JP2015167188A - Electrochemical cell and manufacturing method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrochemical cell, formed by an electrolyte being encapsulated, excellent in electrolyte encapsulation performance.SOLUTION: The electrochemical cell includes: two substrates having no electrolyte injection port; an electrolyte layer disposed between the two substrates; and a first encapsulation part, disposed between the two substrates, enclosing and encapsulating the electrolyte layer. The first encapsulation part has a solubility parameter different from a solubility parameter of the electrolyte by 4 or more, and is a cured material of a first curable resin composition having photocurable properties.

Description

  The present invention relates to an electrochemical cell and a method for producing the same.

In an electrochemical cell sealed with an electrolyte solution such as a dye-sensitized solar cell, a hot-melt type heat seal material has been conventionally used as a sealing material for sealing the electrolyte solution. The hot melt type heat seal material is a solid material and may not be able to fill in fine steps on the substrate surface, and heat resistance and moisture resistance are not always sufficient. In some cases, sufficient electrolytic solution sealing performance cannot be exhibited. Furthermore, since an electrolyte inlet is required, the electrolyte inlet must be sealed.
On the other hand, a technique using a liquid sealant for sealing an electrolytic solution in an electrochemical cell is known (for example, see Patent Document 1). In addition, a technique for manufacturing an electrochemical cell by a bonding method under reduced pressure without providing an electrolyte inlet (see, for example, Patent Document 2).

JP 2010-180258 A JP 2007-220608 A

When manufacturing an electrochemical cell using a conventional liquid sealant by a bonding method under reduced pressure, a problem occurs in the sealed part due to contact between the uncured liquid sealant and the electrolyte. was there. Moreover, the adhesiveness with respect to the base material of a sealing part may not be acquired sufficiently.
The present invention has been made in view of the above problems, and is an electrochemical cell in which an electrolytic solution is sealed, and an object thereof is to provide an electrochemical cell excellent in electrolytic solution sealing performance and a method for producing the same. And

Specific means for solving the above problems are as follows.
<1> Two substrates not having an electrolyte inlet, an electrolyte layer disposed between the two substrates, and disposed between the two substrates to surround the electrolyte layer A first sealing portion that is sealed, and the first sealing portion has a solubility parameter different from that of the electrolyte by 4 or more, and the first curable resin composition having photocurability is cured. It is an electrochemical cell.
<2> The electrochemical cell according to <1>, further including a second sealing portion that is disposed so as to surround the first sealing portion and is a cured product of the second curable resin composition.
<3> The electrochemical cell according to <1> or <2>, wherein the second curable resin composition is a cationic curable epoxy resin composition containing an epoxy compound having an aromatic ring group.
<4> The first curable resin composition has a skeleton derived from at least one resin selected from the group consisting of polybutene, polybutadiene, polyisoprene, hydrogenated polybutene, hydrogenated polybutadiene, and hydrogenated polyisoprene. It is an electrochemical cell as described in any one of <1>-<3> containing a (meth) acrylate compound.
<5> The electrochemical cell according to any one of <1> to <4>, which is a dye-sensitized solar cell, an antiglare mirror, or a display body.

<6> A method for producing an electrochemical cell having an electrolyte layer sealed between a first substrate and a second substrate, wherein the electrolyte and solubility parameter are 4 on the first substrate. Different from the above, the step of forming the first curable resin composition layer by applying the first curable resin composition having photocurability to the frame shape, and the frame formed on the first substrate A step of forming an electrolyte layer by applying an electrolyte solution therein, laminating a second substrate on the electrolyte layer and the first curable resin composition layer to obtain a laminate, and a first curing A step of photocuring the curable resin composition layer to form a first sealing portion, and a second curable resin composition that is applied so as to surround the first sealing portion and second cured. It is a manufacturing method of the electrochemical cell including the process of forming a curable resin composition layer, and the process of hardening a 2nd curable resin composition layer and forming a 2nd sealing part.
<7> A method for producing an electrochemical cell having an electrolyte layer sealed between a first substrate and a second substrate, wherein the electrolyte and solubility parameter are 4 on the first substrate. Different from the above, a step of forming a first curable resin composition layer by applying a first curable resin composition having photocurability to a frame shape, a first curable resin composition and a solubility parameter The second curable resin composition is applied on the first substrate so as to surround and surround the second curable resin composition having a difference of 2 or more in contact with the frame-shaped first curable resin composition layer. A step of forming a physical layer, an electrolytic solution is formed in a frame formed on the first substrate to form an electrolytic solution layer, and the electrolytic solution layer and the first and second curable resin composition layers A process of obtaining a laminate by laminating a second base material thereon, and curing the first curable resin composition layer and the second curable resin composition layer to form a first sealing And a step of forming a second sealing portion.

<8> A first containing a (meth) acrylate compound having a skeleton derived from at least one resin selected from the group consisting of polybutene, polybutadiene, polyisoprene, hydrogenated polybutene, hydrogenated polybutadiene, and hydrogenated polyisoprene. An electrolyte solution sealant set for an electrochemical cell comprising: a curable resin composition; and a second curable resin composition that is a cationic curable epoxy resin composition containing an epoxy compound having an aromatic ring group. .

  ADVANTAGE OF THE INVENTION According to this invention, it is an electrochemical cell by which electrolyte solution is sealed, Comprising: The electrochemical cell excellent in electrolyte solution sealing performance, and its manufacturing method can be provided.

(A)-(C) are schematic process drawings which show one Embodiment of the manufacturing method of an electrochemical cell, (D) is a schematic sectional drawing of an electrochemical cell. (A) And (B) is a schematic process drawing which shows other embodiment of the manufacturing method of an electrochemical cell, (C) is a schematic sectional drawing of an electrochemical cell.

In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. . Moreover, the numerical range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively. Further, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.
The (meth) acryloyl group means at least one of an acryloyl group and a methacryloyl group, and the (meth) acrylate compound means at least one of an acrylate compound and a methacrylate compound.

<Electrochemical cell>
The electrochemical cell of the present invention is disposed between two substrates having no electrolyte inlet, an electrolyte layer disposed between the two substrates, and the two substrates, A first sealing part that surrounds and seals the electrolytic solution layer, and the first sealing part has a solubility parameter that differs from the electrolytic solution by 4 or more and has a photo-curing property. It is a cured product of the resin composition.
The solubility parameter of the first curable resin composition forming the first sealing portion is 4 or more different from the solubility parameter of the electrolyte solution sealed in the electrochemical cell. For example, the electrolyte solution can be sufficiently sealed for a long time, and leakage of the electrolyte solution is suppressed. If the difference in solubility parameter between the first curable resin composition and the electrolytic solution is less than 4, the first curable resin composition and the electrolytic solution are compatible with each other, and sufficient electrolytic solution sealing performance is obtained. Difficult to achieve.

  The difference in solubility parameter between the first curable resin composition and the electrolytic solution is 4 or more, but is preferably 4 to 7, and more preferably 4 to 5. It is also preferable that the solubility parameter of the first curable resin composition is smaller than the solubility parameter of the electrolytic solution.

  Here, the solubility parameter (hereinafter also referred to as “SP value”) is a value represented by the square root of the molecular aggregation energy, and is generally used as a scale representing the polarity of a compound. Solubility parameters such as the first curable resin composition and the electrolytic solution in the present invention are Polym. Eng. Sci. , 14 [2], 147-154 (1974).

  The electrochemical cell has a second sealing portion which is a cured product of the second curable resin composition having a configuration different from that of the first curable resin composition (preferably a configuration having a different SP value). It is preferable that the first sealing portion is surrounded and sealed. That is, the electrochemical cell includes a first sealing portion in which an electrolyte layer disposed between two substrates is a cured product of the first curable resin composition, and a first sealing portion. It is preferable that the second curable resin composition that surrounds and seals is sealed twice with a second sealing portion that is a cured product. Since the electrochemical cell is configured by sealing the electrolyte solution twice, the electrolyte solution sealing performance is further improved.

[First curable resin composition]
The electrolyte layer of the electrochemical cell is sealed with two base materials and a first sealing portion that is a cured product of the first curable resin composition.
The first curable resin composition has photocurability, and its configuration is not particularly limited as long as the difference in SP value from the electrolytic solution is 4 or more. A 1st curable resin composition contains a (meth) acrylate compound and a photoinitiator, for example, and can contain another additive as needed.

  The SP value of the first curable resin composition is preferably 6 to 9, and more preferably 8 to 9. When the first curable resin composition contains a (meth) acrylate compound, the SP value of the first curable resin composition can be calculated as the SP value of the (meth) acrylate compound.

(Meth) acrylate compound The (meth) acrylate compound is a polymerizable compound having at least one (meth) acryloyl group and capable of setting the SP value of the first curable resin composition to a desired value. There is no particular limitation. Among these, (meth) acrylate compounds are polybutene, polybutadiene, polyisoprene, hydrogenated polybutene, hydrogenated polybutadiene and hydrogenated polybutadiene, which have small cohesive energy density and molar molecular volume, respectively, from the viewpoint of SP value calculated by the Fedors method. It preferably has a skeleton derived from at least one resin selected from the group consisting of isoprene, and has a skeleton derived from at least one resin selected from the group consisting of hydrogenated polybutadiene and hydrogenated polyisoprene. Is more preferable.

When the (meth) acrylate compound has a skeleton derived from at least one resin selected from the group consisting of polybutene, polybutadiene, polyisoprene, hydrogenated polybutene, hydrogenated polybutadiene and hydrogenated polyisoprene, Examples thereof include 1,4-polybutadiene, 1,2-polybutadiene, and a copolymer of 1,4-polybutadiene and 1,2-polybutadiene. Examples of polyisoprene include 1,4-polyisoprene, 1,2-polyisoprene, a copolymer of 1,4-polyisoprene and 1,2-polyisoprene, and the like. In addition, hydrogenated polybutene, hydrogenated polybutadiene, and hydrogenated polyisoprene, which are these hydrogenated products, are polymers obtained by adding hydrogen to at least some of the unsaturated bonds contained in the polymer and reducing them to saturated bonds. Each means.
The number average molecular weights of polybutene, polybutadiene, polyisoprene, hydrogenated polybutene, hydrogenated polybutadiene, and hydrogenated polyisoprene are each preferably in the range of 1000 to 10,000, and more preferably in the range of 2000 to 4000. .

  The (meth) acrylate compound is a polybutene, polybutadiene, polyisoprene, hydrogenated polybutene, hydrogenated polybutadiene, and hydrogenated polyisoprene, each having a small cohesive energy density and a molar molecular volume from the viewpoint of the SP value calculated by the Fedors method. It is also preferably a urethane-modified (meth) acrylate compound having a skeleton derived from at least one resin selected from the group consisting of polybutene, polybutadiene, polyisoprene, hydrogenated polybutene, hydrogenated polybutadiene, and hydrogenated poly More preferably, it is a urethane-modified (meth) acrylate compound having a skeleton derived from at least one resin selected from the group consisting of isoprene and having two or more (meth) acryloyl groups, hydrogenated polybutadiene and water From polyisoprene It has a skeleton derived from at least one resin selected from that group, more preferably a urethane-modified (meth) acrylate compound having two or more (meth) acryloyl groups.

  Urethane modification having a skeleton derived from at least one resin selected from the group consisting of polybutene, polybutadiene, polyisoprene, hydrogenated polybutene, hydrogenated polybutadiene, and hydrogenated polyisoprene (hereinafter also referred to as “specific resin”) ( The meth) acrylate compound includes, for example, a specific resin having at least one (preferably two or more) hydroxy group in the molecule, a polyisocyanate compound having two or more isocyanato groups in the molecule, and an isocyanato group in the molecule. It can manufacture from the functional group which can react, and the (meth) acryl compound which has a (meth) acryloyl group. Specifically, it can be produced by reacting a specific resin having a hydroxy group with a polyisocyanate compound and then reacting the remaining isocyanate group with a (meth) acrylic compound.

  Specific examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, polyphenylene Aromatic polyisocyanate compounds such as polymethylene polyisocyanate, 1,5-naphthylene diisocyanate, 1,4-naphthylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, Aliphatic polyisocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, - methylcyclohexane-2,4-diisocyanate, isophorone diisocyanate, although an alicyclic polyisocyanate compounds such as dicyclohexylmethane-4,4'-diisocyanate are exemplified, but the invention is not limited thereto. These may be used alone or in combination of two or more.

  (Meth) acrylate compounds and urethane-modified (meth) acrylate compounds having a skeleton derived from at least one resin selected from the group consisting of polybutene, polybutadiene, polyisoprene, hydrogenated polybutene, hydrogenated polybutadiene, and hydrogenated polyisoprene (Meth) acrylate compounds other than may be included. Specific examples include dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethylene acrylate, dimethylol dicyclopentane diacrylate, isobornyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexa Hydrophthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerin di (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate and the like can be mentioned. The present invention is not limited to. These may be used alone or in combination of two or more.

A commercially available product may be used as the urethane-modified (meth) acrylate compound. Examples of commercially available products include UA-1 (hydrogenated polyisoprene urethane acrylate, manufactured by Light Chemical Co., Ltd.), TE-2000 (polybutadiene urethane methacrylate, manufactured by Nippon Soda Co., Ltd.), and the like.
The 1st curable resin composition may contain the (meth) acrylate compound individually by 1 type, and may contain it in combination of 2 or more type. When included in combination, a (meth) acrylate compound having a skeleton derived from at least one resin selected from the group consisting of polybutene, polybutadiene, polyisoprene, hydrogenated polybutene, hydrogenated polybutadiene and hydrogenated polyisoprene (preferably The ratio of the urethane-modified (meth) acrylate compound) is preferably 50% by mass or more, and more preferably 75% by mass or more of the total (meth) acrylate compound ratio.

Photoinitiator The first curable resin composition preferably contains at least one photoinitiator. Photoinitiators include radical photoinitiators that generate radical species by energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and cationic photoinitiators that generate cationic species such as Bronsted acid and Lewis acid. Etc. are known. The (meth) acrylate compound is polymerized by the generated radical species, and the curable resin composition is cured. Moreover, the cationic curable epoxy resin composition containing an epoxy compound is cured by the generated cationic species.

  Specific examples of radical photoinitiators include benzophenone photoinitiators such as benzophenone, 4-phenylbenzophenone, benzoylbenzoic acid and bisdiethylaminobenzophenone; acetophenone photoinitiators such as 2,2-diethoxyacetophenone; benzyl, Benzoin photoinitiators such as benzoin and benzoin isopropyl ether; alkylphenone photoinitiators such as benzyldimethyl ketal; thioxanthone photoinitiators such as thioxanthone; 1-hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) 2 -Hydroxy-2-methylpropan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl -1 Hydroxyalkylphenone photoinitiators such as phenylpropan-1-one and oligo [2-hydroxy-2-methyl-1-{-4 (1-methylvinyl) phenyl} propanone], 2,4,6-trimethylbenzoyl Acylphosphine oxide photoinitiators such as diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide Camphorquinone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone 1 and other ketone photoinitiators, among which oligo [ 2-hydroxy-2-methyl-1- {4- (1-methylvinyl) phenyl} propanone] is preferred, but is not limited thereto.

  Specific examples of the cationic photoinitiator include diazonium salts, sulfonium salts, iodonium salts and the like. Examples of the diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate. Examples of the sulfonium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis [diphenylsulfonio] diphenyl sulfide, bishexafluorophosphate, 4 , 4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenylsulfide bishexafluoroantimonate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenylsulfide bishexafluorophosphate, 7- [Di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate, 7- [Di (p-toluyl) sulfonio] -2 Isopropylthioxanthone tetrakis (pentafluorophenyl) borate, 4-phenylcarbonyl-4′-diphenylsulfonio-diphenyl sulfide hexafluorophosphate, 4- (p-tert-butylphenylcarbonyl) -4′-diphenylsulfonio-diphenylsulfide hexa Fluoroantimonate, 4- (p-tert-butylphenylcarbonyl) -4′-di (p-toluyl) sulfonio-diphenyl sulfide tetrakis (pentafluorophenyl) borate and the like can be mentioned. Examples of the iodonium salt include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and the like. However, the cationic photoinitiator is not limited to these.

The content of the photoinitiator in the first curable resin composition is not particularly limited and can be appropriately selected according to the type of the photoinitiator. For example, content of a photoinitiator can be 0.1-10 mass parts with respect to 100 mass parts of (meth) acrylate compounds, and it is preferable that it is 0.5-6 mass parts.
The 1st curable resin composition may contain 1 type of photoinitiators individually, and may contain it in combination of 2 or more types.

Other Additives The first curable resin composition includes a coupling agent; a polymerization inhibitor; a coloring agent such as a pigment and a dye; metal powder, calcium carbonate, talc, silica, Inorganic fillers such as amorphous silica, alumina and aluminum hydroxide; flame retardants; organic fillers; plasticizers; antioxidants; antifoaming agents; leveling agents; and rheology control agents. With these additives, a curable resin composition excellent in cured resin strength, adhesive strength, workability, storage stability, and the like and a cured product thereof can be obtained.

Coupling agent As coupling agent, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxy Silane coupling agents having an epoxy group such as propyltriethoxysilane; p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 -Silane coupling agent having an ethylenically unsaturated bond such as acryloxypropyltrimethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-amino Propyltri Methoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N- Silane coupling agent having an amino group such as phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; 3-ureidopropyltrimethoxysilane , 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, and the like.
Among these, from the viewpoint of adhesiveness, a silane coupling agent having an ethylenically unsaturated bond such as a (meth) acryloyl group or a vinyl group is preferable.

  When a 1st curable resin composition contains a coupling agent, the content can be 0.1-10 mass parts with respect to 100 mass parts of a (meth) acrylate compound, 0.5-5 It is preferable that it is a mass part.

  A coupling agent may be used alone or in combination of two or more. When the first curable resin composition contains two or more coupling agents, the content ratio thereof is not particularly limited and is appropriately selected depending on the purpose and the like. When the first curable resin composition contains two types of coupling agents, the content ratio can be 4: 1 to 1: 4, and preferably 2: 1 to 1: 2.

[Second curable resin composition]
In the electrochemical cell, the first sealing portion that contacts and seals the electrolyte layer is further sealed by a second sealing portion that is a cured product of the second curable resin composition. It is preferable. The second curable resin composition is not particularly limited as long as it contains at least a curable resin and has a configuration different from that of the first curable resin composition, and the configuration is appropriately selected according to the purpose and the like. be able to.

  For example, the second curable resin composition may have a configuration in which the SP value is different from that of the first curable resin composition. More preferably. The SP value of the second curable resin composition is preferably larger than the SP value of the first curable resin composition. When the SP value of the second curable resin composition is larger than the SP value of the first curable resin composition, the adhesion to the substrate is further improved, and the electrolyte sealing performance tends to be further improved. is there.

The SP value of the second curable resin composition can be, for example, 10 or more, and preferably 11 or more. The upper limit value is not particularly limited, but is 15, for example.
The SP value of the second curable resin composition can be calculated as the SP value of the curable resin (preferably an epoxy compound) as the main component.

The second curable resin composition may be thermosetting or photocurable.
The second curable resin composition preferably includes at least one of an epoxy compound or an oxetane compound as the curable resin, more preferably includes an epoxy compound, and further includes an epoxy compound having an aromatic ring. A cationically curable epoxy resin composition containing an epoxy compound having an aromatic ring is particularly preferable.
The cation curable epoxy resin composition containing an epoxy compound having an aromatic ring includes, for example, an epoxy compound having an aromatic ring and an acid generator, and, if necessary, other inorganic fillers, coupling agents and the like. And an additive.

Curable resin It is preferable that the 2nd curable resin composition contains at least 1 sort (s) of an epoxy compound or an oxetane compound as curable resin. Examples of the epoxy compound include bisphenol A type epoxy compounds having a weight average molecular weight of 4 million or less, bisphenol F type epoxy compounds, novolac type epoxy compounds, polycyclic aromatic epoxy compounds, their modified epoxy compounds, and alicyclic epoxy compounds. One type of liquid compound may be used alone, or two or more types may be used in combination. Further, these epoxy compounds may be used by dissolving a solid or highly viscous epoxy compound at room temperature. Examples of the solid epoxy compound include N655, HP-4700, EXA-4710, HP-4770, HP-7200 (manufactured by DIC), EHPE3150 (manufactured by Daicel). Examples of the highly viscous epoxy compound include an epoxy compound having a viscosity of 10,000 mPa · s or more. Examples of the highly viscous epoxy compound include HP-4032D, N740 (manufactured by DIC Corporation), jER152 (manufactured by Mitsubishi Chemical Corporation), and the like.
Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane (OXA), 1,4-bis [{(3-ethyl-3-oxetanyl) methoxy} methyl] benzene (XDO), 3-ethyl-3- ( Phenoxymethyl) oxetane (OXT-211 (POX)), 2-ethylhexyloxetane (OXT-212 (EHOX)), xylylene bisoxetane (OXT-121 (XDO)), bis (3-ethyl-3-oxetanylmethyl) Examples include ether (OXT-221 (DOX)), 3-ethyl-[(3-triethoxysilylpropoxy) methyl] oxetane, oxetanylsilsesquioxane, phenol novolak oxetane, and the like. The parentheses indicate the product numbers of Toagosei Co., Ltd.
An epoxy compound and an oxetane compound may be used individually by 1 type, or may be used in combination of 2 or more type.

  The content of the curable resin in the second curable resin composition can be appropriately selected depending on the purpose and the like. For example, the content of the curable resin is preferably 30% by mass or more, and more preferably 50% by mass or more in the total mass of the second curable resin composition.

Acid generator The acid generator may be a photoacid generator or a thermal acid generator. Examples of the photoacid generator include the cationic photoinitiators in the photoinitiators described above. Examples of the thermal acid generator include onium salt-based thermal acid generators such as sulfonium salts, iodonium salts, and quaternary ammonium salts.

The content of the acid generator in the second curable resin composition is not particularly limited, and can be appropriately selected according to the type of the acid generator. For example, content of an acid generator can be 0.1-10 mass parts with respect to 100 mass parts of curable resin, and it is preferable that it is 1-5 mass parts.
The 2nd curable resin composition may contain the acid generator individually by 1 type, and may contain it in combination of 2 or more type.

Other Additives The second curable resin composition includes a coupling agent, a colorant such as a pigment and a dye, an inorganic filler, a flame retardant, an organic filler, and a polymerization inhibitor as long as the characteristics of the present invention are not impaired. An additive such as a plasticizer; an antioxidant; an antifoaming agent; a leveling agent; and a rheology control agent. With these additives, a second curable resin composition excellent in resin strength, adhesive strength, workability, storage stability, and the like and a cured product thereof can be obtained.

Filler The second curable resin composition preferably contains at least one of an inorganic filler and an organic filler from the viewpoint of electrolytic solution sealing performance.
Examples of the inorganic filler include metal powder, calcium carbonate, talc, silica, amorphous silica, alumina, aluminum hydroxide, cordierite, magnesium metasilicate, and magnesium orthosilicate. Among these, talc, silica and the like can be preferably used. Organic fillers include polyolefins such as polyethylene or polypropylene, alicyclic saturated hydrocarbon resins, polystyrene, styrene butadiene rubber (SBR), polyamide, polyester, polyurethane, poly (meth) acrylate polymer, polyvinyl chloride (PVC), Examples thereof include polyvinyl acetate, polyepoxide, polyacetal, acrylonitrile-butadiene-styrene copolymer (ABS) or a copolymer thereof, polyphenylene oxide, polyvinylidene chloride, or a mixture of these polymers. An inorganic filler or an organic filler may be used alone or in combination of two or more.

  When the second curable resin composition contains an inorganic filler or an organic filler, the content is not particularly limited and can be appropriately selected depending on the purpose and the like. For example, content of an inorganic filler or an organic filler can be 1-100 mass parts with respect to 100 mass parts of epoxy compounds, and it is preferable that it is 30-50 mass parts.

Coupling agent The second curable resin composition preferably contains at least one coupling agent. Examples of the coupling agent in the second curable resin composition include the same coupling agents as described above, and among them, a coupling agent having an epoxy group is preferable.

  When the second curable resin composition contains a coupling agent, the content is not particularly limited and can be appropriately selected depending on the purpose and the like. For example, content of a coupling agent can be 0.1-10 mass parts with respect to 100 mass parts of epoxy compounds, and it is preferable that it is 0.5-5 mass parts.

[Electrolyte]
The electrolytic solution layer in the electrochemical cell contains an electrolytic solution and is sealed by the first sealing portion. The configuration of the electrolytic solution is not particularly limited, and the configuration can be appropriately selected according to the purpose of the electrochemical cell. For example, when the electrochemical cell is a dye-sensitized solar cell, an antiglare mirror, or a display body, the electrolytic solution includes, for example, an organic solvent, a redox agent, and an additive that is included as necessary. The

The SP value of the electrolytic solution differs from the SP value of the first curable resin composition forming the first sealing portion by 4 or more, but is preferably 4 to 7 different. Moreover, it is preferable that SP value of electrolyte solution is larger than SP value of a 1st curable resin composition. For example, the SP value of the electrolytic solution is preferably 12 or more, and more preferably 12 to 15.
In addition, SP value of electrolyte solution can be calculated as SP value of the organic solvent which is a main component.

Organic Solvent The organic solvent contained in the electrolytic solution is preferably a highly polar organic solvent, and can be appropriately selected from known highly polar organic solvents as a reaction medium in an electrochemical reaction. Specific examples of the organic solvent include cyclic carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate; acyclic carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, and ethylene glycol dialkyl. Ethers such as ether, propylene glycol dialkyl ether, polyethylene glycol monoalkyl ether and polyethylene glycol dialkyl ether; Nitriles such as acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile and benzonitrile; Sulfoxides such as dimethyl sulfoxide and sulfolane Alcohols such as methanol and ethanol; alkylene glycol Monoalkyl ethers; lactones γ- butyrolactone; can be exemplified 3-methyl-2-heterocycles such as oxazolinone like; dimethylformamide, dimethylacetamide, N- amides such as methylpyrrolidone.
The organic solvent may be used alone or in combination of two or more.

Redox agent As the redox agent used in the electrochemical cell, iodine and a metal iodine compound are preferable. Examples of the metal iodine compound include lithium iodide, sodium iodide, potassium iodide, cesium iodide and the like. The redox agent combined with iodine includes not only metal iodine compounds but also iodide salts of quaternary pyridinium salts and quaternary imidazolium salts. Furthermore, hetero compounds such as amines and thiols can also be used as redox aids, and redox catalysts such as ferrocyanate, ferricyanate, ferrocene, and ferrocyanium ion salts can be added. .
The combination of these redox agents and redox aids is particularly preferably iodine and iodide salt systems.
The density | concentration in the electrolyte solution of a redox agent is 0.01-2 mol / L, for example, and the range of 0.01-0.05 mol / L is preferable.

Additives The type and content of the additive are appropriately selected from known additives according to the purpose of the electrochemical cell. Specific examples of the additive include 4-tert-butylpyridine which prevents reverse current and increases open electromotive force.

[Base material]
The electrochemical cell has two substrates that do not have an electrolyte inlet. Here, “having no electrolyte injection port” does not mean that a through hole that is an electrolyte injection port opened in the base material is not formed, but a once formed through hole. It is also meant that a closed through hole is not formed.

The material, size, etc. of the substrate are appropriately selected according to the purpose of the electrochemical cell.
Specific examples of the material of the base material include an inorganic base material such as glass, and an organic base material such as polycarbonate (PC) resin, polyethylene naphthalene (PEN) resin, and polyethylene naphthalate (PET) resin. Can do. The surface of the substrate that is in contact with the electrolyte layer (hereinafter also referred to as “substrate surface”) may be provided with a light-transmitting conductive layer or the like, if necessary. Examples of the conductive layer include a compound composed of indium oxide and tin oxide (ITO), and tin oxide doped with fluorine (FTO). For example, if the electrochemical cell is a dye-sensitized solar cell, a semiconductor layer such as a titania layer on which a dye is adsorbed is provided on the surface of the substrate opposite to the surface in contact with the electrolyte layer. It may be.
The thickness of the substrate is not particularly limited and can be appropriately selected depending on the purpose. The thickness of a base material can be 0.5-2.0 mm, for example.

In the electrochemical cell of the present invention, an electrolyte layer is disposed between two substrates. The thickness of the electrolyte layer is not particularly limited and can be appropriately selected according to the purpose of the electrochemical cell. The thickness of the electrolytic solution layer can be set to 30 to 100 μm, for example.
The electrolytic solution layer is disposed between the two base materials and is sealed by a first sealing portion that surrounds the electrolytic solution layer. That is, the electrolytic solution layer is sealed in the frame of the first sealing portion formed in a frame shape. The width of the frame of the first sealing portion formed in the frame shape is not particularly limited. The width | variety of a 1st sealing part can be 0.3-2.0 mm, for example, and it is preferable that it is 0.5-1.0 mm.

The first sealing portion is a cured product of the first curable resin composition having photocurability. The curing conditions for the first curable resin composition are not particularly limited as long as a cured product is obtained. Curing of the first curable resin composition may, for example, can be done in curing conditions to impart light energy 2000~12000mJ / cm ^2, a curing condition for imparting light energy 3000~6000mJ / cm ² Is preferred.

In the preferable aspect of an electrochemical cell, the 1st sealing part is enclosed and sealed with the 2nd sealing part which is the hardened | cured material of a 2nd curable resin composition. That is, the electrolyte solution layer disposed between the two substrates is double-sealed with the first sealing portion and the second sealing portion. Thereby, it becomes possible to achieve more excellent electrolyte sealing performance.
The second sealing portion may be disposed so as to surround the first sealing portion, and may be disposed between the two base materials in contact with the outer periphery of the first sealing portion. It may be disposed in contact with the first sealing portion and a surface perpendicular to the substrate surface of the substrate (hereinafter also referred to as “substrate end surface”), and is in contact with the outer periphery of the first sealing portion. And may be disposed both between the two substrates and on the end surface of the substrate.

When the second sealing portion is disposed between the two base materials, the thickness in the direction parallel to the base material surface of the second sealing portion surrounding the first sealing portion, that is, the second The width of the sealing portion is not particularly limited and can be appropriately selected depending on the purpose and the like. The width | variety of a 2nd sealing part can be 0.3-2.0 mm, for example, and it is preferable that it is 0.5-1.0 mm.
In addition, when the second sealing portion is disposed in contact with the end surface of the base material, the thickness of the second sealing portion in the base material surface direction is not particularly limited, depending on the purpose, the base material thickness, and the like. It can be selected appropriately. For example, when the thickness of the base material is 1.0 mm, the thickness of the second sealing portion can be set to 0.5 to 2.0 mm, and preferably 1.0 to 2.0 mm.

  The use of the electrochemical cell of the present invention is not particularly limited, and examples thereof include a dye-sensitized solar cell, an antiglare mirror, a display body, a capacitor, and a battery. Among these, a dye-sensitized solar cell, an antiglare mirror, or a display body is preferable.

<Method for producing electrochemical cell>
1st aspect of the manufacturing method of the electrochemical cell of this invention is a manufacturing method of the electrochemical cell which has the electrolyte solution layer sealed between the 1st base material and the 2nd base material, A step of forming a first curable resin composition layer by applying a first curable resin composition having a solubility parameter different from that of the electrolyte solution by 4 or more and having photocurability to a frame shape on the substrate. (Hereinafter, also referred to as “Step A”), an electrolyte solution is applied in a frame formed on the first substrate to form an electrolyte solution layer, and the electrolyte solution layer and the first curable resin composition A step of obtaining a laminate by laminating a second base material on the layer (hereinafter also referred to as “step B”), and photocuring the first curable resin composition layer to form a first sealing portion. A step of forming (hereinafter, also referred to as “step C”) and a second curable resin composition layer are provided by surrounding the first sealing portion with the second curable resin composition. A step of forming (hereinafter also referred to as “step D”), a step of curing the second curable resin composition layer to form a second sealing portion (hereinafter also referred to as “step E”), including. The method for producing an electrochemical cell may include other steps as necessary.

[Step A]
In step A, a first curable resin composition having a solubility parameter of 4 or more different from that of the electrolytic solution on the first substrate and having photocurability is provided in a frame shape. A physical layer is formed. The details of the first substrate and the first curable resin composition are as described above.
The method for providing the first curable resin composition in a frame shape is not particularly limited, and can be appropriately selected from commonly used methods. Examples of the application method include a dispensing method and a screen printing method.

  The application amount of the first curable resin composition layer is not particularly limited and can be appropriately selected depending on the purpose and the like. The thickness of the first curable resin composition layer in the direction perpendicular to the substrate surface can be, for example, 30 to 100 μm, and preferably 40 to 60 μm. The thickness of the first curable resin composition layer in the direction parallel to the substrate surface can be, for example, 0.3 to 2.0 mm, and preferably 0.5 to 1.0 mm.

[Step B]
In step B, an electrolytic solution is formed in a frame formed on the first base material to form an electrolytic solution layer, and the second base material is formed on the electrolytic solution layer and the first curable resin composition layer. To obtain a laminate. Examples of a method for applying the electrolytic solution include a dispensing method. Moreover, the application amount of the electrolytic solution is not particularly limited, and can be appropriately selected according to the size of the frame formed by the first curable resin composition layer. The details of the electrolytic solution used in step B are as described above.

  The method for laminating the second substrate on the electrolytic solution layer and the first curable resin composition layer is not particularly limited. It may be a method of laminating under normal pressure or a method of laminating under reduced pressure. The method of laminating is preferably a method of laminating under reduced pressure. When laminating under reduced pressure, the pressure can be, for example, 200 hPa or less, preferably 150 hPa or less, and more preferably 80 to 120 hPa.

[Step C]
In step C, the first curable resin composition layer is photocured to form a first sealing portion. Photocuring of the first curable resin composition layer can be performed by irradiating the laminate obtained in Step B with light. The energy amount of light irradiation is not particularly limited, and may be appropriately selected according to the first curable resin composition layer. The energy amount of light irradiation can be 2000-12000 mJ / cm < ² >, for example, and it is preferable that it is 3000-6000 mJ / cm < ² >.

[Step D]
In step D, the second curable resin composition is applied so as to surround the first sealing portion to form a second curable resin composition layer. The details of the second curable resin composition used in Step D are as described above.

The method for applying the second curable resin composition so as to surround the first sealing portion is not particularly limited, and can be appropriately selected from commonly used methods. Examples of the application method include a dispensing method. The second curable resin composition is preferably applied so as to be in contact with and surround the first sealing portion.
The second curable resin composition may be applied so as to surround the first sealing portion, or may be applied between the two substrates so as to be in contact with the first sealing portion, It may be provided so as to be in contact with the first sealing portion and the end surface of the substrate, and is provided between both of the base materials and the end surface of the substrate so as to be in contact with the first sealing portion. May be.

The amount of the second curable resin composition layer applied is not particularly limited and can be appropriately selected according to the purpose. When the second curable resin composition is applied between two substrates, the thickness in the direction parallel to the substrate surface of the second curable resin composition layer surrounding the first sealing portion That is, the width of the second curable resin composition layer is not particularly limited and can be appropriately selected depending on the purpose and the like. The width | variety of a 2nd curable resin composition layer can be 0.3-2.0 mm, for example, and it is preferable that it is 0.5-1.0 mm.
Further, when the second curable resin composition is applied so as to be in contact with the end surface of the substrate, the thickness of the second curable resin composition layer in the substrate surface direction is not particularly limited, and the purpose and the base It can select suitably according to material thickness etc. For example, when the substrate thickness is 1.0 mm, the thickness of the second curable resin composition layer can be set to 0.5 to 2.0 mm, and preferably 1.0 to 2.0 mm.

[Step E]
In step E, the second curable resin composition layer is cured to form a second sealing portion. The method for curing the second curable resin composition layer is appropriately selected according to the configuration of the second curable resin composition. When the second curable resin composition is photocurable, the second sealing portion can be formed by irradiating the second curable resin composition layer with light. The energy amount of light irradiation is not particularly limited, and may be appropriately selected according to the second curable resin composition layer. The energy amount of light irradiation can be 4000-18000 mJ / cm < ² >, for example, and it is preferable that it is 5000-8000 mJ / cm < ² >. Furthermore, it is preferable to apply heat, preferably 60 to 90 ° C. for 60 to 90 ° C., and 120 ° C. for 5 to 10 minutes.
Moreover, when the second curable resin composition is thermosetting, the second sealing portion can be formed by applying heat to the second curable resin composition layer. The amount of heat energy is not particularly limited, and may be appropriately selected according to the second curable resin composition layer. The application of heat can be, for example, 60 to 120 ° C. for 5 to 180 minutes, and preferably 80 to 100 ° C. for 60 to 120 minutes.

  The second aspect of the method for producing an electrochemical cell of the present invention is a method for producing an electrochemical cell having an electrolyte layer sealed between a first substrate and a second substrate. A step of forming a first curable resin composition layer by applying a first curable resin composition having a solubility parameter different from that of the electrolyte solution by 4 or more and having photocurability to a frame shape on the substrate. (Hereinafter also referred to as “step a”), the second curable resin composition having a solubility parameter different from that of the first curable resin composition by 2 or more is used for the first curable resin composition layer having a frame shape. A step of forming a second curable resin composition layer by applying on the first base so as to be in contact with the outer periphery (hereinafter also referred to as “step b”), formed on the first base An electrolytic solution is applied in the frame to form an electrolytic solution layer, and a second substrate is laminated on the electrolytic solution layer and the first and second curable resin composition layers A step of obtaining a laminate (hereinafter also referred to as “step c”), and curing the first curable resin composition layer and the second curable resin composition layer to obtain the first sealing portion and the second sealing portion. Forming a sealing portion (hereinafter also referred to as “step d”). The method for producing an electrochemical cell may include other steps as necessary.

[Step a]
In step a, the first curable resin composition is provided on the first base material by providing a first curable resin composition having a solubility parameter different from that of the electrolyte solution by 4 or more and having photocurability in a frame shape. A physical layer is formed. The details of step a are the same as step A in the first embodiment of the manufacturing method.

[Step b]
In step b, a second curable resin composition having a solubility parameter different from that of the first curable resin composition by 2 or more is surrounded by being in contact with the outer periphery of the first curable resin composition layer formed in a frame shape. To give a second curable resin composition layer. The detail of the process b is the same as that of the case where the 2nd curable resin composition of the process D in the 1st aspect of a manufacturing method is provided between two base materials.

[Step c]
In step c, an electrolytic solution is applied to the frame formed on the first substrate to form an electrolytic solution layer, and the second substrate is formed on the electrolytic solution layer and the first curable resin composition layer. To obtain a laminate. The details of step c are the same as step B in the first embodiment of the manufacturing method.

  In step d, the first curable resin composition layer and the second curable resin composition layer are cured to form a first sealing portion and a second sealing portion. The details of step d are the same as step C and step E in the first aspect of the manufacturing method.

  An example of a method for producing an electrochemical cell will be described with reference to FIG. In FIG. 1A, a first curable resin composition is applied in a frame shape on a substrate 1 to form a first curable resin composition layer 2, and an electrolytic solution is formed in the formed frame. To form the electrolyte layer 3. In FIG. 1B, a base material 1 ′ is laminated on the first curable resin composition layer 2 and the electrolyte solution layer 3 to obtain a laminate. Next, a first sealing portion is formed by photocuring treatment. In FIG. 1C, the second curable resin composition layer 4 is formed by applying the second curable resin composition so as to be in contact with the first sealing portion and the end surface of the substrate. Next, the second curable resin composition layer 4 is cured to form a second sealing portion to obtain an electrochemical cell. FIG. 1D shows a cross-sectional view between a and b of the electrochemical cell. In FIG. 1D, the electrolyte layer 3 is disposed between the two substrates 1 and 1 ′, and the first sealing portion 2 that surrounds and seals the electrolyte layer 3 is the substrate 1 and It arrange | positions between 1 ', the 2nd sealing part 4 is arrange | positioned in contact with the 1st sealing part 2 and a base-material end surface, and surrounding these.

  Another example of the electrochemical cell manufacturing method will be described with reference to FIG. In FIG. 2A, a first curable resin composition is applied in a frame shape on a substrate 1 to form a first curable resin composition layer 2, and then a second curable resin composition is formed. After the product is applied so as to be in contact with the outer periphery of the first curable resin composition layer 2 to form the second curable resin composition layer 4, an electrolytic solution is applied to the formed frame to provide an electrolytic solution. Layer 3 is formed. In FIG. 2 (B), the base material 1 'is laminated on the first curable resin composition layer 2, the second curable resin composition layer 4, and the electrolytic solution layer 3 to obtain a laminate. Next, first and second sealing portions are formed by photocuring treatment to obtain an electrochemical cell. FIG. 2C is a cross-sectional view taken along line cd of the electrochemical cell. In FIG. 2C, the electrolyte layer 3 is disposed between the two substrates 1 and 1 ′, and the first sealing portion 2 that surrounds and seals the electrolyte layer 3 is the substrate 1 and The second sealing portion 4 is disposed between and in contact with the first sealing portion 2 so as to surround the first sealing portion 2.

  Since the method for producing an electrochemical cell according to the present invention is suitable for a bonding method that does not require an electrolyte inlet, the production process can be simplified. Moreover, the electrochemical cell manufactured with the manufacturing method of the electrochemical cell of this invention can maintain sufficient electrolyte solution sealing performance over a long period of time.

<Electrolyte sealant set>
The electrolyte sealant set of the present invention is for electrochemical cell formation, and is at least one selected from the group consisting of polybutene, polybutadiene, polyisoprene, hydrogenated polybutene, hydrogenated polybutadiene, and hydrogenated polyisoprene. A second curable resin composition which is a first curable resin composition containing a (meth) acrylate compound having a skeleton derived from a resin and a cationic curable epoxy resin composition containing an epoxy compound having an aromatic ring group And including.
By using the electrolytic solution sealant set, it is possible to maintain a sufficient electrolytic solution sealing performance for a long period of time by sealing the electrolytic solution of the electrochemical cell.

The details of the first curable resin composition and the second curable resin composition in the electrolytic solution sealant set are as described above, and preferred embodiments are also the same. The electrolyte solution sealant set may further include other components as necessary. Examples of other components include a method for sealing an electrolytic solution of an electrochemical cell using an electrolytic solution sealant set, preferably an instruction manual describing a method for producing an electrochemical cell, and the like. it can.
The electrolyte sealant set of the present invention can be suitably used, for example, in the method for producing an electrochemical cell of the present invention.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

(Preparation Example 1)
Preparation of first curable resin composition Hydrogenated polyisoprene urethane acrylate (UA-1, LA cut product, manufactured by Light Chemical Co.) 100 parts by mass, photoinitiator (KIP150, manufactured by Lamberti) 3 parts by mass, 1 part by mass of a coupling agent (acrylic group-containing silane coupling agent, KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) and 1 part by mass of a coupling agent (vinyl silane coupling agent, KBM1003, manufactured by Shin-Etsu Chemical Co., Ltd.) A first curable resin composition was prepared.
The solubility parameter of the first curable resin composition was 8.7.

(Preparation Example 2)
Preparation of second curable resin composition 100 parts by mass of a bisphenol A type epoxy resin (850S, manufactured by DIC), 50 parts by mass of talc (P-2, manufactured by Nippon Talc), and a photoacid generator (SP- 172, manufactured by ADEKA) and 1.5 parts by mass of a coupling agent (epoxysilane coupling agent, KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed with a cationic curable epoxy resin composition. A certain second curable resin composition was prepared.
The solubility parameter of the second curable resin composition was 10.9.

(Preparation Example 3)
Preparation of electrolyte solution To propylene carbonate (PC, solubility parameter 13), the concentration of potassium iodide was 0.5 mol / L, the concentration of iodine was 0.05 mol / L, and the concentration of 4-tert-butylpyridine was 0.5 mol / L. Each component was dissolved so as to be L to prepare an electrolytic solution.

Example 1
Two glass plates (20 mm × 24 mm, thickness 1.0 mm) coated with an FTO (Fluorine-doped tin oxide) transparent conductive film were prepared as substrates. 3.5 ± 0.5 mg of the first curable resin composition was applied on the FTO film of the prepared glass plate so as to form a frame having a width of 1 mm when the two substrates were bonded together. After injecting 8 to 9 mg of the electrolyte into the frame, another glass plate was overlaid so that the FTO films face each other, and bonded together under the condition of a degree of vacuum of 100 hPa to temporarily seal the electrolyte.
Using a spot type UV irradiator (manufactured by Hamamatsu Photonics) as a light source, the first curable resin composition is cured by irradiating with light so that the light energy amount is 6000 mJ / cm ² . An electrolytic cell for evaluation was obtained by sealing the electrolytic solution between glass substrates.

[Evaluation]
(Appearance observation)
When the interface (at the time of sealing) of the electrolyte solution and sealing part of the obtained electrochemical cell for evaluation was observed with a metal microscope, it was not compatible at the time of sealing and was in a good sealed state.

(Electrolytic solution maintenance rate)
The obtained electrochemical cell for evaluation was left in a thermostatic bath at 85 ° C., the mass after 72 hours and 240 hours was measured, and the electrolytic solution maintenance rate (%) was defined as 100% before being put into the thermostatic bath. Calculated. Moreover, it evaluated in accordance with the following evaluation criteria about the electrolyte solution maintenance factor. The results are shown in Table 1.
Evaluation criteria A: Excellent.
B: Within practically acceptable range.
C: Outside practically acceptable range.
D: Cannot be measured.

(Example 2)
Two glass plates (20 mm × 24 mm, thickness 1.0 mm) coated with an FTO (Fluorine-doped tin oxide) transparent conductive film were prepared as substrates. 1.7 ± 0.2 mg of the first curable resin composition was applied on the FTO film of the prepared glass plate so as to form a frame having a width of 0.5 mm when two substrates were bonded together. . Next, the second curable resin composition is encased in a frame having a width of 0.5 mm when the two substrates are bonded so as to surround the first curable resin composition. 0.0 ± 0.2 mg. After injecting 8 to 9 mg of the electrolyte into the frame, another glass plate was overlaid so that the FTO films face each other, and bonded together under the condition of a degree of vacuum of 100 hPa to temporarily seal the electrolyte.
Using a spot type UV irradiator (manufactured by Hamamatsu Photonics) as a light source, the first curable resin composition is cured by irradiating with light so that the light energy amount is 6000 mJ / cm ² . An electrolytic cell for evaluation was obtained by sealing the electrolytic solution between glass substrates.
As a result of appearance observation, the obtained electrochemical cell for evaluation was not compatible when sealed, and was in a good sealed state. The electrolytic solution maintenance ratio (%) is shown in Table 1.

(Example 3)
In Example 2, an electrochemical cell for evaluation was similarly obtained and evaluated in the same manner except that a heat treatment was further performed at 80 ° C. for 60 minutes after photocuring of the curable resin composition.
As a result of appearance observation, the obtained electrochemical cell for evaluation was not compatible when sealed, and was in a good sealed state. The electrolytic solution maintenance ratio (%) is shown in Table 1.

(Comparative Example 1)
In Example 1, an electrochemical cell for evaluation was obtained in the same manner except that the second curable resin composition was used instead of the first curable resin composition, and evaluated in the same manner.
As a result of appearance observation, the obtained electrochemical cell for evaluation was compatible when sealed, and the sealing state was poor. Moreover, the electrolyte retention rate could not be measured due to the poor sealing state.

(Comparative Example 2)
In Comparative Example 1, an electrochemical cell for evaluation was obtained in the same manner except that heat treatment was further performed at 80 ° C. for 1 hour after photocuring of the second curable resin composition, and evaluation was performed in the same manner.
As a result of appearance observation, the obtained electrochemical cell for evaluation was compatible when sealed, and the sealing state was poor. Moreover, the electrolyte retention rate could not be measured due to the poor sealing state.

  From Table 1, it can be seen that the electrochemical cell of the present invention has a good appearance in a sealed state and an excellent electrolyte retention rate.

1, 1 ': base material, 2: first sealing portion, 3: electrolyte layer, 4: second sealing portion

Claims (8)

Two substrates without an electrolyte inlet,
An electrolyte layer disposed between two substrates;
A first sealing portion disposed between the two base materials and surrounding and sealing the electrolyte layer;
The electrochemical cell which is a hardened | cured material of the 1st curable resin composition in which a 1st sealing part differs in solubility parameter and 4 or more from electrolyte solution, and has photocurability.   The electrochemical cell according to claim 1, further comprising a second sealing portion that is disposed so as to surround the first sealing portion and is a cured product of the second curable resin composition.   The electrochemical cell according to claim 2, wherein the second curable resin composition is a cationic curable epoxy resin composition containing an epoxy compound having an aromatic ring group.   The first curable resin composition has a skeleton derived from at least one resin selected from the group consisting of polybutene, polybutadiene, polyisoprene, hydrogenated polybutene, hydrogenated polybutadiene, and hydrogenated polyisoprene (meth) The electrochemical cell according to any one of claims 1 to 3, comprising an acrylate compound.   It is a dye-sensitized solar cell, an anti-glare mirror, or a display body, The electrochemical cell of any one of Claims 1-4. A method for producing an electrochemical cell having an electrolyte layer sealed between a first substrate and a second substrate,
A first curable resin composition layer having a solubility parameter of 4 or more different from that of the electrolytic solution on the first substrate and having photocurability is provided in a frame shape to form a first curable resin composition layer. And a process of
An electrolyte solution is applied in a frame formed on the first substrate to form an electrolyte solution layer, and a second substrate is laminated on the electrolyte solution layer and the first curable resin composition layer. Obtaining a laminate,
A step of photocuring the first curable resin composition layer to form a first sealing portion;
Applying the second curable resin composition so as to surround the first sealing portion to form a second curable resin composition layer;
A step of curing the second curable resin composition layer to form a second sealing portion;
A method for producing an electrochemical cell comprising: A method for producing an electrochemical cell having an electrolyte layer sealed between a first substrate and a second substrate,
A first curable resin composition layer having a solubility parameter of 4 or more different from that of the electrolytic solution on the first substrate and having photocurability is provided in a frame shape to form a first curable resin composition layer. And a process of
The second curable resin composition having a solubility parameter different from that of the first curable resin composition by 2 or more on the first substrate so as to surround and surround the frame-shaped first curable resin composition layer. And forming a second curable resin composition layer by applying to
An electrolyte solution is applied in a frame formed on the first substrate to form an electrolyte solution layer, and a second substrate is placed on the electrolyte solution layer and the first and second curable resin composition layers. Laminating to obtain a laminate;
Curing the first curable resin composition layer and the second curable resin composition layer to form the first sealing portion and the second sealing portion;
A method for producing an electrochemical cell comprising: First curable resin comprising a (meth) acrylate compound having a skeleton derived from at least one resin selected from the group consisting of polybutene, polybutadiene, polyisoprene, hydrogenated polybutene, hydrogenated polybutadiene, and hydrogenated polyisoprene A composition;
An electrolyte solution sealant set for an electrochemical cell, comprising: a second curable resin composition that is a cationic curable epoxy resin composition containing an epoxy compound having an aromatic ring group.