WO2015119197A1 - 電極および電極の製造方法 - Google Patents
電極および電極の製造方法 Download PDFInfo
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- WO2015119197A1 WO2015119197A1 PCT/JP2015/053240 JP2015053240W WO2015119197A1 WO 2015119197 A1 WO2015119197 A1 WO 2015119197A1 JP 2015053240 W JP2015053240 W JP 2015053240W WO 2015119197 A1 WO2015119197 A1 WO 2015119197A1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
- A61B5/25—Bioelectric electrodes therefor
- A61B5/279—Bioelectric electrodes therefor specially adapted for particular uses
- A61B5/291—Bioelectric electrodes therefor specially adapted for particular uses for electroencephalography [EEG]
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
Definitions
- the present invention relates to an electrode and a method for manufacturing the electrode.
- This application claims priority based on Japanese Patent Application No. 2014-021782 for which it applied to Japan on February 6, 2014, and uses the content here.
- an electrode that is used by being attached to the living body or embedded in the living body is used.
- an electrode a sword mountain-shaped electrode array in which a plurality of electrode elements made of platinum or gold are inserted into a living tissue is known (for example, Patent Document 1).
- Patent Document 1 a sword mountain-shaped electrode array in which a plurality of electrode elements made of platinum or gold are inserted into a living tissue.
- Patent Document 2 describes an electrode that is minimally invasive by using a fine metal wire as an electrode element.
- an electrode element made of a metal such as platinum or gold is basically harmless to the human body.
- a reaction inflammatory reaction
- it is difficult to perform long-term biological information observation.
- hard metal is rubbed in a soft living body, there is a problem that damage to the living body due to friction is large.
- Non-Patent Document 1 discloses a technique for forming a silicone insulating wall around an electrode element.
- the insulating wall made of silicone is coated with a photoresist on the electrode element on the electrode base material, and a thermosetting silicone prepolymer is spin-coated thereon, followed by heating to cure the polysiloxane compound. It is obtained by removing the photoresist.
- Non-Patent Document 2 also describes that a polysiloxane compound having a vinyl ether group at the terminal is spin-coated on an electrode substrate, and an insulating portion of the electrode is formed by a photolithography method using photopolymerization.
- thermosetting polysiloxane compound described in Non-Patent Document 1 has a problem in productivity because it takes a long time to cure.
- the polysiloxane compound having a vinyl ether group at the terminal described in Non-Patent Document 2 is considered to have a problem in patternability because the radical polymerization reaction hardly proceeds.
- An object of this invention is to provide the electrode provided with the insulating wall excellent in the patternability and the biocompatibility.
- An electrode according to an embodiment of the present invention for solving the above-described problems includes an electrode element on a base material, two or more (meth) acryloyl groups per molecule formed on the periphery of the electrode element, and a styrenic vinyl.
- FIG. 1 is a diagram schematically showing a cross section of an electrode according to an embodiment of the present invention.
- An electrode 10 shown in FIG. 1 includes an electrode element 2 and an insulating wall 4 formed around the electrode element 2 on a base material 1.
- the base material 1 of the electrode 10 is not particularly limited, it is preferable that the base material 1 has a strength as a base of the electrode 10 and maintains flexibility. Specifically, the Young's modulus is preferably 0.1 GPa to 10 GPa.
- the substrate for example, polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polytetrafluoroethylene (Teflon (registered trademark)), or the like can be used.
- the thickness of the substrate 1 is preferably thinner than the thickness of the insulating wall 4 described later. Since the insulating wall 4 to be described later generally has a low Young's modulus and is soft, the flexibility of the electrode 10 can be ensured by making the thickness of the substrate 1 thinner than the thickness of the insulating wall 4. Specifically, the thickness of the substrate 1 is preferably 1 ⁇ m or more and 50 ⁇ m or less. If the thickness of the substrate 1 is thinner than 1 ⁇ m, the strength is not sufficient as a base of the electrode 10 and the overall mechanical strength is lowered. When the thickness of the base material 1 is thicker than 50 ⁇ m, it is difficult to ensure sufficient flexibility of the electrode. Therefore, the followability to a complicated shape such as the brain is deteriorated.
- the material of the electrode element 2 is not particularly limited, but a metal such as gold or platinum, an organic conductive material PEDOT / PSS, a carbon nanomaterial, or a biocompatible conductive substance may be used. it can.
- the electrode element 2 In order to increase the sensitivity of the electrode element 2, it is preferable to use highly conductive metals such as gold and platinum. In order to prevent an adverse effect on the living body due to a defense reaction, friction, or the like, it is preferable to cover the electrode element 2 with a biological buffer layer 3 having biocompatibility as described later.
- the insulating wall 4 constitutes a polysiloxane compound having a functional group selected from the group consisting of two or more (meth) acryloyl groups, styrenic vinyl groups, vinyl ester groups, maleate groups and maleimide groups per molecule. As a component, it is formed from a polymer obtained by polymerization of the functional group.
- a functional group selected from the group consisting of (meth) acryloyl group, styrenic vinyl group, vinyl ester group, maleate group and maleimide group is collectively referred to as “polymerizable functional group”.
- polysiloxane compound having a functional group selected from the group consisting of two (meth) acryloyl groups, a styrenic vinyl group, a vinyl ester group, a maleate group and a maleimide group” per molecule is designated as “Component A "
- the number average molecular weight of component A is preferably 6000 or more. When the number average molecular weight of component A is in this range, a polymer having excellent flexibility and excellent mechanical properties such as bending resistance can be obtained.
- the number average molecular weight of component A is preferably 8000 or more, more preferably in the range of 8000 to 100,000, and more preferably in the range of 9000 to 70000, because a polymer excellent in mechanical properties such as bending resistance can be obtained. More preferably, it is most preferably in the range of 10,000 to 50,000. When the number average molecular weight of component A is too small, mechanical properties such as bending resistance tend to be low. When the number average molecular weight of component A is too large, flexibility and transparency tend to decrease.
- the number average molecular weight of the compound is a polystyrene-equivalent number average molecular weight measured by a gel permeation chromatography method (GPC method) using chloroform as a solvent.
- GPC method gel permeation chromatography method
- the values measured by the same method are used for the mass average molecular weight and the dispersity (value obtained by dividing the mass average molecular weight by the number average molecular weight).
- the dispersity (the value obtained by dividing the mass average molecular weight by the number average molecular weight) of component A is preferably 6 or less, more preferably 3 or less, still more preferably 2 or less, and most preferably 1.5 or less.
- the degree of dispersion of component A is small, compatibility with other components is improved, and there are advantages such as reduction of impurities contained in the resulting polymer and reduction in shrinkage due to polymer molding.
- Component A is preferably a compound having the structure of the following general formula (A1).
- X 1 and X 2 each independently represent a functional group selected from the group consisting of a (meth) acryloyl group, a styrenic vinyl group, a vinyl ester group, a maleate group, and a maleimide group.
- R 1 to R 6 each independently represents a substituent selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, a phenyl group, and a fluoroalkyl group having 1 to 20 carbon atoms.
- L 1 and L 2 each independently represents a divalent group.
- a is the number of repeating siloxane units and represents an integer of 1 to 3000.
- X 1 and X 2 are most preferably a (meth) acryloyl group.
- hydrogen, an alkyl group, and a fluoroalkyl group can be used as preferred specific examples of R 1 to R 6 .
- the alkyl group include alkyl groups having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, decyl group, dodecyl group, and octadecyl group.
- Fluoroalkyl groups include phenyl, trifluoromethyl, trifluoroethyl, trifluoropropyl, tetrafluoropropyl, hexafluoroisopropyl, pentafluorobutyl, heptafluoropentyl, nonafluorohexyl, hexa Fluorobutyl, heptafluorobutyl, octafluoropentyl, nonafluoropentyl, dodecafluoroheptyl, tridecafluoroheptyl, dodecafluorooctyl, tridecafluorooctyl, hexadecafluorodecyl, heptadecafluoro Decyl, tetrafluoropropyl, pentafluoropropyl, tetradecafluorooctyl, pentadecafluorooctyl
- L 1 and L 2 are preferably an alkyl group having 1 to 20 carbon atoms or a fluoroalkyl group.
- a group represented by any one of the following formulas (LE1) to (LE12) is preferable, and a group represented by the following formula (LE1), (LE3), (LE9) or (LE11) is more preferable.
- a group represented by (LE1) or (LE3) is more preferred, and a group represented by the following formula (LE1) is most preferred.
- the compound of the general formula (A1) is easily obtained with high purity.
- Formula (LE1) ⁇ (LE12) the terminal of the left is attached to the polymerizable functional group X 1 or X 2, is depicted as an end of the right side is attached to a silicon atom.
- the value of a is preferably 80 or more, more preferably 100 or more, more preferably 100 to 1400, more preferably 120 to 950, and still more preferably 130 to 700.
- a is preferably 80 to 1500, more preferably 100 to 1400, more preferably 120 to 950, and still more preferably 130 to 700.
- the polymer forming the insulating wall 4 is a functional group (polymerizable) selected from the group consisting of one (meth) acryloyl group, styrenic vinyl group, vinyl ester group, maleate group and maleimide group per molecule.
- a copolymer of component M, which is a polysiloxane compound having a functional group), and component A may be used.
- the number average molecular weight of component M is preferably 300 to 120,000. When the number average molecular weight of component M is in this range, a polymer having excellent flexibility and excellent mechanical properties such as bending resistance can be obtained.
- the number average molecular weight of the component M is preferably 500 or more, more preferably in the range of 1000 to 25000, and still more preferably in the range of 5000 to 15000. If the number average molecular weight of the component M is too small, mechanical properties such as bending resistance and shape recovery tend to be low. When the number average molecular weight of the component M is too large, the flexibility tends to decrease.
- Component M preferably has a structure represented by the following general formula (M1).
- X 3 is most preferable because the (meth) acryloyl group has the highest polymerizability.
- preferred specific examples of R 7 to R 13 are the same as those listed as preferred examples of R 1 to R 6 in the general formula (1).
- Preferred specific examples of L 3 are the same as those listed as preferred examples of L 1 and L 2 in the general formula (1).
- b represents an integer of 1 to 1400. b is preferably 3 or more, more preferably 10 or more, further preferably 10 to 500, still more preferably 30 to 300, and most preferably 50 to 200. In particular, when R 7 to R 13 are all methyl groups, b is preferably 3 to 700, more preferably 10 to 500, still more preferably 30 to 300, and still more preferably 50 to 200.
- the mass ratio of the component A and the component M contained in the polymer constituting the insulating wall 4 is preferably 5 to 200 parts by mass, more preferably 7 to 150 parts by mass with respect to 100 parts by mass of component A. More preferred is 10 to 100 parts by mass.
- the polymer contains an appropriate amount of the component M, the crosslinking density is reduced, the degree of freedom of the polymer is increased, and a moderately soft polymer having a low Young's modulus can be realized.
- the content of the component M is less than 5 parts by mass with respect to 100 parts by mass of the component A, the crosslinking density increases and the polymer tends to be hard.
- the content of Component M exceeds 200 parts by mass with respect to 100 parts by mass of Component A, the content tends to be too soft.
- the component M may be used alone or in combination of two or more.
- the polymer forming the insulating wall 4 is composed of a fluoroalkyl group, one or more (meth) acryloyl groups per molecule, a styrenic vinyl group, a vinyl with respect to Component A or the copolymer of Component A and Component M. It is also preferably a copolymer obtained by copolymerizing Component B, which is a compound having a functional group (polymerizable functional group) selected from the group consisting of an ester group, a maleate group and a maleimide group.
- Component B has water and oil repellency properties due to a decrease in critical surface tension resulting from the fluoroalkyl group, and thereby has an effect of suppressing contamination of the polymer surface with components such as lipids.
- Component B has the effect of giving an electrode that is flexible and excellent in mechanical properties such as bending resistance.
- Preferred specific examples of the fluoroalkyl group of Component B are trifluoromethyl group, trifluoroethyl group, trifluoropropyl group, tetrafluoropropyl group, hexafluoroisopropyl group, pentafluorobutyl group, heptafluoropentyl group, nonafluoro group.
- it is a C2-C8 fluoroalkyl group such as a trifluoroethyl group, a tetrafluoropropyl group, a hexafluoroisopropyl group, an octafluoropentyl group, and a dodecafluorooctyl group, most preferably trifluoroethyl group It is a group.
- the polymerizable functional group of component B is most preferably a (meth) acryloyl group.
- (Meth) acrylic acid fluoroalkyl ester is most preferred as component B because it has a great effect of obtaining an electrode that is flexible and excellent in mounting feeling and has excellent mechanical properties such as bending resistance.
- Specific examples of such (meth) acrylic acid fluoroalkyl esters include trifluoroethyl (meth) acrylate, tetrafluoroethyl (meth) acrylate, trifluoropropyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, and pentafluoropropyl.
- Trifluoroethyl (meth) acrylate, tetrafluoroethyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, and dodecafluorooctyl (meth) acrylate are preferably used. Most preferred is trifluoroethyl (meth) acrylate.
- the content of Component B in the copolymer is preferably 10 to 500 parts by weight, more preferably 20 to 400 parts by weight, and even more preferably 20 to 200 parts by weight with respect to 100 parts by weight of Component A.
- component B In the polymer constituting the insulating wall 4, only one type of component B may be used, or two or more types may be used in combination.
- Component C is preferably one that lowers the glass transition point of the copolymer to room temperature or 0 ° C. or lower. Since these reduce the cohesive energy, they have the effect of imparting rubber elasticity and softness to the copolymer.
- Examples of the component C that lowers the glass transition point of the copolymer to room temperature or below 0 ° C. are (meth) acrylic acid alkyl esters, preferably (meth) acrylic acid alkyl esters having an alkyl group having 1 to 20 carbon atoms. It is.
- n-butyl (meth) acrylate, n-octyl (meth) acrylate, n-lauryl (meth) acrylate, and n-stearyl (meth) acrylate are more preferable.
- (meth) acrylic acid alkyl esters having an alkyl group with 1 to 10 carbon atoms are more preferred.
- an aromatic vinyl compound such as styrene, tert-butylstyrene, ⁇ -methylstyrene or the like as Component C.
- an aromatic vinyl compound such as styrene, tert-butylstyrene, ⁇ -methylstyrene or the like.
- the insulating wall 4 preferably has a degree of crosslinking in the range of 2.0 to 18.3.
- the degree of crosslinking is represented by the following formula (Q1).
- Qn represents the total millimolar amount of the monomer having n polymerizable functional groups per molecule
- Wn represents the total mass (kg) of the monomer having n polymerizable groups per molecule.
- the degree of cross-linking of the insulating wall 4 is smaller than 2.0, it is too soft and easily damaged, and when it is larger than 18.3, it tends to be too hard and poor adhesion to a living body.
- the degree of crosslinking is more preferably from 3.5 to 16.0, even more preferably from 8.0 to 15.0, and most preferably from 9.0 to 14.0.
- the insulating wall 4 preferably has a Young's modulus of 0.5 MPa to 2000 MPa, preferably 1 MPa to 1000 MPa. Since the insulating wall 4 has such hardness, the insulating wall 4 can support the base material 1 and the biological buffer layer 3 like a skeleton, and the mechanical strength of the electrode can be increased.
- the tensile elongation (breaking elongation) of the insulating wall 4 is preferably 50% or more, more preferably 150% or more, further preferably 170% or more, more preferably 200% or more, still more preferably 300% or more, 400% The above is particularly preferable.
- the tensile elongation of the insulating wall 4 is preferably 3000% or less, more preferably 2500% or less, further preferably 2000% or less, still more preferably 1500% or less, and most preferably 1000% or less. If the tensile elongation is small, the insulating wall is easily broken, which is not preferable. When the tensile elongation is too large, the insulating wall tends to be easily deformed, which is not preferable.
- the material of the insulating wall 4 preferably has high oxygen permeability.
- the oxygen permeability coefficient [ ⁇ 10 ⁇ 11 (cm 2 / sec) mLO 2 / (mL ⁇ hPa)] is preferably 50 or more, more preferably 100 or more, further preferably 200 or more, and most preferably 300 or more.
- the oxygen permeability coefficient is preferably 2000 or less, more preferably 1500 or less, further preferably 1000 or less, and most preferably 700 or less. If the oxygen permeability is too large, other physical properties such as mechanical properties may be adversely affected.
- the resistivity of the insulating wall 4 is preferably 1 k ⁇ m or more, more preferably 10 k ⁇ m or more, and further preferably 100 k ⁇ m or more. Since the insulating wall 4 is required to have such a high resistance value, it is preferable that the moisture content is low.
- the moisture content of the insulating wall 4 is preferably 10% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less.
- the moisture content is calculated from the mass in the dry state of the film-shaped test piece and the mass in the wet state by the borate buffer, [ ⁇ (mass in the wet state) ⁇ (mass in the dry state) ⁇ / (Mass in wet state)] ⁇ 100.
- the wet state means a state where the sample is immersed in pure water or borate buffer at room temperature (25 ° C.) for 24 hours or more.
- the measurement of physical properties in a wet state is carried out as soon as possible after removing the sample from pure water or borate buffer and wiping the surface moisture.
- a dry state means the state which vacuum-dried the sample of the wet state at 40 degreeC for 16 hours.
- the degree of vacuum in the vacuum drying is 2 hPa or less.
- the measurement of physical property values in a dry state is performed as soon as possible after the vacuum drying.
- the borate buffer is a “salt solution” described in Example 1 of JP-T-2004-517163.
- the arrangement of the insulating wall 4 only needs to surround individual electrode elements, and the arrangement is not particularly limited, such as a square lattice arrangement, a honeycomb lattice arrangement, a random arrangement, and a rectangular lattice arrangement. From the viewpoint of ease of production, a square lattice arrangement is preferable. From the viewpoint of mechanical strength, a honeycomb lattice arrangement is preferable.
- the insulating wall does not need to stand vertically with respect to the base material, and may be inclined.
- the electrode 10 includes a step of disposing the electrode element 2 on the substrate 1 and a group consisting of two or more (meth) acryloyl groups, styrenic vinyl groups, vinyl ester groups, maleate groups and maleimide groups per molecule.
- the photocurable material contains at least a polysiloxane compound having a polymerizable functional group (component A) and a photoradical polymerization initiator, but may further contain the aforementioned component M, component B or component C. Details of these components are as described above.
- photo radical polymerization initiator examples include carbonyl compounds, peroxides, azo compounds, sulfur compounds, halogen compounds, and metal salts. These polymerization initiators are used alone or in combination.
- the amount of the polymerization initiator is preferably up to 5% by mass with respect to the polymerization mixture.
- the photocurable material preferably further contains a polymerization solvent.
- a polymerization solvent both organic and inorganic solvents are applicable.
- examples of polymerization solvents include water, alcohol solvents, glycol ether solvents, ester solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ketone solvents, aromatic hydrocarbon solvents and petroleum solvents. Can be used.
- the alcohol solvent examples include methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, t-butyl alcohol, t-amyl alcohol, tetrahydrolinalol, ethylene glycol, diethylene glycol, triethylene glycol, Tetraethylene glycol and polyethylene glycol can be used.
- Glycol ether solvents include methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and Polyethylene glycol dimethyl ether or the like can be used.
- the ester solvent ethyl acetate, butyl acetate, amyl acetate, ethyl lactate, methyl benzoate and the like can be used.
- aliphatic hydrocarbon solvent normal hexane, normal heptane, normal octane, or the like can be used.
- alicyclic hydrocarbon solvent cyclohexane, ethylcyclohexane, or the like can be used.
- ketone solvent acetone, methyl ethyl ketone, methyl isobutyl ketone, or the like can be used.
- aromatic hydrocarbon solvent benzene, toluene, xylene and the like can be used. These solvents may be used alone or in combination of two or more.
- the insulating wall 4 can be formed by irradiating the photocurable material with electromagnetic waves such as ultraviolet rays, visible rays, or a combination thereof.
- the electromagnetic wave to be irradiated is preferably an electromagnetic wave having a wavelength of 200 to 500 nm.
- irradiation with light including ultraviolet light such as light from a mercury lamp or an ultraviolet lamp (for example, FL15BL, Toshiba) is performed for a short time (usually 1 hour or less).
- a preferred method of forming the insulating wall 4 by electromagnetic wave irradiation is as follows. First, a spacer is installed so as to surround the electrode element 2 on the substrate 1, and a photocurable material is filled in the space surrounded by the spacer. And, by irradiating the filled photocurable material with an electromagnetic wave after arranging a mask that is patterned so as to prevent electromagnetic wave irradiation on the electrode element 2, and then washing away the uncured photocurable material, The hardened insulating wall can be formed only in the portion irradiated with the electromagnetic wave, that is, only the portion other than the upper portion of the electrode element.
- Heat polymerization may be further performed after photopolymerization by electromagnetic wave irradiation, or heat polymerization may be performed auxiliary before photopolymerization. It is preferable to perform plasma ashing on the base material before placing the photocurable material, because the surface of the base material is modified and the adhesion to the insulating wall is further improved.
- the electrode 10 further has a biological buffer layer 3 formed on the electrode element 2 so as to prevent contact between the electrode element 2 and the living body.
- FIG. 2A is a diagram schematically showing a cross section of an electrode having a biological buffer layer
- FIG. 2B is a schematic perspective view of an electrode having a biological buffer layer.
- the electrode 20 has a plurality of electrode elements 2 arranged on the same plane on the substrate 1, a biological buffer layer 3, and an insulating wall 4 arranged around the electrode elements 2. Is provided.
- the biological buffer layer 3 is an electrically conductive layer that can transmit an electrical signal from the living body to the electrode element and has biocompatibility, and suppresses the defense reaction of the living body due to the direct contact between the electrode element and the living body. It is a layer to do.
- the insulating wall 4 may be provided with a ground wiring 5 inside or below.
- a material obtained by uniformly dispersing a conductive material in a hydrophilic gel material, a biocompatible polymer medium, or the like can be used.
- the hydrophilic gel material include hydrogels such as poly 2-hydroxyethyl methacrylate (common name: polyhema), silicone hydrogel, polyrotaxane, and polyvinyl alcohol hydrogel.
- the conductive material fine metal particles, graphite, carbon black, carbon nanomaterials and the like can be used.
- a gel in which a carbon nanomaterial double-coated with a molecule constituting a hydrophilic ionic liquid and a water-soluble polymer is dispersed in a water-soluble polymer medium and the water-soluble polymer is crosslinked.
- a conductive material conductive gel may be used.
- the contact surface can follow the complex shape of the living body, and the sensitivity of the electrode can be increased.
- the base material In the laminated structure of the base material 1 and the biological buffer layer 3, in order to realize the followability of the contact surface to the complex shape surface of the living body at an extremely high level, the base material only has both flexibility and strength. It is important that the thickness and Young's modulus be the same as the living body buffer layer and the thickness that follows the contact surface. Therefore, the relationship of the thickness of the base material 1 ⁇ the thickness of the biological buffer layer 3 and the Young's modulus of the base material 1> the Young's modulus of the biological buffer layer 3 is a suitable condition.
- the Young's modulus of the biological buffer layer 3 can be appropriately determined according to the use, but is generally preferably 1 kPa to 100 kPa.
- the Young's modulus of the brain is approximately in this range, and by setting the Young's modulus of the biological buffer layer 3 to be in this range, it can be applied to soft and complex shapes such as the brain.
- the thickness of the biological buffer layer 3 is preferably 0.002 mm or more and 5 mm or less. If the thickness of the biological buffer layer 3 is less than 0.002 mm, there is a problem that the rigidity of the electrode element cannot be sufficiently absorbed and the rigidity of the surface of the biological buffer layer is increased. On the other hand, if it is thicker than 5 mm, there is a problem that the spatial resolution cannot be increased and a problem that it cannot be inserted into a narrow gap.
- the height of the insulating wall 4 is preferably substantially the same as the thickness of the biological buffer layer 3, but may be slightly higher or lower than the biological buffer layer 3. Even when the height of the insulating wall 4 is slightly lower than the thickness of the biological buffer layer 3, current leakage can be sufficiently prevented.
- the living body buffer layer 3 can sufficiently follow the living body by pressing the electrode against the living body. Can be transmitted to the electrode element.
- “slightly” means a range within 30% of the thickness of the biological buffer layer.
- the biological buffer layer and the electrode element cannot obtain strong adhesion, the biological buffer layer may be peeled off from the substrate.
- both the insulating wall 4 and the biological buffer layer 3 have substantially the same height, the contact surface between the biological buffer layer 3 and the insulating wall 4 is increased, and there is an effect that peeling of the biological buffer 4 layer can be prevented.
- the electrode 10 having the biological buffer layer 3 can be manufactured through a process of laminating the biological buffer layer 3 in addition to the above-described manufacturing method of the electrode 10.
- Such an electrode including a plurality of electrode elements may be referred to as an “electrode array”.
- FIG. 3A is a diagram schematically illustrating the operation of an electrode array having no insulating wall
- FIG. 3B is a diagram schematically illustrating the operation of an electrode array having an insulating wall according to an embodiment of the present invention. is there.
- the electrode array is in contact with the living body via the biological buffer layer 3.
- an electrical signal emitted from the nerve cell 6 diffuses to the surroundings through the biological buffer layer 3 having conductivity in the form of current. .
- the electrode element 2 closest to the nerve cell 6 measures this current most strongly, but the current leaks to the surrounding electrode elements 2 as well. This phenomenon is called crosstalk. Therefore, the electrical signal emitted from the nerve cell 6 is received in a blurred state in the entire electrode array 30, and the electrode array 30 cannot obtain a sufficient spatial resolution.
- the electrode array 20 in the case of the electrode array 20 according to the embodiment of the present invention having the insulating wall 4, since the insulating wall 4 has insulating properties, the current diffuses to the surroundings through the biological buffer layer. Inhibits. Therefore, the electrical signal emitted from the nerve cell 6 is received more strongly by the electrode element 2 closest to the nerve cell 6 and is prevented from leaking to the surrounding electrode element 2. Therefore, the electrode array 20 can exhibit high spatial resolution and sensitivity.
- the electrode array preferably includes a ground wiring 5 inside or below the insulating wall 4.
- the insulation wall 4 alone cannot sufficiently insulate, and crosstalk occurs. Therefore, by providing the ground wiring 5 in the insulating wall 4 or at the lower part of the insulating wall 4, it is possible to cut an electric signal leaking through the insulating wall 4 and to further suppress crosstalk. That is, the sensitivity of the electrode array 20 can be further increased.
- the ground wiring 5 should just have electroconductivity, A metal, an indium tin oxide (ITO), etc. can be used.
- Example 1 Polydimethylsiloxane having a methacrylate group at both ends as component A (FM7726, JNC Corporation, mass average molecular weight 29,000, number average molecular weight 26,000) (28 parts by mass), component M is a methacrylate group at one end Polydimethylsiloxane (FM0721, JNC Corporation, molecular weight 5000) (7 parts by mass), trifluoroethyl acrylate (Biscoat 3F, Osaka Organic Chemical Industry) (59.5 parts by mass) as component B, 2- Ethylhexyl acrylate (2EHA, Tokyo Chemical Industry Co., Ltd.) (5.0 parts by mass), Irgacure (IC, registered trademark) 819 (Ciba Specialty Chemicals, 0.5 parts by mass) and t-amyl alcohol (TAA, Tokyo) (Chemical Industry Co., Ltd., 10 parts by mass) was mixed and stirred.
- component A FM7726, JNC Corporation, mass average molecular weight 29,000
- a uniform and transparent photocurable material was obtained.
- This photocurable material was put into a test tube, deaerated under a reduced pressure of 20 Torr (27 hPa) while stirring with a touch mixer, and then returned to atmospheric pressure with argon gas. This operation was repeated three times.
- a glass plate was prepared as a substrate.
- An OHP sheet was placed on the substrate, and a 0.5 mm thick spacer was placed. The region surrounded by the spacer was filled with the photocurable material.
- the photocurable material was cured by UV exposure through a glass plate.
- the UV exposure at this time was carried out using a light box (W532 ⁇ D450 ⁇ H100 mm) manufactured by SUNHAYATO, using Black light FL15BL (trade name) manufactured by NEC having a UV wavelength of 300 nm to 400 nm as a light source.
- a film-shaped polymer was formed on the glass substrate.
- the obtained polymer had Young's modulus and tensile elongation as shown in Table 1. It was very flexible and excellent in mechanical strength.
- Example 2 A film-shaped polymer was formed in the same manner as in Experimental Example 1 except that the composition was changed as shown in Table 1.
- the obtained polymer had Young's modulus and tensile elongation as shown in Table 1.
- Example 9 Polyethylene glycol # 200 dimethacrylate (4G, Shin-Nakamura Chemical Co., Ltd.) (1 part by mass) as a crosslinking agent, FM7726 (mass average molecular weight 29,000, number average molecular weight 26,000) (28 parts by mass) as component A ), FM0721 (molecular weight 5000) (7 parts by mass) as component M, Biscoat 3F (59.5 parts by mass) as component B, 2EHA (5.0 parts by mass) as other components, IC819 (0.5 parts by mass) and TAA (10 parts by mass) was mixed and stirred. A uniform and transparent photocurable material was obtained. Other than that was carried out similarly to Experimental Example 1, and formed the film-shaped polymer. The obtained polymer had Young's modulus and tensile elongation as shown in Table 1.
- Example 12 A film-shaped polymer was formed in the same manner as in Experimental Example 1 except that trimethylolpropane trimethacrylate (TMPTM, Wako Pure Chemical Industries, Ltd.) was used as a crosslinking agent and the composition was as shown in Table 1.
- TMPTM trimethylolpropane trimethacrylate
- Table 1 The obtained polymer had Young's modulus and tensile elongation as shown in Table 1.
- Example 14 to 21 A film-shaped polymer was prepared in the same manner as in Experimental Example 1 except that methacryl-modified dimethyl silicone oil (FM7711, JNC Corporation, molecular weight 10,000) was used as a crosslinking agent and the composition was as shown in Tables 1 and 2. Formed. The Young's modulus and tensile elongation of the obtained polymer were as shown in Tables 1 and 2.
- methacryl-modified dimethyl silicone oil FM7711, JNC Corporation, molecular weight 10,000
- Example 22 A film-shaped polymer was formed in the same manner as in Experimental Example 1 except that the composition was changed as shown in Table 2.
- the obtained polymer had Young's modulus and tensile elongation as shown in Table 2.
- Example 26 Except that 2-hydroxy-2-methylpropiophenone (Sigma Aldrich Japan Co., Ltd., CAS No. 7473-98-5) (4.5 parts by mass) (4.5 parts by mass) was used as the photopolymerization initiator and the composition was as shown in Table 1. In the same manner as in Experimental Example 25, UV exposure was performed. Exposure was continued for 30 minutes, but no film-shaped polymer was obtained.
- 2-hydroxy-2-methylpropiophenone Sigma Aldrich Japan Co., Ltd., CAS No. 7473-98-5
- UV exposure was performed. Exposure was continued for 30 minutes, but no film-shaped polymer was obtained.
- Example 1 A polyimide film having a film thickness of 12 ⁇ m was prepared as a substrate. Gold was vapor-deposited on the polyimide film through a mask, and 64 7 mm ⁇ 7 mm square electrode elements were formed in 8 ⁇ 8 ⁇ 8 rows at 1 mm intervals. Next, a 1 mm-thick spacer was placed around the substrate, and the photo-curable material described in Experimental Example 1 was filled in the area surrounded by the spacer. On top of that, a mask in which lines with a width of 1 mm are formed in a grid pattern with an interval of 7 mm is arranged so that the lines coincide with a grid pattern on which no electrode elements are formed, and UV exposure is performed. The photocurable material was cured.
- FIG. 4 is a plan view photograph of the electrode (electrode array) produced in this example.
- Example 2 Composition in which carbon nanotubes covered with molecules constituting N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate (DEMBF 4 ) are dispersed in polyrotaxane as a biological buffer layer
- N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate (DEMBF 4 ) are dispersed in polyrotaxane as a biological buffer layer
- 30 mg of carbon nanotube (Showa Denko KK, VGCF-X, length 3 ⁇ m, diameter 15 nm) and hydrophilic ionic liquid, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium Tetrafluoroborate (DEMEBF 4 ) 60 mg was mixed and stirred in deionized water at 25 ° C.
- This gel-like substance was filled in a cell surrounded by an insulating wall of an electrode produced in the same manner as in Example 1.
- the polyrotaxane was crosslinked by UV exposure, and the carbon nanotubes covered with the molecules constituting the DEMEBF 4 were dispersed in the polyrotaxane medium, thereby producing a biological buffer layer in which the polyrotaxane was crosslinked.
- the UV exposure at this time was carried out using a light box (W532 ⁇ D450 ⁇ H100 mm) manufactured by SUNHAYATO, using Black light FL15BL (trade name) manufactured by NEC having a UV wavelength of 300 nm to 400 nm as a light source.
- the thickness of the biological buffer layer and the height of the insulating wall were set to 1 mm.
- Example 2 UV exposure was performed in the same manner as in Example 1 except that the photocurable material described in Experimental Example 26 was used. Although UV exposure was performed for 30 minutes and the photocurable material in the non-exposed part was washed, an insulating wall was not formed.
- Example 3 A spacer having a thickness of 1 mm was placed around the substrate, the composition surrounded by the spacer was filled with the composition described in Example 2, and cured by UV exposure to form a biological buffer layer. Insulating walls were not formed.
- FIG. 5A is a graph showing an output result measured by an electrode facing a portion where the input voltage is applied when an input voltage of 100 mV is applied to a certain point of the electrode array of the example.
- FIG. 5B is a graph showing an output result measured by an electrode facing a portion where the input voltage is applied when an input voltage of 100 mV is applied to a certain point of the electrode array of the example.
- the vertical axis represents output voltage
- the XY axis represents position coordinates.
- XY is 7 mm ⁇ 7 mm, which is one cell size surrounded by an insulating wall in Example 1, and this output result is an output result measured by one electrode element facing the point to which the input voltage is applied.
- the electrode array of Example 1 shows an output result of 45 mV with respect to an input voltage of 100 mV
- the electrode array of Comparative Example 3 shows only an output result of 23 mV with respect to an input voltage of 100 mV. I understand that there is no. Also, it can be seen from the graph that the electrode array of Example 1 shows a detection result with a higher peak, and the sensitivity of the electrode array is higher.
- the size of the finite difference grid is a cube having a side of 1 mm, a grid of 58 ⁇ 58 in the direction parallel to the base material, and one grid in the thickness direction perpendicular to the base material.
- the electrode array of Example 1 shows an output result of 100 mV for an input voltage of 100 mV
- the electrode array of Comparative Example 3 shows only an output result of 30 mV for an input voltage of 100 mV. I understand that there is no. Also, it can be seen from the graph that the electrode array of Example 1 shows a detection result with a higher peak, and the sensitivity is higher.
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Abstract
Description
本願は、2014年2月6日に、日本に出願された特願2014-021782に基づき優先権を主張し、その内容をここに援用する。
本発明は、パターニング性に優れるとともに、生体適合性にも優れた絶縁壁を備えた電極を提供することを目的とする。
成分Aの数平均分子量は6000以上であることが好ましい。成分Aの数平均分子量がこの範囲にあると、特にフレキシブル性に優れ、しかも耐折り曲げ性などの機械物性に優れた重合体が得られる。成分Aの数平均分子量は、耐折り曲げ性などの機械物性により優れた重合体が得られることから、8000以上が好ましく、8000~100000の範囲にあることがより好ましく、9000~70000の範囲にあることがさらに好ましく、10000~50000の範囲にあることが最も好ましい。成分Aの数平均分子量が小さすぎる場合には耐折り曲げ性などの機械物性が低くなる傾向がある。成分Aの数平均分子量が大きすぎる場合には、柔軟性や透明性が低下する傾向がある。
成分Aとしては、下記一般式(A1)の構造を有する化合物が好ましい。
一般式(A1)中、R1~R6の好適な具体例は、水素、アルキル基、フルオロアルキル基を用いることができる。アルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、t-ブチル基、デシル基、ドデシル基及びオクタデシル基などの炭素数1~20のアルキル基が挙げられる。フルオロアルキル基としては、フェニル基、トリフルオロメチル基、トリフルオロエチル基、トリフルオロプロピル基、テトラフルオロプロピル基、ヘキサフルオロイソプロピル基、ペンタフルオロブチル基、ヘプタフルオロペンチル基、ノナフルオロヘキシル基、ヘキサフルオロブチル基、ヘプタフルオロブチル基、オクタフルオロペンチル基、ノナフルオロペンチル基、ドデカフルオロヘプチル基、トリデカフルオロヘプチル基、ドデカフルオロオクチル基、トリデカフルオロオクチル基、ヘキサデカフルオロデシル基、ヘプタデカフルオロデシル基、テトラフルオロプロピル基、ペンタフルオロプロピル基、テトラデカフルオロオクチル基、ペンタデカフルオロオクチル基、オクタデカフルオロデシル基、およびノナデカフルオロデシル基などの炭素数1~20のフルオロアルキル基が挙げられる。重合体に良好な機械物性を与えるという観点から、水素およびメチル基が好ましく、メチル基が最も好ましい。すなわち、A1としてはポリジメチルシロキサン構造を有する化合物が最も好ましい。
成分Mは、下記一般記式(M1)の構造を有するものが好ましい。
一般式(M1)中、R7~R13の好適な具体例は、前述の一般式(1)のR1~R6の好適な例として列挙したものと同様である。L3の好適な具体例は、前述の一般式(1)のL1およびL2の好適な例として列挙したものと同様である。
一般式(M1)中、bは1~1400の整数を表す。bは3以上が好ましく、10以上がより好ましく、10~500がさらに好ましく、30~300が一層好ましく、50~200が最も好ましい。特に、R7~R13が全てメチル基の場合、bは3~700が好ましく、10~500がより好ましく、30~300がさらに好ましく、50~200が一層好ましい。
絶縁壁4を形成する重合体は、成分A又は成分Aと成分Mの共重合体に対して、フルオロアルキル基と、1分子あたり1個以上の(メタ)アクリロイル基、スチレン性ビニル基、ビニルエステル基、マレイン酸エステル基およびマレイミド基からなる群より選択される官能基(重合性官能基)とを有する化合物である成分Bが共重合した共重合体であることも好ましい。成分Bはフルオロアルキル基に起因する臨界表面張力の低下により、撥水撥油性の性質を持ち、これにより、重合体表面が脂質などの成分によって汚染されることを抑える効果がある。
柔軟で装着感に優れ、しかも耐折り曲げ性などの機械物性に優れた電極が得られる効果が大きいことから、成分Bとして最も好ましいのは(メタ)アクリル酸フルオロアルキルエステルである。かかる(メタ)アクリル酸フルオロアルキルエステルの具体例としては、トリフルオロエチル(メタ)アクリレート、テトラフルオロエチル(メタ)アクリレート、トリフルオロプロピル(メタ)アクリレート、テトラフルオロプロピル(メタ)アクリレート、ペンタフルオロプロピル(メタ)アクリレート、ヘキサフルオロブチル(メタ)アクリレート、ヘキサフルオロイソプロピル(メタ)アクリレート、ヘプタフルオロブチル(メタ)アクリレート、オクタフルオロペンチル(メタ)アクリレート、ノナフルオロペンチル(メタ)アクリレート、ドデカフルオロペンチル(メタ)アクリレート、ドデカフルオロヘプチル(メタ)アクリレート、ドデカフルオロオクチル(メタ)アクリレート、およびトリデカフルオロヘプチル(メタ)アクリレートが挙げられる。トリフルオロエチル(メタ)アクリレート、テトラフルオロエチル(メタ)アクリレート、ヘキサフルオロイソプロピル(メタ)アクリレート、オクタフルオロペンチル(メタ)アクリレート、ドデカフルオロオクチル(メタ)アクリレートが好ましく用いられる。最も好ましくはトリフルオロエチル(メタ)アクリレートである。
共重合体中における成分Bの好ましい含有量は、成分Aを100質量部に対して、10~500質量部が好ましく、20~400質量部がより好ましく、20~200質量部がさらに好ましい。
絶縁壁4に用いる共重合体としては、前述の成分A、成分Mおよび成分B同様の重合性官能基を有するさらに別の成分(以下「成分C」という)をさらに共重合させたものを用いてもよい。成分Cとしては、共重合体のガラス転移点を室温あるいは0℃以下に下げるものがよい。これらは凝集エネルギ-を低下させるので、共重合体にゴム弾性と柔らかさを与える効果がある。
重合体の寸法安定性を向上させるためには、例えばエチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールテトラメタクリレート、ビスフェノールAジメタクリレート、ビニルメタクリレート、アクリルメタクリレートおよびこれらのメタクリレート類に対応するアクリレート類、ジビニルベンゼン、トリアリルイソシアヌレート等を成分Cとして共重合させることが好ましい。
絶縁壁4は、架橋度が2.0~18.3の範囲であることが好ましい。架橋度は、下記式(Q1)で表される。
光硬化性材料を配置する前に、基材にプラズマアッシングを行うと、基材の表面が改質され、絶縁壁との密着性がより向上するため好ましい。
図2A及び図2Bに示される電極20は、基材1上に、同一平面上に配置された複数の電極素子2と、生体バッファ層3と、電極素子2の周囲に配置された絶縁壁4を備える。生体バッファ層3は、導電性を有し生体からの電気信号を電極素子に伝えることができ、かつ生体適合性を有する層であり、電極素子と生体の直接的接触による生体の防御反応を抑制するための層である。絶縁壁4は、その内部又は下部にアース配線5を備えていてもよい。
絶縁壁4の高さは、生体バッファ層3の厚みとほぼ同じであることが好ましいが、生体バッファ層3より僅かに高くても低くてもよい。絶縁壁4の高さが僅かに生体バッファ層3の厚みより低い場合でも、十分に電流の漏れを防ぐことができる。絶縁壁4の高さが僅かに生体バッファ層3の厚みより高い場合でも、生体に電極を押し付けることで、生体バッファ層3が十分生体に追従することができるため、生体からの電気信号を十分電極素子に伝えることができる。ここでいう「僅かに」とは、生体バッファ層の厚みの3割以内の範囲をいう。一般に、生体バッファ層と電極素子は強い密着を得ることができないため、基材から生体バッファ層が剥がれてしまうことがある。しかし、絶縁壁4と生体バッファ層3の両方がほぼ同じ高さであることにより、生体バッファ層3と絶縁壁4の接触面が増え、生体バッファ4層の剥離を防止できる効果もある。
複数の電極素子2が基材1上に規則的に配置されており、前述の重合体により形成される絶縁壁4が当該複数の電極素子2同士を絶縁するよう形成されている電極10は、本発明の電極の好適な実施態様である。このような複数の電極素子を含む電極を指して「電極アレイ」と呼ぶ場合がある。
図3Aに示すように、絶縁壁を有しない電極アレイ30の場合、例えば神経細胞6から発せられた電気信号は、電流という形で導電性を有する生体バッファ層3を介して、周囲に拡散する。神経細胞6から最も近い電極素子2が、この電流を最も強く計測するが、その周囲の電極素子2にも電流は漏れ出る。この現象をクロストークと呼ぶ。そのため、神経細胞6から発せられた電気信号は、電極アレイ30全体ではぼやけた状態で受信されることとなり、電極アレイ30は十分な空間分解能を得ることができない。
(1)ヤング率、引張伸度(破断伸度)
フィルム形状重合体から規定の打抜型を用いて幅(最小部分)5.0mm、長さ14.0mmの試験片を切り出した。該試験片を用い、オリエンテック社製のRTG-1210型試験機(ロードセルUR-10N-D型)を用いて引張試験を実施した。引張速度は100mm/分で、グリップ間の距離(初期)は5mmであった。
成分Aとして両末端にメタクリレート基を有するポリジメチルシロキサン(FM7726、JNC株式会社、質量平均分子量2.9万、数平均分子量2.6万)(28質量部)、成分Mとして片末端にメタクリレート基を有するポリジメチルシロキサン(FM0721、JNC株式会社、分子量5000)(7質量部)、成分Bとしてトリフルオロエチルアクリレート(ビスコート3F、大阪有機化学工業)(59.5質量部)、その他成分として2-エチルヘキシルアクリレート(2EHA、東京化成工業株式会社)(5.0質量部)、イルガキュア(IC、登録商標)819(チバ・スペシャリティー・ケミカルズ、0.5質量部)およびt-アミルアルコール(TAA、東京化成工業株式会社、10質量部)を混合し撹拌した。均一で透明な光硬化性材料が得られた。
この光硬化性材料を試験管に入れ、タッチミキサーで攪拌しながら減圧20Torr(27hPa)にして脱気を行い、その後アルゴンガスで大気圧に戻した。この操作を3回繰り返した。
その結果、フィルム形状の重合体をガラス基材上に形成した。得られた重合体のヤング率、引張伸度は表1の通りであり、非常にフレキシブルであり、かつ機械的強度に優れていた。
組成を表1の通りに変える以外は実験例1と同様にして、フィルム形状の重合体を形成した。得られた重合体のヤング率、引張伸度は表1の通りであった。
架橋剤としてポリエチレングリコール#200ジメタクリレート(4G、新中村化学工業株式会社)(1質量部)、成分AとしてFM7726(質量平均分子量2.9万、数平均分子量2.6万)(28質量部)、成分MとしてFM0721(分子量5000)(7質量部)、成分Bとしてビスコート3F(59.5質量部)、その他成分として2EHA(5.0質量部)、IC819(0.5質量部)およびTAA(10質量部)を混合し撹拌した。均一で透明な光硬化性材料が得られた。それ以外は実験例1と同様にし、フィルム形状の重合体を形成した。得られた重合体のヤング率、引張伸度は表1の通りであった。
組成を表1の通りにする以外は、実験例9と同様にし、フィルム形状の重合体を形成した。得られた重合体のヤング率、引張伸度は表1の通りであった。
架橋剤としてトリメチロールプロパントリメタクリレート(TMPTM、和光純薬工業株式会社)を用い、組成を表1の通りにする以外は実験例1と同様にし、フィルム形状の重合体を形成した。得られた重合体のヤング率、引張伸度は表1の通りであった。
架橋剤として両末端メタクリル変性ジメチルシリコーンオイル(FM7711、JNC株式会社、分子量1万)を用い、組成を表1及び表2の通りにする以外は実験例1と同様にし、フィルム形状の重合体を形成した。得られた重合体のヤング率、引張伸度は、表1及び表2の通りであった。
組成を表2の通りに変える以外は実験例1と同様にして、フィルム形状の重合体を形成した。得られた重合体のヤング率、引張伸度は表2の通りであった。
メチルメタクリレート(MMA、東京化成工業株式会社)(99.5質量部)、IC819(0.5質量部)およびTAA(10質量部)を混合し撹拌し、光硬化性材料が得られた。それ以外は実験例1と同様にし、フィルム形状の重合体をガラス基材上に形成した。得られた重合体のヤング率、引張伸度は表2の通りであり、非常に硬く、伸縮性のないものであった。
IC819(0.5質量部)およびTAA(20質量部)を混合した。そこに以下の下記式(S1)で表されるビニルエーテル基を有するポリシロキサン化合物であるSylgard184(シグマアルドリッチジャパン株式会社:登録商標)(99.5質量部)を加え、撹拌し、光硬化性材料が得られた。それ以外は実験例1と同様にし、UV露光を行った。露光を30分続けたがフィルム形状の重合体は得られなかった。
光重合開始剤として2-ヒドロキシ-2-メチルプロピオフェノン(シグマアルドリッチジャパン株式会社、CAS番号7473-98-5)(4.5質量部)を用い、組成を表1の通りにする以外は、実験例25と同様にして、UV露光を行った。露光を30分続けたがフィルム形状の重合体は得られなかった。
組成を表2の通りにする以外は、実験例26と同様にして、UV露光を行った。露光を30分続けたがフィルム形状の重合体は得られなかった。
基材として、膜厚12μmのポリイミドフィルムを準備した。当該ポリイミドフィルム上にマスクを介して金を蒸着し、7mm×7mmの正方形の電極素子を1mm間隔で縦8列×横8列、64個形成した。
次に、基材の周囲に1mm厚のスペーサーを設置し、そのスペーサーに囲まれた領域に、実験例1に記載の光硬化性材料を充填した。その上に、幅1mmのラインが7mm間隔で格子状に形成されているマスクを、当該ラインが基材上の電極素子が形成されていない格子状部分と合致するように配置し、UV露光して光硬化性材料を硬化させた。このときのUV露光は、UV波長300nm~400nmのNEC社のBlack light FL15BL(商品名)を光源として、SUNHAYATO社のLight box(W532×D450×H100mm)を用いて行った。次に、未露光部の光硬化性材料を、イソプロピルアルコールで洗い流し、格子形状の絶縁壁を現像した。その後、絶縁壁にUV露光し、さらに後硬化させた。
その結果、一個のセルが7mm×7mmで、8行8列の格子形状の絶縁壁を基材上に形成した。このとき絶縁壁の高さは1mmであった。図4は、本実施例で作製した電極(電極アレイ)の平面視写真である。
生体バッファ層として、N,N-ジエチル-N-メチル-N-(2-メトキシエチル)アンモニウム テトラフルオロボレート(DEMEBF4)を構成する分子に覆われたカーボンナノチューブがポリロタキサンに分散されてなる組成物下記のように調製した。
カーボンナノチューブ(昭和電工株式会社製、VGCF-X、長さ3μm、直径15nm)30mgと、親水性のイオン液体である、N,N-ジエチル-N-メチル-N-(2-メトキシエチル)アンモニウム テトラフルオロボレート(DEMEBF4)60mgを混合し、磁気スターラーを用いて700rpm以上の回転数で1週間、25℃、脱イオン水中で撹拌した。得られた懸濁液を、高圧ジェットミルホモジナイザー(60MPa;Nano-jet pal, JN10, Jokoh)によって処理して、黒い物質を得た。得られたCNTゲルを含む溶液を生理食塩水で濯いだ後に、光重合開始剤(IC2959、長瀬産業株式会社製)1mgと、ポリロタキサンゲル(「光架橋性環動ゲル」、アドバンストソフトマテリアルズ株式会社製)1000mgとを混合し、上記組成物を作製した。
実験例25に記載の光硬化性材料を用いる以外は、実施例1と同様にし、UV露光を行った。UV露光を30分行い、非露光部の光硬化性材料を洗浄したが、絶縁壁は形成されなかった。
実験例26に記載の光硬化性材料を用いる以外は、実施例1と同様にし、UV露光を行った。UV露光を30分行い、非露光部の光硬化性材料を洗浄したが、絶縁壁は形成されなかった。
基材の周囲に1mm厚のスペーサーを設置し、そのスペーサーに囲まれた領域に、実施例2に記載の組成物を充填し、UV露光によって硬化させ、生体バッファ層を形成した。絶縁壁は形成しなかった。
図5Aは、実施例の電極アレイのある一点に、100mVの入力電圧を印加した際の、その入力電圧をした箇所に対向する電極が測定した出力結果を示したグラフである。図5Bは、実施例の電極アレイのある一点に、100mVの入力電圧を印加した際の、その入力電圧をした箇所に対向する電極が測定した出力結果を示したグラフである。これらのグラフにおいて、縦軸は出力電圧であり、XY軸は位置座標を示す。グラフのXYは7mm×7mmであり、実施例1において絶縁壁で囲まれた一つのセルサイズであり、この出力結果は、入力電圧を印加した点に対向する一つの電極素子が測定した出力結果である。
この結果、実施例1の電極アレイが100mVの入力電圧に対し、45mVの出力結果を示しているのに対し、比較例3の電極アレイが100mVの入力電圧に対し、23mVの出力結果しか示していないことが分かる。またグラフからも明らかに、実施例1の電極アレイの方が、ピークの高い検出結果を示しており、電極アレイの感度が高いことが分かる。
シミュレーションは、静電場解析を、有限差分法を用いて行った。有限差分格子のサイズは一辺が1mmの立方体とし、基材に平行な方向に58×58の格子、基材に垂直な厚さ方向に1格子である。
この結果、実施例1の電極アレイが100mVの入力電圧に対し、100mVの出力結果を示しているのに対し、比較例3の電極アレイが100mVの入力電圧に対し、30mVの出力結果しか示していないことが分かる。またグラフからも明らかに、実施例1の電極アレイの方が、ピークの高い検出結果を示しており、感度が高いことが分かる。
Claims (10)
- 基材上に、電極素子と、
前記電極素子の周囲に形成され、1分子あたり2個以上の(メタ)アクリロイル基、スチレン性ビニル基、ビニルエステル基、マレイン酸エステル基およびマレイミド基からなる群より選択される官能基を有するポリシロキサン化合物(成分A)を構成成分とし、前記官能基の重合によって得られる重合体から形成された絶縁壁とを備える電極。 - 前記成分(A)の数平均分子量が6000以上である、請求項1または2のいずれかに記載の電極。
- 前記重合体は、前記成分Aと、
1分子あたり1個の(メタ)アクリロイル基、スチレン性ビニル基、ビニルエステル基、マレイン酸エステル基およびマレイミド基からなる群より選択される官能基を有するポリシロキサン化合物(成分M)と、が共重合した共重合体である、請求項1~3のいずれか一項に記載の電極。 - 前記重合体は、前記成分A又は前記成分Aと前記成分Mの共重合体と、
フルオロアルキル基と1分子あたり1個以上の(メタ)アクリロイル基、スチレン性ビニル基、ビニルエステル基、マレイン酸エステル基およびマレイミド基からなる群から選択される官能基より選択される官能基とを有する化合物(成分B)と、
が共重合した共重合体である、請求項1~5のいずれか一項に記載の電極。 - 前記成分Bが(メタ)アクリル酸フルオロアルキルエステルである、請求項6に記載の電極。
- 前記電極素子が前記基材上に複数配置されており、前記絶縁壁は前記複数の電極素子同士を絶縁するよう形成されている、請求項1~7のいずれか一項に記載の電極。
- 前記絶縁壁は、電磁波照射により前記成分(A)、成分(B)および/または成分(M)を重合させて形成されたものである、請求項1~8のいずれか一項に記載の電極。
- 基板上に電極素子を配置する工程と、
1分子あたり2個以上の(メタ)アクリロイル基、スチレン性ビニル基、ビニルエステル基、マレイン酸エステル基およびマレイミド基からなる群から選択される官能基を有するポリシロキサン化合物(成分A)および光ラジカル重合開始剤を含む光硬化性材料を、前記電極素子の周囲に配置する工程と、
前記光硬化性材料に電磁波を照射して硬化させ、前記絶縁壁を形成する工程とを有する電極の製造方法。
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