WO2023090304A1 - Polymère, élastomère, son procédé de production, actionneur et capteur - Google Patents

Polymère, élastomère, son procédé de production, actionneur et capteur Download PDF

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WO2023090304A1
WO2023090304A1 PCT/JP2022/042314 JP2022042314W WO2023090304A1 WO 2023090304 A1 WO2023090304 A1 WO 2023090304A1 JP 2022042314 W JP2022042314 W JP 2022042314W WO 2023090304 A1 WO2023090304 A1 WO 2023090304A1
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elastomer
meth
polymer
group
monomer
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PCT/JP2022/042314
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Japanese (ja)
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真 楠
幸樹 椿
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大阪有機化学工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N11/00—Generators or motors not provided for elsewhere; Alleged perpetua mobilia obtained by electric or magnetic means

Definitions

  • the present invention relates to polymers, elastomers, manufacturing methods thereof, actuators, and sensors, and particularly to polymers and elastomers that can be suitably used as dielectric elastomers.
  • dielectric elastomers that can be deformed by voltage application are known as elastomers used for dielectric materials.
  • Dielectric elastomers can be used in applications such as actuators, sensors used in industrial robots and the like, power generation elements, speakers, microphones, noise cancellers, transducers, artificial muscles, small pumps, and medical instruments.
  • a technology related to a dielectric elastomer using a copolymer having a polar group has been proposed (see, for example, Patent Document 1 below).
  • Patent Document 1 discloses the use of a monomer in which a polar group is bonded to a polymer main chain via three or more atoms that are linearly connected. groups are exemplified.
  • the polymer according to ⁇ 1> above, wherein the (meth)acrylate monomer having an ether structure is represented by the following formula (1).
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents an alkyl group having 1 to 5 carbon atoms which may have a halogen atom.
  • X 1 has a halogen atom.
  • ⁇ 3> The polymer according to ⁇ 1> or ⁇ 2>, wherein the (meth)acrylamide having a cyano group is represented by the following formula (2).
  • R 1 represents a hydrogen atom or a methyl group.
  • R 3 represents a hydrogen atom or a methyl group.
  • X 2 represents an alkylene group having 1 to 10 carbon atoms, which may have a halogen atom. show.
  • ⁇ 4> The polymer according to any one of ⁇ 1> to ⁇ 3>, which has a weight average molecular weight of 200,000 to 4,000,000.
  • ⁇ 5> An elastomer comprising the polymer according to any one of ⁇ 1> to ⁇ 4>.
  • ⁇ 6> The method for producing the elastomer according to ⁇ 5>, obtaining a polymer by polymerizing a (meth)acrylate monomer having an ether structure and a (meth)acrylamide having a cyano group;
  • a method of making an elastomer comprising: ⁇ 7>
  • An actuator comprising the elastomer according to ⁇ 5>.
  • ⁇ 9> A sensor comprising the elastomer according to ⁇ 5>.
  • the polymer which has a high dielectric constant and can constitute an elastomer excellent in the displacement amount at the time of voltage application can be provided. Further, according to the present invention, it is possible to provide an elastomer that has high flexibility and dielectric constant and is excellent in the amount of displacement when a voltage is applied, a method for producing the same, and an actuator and a sensor using the elastomer. .
  • FIG. 4 is a schematic plan view showing one embodiment of an actuator
  • FIG. 2 is a schematic cross-sectional view of the actuator shown in FIG. 1 taken along line AA
  • FIG. 4 is a schematic diagram for explaining displacement of an elastomer
  • 4 is a graph for explaining hysteresis loss
  • (meth)acrylate or the like means “acrylate” or “methacrylate”.
  • alkyl group includes linear, branched and alicyclic alkyl groups.
  • the polymer of the present embodiment includes units (A) derived from a (meth)acrylate monomer having an ether structure (hereinafter sometimes simply referred to as “units (A)”) and (meth)acrylamide having a cyano group. and a unit (B) derived from (hereinafter sometimes simply referred to as "unit (B)").
  • the "polymer of the present embodiment” means a polymer containing units (A) and units (B) as structural units, and may be liquid, solid, uncured, or cured. Also includes state.
  • the "elastomer of the present embodiment” is an elastomer (elastic body) containing the polymer of the present embodiment. itself can be referred to as the elastomer of this embodiment.
  • the elastomer of the present embodiment may contain various additives as necessary.
  • the polymer of the present embodiment is a relatively highly polar and flexible unit (A) derived from a (meth)acrylate monomer having an ether structure (hereinafter sometimes simply referred to as "monomer (A)”), (Meth)acrylamide having a cyano group (hereinafter sometimes simply referred to as “monomer (B)”) and a highly polar unit (B) derived from the unit (B), which provides excellent dielectric constant and when voltage is applied It is possible to make both the displacement amount in and the high dimension compatible.
  • the polymer of this embodiment can be used for applications such as actuators, sensors used in industrial robots, power generation elements, speakers, microphones, noise cancellers, transducers, artificial muscles, small pumps, and medical instruments.
  • the amount of displacement when a voltage is applied can be increased by achieving both a high dielectric constant and a high flexibility (low Young's modulus) of the polymer or elastomer.
  • the polymer of the present embodiment contains, as a structural unit, a unit (A) derived from a (meth)acrylate monomer having an ether structure (monomer (A)).
  • the monomer (A) is a (meth)acrylate having a (meth)acrylate structure in its structure and containing at least one ether structure (--C--O--C--) other than the structure.
  • the number of ether structures other than the (meth)acrylate structure in the unit (A) is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2, from the viewpoint of the balance between dielectric constant and flexibility. 1 is more preferred.
  • the monomer (A) has a high dissolving power (solubility) with respect to the monomer (B) to be combined.
  • the monomer (A) having the high dissolving power is used, the monomer (B) can be dissolved even when the monomer (B) is a solid substance at room temperature, thereby eliminating the use of a solvent.
  • the polymer of the present embodiment can be synthesized by the bulk polymerization method described below. According to the bulk polymerization method, the polymer of the present embodiment can be increased in molecular weight as desired.
  • the solubility of the monomer (B) in 100 g of the monomer (A) (under 1 atm, liquid temperature 25° C.) is preferably 1% by mass or more, and 10% by mass, from the viewpoint of improving the dielectric constant and improving the amount of displacement when voltage is applied. % or more, more preferably 30 mass % or more, and particularly preferably 40 mass % or more.
  • the solubility is determined, for example, by adding the monomer (B) dropwise to 10 g of the monomer (A), heating and mixing at 50 ° C., and checking the state after cooling.
  • the solubility of the monomer (B) can be used as the upper limit concentration for a solution.
  • a monomer (A) represented by the following formula (1) can be used as the (meth)acrylate monomer having an ether structure.
  • the monomer (A) represented by formula (1) has a relatively high dielectric constant and excellent flexibility.
  • the monomer (A) represented by formula (1) is also advantageous in terms of dissolving power for the monomer (B) represented by formula (2) described below.
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents an alkyl group having 1 to 5 carbon atoms which may have a halogen atom.
  • X 1 has a halogen atom. represents an alkylene group having 1 to 10 carbon atoms, and n represents an integer of 1 to 3.
  • R 1 is a hydrogen atom or a methyl group.
  • a hydrogen atom is preferable from the viewpoint of facilitating polymerization and obtaining a polymer having a low Young's modulus.
  • R 2 is an alkyl group having 1 to 5 carbon atoms which may have a halogen atom.
  • the alkyl group may be linear, branched, or cyclic, but from the viewpoint of dielectric constant, it is preferably a linear alkyl group.
  • alkyl groups having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isoamyl group, and the like.
  • R 2 is preferably a straight-chain alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, or a propyl group, from the viewpoint of dielectric constant.
  • the halogen atom that can be contained in the alkyl group includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
  • the number of halogen atoms contained in the alkyl group varies depending on the number of carbon atoms in the alkyl group, etc., and cannot be determined indiscriminately.
  • alkyl group having 1 to 5 carbon atoms and having a halogen atom examples include trifluoromethyl group, trifluoroethyl group, trifluoro n-propyl group, trifluoroisopropyl group, trifluoro n-butyl group and trifluoroisobutyl group. , a trifluorotert-butyl group, etc., but the present embodiment is not limited to these examples.
  • X 1 is an alkylene group having 1 to 10 carbon atoms which may have a halogen atom.
  • the alkylene group may be linear, branched, or cyclic, but is preferably a linear alkylene group from the viewpoint of dielectric constant.
  • alkylene group having 1 to 10 carbon atoms examples include methylene group, ethylene group, n-prolene group, isopropylene group, n-butylene group, isobrene group, tert-butylene group, sec-butylene group and n-pentylene. group, n-hexylene group, n-heptylene group, and the like.
  • X 1 is preferably a straight-chain alkylene group having 1 to 6 carbon atoms from the viewpoint of dielectric constant, more preferably a straight-chain alkylene group having 1 to 4 carbon atoms, and a methylene group and an ethylene group.
  • the alkylene group represented by X 1 may have the above-described halogen atom as a substituent.
  • n is an integer of 1-3. Although not particularly limited, n is preferably 1 or 2, more preferably 1, from the viewpoint of dielectric constant.
  • Examples of the monomer (A) represented by formula (1) include methoxyethyl (meth)acrylate (MTA), ethoxyethyl (meth)acrylate, methoxymethyl (meth)acrylate, methoxypropyl (meth)acrylate, ethoxymethyl ( meth)acrylates, and (meth)acrylate monomers having alkyl groups containing multiple ether structures (e.g., methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, etc.). Ethyl (meth)acrylate (MTA) and methoxypropyl (meth)acrylate are preferred. Each of these monomers (A) may be used alone, or two or more of them may be used in combination.
  • examples of the monomer (A) other than the monomer (A) represented by formula (1) include (meth)acrylate monomers having an alkyl group containing a cyclic ether structure such as tetrahydrofurfuryl acrylate.
  • the polymer of the present embodiment contains, as a structural unit, a unit (B) derived from (meth)acrylamide (monomer (B)) having a cyano group.
  • the monomer (B) is a (meth)acrylamide having a (meth)acrylamide structure in its structure and further containing at least one cyano group (CN--).
  • the number of cyano groups in the unit (B) is not particularly limited, but is preferably 1 to 2, preferably 1, from the viewpoint of dielectric constant.
  • a monomer (B) represented by the following formula (2) can be used as the (meth)acrylamide having a cyano group.
  • the monomer (B) represented by formula (2) has a particularly high dielectric constant.
  • R 1 represents a hydrogen atom or a methyl group.
  • R 3 represents a hydrogen atom or a methyl group.
  • X 2 represents an alkylene group having 1 to 10 carbon atoms, which may have a halogen atom. show.
  • R 1 is a hydrogen atom or a methyl group.
  • a hydrogen atom is preferable from the viewpoint of facilitating polymerization and obtaining a polymer having a low Young's modulus.
  • R3 is a hydrogen atom or a methyl group.
  • a hydrogen atom is preferable from the viewpoint of Young's modulus.
  • X 2 is an alkylene group having 1 to 10 carbon atoms which may have a halogen atom.
  • the alkylene group may be linear, branched, or cyclic, but is preferably a linear alkyl group from the viewpoint of dielectric constant.
  • alkylene group having 1 to 10 carbon atoms examples include methylene group, ethylene group, n-prolene group, isopropylene group, n-butylene group, isobrene group, tert-butylene group, sec-butylene group and n-pentylene. group, n-hexylene group, n-heptylene group, and the like.
  • X 2 is preferably a linear alkylene group having 1 to 5 carbon atoms from the viewpoint of dielectric constant, more preferably a linear alkylene group having 1 to 3 carbon atoms, and a methylene group and an ethylene group. preferable.
  • the alkylene group represented by X2 may have the above-mentioned halogen atom as a substituent.
  • Examples of the monomer (B) represented by the formula (2) include cyanoethylacrylamide (CEAAM), N-(2-cyanoethyl)-N-methylacrylamide, cyanomethylacrylamide, and the like. Cyanoethylacrylamide (CEAAM) is preferred in terms of balance. Each of these monomers (B) may be used alone, or two or more of them may be used in combination.
  • monomer (B) other than the monomer (B) represented by formula (2) include N,N-bis(2-cyanoethyl)acrylamide and N,N-bis(2-cyanomethyl)acrylamide. be done.
  • the polymer of the present embodiment optionally has units (C) derived from a monomer (C) other than the monomers (A) and (B).
  • the monomer (C) include alkyl (meth)acrylate monomers, halogen-substituted alkyl (meth)acrylate monomers, hydroxyalkyl (meth)acrylate monomers, (meth)acryloxyalkyl isocyanate monomers, and carboxyl group containing monomers, aryl group-containing monomers, styrene-based monomers, fatty acid vinyl ester-based monomers, betaine monomers, etc., but the present embodiment is not limited to these examples. These monomers may be used alone, respectively, or two or more of them may be used in combination.
  • alkyl (meth)acrylate monomer examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, Acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, n-pentyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, methylpentyl (meth)acrylate, cyclohexyl (meth)acrylate ) acrylates and the like.
  • halogen-substituted alkyl (meth)acrylate monomer examples include 2,2,2-trifluoroethyl acrylate.
  • hydroxyalkyl (meth)acrylate monomers examples include hydroxyethyl acrylate, 4-hydroxybutyl acrylate (4HBA), 1-acryloyloxy-3-hydroxyadamantane, and 1,3-cyclohexanedimethanol monoacrylate.
  • Examples of the (meth)acryloxyalkyl isocyanate monomer include (meth)acryloxyethyl isocyanate, 2-methacryloxyethyl isocyanate ethylene glycol (MOI-EG), 1,1-(bisacryloyloxymethyl)ethyl isocyanate (BEI) and the like.
  • the content of the units (A) in the polymer of the present embodiment is not particularly limited, but from the viewpoint of low Young's modulus, dielectric properties, and solubility in the monomer (B), the total amount of the monomers of the present embodiment is On the other hand, 10 to 99 mol% is preferable, 30 to 95 mol% is more preferable, and 60 to 70 mol% is particularly preferable.
  • the content of the unit (B) in the polymer of the present embodiment is not particularly limited, but from the viewpoint of low Young's modulus and dielectric properties, it is preferably 1 to 90 mol% with respect to the total amount of the monomers of the present embodiment. 5 to 70 mol % is more preferred, and 30 to 40 mol % is particularly preferred.
  • the polymer of the present embodiment can be copolymerized with other units (units (C1) described later), and further units C1 with other units (C2 described later). can be combined.
  • the content of the unit (C1) in the polymer is not particularly limited, but it is preferably 0 in terms of rebound property and low Young's modulus of the resulting elastomer per 100 mol parts of the total amount of the monomers. 0.05 to 10 mol parts, more preferably 0.1 to 5 mol parts, and particularly preferably 0.25 to 2.5 mol parts.
  • the weight average molecular weight (Mw) of the polymer of the present embodiment is preferably 200,000 to 4,000,000 from the viewpoint of film-forming properties and mechanical properties (low Young's modulus, low hysteresis loss). , 500,000 to 3,800,000 are more preferred, and 1,000,000 to 3,500,000 are particularly preferred.
  • the weight average molecular weight of the polymer of the present embodiment was determined by gel permeation chromatography [manufactured by Tosoh Corporation, product number: HLC-8320GPC, column: manufactured by Tosoh Corporation, product number: TSKgel GMHH-R, solvent: tetrahydrofuran, Flow rate: 0.6 mL/min] can be used for measurement in terms of polystyrene.
  • the combination of each structural unit is not particularly limited, but from the viewpoint of achieving both dielectric constant and flexibility at a high level, the following combinations may be mentioned, for example.
  • Examples of the polymer of this embodiment include a polymer having a structure represented by the following formula (3).
  • R 1 , R 2 , R 3 , X 1 and X 2 have the same meanings as those described in Formulas (1) and (2) above. Further, n is 1 to 3 is an integer, m is 150 to 25,000, and l is 150 to 25,000.
  • the elastomer of the present embodiment is an elastomer (elastic body) containing the polymer of the present embodiment.
  • the coalescence itself can be referred to as the elastomer of this embodiment.
  • Shapes such as width, thickness and length of the elastomer of this embodiment are not particularly limited.
  • the Young's modulus of the elastomer of the present embodiment is preferably 1 MPa or less, more preferably 0.5 MPa or less, and particularly preferably 0.2 MPa or less.
  • the elongation rate, Young's modulus, and hysteresis loss of the elastomer of the present embodiment can be measured, for example, using a tensile tester according to the methods described in Examples below.
  • the elongation rate of the elastomer of this embodiment is preferably 200% or more, more preferably 400% or more, and particularly preferably 700% or more.
  • the hysteresis loss is preferably 10% or less, more preferably 5% or less.
  • the dielectric constant of the elastomer of the present embodiment is not particularly limited, it is preferably 6 or more, more preferably 8 or more, and particularly preferably 10 or more for use as a dielectric actuator.
  • the dielectric constant of the elastomer of the embodiment can be measured by the method described in Examples below.
  • the rate of change when a voltage is applied to the elastomer of this embodiment can be measured by the method described in Examples below, and is not particularly limited.
  • the displacement @ 1 kV (%) is preferably 0.1% or more, more preferably 0.3% or more, and particularly preferably 0.5% or more.
  • the maximum change rate (%) of the displacement (Max) is preferably 2% or more, more preferably 5% or more, and particularly preferably 10% or more.
  • the withstand voltage of the elastomer of this embodiment is preferably 10 (v/ ⁇ m) or more, more preferably 20 (v/ ⁇ m) or more, in the case of dielectric actuator applications.
  • the glass transition temperature of the elastomer of the present embodiment is not particularly limited, but from the viewpoint of low Young's modulus, it is preferably 30° C. or lower, more preferably 0° C. or lower, and ⁇ 20° C. or lower. is particularly preferred.
  • the glass transition temperature is measured according to JIS. K6240:2011 can be complied with.
  • the method for producing the polymer and elastomer of the present embodiment is not particularly limited, and synthesis can be performed appropriately by known methods such as bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization.
  • the present embodiment is not limited only to such examples.
  • the bulk polymerization method and the emulsion polymerization method are preferred, the bulk polymerization method is more preferred, and the photo-bulk polymerization method is still more preferred, from the viewpoint of increasing the molecular weight.
  • the elastomer of the present embodiment is polymerized by a bulk polymerization method, it is not necessary to use a dispersant, solvent, etc. during synthesis, so it is necessary to remove the dispersant, solvent, etc. from the system in which the polymer is synthesized. and excellent productivity.
  • the elastomer of the present embodiment is produced by, for example, polymerizing a (meth)acrylate monomer having an ether structure (monomer (A)) and a (meth)acrylamide having a cyano group (monomer (B)). It is possible to manufacture the elastomer by a process for producing the elastomer, including the step of obtaining coalescence. Further, in the step of obtaining the above polymer, a (meth)acrylate monomer having an ether structure (monomer (A)) and a (meth)acrylamide having a cyano group (monomer (B)) are polymerized by bulk photopolymerization. be able to.
  • the monomer (A) and the monomer (B) can be polymerized (for example, bulk polymerization by ultraviolet irradiation) using a polymerization initiator as necessary to synthesize a polymer composed of the structural units (A) and (B).
  • the atmosphere in which the polymer or the like of the present embodiment is polymerized is not particularly limited, and may be air or an inert gas such as nitrogen gas or argon gas.
  • the temperature at which the polymer of the present embodiment is polymerized is not particularly limited, and a temperature of about 5 to 100°C is usually preferred.
  • the time required to polymerize the monomer components varies depending on the polymerization conditions and cannot be generally determined.
  • the polymerization reaction can optionally be terminated when the amount of remaining monomer components is 20% by weight or less.
  • the amount of the remaining monomer component can be measured using, for example, gel permeation chromatography.
  • a photopolymerization initiator to be described later may be used.
  • the conditions for bulk polymerization of the polymer of the present embodiment are not particularly limited, but from the viewpoint of obtaining a polymer with the preferred molecular weight range described above and from the viewpoint of low hysteresis loss, an ultraviolet illumination intensity of 10 mW/cm 2 or less is preferable. 1 mW/cm 2 or less is more preferable, and 0.6 mW/cm 2 or less is even more preferable. From the viewpoint of polymerizability, it is preferably 0.01 mW/cm 2 or more.
  • a polymerization initiator (photopolymerization initiator, thermal polymerization initiator), a chain transfer agent, etc. may be used in order to polymerize the above monomer components to synthesize the polymer of the present embodiment.
  • known ones can be appropriately selected and used.
  • a photopolymerization initiator is a compound that is activated by various actinic rays such as ultraviolet rays to initiate a polymerization reaction.
  • photopolymerization initiators include radical photopolymerization initiators, cationic photopolymerization initiators, and anionic photopolymerization initiators.
  • One of these photopolymerization initiators may be used alone, or two or more thereof may be used in combination.
  • two or more radical photopolymerization initiators can be used in combination.
  • the photopolymerization initiator it is desirable to appropriately select a compound having absorption at the exposure wavelength when the polymer of the present embodiment is photocured.
  • the content of the photopolymerization initiator in the polymer of the present embodiment varies depending on the type of the photopolymerization initiator, and cannot be generally determined. , about 0.01 to 20 parts by mass.
  • a surfactant may be used in synthesizing the polymer or the like of the present embodiment.
  • the polymer or the like of the present embodiment contains a surfactant, it is possible to form a film or membrane with less unevenness on the surface.
  • the content of the surfactant in the polymer of the present embodiment is not particularly limited, but from the viewpoint of suppressing the occurrence of unevenness on the surface of the coating film during application, the total amount of the polymer of the present embodiment is 0.5. 01 to 1% by mass is preferable, 0.05 to 0.5% by mass is more preferable, and 0.1 to 0.3% by mass is particularly preferable.
  • the surfactant examples include dimethylsiloxane-based surfactants and fluorine-based surfactants, with dimethylsiloxane-based surfactants being preferred.
  • a surfactant having a crosslinkable functional group such as acryloyl group-containing polyether-modified dimethylsiloxane is preferable.
  • the crosslinkable functional group examples include a (meth)acryloyl group and an allyl group.
  • dimethylsiloxane-based surfactants examples include commercial products such as BYK-UV3500, BYK-UV3505, BYK-UV3510, BYK-UV3535, BYK-UV3570, BYK-UV3575, and BYK-UV3576 manufactured by BYK Additives & Instruments. etc. can be used, and among them, BYK-UV3500 is preferable.
  • the polymer of the present embodiment can be used in combination with a chain transfer agent, a thermal polymerization initiator, a photosensitizer, etc., as desired, as long as the effects of the present invention are not impaired.
  • the polymer etc. of the present embodiment uses a monomer (C1) having a substituent such as a hydroxyl group (for example, a hydroxyalkyl (meth)acrylate monomer such as 4HBA).
  • a crosslinked structure can also be imparted to the polymer or the like of the present embodiment.
  • a polymer obtained by polymerizing the monomers (A) to (C1) is dissolved in a solvent to form a solution, and a monomer (C2) (for example, isocyanate
  • a monomer having a group for example, isocyanate
  • the monomer (C2) that serves as a cross-linking agent is bonded to the polymer unit (C1), and the monomer (C2) is polymerized with each other.
  • a polymer having a crosslinked structure can be obtained by forming chains, forming hydrogen bonds between the side chains of each polymer, or intertwining the main chains and side chains of each polymer. It is considered to be done.
  • a monomer (C1) having a substituent such as a hydroxyl group e.g., a hydroxyalkyl (meth)acrylate monomer such as 4HBA
  • a monomer (C2) serving as a cross-linking agent e.g., a monomer having an isocyanate group
  • a polymer having such a crosslinked structure is also included in the polymer or the like of the present embodiment.
  • the polymer or the like of the present embodiment can be dissolved in a solvent to form a resin solution.
  • the solvent is not particularly limited, but for example, benzene-based solvents, ketone-based solvents, ester-based solvents and the like can be used. Specifically, toluene, cyclopentanone, butyl acetate, carbitol acetate and the like can be used. can be mentioned.
  • a catalyst when imparting a crosslinked structure to the polymer or the like of the present embodiment, a catalyst can be used together with the monomer (C2) functioning as a crosslinker.
  • the catalyst is mainly added for the purpose of adding the monomer (C2) such as isocyanate used as a cross-linking agent to the hydroxyl groups of the units (C1) in the polymer and the like of the present embodiment.
  • the catalyst is not particularly limited, for example, a tin catalyst or the like can be used.
  • the monomer (C1) can be appropriately selected from the monomers (C) described above, and for example, hydroxyalkyl (meth)acrylate monomers, carboxyl group-containing monomers, and the like can be used.
  • the monomer (C2) used as a cross-linking agent can be appropriately selected from the monomers (C) described above, and for example, a (meth)acryloxyalkyl isocyanate monomer or the like can be used.
  • the content of the monomer (C2) is set to the monomer (C1 ) is preferably from 25 to 800 mol %, more preferably from 50 to 400 mol %, and particularly preferably from 100 to 200 mol %.
  • the reaction conditions for the reaction between the hydroxyl group of the unit (C1) in the polymer etc. of the present embodiment and the isocyanate etc. of the unit (C2) in the polymer etc. of the present embodiment are not particularly limited.
  • the heating temperature is preferably 40 to 100°C, more preferably 60 to 80°C; the heating time is preferably 0.5 to 12 hours, and 1 to 6 hours. More preferred.
  • the light irradiation conditions are not particularly limited, but ultraviolet light or the like is used.
  • the ultraviolet illuminance is preferably from 10 to 10,000 mW/cm 2 and more preferably from 100 to 1,000 mW/cm 2 from the viewpoints of reliably forming a crosslinked structure and the necessary and sufficient irradiation dose. It is preferable that the cumulative ultraviolet irradiation amount is 100 mJ/cm 2 or more.
  • ⁇ Usage form of elastomer>> The shape and the like of the elastomer of this embodiment can be appropriately designed according to the intended use.
  • the elastomer of the present embodiment can be used, for example, as a sheet-like elastomer or a laminate obtained by laminating elastomers.
  • the thickness of the sheet is not particularly limited. Further, when the elastomer of the present embodiment is used as a laminate, for example, in the case of a dielectric elastomer application, it can be formed by laminating 100 to 300 sheet-like elastomer sheets having a thickness of 10 ⁇ m to 50 ⁇ m.
  • the elastomer of this embodiment may contain an appropriate amount of other polymer according to the desired purpose, such as adjusting its viscosity.
  • Other polymers include, for example, acrylic resins, polyacrylonitrile, poly(meth)acrylamide, polyamide, polyvinyl chloride, polyurethane, polyester, carboxymethylcellulose, etc., but the present embodiment is limited only to these examples. not a thing These other polymers may be used alone or in combination of two or more.
  • the elastomer of this embodiment may contain a neutralizing agent, if necessary.
  • neutralizing agents include inorganic basic compounds such as sodium hydroxide and potassium hydroxide; monoethanolamine, dimethylethanolamine, diethylethanolamine, triethanolamine, morpholine, aminomethylpropanol, aminomethylpropanediol, octyl
  • organic basic compounds such as amine, tributylamine, and aniline, but the present embodiment is not limited to such examples. These neutralizing agents may be used alone or in combination of two or more.
  • the elastomer of the present embodiment may contain additives within a range that does not hinder the purpose of the present embodiment.
  • additives include coloring agents, antioxidants, ultraviolet absorbers, anti-aging agents, thermally conductive fillers, conductive fillers, etc.
  • the present embodiment is not limited only to such examples. do not have.
  • the elastomer of the present embodiment When the elastomer of the present embodiment is made into a sheet, it can be used as it is depending on the application. Stretched is more preferable.
  • the draw ratio of the sheet is preferably 1.2 times or more, more preferably 1.5 times or more, and still more preferably 2 times or more from the viewpoint of imparting toughness. Although it depends on the thickness of the film, From the viewpoint of preventing breakage during stretching, it is preferably 8 times or less, more preferably 6 times or less, and still more preferably 5 times or less.
  • stretching the sheet it may be heated, if necessary.
  • the elastomer of this embodiment can be used as a dielectric elastomer whose thickness and size change according to the applied voltage.
  • the dielectric elastomer of the present embodiment can be used, for example, in electric devices such as actuators, sensors used in industrial robots, power generating elements, speakers, microphones, noise cancellers, transducers, artificial muscles, small pumps, and medical instruments. There is expected.
  • the elastomer of this embodiment can be designed to exhibit a large amount of displacement even when the applied voltage is low, so it can be suitably used for an actuator.
  • FIG. 1 is a schematic plan view showing one embodiment of the actuator of the present invention.
  • FIG. 2 is a schematic cross-sectional view of the actuator shown in FIG. 1 taken along line AA.
  • FIG. 3 is a schematic diagram for explaining displacement of an elastomer.
  • the actuator 1 is made up of a film-like elastomer 2 and a pair of electrodes 3A and 3B.
  • the elastomer 2 and the electrodes 3A and 3B can be adhered with, for example, a conductive paste (not shown).
  • conductive pastes include conductive pastes containing conductive fillers such as carbon and silver.
  • the elastomer 2 is preferably uniaxially stretched or biaxially stretched, preferably biaxially stretched.
  • the draw ratio of the elastomer 2 is not particularly limited, but from the viewpoint of imparting toughness, it is preferably 1.2 times or more, more preferably 1.5 times or more, and still more preferably 2 times or more. Although it depends on the thickness of the elastomer, it is preferably 8 times or less, more preferably 6 times or less, and even more preferably 5 times or less from the viewpoint of preventing breakage during stretching.
  • the thickness of the elastomer 2 is preferably 1 to 100 ⁇ m, more preferably 1 to 80 ⁇ m, even more preferably 1 to 50 ⁇ m, and even more preferably 1 to 50 ⁇ m, from the viewpoint of allowing the actuator 1 to exhibit a large amount of displacement even when the applied voltage is low. is 1 to 30 ⁇ m.
  • Electrode materials include, for example, indium tin oxide (ito), antimony tin oxide (ato), fluorine-doped tin oxide (fto), fluorine tin oxide (fto), aluminum zinc oxide (azo), gallium zinc oxide ( gzo), tin oxide (nesa), indium zinc oxide (izo), silver oxide, vanadium oxide, molybdenum oxide, gold, silver, platinum, copper, indium, chromium and other metals and metal oxides, polycrystalline silicon, amorphous silicon and carbon materials such as carbon black, graphite, and glassy carbon, but the present invention is not limited to these examples. Each of these electrode materials may be used alone, or two or more of them may be used in combination.
  • the shape, size and thickness of the electrodes 3A and 3B are not particularly limited and can be arbitrarily determined according to the application of the actuator 1. Examples of shapes of the electrodes 3A and 3B include circular, elliptical, triangular, square, and rectangular. As an example of the size of the electrodes 3A and 3B, a circular one having a diameter of 1 to 20 mm can be mentioned. Although the thickness of the electrodes 3A and 3B is not particularly limited, it is usually about 50 to 500 ⁇ m.
  • a terminal 4A is arranged on the diametrical outer peripheral surface of the electrode 3A, and a terminal 4B is arranged on the diametrical outer peripheral surface of the electrode 3B.
  • the terminals 4A and 4B are connected to the power source 6 through the conductors 5A and 5, respectively.
  • the displacement of the actuator 1 when voltage is applied to the electrodes 3A and 3B can be measured by the displacement gauge 8.
  • Example 1 Synthesis of elastomer 21.0 g of methoxyethyl acrylate (MTA; monomer (A)), 223 g of cyanoethylacrylamide (CEAAM; monomer (B)), and 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a polymerization initiator [manufactured by BASF, commercial name: Irgacure TPO] to obtain a monomer component containing a polymerization initiator.
  • MTA methoxyethyl acrylate
  • CEAAM cyanoethylacrylamide
  • Irgacure TPO 2,4,6-trimethylbenzoyldiphenylphosphine oxide
  • the resulting monomer component was filled in a SUS molded container (length: 43 cm, width: 43 cm, depth: 2 mm) and covered with transparent glass (length: 43 cm, width: 43 cm, thickness: 2 mm). After that, the monomer component was irradiated with ultraviolet rays from above so that the illuminance was 0.58 mW/cm 2 , and the monomer component was subjected to bulk polymerization for 2 hours to obtain a sheet-like elastomer having the following MTA-CEAAM structure. rice field.
  • Example 2 to 4 Each elastomer (sheet) was produced in the same manner as in Example 1, except that the monomers (A) and (B) and their amounts were changed according to the table below.
  • BA butyl acrylate
  • CNEA cyanoethyl acrylate
  • the thickness of each elastomer sheet was measured using a thickness gauge (manufactured by Nikon Corporation, product name: DIGIMICRO MFC-101A). In addition, the measurement was performed 5 times for an arbitrary portion, and the average value was taken as the thickness of the sheet.
  • a test piece was obtained by punching each elastomer sheet into a dumbbell-shaped No. 7 shape defined in 6.1 of JIS K6251.
  • the obtained test piece was attached to a tensile tester [manufactured by A&D Co., Ltd., product number: Tensilon RTG-1310] so that the distance between chucks was 19 mm, and the test piece was broken at a tensile speed of 100 mm / min.
  • the Young's modulus was measured by applying a tensile load until the tension was reached.
  • a displacement measurement marker was attached to one electrode of the actuator, and a DC voltage (1000 V) was applied between the electrodes with a voltage amplifier [manufactured by Matsusada Precision Co., Ltd., product number: HEOPS-10B2]. At this time, the amount of displacement (mm) of the marker was measured with a displacement meter [manufactured by Keyence Corporation, product number: LK-GD500].
  • An elastomer was obtained by subjecting the obtained monomer component to bulk polymerization for 2 hours in the same manner as in Example 1, except that the obtained monomer component was irradiated with ultraviolet rays from above so that the illuminance was 0.62 mW/cm 2 . .
  • a resin solution was obtained by dissolving 112 g of the obtained elastomer in 1011 g of butyl acetate.
  • 2,4,6-trimethylbenzoyldiphenylphosphine oxide [manufactured by BASF Corporation, trade name : Irgacure TPO] and 1.13 g of a surfactant (manufactured by BYK Additives & Instruments, trade name: BYK-UV3500) were added and stirred to prepare a curable resin composition.
  • Another release film was adhered to the obtained coating film, and pressed with a heated laminator (manufactured by FUJIPLA, used at 90° C.).
  • the resulting film-like coating film was cured in an air atmosphere at an ultraviolet illuminance of 500 mW/cm 2 ⁇ for 2.4 seconds ⁇ 1 pass (accumulated irradiation amount: 1200 mJ/cm 2 ) to form a front side film and a back side film.
  • An elastomer (sheet) sandwiched between was produced, and the same evaluation as in Example 1 was performed.
  • Hysteresis loss was derived as an evaluation index for the resilience of the elastomer sheets obtained in Examples 1 and 5. Specifically, the following measurements were performed using the test piece and tensile tester described above, and the hysteresis loss was calculated using the obtained graph.
  • the measurement is performed by applying a tensile load to the test piece to 100% elongation (an operation to set the distance between chucks to 38 mm) and an operation to return the test piece that has reached 100% to 0% (distance between chucks of 38 mm to 19 mm Return operation) (both 100 mm/min) was performed as one cycle, and two cycles were performed, and the hysteresis loss was calculated from the graph of the measurement results of the second cycle.
  • the data storage interval was 0.1 seconds.
  • FIG. 4 is a graph for explaining hysteresis loss.
  • the horizontal axis represents film elongation and the vertical axis represents normalized stress. Normalized stress is the value obtained by dividing the observed stress at each time by the observed stress at 100% film elongation.
  • the hysteresis loss was calculated by calculating the area of the area surrounded by the dotted line (outward path) and the solid line (return path) in FIG. A smaller hysteresis loss indicates better followability. The area was calculated as follows.
  • ⁇ t be the elongation of the film at a certain time t.
  • Example 1 the combination of MTA/CEAAM using CEAAM with higher polarity (Example 1 ) yielded an elastomer with a higher dielectric constant and higher displacement. For this reason, it was found that copolymerization of acrylamide having a cyano group with MTA resulted in a higher dielectric constant and a higher displacement than acryl having a cyano group. From the comparison of Example 1 and Comparative Example 5, it can be seen that MTA, which is as flexible as BA and has a high polarity, is copolymerized more than Comparative Example 5, which is a copolymer of highly polar CEAAM and butyl acrylate (BA). In Example 1, the dielectric constant and the amount of displacement were larger. Therefore, it was found that the dielectric constant and the displacement amount can be increased by copolymerizing the highly polar CEAAM with the soft and relatively highly polar MTA.
  • BA butyl acrylate
  • Example 5 Furthermore, from a comparison between Example 1 and Example 5, 4HBA as a cross-linking group was introduced in order to improve the reversion property, MOI-EG was added to the hydroxy group, and then a cross-linked structure was imparted by a photo-cross-linking reaction.
  • the elastomer (Example 5) was able to reduce the hysteresis loss compared to Example 1.
  • the elastomer of the present invention is not particularly limited, but is useful as a dielectric elastomer. It is expected to be used for small pumps and medical instruments.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un polymère contenant : une unité (A) issue d'un monomère (méth)acrylate ayant une structure éther ; et une unité (B) issue de (méth)acrylamide ayant un groupe cyano.
PCT/JP2022/042314 2021-11-16 2022-11-15 Polymère, élastomère, son procédé de production, actionneur et capteur WO2023090304A1 (fr)

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JP2018168480A (ja) * 2017-03-29 2018-11-01 三菱ケミカル株式会社 炭素繊維前駆体アクリル繊維および炭素繊維束の製造方法
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