aids), colorants, stabilizers, tackifiers (coumarone resin, cumarone/indene resin, etc.), conductivity Various additives such as property imparting agents, thermal conductivity imparting agents, surface non-adhesive agents, flexibility imparting agents, heat resistance improving agents, flame retardants, foaming agents, and antioxidants described in WO 2012/023485. One or more commonly used cross-linking agents and cross-linking accelerators different from those described above may be blended.
- fillers carbon black, bituminous coal, barium sulfate, diatomaceous earth, calcined clay, talc, wo
- carbon black thermal carbon black and furnace carbon black are preferred, and MT carbon black, FT carbon black and SRF carbon black are more preferred.
- carbon black or carbon black with a relatively large particle size such as FT carbon black is blended, a molded product with excellent compression set properties can be obtained, and when blended with carbon black with a fine particle size, molded products with excellent strength and elongation can be obtained. is obtained.
- the above properties can be balanced.
- Barium sulfate and wollastonite are preferable as fillers other than carbon black.
- Processing aids include, but are not limited to, plasticizers and mold release agents, for example, aliphatic amines such as stearylamine, fatty acid amides such as stearic acid amide, Fatty alcohols, synthetic waxes such as polyethylene wax, phosphate esters such as tricresyl phosphate, silicone-based processing aids, etc. may be blended. Good balance between mold releasability and physical properties of molded products.
- Processing aids may be blended within a range that does not impair the effects of the present disclosure.
- the content of the filler such as carbon black is not particularly limited, but it is preferably 0 to 300 parts by mass, and 1 to 150 parts by mass with respect to 100 parts by mass of the polyol-crosslinkable fluororubber. More preferably 2 to 100 parts by mass, particularly preferably 2 to 75 parts by mass.
- the fluororubber cross-linking composition comprises a fluororubber (a), a cross-linking agent (b), a cross-linking accelerator (c), an alkaline earth metal oxide (d), an acid acceptor (e), and a carboxylic acid ester-based processing It can be obtained by kneading auxiliary agent (f), dialkylsulfone compound (g), other component (h) and the like using a generally used rubber kneading device.
- a rubber kneading device rolls, kneaders, Banbury mixers, internal mixers, twin-screw extruders and the like can be used.
- the fluororubber (a), the cross-linking agent (b) and the cross-linking accelerator (c) are mixed at 100 to 200°C using a closed kneading device such as a kneader.
- a closed kneading device such as a kneader.
- a method of kneading (h) etc. at a relatively low temperature below this may also be used.
- the fluororubber (a), the cross-linking agent (b), the cross-linking accelerator (c), and the dialkylsulfone compound (g) are mixed in a closed type mixer such as a kneader. After kneading while melting at a high temperature of 100 to 200 ° C. using a kneading device, alkaline earth metal oxide (d), acid acceptor (e), carboxylic acid ester processing aid (f), dialkyl A method of kneading the sulfone compound (g) or the like at a relatively low temperature below this may also be used.
- fluororubber (a), cross-linking agent (b), cross-linking accelerator (c), alkaline earth metal oxide (d), acid acceptor (e), carboxylic acid ester processing aid (f),
- the dispersibility can be further enhanced by kneading the dialkylsulfone compound (g), the other component (h), etc., and then kneading the mixture again after leaving the mixture at room temperature for 12 hours or more.
- the molded article of the present disclosure can be obtained by cross-linking the fluorororubber cross-linking composition.
- the molded article of the present disclosure can also be obtained by molding the fluororubber cross-linking composition and cross-linking it.
- the fluororubber cross-linking composition can be molded by a conventionally known method.
- the method and conditions for molding and crosslinking may be within the range of known methods and conditions for molding and crosslinking to be employed.
- the order of molding and crosslinking is not limited, and crosslinking may be performed after molding, molding may be performed after crosslinking, or molding and crosslinking may be performed simultaneously.
- molding methods include compression molding, injection molding, injection molding, extrusion molding, and molding using a roto-curing method, but are not limited to these.
- a steam cross-linking method, a cross-linking method by heating, a radiation cross-linking method, or the like can be employed.
- the steam cross-linking method and the cross-linking method by heat are preferable.
- Specific cross-linking conditions that are not limited generally include a cross-linking agent (b), a cross-linking accelerator (c), and alkaline earth metal oxidation within a temperature range of 140 to 250° C. and a cross-linking time of 1 minute to 24 hours. (d), acid acceptor (e), carboxylic acid ester processing aid (f), and dialkylsulfone compound (g).
- Specific cross-linking conditions that are not limited generally include a cross-linking agent (b), a cross-linking accelerator (c), and an alkaline earth metal oxide ( d), the acid acceptor (e), the carboxylic acid ester processing aid (f), and the dialkylsulfone compound (g).
- the molded article of the present disclosure is excellent in various properties such as heat resistance, oil resistance, chemical resistance, and flexibility, and is also excellent in compression set properties at high temperatures. Therefore, the molded article of the present disclosure is generally used for parts intended to slide in contact with other materials, seal and seal other materials and substances, and be used for vibration and sound insulation. , as various parts in various fields such as the semiconductor industry. In particular, the molded article of the present disclosure is excellent in compression set properties at high temperatures, so it can be suitably used as a sealing material.
- Fields of use include, for example, the semiconductor-related field, the automobile field, the aircraft field, the space and rocket field, the ship field, the chemical field such as chemical plants, the chemical field such as pharmaceuticals, the photographic field such as developing machines, and the printing machine.
- printing field such as coating equipment, analysis/physical and chemical machinery field such as analytical instruments and instruments, food equipment field including food plant equipment and household goods, beverage and food manufacturing equipment field, pharmaceutical manufacturing equipment field, medical parts field, Chemical transportation equipment field, nuclear power plant equipment field, iron and steel field such as iron plate processing equipment, general industry field, electrical field, fuel cell field, electronic parts field, optical equipment parts field, space equipment parts field, petrochemical plant equipment fields, oil, gas and other energy resource exploration and mining equipment parts fields, petroleum refining fields, petroleum transportation equipment parts fields, and the like.
- Usage forms of molded products include, for example, rings, packings, gaskets, diaphragms, oil seals, bearing seals, lip seals, plunger seals, door seals, lip and face seals, gas delivery plate seals, wafer support seals, barrel seals, etc. and various sealing materials and packings.
- a sealing material it can be used in applications requiring heat resistance, solvent resistance, chemical resistance, and non-adhesiveness.
- tubes hoses, rolls, various rubber rolls, flexible joints, rubber plates, coatings, belts, dampers, valves, valve seats, valve bodies, chemical-resistant coating materials, laminating materials, lining materials, etc. can.
- the cross-sectional shapes of the rings, packings, and seals may be of various shapes. , T-shaped, V-shaped, X-shaped, and Y-shaped.
- semiconductor manufacturing equipment liquid crystal panel manufacturing equipment, plasma panel manufacturing equipment, plasma display panel manufacturing equipment, plasma addressed liquid crystal panel manufacturing equipment, organic EL panel manufacturing equipment, field emission display panel manufacturing equipment, solar It can be used for battery substrate manufacturing equipment, semiconductor transport equipment, and the like.
- examples of such devices include CVD devices, gas control devices such as gas control devices for semiconductors, dry etching devices, wet etching devices, plasma etching devices, reactive ion etching devices, reactive ion beam etching devices, and sputter etching devices.
- Specific usages in the semiconductor-related field include, for example, gate valves, quartz windows, chambers, chamber lits, gates, bell jars, couplings, O-rings for pumps, gaskets and other sealing materials; resist developer and stripping.
- sealing materials such as O-rings for liquids, hoses and tubes; linings and coatings for resist developer tanks, stripping liquid tanks, wafer cleaning liquid tanks, and wet etching tanks; pump diaphragms; wafer transport rolls; wafer cleaning liquids hose tubes; sealing materials for clean facilities such as sealants for clean facilities such as clean rooms; sealing materials for storages that store devices such as semiconductor manufacturing equipment and wafers; mentioned.
- the engine body main motion system, valve train system, lubrication / cooling system, fuel system, intake / exhaust system, drive system transmission system, chassis steering system, brake system, basic electrical parts, control It can be used for electrical components such as system electrical components and equipment electrical components.
- the automobile field also includes motorcycles.
- molded products can be used for various sealing materials that require heat resistance, oil resistance, fuel oil resistance, engine cooling antifreeze resistance, and steam resistance.
- sealing materials include seals such as gaskets, shaft seals, and valve stem seals; non-contact or contact type packings such as self-seal packings, piston rings, split ring packings, mechanical seals, and oil seals;
- seals such as gaskets, shaft seals, and valve stem seals
- non-contact or contact type packings such as self-seal packings, piston rings, split ring packings, mechanical seals, and oil seals
- electric wires, cushioning materials, anti-vibration materials, various sealing materials used in belt AT devices, and the like can be used.
- Specific usage patterns in the above brake system include masterbacks, hydraulic brake hoses, air brakes, diaphragms used in brake chambers of air brakes, etc.; hoses used in brake hoses, brake oil hoses, vacuum brake hoses, etc.; oil seals. , O-rings, packings, brake piston seals, etc.; atmospheric valves and vacuum valves for masterbacks, check valves for brake valves; piston cups (rubber cups) and brake cups for master cylinders; hydraulic brakes master cylinders and vacuum boosters, boots for hydraulic brake wheel cylinders, O-rings and grommets for anti-lock braking systems (ABS).
- ABS anti-lock braking systems
- Specific usage patterns in control system electrical components include coating materials for various sensor wires.
- Specific usages in the intake/exhaust system include packing used for intake manifolds, exhaust manifolds, etc., throttle body packing for throttles; EGR (exhaust gas recirculation), pressure control (BPT), waste gate, turbo waist Diaphragms used for gates, actuators, variable turbine geometry (VTG) turbo actuators, exhaust purification valves, etc.; EGR (exhaust gas recirculation) control hoses, emission control hoses, turbocharger turbo oil hoses (supply), turbos Oil hose (return), turbo air hose, intercooler hose, turbocharger hose, hose connected to compressor of turbo engine with intercooler, exhaust gas hose, air intake hose, turbo hose, DPF (Diesel Particulate Filter) sensor hose air ducts and turbo air ducts; intake manifold gaskets; EGR sealing materials, afterburn prevention valve seats for AB valves, turbine shaft seals (for turbochargers, etc.), and rocker covers and air intakes used
- seals used for steam recovery canisters, catalytic converters, exhaust gas sensors, oxygen sensors, etc., solenoid armature seals for steam recovery and steam canisters, intake system manifold gaskets, etc. can be done.
- O-ring seals for direct injectors, rotary pump seals, control diaphragms, fuel hoses, EGR, priming pumps, boost compensator diaphragms, etc. It can also be used for O-rings, sealing materials, hoses, tubes, diaphragms, gasket materials, pipes used in urea SCR systems, urea water tank bodies of urea SCR systems, and seal materials for urea water tanks. .
- transmission-related bearing seals examples include transmission-related bearing seals, oil seals, O-rings, packings, torque converter hoses, and the like.
- Transmission oil seals, AT transmission oil hoses, ATF hoses, O-rings, packings, etc. can also be mentioned.
- Transmissions include AT (automatic transmission), MT (manual transmission), CVT (continuously variable transmission), and DCT (dual clutch transmission).
- oil seals, gaskets, O-rings and packings for manual and automatic transmissions oil seals, gaskets, O-rings and packings for continuously variable transmissions (belt type or toroidal type), ATF linear solenoids , oil hoses for manual transmissions, ATF hoses for automatic transmissions, and CVTF hoses for continuously variable transmissions (belt type or toroidal type).
- Specific uses in the steering system include power steering oil hoses and high pressure power steering hoses.
- Forms used in the engine body of automobile engines include, for example, gaskets such as cylinder head gaskets, cylinder head cover gaskets, oil pan packings, general gaskets, O-rings, packings, seals such as timing belt cover gaskets, control hoses, etc.
- Gaskets such as cylinder head gaskets, cylinder head cover gaskets, oil pan packings, general gaskets, O-rings, packings, seals such as timing belt cover gaskets, control hoses, etc.
- Hoses anti-vibration rubber for engine mounts, control valve diaphragms, camshaft oil seals, etc.
- shaft seals such as crankshaft seals and camshaft seals.
- valve system of automobile engines it can be used for engine valve stem oil seals, butterfly valve valve seats, etc.
- radiator hoses In the lubrication and cooling system of automobile engines, engine oil cooler hoses, oil return hoses, seal gaskets for engine oil coolers, water hoses around radiators, radiator seals, radiator gaskets, radiator O-rings, vacuum pumps In addition to vacuum pump oil hoses, it can be used for radiator hoses, radiator tanks, oil pressure diaphragms, fan coupling seals, etc.
- P. S. diaphragms and O-rings gasoline pressure release valves, engine cylinder sleeve O-rings and gaskets, wet cylinder sleeve O-rings and gaskets, differential gear seals and gaskets (gear oil seals and gaskets), power steering devices seals and gaskets (PSF seals and gaskets), shock absorber seals and gaskets (SAF seals and gaskets), constant velocity joint seals and gaskets, wheel bearing seals and gaskets, coating agents for metal gaskets, caliper seals, Boots, wheel bearing seals, bladders used in tire vulcanization molding, etc.
- lip seals for example, lip seals, diaphragms, O-rings for spacecraft, jet engines, missiles, etc., O-rings for gas-resistant turbine engine oil, anti-vibration pads for missile ground control, etc. can be used.
- the field of photography such as the developing machine
- the field of printing such as printing machines
- the field of coating such as coating equipment
- it can be used as rolls, belts, seals, valve parts, etc. of dry copying machines.
- Specific usages in the fields of photography, printing and coating include the surface layer of transfer rolls of copying machines, cleaning blades of copying machines, belts of copying machines; Rolls (for example, fixing rolls, pressing rolls, pressure rolls, etc.), belts; rolls, roll blades, belts of PPC copiers; rolls of film developing machines and X-ray film developing machines; printing rolls of printing machines , scrapers, tubes, valve parts, belts; ink tubes, rolls, belts for printers; coating rolls, scrapers, tubes, valve parts for coating equipment; developing rolls, gravure rolls, guide rolls, magnetic tape manufacturing coating lines Examples include guide rolls, gravure rolls for magnetic tape manufacturing and coating lines, and coating rolls.
- Specific usages in the food equipment field include plate heat exchanger seals, vending machine solenoid valve seals, jar pot packing, sanitary pipe packing, pressure cooker packing, water heater seals, and heat exchange.
- Delicate gaskets, diaphragms and packings for food processing equipment, rubber materials for food processing equipment for example, heat exchanger gaskets, diaphragms, various seals such as O-rings, piping, hoses, sanitary packing, valve packing, filling packing used as a joint between the mouth of a bottle and the filler), and the like.
- packings, gaskets, tubes, diaphragms, hoses, and joint sleeves used in products such as alcoholic beverages and soft drinks, filling equipment, food sterilizers, brewing equipment, water heaters, and various automatic food vending machines.
- Specific usages in the above general industrial fields include sealing materials for hydraulic equipment such as machine tools, construction machinery, and hydraulic machinery; seals and bearing seals for hydraulic and lubricating machinery; sealing materials used for mandrels, etc.; dry cleaning equipment.
- Gaskets and sealing materials for equipment used in the papermaking process sealing agents for clean room filter units, building sealing agents, protective coating agents for concrete and cement, glass cloth impregnation materials, processing aids for polyolefin, and molding of polyethylene. It can also be used as a property-improving additive, a fuel container for small generators and lawn mowers, and a pre-coated metal obtained by applying a primer treatment to a metal plate. In addition, it can also be used as a sheet or belt by impregnating a woven fabric and baking it.
- Specific usage patterns in the steel field include iron plate processing rolls for iron plate processing equipment.
- Specific uses in the electrical field include insulating oil caps for bullet trains, venting seals for liquid-sealed transformers, seals for transformers, jackets for oil well cables, seals for ovens such as electric furnaces, and window frames for microwave ovens. Seals, sealing materials used to bond wedges and necks of CRTs, sealing materials for halogen lamps, fixing agents for electrical parts, sealing materials for terminal treatment of sheathed heaters, insulation and moisture-proofing of lead wire terminals of electrical equipment. and sealing materials that can be used.
- oil-resistant/heat-resistant wires can be used as a coating material for oil-resistant/heat-resistant wires, highly heat-resistant wires, chemical-resistant wires, highly insulated wires, high-voltage transmission wires, cables, wires used in geothermal power generation equipment, wires used around automobile engines, etc. can also It can also be used for oil seals and shaft seals for vehicle cables.
- electrical insulating materials for example, insulating spacers for various electrical equipment, insulating tapes used for cable joints and ends, materials used for heat-shrinkable tubes, etc.
- electrical and It can also be used for electronic device materials (for example, lead wire materials for motors, wire materials around high-temperature furnaces). It can also be used as a sealing layer or protective film (back sheet) for solar cells.
- sealing materials between electrodes and between electrodes and separators sealing materials for piping such as hydrogen, oxygen, and generated water, packing, separators and so on.
- Hard disk drive buffer rubber (crash stopper), electrode active material binder for nickel metal hydride secondary batteries, lithium ion battery active material binder, lithium secondary battery polymer electrolyte, alkaline storage battery positive electrode binder, Binders for EL elements (electroluminescence elements), binders for electrode active materials in capacitors, sealants, sealants, quartz coating materials for optical fibers, films and sheets such as optical fiber coating materials, CMOS electronic circuits, transistors, integration Circuits, organic transistors, light-emitting elements, actuators, memories, sensors, coils, capacitors, electronic parts such as resistors, potting, coating and adhesive seals for circuit boards, fixing agents for electronic parts, modifiers for sealants such as epoxy, Coating agents for printed circuit boards, modifiers for printed wiring board prepreg resins such as epoxy,
- Specific usage forms in the field of energy resource exploration and mining equipment parts include drill bit seals, pressure adjustment diaphragms, horizontal drilling motor (stator) seals, stator bearing (shaft) seals, blowout prevention devices (BOP). sealing materials used for rotating blowout prevention devices (pipe wipers), sealing materials and gas-liquid connectors used for MWD (real-time drilling information detection system), logging equipment (logging equipment) Tool seals (e.g., O-rings, seals, packing, air-liquid connectors, boots, etc.), expansion packers and completion packers and packer seals used for them, seals and packings used in cementing equipment, perforators (drilling equipment) ), seals and packings used in mud pumps, motor linings, ground hearing detector covers, U-cups, composition seating cups, rotary seals, laminated elastomeric bearings, flow control seals, sand volume control Seals, safety valve seals, fracturing equipment seals, linear packer and linear hanger seals and packings,
- joint seals for kitchens, bathrooms, washrooms, etc. cloth for outdoor tents; seals for stamping materials; rubber hoses for gas heat pumps, fluorocarbon-resistant rubber hoses; It can also be used for tanks such as laminated steel plates used in .
- metal such as aluminum
- usage patterns include door seals, gate valves, pendulum valves, solenoid tips, piston seals and diaphragms bonded to metal, and metal rubber parts bonded to metal such as metal gaskets.
- molded products can be applied to belts.
- Power transmission belts including flat belts, V-belts, V-ribbed belts, toothed belts, etc.
- transport belts Conveyor belts
- various high-temperature parts such as around engines of agricultural machinery, machine tools, industrial machinery, etc.
- Conveyor belts for conveying bulk and granular materials such as coal, crushed stone, earth and sand, ores, and wood chips in high-temperature environments;
- Conveyor belts used in steelworks such as blast furnaces;
- Conveyor belts for applications exposed to high temperature environments such as equipment assembly plants and food factories; agricultural machinery, general equipment (e.g. OA equipment, printing machines, commercial dryers, etc.), V belts for automobiles, etc.
- timing belts are representative of toothed belts for automobiles.
- the belt may have a single-layer structure or a multi-layer structure.
- the belt may consist of a layer obtained by cross-linking a fluororubber cross-linking composition and a layer of another material.
- layers made of other materials include layers made of other rubbers, layers made of thermoplastic resin, various fiber reinforcement layers, canvas, metal foil layers, and the like.
- Molded products can also be used for industrial anti-vibration pads, anti-vibration mats, railway slab mats, pads, anti-vibration rubber for automobiles, etc.
- Anti-vibration rubbers for automobiles include anti-vibration rubbers for engine mounts, motor mounts, member mounts, strut mounts, bushes, dampers, muffler hangers, and center bearings.
- joint members such as flexible joints and expansion joints, boots, and grommets.
- marine field for example, marine pumps and the like can be mentioned.
- a joint member is a joint used in piping and piping equipment.It prevents vibration and noise generated from the piping system, absorbs expansion and contraction and displacement due to temperature and pressure changes, absorbs dimensional fluctuations, earthquakes, and ground subsidence. It is used for purposes such as mitigation and prevention of the impact of
- Flexible joints and expansion joints are preferably used as complex-shaped moldings for, for example, shipbuilding piping, mechanical piping such as pumps and compressors, chemical plant piping, electrical piping, civil engineering/water supply piping, and automobiles.
- Boots include, for example, constant velocity joint boots, dust covers, rack-and-pinion steering boots, pin boots, piston boots, etc.
- Boots for automobiles boots for agricultural machinery, boots for industrial vehicles, boots for construction machinery, boots for hydraulic machinery, air It can be preferably used as complex-shaped moldings such as various industrial boots such as compression machine boots, centralized lubricator boots, liquid transfer boots, firefighting boots, and various liquefied gas transfer boots.
- Molded products can also be used for filter press diaphragms, blower diaphragms, water supply diaphragms, liquid storage tank diaphragms, pressure switch diaphragms, accumulator diaphragms, air spring diaphragms for suspensions, etc.
- the molded product can also be used as a cushioning material for heat press molding when manufacturing decorative plywood, printed circuit boards, electrical insulating boards, rigid polyvinyl chloride laminates, etc., using melamine resin, phenolic resin, epoxy resin, etc. can be done.
- Molded articles can also contribute to the impermeability of various supports such as weapons-related sealing gaskets and protective clothing against contact with aggressive chemical agents.
- lubricating oils engine oil, transmission oil, gear oil, etc.
- amine additives especially amine additives used as antioxidants and detergent dispersants
- O square-rings, V-rings, X-rings, packings, gaskets, diaphragms, oil seals, bearing seals, lip seals used for sealing and sealing oil, fuel oil, and grease (especially urea-based grease)
- plunger seals door seals, lip and face seals
- gas delivery plate seals wafer support seals
- barrel seals and other various sealing materials tubes, hoses, various rubber rolls, coatings, belts, and valve bodies of valves. etc.
- It can also be used as a laminate material and a lining material.
- examples of fuels related to automobiles include light oil, gasoline, and fuels for diesel engines (including biodiesel fuel).
- the molded product can also be used as a sealing member for rolling bearings.
- the above rolling bearings include ball bearings, roller bearings, bearing units, linear bearings, and the like.
- Ball bearings include radial ball bearings, thrust ball bearings, and thrust angular ball bearings.
- Examples of the radial ball bearings include deep groove ball bearings, angular contact ball bearings, four-point contact ball bearings, and self-aligning ball bearings.
- the above deep groove ball bearings are used, for example, in electric motors, household electrical appliances, OA equipment, and the like.
- the angular contact ball bearings include single-row angular contact ball bearings, paired angular contact ball bearings, double-row angular contact ball bearings, and the like. It is also used for hydraulic pumps and vertical pumps that are subject to axial loads. Hybrid angular contact ball bearings are used for spindles of machine tools, grinding spindles, etc., where improved rotational accuracy and increased rigidity are required. Double-row angular contact ball bearings are used in electromagnetic clutches for automotive air conditioners and the like.
- the above four-point contact ball bearings are used in speed reducers, etc. where axial loads are applied from both directions and a large space for the bearing width cannot be secured.
- the above thrust ball bearings include single thrust ball bearings and double thrust ball bearings, and can be applied to conventionally known applications in which these ball bearings are used.
- the above thrust angular contact ball bearing is used in combination with a double-row cylindrical roller bearing as an axial load receiver for the main shaft of machine tools.
- roller bearings examples include radial roller bearings and thrust roller bearings.
- the above radial roller bearings include cylindrical roller bearings, needle roller bearings, tapered roller bearings, and self-aligning roller bearings.
- the above cylindrical roller bearings are used in general machines, machine tools, electric motors, reduction gears, railway axles, aircraft, etc.
- Needle roller bearings are used in general machinery, automobiles, electric motors, etc.
- Tapered roller bearings are used in machine tools, automobile and railway axles, rolling mills, reduction gears, etc.
- Spherical roller bearings are used in general machinery, rolling mills, paper manufacturing machinery, axles, etc.
- thrust roller bearing examples include a thrust cylindrical roller bearing, a thrust needle roller bearing, a thrust tapered roller bearing, a thrust self-aligning roller bearing, and the like.
- Thrust cylindrical roller bearings are used in machine tools, general machinery, etc.
- Thrust needle roller bearings are used in automobiles, pumps, general machinery, etc.
- Thrust tapered roller bearings are used in general machinery, rolling mills, etc.
- Thrust self-aligning roller bearings are used in cranes, extruders, general machinery, etc.
- the fluororubber cross-linking composition can be used as various parts in various industrial fields in addition to being cross-linked and used as molded articles. Next, the use of the fluororubber cross-linking composition will be described.
- Fluorororubber cross-linking compositions are used as surface modifiers for metals, rubbers, plastics, glass, etc.; sealing materials and coatings that require heat resistance, chemical resistance, oil resistance, and non-adhesiveness, such as metal gaskets and oil seals.
- Non-adhesive coating materials such as rolls for OA equipment and belts for OA equipment, or bleed barriers; can be used for impregnation on woven fabric sheets and belts, application by baking, and the like.
- the fluororubber cross-linking composition By increasing the viscosity and concentration of the fluororubber cross-linking composition, it can be used as sealing materials, linings, and sealants of complicated shapes in the usual way. It can also be used for coating pre-coated metals, O-rings, diaphragms and reed valves by making it medium viscosity.
- Article substrates to be coated with a fluororubber cross-linking composition include metals such as iron, stainless steel, copper, aluminum, and brass; glass products such as glass plates, glass fiber woven fabrics and non-woven fabrics; polypropylene and polyoxymethylene. , polyimide, polyamideimide, polysulfone, polyethersulfone, polyetheretherketone, etc. General-purpose and heat-resistant resin moldings and coatings; General-purpose rubbers such as SBR, butyl rubber, NBR, EPDM, silicone rubbers, fluorine rubbers, etc. woven and non-woven fabrics of natural and synthetic fibers; and the like.
- Coatings formed from the fluororubber cross-linking composition can be used in fields requiring heat resistance, solvent resistance, lubricity, and non-adhesiveness.
- rolls e.g., fuser rolls, crimp rolls
- conveyor belts for OA equipment; sheets and belts; O-rings, diaphragms, chemical resistant tubes, fuel hoses, valve seals, chemical plant gaskets, engine gaskets, etc. be done.
- the fluororubber cross-linking composition can also be dissolved in a solvent and used as a paint or adhesive. It can also be used as a paint as an emulsified dispersion (latex).
- Fluorororubber cross-linking compositions are used for various devices, sealing materials and linings for piping, metals, ceramics, glass, stone, concrete, plastics, rubber, wood, paper, fibers, and other inorganic and organic base materials. It is used as a surface treatment agent.
- the fluororubber cross-linking composition can be applied to the substrate or the like by dispenser coating or screen printing coating.
- the fluoroelastomer cross-linking composition may be used as a coating composition for casting films or for impregnating substrates such as fabrics, plastics, metals, or elastomers.
- the fluoroelastomer cross-linking composition in the form of latex, is used in coated fabrics, protective gloves, impregnated fibers, O-ring coatings, fuel system quick connect O-ring coatings, fuel system sealing coatings, fuel tank rollover valves.
- silicone rubber, nitrile rubber, and other elastomers are useful for coating silicone rubber, nitrile rubber, and other elastomers. They are also useful in coating parts made from such elastomers for the purpose of enhancing both the permeation and chemical resistance of the base elastomer as well as its thermal stability. Other applications include coatings for heat exchangers, expansion joints, vats, tanks, fans, flue ducts and other conduits, and containment structures such as concrete containment structures.
- the fluoroelastomer cross-linking composition may be applied to exposed cross-sections of multi-layer component structures, for example, in hose structures and diaphragm manufacturing processes.
- Sealing members at connections and joints often consist of hard materials, and fluoroelastomer crosslinking compositions provide improved frictional interfaces, increased dimensional tightness with reduced microleakage along the sealing surfaces. Provide a fit.
- the latex enhances seal durability in various automotive system applications.
- fluoroelastomer cross-linking compositions can also be used in the manufacture of power steering systems, fuel systems, air conditioning systems, and any joint where hoses and tubes are connected to another component.
- a further utility of fluoroelastomer cross-linking compositions is in repairing manufacturing defects (and damage due to use) in multi-layer rubber constructions such as tri-layer fuel hoses.
- the fluoroelastomer cross-linking composition is also useful for coating thin steel sheets that may be formed or embossed before or after the coating is applied. For example, multiple layers of coated steel can be assembled to create a gasket between two rigid metal members. A sealing effect is obtained by applying a fluororubber cross-linking composition between the layers. This process reduces bolt force and strain in the assembled parts, while engine head gaskets and exhaust manifold gaskets for the purpose of providing good fuel economy and low emissions due to low cracking, deflection, and hole strain. can be used to manufacture
- the fluororubber cross-linking composition is used as a coating agent; base-integrated gaskets and packings formed by dispenser molding on a base material containing inorganic materials such as metals and ceramics; base materials containing inorganic materials such as metals and ceramics. It can also be used as a multilayer product etc. coated with.
- the fluororubber cross-linking composition is also suitable as a light and bendable wiring material for electronic devices, and can be used for known electronic components.
- Electronic components such as CMOS electronic circuits, transistors, integrated circuits, organic transistors, light-emitting elements, actuators, memories, sensors, coils, capacitors, and resistors.
- Flexible electronic devices such as solar cells, various displays, sensors, actuators, electronic artificial skin, sheet-type scanners, braille displays, and wireless power transmission sheets can be obtained by using this material.
- Tg Glass transition temperature
- Fluororubber A Vinylidene fluoride/hexafluoropropylene molar ratio: 78/22 Fluorine content: 66% Mooney viscosity (ML1 + 10 (121 ° C)): 43 Glass transition temperature: -18°C Heat of fusion: Not observed in second run Acid value: 0.15 KOHmg/g Fluororubber B: Vinylidene fluoride/hexafluoropropylene molar ratio: 78/22 Fluorine content: 66% Mooney viscosity (ML1 + 10 (121 ° C)): 98 Glass transition temperature: -18°C Heat of fusion: Not observed in second run Acid value: 0.56 KOHmg/g Fluororubber C: Vinylidene fluoride/hexafluoropropylene molar ratio: 78/22 Fluorine content: 66% Mooney viscosity (ML1 + 10 (121 ° C)): 20 Glass transition temperature:
- Sulfolane cross-linking accelerator A a mixture of 91% by mass of benzyldimethyloctadecylammonium chloride and 9% by mass of isopropyl alcohol
- Cross-linking accelerator B benzyltriphenylphosphonium chloride
- Cross-linking agent -A 4,4'-biphenol cross-linking agent -B: 2,6-dihydroxyanthraquinone cross-linking agent -C: hydroquinone cross-linking agent -D: bisphenol A
- Crosslinker-E 2-methylresorcinol crosslinker-F: 1,5-dihydroxyanthraquinone crosslinker-G: 1,4-dihydroxyanthraquinone crosslinker-H: 1,8-dihydroxyanthraquinone crosslinker-I: 4,4 '-dihydroxydiphenyl ether cross-linking agent -J: bis (4-hydroxyphenyl) sulfone cross-linking agent -K: 4,4'-dihydroxybenzophenone processing aid -A: carnauba wax (carboxylic acid ester-based processing aid) Processing aid-B: stearyl stearate (carboxylic acid ester-based processing aid) Processing aid -C: stearyl
- Examples 1-18 and Comparative Examples 1-9 Each component was blended according to the recipes in Tables 1 to 4 and kneaded on an open roll to prepare a fluororubber cross-linking composition.
- Tables 1 to 4 show the maximum torque (MH) and optimum cross-linking time (T90) of the obtained fluororubber cross-linking composition.
- the fluororubber cross-linking composition is cross-linked by primary cross-linking (press cross-linking) under the conditions described in Tables 1 to 4 and secondary cross-linking (oven cross-linking) at 230 ° C. for 24 hours to form a cross-linked sheet (thickness 2 mm) and small specimens for compression set measurements were obtained.
- Tables 1 to 4 show the evaluation results and compression set test results of the obtained crosslinked sheets.
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Abstract
Description
本開示のフッ素ゴム架橋用組成物において、架橋剤(b)の含有量が、フッ素ゴム(a)100質量部に対し、1.0~50mmolであることが好ましい。
本開示のフッ素ゴム架橋用組成物は、架橋促進剤(c)をさらに含有することが好ましい。
本開示のフッ素ゴム架橋用組成物は、アルカリ土類金属の酸化物(d)をさらに含有することが好ましい。
本開示のフッ素ゴム架橋用組成物は、受酸剤(e)をさらに含有することが好ましい。
本開示のフッ素ゴム架橋用組成物は、金属酸化物(ただし、アルカリ土類金属の酸化物を除く)、金属水酸化物、アルカリ金属ケイ酸塩、弱酸の金属塩およびハイドロタルサイトからなる群より選択される少なくとも1種の受酸剤(e)をさらに含有することが好ましい。
本開示のフッ素ゴム架橋用組成物は、フッ素ゴム(a)100質量部に対して、1~10質量部のハイドロタルサイトおよび2.5~8質量部の酸化マグネシウムをさらに含有することが好ましい。
本開示のフッ素ゴム架橋用組成物は、水酸化カルシウムを含まないことが好ましい。
本開示のフッ素ゴム架橋用組成物は、カルボン酸エステル系加工助剤(f)をさらに含有することが好ましい。
本開示のフッ素ゴム架橋用組成物は、ジアルキルスルホン化合物(g)を含有することが好ましい。
本開示のフッ素ゴム架橋用組成物において、架橋剤(b)が、4,4’-ビフェノール、2,6-ジヒドロキシアントラキノン、2,7-ジヒドロキシアントラキノン、および、これらの化合物のいずれかと、アルカリ金属、アルカリ土類金属またはオニウム化合物との塩からなる群より選択される少なくとも1種であることが好ましい。
本開示で用いるポリオール架橋可能なフッ素ゴムは、ポリオール架橋可能な部位を有するフッ素ゴムである。本開示において、フッ素ゴムとは、非晶質フルオロポリマーである。「非晶質」とは、フルオロポリマーの示差走査熱量測定〔DSC〕(昇温速度20℃/分)あるいは示差熱分析〔DTA〕(昇温速度20℃/分)において現われた融解ピーク(ΔH)の大きさが4.5J/g以下であることをいう。フッ素ゴムは、架橋することにより、エラストマー特性を示す。エラストマー特性とは、ポリマーを延伸することができ、ポリマーを延伸するのに必要とされる力がもはや適用されなくなったときに、その元の長さを保持できる特性を意味する。
特開2003-277563号公報に記載の極性末端基が実質的にないフッ化ビニリデン(VDF)系フルオロエラストマー、
特表2018-527449号公報に記載のフッ化ビニリデン(VDF)に由来する繰り返し単位および少なくとも1種の追加の(ペル)フッ素化モノマーに由来する繰り返し単位を含むフッ化ビニリデンベースフルオロエラストマー、
特開平7-316377号公報に記載の67重量%未満の少量のフッ素を有し、40から68重量%のフッ化ビニリデン(VDF)単位と、20から50重量%のヘキサフルオロプロピレン(HFP)単位とを、合計で100になるように含有し、任意に、不飽和エチレンを有する1つまたはそれ以上のコモノマー類を含有してなる100部(phr)の硬化フルオロエラストマー
などであってよい。
(式中、構造単位M1はビニリデンフルオライド(m1)由来の構造単位であり、構造単位M2は含フッ素エチレン性単量体(m2)由来の構造単位であり、構造単位N1は単量体(m1)および単量体(m2)と共重合可能な単量体(n1)由来の繰り返し単位である)
CF2=CFO(Rf1O)q(Rf2O)rRf3 (2)
(式中、Rf1およびRf2はそれぞれ独立に炭素数1~6の直鎖または分岐したパーフルオロアルキレン基、Rf3は炭素数1~6の直鎖または分岐したパーフルオロアルキル基、qおよびrはそれぞれ独立に0~6の整数(ただし0<q+r≦6を満たす)である)で表される含フッ素単量体、一般式(3):
CHX11=CX12Rf4 (3)
(式中、X11およびX12は、一方がHであり、他方がFであり、Rf4は炭素数1~12の直鎖または分岐したフルオロアルキル基である)で表される含フッ素単量体、フッ化ビニルなどの含フッ素単量体があげられるが、これらのなかでも、TFE、HFP、PAVEが好ましい。
CY1 2=CY1-Rf5CHR1X1 (4)
(式中、Y1は、独立に、水素原子、フッ素原子または-CH3、Rf5は、フルオロアルキレン基、パーフルオロアルキレン基、フルオロポリオキシアルキレン基またはパーフルオロポリオキシアルキレン基、R1は、水素原子または-CH3、X1は、ヨウ素原子または臭素原子)で表されるヨウ素または臭素含有単量体、一般式(5):
CF2=CFO(CF2CF(CF3)O)m(CF2)n-X2 (5)
(式中、mは、0~5の整数、nは、1~3の整数、X2は、シアノ基、カルボキシル基、アルコキシカルボニル基、臭素原子、ヨウ素原子)で表される単量体、一般式(6):
CH2=CH(CF2)pI (6)
(式中、pは1~10の整数)で表される単量体などがあげられ、たとえば特公平5-63482号公報、特開平7-316234号公報に記載されているようなパーフルオロ(6,6-ジヒドロ-6-ヨード-3-オキサ-1-ヘキセン)やパーフルオロ(5-ヨード-3-オキサ-1-ペンテン)などのヨウ素含有単量体、特開平4-217936号公報記載のCF2=CFOCF2CF2CH2Iなどのヨウ素含有単量体、特開昭61-55138号公報に記載されている4-ヨード-3,3,4,4-テトラフルオロ-1-ブテンなどのヨウ素含有単量体、特開平4-505341号公報に記載されている臭素含有単量体、特開平4-505345号公報、特開平5-500070号公報に記載されているようなシアノ基含有単量体、カルボキシル基含有単量体、アルコキシカルボニル基含有単量体などがあげられる。これらをそれぞれ単独で、または任意に組合わせて用いることができる。
またビスオレフィン化合物としては特開平8-12726号公報に記載されたものを用いることができる。
本開示のフッ素ゴム架橋用組成物は、架橋剤を含有する。架橋剤は、下記一般式(b1)で示される化合物、下記一般式(b2)で示される化合物、これらの化合物のいずれかとアルカリ金属との塩、これらの化合物のいずれかとアルカリ土類金属との塩、および、これらの化合物のいずれかとオニウム化合物との塩からなる群より選択される少なくとも1種である。
本開示のフッ素ゴム架橋用組成物は、架橋促進剤をさらに含有することができる。架橋促進剤を用いると、フッ素ゴム主鎖の脱フッ酸反応における分子内二重結合の形成を促進することにより架橋反応を促進することができる。架橋剤として、一般式(b1)で示される化合物、または、一般式(b2)で示される化合物を用いる場合には、架橋促進剤を架橋剤とともに用いることが好ましい。架橋剤としてオニウム塩を用いる場合でも、架橋促進剤を架橋剤とともに用いることができるが、必ずしも用いる必要はない。架橋条件や成形品の物性により適宜架橋促進剤の量を調整することができる。架橋促進剤を増量すれば、架橋反応は早くなり、またはより低温で架橋できるようになるが、圧縮永久歪み特性は悪化する傾向にある。逆に架橋促進剤を減量すれば架橋反応は遅くなるが、圧縮永久歪み特性は良くなる傾向にある。
フッ素ゴム架橋用組成物において、アルカリ土類金属の酸化物をさらに含有することが好ましい。
本開示のフッ素ゴム架橋用組成物は、受酸剤をさらに含有してもよい、受酸剤を含有することにより、フッ素ゴム架橋用組成物の架橋反応が一層円滑に進行し、高温での圧縮永久歪み特性が一層向上する。
[(M1 2+)1-xM3+ x(OH)2]x+[An- x/n・mH2O]x-
(式中、M1 2+は2価の金属イオンであり、M3+は3価の金属イオンであり、An-はn価のアニオンであり、xは0<x<0.5を満たす数であり、mは0≦mを満たす数である。)で示される化合物であることが入手容易の点からより好ましい。ハイドロタルサイトとしては、天然品であっても合成品であってもよい。
フッ素ゴム架橋用組成物は、カルボン酸エステル系加工助剤を含んでいてもよい。ビスフェノールAFなどの架橋剤を使用した従来のフッ素ゴム架橋用組成物においては、加工助剤は、混練り時の加工性の向上、または成形時の金型離型性の向上を目的として配合されるが、しばしば架橋反応に影響を与え、得られる成形品の物性、特に高温での圧縮永久歪み性が悪くなる傾向にある。架橋剤(c)を配合する本開示のフッ素ゴム架橋用組成物において、カルボン酸エステル系加工助剤(f)を配合すると、架橋反応に与える影響が小さく、得られる成形品の物性を損なうことなく、混練り時の加工性が向上したり、または成形時の金型離型性が向上したりする。
フッ素ゴム架橋用組成物は、ジアルキルスルホン化合物を含有してもよい。ジアルキルスルホン化合物を含有することにより、フッ素ゴム架橋用組成物の架橋効率が高まったり、架橋速度が速くなったり、圧縮永久歪み特性がより一層向上したり、ゴム生地の流動性が向上する。ジアルキルスルホン化合物(g)としては、ジメチルスルホン、ジエチルスルホン、ジブチルスルホン、メチルエチルスルホン、ジフェニルスルホン、スルホラン等が挙げられる。なかでも、架橋効率および圧縮永久歪み特性の観点、ならびに、沸点が適当であることから、スルホランが好ましい。
フッ素ゴム架橋用組成物は、必要に応じてフッ素ゴム架橋用組成物に配合される通常の添加物、たとえば充填剤(カーボンブラック、瀝青炭、硫酸バリウム、珪藻土、焼成クレー、タルク、ウォラストナイト、カーボンナノチューブ等)、加工助剤(ただし、カルボン酸エステル系加工助剤を除く)、着色剤、安定剤、粘着性付与剤(クマロン樹脂、クマロン・インデン樹脂等)、導電性付与剤、熱伝導性付与剤、表面非粘着剤、柔軟性付与剤、耐熱性改善剤、難燃剤、発泡剤、国際公開第2012/023485号に記載の酸化防止剤などの各種添加剤を配合することができ、前記のものとは異なる常用の架橋剤、架橋促進剤を1種またはそれ以上配合してもよい。
フッ素ゴム架橋用組成物を架橋することにより、本開示の成形品を得ることができる。また、フッ素ゴム架橋用組成物を成形し、架橋することによっても、本開示の成形品を得ることができる。フッ素ゴム架橋用組成物は、従来公知の方法で成形することができる。成形および架橋の方法および条件としては、採用する成形および架橋において公知の方法および条件の範囲内でよい。成形および架橋の順序は限定されず、成形した後架橋してもよいし、架橋した後成形してもよいし、成形と架橋とを同時に行ってもよい。
ブーツは、たとえば、等速ジョイントブーツ、ダストカバー、ラックアンドピニオンステアリングブーツ、ピンブーツ、ピストンブーツなどの自動車用ブーツ、農業機械用ブーツ、産業車両用ブーツ、建築機械用ブーツ、油圧機械用ブーツ、空圧機械用ブーツ、集中潤滑機用ブーツ、液体移送用ブーツ、消防用ブーツ、各種液化ガス移送用ブーツなどの各種産業用ブーツなどの複雑形状成形体として好ましく用いることができる。
19F-NMR(Bruker社製AC300P型)を用いて測定した。
19F-NMRにて測定されたフッ素ゴムの組成から計算によって求めた。
ASTM D1646-15およびJIS K6300-1:2013に準拠して測定した。測定温度は121℃である。
示差走査熱量計(メトラー・トレド社製、DSC822e、もしくは、日立ハイテクサイエンス社製、X-DSC7000)を用い、試料10mgを20℃/分で昇温することによりDSC曲線を得て、DSC曲線の二次転移前後のベースラインの延長線と、DSC曲線の変曲点における接線との交点を示す温度をガラス転移温度とした。
示差走査熱量計(メトラー・トレド社製、DSC822e、もしくは、日立ハイテクサイエンス社製、X-DSC7000)を用い、試料10mgを20℃/分で昇温することによりDSC曲線を得て、DSC曲線において現われた融解ピーク(ΔH)の大きさから融解熱を算出した。
0.1モル/Lの水酸化カリウムエタノール溶液の代わりに、0.01モル/Lの水酸化カリウムエタノール溶液を用いたこと以外はJIS K0070の電位差滴定法に準拠して測定した。
フッ素ゴム架橋用組成物について、一次架橋時に加硫試験機(エムアンドケー社製 MDR H2030)を用いて、表1~4に記載の温度で架橋曲線を求め、トルクの変化より、最大トルク(MH)および最適架橋時間(T90)を求めた。
厚さ2mmの架橋シートを用いて、ダンベル6号形状の試験片を作製した。得られた試験片および引張試験機(エー・アンド・デイ社製テンシロンRTG-1310)を使用して、JIS K6251:2010に準じて、500mm/分の条件下、23℃における100%モジュラス(M100)、引張強さおよび切断時伸びを測定した。
厚さ2mmの架橋シートを3枚重ねて、JIS K6251-3:2012に準じて、デュロメータ硬さ(タイプA、ピーク値、3秒後の値)を測定した。
厚さ2mmの架橋シートを用いて、ダンベル6号形状の試験片を作製した。得られた試験片を275℃で72時間熱処理した後、上記した方法で、熱処理後の試験片の引張強さを測定した。そして、引張強さについて、熱処理前後の測定値の変化率を以下の式に従って算出した。
ΔX=(X-X0)/X0×100
ΔX:変化率(%)
X0:熱処理前の測定値
X:熱処理後の測定値
圧縮永久歪み測定用小形試験片を用いて、JIS K6262:2013のA法に準じて、圧縮率25%、試験温度200℃、試験時間72時間で測定した。
フッ素ゴムA:
フッ化ビニリデン/ヘキサフルオロプロピレンのモル比: 78/22
フッ素含有率:66%
ムーニー粘度(ML1+10(121℃)):43
ガラス転移温度:-18℃
融解熱:セカンドランでは認めず
酸価:0.15KOHmg/g
フッ素ゴムB:
フッ化ビニリデン/ヘキサフルオロプロピレンのモル比:78/22
フッ素含有率:66%
ムーニー粘度(ML1+10(121℃)):98
ガラス転移温度:-18℃
融解熱:セカンドランでは認めず
酸価:0.56KOHmg/g
フッ素ゴムC:
フッ化ビニリデン/ヘキサフルオロプロピレンのモル比:78/22
フッ素含有率:66%
ムーニー粘度(ML1+10(121℃)):20
ガラス転移温度:-18℃
融解熱:セカンドランでは認めず
酸価:0.30KOHmg/g
水酸化カルシウム
酸化マグネシウム
ハイドロタルサイト:DHT-4A(協和化学工業株式会社製)
スルホラン
架橋促進剤A:ベンジルジメチルオクタデシルアンモニウムクロリド91質量%とイソプロピルアルコール9質量%との混合物
架橋促進剤B:ベンジルトリフェニルホスホニウムクロリド
架橋剤-B:2,6-ジヒドロキシアントラキノン
架橋剤-C:ハイドロキノン
架橋剤-D:ビスフェノールA
架橋剤-E:2-メチルレゾルシノール
架橋剤-F:1,5-ジヒドロキシアントラキノン
架橋剤-G:1,4-ジヒドロキシアントラキノン
架橋剤-H:1,8-ジヒドロキシアントラキノン
架橋剤-I:4,4’-ジヒドロキシジフェニルエーテル
架橋剤-J:ビス(4-ヒドロキシフェニル)スルホン
架橋剤-K:4,4’-ジヒドロキシベンゾフェノン
加工助剤-A:カルナバワックス(カルボン酸エステル系加工助剤)
加工助剤-B:ステアリン酸ステアリル(カルボン酸エステル系加工助剤)
加工助剤-C:ステアリルアミン
加工助剤-D:リン酸トリクレジル
表1~4の処方に従ってそれぞれの成分を配合し、オープンロール上で混練りして、フッ素ゴム架橋用組成物を調製した。得られたフッ素ゴム架橋用組成物の最大トルク(MH)および最適架橋時間(T90)を表1~4に示す。次に、表1~4に記載の条件の一次架橋(プレス架橋)、および、230℃で24時間の二次架橋(オーブン架橋)により、フッ素ゴム架橋用組成物を架橋させ、架橋シート(厚さ2mm)および圧縮永久歪み測定用小形試験片を得た。得られた架橋シートの評価結果および圧縮永久ひずみ試験の結果を表1~4に示す。
Claims (14)
- ポリオール架橋可能なフッ素ゴム(a)および架橋剤(b)を含有し、架橋剤(b)が、下記一般式(b1)で示される化合物、下記一般式(b2)で示される化合物、および、これらの化合物のいずれかと、アルカリ金属、アルカリ土類金属またはオニウム化合物との塩からなる群より選択される少なくとも1種であるフッ素ゴム架橋用組成物。
(式中、mおよびnは独立に1~5の整数を表す。2つのベンゼン環に結合する水素原子は、任意の置換基(ただし、ヒドロキシ基、スルファニル基、アミノ基、酸基、ハロゲン原子およびハロゲン原子を含む基を除く)により置換されていてもよい。)
(式中、pは0~3の整数を表し、qは1~4の整数を表す。2つのベンゼン環に結合する水素原子は、任意の置換基(ただし、ヒドロキシ基、スルファニル基、アミノ基、酸基、ハロゲン原子およびハロゲン原子を含む基を除く)により置換されていてもよい。) - フッ素ゴム(a)が、ビニリデンフルオライド単位を含有する請求項1に記載のフッ素ゴム架橋用組成物。
- 架橋剤(b)の含有量が、フッ素ゴム(a)100質量部に対し、1.0~50mmolである請求項1または2に記載のフッ素ゴム架橋用組成物。
- 架橋促進剤(c)をさらに含有する請求項1~3のいずれかに記載のフッ素ゴム架橋用組成物。
- アルカリ土類金属の酸化物(d)をさらに含有する請求項1~4のいずれかに記載のフッ素ゴム架橋用組成物。
- 受酸剤(e)をさらに含有する請求項1~5のいずれかに記載のフッ素ゴム架橋用組成物。
- 金属酸化物(ただし、アルカリ土類金属の酸化物を除く)、金属水酸化物、アルカリ金属ケイ酸塩、弱酸の金属塩およびハイドロタルサイトからなる群より選択される少なくとも1種の受酸剤(d)をさらに含有する請求項1~6のいずれかに記載のフッ素ゴム架橋用組成物。
- フッ素ゴム(a)100質量部に対して、1~10質量部のハイドロタルサイトおよび2.5~8質量部の酸化マグネシウムをさらに含有する請求項1~7のいずれかに記載のフッ素ゴム架橋用組成物。
- 水酸化カルシウムを含まない請求項1~8のいずれかに記載のフッ素ゴム架橋用組成物。
- カルボン酸エステル系加工助剤(f)をさらに含有する請求項1~9のいずれかに記載のフッ素ゴム架橋用組成物。
- ジアルキルスルホン化合物(g)をさらに含有する請求項1~10のいずれかに記載のフッ素ゴム架橋用組成物。
- 架橋剤(b)が、4,4’-ビフェノール、2,6-ジヒドロキシアントラキノン、2,7-ジヒドロキシアントラキノン、および、これらの化合物のいずれかと、アルカリ金属、アルカリ土類金属またはオニウム化合物との塩からなる群より選択される少なくとも1種である請求項1~11のいずれかに記載のフッ素ゴム架橋用組成物。
- 請求項1~12のいずれかに記載のフッ素ゴム架橋用組成物から得られる成形品。
- 請求項1~12のいずれかに記載のフッ素ゴム架橋用組成物から得られるシール材。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2022191171A (ja) * | 2021-06-15 | 2022-12-27 | ダイキン工業株式会社 | フッ素ゴム架橋用組成物、成形品およびシール材 |
| JP7385152B2 (ja) | 2021-06-15 | 2023-11-22 | ダイキン工業株式会社 | フッ素ゴム架橋用組成物、成形品およびシール材 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP4317284A1 (en) | 2024-02-07 |
| EP4317284A4 (en) | 2025-04-02 |
| CN117043259A (zh) | 2023-11-10 |
| EP4317283A1 (en) | 2024-02-07 |
| JP7572652B2 (ja) | 2024-10-24 |
| US20240026139A1 (en) | 2024-01-25 |
| EP4317283A4 (en) | 2025-04-02 |
| KR20230164132A (ko) | 2023-12-01 |
| US20240034856A1 (en) | 2024-02-01 |
| TW202307121A (zh) | 2023-02-16 |
| KR102877391B1 (ko) | 2025-10-28 |
| JP7549273B2 (ja) | 2024-09-11 |
| TWI870653B (zh) | 2025-01-21 |
| KR20230164133A (ko) | 2023-12-01 |
| WO2022210044A1 (ja) | 2022-10-06 |
| CN117043260A (zh) | 2023-11-10 |
| TW202307124A (zh) | 2023-02-16 |
| JPWO2022210044A1 (ja) | 2022-10-06 |
| JPWO2022210042A1 (ja) | 2022-10-06 |
| TWI889966B (zh) | 2025-07-11 |
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