TW201607110A - Electrochemical cell and method for manufacturing same - Google Patents

Abstract

Provided is an electrochemical cell having two substrates that do not have an electrolyte injection port, an electrolyte layer arranged between the two substrates, and a first sealing part arranged between the two substrates to enclose and seal the electrolyte layer, the first sealing part having four or more solubility parameters different from the electrolyte and being a cured substance of a first curing resin composition having a photocurable property.

Description

Electrochemical battery and method of manufacturing same

The present invention relates to electrochemical cells and methods of making the same.

In an electrochemical cell in which the electrolyte of the dye-sensitized solar cell is sealed, as a sealing material for the sealing electrolyte, a hot-melt type heat sealing material has been used from the past. The hot-melt type heat sealing material is a solid material, and the fine step of the surface of the substrate is not filled, and the heat resistance or the moisture resistance is not necessarily sufficient, and the leakage of the electrolyte may not be possible. A sufficient electrolyte sealing performance is exhibited for a long period of time. Further, it is necessary to have an electrolyte injection port, and therefore it is necessary to seal the electrolyte injection port.

On the other hand, a technique of using a liquid sealant for electrolytic solution sealing of an electrochemical cell is known (for example, refer to Japanese Laid-Open Patent Publication No. 2010-180258). Further, a technique of manufacturing an electrochemical cell without providing an electrolyte injection port by a method of bonding under reduced pressure is known (for example, refer to Japanese Laid-Open Patent Publication No. 2007-220608).

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-180258

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-220608

When an electrochemical cell is produced by a method of bonding under reduced pressure using a conventional liquid sealant, a liquid sealant in an unhardened state may be in contact with the electrolyte solution, which may cause a problem in the seal portion. Further, there is a case where the adhesion to the base material of the sealing portion cannot be sufficiently obtained.

The present invention has been made in view of the above problems, and an object thereof is to provide an electrochemical cell in which an electrolytic solution is sealed, and an electrochemical cell having excellent electrolyte sealing performance and a method for producing the same.

Specific means for solving the above problems are as follows. The present invention includes the following aspects.

<1> An electrochemical cell comprising: two substrates having no electrolyte injection port; an electrolyte layer disposed between two substrates; and being disposed between two substrates, surrounding and sealed The first sealing portion of the electrolyte layer, and the first sealing portion is a cured product of a photocurable first curable resin composition having a solubility parameter and an electrolyte solution of 4 or more.

<2> The electrochemical cell according to <1>, further comprising a cured product which is disposed so as to surround the first sealing portion and is a second curable resin composition Two sealing parts.

<3> The electrochemical cell according to <1> or <2>, wherein the second curable resin composition is a cationically curable epoxy resin composition containing an epoxy compound having an aromatic ring group.

<4> The electrochemical cell according to any one of <1> to <3> wherein the first curable resin composition comprises from the group consisting of polybutene, polybutadiene, polyisoprene, hydrogenation. A (meth) acrylate compound having a skeleton of at least one of a group of polybutene, hydrogenated polybutadiene, and hydrogenated polyisoprene.

<5> The electrochemical cell according to any one of <1> to <4> which is a dye-sensitized solar cell, an anti-glare mirror or a display body.

<6> 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, the method comprising: on the first substrate, a step of forming a first curable resin composition layer by forming a first curable resin composition having a photocuring property and a first curable resin composition having a photohardenability difference of 4 or more; and forming a frame on the first substrate The electrolyte solution is supplied to form an electrolyte layer, and the second substrate is laminated on the electrolyte layer and the first curable resin composition layer to obtain a laminate; and the first curable resin composition layer is photocured to form a step of supplying a second curable resin composition to surround the first sealing portion to form a second curable resin composition layer; and curing the second curable resin composition layer to form a second The step of sealing.

<7> A method for producing an electrochemical cell, which has a seal A method for producing an electrochemical cell of an electrolyte layer between a first substrate and a second substrate, the method comprising: having a solubility parameter of 4 or more on the first substrate, and having photohardenability The first curable resin composition is supplied in a frame shape to form a first curable resin composition layer, and the second curable resin composition having a solubility parameter different from the first curable resin composition by 2 or more is contacted. a step of forming a second curable resin composition layer on the first substrate so as to surround the frame-shaped first curable resin composition layer; and supplying an electrolyte solution in a frame formed on the first substrate to form a step of laminating a second substrate on the electrolyte layer and the first and second curable resin composition layers to obtain a laminate; and the first curable resin composition layer and the second curable resin The step of hardening the composition layer to form the first sealing portion and the second sealing portion.

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

According to the present invention, an electrochemical cell in which an electrolyte solution is sealed and an electrolyte battery excellent in electrolyte sealing performance and a method for producing the same can be provided.

1‧‧‧Substrate

1'‧‧‧Substrate

2‧‧‧First hardened resin composition layer

3‧‧‧ electrolyte layer

4‧‧‧Second hardening resin composition layer

Fig. 1A is a schematic perspective view showing a step of an embodiment of a method of manufacturing an electrochemical cell.

Fig. 1B is a schematic perspective view showing a step of an embodiment of a method of manufacturing an electrochemical cell.

Fig. 1C is a schematic perspective view showing a step of an embodiment of a method of manufacturing an electrochemical cell.

[Fig. 1D] A schematic cross-sectional view of an electrochemical cell.

Fig. 2A is a schematic perspective view showing a step of another embodiment of a method of manufacturing an electrochemical cell.

Fig. 2B is a schematic perspective view showing a step of another embodiment of the method for producing an electrochemical cell.

[Fig. 2C] A schematic cross-sectional view of an electrochemical cell.

The term "step" in this specification is not only an independent step, but even if it is not clearly distinguishable from other steps, it is included in the term as long as the desired purpose of the step is achieved. Further, the numerical range indicated by "~" indicates a range including the numerical values described before and after "~" as the minimum value and the maximum value. Further, when the content of each component in the composition is a plurality of substances corresponding to the respective components in the composition, unless otherwise specified, it means the total amount of the plurality of substances present in the composition.

Further, the (meth) acrylonitrile group means at least one of an acryloyl group and a methacryl oxime group, and a (meth) acrylate compound means at least one of an acrylate compound and a methacrylate compound.

<Electrochemical battery>

The electrochemical cell of the present invention has two substrates which do not have an electrolyte injection port, an electrolyte layer which is disposed between the two substrates, and is disposed between the two substrates to surround and seal the electrolyte layer. The first sealing portion is a cured product of the first curable resin composition having a photohardenability and a difference in solubility parameter from the electrolyte solution of 4 or more.

The solubility parameter of the first curable resin composition forming the first sealing portion is excellent in sealing performance of the electrolyte by a solubility difference of 4 or more compared to the electrolyte sealed in the electrochemical cell, for example, it can be sufficiently long-term Seal the electrolyte to prevent leakage of the electrolyte. When the difference in solubility parameter between the first curable resin composition and the electrolytic solution is less than 4, the first curable resin composition is compatible with the electrolytic solution, and it is difficult to achieve sufficient electrolyte sealing performance.

The difference between the solubility parameter of the first curable resin composition and the electrolytic solution is 4 or more, preferably 4 to 7, more preferably 4 to 5. Further, the solubility parameter of the first curable resin composition is preferably less than the solubility parameter of the electrolyte.

Here, the solubility parameter (hereinafter also referred to as "SP value") means a value expressed by the square root of the molecular aggregation energy, and is generally used as a scale indicating the polarity of the compound. The first curable resin in this specification The solubility parameters of the composition, the electrolytic solution, and the like are calculated based on the Fedors method described in Polym. Eng. Sci., 14 [2], 147-154 (1974), respectively.

Further, in the electrochemical cell, it is preferable that the second sealing portion surrounds and seals the first sealing portion, and the second sealing portion has a configuration different from the first curable resin composition (preferably, a configuration having a different SP value) A cured product of a second curable resin composition. That is, the electrochemical cell is preferably an electrolyte layer disposed between two substrates, and is a first sealing portion which is a cured product of the first curable resin composition, and a first sealing portion that surrounds and seals the first sealing portion. The second sealing portion, which is a cured product of the second curable resin composition, is double-sealed. By configuring the electrochemical cell to reseal the electrolyte 2, the electrolyte sealing performance is further improved.

[First Curable Resin Composition]

The electrolyte layer of the electrochemical cell is sealed by two base materials and a first sealing portion which is a cured product of the first curable resin composition.

The first curable resin composition is not particularly limited as long as it has photocurability and the difference in SP value from the electrolytic solution is 4 or more. The first curable resin composition contains, for example, a (meth) acrylate compound and a photoinitiator, and may contain other additives as needed.

The SP value of the first curable resin composition is preferably 6 to 9, 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 not particularly limited as long as it has at least one (meth) acrylonitrile group and the SP value of the first curable resin composition can be a desired value. . The (meth) acrylate compound, in terms of the SP value calculated by the Fedors method, particularly having a small cohesive energy density and a molar molecular volume, respectively, is selected from the group consisting of polybutene, polybutadiene, and poly Preferably, at least one resin of the group consisting of isoprene, hydrogenated polybutene, hydrogenated polybutadiene and hydrogenated polyisoprene has a skeleton; more preferably has a hydrogenated polybutadiene and hydrogenated from A skeleton of at least one resin in a group of polyisoprene.

a (meth) acrylate compound having at least one selected from the group consisting of polybutene, polybutadiene, polyisoprene, hydrogenated polybutene, hydrogenated polybutadiene, and hydrogenated polyisoprene In the case of the skeleton of one type of resin, examples of the polybutadiene include copolymerization of 1,4-polybutadiene, 1,2-polybutadiene, 1,4-butadiene and 1,2-butadiene. Things and so on. Examples of the polyisoprene include 1,4-polyisoprene, 1,2-polyisoprene, a copolymer of 1,4-isoprene and 1,2-isoprene, and the like. . Further, such hydrogenated bodies, that is, hydrogenated polybutene, hydrogenated polybutadiene, and hydrogenated polyisoprene, respectively, mean that at least a part of the unsaturated bonds contained in the polymer are hydrogenated to be reduced to a saturated bond. Polymer.

The number average molecular weights of polybutene, polybutadiene, polyisoprene, hydrogenated polybutene, hydrogenated polybutadiene and hydrogenated polyisoprene are preferably in the range of 1000 to 10,000, respectively. For the range of 2000~4000 Inside.

The (meth) acrylate compound is preferably selected from the group consisting of polybutene, polybutadiene, and poly, from the viewpoint of the SP value calculated by the Fedors method, and having a small cohesive energy density and a molar molecular volume, respectively. a urethane-modified (meth) acrylate compound of a skeleton of at least one resin in the group consisting of isoprene, hydrogenated polybutene, hydrogenated polybutadiene, and hydrogenated polyisoprene; Preferably, the skeleton 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. And a urethane-modified (meth) acrylate compound having 2 or more (meth) acryloyl fluorenyl groups; more preferably having a olefin selected from the group consisting of hydrogenated polybutadiene and hydrogenated polyisoprene A urethane-modified (meth) acrylate compound having a skeleton of at least one type of resin and having two or more (meth) acrylonitrile groups.

Having 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 The urethane-modified (meth) acrylate compound of the skeleton of the "specific resin" may have, for example, a specific resin having at least one (preferably two or more) hydroxyl groups in the molecule, and two molecules in the molecule. The polyisocyanate compound of the above isocyanate group is produced by a (meth)acrylic compound having a functional group capable of reacting with an isocyanate group and a (meth)acryl fluorenyl group in the molecule. Specifically, it can be produced by reacting a specific resin having a hydroxyl group with a polyisocyanate compound, and then reacting a residual isocyanate group with a (meth)acrylic compound.

Specific examples of the polyisocyanate compound can be exemplified by 2, 4- Methyl phenyl diisocyanate, 2,6-methylphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenyl Methane diisocyanate, polyphenylene polymethylene polyisocyanate, 1,5-naphthyl diisocyanate, 1,4-naphthyl diisocyanate, p-phenylene diisocyanate, m- An aromatic polyisocyanate compound such as phenyl diisocyanate, o-dimethylphenyl diisocyanate or m-dimethylphenyl diisocyanate; tetramethylene diisocyanate, hexamethylene diisocyanate, 2-methyl An aliphatic polyisocyanate compound such as benzyl-1,5-pentane diisocyanate; 1-methylcyclohexane-2,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-di An alicyclic polyisocyanate compound such as an isocyanate, etc., but is not limited thereto. Further, these may be used alone or in combination of two or more.

The first curable resin composition may also contain a group selected from the group consisting of polybutene, polybutadiene, polyisoprene, hydrogenated polybutene, hydrogenated polybutadiene, and hydrogenated polyisoprene. A (meth) acrylate compound having a skeleton of at least one type of resin and a (meth) acrylate compound other than the urethane-modified (meth) acrylate compound. Specific examples of the other (meth) acrylate compound include dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dimethylol dicyclopentane diacrylate, and acrylic acid. Isodecyl ester, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (A) Acrylic acid, 2-(methyl) propylene methoxyethyl succinic acid, 2-(methyl) propylene oxy ethoxylate Hexahydrophthalic acid, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, glycerol di(meth) acrylate, 2-(methyl) propylene decyloxy Ethyl acid phosphate or the like, but is not limited thereto. Further, these may be used alone or in combination of two or more.

A urethane-modified (meth) acrylate compound can also be used as a commercial item. Commercially available products include UA-1 (hydrogenated polyisoprene urethane acrylate, manufactured by Light Chemical Co., Ltd.), TE-2000 (polybutadienyl methacrylate methacrylate, and Japan Soda Corporation). System) and so on.

The first curable resin composition may contain one type of (meth) acrylate compound alone or two or more types in combination. When combined, having at least one resin selected from the group consisting of polybutene, polybutadiene, polyisoprene, hydrogenated polybutene, hydrogenated polybutadiene, and hydrogenated polyisoprene The ratio of the (meth) acrylate compound (preferably the urethane-modified (meth) acrylate compound) of the skeleton is preferably 50% by mass or more based on the total amount of the (meth) acrylate compound. More preferably, it is 75 mass% or more.

Photoinitiator

The first curable resin composition preferably contains at least one photoinitiator. A photoinitiator is known as a radical photoinitiator which generates a radical species by energy rays such as visible light, ultraviolet rays, X-rays, electron beams, etc.; and a cationic species such as Brucenic acid or Lewis acid. a cationic photoinitiator or the like. The (meth) acrylate compound is polymerized by the radical species generated, and the curable resin composition is hardened. Further, a cationically curable epoxy resin containing an epoxy compound by the cationic species produced The composition will harden.

Specific examples of the radical photoinitiator include benzophenones such as benzophenone, 4-phenylbenzophenone, benzamidine benzoic acid, and bisdiethylaminobenzophenone. Photoinitiator; acetophenone photoinitiator such as 2,2-diethoxyacetophenone; benzoin system such as diphenylethylenedione, benzoin, benzoin isopropyl ether Photoinitiator; alkyl benzophenone photoinitiator such as benzyl dimethyl ketal; thioxanthone photoinitiator 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-phenylpropan-1-one, oligo[2-hydroxy-2-methyl-1-{-4(1-methylvinyl) a hydroxyalkylphenone photoinitiator such as phenyl}acetone]; 2,4,6-trimethylbenzylidenediphenylphosphine oxide, bis(2,4,6-trimethylbenzylhydrazine) Light-based phosphine oxide based on phenylphosphine oxide, bis(2,6-dimethoxybenzyl)-2,4,4-trimethyl-pentylphosphine oxide Agent; camphorquinone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinylpropan-1-one, 2-benzyl-2 a ketone-based photoinitiator such as dimethylamino-1-(4-morpholinophenyl)-1-butanone-1, etc., among which oligo [2-hydroxy-2-methyl The hydroxyalkylphenone-based photoinitiator such as -1-{4-(1-methylvinyl)phenyl}acetone] is preferably, but not limited thereto.

Specific examples of the cationic photoinitiator include a diazonium salt, a phosphonium salt, a phosphonium salt and the like. Examples of the diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate. Examples of the onium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium (pentafluorophenyl)borate, and 4,4'-bis[diphenyldiene. Hydrogenthio]diphenyl sulfide dihexafluorophosphate, 4,4'-bis[bis(β-hydroxyethoxy)phenyldihydrothio]diphenyl sulfide dihexafluoroantimonate, 4,4'-bis[bis(β-hydroxyethoxy)phenyldihydrothio]diphenyl sulfide dihexafluorophosphate, 7-[bis(p-tolylmethyl)dihydrothio -2- isopropyl thioxanthone hexafluoroantimonate, 7-[bis(p-tolylmethyl)dihydrothio]-2-isopropylthioxanthone oxime (pentafluorophenyl)boronic acid Salt, 4-phenylcarbonyl-4'-diphenyldihydrothio-diphenyl sulfide hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4'-diphenyl Hydrogenthio-diphenyl sulfide hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-di(p-tolylmethyl)dihydrothio-diphenyl sulfide Ether quinone (pentafluorophenyl) borate or the like. Examples of the onium salt include diphenylphosphonium (pentafluorophenyl)borate, diphenylphosphonium hexafluorophosphate, diphenylphosphonium hexafluoroantimonate, and bis(4-mercaptophenyl)phosphonium hexafluorophosphate. Salt and so on. However, the cationic photoinitiator is not limited thereto.

The content of the photoinitiator in the first curable resin composition is not particularly limited, and may be appropriately selected depending on the kind of the photoinitiator or the like. For example, the content of the photoinitiator may be 0.1 to 10 parts by mass, preferably 0.5 to 6 parts by mass, per 100 parts by mass of the (meth) acrylate compound.

The first curable resin composition may contain one type of photoinitiator alone or two or more types in combination.

Other additives

The first curable resin composition may contain a coupling agent, a polymerization inhibiting agent, a coloring agent for pigments, dyes, and the like; metal powder, calcium carbonate, talc, cerium oxide, and non-degradable, without impairing the characteristics of the present invention. Crystalline oxidation Inorganic fillers such as barium, alumina, aluminum hydroxide; flame retardants; organic fillers; plasticizers; antioxidants; defoamers; leveling agents; rheology control agents and the like. By such an additive, a curable resin composition excellent in cured resin strength, adhesion strength, workability, storage stability, and the like, and a cured product thereof can be obtained.

Coupler

The coupling agent may, for example, be 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldi a decane coupling agent having an epoxy group such as ethoxy decane or 3-glycidoxypropyltriethoxy decane; p-styryl trimethoxy decane, 3-methyl propylene methoxy propyl group Methyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxy a decane coupling agent having an ethylenically unsaturated bond such as decane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)- 3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-triethoxy Base alkyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltriethoxydecane, N-(vinylbenzyl)-2-amine a decane coupling agent having an amine group such as a hydrochloride of ethyl ethyl-3-aminopropyltrimethoxydecane; 3-ureidopropyltrimethoxydecane, 3- Propyltrimethoxydecane, 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropyltrimethoxydecane, bis(triethoxydecylpropyl)tetrasulfide, 3-isocyanatepropyl Triethoxy decane and the like.

Among these, a decane coupling agent having an ethylenically unsaturated bond such as a (meth) acrylonitrile group or a vinyl group is preferred from the viewpoint of adhesion.

When the first curable resin composition contains a coupling agent, the content thereof may be 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, per 100 parts by mass of the (meth) acrylate compound.

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

[Second hardening resin composition]

In the electrochemical cell, it is preferable that the first sealing portion that is sealed by contacting the electrolyte layer is further sealed by the second sealing portion which is a cured product of the second curable resin composition. The second curable resin composition is not particularly limited as long as it contains at least a curable resin and has a composition different from that of the first curable resin composition, and can be appropriately selected depending on the purpose.

The second curable resin composition may have a configuration different from the SP value of the first curable resin composition, and more preferably has a configuration in which the SP value differs by at least 1 and more preferably has a difference of 2 or more. Further, 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 is further improved.

The SP value of the second curable resin composition may be, for example, 10 or more, preferably 11 or more. The upper limit is not particularly limited and is, for example, 15.

Further, 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 a main component.

The second curable resin composition may be thermosetting or photocurable.

Further, the second curable resin composition preferably contains at least one of an epoxy compound or an oxetane compound as a curable resin, more preferably an epoxy compound, and more preferably an aromatic ring. An epoxy compound; particularly preferably a cationically curable epoxy resin composition comprising an epoxy compound having an aromatic ring.

The cationically curable epoxy resin composition containing an epoxy compound having an aromatic ring is composed of, for example, an epoxy compound having an aromatic ring, an acid generator, and other additives such as an inorganic filler and a coupling agent as needed.

Curable resin

The second curable resin composition preferably contains at least one of an epoxy compound and an oxetane compound as a curable resin. As the epoxy compound, for example, a bisphenol A type epoxy compound having a weight average molecular weight of 4 million or less, a bisphenol F type epoxy compound, a novolac type epoxy compound, a polycyclic aromatic epoxy compound, or the like can be used alone. One of a liquid epoxy compound, an alicyclic epoxy compound, etc., which is a liquid compound; Use two or more types. Further, an epoxy compound having a solid temperature or a high viscosity at room temperature can be used in the epoxy compound. Examples of the solid epoxy compound include N655, HP-4700, EXA-4710, HP-4770, HP-7200 (manufactured by DIC Corporation), and EHPE3150 (manufactured by Daicel Co., Ltd.). Highly viscous epoxy compounds, for example, a viscosity of 10,000 mPa. An epoxy compound above s. Examples of the highly viscous epoxy compound include HP-4032D, N740 (manufactured by DIC Corporation), and jER152 (manufactured by Mitsubishi Chemical Corporation).

Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane (OXA) and 1,4-bis[{(3-ethyl-3-oxetanyl)). Methoxy]methyl]benzene (XDO), 3-ethyl-3-(phenoxymethyl)oxetane (OXT-211(POX)), 2-ethylhexyloxetane (OXT-212 (EHOX)), Dimethyl phenyl dioxetane (OXT-121 (XDO)), bis(3-ethyl-3-oxetanylmethyl) ether (OXT) -221(DOX)), 3-ethyl-[(3-triethoxydecylpropoxy)methyl]oxetane, oxetane sesquioxane, phenol novolac Oxetane and the like. Furthermore, the brackets indicate the model of the East Asian Synthetic Company.

The epoxy compound and the oxetane compound may be used alone or in combination of two or more.

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 based on the total mass of the second curable resin composition.

Acid generator

The acid generator may be a photoacid generator or a thermal acid generator. The photoacid generator may, for example, be a cationic photoinitiator in the above photoinitiator. Further, examples of the thermal acid generator include a cerium salt-based thermal acid generator such as a phosphonium salt or a phosphonium salt or a quaternary ammonium salt.

The content of the acid generator in the second curable resin composition is not particularly limited, and may be appropriately selected depending on the type of the acid generator or the like. For example, the content of the acid generator may be 0.1 to 10 parts by mass, preferably 1 to 5 parts by mass, per 100 parts by mass of the curable resin.

The second curable resin composition may contain one type of acid generator alone or two or more types in combination.

Other additives

The second curable resin composition may further contain a coupling agent, a coloring agent such as a pigment or a dye, an inorganic filler, a flame retardant, an organic filler, and a polymerization inhibiting agent, within a range not impairing the characteristics of the present invention; Additives such as plasticizers; antioxidants; defoamers; leveling agents; rheology control agents. By the additive such as this, a second curable resin composition excellent in resin strength, adhesion strength, workability, preservability, 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 or an organic filler from the viewpoint of electrolyte sealing performance.

Examples of the inorganic filler include metal powder, calcium carbonate, talc, cerium oxide, amorphous cerium oxide, aluminum oxide, aluminum hydroxide, cordierite, and hemiplegia. Magnesium acid, magnesium orthosilicate. Among these, talc, cerium oxide, or the like is particularly preferably used. Examples of the organic filler include polyolefins such as polyethylene or polypropylene; alicyclic saturated hydrocarbon resins, polystyrene, styrene butadiene rubber (SBR), polyamine, polyester, and polyurethane. , poly(meth)acrylate polymer, polyvinyl chloride (PVC), polyvinyl acetate, polyepoxide, polyacetal, acrylonitrile-butadiene-styrene copolymer (ABS) or the like Copolymer, polyphenylene ether, polyvinylidene chloride or a mixture of such polymers, and the like. The inorganic filler or the organic filler may be used singly or in combination of two or more.

When the second curable resin composition contains an inorganic filler or an organic filler, the content thereof is not particularly limited, and may be appropriately selected depending on the purpose and the like. For example, the content of the inorganic filler or the organic filler may be 1 to 100 parts by mass, preferably 30 to 50 parts by mass, per 100 parts by mass of the epoxy compound.

Coupler

The second curable resin composition preferably contains at least one of a coupling agent. The coupling agent in the second curable resin composition may be the same as the above-mentioned coupling agent, and among them, a coupling agent having an epoxy group is particularly preferable.

When the second curable resin composition contains a coupling agent, the content thereof is not particularly limited, and may be appropriately selected depending on the purpose and the like. For example, the content of the coupling agent may be 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, per 100 parts by mass of the epoxy compound.

[electrolyte]

The electrolyte layer in the electrochemical cell contains an electrolyte and is sealed by the first sealing portion. The composition of the electrolytic solution is not particularly limited, and the constitution can be appropriately selected depending on the purpose of the electrochemical battery or the like. For example, when the electrochemical cell is a dye-sensitized solar cell, an anti-glare mirror, or a display, the electrolytic solution is composed of, for example, an organic solvent, a redox agent, and an additive contained as needed.

The SP value of the electrolytic solution is different from the SP value of the first curable resin composition forming the first sealing portion by 4 or more, and preferably 4 to 7. Further, the SP value of the electrolytic solution is preferably larger than the SP value of the first curable resin composition. The SP value of the electrolytic solution is, for example, preferably 12 or more, more preferably 12 to 15.

Further, the SP value of the electrolytic solution can be calculated as the SP value of the organic solvent which is the main component.

Organic solvents

The organic solvent contained in the electrolytic solution is preferably a highly polar organic solvent, and can be suitably selected from highly polar organic solvents known as a reaction medium in an electrochemical reaction. Specific examples of the organic solvent include cyclic carbonates such as ethyl carbonate, propyl carbonate, and butyl carbonate; and non-cyclic carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate. Esters; ethers of dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol monoalkyl ether, polyethylene glycol dialkyl ether, etc. a nitrile such as acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile or benzonitrile; a hydrazine such as dimethyl hydrazine or cyclobutyl hydrazine; methanol, ethanol, etc. Alcohols; alkanediol monoalkyl ethers; lactones such as γ-butyrolactone; guanamines such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; a heterocyclic group such as 3-methyl-2-oxazolinone or the like.

The organic solvent may be used singly or in combination of two or more.

Redox agent

The redox agent used in the electrochemical cell is preferably an iodine and a metal iodine compound. Examples of the metal iodine compound include lithium iodide, sodium iodide, potassium iodide, and cesium iodide. Further, the redox agent combined with iodine is not only a metal iodine compound, but also an iodide salt of a quaternary pyridinium salt or a quaternary imidazolium salt. Further, a hetero compound such as an amine or a thiol may be used as a redox auxiliary, and a redox group, a ferric cyanide, a ferrocene, a ferrocenium ion salt or the like may be added for oxidation reduction. Catalyst.

A combination of such a redox agent and a redox auxiliary agent is particularly preferably a system of iodine and iodide salts.

The concentration of the redox agent in the electrolytic solution is, for example, in the range of 0.01 to 2 mol/L, preferably 0.01 to 0.05 mol/L.

additive

The type and content of the additive are appropriately selected from known additives depending on the purpose of the electrochemical cell or the like. Specific examples of the additive include 4-tert-butylpyridine which prevents the reverse current and increases the open voltage.

[substrate]

The electrochemical cell has two substrates that do not have an electrolyte injection port. Here, "there is no electrolyte injection port" means not only a through hole which is not formed in the electrolyte injection port of the substrate opening, but also a through hole in which the through hole formed at the time is closed and closed.

The material and size of the substrate are appropriately selected depending on the purpose of the electrochemical cell or the like.

Specific examples of the material of the substrate include a substrate made of an inorganic material such as glass, and an organic material such as polycarbonate (PC) resin, polyethylene naphthalene (PEN) resin, or polyethylene naphthalate (PET) resin. The substrate. A 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 as needed. The conductive layer may, for example, be a compound (ITO) composed of indium oxide and tin oxide, or may be exemplified by fluorine (FTO) doped with tin oxide. In the case where the electrochemical cell is a dye-sensitized solar cell, for example, when the electrochemical cell is a dye-sensitized solar cell, a semiconductor layer or the like which adsorbs a titanium oxide layer of a dye or the like may be provided.

The thickness of the substrate is not particularly limited and may be appropriately selected depending on the purpose and the like. The thickness of the substrate may be, for example, 0.5 mm to 2.0 mm.

In an electrochemical cell, an electrolyte layer is disposed between two substrates. The thickness of the electrolyte layer is not particularly limited and may be appropriately selected depending on the purpose of the electrochemical cell or the like. The thickness of the electrolyte layer may be, for example, 30 μm to 100 μm.

The electrolyte layer is disposed between the two substrates, and is sealed by the first sealing portion surrounding the electrolyte layer. That is, the electrolyte layer is sealed in a frame formed in a frame-shaped first sealing portion. a frame formed into a frame-shaped first sealing portion There is no special limit to the width of the width. The width of the first sealing portion may be, for example, 0.3 mm to 2.0 mm, preferably 0.5 mm to 1.0 mm.

The first sealing portion is a cured product of a photocurable first curable resin composition. The curing conditions of the first curable resin composition are not particularly limited as long as a cured product can be obtained. The curing of the first curable resin composition can be carried out, for example, under a curing condition of supplying light energy of 2,000 to 12,000 mJ/cm ² , and is preferably a curing condition of light energy of 3,000 to 6,000 mJ/cm ² .

In a preferred embodiment of the electrochemical cell, the first sealing portion is sealed by being surrounded by the second sealing portion which is a cured product of the second curable resin composition. That is, the electrolyte layer disposed between the two substrates is double-sealed by the first sealing portion and the second sealing portion. By this configuration, a more excellent electrolyte sealing performance can be achieved.

The second sealing portion may be disposed so as to surround the first sealing portion, and is disposed in contact with the outer periphery of the first sealing portion, and is disposed between the two substrates, is in contact with the first sealing portion, and is orthogonal to the substrate surface of the substrate. The surface (hereinafter also referred to as "substrate end surface") is disposed so as to be in contact with the outer periphery of the first sealing portion, and is disposed between the two substrates and the end surface of the substrate.

When the second sealing portion is disposed between the two base materials, the thickness of the second sealing portion surrounding the first sealing portion in a direction parallel to the surface of the substrate, that is, the width of the second sealing portion is not particularly limited. Choose according to the purpose and so on. The width of the second sealing portion may be, for example, 0.3 mm to 2.0 mm, preferably 0.5 mm to 1.0 mm.

Further, when the second sealing portion is placed in contact with the end surface of the base material, the second dense portion The thickness of the base surface of the sealing portion is not particularly limited, and may be appropriately selected depending on the purpose, the thickness of the substrate, and the like. For example, when the thickness of the substrate is 1.0 mm, the thickness of the second sealing portion may be 0.5 mm to 2.0 mm, preferably 1.0 mm to 2.0 mm.

The use of the electrochemical cell is not particularly limited, and examples thereof include a dye-sensitized solar cell, an anti-glare mirror, a display, a capacitor, and a battery. Among them, a pigment-sensitized solar cell, an anti-glare mirror or a display body is preferable.

<Method of Manufacturing Electrochemical Cell>

The first aspect of the method for manufacturing an electrochemical cell is a method for manufacturing an electrochemical cell having an electrolyte layer sealed between a first substrate and a second substrate, comprising: on the first substrate, The solubility parameter is different from the electrolyte solution by 4 or more, and the photocurable first curable resin composition is supplied in a frame shape, and the first curable resin composition layer is formed (hereinafter also referred to as "step A"). a step of supplying an electrolytic solution in a frame formed on a first substrate to form an electrolyte layer, and laminating a second substrate on the electrolyte layer and the first curable resin composition layer to obtain a laminate (hereinafter also referred to as a laminate) "Step B"), a step of forming a first sealing portion by photocuring the first curable resin composition layer (hereinafter also referred to as "Step C"), and supplying the second curable resin composition to surround the first sealing a step of forming a second curable resin composition layer (hereinafter also referred to as "step D") and a step of curing the second curable resin composition layer to form a second sealing portion (hereinafter also referred to as "step E"). The method of manufacturing the electrochemical cell may also include other steps as needed.

[Step A]

In the step A, the first curable resin composition layer is formed by supplying a first curable resin composition having a photocuring property to a frame shape with a solubility parameter of 4 or more. The details of the first substrate and the first curable resin composition are as described above.

The method of supplying the first curable resin composition into a frame shape is not particularly limited, and can be appropriately selected from the methods generally used. Examples of the supply method include a dispensing method, a screen printing method, and the like.

The supply amount of the first curable resin composition layer is not particularly limited, and may 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 may be, for example, 30 μm to 100 μm, or preferably 40 μm to 60 μm. Further, the thickness of the first curable resin composition layer in the direction parallel to the substrate surface may be, for example, 0.3 mm to 2.0 mm, preferably 0.5 mm to 1.0 mm.

[Step B]

In the step B, the electrolytic solution is supplied into the frame formed on the first substrate to form an electrolyte layer, and the second substrate is laminated on the electrolyte layer and the first curable resin composition layer to obtain a laminate. The method of supplying the electrolytic solution may, for example, be an addition method or the like. Further, the supply amount of the electrolytic solution is not particularly limited, and can be appropriately selected depending on the size of the frame formed by the first curable resin composition layer. Further, the details of the electrolytic solution used in the step B are as described above.

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

[Step C]

In the step C, the first curable resin composition layer is photocured to form a first sealing portion. The photohardening of the first curable resin composition layer can be carried out by irradiating the laminate obtained in the step B with light. The amount of energy of light irradiation is not particularly limited, and may be appropriately selected depending on the first curable resin composition layer. The amount of energy of light irradiation may be, for example, 2,000 to 12,000 mJ/cm ² , preferably 3,000 to 6,000 mJ/cm ² .

[Step D]

In the step D, the second curable resin composition is supplied 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 the step D are as described above.

The method of supplying the second curable resin composition so as to surround the first sealing portion is not particularly limited, and may be appropriately selected from the methods generally used. The supply method may, for example, be an addition method or the like. The second curable resin composition is preferably supplied to contact and surround the first sealing portion.

The second curable resin composition may be supplied to surround the first sealing portion, and may be supplied between the two substrates so as to be in contact with the first sealing portion, and may be provided with the first sealing portion and the substrate end portion. Surface contact, supply It can also be supplied between the two base materials and the end surface of the base material in contact with the first seal portion.

The supply amount of the second curable resin composition layer is not particularly limited, and may be appropriately selected depending on the purpose and the like. When the second curable resin composition is supplied between the two base materials, the thickness of the second curable resin composition layer surrounding the first seal portion in the direction parallel to the substrate surface, that is, the second curable resin composition The width of the layer is not particularly limited and may be appropriately selected depending on the purpose and the like. The width of the second curable resin composition layer may be, for example, 0.3 mm to 2.0 mm, preferably 0.5 mm to 1.0 mm.

Further, when the second curable resin composition is supplied in contact with the end surface of the substrate, the thickness of the second curable resin composition layer in the direction of the substrate surface is not particularly limited, and may be depending on the purpose and the thickness of the substrate. Come to the appropriate choice. For example, when the thickness of the substrate is 1.0 mm, the thickness of the second curable resin composition layer may be from 0.5 mm to 2.0 mm, preferably from 1.0 mm to 2.0 mm.

[Step E]

In the step E, the second curable resin composition layer is cured to form a second sealing portion. The method of hardening the second curable resin composition layer is appropriately selected depending on the constitution of the second curable resin composition. When the second curable resin composition is photocurable, the second curable resin composition layer can be irradiated with light to form a second sealing portion. The amount of energy of light irradiation is not particularly limited, and may be appropriately selected depending on the second curable resin composition layer. The amount of energy of light irradiation may be, for example, 4,000 to 18,000 mJ/cm ² , preferably 5,000 to 8,000 mJ/cm ² . Further, it is preferable to impart heat, and it is 60 to 90 minutes for 60 to 80 ° C, and 5 to 10 minutes for 120 ° C.

Further, 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 in accordance with the second curable resin composition layer. The heat can be, for example, 60 to 120 ° C, 5 to 180 minutes, preferably 80 to 100 ° C, and 60 to 120 minutes.

The second aspect of the method for manufacturing an electrochemical cell is a method for manufacturing an electrochemical cell having an electrolyte layer sealed between a first substrate and a second substrate, comprising: on the first substrate, a step in which the first curable resin composition having photocurability is supplied in a frame shape, and the first curable resin composition layer is formed (hereinafter also referred to as "step a"), The second curable resin composition having a difference in solubility parameter from the first curable resin composition of 2 or more is supplied to the first substrate so as to contact and surround the outer periphery of the frame-shaped first curable resin composition layer. a step of the second curable resin composition layer (hereinafter also referred to as "step b"), supplying an electrolyte solution in a frame formed on the first substrate to form an electrolyte layer, and in the electrolyte layer, first and a step of laminating a second base material on the second curable resin composition layer to obtain a laminate (hereinafter also referred to as "step c"), and a first curable resin composition layer and a second curable resin composition layer Hardening to form the first seal and the first Step sealing portion of (hereinafter also referred to as "step d"). The method of manufacturing the electrochemical cell may also include other steps as needed.

[Step a]

In the step a, the first curable resin composition layer is formed by disposing a solubility parameter between the solubility parameter and the electrolyte solution of 4 or more, and the photocurable first curable resin composition is supplied in a frame shape. . The details of step a are the same as step A in the first aspect of the manufacturing method.

[Step b]

In the step b, the second curable resin composition having a difference between the solubility parameter and the first curable resin composition of 2 or more is supplied so as to contact and surround the outer periphery of the first curable resin composition layer formed in a frame shape. A second curable resin composition layer is formed. The details of the step b are the same as those in the first aspect of the production method in the case where the second curable resin composition is supplied between the two substrates in the step D.

[Step c]

In the step c, the electrolytic solution is supplied into the frame formed on the first substrate to form an electrolyte layer, and the second substrate is laminated on the electrolyte 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 aspect of the manufacturing method.

In the 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 those of step C and step E in the first aspect of the manufacturing method.

Referring to FIG. 1A to FIG. 1D, the system of electrochemical cells will be described. An example of a method of making. In FIG. 1A, the first curable resin composition is supplied in a frame shape on the substrate 1, and the first curable resin composition layer 2 is formed, and an electrolytic solution is supplied into the formed frame to form an electrolyte layer 3. . In Fig. 1B, the substrate 1' is laminated on the first curable resin composition layer 2 and the electrolyte layer 3 to obtain a laminate. The first sealing portion is then formed by photohardening treatment. In FIG. 1C, the second curable resin composition is supplied in contact with the first sealing portion and the end surface portion of the substrate to form the second curable resin composition layer 4. Next, the second curable resin composition layer 4 is hardened to form a second sealing portion, thereby obtaining an electrochemical cell. Figure 1D illustrates a cross-sectional view of a-b of an electrochemical cell. In FIG. 1D, the electrolyte layer 3 is disposed between the two substrates 1 and 1', and the first sealing portion 2 surrounding and sealing the electrolyte layer 3 is disposed between the substrates 1 and 1', and the second sealing is performed. The portion 4 is disposed in contact with the first sealing portion 2 and the end surface of the substrate and surrounds the portion.

Further, another example of the method of manufacturing the electrochemical battery will be described with reference to FIGS. 2A to 2C. In FIG. 2A, the first curable resin composition is supplied in a frame shape on the substrate 1, and the first curable resin composition layer 2 is formed, and then the second curable resin composition is composed of the first curable resin. The material layer 2 is supplied in the outer peripheral contact manner, and after the second curable resin composition layer 4 is formed, an electrolytic solution is supplied into the formed frame to form the electrolytic solution layer 3. In Fig. 2B, the first curable resin composition layer 2, the second curable resin composition layer 4, and the electrolyte layer 3 are laminated on the substrate 1' to obtain a laminate. Then, the first and second sealing portions are formed by photohardening treatment to obtain an electrochemical cell. Figure 2C depicts a cross-sectional view of c-d between electrochemical cells. In Fig. 2C, the electrolyte layer 3 is disposed between the two substrates 1 and 1'. The first sealing portion 2 that surrounds and seals the electrolyte layer 3 is disposed between the substrates 1 and 1', and the second sealing portion 4 is disposed to be in contact with the first sealing portion 2 and surrounded.

The method for producing an electrochemical cell is suitable for a bonding method that does not require an injection port of an electrolytic solution, so that the manufacturing steps can be simplified. Further, the electrochemical cell produced by the method for producing an electrochemical cell of the present invention can maintain sufficient electrolyte sealing performance for a long period of time.

<Electrolyte sealant group>

The electrolyte sealant group is used for forming an electrochemical cell, comprising a first curable resin composition and a second curable resin composition, the first curable resin composition having a selected from the group consisting of polybutene and polybutadiene a (meth) acrylate compound of a skeleton of at least one resin in the group of a olefin, a polyisoprene, a hydrogenated polybutene, a hydrogenated polybutadiene, and a hydrogenated polyisoprene, the second sclerosing property The resin composition is a cationically curable epoxy resin composition containing an epoxy compound having an aromatic ring group.

Sealing the electrolyte of the electrochemical cell by using an electrolyte sealant group maintains sufficient electrolyte sealing performance for a long period of time.

The details of the first curable resin composition and the second curable resin composition in the electrolyte sealant group are as described above, and the preferred aspects are also the same. The electrolyte sealant group may further contain other constituent elements as needed. Other components include, for example, a method of sealing an electrolytic solution of an electrochemical cell using an electrolyte sealant group, an operation manual of a method for producing an electrochemical cell, and the like.

The electrolyte sealant group can be suitably used, for example, in a method of manufacturing an electrochemical cell. That is, in one aspect of the invention, the use of an electrolyte sealant set in the manufacture of an electrochemical cell.

[Examples]

The invention is illustrated by the following examples, but the invention is not limited by the examples.

(Preparation Example 1)

Preparation of the first curable resin composition

100 parts by mass of hydrogenated polyisoprene urethane acrylate (UA-1, LA cut, manufactured by Light Chemical Co., Ltd.), 3 parts by mass of a photoinitiator (KIP150, manufactured by Lamberti Co., Ltd.), and a coupling agent ( 1 part by mass of an acryl-based decane coupling agent, KBM 503, manufactured by Shin-Etsu Chemical Co., Ltd., and 1 part by mass of a coupling agent (vinyl decane coupling agent, KBM1003, manufactured by Shin-Etsu Chemical Co., Ltd.) to prepare a first curable resin Composition.

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 bisphenol A type epoxy resin (850S, manufactured by DIC Corporation), 50 parts by mass of talc (P-2, manufactured by Nippon Talc Co., Ltd.), and 1.5 parts by mass of photoacid generator (SP-172, manufactured by ADEKA Co., Ltd.) And coupling agent 1.5 parts by mass of an alkane coupling agent, KBM403, and Shin-Etsu Chemical Co., Ltd.) were mixed to prepare a second curable resin composition which is a cationically curable epoxy resin composition.

The solubility parameter of the second curable resin composition was 10.9.

(Preparation Example 3)

Preparation of electrolyte

In the case of propylene carbonate (PC, solubility parameter 13), the concentration of potassium iodide is 0.5 mol/L, the concentration of iodine is 0.05 mol/L, and the concentration of 4-tert-butylpyridine is 0.5 mol/L. The components were dissolved to prepare an electrolyte.

(Example 1)

Two glass plates (20 mm × 24 mm, thickness: 1.0 mm) coated with a FTO (Fluorine-doped tin oxide) transparent conductive film were prepared as a substrate. On the FTO film of the prepared glass plate, 3.5 ± 0.5 mg of the first curable resin composition was applied, and when two substrates were bonded together, a frame shape of 1 mm in width was obtained. After injecting 8 to 9 mg of the electrolyte into the frame, the other glass plate was laminated to make the FTO films face each other, and the pressure was 100 hPa to temporarily seal the electrolyte.

A spot type UV irradiator (manufactured by Hamamatsu Photonics Co., Ltd.) was used as a light source, and light irradiation was performed so as to become light energy of 6000 mJ/cm ² to cure the first curable resin composition, thereby sealing the electrolyte solution to two glass bases. The electrolyte between the materials was obtained for evaluation of the electrochemical cell.

[assessment]

(appearance observation)

When the interface between the electrolytic solution of the electrochemical cell for evaluation and the sealing portion (at the time of sealing) was observed with a metal microscope, it was incompatible at the time of sealing, and was in a good sealed state.

(electrolyte retention rate)

The obtained electrochemical cell for evaluation was placed in a thermostat at 85 ° C, and the mass after 72 hours and 240 hours was measured, and the electrolyte retention rate (%) was calculated to be 100% before being placed in the constant temperature bath. Further, the electrolyte retention rate was evaluated in accordance with the following evaluation criteria. The results are shown in Table 1.

Evaluation basis

A: Excellent.

B: Within the practical limits.

C: It is practically outside the allowable range.

D: Unable to measure.

(Example 2)

Two glass plates (20 mm × 24 mm, thickness: 1.0 mm) coated with a FTO (Fluorine-doped tin oxide) transparent conductive film were prepared as a substrate. The first curable resin composition was applied with 1.7±0.2 mg on the FTO film of the prepared glass plate, and when two substrates were bonded together, a frame shape of 0.5 mm in width was obtained. Next, the first part is supplied so as to surround the first curable resin composition. The second curable resin composition was 2.0 ± 0.2 mg, and when two substrates were bonded together, it was framed to have a width of 0.5 mm. After injecting 8 to 9 mg of the electrolyte into the frame, the other glass plate was laminated to make the FTO films face each other, and the pressure was 100 hPa to temporarily seal the electrolyte.

A spot type UV irradiator (manufactured by Hamamatsu Photonics Co., Ltd.) was used as a light source, and light irradiation was performed so as to become light energy of 6000 mJ/cm ² to cure the first curable resin composition, thereby sealing the electrolyte solution to two glass bases. Between the materials, an electrochemical cell was evaluated.

As a result of the appearance observation, the obtained electrochemical cell for evaluation was incompatible at the time of sealing, and was in a good sealed state. Further, the electrolyte retention rate (%) is shown in Table 1.

(Example 3)

In the same manner as in Example 2, after the photocuring of the curable resin composition, the electrochemical cell for evaluation was obtained in the same manner as the heat treatment at 80 ° C for 60 minutes, and the evaluation was carried out in the same manner.

As a result of the appearance observation, the obtained electrochemical cell for evaluation was incompatible at the time of sealing, and was in a good sealed state. Further, the electrolyte retention rate (%) is shown in Table 1.

(Comparative Example 1)

An electrochemical cell for evaluation was obtained in the same manner as in Example 1 except that the second curable resin composition was used instead of the first curable resin composition, and the evaluation was performed in the same manner.

As a result of the appearance observation, the obtained electrochemical cell for evaluation was compatible at the time of sealing, and the sealing state was poor. Further, since the sealing state was poor, the electrolyte retention rate could not be measured.

(Comparative Example 2)

In addition, in Comparative Example 1, after the photocuring of the second curable resin composition, the electrochemical cell for evaluation was further obtained in the same manner as the heat treatment at 80 ° C for 1 hour, and the evaluation was performed in the same manner.

As a result of the appearance observation, the obtained electrochemical cell for evaluation was compatible at the time of sealing, and the sealing state was poor. Further, since the sealing state was poor, the electrolyte retention rate could not be measured.

As is apparent from Table 1, the electrochemical cell of the present invention exhibits a good appearance in a sealed state and exhibits an excellent electrolyte retention rate.

The disclosure of Japanese Patent Application No. 2014-041505 (filed on March 4, 2014) is incorporated herein by reference.

All documents, patent applications, and technical specifications described in this manual The descriptions refer to and apply to the specification, with reference to the respective documents, patent applications, and technical specifications.

1‧‧‧Substrate

1'‧‧‧Substrate

2‧‧‧First hardened resin composition layer

3‧‧‧ electrolyte layer

4‧‧‧Second hardening resin composition layer

Claims (8)

An electrochemical cell comprising: two substrates without an electrolyte injection port; an electrolyte layer disposed between two substrates; and disposed between two substrates to surround and seal the electrolyte layer The first sealing portion is a cured product of a first curable resin composition having a photohardenability and a solubility difference of 4 or more in solubility parameter and electrolyte solution. The electrochemical cell of claim 1, further comprising a second sealing portion configured to surround the first sealing portion and being a cured product of the second curable resin composition. The electrochemical cell according to claim 2, wherein the second curable resin composition is a cationically curable epoxy resin composition containing an epoxy compound having an aromatic ring group. The electrochemical cell of claim 1, wherein the first curable resin composition comprises from the group consisting of polybutene, polybutadiene, polyisoprene, hydrogenated polybutene, hydrogenated polybutadiene, and A (meth) acrylate compound having a skeleton of at least one resin in a group of hydrogenated polyisoprene. An electrochemical cell according to claim 1, which is a dye-sensitized solar cell, an anti-glare mirror or a display. A method for producing an electrochemical cell, which is a method for producing an electrochemical cell having an electrolyte layer sealed between a first substrate and a second substrate, the method comprising: dissolving solubility on the first substrate The parameter and electrolyte gap is more than 4, And the first curable resin composition having photocurability is supplied in a frame shape to form a first curable resin composition layer, and an electrolyte solution is supplied to a frame formed on the first substrate to form an electrolyte layer. And a step of laminating the second substrate on the electrolyte layer and the first curable resin composition layer to obtain a laminate, and step of curing the first curable resin composition layer to form the first sealing portion, and second The curable resin composition is supplied to surround the first sealing portion, to form a second curable resin composition layer, and to cure the second curable resin composition layer to form a second sealing portion. A method for producing an electrochemical cell, which is a method for producing an electrochemical cell having an electrolyte layer sealed between a first substrate and a second substrate, the method comprising: dissolving solubility on the first substrate The difference between the parameter and the electrolyte is 4 or more, and the photocurable first curable resin composition is supplied in a frame shape, the first curable resin composition layer is formed, and the solubility parameter is different from the first curable resin composition. 2 or more of the second curable resin composition is supplied onto the first substrate so as to contact and surround the frame-shaped first curable resin composition layer, and the second curable resin composition layer is formed to form a step of supplying an electrolyte solution in a frame on the first substrate to form an electrolyte layer, and laminating the second substrate on the electrolyte layer and the first and second curable resin composition layers to obtain a laminate, and 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. An electrolyte sealant group for an electrochemical cell, comprising: having a selected from the group consisting of polybutene, polybutadiene, polyisoprene, hydrogenated polybutene, hydrogenated polybutadiene, and hydrogenated polyiso A first curable resin composition of a (meth) acrylate compound having a skeleton of at least one resin of a group of pentadiene, and a cation-curable epoxy resin composition containing an epoxy compound having an aromatic ring group That is, the second curable resin composition.