JP6503924B2 - Electrode sheet and sensor using the same - Google Patents

Description

  The present invention relates to a proximity sensor in a daily life scene, an electrode sheet that can be used for a biological sensor, and a sensor using the same.

2. Description of the Related Art In recent years, sensing of biological information such as heart rate and body movement has become popular as daily health information, as consumers have become more aware of their health. In addition, with the advancement of the elderly society, confirmation of the safety of the elderly living alone has become a social problem, but a sensing system for detecting biological information for that purpose and proximity to objects and areas has begun to be advocated.
In addition, with advances in the technology for reducing the size and weight of measurement instruments, development of terminals that can be carried easily, easily and easily, including wearable instruments that can be worn, has become active.
A conductive electrode is generally used for the sensor part that detects biological information. For example, when using these electrodes in a wearable portable terminal, it is ideal to be provided in the surroundings of the human body such as cards, bags, watches, clothes, shoes, etc., and flexibility and flexibility of the electrodes themselves Is preferred.
However, the electrodes used so far in such cases are rigid electrodes such as copper foil, meshed conductive cloth, copper plate, etc., which lack flexibility and flexibility and can be bent or pulled. By doing this, the electrode is easily damaged or a person feels a strong sense of discomfort when used for a long time, and therefore, it was not suitable for wearable applications (Patent Document 1, Patent Document 2).
In living environments, a capacitive touch screen panel may be mentioned as an example of a proximity sensor, but since the electrode used in this mode is basically a rigid and plate-like electrode, a capacitive touch sensor When applying the electrode of a proximity sensor like this to the object of a three-dimensional curved surface shape and a complicated shape, it is difficult to install along the shape of an object, and there is no durability by bending.

  As a living body sensor, patent document 1 has a literature of a measuring device and a measuring method of myoelectricity using a capacitance type electrode.

  Patent document 2 is mentioned as an example of the electrode in a wearable terminal.

JP, 2009-261735, A Patent No. 4653200 gazette

  The present invention overcomes the problems of the conventional sensor electrode and is light in weight and has high adhesiveness such as stretchability and bendability and durability while exhibiting excellent electric properties such as conductivity and capacitance. It aims at provision of a sheet, a living body sensor using the electrode sheet, a proximity sensor, and a bioimpedance measuring machine.

  In the present invention, thermosetting resin (A) having a carboxyl group (however, epoxy resin (B), except in the case of an elastomer (C) having a reactive functional group), epoxy resin (B), reactivity The present invention relates to a conductive layer-forming material for a sensor comprising an elastomer (C) having a functional group, a conductive filler (D) and a curing agent (E).

  The present invention also relates to an electrode sheet having a conductive layer (X), wherein the conductive layer (X) is formed by curing the above-described conductive layer forming material for a sensor.

  The present invention further relates to the above-mentioned electrode sheet for a sensor characterized in that an insulating layer (Y) is provided on at least one surface of the conductive layer (X).

  Further, the present invention is an electrode sheet having a configuration in which a conductive layer (X1) / a dielectric layer (Z) / a conductive layer (X2) is laminated in the order, and the conductive sheet (X1) and the conductive layer (X2) The present invention relates to an electrode sheet for a sensor, wherein at least one of them is formed by curing the conductive layer-forming material.

  Furthermore, the present invention relates to the above-mentioned electrode sheet for a sensor, which further comprises an insulating layer (Y1) provided on the outside of at least one of the conductive layer (X1) and the conductive layer (X2).

  In the present invention, the conductive layer (X3) / dielectric layer (Z1) / conductive layer (X4) / insulating layer (Y2) / conductive layer (X5) / dielectric layer (Z2) / conductive layer (X6) are stacked in this order. The conductive layer (X3), the conductive layer (X4), the conductive layer (X5), and the conductive layer (X6) are formed by curing the conductive layer-forming material. The present invention relates to a sensor electrode sheet characterized by

  The present invention also relates to the above-mentioned electrode sheet for a sensor, which further comprises an insulating layer (Y3) provided on the outside of at least one of the conductive layer (X3) and the conductive layer (X6).

  Further, the present invention relates to a capacitance type proximity sensor using the above-mentioned electrode sheet for sensor.

  The present invention also relates to a capacitance type biosensor using the sensor electrode sheet.

  The present invention also relates to a bioimpedance measuring device using the above-described electrode sheet for a sensor.

  The conductive layer (X) formed by curing the conductive layer forming material for a sensor according to the present invention can exhibit high conductivity, adhesiveness, durability and flexibility.

  According to the present invention, an electrode sheet exhibiting excellent stretchability, bendability and high durability, and excellent interlayer adhesion when laminated with other members, and a capacitive biosensor using the same Providing a proximity sensor and a bioimpedance measuring machine.

It is a schematic diagram which shows the cross section of the various aspects of the electrode sheet for sensors of this invention. It is a schematic diagram which shows the cross section of another aspect of the electrode sheet for sensors of this invention. It is a schematic diagram which shows the cross section of another aspect of the electrode sheet for sensors of this invention. It is a schematic diagram which shows another aspect of the electrode sheet for sensors of this invention. It is a schematic diagram which shows another aspect of the electrode sheet for sensors of this invention.

The conductive layer (X) of the present invention is a thermosetting resin (A) having a carboxyl group (hereinafter, a thermosetting resin (A), an epoxy resin (B), an elastomer having a reactive functional group (C), conductivity And the curing agent (E).
In the electrode sheet of the present invention, the conductive layer (X) itself obtained by curing the conductive layer type material for a sensor can be used as an electrode sheet. In addition, as another method of use, by appropriately laminating the conductive layer (X), the insulating layer (Y), and the dielectric layer (Z) according to the purpose, a capacitive proximity sensor, a capacitive biosensor, a living body It can be used as an electrode sheet for impedance measuring machines.

  The electrode sheet is formed by curing the conductive layer-forming material, but as a cured form, the curing agent (E) in the conductive layer-forming material reacts at the time of sheet formation to cure. The curing method changes depending on how fast the curing agent is reacted. For example, the conductive layer is brought into a so-called semi-cured state in the temporary curing step, and a curing method in which durability is obtained by reacting the epoxy resin (B) in the subsequent main curing step, or a curing agent (E And epoxy resin (B), a thermosetting resin (A), and a curing method that causes a curing reaction with the elastomer (C), but it is needless to say that other curing methods can be arbitrarily adopted.

<Thermosetting resin (A)>
In the present invention, the thermosetting resin (A) is a thermosetting resin which can exhibit heat resistance, flexibility and durability which can be used in the electrode sheet. Therefore, it is necessary to include a carboxyl group as a reactive functional group. Specifically, urethane resin, urethane urea resin, epoxy ester resin, acrylic resin and phenol resin are preferable. Among these, urethane urea resins, epoxy ester resins and acrylic resins are more preferable in terms of heat resistance and processability.

  3-25 mgKOH / g is preferable and, as for the acid value of a thermosetting resin (A), 7-20 mgKOH / g is more preferable. When the acid value is 3 mgKOH / g or more, crosslinking with the epoxy resin (B) is improved, and heat resistance is further improved. In addition, when the acid value is 25 mg KOH / g or less, the adhesion strength with other layers constituting the electrode sheet is further improved.

  The weight average molecular weight of the thermosetting resin (A) is preferably 5,000 to 300,000. When the weight average molecular weight is 5000 or more, the heat resistance is further improved. Moreover, when it becomes 300000 or less, a viscosity will fall and handling will become easier.

  Hereinafter, although the synthesis | combining method of a polyurethane urea resin is demonstrated as one example of a thermosetting resin (A), it can not be overemphasized that a thermosetting resin (A) is limited and interpreted as polyurethane urea resin.

  The polyurethaneurea resin may be a polyurethaneurea resin having a carboxyl group. An example of the method for obtaining the polyurethaneurea resin (a) is shown below. First, a first step of reacting a diol compound (b1) having a carboxyl group, a polyol compound (b2) having no carboxyl group and an organic diisocyanate (b3) to obtain a urethane prepolymer (b4) having an isocyanate group. Next, it can be obtained in the second step of reacting the obtained urethane prepolymer (b4) having an isocyanate group with the polyamino compound (b5). In the second step, a reaction terminator can be used as needed.

Examples of the diol compound (b1) having a carboxyl group include dimethylolalkanoic acid such as dimethylolacetic acid, dimethylol propionic acid, dimethylol butanoic acid, and dimethylol pentanoic acid, dihydroxysuccinic acid, and dihydroxybenzoic acid. Among these, dimethylol propionic acid and dimethylol butanoic acid are preferable because they improve the reactivity and solubility.

  The polyol compound (b2) having no carboxyl group is generally known as a polyol component constituting a polyurethane resin, and examples thereof include polyether polyol, polyester polyol, polycarbonate polyol, and polybutadiene glycol. These can be used alone or in combination of two or more.

  Examples of the polyether polyol include homopolymers or copolymers of ethylene oxide, propylene oxide, and tetrahydrofuran.

  Examples of the polyester polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1, Saturated and unsaturated low molecular weight diols such as 5-pentanediol, hexanediol, octanediol, 1,4-butylenediol, diethylene glycol, triethylene glycol, dipropylene glycol, dimer diol, etc., adipic acid, phthalic acid, isophthalic acid Acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, glomerular acid, suberic acid, suberic acid, azelaic acid, dicarboxylic acids such as sebacic acid, and their anhydrides by dehydration condensation Obtained police Le polyol and cyclic ester compound to ring opening polymerization in polyester polyols obtained can be mentioned.

As the polycarbonate polyol, 1) a reaction product of a diol or bisphenol and a carbonic ester, and 2) a reaction product obtained by reacting phosgene on the diol or bisphenol in the presence of an alkali can be used. Examples of the carbonate include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate and the like. Further, as the diol, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3 '-Dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9 Nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl, 2,2 , 8, Examples of the bisphenol include bisphenol A and bisphenol F, and bisphenols obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to bisphenols. .
Among these, polyester polyols are preferable, and polyester diols are more preferable.

  Usually, 500-8000 are preferable and, as for the number average molecular weight (Mn) of the polyol compound (b2) which does not have a carboxyl group, 1000-5000 are more preferable. When the Mn is 500 or more, an appropriate urethane bond can be introduced into the polyurethane polyurea resin (a), which makes it easy to obtain adhesive strength. In addition, when the Mn is 8000 or less, the distance between urethane bonds is likely to be appropriate and the heat resistance is easily obtained.

The organic diisocyanate (b3) is preferably an aromatic diisocyanate, an aliphatic diisocyanate, an alicyclic isocyanate or the like.
Examples of the aromatic diisocyanate include 1,5-naphthyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-benzylisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate and the like can be mentioned.

  Examples of the aliphatic diisocyanates include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.

  Examples of the alicyclic diisocyanates include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, norbornane diisocyanate methyl, bis (4-isocyanatocyclohexyl) methane, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate and the like. It can be mentioned.

  Among these, isophorone diisocyanate is preferable. These can be used alone or in combination of two or more

  The reaction conditions in the first step are not particularly limited except that the isocyanate group is made excessive, but the equivalent ratio of isocyanate group / hydroxyl group is preferably 1.05 / 1 to 3/1, and 1.2 / 1-2 / 1 is more preferable. Moreover, it is preferable to select reaction temperature 20 ~ 150 degreeC suitably, and 60 ~ 120 degreeC is more preferable.

  The polyamino compound (b5) used in the second step is used as a chain extender. Specifically, for example, ethylene diamine, propylene diamine, hexamethylene diamine, diethylene triamine, triethylene tetramine, isophorone diamine, dicyclohexylmethane-4,4'-diamine, norbornane diamine, 2- (2-aminoethylamino) ethanol, 2- Hydroxyethyl ethylenediamine, 2-hydroxyethyl propylene diamine, di-2-hydroxyethyl ethylene diamine, and di-2-hydroxy propyl ethylene diamine etc. are mentioned. Among these, isophorone diamine is preferable.

  Examples of the reaction terminator that can be used in the second step include dialkylamines such as di-n-butylamine, and dialkanolamines such as diethanolamine, ethanol, and alcohols such as isopropyl alcohol.

The reaction conditions for the second step are as follows: 1 equivalent of free isocyanate groups at both ends of the urethane prepolymer, the amino groups in the polyamino compound (b5) and the reaction terminator (when used) The total equivalent is preferably 0.5 to 1.3, and 0.8 to 1.
05 is more preferable. When the total equivalent weight of amino groups is 0.5 or more, polyurethaneurea resin (a) can be made to have a higher molecular weight. If it is 1.3 or more, the storage stability of the conductive layer forming material may be reduced.

  The weight average molecular weight of the polyurethane urea resin is preferably 5,000 to 200,000. When the weight average molecular weight is 5000 or more, the heat resistance is further improved. Moreover, when it becomes 200,000 or less, the viscosity of the conductive layer forming material for sensors will fall, and handling will become easier.

  The polyurethane urea resin may be synthesized by using one or two solvents appropriately selected from ester solvents, ketone solvents, glycol ether solvents, aliphatic solvents, aromatic solvents, alcohol solvents, carbonate solvents, water and the like. It can be used above.

  Examples of the ester solvents include ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, ethyl lactate and the like.

  Examples of the ketone-based solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, diacetone alcohol, isophorone, cyclohexanenone and the like.

  Examples of the glycol ether solvents include ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, acetates of these monoethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, and acetic acid esters of these monoethers can be mentioned.

  Examples of the aliphatic solvents include n-heptane, n-hexane, cyclohexane, methylcyclohexane and ethylcyclohexane.

  Examples of the aromatic solvent include toluene and xylene.

  Examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, cyclohexanol and the like.

  Examples of the carbonate-based solvent include dimethyl carbonate, ethyl methyl carbonate, di-n-butyl carbonate and the like.

<Epoxy (B)>
In the present invention, the epoxy resin (B) is a compound having two or more epoxy groups in one molecule. Its property may be liquid or solid.
The epoxy resin (B) is preferably a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, a cyclic aliphatic (alicyclic type) epoxy resin, or the like.

  The glycidyl ether type epoxy resin is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, α-naphthol novolac type epoxy resin Resin, bisphenol A novolac epoxy resin, dicyclopentadiene epoxy resin, tetrabromo bisphenol A epoxy resin, brominated phenol novolac epoxy resin, tris (glycidyloxyphenyl) methane, tetrakis (glycidyloxyphenyl) ethane, etc. Can be mentioned.

  Examples of the glycidyl amine type epoxy resin include tetraglycidyldiaminodiphenylmethane, triglycidyl paraaminophenol, triglycidyl metaaminophenol, and tetraglycidyl metaxylylene diamine.

  Examples of the glycidyl ester type epoxy resin include diglycidyl phthalate, diglycidyl hexahydrophthalate and diglycidyl tetrahydrophthalate.

Examples of the cycloaliphatic (alicyclic) epoxy resin include epoxycyclohexylmethyl-epoxycyclohexanecarboxylate, bis (epoxycyclohexyl) adipate and the like.
Among these, bisphenol A epoxy resin, cresol novolac epoxy resin, phenol novolac epoxy resin, tris (glycidyloxyphenyl) methane, and tetrakis (glycidyloxyphenyl) ethane are preferable because they further improve adhesion strength and heat resistance. .

  It is preferable to mix | blend 3-200 weight parts with respect to 100 weight parts of thermosetting resin (A), and, as for an epoxy resin (B), 5-100 weight parts is more preferable. Blending 3 to 200 parts by weight, higher heat resistance and higher adhesive strength can be obtained. In addition, 5 to 40 weight% is preferable for the said compounding quantity.

<Elastomer (C)>
In the present invention, the elastomer (C) is an elastomer having a reactive functional group. Here, the elastomer is an elastic body and a block copolymer is preferable, and a styrene-based elastomer, an ethylene-based elastomer, a urethane-based elastomer, a polyamide-based elastomer, a styrene acrylic elastomer and the like are preferable. The reactive functional group may be a functional group capable of reacting with at least one of the epoxy resin (B) and the curing agent (E). Specifically, carboxyl group, amino group, hydroxyl group and the like are preferable.

The styrene-based elastomer is, for example, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene-isoprene-styrene block copolymer, and styrene-butadiene-isoprene-styrene block copolymer As well as these hydrogenates.
Examples of the ethylene-based elastomer include ethylene-vinyl acetate copolymer, ethylene-methacrylic acid ester copolymer), ethylene-acrylic acid ester copolymer, and amorphous polyalphaolefin copolymer.
These elastomers can have carboxyl groups by carboxy modification.
Examples of the urethane elastomer include a urethane-urea block copolymer, a urethane-ester block copolymer, and a urethane-amide block copolymer.
Examples of the polyamide elastomer include polyether ester-amide block copolymer, and polyester-amide block copolymer.
Examples of the styrene acrylic elastomer include styrene acrylonitrile copolymer and styrene methacrylic acid.

    The elastomer (C) preferably has a durometer D hardness of 25 to 40. The temporary sticking aptitude and the punching processability can be further improved by being in this range. The durometer D hardness can be measured by a test method in accordance with JIS K 7155: 1999.

  In addition, the elastomer (C) preferably has a storage elastic modulus at 25 ° C. of 5 MPa to 55 MPa. If the storage elastic modulus is in the above range, the temporary bonding suitability and the heat resistance are further improved. The storage elastic modulus of the elastomer (C) is more preferably 10 MPa to 50 MPa.

    When an elastomer (C) has an acid value, 3-8 mgKOH / g is preferable.

  It is preferable to mix | blend 3-200 weight parts with respect to 100 weight parts of polyurethane urea resin (A), and, as for an elastomer (C), 5-100 weight parts is more preferable. By blending 3 to 200 parts by weight, it is possible to further improve the temporary sticking appropriateness.

  The elastomer (C) preferably has a glass transition temperature (hereinafter referred to as Tg) of -70 to 0 ° C. Heat resistance improves more because Tg becomes -70 degreeC or more. In addition, when the Tg is 0 ° C. or less, the temporary sticking appropriateness is further improved. As for Tg of an elastomer (C), -65 ° C--5 ° C are more preferred, and -60 ° C--10 ° C are still more preferred.

  The reactive functional group of the elastomer (C) is preferably 2 to 5 g / Eq. It becomes easy to maintain heat resistance because it is the said range.

    The elastomer (C) is more preferably a polyamide-based elastomer. Moreover, if it is a range which does not impair heat resistance, the elastomer which does not have a reactive functional group can also be used together.

<Conductive filler (D)>
In the present invention, the conductive filler (D) imparts conductivity to the conductive layer (X). Specifically, for example, conductive metal particles made of metals such as gold, silver, copper, platinum, tin, palladium, aluminum, lead, zinc, iron and nickel, and alloys thereof, composite particles of the conductive metal, ITO And metal oxide particles such as ATO and FTO, and carbon materials such as carbon black, carbon nanotubes, graphene, and carbon fibers. Examples of the composite particles include silver-coated copper particles, silver-coated nickel particles, gold-coated copper particles, and gold-coated nickel particles.

  The shape of the conductive filler (D) is preferably, for example, a spherical shape, a flake shape, a circular shape, a dendritic shape, a needle shape, or an irregular shape. The average particle diameter of the conductive filler (D) is preferably 1 to 50 μm. The average particle size is a value obtained by averaging about 10 to 20 particles from a magnified image (for example, 1,000 times to 10,000 times) of a scanning electron microscope. In addition, when the conductive filler (D) is significantly different in length in the longitudinal direction and in the lateral direction, the average particle diameter is calculated in the longitudinal direction.

    It is preferable to mix | blend 200-1000 weight part with respect to 100 weight part of thermosetting resin (A), and, as for a conductive filler (D), 300-600 weight part is more preferable. By blending 200 to 1000 parts by weight, the conductivity is further improved.

<Hardener (E)>
In the present invention, the curing agent (E) can function to bring the conductive layer (X) into a semi-cured state when the sensor electrode sheet is formed by a crosslinking reaction, but does not react at the time of sheet formation, A curing agent that reacts during the reaction can also be selected appropriately. The curing agent (E) is preferably an isocyanate curing agent, an amine curing agent, an aziridine curing agent, an imidazole curing agent or the like.

  Examples of isocyanate curing agents include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, 1,5-naphthalene diisocyanate, tetramethyl xylylene diisocyanate, trimethylhexamethylene diisocyanate and the like. It can be mentioned.

  Examples of the amine-based curing agent include diethylenetriamine, triethylenetetramine, methylenebis (2-chloroaniline), methylenebis (2-methyl-6-methylaniline), 1,5-naphthalenediisocyanate, n-butylbenzylphthalic acid and the like. .

  Aziridine-based curing agents include, for example, trimethylolpropane-tri-β-aziridinyl propionate, tetramethylolmethane-tri-β-aziridinyl propionate, N, N'-diphenylmethane-4,4'-bis (1-aziridine carboxamide), N, N'-hexamethylene-1,6-bis (1-aziridine carboxamide), etc. may be mentioned.

Examples of the imidazole-based curing agent include 2-methylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate and the like.

  It is preferable to mix | blend 0.3-20 weight part with respect to 100 weight part of thermosetting resin (A), and, as for a hardening agent (E), 1-15 weight part is more preferable. By blending 0.3 to 20 parts by weight, the material for forming a conductive layer for a sensor can be difficult to flow after semi-curing, and thus blocking can be easily suppressed.

The conductive layer forming material for a sensor of the present invention preferably further contains an inorganic filler (F). By including the inorganic filler (F), the heat resistance of the electrode sheet is further improved.
The inorganic filler (F) is, for example, silica, alumina, aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium carbonate, titanium oxide, zinc oxide, antimony trioxide, magnesium oxide, talc, montmorillonite, kaolin, bentonite, etc. Inorganic compounds are mentioned. Among these, silica, alumina, and aluminum hydroxide are preferable from the viewpoint of their excellent dispersibility. Furthermore, hydrophobic silica obtained by reacting a silanol group on the silica surface with a halogenated silane is more preferable because the moisture content of the conductive layer forming material for a sensor can be reduced. In the present invention, the inorganic filler (F) does not contain the conductive filler (D).

  It is preferable to mix | blend 7-50 weight parts with respect to 100 weight parts of thermosetting resin (A), and, as for an inorganic filler (F), 15-40 weight parts is more preferable. By blending 7 to 50 parts by weight, the elongation percentage of the conductive layer (A) according to the S (Stress) -S (Strain) curve can be made in an appropriate range, so that the processability can be further improved. 80% or more is preferable and 100% or more of the elongation rate lower limit of a SS curve is more preferable. Processability improves more by being 80% or more. The upper limit is preferably 300% or less, more preferably 250% or less.

The conductive layer forming material for a sensor of the present invention preferably further comprises a silane coupling agent (G). By reacting the alkoxysilyl group of the silane coupling agent (G), the heat resistance can be further improved, for example, the conductive layer (X) is less likely to generate foaming or the like even at a high processing temperature.
The silane coupling agent (G) is preferably a vinyl based silane coupling agent, an epoxy based silane coupling agent, an amino based silane coupling agent, an isocyanate based silane coupling agent or the like.

  Examples of the vinyl-based silane coupling agent include vinyltrimethoxysilane and vinyltriethoxysilane.

  Epoxy-based silane coupling agents are, for example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Examples include xypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and the like.

  The amino type silane coupling agent is, for example, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane and the like.

  As an isocyanate type silane coupling agent, 3-isocyanate propyl triethoxysilane is mentioned, for example.

  It is preferable to mix | blend 0.5-25 weight part with respect to 100 weight part of thermosetting resin (A), and, as for a silane coupling agent (G), 0.75-15 weight part is more preferable. By blending 0.5 to 25 parts by weight, the heat resistance is further improved.

In the conductive layer forming material for a sensor of the present invention, a heat resistant stabilizer, a pigment, a dye, a tackifier resin, a plasticizer, an ultraviolet absorber, an antifoaming agent, a leveling regulator and the like can be blended as other optional components.
For example, when a heat resistant stabilizer is blended, decomposition of the resin can be suppressed, and heat resistance can be further improved. Specifically, hindered phenol compounds, phosphorus compounds, lactone compounds, hydroxylamine compounds, sulfur compounds and the like are preferable, and hindered phenol compounds are more preferable.

  The conductive layer forming material for a sensor of the present invention comprises 3 to 50% by weight of (A), 3 to 50% by weight of (B) and (C) in 100% by weight of the total of (A) to (E). It is preferable that 0.5 to 30% by weight, (D) be 40 to 80% by weight, and (E) be 0.02 to 5% by weight.

The sensor electrode sheet of the present invention is, for example, a sheet obtained by curing a semi-cured conductive layer forming material for a sensor obtained by applying the conductive layer forming material for a sensor to a peelable sheet. As described above, except in the case where the conductive layer forming material for sensor is cured alone and used as an electrode sheet for sensor, after laminating the insulating layer and the dielectric layer to be described later and the conductive layer forming material for sensor, It may be cured.
High adhesion strength and heat resistance can be obtained by performing main curing by high temperature heating after temporarily attaching to another layer. The gel fraction of the semi-cured conductive layer forming material for sensor is preferably 60 to 95%. When the gel fraction is in this range, the cohesion is improved, and the temporary sticking appropriateness and the punching processability are further improved. The gel fraction is more preferably 65 to 90%. In the present invention, sheet is synonymous with film and tape. Moreover, since a semi-hardened state means that an epoxy resin is in an unreacted state, there is no intention of excluding gel fraction 0%.

The coating is performed on the release surface of the release sheet, for example, knife coating, die coating, lip coating, roll coating, curtain coating, bar coating, gravure coating, flexo coating, dip coating, spray coating, silk screen, inkjet, and spin A conductive layer (X) can be formed by coating the conductive layer forming material for a sensor by a method such as coating and heating to a temperature of usually 40 to 150 ° C.
The thickness of the conductive layer (X) is preferably 5 μm to 500 μm, and more preferably 10 μm to 100 μm.

<Insulating layer (Y)>
The insulating layer (Y) is formed of an insulating layer forming material for a sensor, and is flexible and flexible. The insulating layer (Y) electrically insulates the outside from the conductive layer (X) and physically protects the conductive layer (X). If the material for forming the insulating layer for a sensor is a film or sheet, The materials can be used as they are or, if necessary, pasted together via an adhesive.
When the insulating layer forming material for a sensor is liquid, it is possible to use a resin coating film or the like which is formed by coating and drying, if necessary, and curing.

  Specifically, the insulating layer forming material for the sensor is, for example, fluorine resin, acrylic resin, polyester resin, polyester urethane, polyether urethane, urethane resin such as polycarbonate urethane, or urethane such as polyester urethane urea or polycarbonate urethane urea. Urea resin, polyester urea or polyether urea, urea resin such as polycarbonate urea, polyethylene, polypropylene, olefin resin such as acrylonitrile-butadiene-styrene resin, polyacetal resin such as polyvinyl alcohol or polyvinyl butyral, polyamide resin Polyimide resin, epoxy resin, phenoxy resin, polyphenol resin, nylon resin, vinylon resin, aramid resin, cellulose resin, etc. It contains a synthetic resin as the main component, and if necessary, contains a curing agent for crosslinking these resins, a catalyst for its acceleration, and various additives for imparting coatability, stability, durability, etc. Examples thereof include resin compositions or non-woven fabrics using them, natural fibers such as cotton, silk, hemp, wool and the like, glass fibers and the like.

  The insulating layer (Y) may have a practically optimal thickness for electrically insulating the conductive layer (X) from the external world and physically protecting the conductive layer (X). It becomes difficult to ensure physical protection of X) and insulation from the outside world. Moreover, since flexibility will be impaired if too thick, it is preferable that they are 5 micrometers or more and less than 100000 micrometers.

The insulating layer forming material for sensor containing a carboxyl group-containing modified ester resin as an example of the insulating layer forming material for sensor will be described in detail below.
The insulating layer-forming material for sensor is a compound (B3) which is at least one selected from the group consisting of carboxyl group-containing modified ester resin (A3), epoxy group-containing compound, isocyanate group-containing compound, and blocked isocyanate group-containing compound And a thermosetting coagent (C3), which is cured to form an insulating layer (Y).
The carboxyl group-containing modified ester resin comprises a polyol compound (a3) and an acid anhydride group-containing compound (b3) which is at least one selected from an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride The reaction is carried out to produce a carboxyl group-containing ester resin (c3), and the carboxyl group-containing ester resin (c3) is reacted with an epoxy compound (d3) having at least two epoxy groups in one molecule to form a side chain. A hydroxyl group-containing modified ester resin (e3) is formed, and further, at least one selected from an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride as a side chain hydroxyl group-containing modified ester resin (e3) It can be obtained by reacting a certain acid anhydride group-containing compound (b3).

  The polyol compound (a3) used in the present invention has two or more hydroxyl groups, and further has a repeating unit having a polymerization degree of 2 or more in its structure. In addition, a compound containing two hydroxyl groups is preferably used as the polyol compound (a3), and the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (hereinafter also referred to as “GPC”) is preferably 500 to 50000. Is a compound of Examples of the polyol compound (a3) include polyester polyols, polycarbonate polyols, polyether polyols, polybutadiene polyols, and polysiloxane polyols. In the present application, unless otherwise specified, the weight average molecular weight means a polystyrene-equivalent weight average molecular weight by GPC measurement.

  Examples of polyester polyols used in the present invention include polyester polyols in which a polyfunctional alcohol component and a dibasic acid component are subjected to a condensation reaction. Among the polyfunctional alcohol components, as a diol, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3 '-Dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, octanediol, butylethyl pentanediol, 2-ethyl-1,3-butadiene Hexanediol, cyclohexanediol, bisphenol A and the like can be mentioned, and as the polyfunctional alcohol component having three or more hydroxyl groups, trimethylolethane, polytrimethylolethane, trimethylolup Bread, poly trimethylol propane, pentaerythritol, poly pentaerythritol, sorbitol, mannitol, arabitol, xylitol, galactitol, glycerol and the like.

  Examples of the dibasic acid component include aliphatic or aromatic dibasic acids or their anhydrides such as terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid and trimellitic acid.

  Also, β-butyrolactone, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-caprolactone, γ-heptanolactone, α-methyl-β-propiolactone, etc. And polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as lactones of

  Polyester polyols having a phosphorus atom can also be used, specifically, 2- (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl) methylsuccinic acid or an acid anhydride thereof; Polycondensates with ethylene glycol, or 2- (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl) methylsuccinic acid bis- (2-hydroxyethyl) -ester, Or the polyester polyol obtained by the polycondensation is mentioned.

  Specifically, Kuraray polyol P series manufactured by Kuraray Co., Ltd. can be used as the polyester polyol. Among them, P-1041, P-2041, P-2010, P-2020, P-1030 and P-2030 are preferable because they have insulation reliability and heat resistance.

  The polycarbonate polyols used in the present invention are those having a structure represented by the following general formula (1) in the molecule.

General formula (1)
-[-R8-O-CO-] m-
(Wherein R 8 represents a divalent organic residue, and m represents an integer of 1 or more).

  Polycarbonate polyols can be obtained, for example, by (1) reaction of glycol or bisphenol with carbonate ester, (2) reaction of reacting glycol or bisphenol with phosgene in the presence of alkali, and the like.

  Specific examples of the carbonate used in the production method of (1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate and the like.

  Specifically as ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol as glycol or bisphenol used in the production method of (1) and (2) , 2-methyl-1,8-octanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3-butanediol, 1,4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethyl pentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, It can be used bisphenols such as bisphenol A, bisphenol F, ethylene oxide to the bisphenols, also bisphenols obtained by adding an alkylene oxide such as propylene oxide. These compounds can be used as one or a mixture of two or more.

  Specifically, Kuraray polyol C series manufactured by Kuraray Co., Ltd. can be used as the polycarbonate polyol. Among them, PMHC-1050, PMHC-2050, C-1090, C-2090, C-1065N, C-2065N, C-1015N and C-2015N are preferable because of their flexibility. In addition, Etanacol UC-100, UM-90 (1/3), UM-90 (1/1), and UM-90 (3/1) manufactured by Ube Industries, Ltd. are preferable because they are excellent in heat resistance.

The polyether polyols used in the present invention include, for example, polymers, copolymers and graft copolymers of alkylene oxides such as tetrahydrofuran, ethylene oxide, propylene oxide and butylene oxide;
Polyether polyols obtained by condensation of hexanediol, methylhexanediol, heptanediol, octanediol or mixtures thereof;
Aromatic diols such as bisphenols formed by adding an alkylene oxide such as ethylene oxide or propylene oxide to bisphenol A or bisphenol F;
Polyhydric alcohols such as trimethylolethane, polytrimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, arabitol, xylitol, galactitol, glycerin etc. are used as part of the raw material The synthesized polyethylene oxide, polypropylene oxide, block copolymer or random copolymer of ethylene oxide / propylene oxide, polytetramethylene glycol, block copolymer or random copolymer of tetramethylene glycol and neopentyl glycol, etc. Polyether polyols;
Those having two or more hydroxyl groups such as can be used.

  The polybutadiene polyols used in the present invention include, for example, those obtained by hydrogenating the unsaturated bond in the molecule, including polyethylene-based polyols, polypropylene-based polyols, polybutadiene-based polyols, hydrogenated polybutadiene polyols, polyisoprene polyols, hydrogenation Polyisoprene polyol etc. are mentioned.

  As commercial products of polybutadiene polyols, liquid polybutadiene having hydroxyl groups at both ends such as NISSSO PB (G series) of Nippon Soda Co., Ltd., Poly-Pd of Idemitsu Petrochemical Co., Ltd .; NISSSO PB (GI series of Nippon Soda Co., Ltd. ), Hydrogenated polybutadiene having hydroxyl groups at both ends such as Polytail H and Polytail HA of Mitsubishi Chemical Corporation; liquid C5 polymers having hydroxyl groups at both ends such as Poly-iP manufactured by Idemitsu Petrochemical Co., Ltd .; Examples thereof include hydrogenated polyisoprene having a hydroxyl group at both terminals of Epol manufactured by Kagaku Co., Ltd. and TH-1, TH-2, TH-3 manufactured by Kuraray Co., Ltd., etc., but it is not limited thereto.

  Examples of polysiloxane polyols used in the present invention include compounds represented by the general formulas (2) and (3).

General formula (2)

(X represents a hydroxyl group, R ¹ and R ² each represent an alkylene group having 1 to 6 carbon atoms, and n represents an integer of 5 or more.)

General formula (3)

(Y represents a hydroxyl group, R ³ is an alkyl group having 1 to 6 carbon atoms, R ⁴ , R ⁵ , R ⁶ each is an alkylene group having 1 to 6 carbon atoms, R ⁷ is a hydrogen atom or 1 to 1 carbon atom Represents an alkyl group of 6 and n
Represents an integer of 5 or more. )

  Among these polyol compounds (a3), polyester diol consisting of 1,4-cyclohexanedicarboxylic acid and 3-methyl-1,5-pentanediol, polycarbonate polyol using only 1,6-hexanediol as glycol, Polycarbonate diol consisting of 1,6-hexanediol and 3-methyl-1,5-pentanediol as glycol, 1,9-nonanediol and 2-methyl-1,8-octanediol as glycol Polycarbonate diol, polytetramethylene glycol, polypropylene glycol, or copolymer polyetherpolyol of tetramethylene glycol and neopentyl glycol, polybutadiene polyol, hydrogenated polybutadiene polyau And polysiloxane polyols are excellent in the electrical insulation, flexibility, heat resistance, moisture resistance, etc. as the carboxyl group-containing modified ester resin of the present invention because they are excellent in flexibility, heat resistance and hydrolysis resistance of the skeleton. , Particularly preferred.

  In the present invention, these polyol compounds (a3) may be used alone or in combination of two or more.

  The present invention is obtained by reacting the above-mentioned polyol compound (a3) with an acid anhydride group-containing compound (b3) which is at least one selected from an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride. The most important feature is that the ester bond group in the carboxyl group-containing ester resin (c3) to be treated is protected by a bulky substituent.

  Examples of the acid anhydride group-containing compound (b3) which is at least one selected from alicyclic polybasic acid anhydride and aromatic polybasic acid anhydride used in the present invention include, for example, methyltetrahydrophthalic anhydride, tetrahydroanhydride Phthalic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, methyl hydride nadic anhydride, stilendostyrene tetrahydrophthalic anhydride, 3,6-endo methylene tetrahydrophthalic anhydride, Alicyclic dibasic acid anhydrides such as methyl end methylene tetrahydrophthalic anhydride and trialkyltetrahydrophthalic anhydride; and alicyclics of tribasic acid or more such as hydrogenated trimellitic anhydride and hydrogenated pyromellitic anhydride Polybasic acid anhydride; phthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride Aromatic dibasic acid anhydrides such as acids; Biphenyltetracarboxylic acid dianhydrides, diphenylethertetracarboxylic acid dianhydrides, pyromellitic anhydride, tribasic acid dianhydrides such as benzophenone tetracarboxylic acid dianhydrides Basic acid anhydrides can be mentioned.

  Among these acid anhydride group-containing compounds (b3), methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, methyl anhydride nadic anhydride When producing a carboxyl group-containing ester resin (c3) by reaction with a polyol compound (a3), an acid or the like protects the ester bond group, which is considered to be inferior in insulation reliability, with a bulky substituent, and this bulk Since the main chain is constituted by an ester bond group protected by a high substituent, the insulation reliability, heat resistance, etc. are remarkably maintained while maintaining high adhesiveness as compared with a resin using a conventional polyester skeleton as the main chain. It is particularly preferable because it can be improved. Moreover, trimellitic anhydride, pyromellitic anhydride and the like can increase the number of terminal carboxyl groups of the carboxyl group-containing ester resin (c3) by reaction with the polyol compound (a3), The reaction with the epoxy compound (d3) having two epoxy groups is preferred in the present invention from the viewpoint of achieving high molecular weight. Since the cohesion of the resin is increased by the high molecular weight formation, it is preferable in that a tough coating film which is more excellent in resistance after forming a coating film can be formed while maintaining the flexibility.

  The hydroxyl group-containing compound (a3-1) optionally used in the present invention is a compound having one or more hydroxyl groups but is a compound excluding the compound belonging to the above-mentioned "polyol compound (a3)", and as a representative example thereof Are, for example, a monoalcohol compound (a3-1-1) having one hydroxyl group in the molecule, a diol compound (a3-1-2) having two hydroxyl groups in the molecule, three in the molecule The compound (a3-1-3) which has the above hydroxyl group can be mentioned. These may have a hydroxyl group and a functional group other than a hydroxyl group in the molecule. Moreover, you may use individually and may be used in combination of multiple.

Examples of monoalcohol compounds (a3-1-1) having one hydroxyl group in the molecule include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tertiary butanol, lauryl alcohol and stearyl Aliphatic monoalcohols such as alcohol;
Alicyclic monoalcohols such as cyclohexanol;
Aromatic monoalcohols such as benzyl alcohol, fluorenol, etc .;
Phenols such as phenol and methoquinone;
Examples of monoalcohol compounds having a functional group other than a hydroxyl group include hydroxyl group-containing carboxylic acid compounds such as 12-hydroxystearic acid, hydroxyl group-containing epoxy compounds such as glycidol, and hydroxyl group-containing oxetane compounds such as oxetane alcohol. Other examples include oligomeric monoalcohols such as one-end methoxylated polyethylene glycol, one-end methoxylated polypropylene glycol, and a caprolactone adduct polymer initiated with a monoalcohol.

  In the present invention, when using a monoalcohol compound (a3-1-1) having one hydroxyl group in these molecules, the end of the obtained carboxyl group-containing ester resin (c3) can be sealed, It can be suitably used when molecular weight adjustment is required, such as when intentionally synthesizing a low molecular weight carboxyl group-containing modified ester resin. In addition, when a hydroxyl group-containing compound having a functional group other than a hydroxyl group is used, a functional group other than a carboxyl group can be introduced to the end of the carboxyl group-containing ester resin (c3). When terminal modification of resin is required, it can be used conveniently. In the present invention, considering the reactivity of hydroxyl group and polymerization control, lauryl alcohol, stearyl alcohol, cyclohexanol, 12-hydroxystearic acid, glycidol, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate It is preferable to use

Also, as a diol compound (a3-1-2) having two hydroxyl groups in the molecule, for example, ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, 2-methyl-2-ethyl 1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-methyl-1,3-propanediol , 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-2,4-pentanediol 1,3,5-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptane, propanedio , 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, 3-butyl-3 -Ethyl-1,5-pentanediol, 2-ethyl-1,6-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, cyclopentadiene dimethanol, dimer diol, hydrogenated bisphenol A, spiro glycol, etc. Aliphatic or alicyclic diols;
1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4'-methylenediphenol, 4,4, 4 '-(2-norbornylidene) diphenol, 4,4'-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4'-isopropylidenephenol, 1,2-indanediol, 1,3 -Naphthalenediol, 1,5-naphthalenediol, 1,7-naphthalenediol, 9,9'-bis (4-hydroxyphenyl) fluorene, 9,9'-bis (3-methyl-4-hydroxyphenyl) fluorene and the like And aromatic diols of the following. In addition, phosphorus atom containing diol, sulfur atom containing diol, bromine atom containing diol etc. are mentioned.

  Moreover, the compound which has functional groups other than a hydroxyl group is also mentioned. Examples of compounds containing a tertiary amino group other than a hydroxyl group include N, N-bis (2-hydroxypropyl) aniline, N, N-bis (2-hydroxyethyl) aniline, N, N-bis ( 2-hydroxyethyl) methylamine, N, N-bis (2-hydroxyethyl) propylamine, N, N-bis (2-hydroxyethyl) butylamine, N, N-bis (2-hydroxyethyl) hexylamine, N Tertiary amino group-containing diol compounds such as N, N-bis (2-hydroxyethyl) octylamine, N, N-bis (2-hydroxyethyl) benzylamine, N, N-bis (2-hydroxyethyl) cyclohexylamine Further, examples of the compound containing a carboxyl group include dimethylol butanoic acid and dimethylol pro. Propionic acid, 3-hydroxy salicylic acid, 4-hydroxy salicylic acid, 5-hydroxy acid, such as 2-carboxy-1,4-cyclohexanedimethanol.

  Among them, dimethylol butanoic acid and dimethylol propionic acid are reacted with an acid anhydride group-containing compound (b3) which is at least one selected from alicyclic polybasic acid anhydride and aromatic polybasic acid anhydride. It is possible to increase the number of terminal carboxyl groups of the resulting carboxyl group-containing ester resin (c3), and to polymerize in subsequent reaction with an epoxy compound (d3) having at least two epoxy groups in one molecule. It is preferable in the present invention in that it can be When a tertiary amino group-containing diol compound such as N, N-bis (2-hydroxypropyl) aniline is used, the cohesion of the finally obtained coating film is increased, and the flexibility is maintained, It is preferable at the point that the tough coating film which is more excellent in tolerance can be formed.

  Moreover, as a compound (a3-1-3) having three or more hydroxyl groups in the molecule, for example, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, mannitol, arabitol, xylitol, galactitol, glycerin and the like And polyhydric alcohol compounds.

  In the present invention, when the compound (a3-1-3) having three or more hydroxyl groups in these molecules is used, the number of terminal carboxyl groups of the obtained carboxyl group-containing ester resin (c3) can be increased. Therefore, the molecular weight of the final product can be increased, and the resistance of the cured coating can be improved. Therefore, in order to further improve the resistance of the cured coating film in the present invention, it may be used as needed. Among the compounds (a3-1-3) having three or more hydroxyl groups in these molecules, trimethylolpropane and pentaerythritol are preferably used in terms of reaction control.

  Here, the polyol compound (a3) and the hydroxyl group-containing compound (a3-1) can be used in any proportion according to the purpose in the present invention, and 1.0 mol of hydroxyl groups in the polyol compound (a3) can be used. The hydroxyl group in the hydroxyl group-containing compound (a3-1) is used in a proportion of 0.01 mol to 1.00 mol, preferably 0.05 mol to 0.50 mol. When less than 0.01 mol of hydroxyl group in hydroxyl group-containing compound (a3-1) is used relative to 1.0 mol of hydroxyl group in polyol compound (a3) (ie, only polyol compound (a3)) In the case of use), even with the polyol compound (a3) alone, sufficient insulation reliability, heat resistance and adhesive strength can be developed, but it becomes difficult to impart higher heat resistance. On the other hand, if it is more than 1.00 mol, the cohesion of the finally obtained coating film tends to increase too much and the adhesive strength tends to decrease.

Moreover, when synthesize | combining a carboxyl group-containing ester resin (c3), the ratio with which the starting material is made to react is contained in these about the polyol compound (a3) and the hydroxyl group containing compound (a3-1) to be added optionally. Acid contained in the acid anhydride group-containing compound (b3), which is at least one selected from alicyclic polybasic acid anhydride and aromatic polybasic acid anhydride, when the total amount of hydroxyl groups to be contained is 1 mole The total of anhydride groups is preferably reacted in the proportion of 0.70 mol to 1.30 mol, and more preferably in the proportion of 0.90 mol to 1.10 mol. When the total amount of acid anhydride groups is less than 0.70 mol, the amount of carboxyl groups in the obtained carboxyl group-containing ester resin (c3) decreases, and an epoxy compound having at least two epoxy groups in one molecule In the reaction step with (d3), a sufficient reaction hardly occurs, and the weight average molecular weight of the finally obtained carboxyl group-containing modified ester resin (A3) may not be sufficiently large. In addition, when the total of acid anhydride groups is more than 1.30 moles, many side reactions occur when reacting with an epoxy compound (d3) having at least two epoxy groups in one molecule in the following, and during the reaction May cause gelation.

In addition, when the reaction is performed at a ratio close to 1.00 mol in the range of 0.90 mol to 1.10 mol, an epoxy compound (d3 having at least two epoxy groups in one molecule)
Since the problems as described above are unlikely to occur in the course of the reaction step with (ii), the weight average molecular weight of the finally obtained carboxyl group-containing modified ester resin (A3) can be made sufficiently large. Heat resistance, flexibility, and adhesion can be improved.

  In the present invention, the synthesis conditions of the carboxyl group-containing ester resin (c3) are not particularly limited, and can be performed under known conditions. For example, a polyol compound (a3) and a solvent [and optionally a hydroxyl group-containing compound (a3-1)] are charged into a flask and uniformly dissolved by heating and stirring at 20 to 120 ° C. in a nitrogen stream, An acid anhydride group-containing compound (b3) which is at least one selected from cyclic polybasic acid anhydride and aromatic polybasic acid anhydride is charged, and heated at 50 to 150 ° C. with stirring to give a carboxyl group Containing ester resin (c3) can be obtained.

  At the time of the reaction, if necessary, a tertiary amino group-containing compound may be used. In addition, a polyol compound (a3) charged in advance in a flask before charging the acid anhydride group-containing compound (b3), which is at least one selected from an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride And the solvent may be heated and stirred at 100 ° C. or higher to partially remove the solvent. This operation is usually performed to remove the water in the system (dehydration treatment), and this operation is an acid which is at least one selected from alicyclic polybasic acid anhydride and aromatic polybasic acid anhydride. In the reaction of the anhydride group-containing compound (b3), the ring-opening reaction of the acid anhydride group with water can be suppressed.

Next, an epoxy compound (d3 having at least two epoxy groups in one molecule of the present invention)
Will be described. The epoxy compound (d3) having at least two epoxy groups in one molecule used in the present invention is preferably a compound containing two epoxy groups in one molecule, and is not particularly limited. Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A epichlorohydrin type epoxy resin, bisphenol F epichlorohydrin type epoxy resin Biphenol / epichlorohydrin type epoxy resin, polyglycidyl ether of glycerin / epichlorohydrin adduct, resorcinol diglycidyl ether, polybutadiene diglycidyl ether, hydroquinone diglycidyl ether, dibromo neopentyl glycol diglycidyl ether, neopentyl glycol Diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A type diglycidyl ether, dihydroxy ane Latex type epoxy resin, polypropylene glycol diglycidyl ether, diphenyl sulfone diglycidyl ether, dihydroxy benzophenone diglycidyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol fluoro orange glycidyl ether, bis cresol fluoro orange glycidyl ether, bis phenoxy ethanol fluoro orange Glycidyl ether, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidyl aniline, N, N-diglycidyl toluidine, JP 2004-156024 A, JP 2004-315595 A Patent Document 1: JP-A-2004-323777 discloses an epoxy compound excellent in flexibility and the following formula (1)-( The epoxy compound of the structure represented by 3) etc. are mentioned.

Formula (1)

Formula (2)

Formula (3)

  Among them, 1,6-hexanediol diglycidyl ether is preferable when giving flexibility to the carboxyl group-containing modified ester resin (A3) finally obtained, and the bisphenol A epichlorohydrin type epoxy resin is the final one. It is preferable when heat resistance is imparted to the carboxyl group-containing modified ester resin (A3) obtained by Thus, in the present invention, the epoxy compound (d3) having at least two epoxy groups in one molecule can be selected according to the purpose, and these may be used alone or a plurality of them. It is also preferred to use in combination.

  Here, the ratio for reacting the carboxyl group-containing ester resin (c3) and the epoxy compound (d3) having at least two epoxy groups in one molecule is 1.0 of the carboxyl group of the carboxyl group-containing ester resin (c3) In the case of mole, it is preferable to react the epoxy group in the epoxy compound (d3) having at least two epoxy groups in one molecule in a ratio of 0.50 mole to 1.50 mole, 0.70 mole It is more preferable to make it react by the ratio of -1.30 mol. When the ratio of the epoxy group in the epoxy compound (d3) having at least two epoxy groups in one molecule is less than 0.50 mol with respect to 1.0 mol of the carboxyl group of the carboxyl group-containing ester resin (c3), The molecular weight of the carboxyl group-containing modified ester resin (A3) finally obtained decreases, and it becomes difficult to obtain desired coating film resistance and film forming property. Moreover, the ratio of the epoxy group in the epoxy compound (d3) which has at least 2 pieces of epoxy groups in 1 molecule with respect to 1.0 mol of carboxyl groups of carboxyl group-containing ester resin (c3) is more than 1.50 mol In this case, an acid anhydride group-containing compound (b3), in which the amount of the terminal epoxy group is increased, and which is at least one selected from alicyclic polybasic acid anhydride and aromatic polybasic acid anhydride in the final synthesis step During the reaction, many side reactions occur, which may cause gelation during the reaction.

  In the present invention, the synthesis conditions of the side chain hydroxyl group-containing modified ester resin (e3) are not particularly limited, and can be performed under known conditions. For example, a flask is charged with a carboxyl group-containing ester resin (c3) and an epoxy compound (d3) having at least two epoxy groups in one molecule, and a solvent, and heated at 100 to 150 ° C. with stirring to produce side chain hydroxyl A group-containing modified ester resin (e3) can be obtained. At this time, if necessary, a catalyst such as triphenylphosphine or a tertiary amino group-containing compound may be used.

  Next, the carboxyl group-containing modified ester resin (A3) of the present invention will be described. The carboxyl group-containing modified ester resin (A3) of the present invention is at least one selected from a side chain hydroxyl group-containing modified ester resin (e3), and an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride. It can be obtained by reacting with a certain acid anhydride group-containing compound (b3).

  Here, when synthesizing the carboxyl group-containing modified ester resin (A3), an acid anhydride group-containing compound (b3) which is at least one selected from an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride The ratio of reacting (a) is selected from alicyclic polybasic acid anhydrides and aromatic polybasic acid anhydrides when the hydroxyl group in the side chain hydroxyl group-containing modified ester resin (e3) is 1.0 mol. Preferably, the acid anhydride group in the acid anhydride group-containing compound (b3), which is at least one kind of component, is reacted in a proportion of 0.05 mol to 1.0 mol, preferably 0.10 mol to 0.90 mol It is more preferred to react in proportions. An acid anhydride group which is at least one selected from alicyclic polybasic acid anhydride and aromatic polybasic acid anhydride with respect to 1.0 mol of hydroxyl group in the side chain hydroxyl group-containing modified ester resin (e3) When the ratio of the acid anhydride group in the contained compound (b3) is less than 0.05 mol, the ratio of modification is too small to obtain the effect of introducing the crosslinkable functional group into the main chain. If the amount is more than 1.0 mol, the excess acid anhydride group-containing compound tends to remain and the flexibility, heat resistance and insulation reliability of the final coating film tend to be lowered.

  In the present invention, the synthesis conditions of the carboxyl group-containing modified ester resin (A3) are not particularly limited, and may be carried out under known conditions. For example, an acid anhydride group-containing compound (b3) which is at least one selected from a side chain hydroxyl group-containing modified ester resin (e3) and an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride in a flask A carboxyl group-containing modified ester resin (A3) can be obtained by charging a solvent and heating at 50 to 100 ° C. while stirring. This reaction proceeds even without a catalyst, but if necessary, a catalyst such as a tertiary amino group-containing compound may be used.

  The acid value of the carboxyl group-containing modified ester resin (A3) of the present invention is preferably 1 to 100 mg KOH / g, more preferably 5 to 90 mg KOH / g. If the acid value is less than 1 mg KOH / g, there are few carboxyl groups that function as a curable group, and it may not be possible to impart sufficient resistance to the coating after curing. On the other hand, when the acid value exceeds 100 mg KOH / g, the hardness of the coating film may be high, and sufficient adhesive strength may not be obtained. In addition, when the acid value is designed in a range close to 1 mg KOH / g in the range of 1 to 100 mg KOH / g, the flexibility and adhesion of the obtained coating film are improved, while the design is made in a range near 100 mg KOH / g In such a case, since the number of crosslinking points is increased, the heat resistance of the finally obtained coating film is improved. Thus, in the present invention, the acid value of the carboxyl group-containing modified ester resin (A3) can be adjusted according to the purpose within the range of 1 to 100 mg KOH / g.

  The weight average molecular weight of the carboxyl group-containing modified ester resin (A3) of the present invention is preferably 5,000 to 500,000, more preferably 10,000 to 300,000. If the weight average molecular weight is less than 5,000, sufficient heat resistance and flexibility may not be obtained. Moreover, when a weight average molecular weight exceeds 500000, the viscosity and handling at the time of coating may become a subject. In addition, when the weight average molecular weight is designed at a value close to 5000 in the range of 5000 to 500,000, a resin rich in crosslinkability can be obtained since the obtained resin has many terminals (that is, carboxyl groups). The heat resistance of the resulting coating film can be improved, and on the other hand, when designing with a value close to 500000, the finally obtained coating film is excellent in adhesion and flexibility. Thus, in the present invention, the weight average molecular weight of the carboxyl group-containing modified ester resin (A3) can be adjusted according to the purpose within the range of 5000 to 500,000.

  The insulating layer forming material for a sensor of the present invention is a compound which is at least one selected from the group consisting of the carboxyl group-containing modified ester resin (A3), an epoxy group containing compound, an isocyanate group containing compound, and a blocked isocyanate group containing compound. And (B3) and a thermosetting coagent (C3). Here, a compound (B3) which is at least one selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, and a blocked isocyanate group-containing compound [hereinafter, also simply referred to as “compound (B3)”. ] Will be described. The insulating layer forming material for a sensor of the present invention is characterized in that the compound (B3) is used as a curing agent for the carboxyl group-containing modified ester resin (A3) described above.

  The epoxy group-containing compound in the present invention is not particularly limited as long as it is a compound containing an epoxy group in the molecule. For example, as a compound which has one epoxy group in a molecule | numerator, compounds, such as N- glycidyl phthalimide, glycidol, glycidyl (meth) acrylate, are mentioned. These can be suitably used in order to control the crosslink density of the cured product by using together with a compound having two or more epoxy groups in the molecule exemplified below, if necessary. Further, as a compound containing two or more epoxy groups in the molecule, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A • epichlorohydrin type epoxy resin, Bisphenol F · epichlorohydrin type epoxy resin, bisphenol S · epichlorohydrin type epoxy resin, bisphenol AD · epichlorohydrin type epoxy resin, biphenol · epichlorohydrin type epoxy resin, ethylene oxide adduct of bisphenol A or bisphenol A Epichlorohydrin type epoxy resin of propylene oxide adduct, polyglycidyl ether of glycerin and epichlorohydrin adduct, naphthalenediol diglycidyl ether, resorcino Diglycidyl ether, polybutadiene diglycidyl ether, hydroquinone diglycidyl ether, dibromo neopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A type diglycidyl ether, polypropylene glycol diglycidyl Ether, diphenyl sulfone diglycidyl ether, dihydroxy benzophenone diglycidyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol fluoro orange glycidyl ether, bis cresol fluoro orange glycidyl ether, bis phenoxy ethanol fluoro orange glycidyl ether, 1,3- bis ( N, N-diglycidyl Minomethyl) cyclohexane, N, N-diglycidyl aniline, N, N-diglycidyl toluidine, the flexibility disclosed in Japanese Patent Application Laid-Open Nos. 2004-156024, 2004-315595, and 2004-323777 And epoxy compounds having a structure represented by the following formulas (4) to (6).

Formula (4)

Formula (5)

Formula (6)

Furthermore, tris hydroxyethyl isocyanurate triglycidyl ether, triglycidyl isocyanurate, "epicoat 1031S", "epicoat 1032H60", "epicoat 604", "epicoat 630" manufactured by Mitsubishi Chemical Corporation, phenol novolac epoxy resin, cresol Novolak type epoxy resin, Japanese Patent Application Laid-Open No. 2001-2406
Dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, polyglycidyl ether of ethylene glycol / epichlorohydrin adduct, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether, N, N, N 'disclosed in JP 54 , N′-tetraglycidyl-m-xylene diamine, and the like. Moreover, the compound which has other thermosetting groups other than an epoxy group can also be used. For example, the silane modified epoxy resin currently disclosed by Unexamined-Japanese-Patent No. 2001-59011 and 2003-48953 is mentioned.

  In particular, isocyanurate ring-containing epoxy compounds such as trishydroxyethyl isocyanurate triglycidyl ether and triglycidyl isocyanurate tend to improve adhesion strength to polyimide and copper when used in the present invention, and are thus preferable. In addition, “epicoat 1031S”, “epicoat 1032H60”, “epicoat 604”, and “epicoat 630” manufactured by Mitsubishi Chemical Corporation are highly preferable in the present invention, because they are multifunctional and excellent in heat resistance. Aliphatic epoxy compounds and epoxy compounds described in JP-A-2004-156024, JP-A-2004-315595, and JP-A-2004-323777 are preferable because they are excellent in the flexibility of a cured coating film. Further, the dicyclopentadiene type epoxy compound described in JP-A-2001-240654, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a biphenol / epichlorohydrin type epoxy resin, etc. are thermally cured in the present invention. It is excellent in the surface of durability of a cured coating film including moisture resistance and hygroscopicity and heat resistance, and is preferable.

  The isocyanate group-containing compound is not particularly limited as long as it is a compound having an isocyanate group in the molecule. Specifically, examples of the diisocyanate compound include aromatic diisocyanates having 4 to 50 carbon atoms, aliphatic diisocyanates, aromatic aliphatic diisocyanates, and alicyclic diisocyanates.

  As aromatic diisocyanate, for example, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6- Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4'-diphenylether diisocyanate, 4,4 ', 4 "-Triphenylmethane triisocyanate etc. can be mentioned.

  Examples of aliphatic diisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2 , 4, 4- trimethylhexamethylene diisocyanate, etc. can be mentioned.

  As aromatic aliphatic diisocyanates, for example, ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1 2,4- tetramethyl xylylene diisocyanate, 1,3- tetramethyl xylylene diisocyanate, etc. can be mentioned.

  As alicyclic diisocyanate, for example, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate [alias: isophorone diisocyanate], 1,3-cyclopentadiisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate Methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatemethyl) Cyclohexane etc. can be mentioned.

  Specific examples of the isocyanate group-containing compound having one or three or more isocyanate groups in the molecule include (meth) acryloyloxyethyl isocyanate as a monofunctional isocyanate having one isocyanate group in one molecule, 1,1-bis [(meth) acryloyloxymethyl] ethyl isocyanate, vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate, isopropenyl-α, α-dimethylbenzyl isocyanate and the like. Also, 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, tolylene 2,4-diisocyanate, toluene diisocyanate, 2,4-diisocyanate Toluene, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate, tetramethyl xylylene diisocyanate, cyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, tolidine diisocyanate, 2,2 , 4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Compounds obtained by reacting equimolar amounts of diisocyanate compounds such as m-tetramethyl xylylene diisocyanate, p-tetramethyl xylylene diisocyanate, and dimer acid diisocyanate with hydroxyl group, carboxyl group, and amide group-containing vinyl monomers are also isocyanates It can be used as an ester compound.

  Further, as polyfunctional isocyanates having three or more isocyanate groups in one molecule, for example, aromatic polyisocyanates, aliphatic polyisocyanates such as lysine triisocyanate, araliphatic polyisocyanates, alicyclic polyisocyanates, etc. Examples thereof include trimethylolpropane adducts of diisocyanates mentioned above, a biuret reacted with water, and a trimer having an isocyanurate ring.

  The blocked isocyanate group-containing compound is not particularly limited as long as it is an isocyanate group-containing compound in which the isocyanate group is protected by ε-caprolactam, MEK oxime or the like. Specifically, what blocked the isocyanate group of the said isocyanate group containing compound by (epsilon) -caprolactam, MEK oxime, cyclohexanone oxime, a pyrazole, a phenol etc. is mentioned.

  In the present invention, the compound (B3) may be used alone or in combination of two or more. The amount of the compound (B3) used may be determined in consideration of the application of the curable resin composition of the present invention, etc., and is not particularly limited, but 100 parts by weight of carboxyl group-containing modified ester resin (A3) It is preferable to add in the ratio of 0.5 parts by weight to 100 parts by weight, and more preferably in the ratio of 1 part by weight to 80 parts by weight. By using the compound (B3), the crosslinking density of the curable resin composition of the present invention can be adjusted to an appropriate value, and thus various physical properties of the coating after curing can be further improved. If the amount of compound (B3) used is less than 0.5 parts by weight, the crosslink density of the coating after heat curing may be too low, and the desired adhesive strength and heat resistance may be insufficient. When the amount used is more than 100 parts by weight, the crosslink density after heat curing becomes too high, and as a result, the flexibility and the flexibility of the coating film may be reduced, and the adhesive strength may be significantly deteriorated. is there.

  Next, the heat curing auxiliary (C3) of the present invention will be described. The thermosetting coagent (C3) of the present invention is a compound that directly contributes to the curing reaction or contributes catalytically when the above compound (B3) and the carboxyl group-containing modified ester resin (A3) undergo a curing reaction. It is a compound.

  The compound which directly contributes to the curing reaction as a thermosetting auxiliary agent (C3) refers to a compound having a functional group which can react with a hydroxyl group, an amino group, an epoxy group, a carboxyl group or the like alone or with heat. Those which belong to B3) are excluded and are preferably used in the thermosetting resin composition of the present invention. Specifically, for example, cyanate ester compounds, aziridine compounds, acid anhydride group-containing compounds, carboxyl group-containing compounds, carbodiimide group-containing compounds, oxetane group-containing compounds, benzoxazine compounds, maleimide compounds, citraconimide compounds, nadiimide compounds, Allyl nadiimide compound, vinyl ether compound, vinyl benzyl ether resin, thiol compound, melamine compound, guanamine compound, amino resin, phenol resin, alkyd resin, acrylic resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, xylene resin, furan Resin, ketone resin, triallyl cyanurate resin, resin containing tris (2-hydroxyethyl) isocyanurate, resin containing triallyl trimellitate, di-sic Pentadiene resins, such as thermosetting resin by trimerization of aromatic dicyanamide and the like.

  As a cyanate ester compound, bis (4-cyanatophenyl) ethane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2-Bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, α, α'-bis (4-cyanatophenyl) -m-diisopropylbenzene, phenol addition The cyanate ester compound etc. of a dicyclopentadiene polymer are mentioned, The prepolymer etc. are used individually or in mixture. Among them, 2,2-bis (4-cyanatophenyl) propane and 2,2-bis (3,5-dimethyl-4-cyanatophenyl) are preferable because the dielectric properties of the cured product are particularly good. When a cyanate ester compound is used, metal-based reaction catalysts are used as necessary, and metal catalysts such as manganese, iron, cobalt, nickel, copper, zinc and the like are used. Specifically, they are used as organic metal salt compounds such as 2-ethylhexanoate and naphthenate and organic metal complexes such as acetylacetone complex. The compounding amount of the metal-based reaction catalyst is preferably 1 to 3000 ppm, more preferably 1 to 1000 ppm, and still more preferably 2 to 300 ppm based on the cyanate ester compound. If the compounding amount of the metal-based reaction catalyst is less than 1 ppm, the effect of addition is difficult to obtain, and if it exceeds 3000 ppm, control of the reaction becomes difficult and curing tends to be too fast but it is not limited.

  As an aziridine compound, for example, N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1-aziridinecarboxite), bisiso Phthaloyl-1- (2-methylaziridine), tri-1-aziridinyl phosphine oxide, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxylate), trimethylolpropane-tri-β -Aziridinyl propionate, tetramethylolmethane-tri-β-aziridinyl propionate, tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, trimethylolpropane tris [ 3- (1-Aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) butyrate ], Trimethylolpropane tris [3- (1- (2-methyl) aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) -2-methyl propionate], 2,2'-bishydroxy Methyl butanol tris [3- (1-aziridinyl) propionate], pentaerythritol tetra [3- (1-aziridinyl) propionate], diphenylmethane-4, 4-bis-N, N'-ethylene urea, 1, 6-hexamethylene Bis-N, N'-ethyleneurea, 2,4,6- (triethyleneimino) -Syn-triazine, bis [1- (2-ethyl) aziridinyl] benzene-1,3-carboxamide, etc. may be mentioned. .

  The acid anhydride group-containing compound is not particularly limited as long as it is a compound containing an acid anhydride group in the molecule including the acid anhydride group containing compound (b3). Specifically, examples of acid anhydride group-containing compounds other than the acid anhydride group-containing compound (b3) include dicarboxylic acid anhydride, hexacarboxylic acid trianhydride, hexacarboxylic acid dianhydride, and maleic anhydride copolymer resin And polyvalent carboxylic acid anhydrides, and the like. More specifically illustrating the acid anhydride group-containing compound, phthalic anhydride, tetrahydrophthalic anhydride and the like, and as maleic anhydride copolymer resin, SMA resin series manufactured by Sartmar, G, SM manufactured by Gifu Shellac Co., Ltd. Series, styrene-maleic anhydride copolymer resin, p-phenylstyrene-maleic anhydride copolymer resin, polyethylene-maleic anhydride α-olefin-maleic anhydride copolymer resin, Daicel Chemical Industries, Ltd. "VEMA" (Copolymer of methyl vinyl ether and maleic anhydride), maleic anhydride acrylic-modified polyolefin ("Auroren series" manufactured by Nippon Paper Chemicals Co., Ltd.), maleic anhydride copolymer acrylic resin, and the like.

Examples of the carboxyl group-containing compound include o-phthalic acid, isophthalic acid, terephthalic acid, 1,4-dimethylterephthalic acid, 1,3-dimethylisophthalic acid, 5-sulfo-1,3-dimethylisophthalic acid, Aromatic dicarboxylic acids such as 4-biphenyl dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, norbornene dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, phenylindane dicarboxylic acid;
Alicyclic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydrophthalic acid and tetrahydrophthalic acid;
Aliphatic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, chloromaleic acid, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, etc. And dicarboxylic acids.

  Examples of the carbodiimide group-containing compound include the Carbodilite series of Nisshinbo Co., Ltd. Among these, carbodilite V-01, 03, 05, 07, 09 is preferable because it is excellent in compatibility with organic solvents.

  Examples of the oxetane group-containing compound include 1,4-bis {[(3-ethyloxetan-3-yl) methoxy] methyl} benzene (manufactured by Toagosei Co., Ltd., trade name; Aron oxetane OXT-121, etc.), 3- Ethyl 3-{[(3-ethyloxetan-3-yl) methoxy] methyl} oxetane [made by Toagosei Co., Ltd., trade name; Aron oxetane OXT-221 etc.], 1,3-bis [(3-ethyl oxetane- 3-yl) methoxy] benzene, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, (2-ethyl-2-oxetanyl) esterified product of ethanol and terephthalic acid, (2- Ethers of ethyl 2-oxetanyl) ethanol and phenol novolac resin, (2-ethyl-2-oxetanyl) ethanol Esterified products of valence carboxylic acid compounds. Examples of the benzoxazine compounds include “Pa”, “P-alp”, “P-ala”, “B-ala” and Macromolecules, 34, 7257 (2001) described in Macromolecules, 36, 6010 (2003). “P-appe”, “B-appe”, “B-a type benzoxazine” manufactured by Shikoku Kasei Co., Ltd., “F-a type benzoxazine”, “B-m type benzoxazine” and the like can be mentioned.

  As a vinyl benzyl ether resin, V-1000X (made by Showa Polymer Co., Ltd.), U.S. Pat. No. 4,116,936, U.S. Pat. No. 4,170,711, U.S. Pat. No. 4,278,708, JP-A 9-31006, JP-A The vinyl benzyl ether resin etc. of 2001-181383, Unexamined-Japanese-Patent 2001-253992, Unexamined-Japanese-Patent 2003-277440, Unexamined-Japanese-Patent 2003-283076, international publication 02/083610 pamphlet are mentioned.

  The maleimide compound is a compound having at least one maleimide group in the molecule, and examples thereof include phenyl maleimide, 1-methyl-2,4-bismaleimide benzene, N, N'-m-phenylene bismaleimide, N , N′-p-phenylenebismaleimide, N, N′-4,4-biphenylenebismaleimide, N, N′-4,4- (3,3-dimethylbiphenylene) bismaleimide, N, N′-4, 4- (3,3-dimethyldiphenylmethane) bismaleimide, N, N'-4,4- (3,3-diethyldiphenylmethane) bismaleimide, N, N'-4,4-diphenylmethane bismaleimide, N, N ' -4,4-Diphenylpropane bismaleimide, N, N'-4,4-diphenylether bismaleimide, N, N'-4,4-diphenyl Rufone bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-s-butyl-3,4- (4-maleimidophenoxy) phenyl] propane, 1, 1-bis [4- (4-maleimidophenoxy) phenyl] decane, 4,4'-cyclohexylidene-bis [1- (4-maleimidophenoxy) phenoxy] -2-cyclohexylbenzene, 2,2-bis [4 There are-(4-maleimidophenoxy) phenyl] hexafluoropropane and the like, which may be used alone or in combination of two or more.

  The citraconic imide compound is a compound having at least one citraconic imide group in the molecule or a polymer thereof, and examples thereof include phenylcitraconimide, 1-methyl-2,4-biscitraconimidobenzene, N, N '-M-phenylenebiscitraconimide, N, N'-p-phenylenebiscitraconimide, N, N'-4,4-biphenylene biscitraconimide, N, N'-4,4- (3,3-dimethyl Biphenylene) biscitraconimide, N, N'-4,4- (3,3-dimethyldiphenylmethane) biscitraconimide, N, N'-4,4- (3,3-diethyldiphenylmethane) biscitraconimide, N, N'-4,4-Diphenylmethane biscitraconimide, N, N'-4,4-diphenylpropane bisit Conimide, N, N'-4,4-diphenylether biscitraconimide, N, N'-4,4-diphenylsulfone biscitraconimide, 2,2-bis [4- (4-citraconimidophenoxy) phenyl] propane, 2,2-bis [3-s-butyl-3,4- (4-citraconimidophenoxy) phenyl] propane, 1,1-bis [4- (4-citraconimidophenoxy) phenyl] decane, 4,4 ' -Cyclohexylidene-bis [1- (4-citraconimidophenoxy) phenoxy] -2-cyclohexylbenzene, 2,2-bis [4- (4-citraconimidophenoxy) phenyl] hexafluoropropane, etc. Two or more types may be mixed and used.

  The nadimide compound is a compound having at least one nadimide group in the molecule or a polymer thereof, and examples thereof include phenyl nadiimide, 1-methyl-2,4-bisnadiimide benzene, N, N ′. -M-phenylenebisnadiimide, N, N'-p-phenylenebisnadiimide, N, N'-4,4-biphenylene bisnadiimide, N, N'-4,4- (3,3-dimethylbiphenylene) bisnadiimide N, N'-4,4- (3,3-dimethyldiphenylmethane) bisnadiimide, N, N'-4,4-diphenylmethane bisnadiimide, N, N'-4,4-diphenylpropane bisnadiimide, N, N ' -4,4-Diphenylether bisnadiimide, N, N'-4,4-diphenylsulfone bisnadiimide, 2,2-bis [4- 4-Nadiimidophenoxy) phenyl] propane, 2,2-bis [3-s-butyl-3,4- (4-nadiimidophenoxy) phenyl] propane, 1,1-bis [4- (4-nadiimide) Phenoxy) phenyl] decane, 4,4'-cyclohexylidene-bis [1- (4-nadiimidophenoxy) phenoxy] -2-cyclohexylbenzene, 2,2-bis [4- (4-nadiimidophenoxy) phenyl Hexafluoropropane may be used alone or in combination of two or more.

  Examples of allyl nadiimide compounds include bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, 1,6-hexane-bis-allylnadiimide And metaxylylene-bis-allyl nadiimide, etc., which may be used alone or in combination of two or more.

  As vinyl ether compounds, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, cyclohexane dimethanol divinyl ether, cyclohexane dimethanol mono vinyl ether, cyclohexyl vinyl ether, cyclohexane methanol vinyl ether, ethylcyclohexanol vinyl ether, methoxyethyl vinyl ether, ethoxy Ethyl vinyl ether, hydroxypropyl vinyl ether, hydroxypentyl vinyl ether, diethylaminoethyl vinyl ether, tricyclodecane epoxy vinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetra Tyrene glycol divinyl ether, pentaerythritol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, neopentyl glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether Glycerin divinyl ether, trimethylolpropane divinyl ether, 1,4-dihydroxyl cyclohexane divinyl ether, 1,4-dihydroxymethyl cyclohexane divinyl ether, hydroquinone divinyl ether, ethylene oxide modified hydroquinone divinyl ether, ethylene oxide modified resorcine divinyl ether, ethylene Oxide modified bisphenol A divinyl ether, ethylene oxide modified bisphenol S divinyl ether, glycerin trivinyl ether, sorbitol tetravinyl ether, trimethylolpropane trivinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol hexavinyl ether, dipentaerythritol polyvinyl ether, ditrimethylol Propane tetravinyl ether, ditrimethylol propane polyvinyl ether, etc. may be used alone or in combination of two or more.

  As thiol compounds, 2,4,6-trimercapto-s-triazole, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-S-triazine, tetraethylene glycol Bis-3-mercaptopropionate, trimethylolpropane tris-3-mercaptopropionate, tris- (ethyl-3-mercaptopropionate) isocyanurate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol Hexa-3-mercaptopropionate and the like may be used alone or in combination of two or more.

  The amino resin may, for example, be an addition compound of urea, melamine, benzoguanamine, acetoguanamine or the like with formaldehyde, or a partial condensate thereof. Moreover, as a phenol resin, the addition compound of compounds, such as phenol, cresols, and bisphenols, and formaldehyde, or its partial condensation product is mentioned. Specifically, resol of phenol resin, cresol resin, t-butyl phenol resin, dicyclopentadiene cresol resin, dicyclopentadiene phenol resin, xylylene modified phenol resin, tetrakis phenol resin, bisphenol A resin, poly-p-vinyl phenol resin Mold resin and novolak resin. In addition, naphthol compounds, trisphenol compounds, phenol aralkyl resins and the like can be mentioned. Among them, resol type resins of phenol resin are very excellent in heat resistance and curability, and can be suitably used in the present invention.

  As a compound which contributes catalytically to the curing reaction as a heat curing auxiliary (C3), tertiary amines and salts thereof, dicyandiamide, carboxylic acid hydrazide, imidazoles, diazabicyclo compounds, phosphines and phosphonium salts can be mentioned. Use of these is preferable because the thermosetting reaction proceeds more efficiently and the coating film has excellent resistance.

Specifically, tertiary amines such as triethylamine, tributylamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N-methylpiperazine, and salts thereof;
2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-dicyano-6- [2-methylimidazolyl-1] Imidazoles such as -ethyl-S-triazine, 2-ethyl-4-methylimidazole tetraphenylborate, and salts thereof;
1,5-diazabicyclo [5,4,0] -7-undecane, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,4-diabicyclo [2,2,2,] octane, 1 , Diazabicyclo compounds such as 8-diazabicyclo [5.4.0] undecene-7-tetraphenylborate;
Phosphines such as tributyl phosphine, triphenyl phosphine, tris (dimethoxyphenyl) phosphine, tris (hydroxypropyl) phosphine, tris (cyanoethyl) phosphine and the like;
Phosphonium salts such as tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium tetraphenylborate, methyltricyanoethylphosphonium tetraphenylborate and the like;
In addition, dicyandiamide, carboxylic acid hydrazide and the like can be mentioned as a compound which is catalytic and which itself directly contributes to the curing reaction. As the carboxylic acid hydrazide, succinic acid hydrazide, adipic acid hydrazide and the like can be mentioned.

  Only one type of these heat curing assistants (C3) may be used, or two or more types may be used in combination. The use amount of the thermosetting auxiliary agent (C3) may be determined in consideration of the curing physical properties of the curable resin composition, and is not particularly limited, but the carboxyl group-containing modified ester resin (A3) of the present invention The range of 0.05 parts by weight to 20 parts by weight is preferable with respect to 100 parts by weight, and the range of 0.1 parts by weight to 10 parts by weight is more preferable. Thereby, it is possible to control the crosslinking speed, the crosslinking density, and the cohesive force of the thermosetting resin composition of the present invention, and various physical properties can be further improved. When the use amount of the heat curing auxiliary (C3) is less than 0.05 parts by weight, the addition effect thereof is difficult to be obtained, and when the use amount is more than 20 parts by weight, an excess heat cure aid (C3) C3) tends to be a cause of lowering the electrical insulation property, adhesive strength and solder heat resistance.

  In addition to the above, the insulating layer-forming material for a sensor according to the present invention may further contain a solvent, a dye, a pigment, a flame retardant, an antioxidant, a polymerization inhibitor, an antifoamer, a leveling agent, an ion A scavenger, a moisturizer, a viscosity modifier, an antiseptic, an antibacterial agent, an antistatic agent, an antiblocking agent, an ultraviolet absorber, an infrared absorber, an electromagnetic wave shielding agent, a filler and the like can be added. In particular, it is used for insulation members (for example, circuit protective film, cover lay layer, interlayer insulation material, etc.) directly in contact with the circuit in electronic material applications, and members (printed wiring board adhesive, support substrate, etc.) When using, it is preferable to use a flame retardant in combination.

  As the flame retardant, for example, melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium ammonium phosphate, ammonium polyphosphate ammonium, phosphate carbamate, polyphosphate carbamate, etc. Phosphate compounds and polyphosphate compounds, red phosphorus, organic phosphoric acid ester compounds, phosphazene compounds, phosphonic acid compounds, aluminum diethylphosphinate, aluminum methylethylphosphinate, aluminum diphenylphosphinate, aluminum ethylbutylphosphinate, Phosphinic acid compounds such as aluminum methylbutylphosphinate, aluminum polyethylenephosphinate, phosphine oxide compounds, phosphorane compounds, phosphoramidation Phosphorus flame retardants, triazine compounds such as melamine, melam, melem, melon, melamine cyanurate, cyanuric acid compounds, isocyanuric acid compounds, triazole compounds, tetrazole compounds, diazo compounds, nitrogen flame retardants such as urea Silicon-based flame retardants such as silicone compounds and silane compounds, low molecular weight halogen-containing compounds such as halogenated bisphenol A, halogenated epoxy compounds and halogenated phenoxy compounds, halogenated flame retardants such as halogenated oligomers and polymers, water Metal oxides such as aluminum oxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide and calcium hydroxide, tin oxide, aluminum oxide, magnesium oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, antimony oxide, Nickel, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, and inorganic flame retardants such as hydrated glass. In the present invention, it is desirable to use a non-halogen based flame retardant such as a phosphorus based flame retardant or a nitrogen based flame retardant, considering the influence on the environment, which has been discussed in recent years, and above all, the thermosetting resin composition of the present invention It is preferable to use a phosphazene compound, a phosphine compound, a melamine polyphosphate, an ammonium polyphosphate, melamine cyanurate and the like which are more effective in flame retardancy, in combination with the above. In the present invention, these flame retardants can be used alone or in combination of two or more.

  As an antifoamer and a leveling agent, a silicone type, hydrocarbon type, an acrylic resin type compound etc. are mentioned.

  As the ion collecting agent, an inorganic or organic ion exchanger is suitably used. In detail, although the inorganic ion exchanger ige of Toa Synthetic Co., Ltd. and the ion exchange resin diaion of Mitsubishi Chemical Co., Ltd. are used, it is not limited thereto as long as it has an ion collecting ability.

  According to the present invention, the adhesive strength, electrical insulation, heat resistance, flexibility, and processability are excellent, and in particular, storage stability and processing stability are simultaneously satisfied, and high heat resistance is achieved while maintaining higher adhesion strength. Further, a material for forming an insulating layer for a sensor, which is compatible in adhesive strength and electrical insulation, heat resistance and flexibility, was obtained. These can be cured and suitably used for the insulating layer (Y).

<Dielectric layer (Z)>
The dielectric layer (Z) is used at a position sandwiched between the two conductive layers (X), and by acting as a dielectric, a sensor electrode sheet of a capacitor structure can be suitably formed.
The dielectric layer (Z) is formed by applying a film / sheet-like resin as it is or through an adhesive if necessary, a coating agent containing a resin, and then drying and curing as required. The resin coating film etc. which were formed can be used.
The electrode sheet of the present invention is required to be flexible and flexible also in the dielectric layer (Z) because it needs flexibility and flexibility. Specifically, fluorine resin, acrylic resin, polyester resin, urethane resin such as polyester urethane or polyether urethane, polycarbonate urethane, urethane urethane resin such as polyester urethane urea or polycarbonate urethane urea, polyester urea or polyether Urea, Urea resin such as polycarbonate Urea, polyethylene, polypropylene, olefin resin such as acrylonitrile-butadiene-styrene resin, polyacetal resin such as polyvinyl alcohol and polyvinyl butyral, polyamide resin, polyimide resin, epoxy resin , Phenoxy resin, polyphenol resin, nylon resin, vinylon resin, aramid resin, cellulose resin, etc. as a main component, if necessary These include curing agents for crosslinking these resins, catalysts for promoting the same, and other resin compositions containing various additives for imparting coating properties, stability, durability, etc. Depending on the requirements, two or more of these materials may be mixed and used.
Among them, in consideration of flexibility and dielectric constant, the main components are halogen-free acrylic or olefin rubber, polyester resin, urethane resin, urethane urea resin, urea resin, epoxy resin and phenoxy resin. It is preferable to do.

  Further, the film thickness of the dielectric layer (Z) is preferably 0.1 μm or more and less than 100000 μm, and more preferably 3 μm or more and less than 50000 μm. If the thickness is less than 0.1 μm, the dielectric layer (Z) is easily broken by a small impact from the outside, and the conductive layers are short-circuited to make it difficult to ensure the stability of the electrical characteristics. It becomes difficult to stably induce an electric field.

  The area and thickness of the dielectric layer (Z) are often determined in advance depending on the application, so to improve the electrical characteristics, the value of the relative dielectric constant (εr) should be as small as possible. Therefore, it is important to reduce the capacitance. The value of the relative dielectric constant (εr) of the dielectric layer (Z) is preferably less than 5, and preferably less than 3, depending on the use application. If it is 5 or more, the value of the electrostatic capacitance (C) is too large, and it becomes difficult to stably detect the electric field.

  Preferably, the dielectric layer (Z) contains air. The inclusion of air in the dielectric layer (Z) makes it possible to lower the relative dielectric constant of the dielectric layer (Z) and also to impart elasticity. As a material, what contained air in the main component of a dielectric layer (Z) is preferable, and a foam coated sheet using these, a urethane foam, a polystyrene foam, etc. are mentioned. In order to include air, a method of physically making a hole in the insulating layer by a laser or a load, a method of forming a hole by a drawing method, a phase separation method, etc., a liquid is melted and applied in a state containing bubbles. There are a method of fixing the air bubbles by cooling, a method of including a foam material, and the like.

  The electrode sheet of the present invention may be processed into a desired shape by punching after main curing. In this case, in the semi-hardened conductive layer (X), better punching processability can be obtained by being in a predetermined elongation range. Specifically, it is preferable that the elongation rate calculated from the SS curve (stress-strain curve) at 25 ° C. be 50% to 300%. When the elongation percentage is 50% or more, the conductive layer (X) after main curing hardly breaks. Moreover, it becomes difficult to produce a punching defect because it becomes 300% or less.

The electrode sheet of the present invention uses the conductive layer (X), for example, temporarily bonds the insulating layer (Y) and the dielectric layer (Z), and then heating at a high temperature to obtain a semi-cured conductive layer (X ) Can be cured. The main curing provides excellent adhesive strength and heat resistance.
130-210 degreeC is preferable and, as for the heating temperature of this hardening, 140-200 degreeC is more preferable. Although it can pressurize in the case of heating, 0.2-12 Mpa is preferable and 0.3-10 Mpa is more preferable.

  The conductive layer (X) and the electrode sheet of the present invention can be used for a capacitance type bio-sensor, a proximity sensor, and a bio-impedance sensor electrode portion of a measuring machine as shown below. However, the present invention is not limited to the configuration examples and usage examples shown here.

An exemplary configuration of a capacitive biosensor is shown below.

An exemplary configuration of a capacitive proximity sensor is shown below.

An example of the configuration of a bioelectrical impedance measuring instrument is shown below.

Various aspects of the sensor electrode sheet of the present invention will be described based on the drawings.
FIG. 1 (1) is an electrode sheet for sensors which consists only of a conductive layer (X).
FIG. 1 (2) is a sensor electrode sheet comprising a conductive layer (X) and an insulating layer (Y), and shows an example of the aspect of the sensor electrode sheet according to claim 3. FIG. 1 (3) is an electrode sheet for sensors which consists of a conductive layer (X) and a dielectric layer (Z), and shows an example of a mode of an electrode sheet for sensors concerning Claim 2. FIG.
FIG. 1 (4) is a sensor electrode sheet including an insulating layer (Y), a conductive layer (X), and a dielectric layer (Z) in this order, and an example of the embodiment of the sensor electrode sheet according to claim 3. Indicates FIG. 1 (5) comprises a dielectric layer (Z) between two conductive layers (X), and shows an example of the aspect of a sensor electrode sheet according to claim 4. Although the two conductive layers (X) are distinguished as (X1) and (X2) in claim 4, they are omitted as (X) in FIG. 1 (5).
FIG. 1 (6) comprises an insulating layer (Y) between two conductive layers (X), and shows an example of an embodiment of a sensor electrode sheet according to claim 3.

In FIG. 1 (7), the other side of one conductive layer (X) of the sensor electrode sheet having a dielectric layer (Z) between two conductive layers (X), that is, the dielectric layer (Z) is not in contact An insulating layer (Y) is provided on the surface,
In FIG. 1 (8), two insulating layers (Y) are provided on the other surface of both conductive layers (X) of a sensor electrode sheet having a dielectric layer (Z) between two conductive layers (X). All show an example of the aspect of the electrode sheet for sensors which concerns on Claim 5, respectively. Although the two conductive layers (X) are distinguished as (X1) and (X2) in claim 5, they are omitted as (X) in FIGS. 1 (7) and (8).
If attention is paid to the units of the conductive layer (X) and the insulating layer (Y), FIGS. 1 (7) to (10) can be said to be other embodiments of the sensor electrode sheet according to claim 3.

FIG. 2 (11) comprises three conductive layers (X) and two dielectric layers (Z), and comprises a dielectric layer (Z) between two conductive layers (X), An example of the aspect of the electrode sheet for sensors which concerns on FIG. In FIG. 2 (1), the symbol distinction of the three conductive layers (X) and the two dielectric layers (Z) is omitted.
If attention is paid to the units of the conductive layer (X) and the insulating layer (Y), FIGS. 2 (12) to 2 (17) can be said to be another aspect of the sensor electrode sheet according to claim 3. Moreover, focusing on the units of the insulating layer (Y), the conductive layer (X) and the dielectric layer (Z), FIGS. 2 (12) to 2 (17) are other embodiments of the sensor electrode sheet according to claim 4. It can also be said.

FIG. 3 (18) is a sensor electrode sheet in which a conductive layer (X), a dielectric layer (Z) and a conductive layer (X) are provided symmetrically on both sides of the insulating layer (Y), respectively. An example of the aspect of the electrode sheet for sensors which concerns on 6 is shown. In the sixth embodiment, four conductive layers (X) are (X3) to (X6), and two dielectric layers (Z) are distinguished as (Z1) and (Z2), but in FIG. ), Omitted as (Z).
Focusing on the units of the conductive layer (X) and the insulating layer (Y), FIG. 3 (18) can be said to be another aspect of the sensor electrode sheet according to claim 3. Moreover, focusing on the units of the insulating layer (Y), the conductive layer (X), and the dielectric layer (Z), FIG. 3 (18) also refers to another aspect of the sensor electrode sheet according to claim 4. it can.

FIG. 3 (19) is obtained by further providing an insulating layer (Y) on the conductive layer (X) which is one surface layer of the sensor electrode sheet shown in FIG. 3 (18).
FIG. 3 (20) is obtained by further providing an insulating layer (Y) on the conductive layer (X) which is both surface layers in the sensor electrode sheet shown in FIG. 3 (18). An example of the aspect of the electrode sheet for sensors which concerns on FIG.
The omission of the symbols is the same as in FIG. 3 (18), and focusing on the units of the conductive layer (X) and the insulating layer (Y), another aspect of the sensor electrode sheet according to claim 3 And focusing on the units of the insulating layer (Y), the conductive layer (X), and the dielectric layer (Z), another aspect of the sensor electrode sheet according to the fourth aspect can be said as well. It is similar to the case of (18).

The sensor electrode sheet of various aspects shown in FIGS. 1 to 3 can be used after being processed into desired various sizes and shapes by punching, a cutter, scissors, a cutting machine or the like.
Or
The electrode sheets for sensors of various embodiments shown in FIGS. 1 (2) to 3 are obtained by temporarily laminating an insulating layer (Y) and a dielectric layer (Z) on the conductive layer before curing, and then punching, cutting, cutting or pinching it. After processing into a desired various size and shape with a cutter or the like, the conductive layer forming material can be cured to form the conductive layer (X).

Furthermore, the sensor electrode sheet of another aspect shown in FIG. 4 is demonstrated.
In FIG. 4 (1), a plurality of strip-shaped stacked portions of a conductive layer (X) and an insulating layer (Y) are provided on one surface of the dielectric layer (Z), and the other surface of the dielectric layer (Z) is conductive A plurality of strip-shaped stacked portions of the layer (X) and the insulating layer (Y) are provided.
4 (2) is a cross-sectional view taken along the line A-A 'of FIG. 4 (1), FIG. 4 (3) is a cross-sectional view taken along the line B-B' of FIG. 4 (1), FIG. FIG. 4 (4) is a view of FIG. 4 (1) viewed from the top side, and FIG. 4 (5) is a view of FIG. 4 (1) viewed from the bottom side. As such, the plurality of strip-shaped stacked portions in each surface are provided to be substantially orthogonal.
The cross-sectional view in the case of cutting along the line CC 'in FIG. 4 (2) is as shown in FIG. 1 (8).
The sensor electrode sheet provided with a plurality of strip-like laminated portions shown in FIG. 4 can be used as it is, or can be separated between the strip-like portions and the strip-like portions, and each small piece can be used as a sensor electrode sheet.

FIG. 5 is different from the case of FIG. 4 in that the laminated portion of the conductive layer (X) and the insulating layer (Y) provided on the dielectric layer (Z) is not a strip but a fragment.
Also in the case of FIG. 5, as in the case of FIG. 4, it can be used as a sensor electrode sheet as it is large, or each piece (section) can be cut off and each piece can be used as a sensor electrode sheet.
Although not shown in the drawings, it is also possible to make the laminated portion provided on one surface of the dielectric layer (Z) into a band shape and to make the laminated portion provided on the other surface a segment.

EXAMPLES The present invention will next be described in more detail by way of examples, which should not be construed as limiting the invention thereto.
In the examples, "part" represents "part by weight" and "%" represents "% by weight". Moreover, "Mn" represents a number average molecular weight and "Mw" represents a weight average molecular weight.

<Method of measuring weight average molecular weight>
The weight average molecular weight is a value in terms of polystyrene calculated by GPC (gel permeation chromatography) measurement. The measurement conditions are as follows.
Device: Shodex GPC System-21 (made by Showa Denko)
Column: A total of three columns of Shodex KF-802, KF-803L, and KF-805L (manufactured by Showa Denko) are used in connection.
Solvent: tetrahydrofuran flow rate: 1.0 ml / min
Temperature: 40 ° C
Sample concentration: 0.2% by weight
Sample injection volume: 100 μl

Synthesis Example 1
A reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing pipe, 195.0 parts of polyoxytetramethylene glycol ("PTG-2000SN", Mn = 2029, Hodogaya Chemical Industry Co., Ltd.), dimethylol 6.70 parts of butanoic acid, 40.8 parts of isophorone diisocyanate and 70.0 parts of toluene are charged, reacted at 90 ° C. for 4 hours under a nitrogen atmosphere, 250 parts of toluene are added thereto, and isocyanate group of Mw = 22,000 is obtained The obtained urethane prepolymer solution was obtained.
Next, the obtained urethane prepolymer solution containing an isocyanate group in a mixture of 6.11 parts of isophorone diamine, 0.59 parts of di-n-butylamine, 112.5 parts of 2-propanol and 184.5 parts of toluene. 506.3 parts were added and reacted at 85 ° C. for 4 hours to obtain a solution of polyurethane urea resin A-1 having Mw = 105,000, acid value = 10.2 mg KOH / g, nonvolatile content 25%.

Synthesis Example 2
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, 173.5 g of Priol 1009 (hydrodistillation dimer acid manufactured by CRODA) as a polybasic acid compound, and priamine as a polyamine compound 157.9 g of 1074 (dimer diamine manufactured by CRODA) was charged and stirred until the temperature of heat generation became constant. After confirming that the temperature was stable, it was heated to 110 ° C., and after confirming the start of the dehydration reaction, the temperature was heated to 120 ° C. over 30 minutes. Thereafter, heating was carried out at a rate at which the temperature was raised by 10 ° C. for 30 minutes. After the temperature reached 230 ° C., the temperature was maintained and the reaction was continued for 3 hours. Then, after holding the state decompressed to the vacuum of about 2 kPa for 1 hour, it cooled. Then, an antioxidant was added to obtain a polyamide resin elastomer C-1 having a weight average molecular weight of 124000, an acid value of 4 mg KOH / g, and a glass transition temperature of -58 ° C.

Synthesis Example 3
Polycarbonate diol (Kuraray polyol C-2090: manufactured by Kuraray Co., Ltd .: 3-methyl-1,5-pentanediol / 1) in a 4-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, an inlet, and a thermometer. , 6-hexanediol = 9/1 (molar ratio) copolymerized polycarbonate diol: hydroxyl value = 56 mg KOH / g, Mw = 2000 292.1 parts, tetrahydrophthalic anhydride (Rikasid TH: manufactured by Shin Nippon Rika Co., Ltd.) 44 .9 parts and 350 parts of toluene as a solvent were charged, and the temperature was raised to 60 ° C while stirring under a nitrogen stream to dissolve uniformly. Subsequently, the flask was heated to 110 ° C. and allowed to react for 3 hours. Then, after cooling to 40 ° C., 62.9 parts of bisphenol A type epoxy resin (YD-8125: manufactured by Tohto Kasei Co., Ltd .: epoxy equivalent = 175 g / eq) and 4 parts of triphenylphosphine as a catalyst are added to 110 ° C. The temperature was raised and reacted for 8 hours. After cooling to room temperature, 11.8 parts of tetrahydrophthalic anhydride was added and allowed to react at 110 ° C. for 3 hours. After cooling to room temperature, the solid content was adjusted to 35% with toluene to obtain a carboxyl group-containing modified ester resin (A) solution of the present invention. The weight average molecular weight of the carboxyl group-containing modified ester resin (A) obtained by this production example was 12600, and the acid value of the resin solid content by measurement was 15.3 mg KOH / g.

[Production Example 1: Production Example of Conductive Layer Forming Material 1 for Sensor]
400 parts of a solution of polyurethane urea resin A-1, 60 parts of bisphenol A type epoxy ("ADECA RESIN EP-4100", epoxy equivalent = 190 g / Eq manufactured by ADEKA), polyamide resin C-1 as an elastomer (glass transition temperature-58 ° C Storage modulus at 25 ° C., 45 MPA, acid number 4, tensile modulus 11 MPA, 75 parts, conductive particles such as copper in the case body, silver in the coating layer (D ₅₀ = 11 μm, Fukuda metal foil powder industry) 300 parts as a curing agent, 3 parts of 2-methylimidazole, 25 parts of silica ("Nipsil SS-50F" manufactured by Tosoh Silica Corporation) as an inorganic filler, n-2- (aminoethyl) -3 as a silane coupling agent -Aminopropylmethyl dimethoxysilane was mixed to obtain a conductive layer forming material.
The conductive layer forming material for a sensor was coated on a peelable sheet and dried at 100 ° C. for 2 minutes to obtain a conductive layer forming material for a sensor with a thickness of 40 μm. It was 80% when the gel fraction of the conductive layer forming material for sensors was calculated | required according to the method mentioned later.

<Gel fraction>
A stainless steel wire mesh of 100 mesh was prepared to have a width of 30 mm and a length of 100 mm, and the weight (W1) was measured. Subsequently, a conductive layer forming material for a sensor was prepared to a size of 10 mm wide and 80 mm long, and the stainless steel wire mesh was used as a test specimen wrapped so that the conductive layer forming material for a sensor was not visible, and the weight (W2) was measured. . The produced test piece was immersed in methyl ethyl ketone (MEK) at room temperature (25 ° C.) and left for 1 hour. The test pieces were then removed from MEK and dried at 150 ° C. for 10 minutes, and then the weight (W3) was measured. Then, the gel fraction was calculated using the lower equation (1).
(W3-W1) / (W2-W1) × 100 [%] Formula (1)

[Production Example 2: Production Example of Insulating Layer Forming Material 1 for Sensor]
400 parts of a solution of polyurethane urea resin A-1, 60 parts of bisphenol A type epoxy ("ADECA RESIN EP-4100", epoxy equivalent = 190 g / Eq manufactured by ADEKA), polyamide resin C-1 as an elastomer (glass transition temperature-58 ° C Storage modulus at 25 ° C., 45 MPA, acid number 4, tensile modulus 11 MPA, 75 parts, curing agent, 3 parts of 2-methylimidazole, inorganic filler, silica ("Nipsil SS-50F" manufactured by Tosoh Silica Corporation), 25 parts N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane was mixed as a silane coupling agent to obtain a sensor insulating layer forming material.
This insulating layer forming material for a sensor was coated on a peelable sheet and dried at 100 ° C. for 2 minutes to obtain a 40 μm thick insulating layer forming material for a sensor.

[Production Example 3: Production Example of Insulating Layer Forming Material 2 for Sensor]
20 parts of polyfunctional glycidyl ether type epoxy resin ("Epicoat 1031S" manufactured by Mitsubishi Chemical Corporation) per 100 parts of solid content of the carboxyl group-containing modified ester resin (A) solution obtained in Synthesis Example 2 and thermosetting 1 part of Chemitite PZ (multifunctional aziridine compound, manufactured by Nippon Shokubai Co., Ltd.) was mixed as an auxiliary agent to obtain a sensor insulating layer forming material 2. This was uniformly coated on the peelable sheet so that the film thickness after drying was 30 μm and dried to obtain a sensor insulating layer forming material 2.

Example 1: Electrode sheet production example 1
A 10 cm × 10 cm, 100 μm thick polyimide film (manufactured by DuPont Co., Ltd., Kapton 400H) is laminated as an insulating layer (Y) on the conductive layer forming material 1 of 10 cm × 10 cm obtained in Production Example 1 The resultant was crimped under conditions of 170 ° C., 2 MPa, and 5 minutes, and then heated for 60 minutes in an electric oven at 160 ° C. to obtain an electrode sheet of an insulating layer / conductive layer having a size of 10 cm × 10 cm. During lamination, place one end of the copper foil side of the 10 mm x 30 mm polyimide copper-clad laminate "Spanex M" by Nippon Steel Corp. on the conductive layer side on the opposite side of the square, and measure the resistance. , It was taken out electrode at the time of measuring electrostatic capacity.

Example 2: Example of electrode sheet production 1-2
The insulating layer forming material 1 for sensor having a size of 10 cm × 10 cm obtained in Production Example 2 is stacked on the conductive layer forming material for a sensor having a size of 10 cm × 10 cm obtained in Manufacturing Example 1 at 170 ° C., 2 MPa, 5 After pressure-bonding treatment under conditions of minutes, heating was performed in an electric oven at 160 ° C. for 60 minutes to obtain an electrode sheet of an insulating layer / conductive layer having a size of 10 cm × 10 cm. During lamination, place one end of the copper foil side of the 10 mm x 30 mm polyimide copper-clad laminate "Spanex M" by Nippon Steel Corp. on the conductive layer side on the opposite side of the square, and measure the resistance. , It was taken out electrode at the time of measuring electrostatic capacity.

Example 3: Production Example of Electrode Sheet 1-3
The insulating layer forming material 2 for sensor having a size of 10 cm × 10 cm obtained in Production Example 3 is stacked on the conductive layer forming material for a sensor having a size of 10 cm × 10 cm obtained in Manufacturing Example 1 and 170 ° C., 2 MPa, 5 After pressure-bonding treatment under conditions of minutes, heating was performed in an electric oven at 160 ° C. for 60 minutes to obtain an electrode sheet of an insulating layer / conductive layer having a size of 10 cm × 10 cm. During lamination, place one end of the copper foil side of the 10 mm x 30 mm polyimide copper-clad laminate "Spanex M" by Nippon Steel Corp. on the conductive layer side on the opposite side of the square, and measure the resistance. , It was taken out electrode at the time of measuring electrostatic capacity.

Example 4: Example of electrode sheet production 2
A 10 cm × 10 cm conductive layer-forming material 1 obtained in Production Example 1 was used as an insulating layer (Y), a polyimide film (Dupont Co., Ltd., Kapton 400H) having a dimension of 10 cm × 10 cm, a dielectric layer As Z), using a foamed hot melt resin (made by Toyo Admiral Co., Ltd.) having a size of 10 cm × 10 cm and a thickness of 700 μm, laminating in the order of insulating layer / conductive layer forming material / dielectric layer / conductive layer forming material / insulating layer, 170 After pressure bonding under conditions of 2 ° C, 2MPa, 5 minutes, it is heated in an electric oven at 160 ° C for 60 minutes, and an electrode sheet of insulating layer / conductive layer / dielectric layer / conductive layer / insulating layer of dimensions 10 cm × 10 cm I got During lamination, place one end of the copper foil side of the 10 mm x 30 mm polyimide copper-clad laminate "Spanex M" by Nippon Steel Corp. on the conductive layer side on the opposite side of the square, and measure the resistance. , It was taken out electrode at the time of measuring electrostatic capacity.

Example 5: Electrode sheet production example 2-1
Insulating layer forming material 1 for a sensor having a size of 10 cm × 10 cm obtained in Production Example 2 is laminated on the conductive layer forming material for a sensor having a size of 10 cm × 10 cm obtained in Production Example 1 to form an insulating layer for a sensor Material / Conductive layer forming material for sensor was obtained.
Insulating layer forming material for sensor / conductive layer forming material for sensor / dielectric layer / conductive layer for sensor, using a foam hot melt resin (made by Toyo Addressee Co., Ltd.) having a dimension of 10 cm × 10 cm as a dielectric layer (Z) Forming material / insulating layer forming material for sensor It laminates in order so as to become a forming material, and after performing pressure bonding processing under conditions of 170 ° C, 2MPa, 5 minutes, it is heated for 60 minutes in an electric oven at 160 ° C, size 10cm × 10cm An electrode sheet of insulating layer / conductive layer / dielectric layer / conductive layer / insulating layer was obtained. During lamination, place one end of the copper foil side of the 10 mm x 30 mm polyimide copper-clad laminate "Spanex M" by Nippon Steel Corp. on the conductive layer side on the opposite side of the square, and measure the resistance. , It was taken out electrode at the time of measuring electrostatic capacity.

Example 6 Production Example of Electrode Sheet 2-2
In Example 5, an electrode of insulating layer / conductive layer / dielectric layer / conductive layer / insulating layer having a dimension of 10 cm × 10 cm is similarly manufactured except that the sensor insulating layer forming material 1 is changed to the sensor insulating layer forming material 2. I got a sheet. During lamination, place one end of the copper foil side of the 10 mm x 30 mm polyimide copper-clad laminate "Spanex M" by Nippon Steel Corp. on the conductive layer side on the opposite side of the square, and measure the resistance. , It was taken out electrode at the time of measuring electrostatic capacity.

Example 7 Electrode Sheet Production Example 3
In the conductive layer-forming material 1 obtained in Production Example 1, a polyimide film having a dimension of 10 cm × 10 cm and a thickness of 100 μm (manufactured by DuPont Co., Ltd., Kapton 400H) as an insulating layer (Y), and a dimension as a dielectric layer (Z) Insulating layer / conductive layer forming material / dielectric layer / conductive layer forming material / insulating layer / conductive layer forming material / dielectric layer / conductive layer using a foamed hot melt resin (made by TOYO ADDRESS Co., Ltd.) having a thickness of 10 cm × 10 cm. After laminating in order of forming material / insulation layer and performing pressure bonding treatment under conditions of 170 ° C., 2 MPa and 5 minutes, heating is performed in an electric oven at 160 ° C. for 60 minutes, and insulating layer / conductive layer / size 10 cm × 10 cm An electrode sheet of dielectric layer / conductive layer / insulating layer / conductive layer / dielectric layer / conductive layer / insulating layer was obtained. During lamination, place one end of the copper foil side of the 10 mm x 30 mm polyimide copper-clad laminate "Spanex M" by Nippon Steel Corp. on the conductive layer side on the opposite side of the square, and measure the resistance. , It was taken out electrode at the time of measuring electrostatic capacity.

Example 8 Production Example of Electrode Sheet 3-1
10 cm × 10 cm conductive layer forming material for sensor obtained in Production Example 1, 10 cm × 10 cm insulating layer forming material for sensor obtained in Production Example 2, dielectric layer (Z), 10 cm ×× Insulating layer forming material for sensor 1 / Conductive layer forming material for sensor 1 / Dielectric layer / Conductive layer forming material for sensor 1 / Insulating layer for sensor using foaming hot melt resin (made by Toyo Address) of 10 cm thickness 700 μm Forming material 1 / Conductive layer forming material for sensor 1 / Dielectric layer / Conductive layer forming material 1 / Insulating layer forming material 1 for sensor in this order and press-bonded under conditions of 170 ° C., 2 MPa, 5 minutes After heating for 60 minutes in an electric oven at 160 ° C., an electrode sheet of insulating layer / conductive layer / dielectric layer / conductive layer / conductive layer / conductive layer / dielectric layer / conductive layer / insulating layer of dimensions 10 cm × 10 cm Obtained. During lamination, place one end of the copper foil side of the 10 mm x 30 mm polyimide copper-clad laminate "Spanex M" by Nippon Steel Corp. on the conductive layer side on the opposite side of the square, and measure the resistance. , It was taken out electrode at the time of measuring electrostatic capacity.

Example 9 Production Example of Electrode Sheet 3-2
In Example 8, the insulating layer / conductive layer / dielectric layer / conductive layer / insulating layer having a size of 10 cm × 10 cm is similarly processed except that the sensor insulating layer forming material 2 is used instead of the sensor insulating layer forming material 1. An electrode sheet of / conductive layer / dielectric layer / conductive layer / insulating layer was obtained. During lamination, place one end of the copper foil side of the 10 mm x 30 mm polyimide copper-clad laminate "Spanex M" by Nippon Steel Corp. on the conductive layer side on the opposite side of the square, and measure the resistance. , It was taken out electrode at the time of measuring electrostatic capacity.

Comparative Example 1 Electrode Sheet Production Example 4
In the electrode sheet production example 1, instead of the insulating layer / conductive layer, an electrode sheet of insulating layer / conductive layer with a size of 10 cm × 10 cm is used using a polyimide copper-clad laminate “Spanex M” manufactured by Nippon Steel Corporation. did. The copper-clad laminate "Spanex M" was processed to provide a lead-out electrode for measuring a resistance of 10 mm x 30 mm and measuring an electrostatic capacitance one by one on the opposite side of the square.

Comparative Example 2 Electrode Sheet Production Example 5
In the electrode sheet production example 2, instead of the insulating layer / conductive layer forming material, a polyimide copper-clad laminate “Spanex M” manufactured by Nippon Steel Corporation is used, and a thickness of 10 cm × 10 cm as a dielectric layer (Z) Insulating layer (polyimide surface of Espanex M) / conductive layer (copper surface of Espanex M) / dielectric layer (Z) / conductive layer (Spanex M) using a foamed hot melt resin (made by Toyo Address) having a thickness of 700 μm. Copper layer / insulation layer (polyamide surface of Espanex) in this order, crimped at 170 ° C., 2 MPa, 5 minutes, and insulating layer / conductive layer / dielectric layer / conductive layer of 10 cm × 10 cm in size The copper-clad laminate sheet “Espanex M” was processed to obtain an electrode sheet of 10 mm × 30 mm, one on each side of the square, and the one for measuring the capacitance. Provided electrodes.

Comparative Example 3 Electrode Sheet Production Example 6
As a material for forming an insulating layer / conductive layer, a polyimide copper-clad laminate "Spanex M" manufactured by Nippon Steel Corporation, as a material for forming an insulating layer, a material for forming an insulating layer for a sensor having a size of 10 cm × 10 cm obtained in Production Example 2 1. As a dielectric layer (Z), using a foamed hot melt resin (made by Toyo Addressee Co., Ltd.) having a dimension of 10 cm × 10 cm and a thickness of 700 μm, insulating layer (polyimide surface of Espanex M) / conductive layer (copper of Espanex M Surface) / dielectric layer (Z) / conductive layer (copper surface of Espanex M / insulating layer (polyimide surface of Espanex) / insulating layer forming material for sensor 1 / insulating layer (polyimide surface of Espanex M) / conductive layer (Copper surface of Espanex M) / Dielectric layer (Z) / Conductive layer (Copper surface of Espanex M / Insulation layer (polyimide surface of Espanex)) laminated in the order of 170 ° C., 2 MP And pressure treatment for 5 minutes to obtain an electrode sheet of insulating layer / conductive layer / dielectric layer / conductive layer / conductive layer / conductive layer / dielectric layer / conductive layer / insulating layer with dimensions of 10 cm × 10 cm Note that the copper-clad laminate "Spanex M" was processed, and one by one on the opposite side of the square, a 10 mm x 30 mm resistance measurement and an extraction electrode for measuring the capacitance were provided.

    The physical properties of the obtained electrode sheet were evaluated as follows.

<Method of measuring capacitance of conductive layer (X)>
The probe was connected to one extraction electrode of the conductive layer of the electrode sheet of Examples 1 to 9 and Comparative Examples 1 to 3 using a digital multimeter "34410A" manufactured by Agilent Technologies, Inc., and the capacitance was measured. The conductive layer side of the electrode sheet obtained in Example 1 (which was used without performing the bending test described later) was used as a counter electrode, and the measurement was performed with the insulating layer side of the electrode sheet to be measured facing. A polyester film (Tetron S10 manufactured by Toray Industries, Inc.) having a size of 10 cm × 10 cm and a thickness of 100 μm was used as a dielectric between the electrodes.

<Method of measuring resistance of conductive layer (X)>
The probe is connected to two lead electrodes located on the opposite side of the square of the conductive layer of the electrode sheets of Examples 1 to 9 and Comparative Examples 1 to 3 using a digital multimeter "34410A" manufactured by Agilent Technologies, Inc. Was measured.

<Bending test>
The electrode sheets obtained in Examples 1 to 9 and Comparative Examples 1 to 3 were bent at 1) 180 degrees in the middle of dimensions 10 cm x 10 cm according to JIS K 7113, and a 1 kg weight was placed on the bent portion for 5 seconds. 2) Next, the bent portion was returned to the original flat state, and a 1 kg weight was placed on the same position for 5 seconds. The operations 1) to 2) were performed 10 times, 30 times, and 50 times on one sample.
The resistance value and the capacitance were measured, and the respective change rates were determined as ◎ to × when the following were made.
However, the rate of change referred to here is the rate of change G = (b−a) / a × 100 [%], where the original value is a and the value after processing is b.
Represents
Change rate of capacitance 0% or more and less than 30%: ◎
30% or more and less than 60%: ○
60% or more and less than 100%: △
100% or more: x

Change rate of resistance value 0% or more and less than 30%: ◎
30% or more and less than 60%: ○
60% or more and less than 100%: △
100% or more: x

Resistance Value and Capacitance Measurement Site in Each Configuration [Examples 1 to 3, Comparative Example 1]
Insulating layer / conductive layer (resistance measurement site 1, capacitance measurement site 1)
[Examples 4 to 6, Comparative Example 2]
Insulating layer / conductive layer (resistance value measurement site 1, capacitance measurement site 1) / dielectric layer / conductive layer (resistance value measurement site 2, capacitance measurement site 2) / insulating layer [Examples 7 to 9, comparison Example 3]
Insulating layer / conductive layer (resistance value measurement site 1, capacitance measurement site 1) / dielectric layer / conductive layer / insulating layer / conductive layer / dielectric layer / conductive layer (resistance value measurement site 2, capacitance measurement site 2) ) / Insulating layer

  As shown in the table, Examples 1 to 9 have a flexible and flexible conductive layer, so they are strong against bending and have a capacitance change rate and a resistance value change rate. It is extremely excellent as a sensor electrode such as a wearable application, a sensor requiring installation of an electrode on a curved surface, and a sensor detecting biological information. On the other hand, in Comparative Examples 1 to 3, the conductive layer is inferior in flexibility and durability, and the conductive layer is broken in the bending test, so the rate of change in capacitance is large, and the resistance is large due to the deterioration of the electrode. As a sensor electrode such as a wearable application, a sensor that requires installation of an electrode on a curved surface, a sensor that detects biological information, etc., the function is insufficient and can not be used.

(X): conductive layer (Y): insulating layer (Z): dielectric layer

Claims (10)

  Thermosetting resin (A) having a carboxyl group (however, epoxy resin (B), except in the case of an elastomer (C) having a reactive functional group), epoxy resin (B), having a reactive functional group A conductive layer forming material for a sensor comprising an elastomer (C), a conductive filler (D) and a curing agent (E).   It is an electrode sheet which comprises a conductive layer (X), and a conductive layer (X) hardens the conductive layer formation material for sensors of Claim 1, The electrode sheet for sensors characterized by the above-mentioned. The sensor electrode sheet according to claim 2, further comprising an insulating layer (Y) provided on at least one side of the conductive layer (X). An electrode sheet having a configuration in which a conductive layer (X1) / a dielectric layer (Z) / a conductive layer (X2) is laminated in this order, wherein at least one of the conductive layer (X1) and the conductive layer (X2) An electrode sheet for a sensor, which is obtained by curing the conductive layer-forming material according to Item 1. The sensor electrode sheet according to claim 4, further comprising an insulating layer (Y1) provided on the outside of at least one of the conductive layer (X1) and the conductive layer (X2). An electrode having a configuration in which a conductive layer (X3) / dielectric layer (Z1) / conductive layer (X4) / insulating layer (Y2) / conductive layer (X5) / dielectric layer (Z2) / conductive layer (X6) is laminated in this order It is a sheet, and at least one of the conductive layer (X3), the conductive layer (X4), the conductive layer (X5) and the conductive layer (X6) is characterized in that the material for forming a conductive layer according to claim 1 is cured. Sensor electrode sheet to be used. The sensor electrode sheet according to claim 6, further comprising an insulating layer (Y3) provided on the outside of at least one of the conductive layer (X3) and the conductive layer (X6). An electrostatic capacitance type proximity sensor using the sensor electrode sheet according to any one of claims 2 to 7. A capacitive biosensor comprising the sensor electrode sheet according to any one of claims 2 to 7. A bioimpedance measuring device using the sensor electrode sheet according to any one of claims 2 to 7.

Images