JP5454285B2 - DYE-SENSITIZED SOLAR CELL ELECTRODE, RESIN COMPOSITION FOR FORMING SHIELD FILM OF DYE-SENSITIZED SOLAR CELL ELECTRODE, SHIELD FILM AND METHOD FOR FORMING THE SAME - Google Patents

Description

  The present invention relates to an electrode for a dye-sensitized solar cell, a resin composition for forming a shield film of an electrode for a dye-sensitized solar cell, a shield film and a method for forming the same, and a dye-sensitized solar cell having a shield film.

  Dye-sensitized solar cells were developed by Gretzel et al. In Switzerland, and have advantages such as high photoelectric conversion efficiency and low manufacturing costs. JP, 1-220380, see Nature (UK), 1991, No. 353, p. 737 by M. Graetzel et al.). A dye-sensitized solar cell includes a working electrode having an oxide semiconductor porous film on which a photosensitizing dye composed of oxide semiconductor fine particles is supported on a transparent electrode substrate, and a counter electrode provided to face the working electrode And an electrolyte layer (charge transfer layer) formed by filling an electrolyte between the working electrode and the counter electrode. In such a dye-sensitized solar cell, the oxide semiconductor fine particles are sensitized by a photosensitizing dye that absorbs incident light such as sunlight, and functions as a photoelectric conversion element that converts light energy into electric power.

As a transparent electrode substrate used in a dye-sensitized solar cell, a transparent conductive film such as tin-added indium oxide (ITO) or fluorine-added tin oxide (FTO) is formed on the surface of a substrate such as high strain point glass. It is common. Tin-added indium oxide (ITO) and fluorine-added tin oxide (FTO) are preferably used from the viewpoints of transparency, resistance to corrosion by an electrolytic solution, film formation ease, and the like. However, the specific resistance of ITO or FTO is about 10 ⁻⁴ [Ω · cm], which is about 100 times the specific resistance of metals such as silver and gold. In such a case, the photoelectric conversion efficiency is reduced.

  As a technique for reducing the resistance of the transparent electrode substrate, it is conceivable to increase the thickness of the transparent conductive film (ITO, FTO, etc.). However, when the film thickness is such that the resistance value is sufficiently reduced, light absorption by the transparent conductive film is possible. Will become bigger. In this case, since the transmission efficiency of incident light through the transparent conductive film is remarkably lowered, the photoelectric conversion efficiency is likely to be lowered. As a solution to this problem, studies have been made to reduce the resistance of the transparent electrode substrate by providing metal wiring on the surface of the transparent electrode substrate to such an extent that the aperture ratio is not significantly impaired (Japanese Patent Laid-Open No. 2003-203681). See the official gazette).

  However, in this case, corrosion of the metal wiring due to the electrolytic solution occurs, and the resistance of the transparent electrode substrate increases with the passage of time, leading to a decrease in photoelectric conversion efficiency. Therefore, when providing the metal wiring on the surface of the transparent electrode substrate in this way, at least the surface portion of the metal wiring needs to be protected by some kind of shielding layer. This shielding layer is required to be capable of densely covering the metal wiring and to have excellent corrosion resistance against the electrolyte solution constituting the electrolyte layer.

  In view of the above situation, Japanese Patent Application Laid-Open No. 2005-197176 discloses conductive particles (ITO, ATO, ZnO, etc.) in order to protect the metal wiring provided on the electrode for the dye-sensitized solar cell from corrosion by the electrolytic solution. ), An organic film made of a transparent resin such as an acrylic resin, a polyester resin, or a polyurethane resin is disclosed on the uppermost layer of the electrode. However, since the conductive particles are dispersed non-uniformly in the transparent resin solution, it is difficult to form a coating film having a uniform thickness on a substrate having a metal wiring step. As a result, the organic film is lost, or the organic film is formed up to the portion where the metal wiring does not exist, so that the photoelectric conversion efficiency is lowered.

  Japanese Patent Application Laid-Open No. 2005-197176 discloses a transparent resin such as an acrylic resin, a polyester resin, or a polyurethane resin so as to cover the surface portion of the metal wiring provided on the dye-sensitized solar cell electrode. A technique for forming an organic film is disclosed. However, it is very difficult to accurately apply the resin composition only to the portion where the metal wiring exists by using screen printing or gravure printing on a substrate having a metal wiring level difference. Even when such a coating method is adopted, the organic film is lost in a part of the metal wiring, or the organic film is formed even in an unnecessary part where the metal wiring does not exist. There is an inconvenience of inviting a drop in

  Therefore, in a dye-sensitized solar cell, it is possible to accurately apply to a substrate having a metal wiring step, and to form a shield film having excellent corrosion resistance while maintaining high photoelectric conversion efficiency. There is a strong demand for the development of a composition for forming a shield film that can be formed. In addition, a shield film is applied to a substrate having a metal wiring step in a dye-sensitized solar cell by bar coating, spin coating, slit die method, etc., and subsequent exposure / development through a photomask. There is no known resin composition that can be formed.

Japanese Patent Laid-Open No. 1-220380 JP 2003-203681 A JP 2005-197176 A

Nature (UK), 1991, No. 353, M. Graetzel et al., P. 737

  The present invention has been made based on the above circumstances, and in a dye-sensitized solar cell electrode in which a metal wiring layer is formed on a base material, the present invention is precisely applied to a substrate having a metal wiring step. By providing a resin composition having a radiation sensitivity that can be applied and can form a shield film having excellent corrosion resistance against corrosion by an electrolyte while maintaining high photoelectric conversion efficiency. is there. Furthermore, a resin composition capable of forming a shield film at a low cost by only a relatively simple process such as a coating process and a heating process, and a dye-sensitized solar cell having a photoelectric conversion efficiency provided with the shield film having this corrosion resistance It is to provide a working electrode.

The present invention made to solve the above problems
A dye-sensitized solar cell electrode comprising a shield film made of a cured product of a resin composition,
[A] a copolymer having at least one reactive functional group selected from the group consisting of [A] carboxyl group, epoxy group and (meth) acryloyl group, and [B] ethylenically unsaturated disilane. A dye-sensitized solar cell electrode comprising a polymerizable compound having a heavy bond.

  The shield film made of the cured product of the resin composition can be formed at a low cost by a relatively simple process such as a coating process and a heating process, and the shield film has excellent corrosion resistance from the electrolyte solution. The dye-sensitized solar cell electrode using this shield film is excellent in photoelectric conversion efficiency.

  The resin composition preferably further contains [B] a polymerizable compound having an ethylenically unsaturated double bond, and the [B] polymerizable compound having an ethylenically unsaturated double bond may be monofunctional. It is preferably at least one selected from the group consisting of (meth) acrylates, bifunctional (meth) acrylates, and trifunctional or higher functional (meth) acrylates. Furthermore, the resin composition preferably contains [C] a radiation-sensitive polymerization initiator, and the [C] radiation-sensitive polymerization initiator is an O-acyl oxime compound and / or an acetophenone compound. It is preferable. By using these compounds, it is possible to obtain a shield film having no film defects and excellent corrosion resistance of the metal wiring.

In addition, the resin composition according to the present invention is
[A] Resin for forming a shield film of an electrode for a dye-sensitized solar cell containing a copolymer having at least one reactive functional group selected from the group consisting of a carboxyl group, an epoxy group and a (meth) acryloyl group It is a composition. The said resin composition can be used suitably as a forming material of the shield film of the electrode for dye-sensitized solar cells.

The resin composition is
[B] A polymerizable compound having an ethylenically unsaturated double bond, and [C] a radiation-sensitive polymerization initiator may be further contained. Since the resin composition has high radiation sensitivity, when used for forming a shield film for an electrode for a dye-sensitized solar cell, the resin composition is uniform only on a portion where the metal wiring exists on a substrate having a step of the metal wiring. It is possible to form a shield film with a sufficient thickness. Therefore, the shield film formed using the resin composition effectively protects the metal wiring from corrosion by the electrolyte, and the dye-sensitized solar cell electrode using the shield film has high photoelectric conversion. Efficiency can be maintained.

  [B] The polymerizable compound having an ethylenically unsaturated double bond is at least one selected from the group consisting of monofunctional (meth) acrylates, bifunctional (meth) acrylates, and trifunctional or higher functional (meth) acrylates. It is preferable that [C] The radiation-sensitive polymerization initiator is preferably an O-acyloxime compound and / or an acetophenone compound. By using these compounds, the polymerization reactivity at the time of exposure is enhanced, and a shield film having an accurate shape and excellent corrosion resistance can be obtained.

  Therefore, the shield film formed using the resin composition and the dye-sensitized solar cell (photoelectric conversion element) having the shield film are portions where metal wiring exists by exposure / development using radiation sensitivity. Since the shield film is accurately formed only on the substrate, it has high photoelectric conversion efficiency.

The method for forming the shield film of the dye-sensitized solar cell electrode of the present invention is as follows:
(1) A step of forming a coating film of a curable resin composition so that at least the entire metal wiring layer is covered on the laminate including the conductive substrate and the metal wiring layer on the surface side of the conductive substrate; And (2) a step of heating the coating film formed in step (1). The formation method requires only a relatively simple process of applying and heating, and can form a shield film at low cost.

As another method for forming the shield film of the electrode for the dye-sensitized solar cell of the present invention,
(1 ′) Any one of claims 7 to 9, wherein at least the entire metal wiring layer is covered with the laminate including the conductive substrate and the metal wiring layer on the surface side of the conductive substrate. A step of forming a coating film of the resin composition described in 1.
(3) A step of irradiating only the part laminated on the metal wiring layer of the coating film formed in step (1 ′),
(4) a step of developing the coating film irradiated with radiation in step (3); and (2 ′) a step of heating the coating film developed in step (4). Here, the “surface” of the conductive substrate means a surface on the counter electrode side in the dye-sensitized solar cell including the conductive substrate. In the method of forming a shield film for a dye-sensitized solar cell electrode using the resin composition having radiation sensitivity, a metal wiring exists because a pattern is formed by exposure and development using radiation sensitivity. It is possible to easily form a pattern having a uniform thickness only on the portion. Therefore, according to the method, it is possible to form a shield film having sufficient resistance against corrosion by the electrolytic solution.

  As described above, since the resin composition having radiation sensitivity forms a pattern by exposure / development using radiation sensitivity, the resin composition on the substrate having a metal wiring step in the dye-sensitized solar cell electrode is used. Thus, it is possible to form a shield film having a uniform thickness only in the portion where the metal wiring exists. Moreover, since the said resin composition which has radiation sensitivity can form a shield film correctly only in the location of metal wiring as mentioned above, the shield film which has sufficient corrosion resistance is obtained. Therefore, the resin composition having radiation sensitivity can be suitably used as a material for forming a shield film of a dye-sensitized solar cell electrode. Furthermore, the resin composition having no radiation sensitivity of the present invention includes a resin composition capable of forming a shield film at a low cost only by a relatively simple process such as a coating process and a heating process, and a shield film having this corrosion resistance. In addition, it is possible to provide a dye-sensitized solar cell electrode having excellent photoelectric conversion efficiency.

FIG. 1 is a schematic cross-sectional view showing each step of a method (Example) for producing an electrode substrate of a dye-sensitized solar cell provided with a shield film of the present invention. FIG. 2 is a schematic cross-sectional view showing each step of a method (Example) for producing a dye-sensitized solar cell using the electrode substrate of FIG.

Dye-sensitized solar cell The dye-sensitized solar cell of the present invention includes a conductive substrate, a working electrode laminated on the conductive substrate, a counter electrode disposed on the working electrode, and an electrode disposed between the electrodes. The charge transfer layer is mainly provided. This working electrode includes a metal wiring layer having a shield film around (except the lower surface) and a porous oxide semiconductor layer disposed between the metal wiring layers.

  As the conductive substrate, a material that is substantially transparent is used. The light transmittance of the conductive substrate is preferably 50% or more, and particularly preferably 80% or more. As the conductive substrate, a base material having conductivity by itself or a base material having a transparent conductive film on the surface can be used. As a substrate having a transparent conductive film on the surface, a glass plate, a ceramic polishing plate such as titanium oxide or alumina, or a plastic sheet can be used. Examples of plastics used in plastic sheets include triacetyl cellulose, polyethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, syndiotactic polystyrene, polycarbonate, polyarylate, polyetherimide, polysulfone, polyethersulfone, cyclic polyolefin, phenoxy Examples thereof include resins and brominated phenoxy resins.

As the conductive material constituting the transparent conductive film, an inorganic conductive material made of a known metal or metal oxide, a polymer conductive material, or the like can be used. Among these conductive materials, inorganic conductive materials are preferably used from the viewpoints of availability and conductivity. Examples of inorganic conductive materials include metals such as platinum, gold, silver, copper, zinc, titanium, aluminum, rhodium, and indium; conductive carbon, tin-doped indium oxide (ITO), tin oxide (SnO ₂ ), Examples thereof include metal oxides such as fluorine-added tin oxide (FTO), antimony-added tin oxide (ATO), and zinc oxide (ZnO ₂ ). The most common inorganic conductive materials are tin-doped indium oxide (ITO) and fluorine-doped tin oxide (FTO). The thickness of the transparent conductive film is preferably about 0.01 to 10 μm, and more preferably about 0.05 to 5 μm.

  The metal wiring layer is disposed on the conductive substrate in order to improve the current collection efficiency of the conductive substrate and further increase the conductivity. This metal wiring layer has a shield film formed as described above. Examples of the material for the metal wiring layer include gold, silver, copper, platinum, aluminum, nickel, indium, titanium, and tungsten. The shape of the metal wiring layer is not particularly limited, but a pattern such as a lattice shape, a stripe shape, or a comb shape is adopted, and it is preferable that the metal wiring layer is disposed so that light is uniformly transmitted through the conductive substrate. A metal wiring layer having a lattice pattern is most commonly used.

  The porous oxide semiconductor film is composed of an aggregate of metal oxide fine particles having semiconductivity such as titanium oxide, tin oxide, tungsten oxide, zinc oxide, zirconium oxide, niobium oxide and the like. The porous oxide semiconductor film is a porous body having countless fine pores inside and fine irregularities on the surface, and the thickness thereof is 5 to 50 μm. This porous oxide semiconductor is typically installed at a location where a metal wiring layer is not provided on a conductive substrate.

  The oxide semiconductor porous film is made of, for example, a conductive colloid liquid or dispersion liquid (using water and / or an organic solvent as a solvent) in which the metal oxide fine particles having an average particle diameter of 5 to 50 nm are dispersed. It can form by the method of apply | coating on well-known board | substrates by well-known application | coating means, such as a screen print, an inkjet print, a roll coat, a doctor coat, a spray coat, and sintering at 300-800 degreeC. This oxide semiconductor porous film carries a photosensitizing dye.

  As the photosensitizing dye, those having absorption in the visible light region and / or the infrared light region and having a lowest vacancy level higher than the conduction band of the semiconductor are preferable. Examples of photosensitizing dyes include azo dyes, quinone dyes, quinone imine dyes, quinacridone dyes, squarylium dyes, cyanine dyes, cyanidin dyes, merocyanine dyes, triphenylmethane dyes, xanthene dyes. Porphyrin dyes, perylene dyes, indigo dyes, phthalocyanine dyes, naphthalocyanine dyes, rhodamine dyes, and the like. As the photosensitizing dye, a metal complex dye is also preferably used. Examples of metals composing the metal complex dye include Cu, Ni, Fe, Co, V, Sn, Si, Ti, Ge, Cr, Zn, Ru, Mg, Al, Pb, Mn, In, Mo, Y, Zr, Nb, Sb, La, W, Pt, Ta, Ir, Pd, Os, Ga, Tb, Eu, Rb, Bi, Se, As, Sc, Ag, Cd, Hf, Re, Au, Ac, Tc, Various metals such as Te and Rh can be mentioned. As an example of a preferable metal complex dye, a metal phthalocyanine dye, a metal porphyrin dye or a ruthenium complex dye is preferable, and a ruthenium complex dye is particularly preferable.

As the counter electrode, similarly to the above-described conductive substrate, a single-layer structure of a base material having conductivity itself, or a base material having a counter electrode conductive film on the surface thereof can be used. In the latter case, as the conductive material and the base material, the same materials as in the case of the conductive substrate can be used. The counter electrode, I ₃ ^- it is preferable to use a reduction reaction of the oxidation reaction and other redox ions such as ions that have a catalytic ability to perform fast enough. Examples of the counter electrode include a platinum electrode, a conductive material surface subjected to platinum plating or platinum deposition, rhodium metal, ruthenium metal, ruthenium oxide, carbon, and the like.

  The charge transfer layer is a layer containing a charge transport material having a function of replenishing electrons to the oxidant of the photosensitizing dye. Examples of the charge transport material constituting the charge transfer layer include a solvent in which a redox counter ion is dissolved, an electrolytic solution such as a room temperature molten salt containing the redox counter ion, and a solution of the redox counter ion in a polymer matrix or a low molecular weight Examples thereof include a gel-like quasi-solidified electrolyte impregnated with a gelling agent or the like.

Examples of the redox counter ion include those containing a redox counter ion such as I ⁻ / I ₃ ⁻ system, Br ⁻ / Br ₃ ⁻ system, ferrocyanate / ferricyanate, ferrocene / ferricinium. Metal redox systems such as metal complexes such as aluminum ions and cobalt complexes; organic redox systems such as alkylthiol-alkyl disulfides, viologen dyes, hydroquinones / quinones; sulfur compounds such as sodium polysulfide and alkylthiols / alkyl disulfides be able to. Examples of the solvent include carbonate compounds such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate; heterocyclic compounds such as 3-methyl-2-oxazolidinone; ether compounds such as dioxane and diethyl ether; ethylene glycol dialkyl ether, propylene Chain ethers such as glycol dialkyl ether, polyethylene glycol dialkyl ether, and polypropylene glycol dialkyl ether; alcohols such as methanol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, and polypropylene glycol monoalkyl ether Tetrahydrofuran, dimethyl sulfoxide, , And the like aprotic polar substances such as Ruforan. Examples of the molten salt electrolyte include electrolytes containing iodine salts such as pyridinium salts, imidazolium salts, and triazolium salts.

  As a method for forming the charge transfer layer between the working electrode and the counter electrode, for example, a method in which the working electrode and the counter electrode are arranged to face each other and then an electrolyte is filled between the electrodes to form the charge transfer layer, a semiconductor A method of forming a charge transfer layer by dropping or applying an electrolytic solution on the electrode or the counter electrode, and then superimposing the other electrode on the charge transfer layer can be used.

  In such a dye-sensitized solar cell (photoelectric conversion element), a shield film is accurately formed only in a portion where a metal wiring exists on the substrate by exposure and development using the resin composition of the present invention. High photoelectric conversion efficiency.

Resin Composition The resin composition for forming a shield film of an electrode for a dye-sensitized solar cell according to the present invention has at least one reaction selected from the group consisting of [A] carboxyl group, epoxy group and (meth) acryloyl group. A copolymer having a functional group (hereinafter sometimes referred to as “[A] copolymer”). Further, [B] a polymerizable compound having an ethylenically unsaturated double bond (hereinafter sometimes referred to as “[B] polymerizable compound”) and [C] a radiation-sensitive polymerization initiator may be further contained. If necessary, it contains other optional components. Hereinafter, each component will be described.

[A] Copolymer [A] The copolymer has at least one reactive functional group selected from the group consisting of a carboxyl group, an epoxy group, and a (meth) acryloyl group. [A] Since the copolymer has these reactive functional groups, it is possible to form a shield film having no film defect and excellent corrosion resistance of the metal wiring. In addition, when the resin composition of the present invention is radiation sensitive, the polymerization reactivity between the [A] copolymer during exposure and curing reaction, the [A] copolymer and the [B] polymerizable compound, and As a result, a shield film having a desired shape can be easily formed.

  A copolymer having a reactive functional group such as a carboxyl group or an epoxy group can be synthesized by copolymerizing a radical polymerizable monomer having such a reactive functional group and another radical polymerizable monomer. A copolymer having a (meth) acryloyl group is synthesized by reacting an isocyanate compound having a (meth) acryloyl group after copolymerizing a radical polymerizable monomer having a hydroxyl group with another radical polymerizable monomer. Can do. [A] The copolymer is composed of a structural unit derived from a radical polymerizable monomer having a reactive functional group such as a carboxyl group, an epoxy group, or a (meth) acryloyl group, and these radical polymerizable monomers and other radical polymerizable monomers. The content is preferably 10 to 90% by mass, particularly preferably 20 to 80% by mass, based on the total of structural units derived from the monomers. [A] In the copolymer, when the resin composition of the present invention is radiation sensitive by exposing 10 to 90% by mass of a structural unit derived from a radical polymerizable monomer having a reactive functional group, exposure is performed. It is possible to increase the curing reactivity during the process.

As an example of a radical polymerizable monomer having a carboxyl group,
Monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid;
Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
The acid anhydride of the said dicarboxylic acid etc. can be mentioned.

As an example of a radical polymerizable monomer having an epoxy group,
4-methacryloyloxymethyl-2-cyclohexyl-1,3-dioxolane glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxybutyl acrylate, -6,7-epoxyheptyl acrylate, acrylic acid Acrylic acid epoxy alkyl esters such as 3,4-epoxycyclohexyl and acrylic acid-3,4-epoxycyclohexylmethyl;
Glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, methacrylic acid-6,7-epoxyheptyl, methacrylic acid-3,4-epoxycyclohexyl, methacrylic acid-3,4-epoxy Methacrylic acid epoxy alkyl esters such as cyclohexylmethyl;
α-alkylacrylic acid epoxy alkyl ester such as α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, α-ethyl acrylate-6,7-epoxyheptyl;
glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether;

3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) ) Methacrylic acid ester having oxetanyl group such as 3-ethyloxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3-methyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane ;
3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) And acrylate esters having an oxetanyl group such as 3-ethyloxetane and 2-ethyl-3- (acryloyloxyethyl) oxetane.

  Among these radically polymerizable monomers having an epoxy group, glycidyl methacrylate, 2-methylglycidyl methacrylate, methacrylic acid-3,4-epoxycyclohexyl, methacrylic acid-3,4-epoxycyclohexylmethyl, 3-methyl- 3-methacryloyloxymethyloxetane and 3-ethyl-3-methacryloyloxymethyloxetane are copolymerizable with other radical polymerizable monomers, and developability when the resin composition of the present invention is radiation sensitive. From the viewpoint, it is particularly preferable.

Examples of radical polymerizable monomers having a hydroxyl group include:
Acrylic acid hydroxyalkyl esters such as acrylic acid-2-hydroxyethyl ester, acrylic acid-3-hydroxypropyl ester, acrylic acid-4-hydroxybutyl ester, acrylic acid-4-hydroxymethyl-cyclohexylmethyl ester;
Methacrylic acid-2-hydroxyethyl ester, methacrylic acid-3-hydroxypropyl ester, methacrylic acid-4-hydroxybutyl ester, methacrylic acid-5-hydroxypentyl ester, methacrylic acid-6-hydroxyhexyl ester, methacrylic acid-4- And methacrylic acid hydroxyalkyl esters such as hydroxymethyl-cyclohexylmethyl ester.

  Among these radical polymerizable monomers having a hydroxyl group, acrylic acid-2-hydroxyethyl ester is used from the viewpoint of copolymerization reactivity with other radical polymerizable monomers and reactivity with an isocyanate compound having a (meth) acryloyl group. Acrylic acid-3-hydroxypropyl ester, acrylic acid-4-hydroxybutyl ester, methacrylic acid-2-hydroxyethyl ester, methacrylic acid-4-hydroxybutyl ester, acrylic acid-4-hydroxymethyl-cyclohexylmethyl ester, methacrylic acid Acid-4-hydroxymethyl-cyclohexylmethyl ester is preferred.

  Examples of isocyanate compounds having a (meth) acryloyl group that are reacted with a radical polymerizable monomer having a hydroxyl group and a copolymer of another radical polymerizable monomer include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and the like. Mention may be made of acrylic acid derivatives or methacrylic acid derivatives. Examples of commercially available products of 2-acryloyloxyethyl isocyanate include Karenz AOI (manufactured by Showa Denko KK), and examples of commercially available products of 2-methacryloyloxyethyl isocyanate include Karenz MOI (manufactured by Showa Denko KK). Can be mentioned.

Examples of other radical polymerizable monomers to be copolymerized with a radical polymerizable monomer having a reactive functional group such as a carboxyl group, an epoxy group, a hydroxyl group,
Alkyl acrylates such as methyl acrylate and i-propyl acrylate;
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate;
Cyclohexyl acrylate, acrylate-2-methylcyclohexyl, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, acrylate-2- (tricyclo [5.2.1.0 ^{2, 6} ] Acrylic alicyclic ester such as decan-8-yloxy) ethyl, isobornyl acrylate;
Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, methacrylic acid-2- (tricyclo [5.2.1.0 ^{2, 6} ] Methacrylic acid alicyclic ester such as decan-8-yloxy) ethyl, isobornyl methacrylate;
Aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate and aralkyl esters of acrylic acid;
Aryl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate and aralkyl esters of methacrylic acid;
Dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Unsaturated 5-membered ring methacrylates and unsaturated 6-membered ring methacrylates containing 1 atom of oxygen such as tetrahydrofurfuryl methacrylate, tetrahydrofuryl methacrylate, tetrahydropyran-2-methyl methacrylate;
4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-cyclohexyl- 2 oxygen atoms such as 1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane Unsaturated heterocyclic 5-membered methacrylates containing:

4-acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2, 2-diethyl- 1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-acryloyloxymethyl-2-cyclopentyl-1,3-dioxolane, 4-acryloyloxymethyl-2- Cyclohexyl-1,3-dioxolane, 4-acryloyloxyethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxypropyl-2-methyl-2-ethyl-1,3-dioxolane, 4- Acryloyloxybutyl-2-methyl-2-ethyl-1,3-dioxola Unsaturated five-membered heterocyclic acrylic ester containing an oxygen diatomic and the like;
Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, 4-isopropenylphenol;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -N-substituted maleimides such as maleimide propionate, N- (9-acridinyl) maleimide;
Conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene;
Other unsaturated compounds such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride and vinyl acetate can be mentioned.

Among these other radical polymerizable monomers, styrene, 4-isopropenylphenol, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, tetrahydrofurfuryl methacrylate, 1,3- Butadiene, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, N-cyclohexylmaleimide, N-phenylmaleimide, benzyl methacrylate and the like are radical polymerizable monomers having the above reactive functional groups and In view of the copolymerization reactivity and developability when the resin composition of the present invention is radiation-sensitive.

[A] The polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) by GPC (gel permeation chromatography) of the copolymer is preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably. Is 5 × 10 ^{3 to} 5 × 10 ⁴ . By setting the Mn of the copolymer to 2 × 10 ³ to 1 × 10 ⁵ , when the resin composition of the present invention is radiation sensitive, the curing reactivity during exposure can be improved.

  [A] The molecular weight distribution “Mw / Mn” of the copolymer (where “Mw” is the polystyrene-equivalent weight average molecular weight of the copolymer measured by gel permeation chromatography) is preferably 5. 0.0 or less, more preferably 3.0 or less. When the Mw / Mn of the copolymer is 5.0 or less, when the resin composition of the present invention is radiation sensitive, it is possible to form a shield film having a desired shape more accurately during development. It becomes.

  [A] As a solvent used in the polymerization reaction for producing the copolymer, for example, alcohols, ethers, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, Examples thereof include propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether propionate, aromatic hydrocarbons, ketones, and other esters.

These solvents include
Examples of alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol;
Ethers such as tetrahydrofuran;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of the diethylene glycol alkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like;
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;

As propylene glycol monoalkyl ether acetate, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and the like;
As propylene glycol monoalkyl ether propionate, for example, propylene monoglycol methyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, etc .;
Examples of aromatic hydrocarbons include toluene and xylene;
Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, etc .;

  Examples of other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, hydroxyacetic acid Methyl, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, Methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, Methyl poxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionate Propyl acid, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxypropionic acid Ethyl, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-metho Butyl cypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxy Examples thereof include propyl propionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

  Among these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and butyl methoxyacetate are preferable, particularly diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate and butyl methoxyacetate are preferred.

[A] What is generally known as a radical polymerization initiator can be used as the polymerization initiator used in the polymerization reaction for producing the copolymer. Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2, Azo compounds such as 4-dimethylvaleronitrile);
And organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane; and hydrogen peroxide.
When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.

[A] In the polymerization reaction for producing the copolymer, a molecular weight modifier can be used in order to adjust the molecular weight. Specific examples of molecular weight regulators include
Halogenated hydrocarbons such as chloroform and carbon tetrabromide;
mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid;
Xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide;
Examples include terpinolene and α-methylstyrene dimer.

[B] Polymerizable compound [B] The polymerizable compound is suitably used in the resin composition of the present invention. [B] Preferred examples of the polymerizable compound include monofunctional (meth) acrylates, bifunctional (meth) acrylates, and trifunctional or higher functional (meth) acrylates. By using these compounds, when the resin composition of the present invention is radiation sensitive, the polymerization reactivity between the compounds of the [B] polymerizable compound when exposed and cured, and the [A] copolymer And [B] the polymerizable compound are enhanced, and as a result, a shield film having an accurate shape and excellent corrosion resistance can be obtained.

  Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl- Examples include 2-hydroxypropyl phthalate. Examples of these monofunctional (meth) acrylate commercial products include Aronix M-101, M-111, M-114 (manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, TC-120S (Japan) Kayaku Co., Ltd.), Biscoat 158, 2311 (Osaka Organic Chemical Co., Ltd.) and the like.

  Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate, and bisphenoxyethanol full orange (meth) acrylate. Examples of commercially available products of these bifunctional (meth) acrylates include Aronix M-210, M-240, M-6200 (manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604. (Nippon Kayaku Co., Ltd.), Biscoat 260, 312 and 335HP (Osaka Organic Chemical Co., Ltd.) are listed.

  Examples of the tri- or more functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, mono- [3- (3- (meth) acryloyloxy-2,2-bis- (meth) acryloyloxymethyl-propoxy) -2 , 2-bis- (meth) acryloyloxymethyl-propyl] ester. Commercially available products of these tri- or higher functional (meth) acrylates include, for example, Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, and M- 8060 (manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPHA-20, DPCA-30, DPCA-30, DPCA-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Biscote 295, 300 360, GPT, 3PA, 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

  Of these polymerizable compounds having an ethylenically unsaturated double bond, a tri- or higher functional (meth) acrylate is preferably used from the viewpoint of improving the curability of the resin composition. Among them, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, succinic acid mono- [3- (3-acryloyloxy-2,2-bis-acryloyloxymethyl) -Propoxy) -2,2-bis-acryloyloxymethyl-propyl] ester is particularly preferred. These polymerizable compounds having an ethylenically unsaturated double bond can be used alone or in admixture of two or more.

  The amount of the [B] polymerizable compound used in the resin composition is preferably 50 to 300 parts by mass, more preferably 60 to 250 parts by mass with respect to 100 parts by mass of the [A] copolymer. [B] By using the polymerizable compound in an amount of 50 to 300 parts by mass, various properties such as adhesion of the formed shield film to the substrate and corrosion resistance to the electrolytic solution are balanced at a higher level. A thing is obtained.

[C] Radiation-sensitive polymerization initiator [C] The radiation-sensitive polymerization initiator is suitably used for the resin composition of the present invention. [C] The radiation-sensitive polymerization initiator is not particularly limited as long as it is a component that generates an active species capable of initiating polymerization of the [B] polymerizable compound in response to radiation. Examples of such [C] radiation-sensitive polymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and the like.

  Examples of the O-acyloxime compound used as a radiation sensitive polymerization initiator include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyl). Oxime), 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.

  Preferred examples of these O-acyloxime compounds include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone -1- [9-Ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime). These O-acyloxime compounds can be used alone or in admixture of two or more.

  Examples of the acetophenone compound used as the radiation sensitive polymerization initiator include an α-aminoketone compound and an α-hydroxyketone compound.

  Examples of α-aminoketone compounds include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and the like can be mentioned.

  Examples of α-hydroxyketone compounds include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone and the like.

  Of these acetophenone compounds, α-aminoketone compounds are preferred, such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl). ) -1- (4-morpholin-4-yl-phenyl) -butan-1-one is particularly preferred. These acetophenone compounds can be used alone or in admixture of two or more.

  As a biimidazole compound used as a radiation sensitive polymerization initiator, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2 is used. '-Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) ) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'- Examples thereof include tetraphenyl-1,2′-biimidazole.

  Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2, 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 5'-tetraphenyl-1,2'-biimidazole is preferred, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole Is particularly preferred. These biimidazole compounds can be used alone or in admixture of two or more.

  In the resin composition of the present invention, when a biimidazole compound is used as the [C] radiation-sensitive polymerization initiator, an aliphatic or aromatic compound having a dialkylamino group (hereinafter referred to as “amino”) is used to sensitize the compound. System sensitizer ") can be added.

  Examples of such amino sensitizers include 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone. Of these amino sensitizers, 4,4'-bis (diethylamino) benzophenone is particularly preferred. The amino sensitizers can be used alone or in admixture of two or more.

  Furthermore, when a biimidazole compound and an amino sensitizer are used in combination, a thiol compound can be added as a hydrogen radical donor. A biimidazole compound is sensitized by an amino sensitizer and cleaved to generate an imidazole radical, but may not exhibit high polymerization initiation ability as it is. However, by adding a thiol compound to a system in which a biimidazole compound and an amino sensitizer coexist, a hydrogen radical is donated from the thiol compound to the imidazole radical. As a result, the imidazole radical is converted to neutral imidazole, and a component having a sulfur radical having a high polymerization initiating ability is generated. Thus, when the resin composition of the present invention is radiation sensitive, As a result, a shield film having a desired shape can be easily formed.

Examples of such thiol compounds include
Aromatic thiol compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole;
Aliphatic monothiol compounds such as 3-mercaptopropionic acid and methyl 3-mercaptopropionate;
Bifunctional or higher aliphatic thiol compounds such as pentaerythritol tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate) can be exemplified. Of these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.

  When a biimidazole compound and an amino sensitizer are used in combination in the resin composition, the addition amount of the amino sensitizer is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the biimidazole compound. More preferably, it is 1-20 mass parts. When the addition amount of the amino sensitizer is 0.1 to 50 parts by mass, when the resin composition of the present invention is radiation sensitive, the curing reactivity during exposure is further enhanced.

  Moreover, when using together a biimidazole compound, an amino-type sensitizer, and a thiol compound, as addition amount of a thiol compound, Preferably it is 0.1-50 mass parts with respect to 100 mass parts of biimidazole compounds, More preferably, it is 1-20 mass parts. By setting the addition amount of the thiol compound to 0.1 to 50 parts by mass, the curing reactivity at the time of exposure is further improved, and it becomes easier to obtain a shield film having a desired shape.

  [C] The radiation-sensitive polymerization initiator preferably contains at least one selected from the group consisting of an O-acyloxime compound and an acetophenone compound, and is selected from the group consisting of an O-acyloxime compound and an acetophenone compound. It is more preferable to contain at least one kind and a biimidazole compound.

  [C] The amount of the radiation-sensitive polymerization initiator used is preferably 5 to 200 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the [A] copolymer. [C] By making the usage-amount of a radiation sensitive polymerization initiator into 5-200 mass parts, when the resin composition of this invention is radiation sensitive, the curing reactivity at the time of exposure can be improved.

  Moreover, as a ratio of the O-acyloxime compound and the acetophenone compound in the radiation sensitive polymerization initiator of [C] radiation sensitive polymerization initiator, the total amount of the radiation sensitive polymerization initiator of [C] radiation sensitive polymerization initiator Is preferably 40% by mass or more, more preferably 45% by mass or more, and particularly preferably 50% by mass or more. By using the O-acyloxime compound and the acetophenone compound at such a ratio, high curing reactivity can be obtained even in the case of a low exposure amount, and as a result, a shield film having a more accurate shape can be formed. Become.

Other optional components In addition to the above [A] copolymer, [B] polymerizable compound and [C] radiation sensitive polymerization initiator, the resin composition of the present invention is within the range not impairing the desired effect. If necessary, additives such as [G] adhesion assistant and [H] surfactant can be contained.

  In the resin composition of the present invention, [G] adhesion assistant can be used to improve the adhesion between the shield film to be formed and the substrate. As such an adhesion assistant, a functional silane coupling agent is preferably used. Examples of functional silane coupling agents include silane coupling agents having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, and epoxy groups. Specific examples of functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ-glycidoxy. Examples include propyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

  [G] The adhesion assistant can be used alone or in admixture of two or more. [G] The amount of the adhesion assistant used is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass with respect to 100 parts by mass of the copolymer of [A] copolymer. [G] By making the usage-amount of adhesion | attachment adjuvant into 0.1-30 mass parts, the adhesiveness with respect to the base material of the shield film formed can be kept at a sufficiently high level.

  In the resin composition of the present invention, [H] surfactant can be used in order to further improve the coating property at the time of coating film formation. Examples of preferable surfactants include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

  Examples of fluorosurfactants include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,1) 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether and other fluoroethers; sodium perfluorododecylsulfonate; 1,1,2 , 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexaph Fluoroalkanes such as orodecane; sodium fluoroalkylbenzenesulfonates; fluoroalkyloxyethylene ethers; fluoroalkylammonium iodides; fluoroalkylpolyoxyethylene ethers; perfluoroalkylpolyoxyethanols; perfluoroalkylalkoxylates And fluorine-based alkyl esters.

  Commercially available products of these fluorosurfactants include BM-1000, BM-1100 (manufactured by BM CHEMIE), MegaFuck F142D, F172, F173, and F183 (manufactured by Dainippon Ink and Chemicals). , FLORARD FC-135, FC-170C, FC-430, FC-431 (manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-141 S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), FTX-218 ( Commercial products such as those manufactured by Neos Co., Ltd. can be mentioned.

  Examples of silicone surfactants are commercially available under the trade names SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (Toray Dow Corning -Silicone Co., Ltd.), KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), F-top EF301, EF303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), and the like.

  Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene dialkyl esters, (meth) acrylic acid copolymers, and the like.

  Examples of the polyoxyethylene alkyl ether include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and the like. Examples of the polyoxyethylene aryl ether include polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Examples of polyoxyethylene dialkyl esters include polyoxyethylene dilaurate and polyoxyethylene distearate. As an example of (meth) acrylic acid-based copolymers, Polyflow No. 57, no. 90 (manufactured by Kyoeisha Chemical Co., Ltd.).

  [H] Surfactants can be used alone or in admixture of two or more. [H] The amount of the surfactant used is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the [A] copolymer. By making the usage-amount of surfactant into 0.01-5 mass parts, generation | occurrence | production of the film | membrane roughness of the shield film surface formed is suppressed, and a uniform coating film can be formed.

Resin Composition The resin composition of the present invention comprises the above [A] copolymer, [B] polymerizable compound, and [C] radiation sensitive polymerization initiator, and optional components ([G] adhesion assistant and / or Or [H] surfactant, etc.) are mixed uniformly. Usually, the resin composition is preferably used after being dissolved in an appropriate solvent and stored in a solution state. For example, a resin composition in a solution state is prepared by mixing [A] copolymer, [B] polymerizable compound and [C] radiation-sensitive polymerization initiator, and optional components in a predetermined ratio in a solvent. can do.

  Solvents used for preparing the resin composition include the above-mentioned [A] copolymer, [B] polymerizable compound and [C] radiation sensitive polymerization initiator, and optional components ([G] adhesion assistant and / or Or [H] surfactant, etc.) are not particularly limited as long as each component is uniformly dissolved and does not react with each component. As such a solvent, the thing similar to the solvent illustrated as a solvent which can be used in order to manufacture a [A] copolymer can be mentioned.

  Among such solvents, for example, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters, diethylene glycol alkyls, from the viewpoints of solubility of each component, non-reactivity with each component, ease of film formation, etc. Ether, propylene glycol monoalkyl ether, and propylene glycol monoalkyl ether acetate are preferably used. Among these, for example, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, methyl 2- or 3-methoxypropionate, ethyl 2- or 3-ethoxypropionate, or 3-methoxybutyl acetate can be particularly preferably used.

  Furthermore, in order to improve the in-plane uniformity of the film thickness of the coating film to be formed, a high boiling point solvent can be used in combination with the solvent. Examples of the high-boiling solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzyl. Ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate , Phenyl cellosolve acetate and the like. Of these high boiling solvents, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferred.

  When a high boiling point solvent is used in combination as the solvent for the resin composition, the amount used can be 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, based on the total amount of the solvent. By setting the use ratio of the high boiling point solvent to 50% by mass or less, it is possible to improve the film thickness uniformity of the coating film and at the same time suppress the decrease in radiation sensitivity.

  When preparing the resin composition in a solution state, components other than the solvent in the solution (that is, [A] copolymer, [B] polymerizable compound and [C] radiation sensitive polymerization initiator, and other optional components) The ratio of (total amount) can be arbitrarily set according to the purpose of use, desired film thickness, etc., but is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 35%. % By mass. The solution of the resin composition thus prepared can be used after being filtered using a Millipore filter having a pore size of about 0.2 μm.

Formation of Shield Film for Dye-Sensitized Solar Cell Electrode Next, a method for forming the shield film of the present invention using the above resin composition will be described. The method of forming the shield film is as follows:
(1) The coating film of the resin composition according to claim 6, so that at least the entire metal wiring layer is covered with the laminate including the conductive substrate and the metal wiring layer on the surface side of the conductive substrate. Forming step,
(2) A method for forming a shield film for an electrode for a dye-sensitized solar cell, comprising a step of heating the coating film formed in step (1).
Are included in this order.

(1) Step of forming a coating film of a resin composition on a substrate In this step, the resin composition of the present invention is formed on a laminate including a conductive substrate and a metal wiring layer on the surface side of the conductive substrate. After applying the solution of the product, the coating surface is heated (prebaked) to form a coating film. The application is performed so that at least the entire metal wiring layer on the surface side of the conductive substrate is covered. Prebaking conditions vary depending on the types and blending ratios of the components, but are preferably about 70 to 110 ° C. for 1 to 10 minutes. The film thickness after pre-baking of the coating film is preferably 0.1 to 5.0 μm, more preferably about 0.3 to 2.0 μm.

  The solid content concentration of the composition solution used for coating is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 15 to 35% by mass. The method for applying the composition solution is not particularly limited, and for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an ink jet coating method is adopted. can do. Among these coating methods, a bar coating method or a slit die coating method is particularly preferable. By applying the composition solution by the bar coating method or the slit die coating method, a defect-free shield film can be formed even on a substrate having a stepped metal wiring layer.

(2) Heating Step After the step (1) above, the coating film is subjected to a heat treatment (post-bake treatment) with an appropriate heating device such as a hot plate or a clean oven. The heating temperature is preferably about 150 to 250 ° C., and the heating time is preferably about 5 to 30 minutes when using a hot plate, and about 30 to 90 minutes when using a clean oven. In this way, a shield film having a desired shape can be formed on the dye-sensitized solar cell electrode.

  Thus, a shield film can be formed on a substrate in an electrode for a dye-sensitized solar cell by forming a shield film by a coating film forming step and a heating step using a resin composition. The formation method requires only a relatively simple process of applying and heating, and can form a shield film at low cost.

As another method for forming the shield film of the electrode for the dye-sensitized solar cell of the present invention, (1 ′) a conductive substrate and a laminate including a metal wiring layer on the surface side of the conductive substrate, Forming a coating film of the resin composition having radiation sensitivity so that the entire wiring layer is covered;
(3) A step of irradiating only the part laminated on the metal wiring layer of the coating film formed in step (1 ′),
(4) A step of developing the coating film irradiated with radiation in the step (3), and (2 ′) a step of heating the coating film developed in the step (4) are included in this order.

(1 ′) Step of forming a coating film of a resin composition having radiation sensitivity on a substrate In this step, on a laminate including a conductive substrate and a metal wiring layer on the surface side of the conductive substrate. After coating the solution of the resin composition having radiation sensitivity, the coated surface is heated (prebaked) to form a coating film. The application is performed so that at least the entire metal wiring layer on the surface side of the conductive substrate is covered. Prebaking conditions vary depending on the types and blending ratios of the components, but are preferably about 70 to 110 ° C. for 1 to 10 minutes. The film thickness after pre-baking of the coating film is preferably 0.1 to 5.0 μm, more preferably about 0.3 to 2.0 μm.

  The solid content concentration of the composition solution used for coating is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 15 to 35% by mass. The method for applying the composition solution is not particularly limited, and for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an ink jet coating method is adopted. can do. Among these coating methods, a bar coating method or a slit die coating method is particularly preferable. By applying the composition solution by the bar coating method or the slit die coating method, a defect-free shield film can be formed even on a substrate having a stepped metal wiring layer.

(3) Step of irradiating the coating film Next, only a portion of the coating film formed in the above step (1 ′) laminated on the metal wiring layer is exposed through a photomask having a predetermined pattern. To do. Examples of the radiation used for exposure include visible light, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays. Among these radiations, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation including ultraviolet light having a wavelength of 365 nm is particularly preferable.

The exposure dose is preferably 100 to 10,000 J / m ² , more preferably 500 to 500, as a value obtained by measuring the intensity of radiation at a wavelength of 365 nm using a luminometer (“OAI model 356” manufactured by Optical Associates Inc.). 3,000 J / m ² .

(4) Development Step Next, the coating film irradiated with radiation in the step (3) is developed to remove the non-irradiated portion of the radiation and form a predetermined pattern. As the developer used for development, an aqueous solution of an alkali (basic substance) is preferably used. Examples of alkalis that can be used include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Etc. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the alkaline aqueous solution.

  As a developing method, any of a liquid piling method, a dipping method, a shower method and the like may be used, and the developing time is preferably about 10 to 180 seconds. After development, for example, after washing with running water for 30 to 90 seconds, a desired pattern is formed by, for example, air drying with compressed air or compressed nitrogen.

(2 ′) Heating Step After the developing step (4) above, a heat treatment (post-bake treatment) is performed on the patterned coating film by a suitable heating device such as a hot plate or a clean oven. The heating temperature is preferably about 150 to 250 ° C., and the heating time is preferably about 5 to 30 minutes when using a hot plate, and about 30 to 90 minutes when using a clean oven. In this way, a shield film having a desired shape can be formed on the dye-sensitized solar cell electrode.

  Thus, using the resin composition having radiation sensitivity, a pattern is formed by a coating film forming process, a radiation irradiation process (exposure process), a developing process, and a heating process, so that an electrode for a dye-sensitized solar cell is formed. A shield film having a uniform thickness can be formed only on the portion where the metal wiring exists on the substrate having the metal wiring level difference. According to such a method, it is possible to accurately form the shield film only in the portion where the metal wiring exists, and it is ensured that the shield film is erroneously formed on the conductive substrate or the oxide semiconductor layer. Therefore, the shield film is not lost on the metal wiring. Moreover, since the metal wiring having the shield film formed in this way has no defect in the shield film, it can exhibit high corrosion resistance against the electrolytic solution.

  EXAMPLES Hereinafter, although a synthesis example and an Example demonstrate this invention further more concretely, this invention is not limited to a following example. In addition, the number average molecular weight and molecular weight distribution (Mw / Mn) measured in the following use GPC chromatograph "HLC-8020" (one TSKgel α-M, one TSKgel α-2500) manufactured by Tosoh Corporation. , Flow rate: 1.0 ml / min, elution solvent: N, N-dimethylformamide, column temperature: measured by gel permeation chromatography (GPC) method under analysis conditions of 35 ° C.

Production of copolymer [Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 40 parts by mass of glycidyl methacrylate, 18 parts by mass of styrene, 20 parts by mass of methacrylic acid, and 22 parts by mass of N-cyclohexylmaleimide were charged, and after the atmosphere was replaced with nitrogen, stirring was started gently. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-1). The solid content concentration of the obtained polymer solution was 33.1% by mass. The number average molecular weight of the obtained copolymer was 7,000, and the molecular weight distribution (Mw / Mn) was 2.

[Synthesis Example 2]
A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 40 parts by mass of 3- (methacryloyloxyethyl) oxetane, 10 parts by mass of styrene, 30 parts by mass of methacrylic acid and 20 parts by mass of N-cyclohexylmaleimide were charged. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-2). The solid content concentration of the obtained polymer solution was 33.1% by mass. The number average molecular weight of the obtained copolymer was 7,300, and the molecular weight distribution (Mw / Mn) was 2.

[Synthesis Example 3]
A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2′-azobisisobutyronitrile and 250 parts by mass of butyl methoxyacetate, followed by 18 parts by mass of methacrylic acid and tricyclomethacrylate [5.2. 1.0 ^2,6 ] 25 parts by mass of decan-8-yl, 5 parts by mass of styrene, 30 parts by mass of methacrylic acid-2-hydroxyethyl ester and 22 parts by mass of benzyl methacrylate were substituted with nitrogen, and then gently The temperature of the solution was raised to 80 ° C. while stirring and the polymerization was carried out while maintaining this temperature for 5 hours, whereby a polymer solution containing a copolymer (β-1) having a solid content concentration of 28.8% by mass was obtained. Obtained.

Next, 14 parts by mass of 2-methacryloyloxyethyl isocyanate (“Karenz MOI” manufactured by Showa Denko KK) and 0.1 part of 4-methoxyphenol were added to the polymer solution containing the copolymer (β-1). After the addition, the mixture was reacted by stirring at 40 ° C. for 1 hour and further at 60 ° C. for 2 hours. Progress of the reaction between the isocyanate group derived from 2-methacryloyloxyethyl isocyanate and the hydroxyl group of the copolymer (β-1) was confirmed by IR (infrared absorption) spectrum. In the IR spectra of the polymer solution containing the initial copolymer (β-1), the solution after reaction for 1 hour, and the solution after reaction at 40 ° C. for 1 hour and further at 60 ° C. for 2 hours, 2-methacryloyloxyethyl isocyanate It was confirmed that the peak in the vicinity of 2270 cm ⁻¹ derived from the isocyanate group was decreasing. By this reaction, a polymer solution containing a copolymer (A-3) having a solid content concentration of 30.0% by mass was obtained. The number average molecular weight of the obtained copolymer was 7,000, and the molecular weight distribution (Mw / Mn) was 2.

[Comparative Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 10 parts by mass of styrene and 90 parts by mass of methyl methacrylate were charged, and after the atmosphere was replaced with nitrogen, stirring was started gently. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (a-1). The obtained polymer solution had a solid content concentration of 34.0% by mass. The number average molecular weight of the obtained copolymer was 8,500, and the molecular weight distribution (Mw / Mn) was 2.

Preparation of resin composition [Example 1]
[A] As a copolymer, a polymer solution containing the copolymer (A-1) of Synthesis Example 1 (amount corresponding to 100 parts by mass (solid content) of the copolymer), [B] as a polymerizable compound ( B-1) 100 parts by mass of dipentaerythritol hexaacrylate (“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.), (C-1) 2-dimethylamino-2- (C) as a radiation-sensitive polymerization initiator 20 parts by mass of 4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (“Irgacure 379” manufactured by Ciba Specialty Chemicals), [G] adhesion assistant “FTX-218” manufactured by Neos Co., Ltd. which is (G-1) 10.0 parts by mass of γ-glycidoxypropyltrimethoxysilane as an agent and (H-1) surfactant as [H] surfactant. Add 0.2 parts by weight Further after the solid concentration was added propylene glycol monomethyl ether acetate so that 22 mass%, was then filtered through a Millipore filter having a pore size of 0.5μm to prepare a solution (S-1) of the resin composition.

[Examples 2 to 13, Comparative Example 1]
[A] to [C] and other optional components, except that the types and amounts shown in Table 1 were used, in the same manner as in Example 1, except that the resin composition solutions (S-2) to (S -13) and (s-1) were prepared.

Preparation of an electrode substrate of a dye-sensitized solar cell An electrode substrate of a dye-sensitized solar cell was prepared according to the procedure shown in FIG.
(1) Preparation of transparent conductive substrate A saturated aqueous solution of ammonium fluoride was added and dissolved in an ethanol solution of tin (IV) chloride pentahydrate to prepare a raw material solution for FTO (fluorine-added tin oxide) film. Next, the substrate 1 (high strain point glass) is placed on a 350 ° C. heater plate so that the back surface of the substrate 1 is in contact with the substrate. A transparent conductive film 2 (film thickness 0.05 to 5 μm) made of FTO was formed by spraying on the surface. In this way, a transparent conductive substrate having the transparent conductive film 2 formed on the surface of the substrate 1 was obtained (see FIG. 1A). The film thickness of the transparent conductive film 2 was 0.2 μm.

(2) Formation of a metal wiring layer On the transparent conductive substrate on which the transparent conductive film 2 was formed in the above (1), a grid-like stencil was used, and a screen printing apparatus (“HR-” manufactured by Neurong Seimitsu Kogyo Co., Ltd.) was used. 320 "formed a lattice-patterned coating film of a silver paste for printing (with a volume resistivity after sintering of 3 × 10 ^-6 [Ω · cm]), and then allowed to stand at 25 ° C. for 10 minutes. After that, it was dried at 130 ° C. for 10 minutes, and further fired at a maximum temperature of 510 ° C. for 2 hours to form a grid-like metal wiring layer 3 made of silver, where the metal wiring layer 3 has a circuit width ( The design value was set to 300 μm and the film thickness was set to 10 μm, and the electrode was formed in a shape extending in a grid pattern from the current collecting terminals (see FIG. 1B).

(3) Formation of porous oxide semiconductor layer Titanium oxide paste (solid content 20) is formed between the metal wiring layers 3 on the transparent conductive substrate on which the transparent conductive film 2 is formed by screen printing similar to (2) above. (Mass% ethanol dispersion) was applied. Subsequently, it baked at 450 degreeC for 1 hour, and the porous oxide semiconductor layer 4 was formed between the grid | lattice-like metal wiring layers 3 (refer FIG.1 (c)).

(4) Formation of shield film of metal wiring layer Laminate prepared in (3) above using an automatic coating device for bar coating (PI-1210 automatic coating device type I manufactured by Tester Sangyo Co., Ltd.) A coating film 5 of the resin composition solution (S-1) of Example 1 was formed on the entire surface (see FIG. 1D), and then the solvent was evaporated and dried at 90 ° C. for 5 minutes. Ultraviolet rays from a high-pressure mercury lamp were irradiated through a photomask having the same design size as the lattice-shaped stencil used in (2) so that the exposure amount at 365 nm was 1,000 J / m ² . The film thickness of the coated film after exposure was 0.6 μm. Next, this coating film was developed with an aqueous potassium hydroxide solution, and further baked in a clean oven at 180 ° C. for 1 hour. As a result, an electrode substrate 7 having a shield film 6 was formed on the surface of the grid-like metal wiring layer (see FIG. 1E). The thickness of the shield film 6 was 0.5 μm. Hereinafter, this electrode substrate is referred to as “sample electrode substrate 1”.

  Instead of the resin composition solution (S-1) of Example 1 and using the resin composition solutions (S-2) to (S-12) of Examples 2 to 12, the same manner as above, The electrode substrate was created by performing the steps (1) to (4). These electrode substrates are referred to as “sample electrode substrate 2” to “sample electrode substrate 12”. Moreover, it replaces with the solution (S-1) of the resin composition of Example 1, and uses the resin composition solution (S-13) of Example 13 and does not carry out the exposure step and the development step. In the same manner as described above, an electrode substrate was prepared. This electrode substrate is referred to as “sample electrode substrate 13”.

  20 parts by mass of ITO fine particles (“X-500” series manufactured by Sumitomo Metal Mining Co., Ltd.) are dispersed with respect to 100 parts by mass of the resin composition solution (s-1) of Comparative Example 1 and contain ITO fine particles. A resin composition solution was prepared. The steps (1) to (4) are performed in the same manner as described above except that the resin composition solution containing the ITO fine particles is used instead of the resin composition solution (S-1) of Example 1. Thus, an electrode substrate was prepared. This electrode substrate is referred to as “comparative sample electrode substrate 1”. In addition, since the resin composition of Comparative Example 1 does not have radiation sensitivity, exposure and development in the step (4) were omitted.

  The steps (1) to (3) were performed, and an electrode substrate was prepared without performing the step (4) (formation of a shield film) (Comparative Example 2). Such an electrode substrate having no shield film is referred to as “comparative sample electrode substrate 2”.

In Table 1, the abbreviations indicating the respective compounds represent the following.
B-1: Dipentaerythritol hexaacrylate (“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.)
B-2: Succinic acid mono- [3- (3-acryloyloxy-2,2-bis-acryloyloxymethyl-propoxy) -2,2-bis-acryloyloxymethyl-propyl] ester C-1: 2-dimethyl Amino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (“Irgacure 379” manufactured by Ciba Specialty Chemicals)
C-2: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (manufactured by Ciba Specialty Chemicals Irgacure OX02 ")
G-1: γ-glycidoxypropyltrimethoxysilane H-1: Fluorine-based surfactant (“FTX-218” manufactured by Neos Co., Ltd.)

Preparation of dye-sensitized solar cell Using the sample electrode substrates 1 to 13 and comparative sample electrode substrates 1 and 2 described above, a dye-sensitized solar cell (photoelectric conversion element) was prepared according to the procedure shown in FIG. .
(A) Adsorption of photosensitizing dye Each of the sample electrode substrates 1 to 13 and the comparative sample electrode substrates 1 and 2 is a acetonitrile / t-butanol solution of a photosensitizing dye ruthenium bipyridine complex (N719 dye) having a concentration of 5% by mass. In (mass ratio 1: 1), the photosensitizing dye was adsorbed on the surface of the porous oxide semiconductor layer of the sample electrode substrate by being immersed for 24 hours or more at 25 ° C., and the photosensitizing dye was supported. A working electrode having a porous oxide semiconductor layer 8 was obtained (see FIG. 2F).

(B) Attaching the counter electrode and injecting the electrolyte solution A platinum layer having a sputtered Ti foil on the surface was used as the counter electrode 9, and this was overlaid on the working electrode prepared in (a) above. In a circulating and purifying glove box filled with an inert gas, the iodine electrolyte solution 10 was injected with a dropper from the gap between the working electrode and the counter electrode. As the iodine electrolyte solution 10, 0.5 M 1,2-dimethyl-3-propylimidazolium iodide and 0.05 M iodine were dissolved in methoxyacetonitrile, and an appropriate amount of lithium iodide and 4-t What added-butyl pyridine was used (refer FIG.2 (g)).

(C) Sealing Adhesive film 11 (“Surlin” manufactured by DuPont) is used and both electrodes are bonded together using a 120 ° C. heating press so that the electrolyte does not spill from the sample prepared in (b) above. And a dye-sensitized solar cell (corresponding to each of the sample electrode substrates 1 to 13 and the comparative sample electrode substrate 1) was prepared (see FIG. 2 (h)).

Evaluation of Dye-Sensitized Solar Cell (I) Confirmation of Shield Film Defect on Sample Electrode Substrate About Sample Electrode Substrates 1 to 13 and Comparative Sample Electrode Substrate 1 having a Shield Film on Metal Wiring The appearance of the shield film surface was observed under the lamp. The portion where the shield film was not formed was defined as a defect in the shield film, and the presence or absence of the defect was evaluated. The case where there was no defect in the shield film was marked as ◯, and the case where the defect in the shield film was confirmed was marked as x. The results are shown in Table 1.

(II) Measurement of photoelectric conversion efficiency (η) The output characteristics of the dye-sensitized solar cell were measured by a method based on the output measurement method of the silicon crystal solar cell of JIS C8913: 1998. Combined with a 300W solar simulator (“YSS-80” manufactured by Yamashita Denso Co., Ltd.) and an air mass filter equivalent to AM1.5G, adjusted to a light intensity of 100 mW / cm ^{2 with} a secondary reference Si solar cell, and used as a measurement light source, Potentiostat (“HSV-100” manufactured by Hokuto Denko Co., Ltd.) is used while irradiating the dye-sensitized solar cell (corresponding to each of sample electrode substrates 1 to 13 and comparative sample electrode substrates 1 and 2). The I-V curve characteristics were measured, and the open circuit voltage (Voc; unit V), short circuit current (Isc; unit mA / cm ² ), and fill factor (FF; no unit) obtained from the IV curve characteristics were measured. Derived. And the short circuit current density (Jsc; unit mA / cm < ² >) and the photoelectric conversion efficiency ((eta); unit%) were computed using the following formula | equation (1), (2). If the value of the photoelectric conversion efficiency calculated in this way is 4% or more, it can be said that the corrosion of the metal wiring does not occur, the iodine electrolyte solution does not fade, and the photoelectric conversion efficiency is good. The results are shown in Table 1. Here, AM1.5G represents the distance that sunlight passes through the atmosphere. The standard is AM1.0G, which is the distance that sunlight just below the equator passes through the atmosphere, and AM1.5G corresponds to the value in Tokyo.

(III) Evaluation of corrosion resistance of metal wiring having shield film Immediately after the measurement of the photoelectric conversion efficiency (η) of (II) above, the appearance inspection of the metal wiring having the shield film was performed. Observe the metal wiring with the naked eye and check the corrosion and discoloration of the wiring. If there is no change, “Good / Good”; if there is a change (corrosion or discoloration), “Fail / ×” evaluated. The results are shown in Table 1.

  As is clear from the results shown in Table 1, the dye-sensitized solar cells (Examples 1 to 12) having a shield film formed using the resin composition having radiation sensitivity are the resins of the prior art. Compared to a dye-sensitized solar cell having a shield film formed using the composition (Comparative Example 1) and a dye-sensitized solar cell having no shield film (Comparative Example 2), the photoelectric conversion efficiency is good. At the same time, it has been found that there is no defect in the shield film and that it has high corrosion resistance to the electrolyte. In particular, from the results of Examples 1 to 4, it was found that the photoelectric conversion efficiency was further improved by using [G] adhesion assistant and / or [H] surfactant, which are optional components. Moreover, from the results of Examples 4 to 12, it was found that good characteristics can be obtained even when various [A] to [C] are used. As described above, by using the radiation-sensitive resin composition, a shield film is accurately formed only on the portion where the metal wiring exists on the substrate having the metal wiring step in the dye-sensitized solar cell electrode. It can be formed, and high corrosion resistance can be obtained while maintaining excellent photoelectric conversion efficiency. Further, from the results of Example 13, the shield film formed using the resin composition having no radiation sensitivity of the present invention has no defects and has high corrosion resistance against the electrolytic solution, and has this shield film. It was found that the dye-sensitized solar cell also has good photoelectric conversion efficiency.

  In the resin composition having radiation sensitivity, a pattern is formed by exposure / development using radiation sensitivity, and therefore metal wiring exists on a substrate having a step of metal wiring in a dye-sensitized solar cell electrode. It is possible to form a shield film having a uniform thickness only on the portion to be formed. Moreover, since the said resin composition which has radiation sensitivity can form a shield film correctly only in the location of a metal wiring, there is no film | membrane defect | deletion and it has sufficient corrosion resistance. The dye-sensitized solar cell electrode having this shield film has high photoelectric conversion efficiency. Therefore, the resin composition having radiation sensitivity can be suitably used as a material for forming a shield film of a dye-sensitized solar cell electrode. Furthermore, the resin composition having no radiation sensitivity of the present invention includes a resin composition capable of forming a shield film at a low cost by only a relatively simple process such as a coating process and a heating process, and a shield film having this corrosion resistance. It is possible to provide a dye-sensitized solar cell electrode having excellent photoelectric conversion efficiency.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Transparent conductive film 3 Metal wiring layer 4 Porous oxide semiconductor layer 5 Coating film 6 Shielding film 7 Electrode substrate having a shielding film 8 Porous oxide semiconductor layer 9 carrying a photosensitizing dye 9 Counter electrode 10 Iodine Electrolyte solution 11 Adhesive film

Claims (12)

A dye-sensitized solar cell electrode comprising a shield film made of a cured product of a resin composition,
[A] a copolymer having at least one reactive functional group selected from the group consisting of [A] carboxyl group, epoxy group and (meth) acryloyl group , and [B] ethylenically unsaturated disilane. A dye-sensitized solar cell electrode, comprising a polymerizable compound having a double bond . [B] The polymerizable compound having an ethylenically unsaturated double bond is at least one selected from the group consisting of monofunctional (meth) acrylates, bifunctional (meth) acrylates, and trifunctional or higher functional (meth) acrylates. The electrode for dye-sensitized solar cells according to claim 1 . The dye-sensitized solar cell electrode according to claim 1 or 2 , wherein the resin composition further contains a [C] radiation-sensitive polymerization initiator. [C] The dye-sensitized solar cell electrode according to claim 3 , wherein the radiation-sensitive polymerization initiator is an O-acyloxime compound and / or an acetophenone compound. [A] a copolymer having at least one reactive functional group selected from the group consisting of a carboxyl group, an epoxy group and a (meth) acryloyl group , and [B] a polymerizability having an ethylenically unsaturated double bond A resin composition for forming a shield film for a dye-sensitized solar cell electrode, comprising a compound. The resin composition according to claim 5 , further comprising [C] a radiation sensitive polymerization initiator . [B] The polymerizable compound having an ethylenically unsaturated double bond is at least one selected from the group consisting of monofunctional (meth) acrylates, bifunctional (meth) acrylates, and trifunctional or higher functional (meth) acrylates. The resin composition according to claim 5 or 6 . [C] The resin composition according to claim 6 or 7 , wherein the radiation-sensitive polymerization initiator is an O-acyloxime compound and / or an acetophenone compound. Dye-sensitized solar cell electrode of the shielding film formed from the resin composition according to any one of claims 5 to claim 8. A dye-sensitized solar cell comprising the shield film according to claim 9 . (1) The coating film of the resin composition according to claim 5 , so that at least the entire metal wiring layer is covered with the laminate including the conductive substrate and the metal wiring layer on the surface side of the conductive substrate. And (2) a method for forming a shield film for an electrode for a dye-sensitized solar cell, the method including a step of heating the coating film formed in step (1). (1 ′) Any one of claims 6 to 8 , wherein at least the entire metal wiring layer is covered with the laminate including the conductive substrate and the metal wiring layer on the surface side of the conductive substrate. A step of forming a coating film of the resin composition described in 1.
(3) A step of irradiating only the part laminated on the metal wiring layer of the coating film formed in step (1 ′),
(4) A dye-sensitized solar cell electrode comprising: a step of developing the coating film irradiated with radiation in step (3); and (2 ′) a step of heating the coating film developed in step (4). A method of forming a shield film.

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