WO2018061864A1 - 架橋性ゴム組成物、ゴム架橋物、および導電性部材 - Google Patents
架橋性ゴム組成物、ゴム架橋物、および導電性部材 Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
- C08L71/03—Polyepihalohydrins
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
- C08G65/24—Epihalohydrins
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/263—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing heterocyclic amine groups
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C08K3/02—Elements
- C08K3/04—Carbon
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
Definitions
- the present invention relates to a crosslinkable rubber composition, a rubber cross-linked product obtained by cross-linking the cross-linkable rubber composition, and a conductive member having the rubber cross-linked product.
- conductive members such as conductive rolls, conductive blades, and conductive belts are used as mechanisms that require semiconductivity. .
- Such a conductive member has a desired range of conductivity (electric resistance value and its variation, environmental dependency, voltage dependency), non-contamination, low hardness, dimensional stability, etc., depending on the application. Various performances are required.
- Patent Document 1 a monomer unit having an onium ion introduced into a polyether rubber using a nitrogen atom-containing aromatic heterocyclic compound such as 1-methylimidazole as an onium agent.
- a technique that contains is disclosed.
- the polyether rubber described in Patent Document 1 is obtained by adding a cross-linking agent to obtain a cross-linkable rubber composition and cross-linking this to obtain a cross-linked rubber product. It can be kept low.
- a crosslinkable rubber composition scorch is likely to occur compared to conventionally used polyether rubber. Therefore, from the viewpoint of workability, Improvements in stability were desired.
- the present invention has been made in view of such a situation, and can provide a rubber cross-linked product having excellent scorch stability and sufficient cross-linking property, and having a low electric resistance value.
- An object is to provide a crosslinkable rubber composition.
- Another object of the present invention is to provide a crosslinked rubber and a conductive member obtained using such a crosslinkable rubber composition.
- the present inventors have determined that specific units and unsaturated oxide monomer units having a group containing a cationic nitrogen-containing aromatic heterocycle have a specific ratio.
- the present inventors have found that the above object can be achieved by a crosslinkable rubber composition obtained by blending a polyether rubber containing a crosslinking agent and zinc peroxide, and have completed the present invention.
- a polyether rubber containing 0.1 to 30 mol% of a unit represented by the following general formula (1) and 1 to 15 mol% of an unsaturated oxide monomer unit, and a crosslinking agent And a crosslinkable rubber composition comprising zinc peroxide.
- a + is a group containing a cationic nitrogen-containing aromatic heterocycle.
- the group containing the cationic nitrogen-containing aromatic heterocycle is the cationic nitrogen-containing aromatic heterocycle. It is bonded to the carbon atom at the position “2” shown in the general formula (1) through one of nitrogen atoms constituting the heterocyclic ring.
- X ⁇ is an arbitrary counter anion.
- the group containing a cationic nitrogen-containing aromatic heterocycle represented by A + in the general formula (1) is a group represented by the following general formula (2).
- N— represented in the general formula (2) is bonded to the carbon atom at the position “2” in the general formula (1) in the general formula (1).
- R represented in the general formula (2) represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
- the polyether rubber further contains an epihalohydrin monomer unit.
- the polyether rubber further contains an ethylene oxide monomer unit.
- the crosslinking agent is a sulfur-containing compound.
- the content of the zinc peroxide is 0.01 to 30 parts by weight with respect to 100 parts by weight of the polyether rubber.
- crosslinking the said crosslinkable rubber composition is provided. Furthermore, according to this invention, the electroconductive member which has the said rubber crosslinked material is provided.
- a crosslinkable rubber composition capable of providing a rubber cross-linked product having excellent scorch stability and sufficient cross-linkability and having a low electric resistance value, and the cross-linkability A rubber cross-linked product and a conductive member obtained by using the rubber composition can be provided.
- the crosslinkable rubber composition of the present invention comprises a polyether rubber containing 0.1 to 30 mol% of a unit represented by the following general formula (1) and 1 to 15 mol% of an unsaturated oxide monomer unit; And a cross-linking agent and zinc peroxide.
- the polyether rubber used in the present invention contains at least 0.1 to 30 mol% of a unit represented by the following general formula (1) and 1 to 15 mol% of an unsaturated oxide monomer unit.
- a + is a group containing a cationic nitrogen-containing aromatic heterocycle.
- the group containing the cationic nitrogen-containing aromatic heterocycle is the cationic nitrogen-containing aromatic heterocycle. It is bonded to the carbon atom at the position “2” shown in the general formula (1) through one of nitrogen atoms constituting the heterocyclic ring.
- X ⁇ is an arbitrary counter anion.
- a + is a group containing a cationic nitrogen-containing aromatic heterocyclic ring.
- the group containing the cationic nitrogen-containing aromatic heterocyclic ring is located at the position “2” shown in the general formula (1) through one of the nitrogen atoms constituting the cationic nitrogen-containing aromatic heterocyclic ring. It is bonded to a carbon atom.
- the nitrogen-containing aromatic heterocyclic ring in the cationic nitrogen-containing aromatic heterocyclic ring in the group containing the cationic nitrogen-containing aromatic heterocyclic ring has a nitrogen atom in the ring and is particularly aromatic if it has aromaticity. It is not limited.
- the heterocyclic ring in addition to the nitrogen atom bonded to the carbon atom at the position “2” shown in the general formula (1), it may have another nitrogen atom, an oxygen atom, a sulfur atom, etc. And may have a heteroatom other than a nitrogen atom, and a part of the atoms constituting the heterocyclic ring may be substituted with a substituent. Further, it may have a polycyclic structure in which two or more rings are condensed.
- nitrogen-containing aromatic heterocycle examples include five-membered heterocycles such as imidazole ring, pyrrole ring, thiazole ring, oxazole ring, pyrazole ring, isoxazole ring; pyridine ring, pyrazine ring, pyrimidine ring, 6-membered heterocycles such as pyridazine ring and triazine ring; quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, cinnoline ring, purine ring, indole ring, isoindole ring, benzimidazole ring, benzoxazole ring, benzoisoxazole ring, etc.
- five-membered heterocycles such as imidazole ring, pyrrole ring, thiazole ring, oxazole ring, pyrazole ring, isoxazole ring
- a + in the unit represented by the general formula (1) is independent, and the polyether rubber contains two or more kinds of cationic nitrogen-containing aromatic heterocycles. Groups may be present.
- the substituent of the nitrogen-containing aromatic heterocycle is not particularly limited, and examples thereof include an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; an arylalkyl group; an alkylaryl group; an alkoxyl group; Alkanol group; hydroxyl group; carbonyl group; alkoxycarbonyl group; amino group; imino group; nitrile group; alkylsilyl group; halogen atom;
- the group containing a cationic nitrogen-containing aromatic heterocycle represented by A + in the general formula (1) is preferably a group represented by the following general formula (2).
- N— represented in the general formula (2) is bonded to the carbon atom at the position “2” in the general formula (1) in the general formula (1).
- R represented in the general formula (2) represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
- R R represented in the general formula (2) is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group.
- the content ratio of the unit represented by the general formula (1) in the polyether rubber used in the present invention is 0.1 to 30 mol%, and 0.5 to 25 mol% in all monomer units. Preferably, it is 0.7 to 12 mol%.
- a polyether rubber capable of giving a rubber cross-linked product having a low compression set and a low electric resistance value can be obtained.
- the content ratio of the unit represented by the general formula (1) is too small, the volume specific resistance value of the obtained rubber cross-linked product may be increased.
- polyether rubber will become hard and the characteristic as a rubber elastic body may be lost.
- the unit represented by the general formula (1) is usually a cationic nitrogen-containing fragrance containing at least part of the halogen atoms constituting the epihalohydrin monomer unit in the polyether rubber containing the epihalohydrin monomer unit. It is obtained by substituting with a group containing a heterocyclic group.
- the epihalohydrin monomer constituting the epihalohydrin monomer unit is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, epiiodohydrin, epifluorohydrin and the like. Of these, epichlorohydrin is preferable.
- An epihalohydrin monomer may be used individually by 1 type, and may use 2 or more types together.
- the epihalohydrin monomer unit constitutes the unit represented by the general formula (1) by substituting at least a part of the halogen atom with a group containing a cationic nitrogen-containing aromatic heterocycle. However, some of them may remain without being substituted with a group containing a cationic nitrogen-containing aromatic heterocycle.
- a compound (hereinafter referred to as “onium agent”) used to replace at least part of the halogen atoms constituting the epihalohydrin monomer unit in the polyether rubber with a group containing a cationic nitrogen-containing aromatic heterocycle Is not particularly limited as long as it is a nitrogen atom-containing aromatic heterocyclic compound, and examples thereof include imidazole, 1-methylimidazole, pyrrole, 1-methylpyrrole, thiazole, oxazole, pyrazole, isoxazole and the like.
- 6-membered heterocyclic compounds such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, 2,6-lutidine; quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, purine, indole, isoindole, benzimidazole, Benzoxazole, benzoisooxy And condensed heterocyclic compounds such as sazol;
- 5-membered heterocyclic compounds and 6-membered heterocyclic compounds are preferable, and 1-methylimidazole is more preferable from the viewpoint of substance stability after the reaction.
- At least a part of the halogen atoms constituting the epihalohydrin monomer unit in the polyether rubber is a group containing a cationic nitrogen-containing aromatic heterocycle (hereinafter sometimes referred to as “onium ion-containing group”).
- onium ion-containing group a group containing a cationic nitrogen-containing aromatic heterocycle
- the substitution method is an application of a known onium reaction, and the known onium reaction is described in Japanese Patent Laid-Open Nos. 50-33271, 51-69434, and 52-52. No. 42481 and the like.
- the above-described onium agent and a polyoxyethylene containing an epihalohydrin monomer unit can be used as a method of substituting at least a part of the halogen atoms constituting the epihalohydrin monomer unit in the polyether rubber with an onium ion-containing group.
- a method of substitution by mixing and reacting with ether rubber may be mentioned.
- the mixing method of the onium agent and the polyether rubber is not particularly limited. For example, a method of mixing these using a solvent through a solvent, a method of mixing substantially without using a solvent, or the like. Can be mentioned. Among these methods, a method of mixing without substantially intervening a solvent is preferable from the viewpoint that the oniumation reaction easily proceeds and the reaction time can be shortened.
- a method of mixing substantially without using a solvent for example, a polyether rubber containing an epihalohydrin monomer unit and an oniumizing agent are kneaded substantially without using a solvent. And the method of making these react is mentioned.
- “performing an oniumation reaction substantially without a solvent” does not mean that the oniumation reaction is carried out without using any solvent, and contains an epihalohydrin monomer unit. It means that a solvent may be used to such an extent that the polyether rubber and the onium forming agent can be kneaded.
- the kneading method of the polyether rubber containing the epihalohydrin monomer unit and the onium agent is not particularly limited, but any dry type such as a kneader, a banbury, an open roll, a calender roll, a biaxial kneader, etc. It is preferable to mix uniformly by combining one or more kneaders.
- the oniumation reaction between the polyether rubber containing the epihalohydrin monomer unit and the onium forming agent may be performed simultaneously with the kneading or separately after the kneading.
- the temperature during the reaction is 40 to 200 ° C., preferably 60 to 190 ° C., more preferably 80 to 180 ° C. If the reaction temperature is too low, the substitution reaction may not proceed. On the other hand, if the reaction temperature is too high, the polyether rubber may be decomposed or the onium agent may be volatilized.
- the reaction time is not particularly limited, and is usually 1 minute to 10 days, preferably 5 minutes to 1 day. If the reaction time is too short, the substitution reaction may be incomplete. On the other hand, if the reaction time is too long, the polyether rubber may be decomposed.
- the method of mixing the polyether rubber containing the epihalohydrin monomer unit and the oniumizing agent is not particularly limited.
- the polyether rubber is used as a solvent.
- a method of adding and mixing an oniumizing agent to a solution obtained by dissolving in a solution a method of adding and mixing a polyether rubber into a solution obtained by dissolving an oniumizing agent in a solvent, and both an oniumizing agent and a polyether rubber.
- a solution prepared by dissolving in a solvent and mixing both solutions may be used.
- the polyether rubber or onium agent may be dispersed in a solvent, and it does not matter whether the polyether rubber or onium agent is dissolved or dispersed in the solvent.
- an inert solvent is preferably used, which may be nonpolar or polar.
- Nonpolar solvents include, for example, aromatic hydrocarbons such as benzene and toluene; chain saturated hydrocarbons such as n-pentane and n-hexane; alicyclic saturated hydrocarbons such as cyclopentane and cyclohexane; It is done.
- Polar solvents include ethers such as tetrahydrofuran, anisole and diethyl ether; esters such as ethyl acetate and ethyl benzoate; ketones such as acetone, 2-butanone and acetophenone; aprotic polar solvents such as acetonitrile, dimethylformamide and dimethyl sulfoxide Protic polar solvents such as ethanol, methanol, water; and the like.
- a mixed solvent of these is also preferably used.
- the amount of the solvent used is not particularly limited, but it is preferably used so that the concentration of the polyether rubber containing the epihalohydrin monomer unit is 1 to 50% by weight, and 3 to 40% by weight. More preferably, it is used.
- the reaction temperature is preferably 20 to 170 ° C.
- the reaction time is preferably 1 minute to 500 hours.
- the amount of the onium agent used is not particularly limited, but may be determined according to the structure of the onium agent used or the polyether rubber, the substitution rate of the onium ion-containing group in the target polyether rubber, and the like. Specifically, the amount of the oniumizing agent used is usually 0.01 to 100 mol, preferably 0.02 to 50 mol, more preferably relative to 1 mol of the halogen atom constituting the epihalohydrin monomer unit to be used. The range is from 0.03 to 10 mol, more preferably from 0.05 to 2 mol.
- the amount of the onium agent is too small, the substitution reaction is slow, and there is a possibility that a polyether rubber having an onium ion-containing group having a desired composition (hereinafter also referred to as “cationized polyether rubber”) cannot be obtained.
- cationized polyether rubber a polyether rubber having an onium ion-containing group having a desired composition
- the amount of the onium agent is too large, it may be difficult to remove the unreacted onium agent from the obtained cationized polyether rubber.
- a cyclic secondary amine such as pyrrole
- a cyclic secondary amine is a nitrogen atom-containing aromatic heterocyclic compound, which is bonded to a nitrogen atom in the ring.
- the amount of the onium agent used is usually 0 with respect to 1 mol of the halogen atom constituting the epihalohydrin monomer unit to be used. The range is from 0.01 to 2 mol, preferably from 0.02 to 1.5 mol, more preferably from 0.03 to 1 mol. If the amount of cyclic secondary amines is too small, the substitution reaction may be slow, and a cationized polyether rubber having a desired composition may not be obtained.
- the hydrogen atom bonded to the nitrogen atom in the ring bonded to the carbon atom at the position “2” shown in the general formula (1) is substituted with a desired group. You can also.
- the base is then mixed, the proton bonded to the nitrogen atom is eliminated, and further, for example, an alkyl halide is mixed and added.
- a desired substituent can be introduced.
- R ′ represents an alkyl group having 1 to 10 carbon atoms
- X ′ represents a halogen atom.
- the arbitrary counter anion represented by X ⁇ in the above general formula (1) is a compound or atom having a negative charge bonded to A + through an ionic bond, and other than having a negative charge Is not particularly limited. Since the counter anion is an ionizable ionic bond, at least a part of the counter anion can be exchanged for an arbitrary counter anion by a known ion exchange reaction. At the stage where the reaction is completed by mixing the oniumizing agent and the polyether rubber containing the epihalohydrin monomer unit, X in the general formula (1) is a halogen atom, but the pair of A + You may perform a well-known anion exchange reaction with respect to the halide ion which is an anion.
- the anion exchange reaction can be performed by mixing an ionic compound having ionization properties with a polyether rubber having an onium ion-containing group.
- the conditions for carrying out the anion exchange reaction are not particularly limited, but may be determined according to the structure of the ionic compound or polyether rubber used, the substitution rate of the target A + counter anion, and the like.
- the reaction may be carried out only with an ionic compound and a polyether rubber having an onium ion-containing group, or may contain other compounds such as an organic solvent.
- the amount of the ionic compound to be used is not particularly limited, but is usually 0.01 to 100 mol, preferably 0.02 to 50 mol, more preferably relative to 1 mol of the halogen atom constituting the epihalohydrin monomer unit to be used.
- the range is 0.03 to 10 mol. If the amount of the ionic compound is too small, the substitution reaction may be difficult to proceed. On the other hand, if the amount is too large, it may be difficult to remove the ionic compound.
- the pressure during the anion exchange reaction is usually from 0.1 to 50 MPa, preferably from 0.1 to 10 MPa, more preferably from 0.1 to 5 MPa.
- the temperature during the reaction is usually ⁇ 30 to 200 ° C., preferably ⁇ 15 to 180 ° C., more preferably 0 to 150 ° C.
- the reaction time is usually 1 minute to 1000 hours, preferably 3 minutes to 100 hours, more preferably 5 minutes to 10 hours, and further preferably 5 minutes to 3 hours.
- the anion species of the counter anion is not particularly limited.
- halide ions such as fluoride ion, chloride ion, bromide ion and iodide ion; sulfate ion; sulfite ion; hydroxide ion; carbonate ion; Ion; nitrate ion; acetate ion; perchlorate ion; phosphate ion; alkyloxy ion; trifluoromethanesulfonate ion; bistrifluoromethanesulfonimide ion; hexafluorophosphate ion; tetrafluoroborate ion; .
- onium ion unit content As a method for examining the content ratio of the unit represented by the general formula (1) in the polyether rubber used in the present invention (hereinafter also referred to as “onium ion unit content”), a known method may be used. Good.
- the content of the onium ion-containing group can be quantified by performing 1 H-NMR measurement on the polyether rubber used in the present invention. Specifically, first, the number of moles B1 of all monomer units (including onium ion units) in the polymer is calculated from the integral value of protons derived from the polyether chain which is the main chain of the cationized polyether rubber. To do.
- the number of moles B2 of the introduced onium ion unit (unit represented by the general formula (1)) is calculated from the integral value of protons derived from the onium ion-containing group.
- the molar amount of the onium agent consumed is the substitution mole of the halogen atom's onium ion-containing group. Equal to the amount. Therefore, the consumed molar amount of the onium agent is calculated by subtracting the residual molar amount A2 after the completion of the reaction from the added molar amount A1 before the start of the reaction, and the polyether rubber (hereinafter referred to as the onium agent) before reacting with the onium agent.
- the onium ion unit content can also be calculated by the following formula by dividing by the molar amount P of all the monomer units of “base polyether rubber”.
- Onium ion unit content (mol%) 100 ⁇ (A1-A2) / P
- a known measurement method may be used.
- the reaction rate is measured using a gas chromatography (GC) equipped with a capillary column and a flame ionization detector (FID). can do.
- GC gas chromatography
- FID flame ionization detector
- the polyether rubber used in the present invention contains an unsaturated oxide monomer unit in addition to the unit represented by the general formula (1).
- the unsaturated oxide monomer unit mainly functions as a crosslinkable monomer unit.
- the unsaturated oxide monomer forming the unsaturated oxide monomer unit includes at least one carbon-carbon unsaturated bond (excluding the aromatic carbon-carbon unsaturated bond) in the molecule and at least one epoxy.
- alkenyl glycidyl ethers such as allyl glycidyl ether and butenyl glycidyl ether; 3,4-epoxy-1-butene, 1,2-epoxy-5 Alkene epoxides such as hexene and 1,2-epoxy-9-decene; Among these, alkenyl glycidyl ethers are preferable, and allyl glycidyl ether is more preferable.
- An unsaturated oxide monomer may be used individually by 1 type, and may use 2 or more types together.
- the content ratio of the unsaturated oxide monomer unit in the polyether rubber is 1 to 15 mol%, preferably 1 to 12 mol%, more preferably 2 to 10 mol%. If the content ratio of the unsaturated oxide monomer unit is too small, crosslinking may be insufficient, and the mechanical properties of the resulting rubber crosslinked product may be deteriorated. Further, if the content ratio of the unsaturated oxide monomer unit is too large, a gelling reaction (three-dimensional crosslinking reaction) or the like in the polymer molecule or between the polymer molecules is likely to occur during the polymerization reaction, and the molding processability is improved. May decrease.
- the halogen atoms constituting the epihalohydrin monomer unit in the polyether rubber containing the epihalohydrin monomer unit is usually cationized.
- the unit represented by the general formula (1) is introduced by substitution with a group containing a nitrogen-containing aromatic heterocyclic ring. In this case, some of the epihalohydrin monomer units are The group containing a cationic nitrogen-containing aromatic heterocycle may remain without being substituted.
- the content ratio of the epihalohydrin monomer unit is preferably 0 to 98.9 mol%, more preferably 10 to 78.5 mol%, based on all monomer units, It is particularly preferably 15 to 57.3 mol%.
- the volume resistivity value can be more appropriately reduced.
- the polyether rubber used in the present invention preferably contains an ethylene oxide monomer unit from the viewpoint of low electrical resistance in addition to the above monomer units.
- the ethylene oxide monomer unit is a unit formed by an ethylene oxide monomer.
- the content ratio of the ethylene oxide monomer unit in the polyether rubber used in the present invention is preferably 0 to 90 mol%, more preferably 20 to 80 mol%, and more preferably 40 to 75 mol%. It is particularly preferred. By making the content rate of the ethylene oxide monomer unit in the polyether rubber within the above range, the polyether rubber can be made excellent in low electrical resistance.
- the polyether rubber used in the present invention is a copolymer containing units of other monomers that can be copolymerized with the monomers forming the respective monomer units, as necessary. Also good. Among other monomer units, an alkylene oxide monomer unit excluding ethylene oxide is preferable.
- the alkylene oxide monomer that forms the alkylene oxide monomer unit excluding ethylene oxide is not particularly limited, and examples thereof include propylene oxide, 1,2-epoxybutane, 1,2-epoxy-4-chloropentane, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxyoctadecane, 1,2-epoxyeicosane, 1,2-epoxyisobutane, 2,3-epoxyisobutane, etc.
- cyclic alkylene oxides such as 1,2-epoxycyclopentane, 1,2-e
- linear alkylene oxide is preferable, and propylene oxide is more preferable.
- alkylene oxide monomers may be used individually by 1 type, and may use 2 or more types together.
- the content of the alkylene oxide monomer unit excluding ethylene oxide is preferably 30 mol% or less, more preferably 20 mol% or less, in all monomer units, More preferably, it is 10 mol% or less. If the content ratio of the alkylene oxide monomer unit excluding ethylene oxide in the polyether rubber is too large, the volume specific resistance value of the resulting rubber cross-linked product may increase.
- copolymerizable monomers other than the alkylene oxide monomer are not particularly limited, and examples thereof include aryl epoxides such as styrene oxide and phenyl glycidyl ether.
- the content of other copolymerizable monomer units excluding the alkylene oxide monomer in the polyether rubber used in the present invention is preferably 20 mol% or less, and preferably 10 mol% in all monomer units. The following is more preferable, and 5 mol% or less is more preferable.
- the soot base polyether rubber can be obtained by ring-opening polymerization of each of the above monomers by a solution polymerization method or a solvent slurry polymerization method.
- the soot polymerization catalyst is not particularly limited as long as it is a general polyether rubber polymerization catalyst.
- the polymerization catalyst include a catalyst obtained by reacting water and acetylacetone with organoaluminum (Japanese Patent Publication No. 35-15797); a catalyst obtained by reacting phosphoric acid and triethylamine with triisobutylaluminum (Japanese Patent Publication No. 46-27534).
- a catalyst obtained by reacting an organic acid salt of diazabicycloundecene with phosphoric acid with triisobutylaluminum Japanese Patent Publication No.
- a catalyst comprising a partial hydrolyzate of aluminum alkoxide and an organic zinc compound Japanese Examined Patent Publication No. 43-2945
- a catalyst comprising an organic zinc compound and a polyhydric alcohol Japanese Examined Patent Publication No. 45-7751
- a catalyst comprising a dialkylzinc and water Japanese Examined Patent Publication No. 36-3394
- tributyl A catalyst comprising tin chloride and tributyl phosphate Japanese Patent No. 3223978
- the polymerization solvent is not particularly limited as long as it is an inert solvent.
- aromatic hydrocarbons such as benzene and toluene
- linear saturated hydrocarbons such as n-pentane and n-hexane
- cyclopentane And cyclic saturated hydrocarbons such as cyclohexane
- aromatic hydrocarbons are preferably used from the viewpoint of solubility of the base polyether rubber, and toluene is more preferable.
- the polymerization reaction temperature is preferably 20 to 150 ° C, more preferably 50 to 130 ° C.
- the polymerization mode can be carried out by any method such as batch system, semi-batch system, and continuous system.
- the base polyether rubber may be either a block copolymer type or a random copolymer type, but in particular, when ethylene oxide is used as the monomer, the random copolymer provides more crystallinity of polyethylene oxide. It is preferable because the rubber elasticity is lowered and the rubber elasticity is not easily lost.
- the method for recovering the base polyether rubber from the solvent is not particularly limited.
- the base polyether rubber is obtained by appropriately combining coagulation, filtration, dehydration, and drying methods.
- a method for solidifying the base polyether rubber from the solution in which the base polyether rubber is dissolved for example, a conventional method such as steam stripping or a precipitation method using a poor solvent can be used.
- examples of the method for filtering the base polyether rubber from the slurry containing the base polyether rubber include a method using a sieve such as a rotary screen or a vibrating screen, if necessary.
- examples of the method for dehydrating the base polyether rubber include a method of dewatering using a centrifugal separator; a compressed water squeezer such as a roll, a Banbury dehydrator, a screw extruder dehydrator, or the like.
- examples of the method for drying the base polyether rubber include a method using a dryer such as a kneader-type dryer, an expander dryer, a hot air dryer, and a vacuum dryer. These methods and the devices to be used are used alone or in combination of two or more.
- the weight average molecular weight of the polyether rubber used in the present invention is preferably 200,000 to 2,000,000, more preferably 400,000 to 1,500,000. If the weight average molecular weight is too high, the Mooney viscosity becomes high and molding may be difficult. On the other hand, if the weight average molecular weight is too low, the compression set of the resulting rubber cross-linked product may be deteriorated.
- the Mooney viscosity (polymer Mooney viscosity, ML1 + 4, 100 ° C.) of the polyether rubber used in the present invention is preferably 10 to 120. If the Mooney viscosity is too high, the molding processability is inferior and it is difficult to form the conductive member. Furthermore, swell (the diameter of the extrudate becomes larger than the diameter of the die at the time of extrusion) may occur, and the dimensional stability may be reduced. On the other hand, if the Mooney viscosity is too low, the mechanical strength of the resulting rubber cross-linked product may be reduced.
- the crosslinking agent used in the present invention is not particularly limited as long as the above-described polyether rubber can be crosslinked.
- examples of such a crosslinking agent include sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur; sulfur monochloride, sulfur dichloride, sulfur-containing morpholine compounds (for example, 4,4 ′ -Dithiodimorpholine, 4,4'-tetrathiodimorpholine, 4-morpholinyl morpholinodithioformate), thiourea compounds (eg trimethylthiourea, diethylthiourea, dibutylthiourea, dilaurylthiourea, diphenylthiourea, ethylenethiourea, thiocarbanilide ), 1,1′-dithiobis (hexahydro-2H-azepin-2-one), phosphorus-containing polysulfides, polymer polys
- Sulfur-containing compounds Sulfur-containing compounds; dicumyl peroxide, ditertiary butyl Organic peroxides such as peroxides; quinone dioximes such as p-quinonedioxime and p, p'-dibenzoylquinonedioxime; triethylenetetramine, hexamethylenediamine carbamate, 4,4'-methylenebis-o-chloroaniline Organic polyamine compounds such as, alkylphenol resins having a methylol group, and the like.
- sulfur and a sulfur-containing compound are preferable, and a sulfur-containing compound is more preferable from the viewpoint that the scorch stability can be further improved.
- the content of the crosslinking agent in the crosslinkable rubber composition of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 0.2 parts by weight based on 100 parts by weight of the polyether rubber used in the present invention. 7 parts by weight, more preferably 0.3 to 5 parts by weight.
- the crosslinkable rubber composition of the present invention contains zinc peroxide in addition to the above-described polyether rubber and crosslinker.
- zinc peroxide ZnO 2
- the rubber composition can have excellent scorch stability while having sufficient crosslinkability, and the obtained rubber cross-linked product can have low electrical resistance. It is.
- the content of zinc peroxide in the crosslinkable rubber composition of the present invention is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 100 parts by weight of the polyether rubber used in the present invention. -15 parts by weight, more preferably 0.5-10 parts by weight, and particularly preferably 0.5-5 parts by weight. By making content of zinc peroxide into the said range, scorch stability can be improved more appropriately, making the crosslinkability of a crosslinkable rubber composition sufficient.
- zinc peroxide is added to the above-described polyether rubber together with a crosslinking agent to obtain the crosslinkable rubber composition of the present invention.
- Zinc oxide may be added directly, or may be added in the form of a mixture of zinc peroxide and rubber, and further added in the form of a mixture of zinc peroxide and resin. Also good.
- the crosslinkable rubber composition of the present invention may contain a compound that acts as a crosslinking accelerator or a crosslinking acceleration aid other than zinc peroxide, and contains sulfur atoms in the chemical structure.
- Agents zinc oxide, stearic acid and the like.
- the content of zinc oxide in the crosslinkable rubber composition of the present invention is the same as that of the present invention. Is preferably limited to the range of 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the polyether rubber used in It is particularly preferable to limit the range to parts.
- the content of zinc oxide is preferably 2 times or less, more preferably 1.5 times or less, particularly preferably 1 time or less, relative to the content of zinc peroxide.
- sulfur-containing crosslinking accelerator containing a sulfur atom in the chemical structure examples include thiuram crosslinking accelerators, thiazole crosslinking accelerators, sulfenamide crosslinking accelerators, dithiocarbamate crosslinking accelerators, and the like. .
- thiuram crosslinking accelerator examples include tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide and the like.
- Specific examples of the thiazole crosslinking accelerator include 2-mercaptobenzothiazole, di-2-benzothiazolyl disulfide, 2-mercaptobenzothiazole zinc, (dinitrophenyl) mercaptobenzothiazole, (N, N-diethyl). And dithiocarbamoyl) benzothiazole.
- sulfenamide-based crosslinking accelerator examples include N-ethyl-2-benzothiazylsulfenamide, Nt-butyl-2-benzothiazylsulfenamide, N-oxydiethylene-2-benzothia Zolylsulfenamide, N-cyclohexyl-2-benzothiazylsulfenamide, N, N-diisopropyl-2-benzothiazylsulfenamide, N, N-dicyclohexyl-2-benzothiazylsulfenamide, etc. It is done.
- dithiocarbamate crosslinking accelerators include lead dimethyldithiocarbamate, lead diamyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diamyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dibenzyldithiocarbamate , Zinc pentamethylenedithiocarbamate, zinc ethylphenyldithiocarbamate, sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium dibutyldithiocarbamate, selenium dimethyldithiocarbamate, selenium diethyldithiocarbamate, tellurium diethyldithiocarbamate, cadmium diethyldithiocarbamate, dimethyldithiocarbamine Acid copper, iron dimethyldithiocarbamate, dimethylmethyld
- the content of the compound that acts as a crosslinking accelerator or crosslinking accelerator other than zinc peroxide and zinc oxide is preferably 100 parts by weight of the polyether rubber used in the present invention. Is 0.01 to 15 parts by weight, more preferably 0.1 to 5 parts by weight, still more preferably 0.5 to 3 parts by weight.
- the crosslinkable rubber composition of the present invention may further contain a filler in addition to the above components.
- a filler For example, carbon black, a silica, a carbon nanotube, a graphene, etc. are mentioned. These fillers can be used alone or in combination of two or more.
- the blending ratio of the filler is not particularly limited, but is preferably 0.01 to 150 parts by weight, more preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the polyether rubber used in the present invention. Part by weight is particularly preferred.
- the blending ratio is 0.01 to 100 parts by weight with respect to 100 parts by weight of the polyether rubber used in the present invention. 60 parts by weight is preferable, 0.1 to 40 parts by weight is more preferable, and 1 to 30 parts by weight is particularly preferable.
- crosslinkable rubber composition of the present invention is a butadiene rubber, styrene butadiene rubber, chloroprene rubber, isoprene rubber, natural rubber, acrylonitrile butadiene rubber, butyl rubber, and partial hydrogen of these rubbers within the range not impairing the effects of the present invention.
- Diene rubbers such as additives (for example, hydrogenated nitrile rubber); rubbers other than diene rubbers such as ethylene propylene rubber, acrylic rubber, polyether rubber (excluding the above-mentioned polyether rubber), fluorine rubber, and silicone rubber
- Thermoplastic elastomers such as olefin thermoplastic elastomers, styrene thermoplastic elastomers, vinyl chloride thermoplastic elastomers, polyester thermoplastic elastomers, polyamide thermoplastic elastomers, polyurethane thermoplastic elastomers; poly salts
- a resin such as vinyl chloride, coumarone resin, or phenol resin may be contained.
- thermoplastic elastomers, and resins can be used alone or in combination of two or more, and the total content thereof is 100 parts by weight with respect to 100 parts by weight of the polyether rubber used in the present invention. Or less, more preferably 70 parts by weight or less, and particularly preferably 50 parts by weight or less.
- thermoplastic elastomers, and resins acrylonitrile butadiene rubber is included from the viewpoint of improving processability when preparing a crosslinkable rubber composition, particularly processability during roll kneading. Is preferred.
- the crosslinkable rubber composition of the present invention may contain other additives usually blended in known rubbers.
- additives include, but are not limited to, acid acceptors; reinforcing agents; anti-aging agents; ultraviolet absorbers; light-resistant stabilizers; tackifiers; surfactants; Colorants (dyes and pigments); flame retardants; antistatic agents;
- the crosslinkable rubber composition of the present invention is prepared by blending and kneading the above-described polyether rubber with a crosslinking agent, zinc peroxide, and each additive used as necessary by a desired method. be able to.
- a crosslinking agent for example, an additive excluding a crosslinking agent, zinc peroxide, a crosslinking accelerator other than zinc peroxide added if necessary, or a compound that acts as a crosslinking acceleration aid and a polyether rubber are kneaded and then mixed into the mixture.
- the crosslinkable rubber composition of the present invention can be obtained by mixing a crosslinking agent, zinc peroxide, a crosslinking accelerator other than zinc peroxide added if necessary, or a compound acting as a crosslinking acceleration aid. .
- kneading and molding machines such as a kneader, a banbury, an open roll, a calender roll, and an extruder may be used for kneading and molding.
- the kneading temperature of the polyether rubber with an additive excluding a crosslinking agent, zinc peroxide, a crosslinking accelerator other than zinc peroxide added as necessary, or a compound acting as a crosslinking promotion aid, and the polyether rubber is 20 to 200 ° C. 20 to 150 ° C. is more preferable, and the kneading time is preferably 30 seconds to 30 minutes.
- the mixing temperature with the compound acting as a crosslinking accelerating aid is preferably 100 ° C. or less, more preferably 0 to 80 ° C.
- the rubber cross-linked product of the present invention is obtained by cross-linking the cross-linkable rubber composition of the present invention described above.
- the method for crosslinking the crosslinkable rubber composition of the present invention is not particularly limited, but the molding and crosslinking may be performed simultaneously or after molding.
- the molding temperature is preferably 20 to 200 ° C, more preferably 40 to 180 ° C.
- the heating temperature at the time of crosslinking is preferably from 130 to 200 ° C, more preferably from 140 to 200 ° C. If the temperature at the time of crosslinking is too low, the crosslinking time may be required for a long time, or the crosslinking density of the resulting rubber crosslinked product may be lowered. On the other hand, if the temperature at the time of crosslinking is too high, there is a risk of forming defects.
- the crosslinking time varies depending on the crosslinking method, crosslinking temperature, shape, etc., but a range of 1 minute or more and 5 hours or less is preferable from the viewpoint of crosslinking density and production efficiency.
- a heating method a method such as press heating, oven heating, steam heating, hot air heating, and microwave heating may be appropriately selected.
- the heating temperature in performing the secondary crosslinking is preferably 100 to 220 ° C, more preferably 130 to 210 ° C.
- the heating time is preferably 30 minutes to 5 hours.
- the volume specific resistance value of the rubber cross-linked product of the present invention is usually at a value of 30 seconds from the start of voltage application under the measurement environment with a temperature of 23 ° C. and a humidity of 50% under two conditions of applied voltage of 100 V and 250 V. 1 ⁇ 10 5.0 to 1 ⁇ 10 9.5 ⁇ ⁇ cm, preferably 1 ⁇ 10 5.2 to 1 ⁇ 10 8.0 ⁇ ⁇ cm, more preferably 1 ⁇ 10 5.5. ⁇ 1 ⁇ 10 7.5 ⁇ ⁇ cm.
- a conductive member excellent in low electrical resistance can be obtained.
- the volume specific resistance value of the rubber cross-linked product is too high, a higher voltage must be applied in order to pass the same current, and the amount of power consumption increases, which is not suitable for a conductive member.
- the volume specific resistance value of the rubber cross-linked product is too low, a current flows in an unintended direction other than the voltage application direction, which may impair the function as a conductive member.
- the rubber cross-linked product of the present invention thus obtained is obtained using the cross-linkable rubber composition of the present invention described above, it has a low electrical resistance value and can be suitably used for various conductive applications. Is.
- the conductive member of the present invention has the rubber cross-linked product of the present invention.
- the rubber cross-linked product of the present invention is useful as a material for various industrial rubber products, taking advantage of its properties, for example, conductive rolls, conductive blades, conductive belts and the like used in copying machines and printing machines.
- the rubber cross-linked product of the present invention has a characteristic of low electric resistance, it can be suitably used for conductive members used in copying machines, printing machines, etc., particularly conductive rolls.
- the onium ion unit content was measured using a nuclear magnetic resonance apparatus ( 1 H-NMR) as follows. After the onium reaction, 30 mg of cationized polyether rubber obtained by coagulation and drying was added to 1.0 ml of dimethyl sulfoxide, and the mixture was shaken for 1 hour to be uniformly dissolved. This solution was subjected to 1 H-NMR measurement to calculate the onium ion unit content. First, from the integral value of protons derived from the polyether chain which is the main chain of the cationized polyether rubber, the number of moles B1 of all monomer units (including onium ion units) in the polymer was calculated.
- the number of moles B2 of the introduced onium ion unit (unit represented by the general formula (1)) was calculated from the integral value of protons derived from the onium ion-containing group.
- the mole number B2 of the introduced onium ion unit (unit represented by the general formula (1)) is divided by the mole number B1 of all monomer units (including the onium ion unit) in the polymer.
- the onium ion unit content was calculated by the following formula.
- Onium ion unit content (mol%) 100 ⁇ B2 / B1
- Mooney scorch time (t 5, t 35) The Mooney scorch time (t 5 , t 35 ) of the crosslinkable rubber composition was measured at 125 ° C. using an L-shaped rotor according to JIS K6300.
- the Mooney scorch time (t 5 ) is the time until the Mooney viscosity increases by 5 points from the minimum value
- the Mooney scorch time (t 35 ) is the time until the Mooney viscosity increases by 35 points from the minimum value. is there.
- the larger the Mooney scorch time (t 5 , t 35 ) the better the scorch stability.
- the crosslinkable rubber composition was subjected to a crosslinkability test at 170 ° C. for 20 minutes using a rubber vulcanization tester (moving die rheometer MDR, manufactured by Alpha Technologies). From the results of the crosslinkability test, the minimum torque “ML” (unit: dN ⁇ m), the maximum torque “MH” (unit: dN ⁇ m), T 10 (unit: min.), And T 90 ( The unit was min.).
- T 10 and T 90 are the time required for the torque to increase 10% from the minimum torque ML, respectively, and 90% increase when “maximum torque MH ⁇ minimum torque ML” is 100%. means the time required for it can be determined that higher crosslinking rate value of T 90 is less fast.
- the crosslinkable rubber composition was molded and cross-linked by pressing at a temperature of 170 ° C. for 20 minutes to obtain a sheet-like rubber cross-linked product (sheet-shaped test piece) having a length of 15 cm, a width of 10 cm, and a thickness of 2 mm. And the volume specific resistance value was measured using the obtained sheet-like rubber crosslinked material.
- the volume resistivity is measured in accordance with the K6271 double ring electrode method.
- the measurement conditions are a temperature of 23 ° C. and a humidity of 50%, and the applied voltage is two conditions of 100 V and 250 V. The value 30 seconds after starting was measured. The smaller the numerical value of the volume resistivity, the better the conductivity.
- the monomer composition ratio of the polyether rubber was 40 mol% epichlorohydrin monomer unit, 56 mol% ethylene oxide monomer unit, allyl glycidyl ether monomer unit. It was 4 mol%.
- the Mooney viscosity of the obtained polyether rubber was 60 [ML1 + 4, 100 ° C.].
- the monomer composition ratio of the obtained cationized polyether rubber was as follows: epichlorohydrin monomer unit 38.8 mol%, ethylene oxide monomer unit 56 mol%, onium ion unit (general formula (1 ) Units) 1.2 mol%, allyl glycidyl ether monomer unit 4 mol%. Further, the Mooney viscosity of the obtained cationized polyether rubber was 54 [ML1 + 4, 100 ° C.].
- Example 1 To an open roll at 40 ° C., 100 parts of the cationized polyether rubber obtained in Production Example 3, 4,4′-dithiodimorpholine (trade name “Barnock R”, manufactured by Ouchi Shinsei Chemical Co., Ltd., sulfur-containing morpholine series Compound) 1 part, trimethylthiourea (trade name “Noxeller TMU”, manufactured by Ouchi Shinsei Chemical Co., Ltd., thiourea-based cross-linking agent) 1 part, zinc peroxide (manufactured by Hux Itec Corp.) 1 part, carbon black (trade name “Sir MAX N990 ", Tokai Carbon Co., Ltd., MT carbon black, 20 parts of filler, and 1 part of stearic acid (crosslinking accelerating aid) are added, kneaded and mixed for 10 minutes to prepare a crosslinkable rubber composition. did. Then, using the obtained crosslinkable rubber composition, Mooney scorch time (t 5 , t 35
- Example 2 A crosslinkable rubber composition was obtained and evaluated in the same manner as in Example 1 except that 4,4′-dithiodimorpholine was not used. The results are shown in Table 1.
- a specific unit having a group containing a cationic nitrogen-containing aromatic heterocycle and an unsaturated oxide monomer unit, a polyether rubber containing a specific ratio, a crosslinking agent As shown in Table 1, a specific unit having a group containing a cationic nitrogen-containing aromatic heterocycle and an unsaturated oxide monomer unit, a polyether rubber containing a specific ratio, a crosslinking agent,
- the crosslinkable rubber composition formed by blending with zinc peroxide has a long Mooney scorch time (t 5 ) and a Mooney scorch time (t 35 ), is excellent in scorch stability, and has sufficient crosslinkability.
- the rubber cross-linked product obtained has a low electric resistance value (Examples 1 and 2).
- the Mooney scorch time (t 5 ) and the Mooney scorch time (t 35 ) while exhibiting sufficient crosslinkability, and the resulting rubber cross-linked product has an electric resistance value.
- the effect of being able to be kept low is a polyether containing a specific unit having a group containing a cationic nitrogen-containing aromatic heterocycle and a specific proportion of an unsaturated oxide monomer unit. It can be confirmed that the effect can be achieved only by adding zinc peroxide to the rubber.
- the Mooney scorch time (t 5 ) can be lengthened, whereby the advantageous effect that molding defects in mold molding, extrusion molding, and the like can be prevented can be achieved. Since the scorch time (t 35 ) can be increased, the advantageous effect that the cross-linking unevenness of the molded product after cross-linking is reduced can be exhibited.
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Abstract
Description
好ましくは、前記ポリエーテルゴムが、さらに、エチレンオキサイド単量体単位を含有する。
好ましくは、前記架橋剤が、含硫黄化合物である。
好ましくは、前記過酸化亜鉛の含有量が、前記ポリエーテルゴム100重量部に対し、0.01~30重量部である。
さらに、本発明によれば、上記ゴム架橋物を有している導電性部材が提供される。
本発明で用いるポリエーテルゴムは、下記一般式(1)で表される単位0.1~30モル%、および不飽和オキサイド単量体単位1~15モル%を少なくとも含有する。
オニウムイオン単位含有率(モル%)=100×B2/B1
オニウムイオン単位含有率(モル%)=100×(A1-A2)/P
消費モル量の測定に関しては、公知の測定方法を用いて構わないが、たとえば、その反応率をキャピラリーカラムと水素炎イオン化型検出器(FID)とを装備したガスクロマトグラフィー(GC)を用いて測定することができる。
本発明で用いる架橋剤としては、上述したポリエーテルゴムを架橋可能なものであれば、特に限定されない。
このような架橋剤としては、たとえば、粉末硫黄、沈降硫黄、コロイド硫黄、不溶性硫黄、高分散性硫黄などの硫黄;一塩化硫黄、二塩化硫黄、硫黄含有モルホリン系化合物(たとえば、4,4’-ジチオジモルホリン、4,4’-テトラチオジモルホリン、モルホリノジチオ蟻酸4-モルホリニル)、チオウレア系化合物(たとえば、トリメチルチオ尿素、ジエチルチオ尿素、ジブチルチオ尿素、ジラウリルチオ尿素、ジフェニルチオ尿素、エチレンチオ尿素、チオカルバニリド)、1,1’-ジチオビス(ヘキサヒドロ-2H-アゼピン-2-オン)、含リンポリスルフィド、高分子多硫化物、トリアジン系化合物(たとえば、s-トリアジン-2,4,6-トリチオール)などの含硫黄化合物;ジクミルペルオキシド、ジターシャリブチルペルオキシドなどの有機過酸化物;p-キノンジオキシム、p,p’-ジベンゾイルキノンジオキシムなどのキノンジオキシム;トリエチレンテトラミン、ヘキサメチレンジアミンカルバメート、4,4’-メチレンビス-o-クロロアニリンなどの有機多価アミン化合物;メチロール基を持つアルキルフェノール樹脂;などが挙げられる。これらのなかでも、硫黄、含硫黄化合物が好ましく、スコーチ安定性をより高めることができるという点より、含硫黄化合物がより好ましく、一塩化硫黄、二塩化硫黄、硫黄含有モルホリン系化合物、チオウレア系化合物、1,1’-ジチオビス(ヘキサヒドロ-2H-アゼピン-2-オン)、含リンポリスルフィドおよび高分子多硫化物がさらに好ましく、硫黄含有モルホリン系化合物およびチオウレア系化合物がなおさらに好ましく、チオウレア系化合物が特に好ましい。これらの架橋剤は、それぞれ単独で、あるいは2種以上を組み合わせて用いられる。
また、本発明の架橋性ゴム組成物は、上述したポリエーテルゴムおよび架橋剤に加えて、過酸化亜鉛を含有する。本発明の架橋性ゴム組成物において、過酸化亜鉛(ZnO2)は、架橋促進剤あるいは架橋促進助剤として作用するものであり、本発明においては、過酸化亜鉛を使用することで、架橋性ゴム組成物を、十分な架橋性を備えながら、優れたスコーチ安定性を有するものとすることができ、しかも、得られるゴム架橋物を電気抵抗値が低く抑えられたものとすることができるものである。
また、チアゾール系架橋促進剤の具体例としては、2-メルカプトベンゾチアゾール、ジ-2-ベンゾチアゾリルジスルフィド、2-メルカプトベンゾチアゾール亜鉛、(ジニトロフェニル)メルカプトベンゾチアゾール、(N,N-ジエチルジチオカルバモイル)ベンゾチアゾールなどが挙げられる。
スルフェンアミド系架橋促進剤の具体例としては、N-エチル-2-ベンゾチアジルスルフェンアミド、N-t-ブチル-2-ベンゾチアジルスルフェンアミド、N-オキシジエチレン-2-ベンゾチアゾリルスルフェンアミド、N-シクロヘキシル-2-ベンゾチアジルスルフェンアミド、N,N-ジイソプロピル-2-ベンゾチアジルスルフェンアミド、N,N-ジシクロヘキシル-2-ベンゾチアジルスルフェンアミドなどが挙げられる。
ジチオカルバミン酸塩系架橋促進剤の具体例としては、ジメチルジチオカルバミン酸鉛、ジアミルジチオカルバミン酸鉛、ジメチルジチオカルバミン酸亜鉛、ジアミルジチオカルバミン酸亜鉛、ジエチルジチオカルバミン酸亜鉛、ジブチルジチオカルバミン酸亜鉛、ジベンジルジチオカルバミン酸亜鉛、ペンタメチレンジチオカルバミン酸亜鉛、エチルフェニルジチオカルバミン酸亜鉛、ジメチルジチオカルバミン酸ナトリウム、ジエチルジチオカルバミン酸ナトリウム、ジブチルジチオカルバミン酸ナトリウム、ジメチルジチオカルバミン酸セレン、ジエチルジチオカルバミン酸セレン、ジエチルジチオカルバミン酸テルル、ジエチルジチオカルバミン酸カドミウム、ジメチルジチオカルバミン酸銅、ジメチルジチオカルバミン酸鉄、ジメチルジチオカルバミン酸ビスマス、ジメチルジチオカルバミン酸ジメチルアンモニウム、ペンタメチレンジチオカルバミン酸ピペリジン、メチルペンタメチレンジチオカルバミン酸ピペコリンなどが挙げられる。
また、本発明の架橋性ゴム組成物は、上記各成分に加えて、充填剤をさらに含有していてもよい。充填剤としては、特に限定されないが、たとえば、カーボンブラック、シリカ、カーボンナノチューブ、およびグラフェンなどが挙げられる。これらの充填剤は、それぞれ単独で、あるいは2種以上を組み合わせて用いることができる。充填剤の配合割合は、特に限定されないが、本発明で用いるポリエーテルゴム100重量部に対して、0.01~150重量部が好ましく、0.1~100重量部がより好ましく、1~60重量部が特に好ましい。これら充填剤のなかでも、カーボンブラック、カーボンナノチューブ、グラフェンなどの導電性充填剤を使用する場合には、その配合割合は、本発明で用いるポリエーテルゴム100重量部に対して、0.01~60重量部が好ましく、0.1~40重量部がより好ましく、1~30重量部が特に好ましい。
本発明のゴム架橋物は、上述した本発明の架橋性ゴム組成物を架橋してなるものである。
本発明の導電性部材は、本発明のゴム架橋物を有しているものである。
各種の物性については、以下の方法に従って評価した。
実施例におけるオニウムイオン単位含有率の測定は、核磁気共鳴装置(1H-NMR)を用いて、以下のように行った。オニウム化反応後、凝固乾燥して得られたカチオン化ポリエーテルゴム30mgを、1.0mlのジメチルスルホキシドに加え、1時間振とうすることにより均一に溶解させた。この溶液を、1H-NMR測定することによりオニウムイオン単位含有率を算出した。まず、カチオン化ポリエーテルゴムの主鎖であるポリエーテル鎖に由来するプロトンの積分値から、ポリマー中の全単量体単位(オニウムイオン単位を含む)のモル数B1を算出した。次に、オニウムイオン含有基に由来するプロトンの積分値から、導入されているオニウムイオン単位(上記一般式(1)で表される単位)のモル数B2を算出した。そして、導入されているオニウムイオン単位(上記一般式(1)で表される単位)のモル数B2を、ポリマー中の全単量体単位(オニウムイオン単位を含む)のモル数B1で除することにより、オニウムイオン単位含有率を、下記式により算出した。
オニウムイオン単位含有率(モル%)=100×B2/B1
架橋性ゴム組成物のムーニースコーチ時間(t5、t35)は、JIS K6300に従って、L形ロータを用いて125℃で測定した。なお、ムーニースコーチ時間(t5)は、ムーニー粘度が最小値から5ポイント増加するまでの時間であり、ムーニースコーチ時間(t35)は、ムーニー粘度が最小値から35ポイント増加するまでの時間である。ムーニースコーチ時間(t5、t35)の値が大きいほど、スコーチ安定性に優れる。
架橋性ゴム組成物について、ゴム加硫試験機(ムービングダイレオメータMDR、アルファテクノロジーズ社製)を用い、170℃、20分の条件で架橋性試験を行った。そして、架橋性試験の結果から、最小トルク「ML」(単位は、dN・m)、最大トルク「MH」(単位は、dN・m)、T10(単位は、min.)およびT90(単位は、min.)を測定した。なお、T10およびT90は、「最大トルクMH-最小トルクML」を100%としたときに、トルクが最小トルクMLから、それぞれ、10%上昇するのに要する時間、および90%上昇するのに要する時間を意味し、T90の値が小さいほど架橋速度が速いと判断できる。
架橋性ゴム組成物を温度170℃、20分間のプレスによって成形、架橋し、縦15cm、横10cm、厚さ2mmのシート状のゴム架橋物(シート状試験片)を得た。そして、得られたシート状のゴム架橋物を用いて、体積固有抵抗値を測定した。なお、体積固有抵抗値の測定は、K6271の2重リング電極法に準拠して行い、測定条件は、温度23℃、湿度50%とし、印加電圧は100Vおよび250Vの2条件とし、電圧の印加を開始してから30秒後の値を測定した。体積固有抵抗値は、数値が小さいほど、導電性に優れている。
密閉した耐圧ガラス容器を窒素置換して、トルエン200部およびトリイソブチルアルミニウム60部を供給した。このガラス容器を氷水に浸漬して冷却後、ジエチルエーテル230部を添加し、攪拌した。次に、氷水で冷却しながら、リン酸13.6部を添加し、さらに攪拌した。この時、トリイソブチルアルミニウムとリン酸との反応により、容器内圧が上昇するので適時脱圧を実施した。次いで、得られた反応混合物を60℃の温水浴内で1時間熟成反応させて触媒溶液を得た。
オートクレーブにエピクロロヒドリン223.5部、アリルグリシジルエーテル27.5部、エチレンオキサイド19.7部、トルエン2585部を入れ、窒素雰囲気下で攪拌しながら内溶液を50℃に昇温し、上記で得た触媒溶液11.6部を添加して反応を開始した。次に、反応開始からエチレンオキサイド129.3部をトルエン302部に溶解した溶液を5時間かけて等速度で連続添加した。また、反応開始後30分毎に触媒溶液6.2部ずつを5時間にわたり添加した。次いで、水15部を添加して攪拌し、反応を終了させた。ここにさらに、老化防止剤として4,4’-チオビス-(6-tert-ブチル-3-メチルフェノール)の5%トルエン溶液45部を添加し、攪拌した。スチームストリッピングを実施してトルエンを除去し、上澄み水を除去後、60℃にて真空乾燥し、ポリエーテルゴム400部を得た。このポリエーテルゴムの単量体組成比は、1H-NMRにより測定した結果、エピクロロヒドリン単量体単位40モル%、エチレンオキサイド単量体単位56モル%、アリルグリシジルエーテル単量体単位4モル%であった。また、得られたポリエーテルゴムのムーニー粘度は60[ML1+4,100℃]であった。
25℃のオープンロールに、製造例2で得られたポリエーテルゴム100部と、1-メチルイミダゾール1.5部とを投入し、5分間混練した後、その混合物を、100℃に加熱した加圧成型機にセットし、24時間反応させた。その後、オーブンから、反応により得られたカチオン化ポリエーテルゴムを、収量101.5部にて回収した。得られたカチオン化ポリエーテルゴムを、上述した方法に従って、1H-NMR測定することにより、オニウムイオン単位含有率を算出した。得られたカチオン化ポリエーテルゴムのオニウムイオン単位含有率は1.2モル%であった。すなわち、得られたカチオン化ポリエーテルゴムの単量体組成比は、エピクロロヒドリン単量体単位38.8モル%、エチレンオキサイド単量体単位56モル%、オニウムイオン単位(一般式(1)で表される単位)1.2モル%、アリルグリシジルエーテル単量体単位4モル%であった。また、得られたカチオン化ポリエーテルゴムのムーニー粘度は54[ML1+4,100℃]であった。
40℃のオープンロールに、製造例3で得られたカチオン化ポリエーテルゴム100部、4,4'-ジチオジモルホリン(商品名「バルノックR」、大内新興化学工業社製、硫黄含有モルホリン系化合物)1部、トリメチルチオ尿素(商品名「ノクセラーTMU」、大内新興化学工業社製、チオウレア系架橋剤)1部、過酸化亜鉛(ハクスイテック社製)1部、カーボンブラック(商品名「サーマックスN990」、東海カーボン社製、MTカーボンブラック、充填剤)20部、およびステアリン酸(架橋促進助剤)1部を投入し、10分間混練し混合することにより、架橋性ゴム組成物を調製した。そして、得られた架橋性ゴム組成物を用いて、上記した方法にしたがって、ムーニースコーチ時間(t5、t35)、架橋性試験、体積固有抵抗値の各測定・評価を行った。結果を表1に示す。
4,4'-ジチオジモルホリンを使用しなかった以外は、実施例1と同様にして、架橋性ゴム組成物を得て、同様に評価を行った。結果を表1に示す。
過酸化亜鉛1部に代えて、酸化亜鉛(亜鉛華2種、正同化学社製)5部を使用した以外は、実施例1と同様にして、架橋性ゴム組成物を得て、同様に評価を行った。結果を表1に示す。
4,4'-ジチオジモルホリン1部およびトリメチルチオ尿素1部に代えて、硫黄(商品名「サルファックスPMC、鶴見化学工業社製」0.5部およびテトラエチルチウラムジスルフィド(商品名「ノクセラーTET」、大内新興化学工業社製、チウラム系架橋促進剤)1部を使用した以外は、比較例1と同様にして、架橋性ゴム組成物を得て、同様に評価を行った。結果を表1に示す。
酸化亜鉛の配合量を5部から2.5部に変更した以外は、比較例2と同様にして、架橋性ゴム組成物を得て、同様に評価を行った。結果を表1に示す。
Claims (8)
- 前記ポリエーテルゴムが、さらに、エピハロヒドリン単量体単位を含有する請求項1または2のいずれかに記載の架橋性ゴム組成物。
- 前記ポリエーテルゴムが、さらに、エチレンオキサイド単量体単位を含有する請求項1~3のいずれかに記載の架橋性ゴム組成物。
- 前記架橋剤が、含硫黄化合物である請求項1~4のいずれかに記載の架橋性ゴム組成物。
- 前記過酸化亜鉛の含有量が、前記ポリエーテルゴム100重量部に対し、0.01~30重量部である請求項1~5のいずれかに記載の架橋性ゴム組成物。
- 請求項1~6のいずれかに記載の架橋性ゴム組成物を架橋してなるゴム架橋物。
- 請求項7に記載のゴム架橋物を有している導電性部材。
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See also references of EP3521369A4 * |
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US20190264026A1 (en) | 2019-08-29 |
CN109642074A (zh) | 2019-04-16 |
KR20190058576A (ko) | 2019-05-29 |
JPWO2018061864A1 (ja) | 2019-07-04 |
JP6981420B2 (ja) | 2021-12-15 |
EP3521369A1 (en) | 2019-08-07 |
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