TWI459611B - Electrode for dye-sensitive solar cell, resin composition for forming shield film of electrode for dye-sensitive solar cell, shield film and method for forming the same as well as dye-sensitive solar cell - Google Patents

Description

Resin composition for forming a dye-sensitized solar cell, a film for forming a film for dye-sensitized solar cells, a masking film, a method for forming the same, and a dye-sensitized solar cell

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

A dye-sensitized solar cell is a material developed by Gratzler et al. in Switzerland. Because of its high photoelectric conversion efficiency and low manufacturing cost, it is attracting attention as a new type of solar cell (see, for example, see Japanese Patent Laid-Open No. 1-220380; M. Graetzel et al., Nature, UK, 1991, No. 353, p. 737). The dye-sensitized solar cell includes a working electrode having an oxide semiconductor porous film on which a photo-sensitized dye is formed, which is formed of oxide semiconductor fine particles, and a counter electrode disposed opposite to the working electrode, on the transparent electrode substrate, And an electrolyte layer (charge moving layer) formed by filling an electrolyte between the working electrode and the counter electrode. In such a dye-sensitized solar cell, an oxide semiconductor fine particle is sensitized by absorbing a light sensitizing dye of incident light such as sunlight, and is used as a photoelectric conversion element that converts light energy into electric power.

As a transparent electrode substrate which can be used for a dye-sensitized solar cell, a transparent conductive film such as tin-doped indium oxide (ITO) or fluorine-doped tin oxide (FTO) is usually used on the surface of a substrate such as a high strain point glass. The resulting substrate was formed into a film. Tin-doped indium oxide (ITO) or fluorine-doped tin oxide (FTO) is preferably used from the viewpoints of transparency, resistance to corrosion by an electrolytic solution, and ease of film formation. However, since the specific resistance of ITO or FTO is about 10 ^-4 [Ω‧cm], and it shows a value of about 100 times the specific resistance of a metal such as silver or gold, it is especially work as a large area. When the electrode is used, it is one of the causes of a decrease in photoelectric conversion efficiency.

As a method of reducing the electric 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 can be sufficiently reduced, the light absorption by the transparent conductive film is changed. Big. At this time, the transmission efficiency of incident light in the transparent conductive film is remarkably lowered, and the photoelectric conversion efficiency is likely to be lowered. As a solution to this problem, the metal wiring is provided on the surface of the transparent electrode substrate to the extent that the aperture ratio is not significantly impaired, and attempts are made to reduce the electric resistance of the transparent electrode substrate (see Japanese Patent Laid-Open Publication No. 2003-203681 ).

However, at this time, corrosion of the metal wiring occurs due to the electrolytic solution, and as time passes, the electric resistance of the transparent electrode substrate becomes large, resulting in a decrease in photoelectric conversion efficiency. Therefore, as described above, when the metal wiring is provided on the surface of the transparent electrode substrate, at least the surface portion of the metal wiring needs to be protected by a certain shielding layer. Further, the shielding layer is required to cover the metal wiring densely, and is excellent in corrosion resistance to the electrolytic solution constituting the electrolyte layer.

In view of the above-mentioned situation, it is disclosed in Japanese Laid-Open Patent Publication No. 2005-197176 that the metal wiring provided in the electrode for dye-sensitized solar cells is protected from corrosion by the electrolyte, and is on the uppermost layer of the electrode. A technique of forming an organic film made of a transparent resin such as an acrylic resin, a polyester resin, or a polyurethane resin containing conductive particles (ITO, ATO, ZnO, etc.). However, since the conductive particles are unevenly dispersed in the transparent resin solution, it is difficult to form a coating film having a uniform thickness on a substrate having a difference in metal wiring. As a result, a defect of the organic film occurs, or an organic film is formed also on the portion where the metal wiring is not present, and thus there is a defect that the photoelectric conversion efficiency is lowered.

Further, JP-A-2005-197176 discloses that an organic film formed of a transparent resin such as an acrylic resin, a polyester resin, or a polyurethane resin is formed and covered with a dye sensitization. A technique of a surface portion of a metal wiring provided in an electrode for a solar cell. However, for a substrate having a difference in metal wiring, it is very difficult to accurately apply a resin composition only on a portion where metal wiring is present by a method of screen printing or gravure printing. When such a coating method is employed, an organic film is formed on a part of the metal wiring, or an organic film is formed on an unnecessary portion where the metal wiring is not present, so that there is still a defect that causes a decrease in photoelectric conversion efficiency. .

Therefore, it has been strongly desired to develop a masking film which can accurately coat a substrate having a metal wiring step difference in a dye-sensitized solar cell, and can form a masking film which maintains high photoelectric conversion efficiency and has excellent corrosion resistance. Use the composition. In addition, the substrate having the metal wiring height difference in the dye-sensitized solar cell can be applied by a bar coating method, a spin coating method, a slit die coating method, or the like, and then exposed and developed through a mask to form a mask. The resin composition of the film is not known.

current technology

[Patent Document 1] Japanese Patent Laid-Open No. 1-220380

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-203681

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2005-197176

[Non-Patent Document 1] M. Graetzel et al., Nature, UK, 1991, No. 353, p. 737

The present invention has been made in view of the above circumstances, and provides an electrode for a dye-sensitized solar cell in which a metal wiring layer is formed on a substrate, which can be accurately coated on a substrate having a metal wiring height difference, and can be formed to maintain high A radiation-sensitive resin composition having a photoelectric conversion efficiency and a masking film having excellent corrosion resistance due to corrosion by an electrolytic solution. Further, there is provided a resin composition capable of forming a mask film at a low cost by only a relatively simple step of a coating step and a heating step, and a dyeing film containing the masking film having corrosion resistance and excellent photoelectric conversion efficiency An electrode for a solar cell.

The present invention is directed to an electrode for a dye-sensitized solar cell, comprising a masking film formed of a resin composition, wherein the resin composition contains [A] having a carboxyl group and a ring. A copolymer of at least one reactive functional group in the group consisting of an oxy group and a (meth) acrylonitrile group.

By forming the mask film of the above resin composition, it is possible to form the mask film at a low cost by only a relatively simple step of the coating step and the heating step, and the mask film is excellent in corrosion resistance to the electrolyte solution, and the masking is used. The electrode for dye-sensitized solar cells of the 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 polymerizable compound having an ethylenically unsaturated double bond as the [B] is preferably selected from a monofunctional group ( At least one of the group consisting of a methyl acrylate, a bifunctional (meth) acrylate, and a trifunctional or higher (meth) acrylate. Further, the resin composition preferably contains a [C] radiation-sensitive polymerization initiator, and as the [C] radiation-sensitive polymerization initiator, an O-mercaptopurine compound and/or an acetophenone compound are preferable. By using these compounds, it is possible to obtain a mask film which is free from defects of the film and which is excellent in corrosion resistance of the metal wiring.

Further, the resin composition according to the present invention is a copolymer containing [A] at least one reactive functional group selected from the group consisting of a carboxyl group, an epoxy group, and a (meth)acryl fluorenyl group. A resin composition for forming a mask film for an electrode for a dye-sensitized solar cell. The resin composition can be preferably used as a masking film forming material for an electrode for a dye-sensitized solar cell.

The resin composition may further contain:

[B] a polymerizable compound having an ethylenically unsaturated double bond, and

[C] Radiation-sensitive linear polymerization initiator.

Since the resin composition has a high-sensitivity radioactivity, it can be used only on the portion where the metal wiring is present on the substrate having the metal wiring height difference when forming a mask film for the dye-sensitized solar cell electrode. A masking film having a uniform thickness is formed. Therefore, the shielding film formed of the resin composition can effectively protect the metal wiring from corrosion caused by the electrolytic solution, and the electrode for the dye-sensitized solar cell using the shielding film can maintain high photoelectric conversion efficiency.

The polymerizable compound having an ethylenically unsaturated double bond as [B] is preferably selected from the group consisting of a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, and a trifunctional or higher (meth) acrylate. At least one of the constituent groups. Further, as the [C] radiation-sensitive polymerization initiator, an O-fluorenyl hydrazine compound and/or an acetophenone compound is preferred. By using these compounds, the polymerization reactivity at the time of exposure can be improved, and a masking film having an accurate shape and excellent corrosion resistance can be obtained.

Therefore, the masking film formed using the resin composition and the dye-sensitized solar cell (photoelectric conversion element) having the masking film can accurately exist only in the presence of metal wiring by radiation-sensitive exposure and development. A masking film is formed on the portion, thus having high photoelectric conversion efficiency.

A method for forming a masking film for an electrode for a dye-sensitized solar cell of the present invention comprises:

(1) a step of forming a coating film of a curable resin composition on a laminate having a conductive substrate and a metal wiring layer on the surface side of the conductive substrate to cover at least the entire metal wiring layer, and

(2) A step of heating the coating film formed in the step (1).

This formation method requires only a relatively simple step of the coating step and the heating step, so that the mask film can be formed at low cost.

A method for forming a masking film for an electrode for a dye-sensitized solar cell of the present invention includes:

(1') A coating film of the resin composition according to any one of claims 7 to 9 is formed on a laminate having a conductive substrate and a metal wiring layer on the surface side of the conductive substrate. a step of covering at least the entirety of the metal wiring layer,

(3) a step of irradiating only a portion of the coating film formed in the step (1') on the metal wiring layer,

(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).

In addition, the "surface" of the conductive substrate as used herein means a surface on the counter electrode side of the dye-sensitized solar cell including the conductive substrate. A method of forming a mask film using an electrode for dye-sensitized solar cells having a radiation-sensitive resin composition can form a pattern by radiation exposure and development, so that it can be easily present only A pattern of uniform thickness is formed on the portion of the metal wiring. Therefore, according to this method, it is possible to form a masking film which is sufficiently resistant to corrosion due to the electrolytic solution.

As described above, the resin composition having a radiation-sensitive linearity can be formed on the substrate having the metal wiring height difference in the electrode for dye-sensitized solar cells by forming a pattern by radiation exposure and development. A mask film having a uniform thickness is formed only on the portion where the metal wiring is present. Further, as described above, since the resin composition having radiation sensitivity is formed, it is possible to accurately form the mask film only at the position of the metal wiring, and thus it is possible to obtain a mask film having sufficient corrosion resistance. Therefore, the resin composition having a radiation-sensing property can be preferably used as a material for forming a masking film for an electrode for a dye-sensitized solar cell. Further, the present invention does not have a radiation-sensitive resin composition, and can provide a resin composition capable of forming a mask film at a low cost by only a relatively simple step of a coating step and a heating step, and contains the corrosion-resistant composition. An electrode for a dye-sensitized solar cell having excellent photoelectric conversion efficiency of a masking film.

Form of implementing the invention Pigment-sensitized solar cell

The dye-sensitized solar cell of the present invention mainly has a conductive substrate, a working electrode laminated on the conductive substrate, a counter electrode disposed on the working electrode, and a charge transporting layer disposed between the electrodes. The working electrode has a metal wiring layer having a shielding film around (except for 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 can be used. The light transmittance of the conductive substrate is preferably 50% or more, and particularly preferably 80% or more. As the conductive substrate, a substrate having conductivity itself or a substrate having a transparent conductive film on its surface can be used. As the substrate having a transparent conductive film on the surface, a ceramic honing plate or a plastic plate such as a glass plate, titanium oxide or aluminum oxide can be used. Examples of the plastic which can be used for the plastic sheet include triethylenesulfonyl cellulose, polyethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, and syndiotactic polystyrene. Polycarbonate, polyarylate, polyetherimide, polyfluorene, polyether oxime, cyclic polyolefin, phenoxy resin, brominated phenoxy resin, and the like.

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

In order to improve the current collecting efficiency of the conductive substrate and further improve the conductivity, a metal wiring layer is disposed on the conductive substrate. The metal wiring layer has a mask film formed as described above. Examples of the material of 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, and may be a pattern such as a lattice shape, a stripe shape, or a comb shape, and is preferably arranged such that light can be 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 exhibiting semiconductivity such as titanium oxide, tin oxide, tungsten oxide, zinc oxide, zirconium oxide or cerium oxide. The porous oxide semiconductor film is a porous body having a large number of fine pores inside and having fine irregularities on the surface, and has a thickness of 5 to 50 μm. The porous oxide semiconductor is typically provided at a position where the metal wiring layer is not disposed on the conductive substrate.

The oxide semiconductor porous film can be formed, for example, by a known coating method such as screen printing, inkjet printing, roll coating, blade coating, or spray coating, and has an average particle diameter of 5 to 50 nm dispersed. A method of applying a colloidal liquid or a dispersion of the metal oxide fine particles (using water and/or an organic solvent as a solvent) to a conductive substrate and sintering at 300 to 800 °C. A photosensitizing dye is supported on the oxide semiconductor porous film.

As the photosensitizing dye, a material having absorption to a visible light region and/or an infrared light region and having a higher minimum hole level than a semiconductor conduction band is preferable. Examples of the photosensitizing dye include an azo dye, a benzoquinone dye, a benzoquinone dye, a quinacridone dye, a squary acid dye, a cyanine dye, and an anthocyanin pigment. , part of the cyanine pigment, triphenylmethane pigment A coloring matter, a porphyrin-based coloring matter, a perylene-based coloring matter, an indigo-based coloring matter, a phthalocyanine-based coloring matter, a naphthalocyanine-based coloring matter, and a rhodamine-based coloring matter. Further, as the photosensitizing dye, it is preferred to use a metal complex compound dye. Examples of the metal constituting the metal complex compound dye include Cu, Ni, Fe, Co, V, Sn, Si, Ti, Ge, Cr, Zn, Ru, Mg, Al, Pb, Mn, In, Mo, and 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, Various metals such as Tc, Te, and Rh. As an example of a preferable metal complex compound 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 and the above-described conductive substrate, a single layer structure of a substrate having conductivity itself or a substrate having a counter electrode conductive film on the surface thereof can be used. In the latter case, as the conductive material and the substrate, the same material as in the case of the above-described conductive substrate can be used. As the counter electrode, a material having a catalytic ability capable of rapidly performing an oxidation reaction of I ₃ ^- ions or the like or a reduction reaction of other redox ions is preferably used. Examples of the counter electrode include a platinum electrode, a material subjected to platinum plating or platinum vapor deposition on the surface of the conductive material, a base metal, a base metal, cerium oxide, carbon, or the like.

The charge transporting layer is a layer containing a charge transporting material having an electron-compensating function for an oxide of a photosensitizing dye. Examples of the charge transporting material constituting the charge transporting layer include an electrolyte in which a redox counterion ion is dissolved, an electrolyte solution containing a normal temperature molten salt of a redox counterion, or the like, or a solution in which a redox counter ion is impregnated in a polymer base. A gel-like solid electrolyte or the like in a material or a low molecular gelling agent or the like.

Examples of the redox counterion include a system containing a redox equilibrium ion such as an I ^- /I ₃ ^- system or a Br ^- /Br ₃ ^- system, ferrocyanate / iron cyanide, ferrocene / two a metal redox system such as a metal complex compound such as a ferrocenium ion or a cobalt complex compound; an organic redox system such as an alkylthiol-alkyl disulfide, a viologen pigment or a hydroquinone/benzophenone; Sulfur compounds such as sodium polysulfide, alkyl mercaptan/alkyl disulfide, and the like. Examples of the solvent include carbonate compounds such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate; 3-methyl-2- Heterocyclic compound such as oxazolidinone; An ether compound such as an alkane or a diethyl ether; a chain ether such as ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether or polypropylene glycol dialkyl ether; methanol, ethanol, and B An alcohol such as a glycol monoalkyl ether, a propylene glycol monoalkyl ether, a polyethylene glycol monoalkyl ether or a polypropylene glycol monoalkyl ether; an aprotic polar substance such as tetrahydrofuran, dimethyl azene or cyclobutadiene. Further, examples of the molten salt electrolyte include an iodide salt electrolyte containing a pyridinium salt, an imidazolium salt, a triazolium salt, and the like.

As a method of forming a charge transporting layer between the working electrode and the counter electrode, for example, a method of arranging the working electrode and the counter electrode oppositely, and then filling the electrolyte between the electrodes to form a charge transporting layer, at the semiconductor electrode or A method of dropping or coating an electrolytic solution on the electrode, thereby forming a charge transporting layer, and then superposing other electrodes on the charge transporting layer.

In the dye-sensitized solar cell (photoelectric conversion element), the resin composition of the present invention is used, and a masking film is formed on only a portion where the metal wiring exists on the substrate by exposure and development, thereby having high photoelectric conversion. effectiveness.

Resin composition

The resin composition for forming a masking film of the electrode for dye-sensitized solar cells according to the present invention contains [A] at least 1 selected from the group consisting of a carboxyl group, an epoxy group, and a (meth)acryl fluorenyl group. A copolymer of a reactive functional group (hereinafter referred to as "[A] copolymer"). Further, it may further contain [B] a polymerizable compound having an ethylenically unsaturated double bond (hereinafter referred to as "[B] polymerizable compound"), [C] a radiation-sensitive polymerization initiator, and if necessary, Any other ingredients. Hereinafter, each component will be described.

[A] copolymer

The [A] copolymer has at least one reactive functional group selected from the group consisting of a carboxyl group, an epoxy group, and a (meth)acrylylene group. [A] The copolymer has such a reactive functional group, and it is possible to form a masking film which is free from defects of the film and which is excellent in corrosion resistance of the metal wiring. Further, in the case where the resin composition of the present invention is radiation sensitive, the polymerization reactivity between [A] copolymers at the time of curing reaction by exposure, and [A] copolymer and [B] polymerization can be improved. The polymerization reactivity between the compounds is such that a masking 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 with another radical polymerizable monomer. A copolymer having a (meth) acrylonitrile group can be reacted with an isocyanate compound having a (meth) acrylonitrile group by copolymerizing a radical polymerizable monomer having a hydroxyl group with another radical polymerizable monomer. synthesis. The [A] copolymer preferably contains 10 to 90% by mass, and particularly preferably contains 20 to 80% by mass of a radical polymerizable single having a reactive functional group such as a carboxyl group, an epoxy group or a (meth)acryl fluorenyl group. The structural unit derived from the body is based on the total of structural units derived from these radical polymerizable monomers and other radical polymerizable monomers. When the structural unit derived from the radically polymerizable monomer having a reactive functional group in the [A] copolymer is from 10 to 90% by mass, in the case where the resin composition of the present invention is radiation sensitive, Improve the curing reactivity at the time of exposure.

Examples of the radical polymerizable monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, 2-propenyloxyethyl succinic acid, and 2-methylpropenyloxyethyl succinic acid. a monocarboxylic acid such as 2-propenyloxyethylhexahydrophthalic acid or 2-methylpropenyloxyethylhexahydrophthalic acid; maleic acid, fumaric acid, citraconic acid, and Zhongkang a dicarboxylic acid such as an acid or itaconic acid; an acid anhydride of the above dicarboxylic acid; and the like.

Examples of the radical polymerizable monomer having an epoxy group include 4-methylpropenyloxymethyl-2-cyclohexyl-1,3-dioxolan acrylate glycidyl ester and acrylic acid 2- Methyl glycidyl ester, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl acrylate Epoxyalkyl acrylate such as methyl ester; glycidyl methacrylate, 2-methyl glycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-cyclomethacrylate Cycloheptyl alkyl methacrylate such as oxyheptyl ester, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methacrylate; α-ethyl acrylate shrinkage A-alkyl acrylate alkyl alkoxylate such as glyceride, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, α-ethyl acrylate 6,7-epoxyheptyl ester; Glycidyl ether such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether; 3-(methacryloxymethyl)oxetane, 3 -(methacryloxymethyl)-3-ethyloxetane, 3-(methacryloxymethyl)-2-methyloxetane, 3-(methyl Propylene oxiranyl ethyl) oxetane, 3-(methacryloxyethyl)-3-ethyloxetane, 2-ethyl-3-(methacryloxyloxy) Ethyl)oxetane, 3-methyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-methylpropenyloxymethyloxetane a methacrylate having an oxetanyl group; 3-(acryloxymethyl)oxetane, 3-(acryloxymethyl)-3-ethyloxetane, 3-(Allyloxymethyl)-2-methyloxetane, 3-(acryloxyethyl)oxetane, 3-(acryloxyethyl)-3- An oxocyclic acrylate such as ethyloxetane or 2-ethyl-3-(acryloxyethyl)oxetane.

Among these epoxy group-containing radical polymerizable monomers, the copolymerization reactivity with other radical polymerizable monomers and the developability in the case where the resin composition of the present invention is radiation sensitive Considered, particularly preferred are glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methacrylate Ester, 3-methyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-methylpropenyloxymethyloxetane.

Examples of the radical polymerizable monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxymethyl-cyclohexylmethyl acrylate, and the like. Hydroxyalkyl acrylate; 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate And hydroxyalkyl methacrylate such as 4-hydroxymethyl-cyclohexylmethyl methacrylate.

Among these radically polymerizable monomers having a hydroxyl group, from the viewpoints of copolymerization reactivity with other radically polymerizable monomers and reactivity with an isocyanate compound having a (meth)acryloyl group, it is preferably 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 4-hydroxymethyl-cyclohexyl methacrylate , 4-hydroxymethyl-cyclohexylmethyl methacrylate.

Examples of the isocyanate compound having a (meth)acryl fluorenyl group which is reacted with a copolymer of a radical polymerizable monomer having a hydroxyl group and another radical polymerizable monomer include 2-propenyloxyethyl isocyanate. An acrylic acid derivative or a methacrylic acid derivative such as 2-methacryloxyethyl isocyanate. An example of a commercially available product of 2-propenyloxyethyl isocyanate is Karenz AOI (manufactured by Showa Denko Co., Ltd.), which is an example of a commercially available product of 2-methylpropenyloxyethyl isocyanate. List Karenz MOI (Showa Denko (share) system).

Examples of the other radical polymerizable monomer copolymerized with the radical polymerizable monomer having a reactive functional group such as a carboxyl group, an epoxy group or a hydroxyl group include alkyl acrylates such as methyl acrylate and isopropyl acrylate. ; alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, butyl methacrylate, butyl methacrylate; cyclohexyl acrylate, acrylic acid 2 -methylcyclohexyl ester, tricyclo[5.1.02.5 ^2,6 ]non-8-yl acrylate, 2-(tricyclo[5.2.1.0 ^2,6 ]non-8-yloxy)ethyl acrylate, Acrylic cycloaliphatic esters such as isobornyl acrylate; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[cyclopropyl] methacrylate [5.2.1.0 ^2,6 ] 癸-8-yl ester, A Acrylic acid alicyclic ester such as 2-(tricyclo[5.2.1.0 ^2,6 ]癸-8-yloxy)ethyl ester or isobornyl methacrylate; acrylic acid such as phenyl acrylate or benzyl acrylate Aryl esters and aralkyl esters of acrylic acid; aryl esters of methacrylic acid such as phenyl methacrylate or benzyl methacrylate; Aralkyl ester; dialkyl dicarboxylate such as diethyl maleate, diethyl fumarate, diethyl itaconate; tetrahydrofurfuryl methacrylate, tetrahydrofuran methacrylate, methyl Unsaturated five-membered heterocyclic methacrylate containing 1 atom of oxygen, such as tetrahydropyran-2-carboxylate, and unsaturated six-membered heterocyclic methacrylate; 4-methylpropenyloxymethyl-2 -methyl-2-ethyl-1,3-dioxolane, 4-methylpropenyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4 -Methethyloxymethyl-2-cyclohexyl-1,3-dioxolan, 4-methylpropenyloxymethyl-2-methyl-2-ethyl-1,3-di Unsaturated five-membered heterocyclic methacrylate containing 2-atomic oxygen, such as oxylan, 4-methylpropenyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane ; 4-propenyloxymethyl-2,2-dimethyl-1,3-dioxolan, 4-propenyloxymethyl-2-methyl-2-ethyl-1,3- Dioxolane, 4-propenyloxymethyl-2,2-diethyl-1,3-dioxolan, 4-propenyloxymethyl-2-methyl-2-isobutyl -1,3-dioxolan, 4-propenyloxymethyl-2-cyclopentyl-1,3-dioxolan Cyclo, 4-propenyloxymethyl-2-cyclohexyl-1,3-dioxolan, 4-propenyloxyethyl-2-methyl-2-ethyl-1,3-dioxo Pento ring, 4-propenyloxypropyl-2-methyl-2-ethyl-1,3-dioxolane, 4-propenyloxybutyl-2-methyl-2-ethyl- Unsaturated five-membered heterocyclic acrylate containing 2-atomic oxygen such as 1,3-dioxolane; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxybenzene a vinyl aromatic compound such as ethylene or 4-isopropenylphenol; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzyl maleimide, N-amber Amine-3-maleimide benzoate, N-succinimide-4-maleimine butyrate, N-succinimide-6-maleimide caproate, N-succinimide-3-maleimide propionate, N-(9-acridinyl)maleimide, N-substituted maleimide, 1,3-butadiene, a conjugated diene compound such as isoprene or 2,3-dimethyl-1,3-butadiene; acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, or partial Dichloroethylene, vinyl acetate, etc. Compound.

Among these other radical polymerizable monomers, styrene, 4-isopropenylphenol, tricyclo[5.2.1.0 ^2,6 ]non-8-yl methacrylate, tetrahydrofurfuryl methacrylate, 1,3-butadiene, 4-propenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, N-cyclohexylmaleimide, N-phenyl Development of a copolymerization reactivity with a radically polymerizable monomer having a reactive functional group, and a development of a resin composition of the present invention in the case where the resin composition of the present invention is radiation-sensitive, such as maleic imine or benzyl methacrylate The sexual aspect is better.

The copolymer of [A] copolymer has a number average molecular weight (hereinafter referred to as "Mn") in terms of polystyrene according to GPC (gel permeation chromatography), preferably 2 × 10 ³ to 1 × 10 ⁵ , and more preferably It is 5 × 10 ³ ~ 5 × 10 ⁴ . When the Mn of the copolymer is 2 × 10 ³ to 1 × 10 ⁵ , when the resin composition of the present invention is radiation-sensitive, the curing reactivity at the time of exposure can be improved.

Further, the molecular weight distribution "Mw/Mn" of the [A] copolymer (here, "Mw" is a polystyrene-equivalent weight average molecular weight of the copolymer measured by gel permeation chromatography) is preferably 5.0 or less, and 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, a mask film having a desired shape can be more accurately formed during development.

Examples of the solvent which can be used in the polymerization reaction for producing the [A] copolymer include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, and propylene glycol singles. Alkyl ether, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether propionate, aromatic hydrocarbons, ketones, other esters, and the like.

Examples of the solvent include, for example, methanol, ethanol, benzyl alcohol, 2-phenylethanol, and 3-phenyl-1-propanol. Examples of the ethers include tetrahydrofuran and the like; and glycol ethers. Examples thereof include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; and examples of the ethylene glycol alkyl ether acetate include methyl cellosolve acetate and ethyl cellosolve B. An acid ester, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc.; as the diethylene glycol alkyl ether, for example, diethylene glycol monomethyl ether, diethylene glycol Alcohol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc.; as the propylene glycol monoalkyl ether, for example, propylene glycol monomethyl ether , propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc.; as the 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, etc.; as propylene glycol monoalkyl ether propionic acid Examples of the ester include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, and propylene glycol monobutyl ether propionate; and examples of the aromatic hydrocarbons include aromatic hydrocarbons. For example, toluene or xylene; and examples of the ketones include methyl ethyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; and other esters include, for example, methyl acetate. , ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, glycolic acid Ester, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxypropionic acid Ester, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate Ethyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propoxy Propyl acetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, 2 -ethyl methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2 -propyl ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, 2 - butyl butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3 - methyl ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, 3 -ethyl propoxy propionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3 An ester such as propyl butoxypropionate or butyl 3-butoxypropionate.

Among these solvents, preferred are ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, butyl methoxyacetate, and Preferably, it is diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, butyl methoxyacetate.

As the polymerization initiator which can be used in the polymerization reaction for producing the [A] copolymer, a material generally known as a radical polymerization initiator can be used. Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azo. An azo compound such as bis(4-methoxy-2,4-dimethylvaleronitrile); benzhydryl peroxide, lauryl peroxide, tertiary butyl peroxypivalate, 1 , an organic peroxide such as 1 '-di (tertiary butyl peroxy) cyclohexane; and hydrogen peroxide.

When a peroxide is used as the radical polymerization initiator, it is also possible to use a peroxide together with a reducing agent to form a redox type initiator.

In the polymerization for producing the [A] copolymer, a molecular weight modifier may be used in order to adjust the molecular weight. Specific examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, and tertiary dodecyl mercaptan. Thiols such as thioglycolic acid; xanthogenates such as dimethyl xanthate sulfide and diisopropyl xanthate disulfide; terpinolene and α-methylstyrene dimer Wait.

[B] Polymeric compound

The [B] polymerizable compound can be preferably used in the resin composition of the present invention. Preferable examples of the [B] polymerizable compound include a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, or a trifunctional or higher (meth) acrylate. By using these compounds, when the resin composition of the present invention is radiation-sensitive, when the curing reaction is carried out by exposure, the polymerization reactivity between the compounds of the [B] polymerizable compound is improved, and [A The polymerization reactivity between the copolymer and the [B] polymerizable compound, therefore, a mask 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, and (meth)acrylic acid 3- Methoxybutyl ester, 2-(meth)acryloxyethyl 2-hydroxypropyl phthalate, and the like. Examples of commercially available products of these monofunctional (meth) acrylates include Aronix M-101, Aronix M-111, Aronix M-114 (manufactured by Toagos Corporation), KAYARAD TC-110S, KAYARAD TC- 120S (Nippon Chemical Co., Ltd.), Viscoat 158, Viscoat 2311 (Osaka Organic Chemical Industry Co., Ltd.), etc.

Examples of the bifunctional (meth) acrylate include ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol di(methyl). Acrylate, polypropylene glycol di(meth) acrylate, tetraethylene glycol di(meth) acrylate, diphenoxyethanol hydrazine di(meth) acrylate, diphenoxyethanol hydrazine di(methyl) Acrylate and the like. As a commercially available product of such a bifunctional (meth) acrylate, for example, Aronix M-210, Aronix M-240, Aronix M-6200 (manufactured by Toagos Corporation), KAYARAD HDDA, KAYARAD HX-220, KAYARAD can be cited. R-604 (manufactured by Nippon Kayaku Co., Ltd.), Viscoat 260, Viscoat 312, and Viscoat 335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Examples of the trifunctional or higher (meth) acrylate include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tris((meth)acryloxyloxy group. Ethyl)phosphate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, succinic acid mono[3- (3-(Methyl)propenyloxy-2,2-di-(methyl)propenyloxymethyl-propoxy)-2,2-di-(methyl)propenyloxymethyl -propyl] ester and the like. As a commercially available product of these trifunctional or higher (meth)acrylates, for example, Aronix M-309, Aronix M-400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060 (East Asia Synthetic Co., Ltd.), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 (Nippon Chemical Co., Ltd.), Viscoat 295 , Viscoat 300, Viscoat 360, Viscoat GPT, Viscoat 3PA, Viscoat 400 (Osaka Organic Chemical Industry Co., Ltd.) and the like.

Among these polymerizable compounds having an ethylenically unsaturated double bond, a trifunctional or higher (meth) acrylate is preferably used from the viewpoint of improving the curability of the resin composition. Among them, trimethylolpropane tri(meth)acrylate, neopentyltetrakis(meth)acrylate, dipentaerythritol hexa(meth)acrylate, succinic acid mono[3-( 3-propenyloxy-2,2-di-acryloxymethyl-propoxy)-2,2-di-acryloxymethyl-propyl] ester. These polymerizable compounds having an ethylenically unsaturated double bond may be used singly or in combination of two or more.

The amount of the [B] polymerizable compound used in the resin composition is preferably 50 to 300 parts by mass, and more preferably 60 to 250 parts by mass, per 100 parts by mass of the [A] copolymer. By using the amount of the [B] polymerizable compound in an amount of 50 to 300 parts by mass, it is possible to obtain a resin having a higher level and a balance of various properties such as adhesion of the formed mask film to the substrate and corrosion resistance to the electrolytic solution. Composition.

[C] sensitizing radiation polymerization initiator

The [C] radiation-sensitive polymerization initiator can be preferably used in the resin composition of the present invention. The [C] radiation-sensitive polymerization initiator is not particularly limited as long as it is a component which generates an active species which can induce polymerization of the [B] polymerizable compound by inducing radiation. Examples of such a [C] radiation-sensitive polymerization initiator include an O-indenyl hydrazine compound, an acetophenone compound, and a diimidazole compound.

As the O-indenyl ruthenium compound which can be used as a radiation-sensitive polymerization initiator, ethyl ketone-1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole-3 can be cited. -yl]-1-(O-acetamidine), 1-[9-ethyl-6-benzylidene-9.H.-oxazol-3-yl]-oct-1-one oxime-O -acetate, 1-[9-ethyl-6-(2-methylbenzhydryl)-9.H.-oxazol-3-yl]-ethan-1-one oxime-O-benzoic acid Acid ester, 1-[9-n-butyl-6-(2-ethylbenzylidene)-9.H.-oxazol-3-yl]-ethan-1-one oxime-O-benzoic acid Ester, ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzylidene)-9.H.-carbazol-3-yl]-1-(O-B醯肟), Ethyl Ketone-1-[9-Ethyl-6-(2-methyl-4-tetrahydropyranylbenzylidene)-9.H.-carbazol-3-yl]-1 -(O-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzylidene)-9.H.-carbazol-3-yl] -1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl) )methoxybenzylidene}-9.H.-carbazol-3-yl]-1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-A 4--4-hydrofuranylmethoxybenzylidene)-9.H.-carbazol-3-yl]-1-(O-acetyl) and the like.

As a preferred example of these O-indenyl ruthenium compounds, ethyl ketone-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1 can be cited. -(O-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9.H.-carbazole-3 -yl]-1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxo) Pentocyclo)methoxybenzylamino}-9.H.-carbazol-3-yl]-1-(O-acetamidine). These O-indenyl ruthenium compounds may be used singly or in combination of two or more.

Examples of the acetophenone compound which can be used as a radiation-sensitive linear polymerization initiator include an α-amino ketone compound and an α-hydroxy ketone compound.

As an example of the α-amino ketone compound, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2-dimethylamino group- 2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-1-butanone, 2-methyl-1-(4-methylthiophenyl)- 2-morpholinyl-1-propanone and the like.

As an example of the α-hydroxyketone compound, 1-phenyl-2-hydroxy-2-methyl-1-propanone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl- 1-Acetone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, and the like.

Among these acetophenone compounds, an α-amino ketone compound is preferred, and 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone is particularly preferred. 2-Dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinyl-4-yl-phenyl)-1-butanone. These acetophenone compounds may be used singly or in combination of two or more.

As a diimidazole compound which can be used as a radiation-sensitive polymerization initiator, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylbenzene) can be mentioned. 1,1,2'-diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2 '-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-di(2,4,6-three Chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole and the like.

Among these diimidazole compounds, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2' is preferred. -bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2,4,6-trichloro Phenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, and particularly preferably 2,2'-bis(2,4-dichlorophenyl)-4,4 ',5,5'-Tetraphenyl-1,2'-diimidazole. These diimidazole compounds may be used singly or in combination of two or more.

When a diimidazole compound is used as the [C] radiation-sensitive polymerization initiator in the resin composition of the present invention, an aliphatic or aromatic compound having a dialkylamine group may be added in order to sensitize the resin composition (hereinafter, It is called "amine sensitizer").

Examples of such an amine-based sensitizer include 4,4'-bis(dimethylamino)benzophenone and 4,4'-di(diethylamino)benzophenone. Among these amine sensitizers, 4,4'-bis(diethylamino)benzophenone is particularly preferred. These amine sensitizers may be used alone or in combination of two or more.

Further, when a diimidazole compound and an amine-based sensitizer are used, a thiol compound may be added as a hydrogen radical-donating agent. The diimidazole compound is sensitized by an amine-based sensitizer to be cracked to form an imidazole radical, but it may not be able to exhibit high polymerization initiation energy by itself. However, by adding a thiol compound to a system in which a diimidazole compound and an amine sensitizer coexist, a hydrogen radical can be supplied from the thiol compound to the imidazole radical. Therefore, when the imidazole radical is converted into a neutral imidazole, a component having a sulfur radical having a high polymerization initiating ability is formed, whereby when the resin composition of the present invention is radiation-sensitive, the exposure can be improved. The curing reactivity is such that a masking film having a desired shape can be easily formed.

Examples of such a thiol compound include 2-mercaptobenzothiazole and 2-mercaptobenzoene. An aromatic thiol compound such as azole, 2-mercaptobenzimidazole or 2-mercapto-5-methoxybenzothiazole; an aliphatic monothiol compound such as 3-mercaptopropionic acid or methyl 3-mercaptopropionate; A bifunctional or higher aliphatic thiol compound such as pentaerythritol tetrakis(mercaptoacetate) or neopentyltetrakis(3-mercaptopropionate). Among these thiol compounds, 2-mercaptobenzothiazole is particularly preferred.

When the diimidazole compound and the amine-based sensitizer are used in combination with the resin composition, the amount of the amine-based sensitizer added is preferably 0.1 to 50 parts by mass, and more preferably 1 to 100 parts by mass of the diimidazole compound. ~20 parts by mass. When the amount of the amine-based sensitizer added is 0.1 to 50 parts by mass, when the resin composition of the present invention is radiation-sensitive, the curing reactivity at the time of exposure can be further improved.

In addition, when the diimidazole compound, the amine sensitizer, and the thiol compound are used, the amount of the thiol compound added is preferably 0.1 to 50 parts by mass, and more preferably 100 parts by mass of the diimidazole compound. 1 to 20 parts by mass. By adding the thiol compound in an amount of 0.1 to 50 parts by mass, the curing reactivity at the time of exposure can be further improved, and a masking film having a desired shape can be more easily obtained.

The [C] radiation-sensitive polymerization initiator is preferably at least one selected from the group consisting of O-mercaptopurine compounds and acetophenone compounds, and more preferably contains a compound selected from O-mercaptopurine compounds. At least one of the group consisting of an acetophenone compound and a diimidazole compound.

The amount of the radiation-sensitive polymerization initiator to be used is preferably 5 to 200 parts by mass, and more preferably 5 to 100 parts by mass, per 100 parts by mass of the [A] copolymer. When the amount of the [C] radiation-sensitive polymerization initiator used is 5 to 200 parts by mass, when the resin composition of the present invention is radiation-sensitive, the curing reactivity at the time of exposure can be improved.

Further, the ratio of the O-mercaptopurine compound and the acetophenone compound in the radiation-sensitive polymerization initiator as the [C] radiation-sensitive polymerization initiator is a radiation-induced linear polymerization with respect to the [C] radiation-sensitive polymerization initiator. The total amount of the 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-fluorenyl ruthenium compound and the acetophenone compound in such a ratio, high curing reactivity can be obtained even at a low exposure amount, and therefore, a mask film having an accurate shape can be formed.

Other optional ingredients

In addition to the above [A] copolymer, [B] polymerizable compound, and [C] radiation-sensitive polymerization initiator, the resin composition of the present invention may contain [G as needed within a range that does not impair the intended effect. Additives such as adhesion aids and [H] surfactants.

In the resin composition of the present invention, in order to improve the adhesion between the formed mask film and the substrate, a [G] adhesion aid may be used. As such an adhesion aid, a functional decane coupling agent is preferably used. Examples of the functional decane coupling agent include a decane coupling agent having a reactive substituent such as a carboxyl group, a methacryl fluorenyl group, an isocyanate group or an epoxy group. Specific examples of the functional decane coupling agent include trimethoxymethyl decyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, and vinyl trimethoxy. Base decane, γ-isocyanate propyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, γ-glycidoxypropyl triethoxy decane, β-(3,4-ring Oxycyclohexyl)ethyltrimethoxydecane, and the like.

[G] Adhesive additives may be used singly or in combination of two or more. The amount of the binder to be used is preferably 0.1 to 30 parts by mass, and more preferably 1 to 25 parts by mass, per 100 parts by mass of the copolymer of the [A] copolymer. By using the [G] adhesion aid in an amount of 0.1 to 30 parts by mass, the adhesion of the formed mask film to the substrate can be maintained at a sufficiently high level.

In the resin composition of the present invention, in order to further improve the coatability at the time of formation of a coating film, a [H] surfactant may be used. Examples of preferred surfactants include fluorine-based surfactants, polyoxyalkylene-based surfactants, and nonionic surfactants.

Examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)ether and 1,1,2,2-tetrafluorooctene. Hexyl hexyl ether, octaethylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether, eight a fluoroether such as propylene glycol di(1,1,2,2-tetrafluorobutyl)ether or hexapropylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether; Sodium alkane sulfonate; fluorine such as 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane Alkane; sodium fluoroalkylbenzenesulfonate; fluoroalkyl oxyethylene ether; fluoroalkylammonium iodide; fluoroalkyl polyoxyethylene ether; perfluoroalkyl polyoxyethylene Classes; perfluoroalkyl alkoxylates; fluoroalkyl esters.

As a commercially available product of these fluorine-based surfactants, BM-1000, BM-1100 (manufactured by BM CHEMIE), Megafac F142D, Megafac F172, Megafac F173, and Megafac F183 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) , Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 (Sumitomo 3M (share) system), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (made by Asahi Glass Co., Ltd.), FTX-218 ( (shares) NEOS system and other commercial products.

Examples of the polyoxyalkylene-based surfactant include commercially available SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, and DC-190 (East). Li Dao Kang Ning, Polyoxane (share), KP341 (Shin-Etsu Chemical Co., Ltd.), EFTOP EF301, EFTOP EF303, EFTOP EF352 (New Akita Chemicals Co., Ltd.).

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene dialkyl ester, and (meth)acrylic copolymer.

Examples of the polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether. Examples of the polyoxyethylene aryl ether include polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether. Examples of the polyoxyethylene dialkyl ester include polyoxyethylene dilaurate and polyoxyethylene distearate. Examples of the (meth)acrylic copolymers include, for example, Polyflow No. 57 and Polyflow No. 90 (manufactured by Kyoeisha Chemical Co., Ltd.).

The [H] surfactant may be used singly or in combination of two or more. The amount of the [H] surfactant to be used is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the [A] copolymer. By using the surfactant in an amount of 0.01 to 5 parts by mass, it is possible to suppress the occurrence of cracks on the surface of the formed mask film and to form a uniform coating film.

Resin composition

The resin composition of the present invention, by uniformly mixing the above [A] copolymer, [B] polymerizable compound, and [C] radiation-sensitive polymerization initiator, and optional components ([G] adhesion aid and/or [H] Modulated by a surfactant, etc.). Usually, the resin composition is preferably stored and used in the form of a solution dissolved in a suitable solvent. For example, a resin composition in a solution state can be prepared by mixing the [A] copolymer, the [B] polymerizable compound, and the [C] radiation-sensitive polymerization initiator and an optional component in a predetermined ratio in a solvent.

As the solvent which can be used for preparation of the resin composition, it is possible to uniformly dissolve the above [A] copolymer, [B] polymerizable compound, and [C] radiation-sensitive polymerization initiator, and optional components ([G] adhesion aid and The component which does not react with each component of [H] surfactant, etc. is not specifically limited. The solvent is the same as the solvent exemplified as the solvent which can be used for the production of the [A] copolymer.

In such a solvent, it is preferred to use, for example, an alcohol, a glycol ether, or an ethylene glycol alkyl ether from the viewpoints of solubility of each component, non-reactivity with each component, and ease of formation of a coating film. Acid esters, esters, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates. Among them, it is particularly preferred to use, for example, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol Alcohol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2- or 3-methoxypropionic acid Methyl ester, ethyl 2- or 3-ethoxypropionate, 3-methoxybutyl acetate.

Further, in order to improve the film thickness surface uniformity of the formed coating film, a high boiling point solvent may be used in combination with the above solvent. As the high boiling point solvent which can be used in combination, for example, N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N can be mentioned. , N-dimethylacetamide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic 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. Among these high boiling solvents, N-methylpyrrolidone, γ-butyrolactone, and N,N-dimethylacetamide are preferred.

When a solvent having a high boiling point solvent is used as the solvent of the resin composition, the amount thereof to be used may be 50% by mass or less, preferably 40% by mass or less, and more preferably 30% by mass or less based on the total amount of the solvent. When the use ratio of the high boiling point solvent is 50% by mass or less, the uniformity of the coating film thickness can be improved, and the decrease in the radiation sensitivity can be suppressed.

When the resin composition is prepared in a solution state, components other than the solvent (that is, the total amount of the [A] copolymer, the [B] polymerizable compound, and the [C] radiation-sensitive polymerization initiator, and other optional components) are in solution. The proportion may be arbitrarily set depending on the purpose of use and the desired film thickness, and 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 may be used after being filtered using a micropore filter having a pore diameter of about 0.2 μm or the like.

Formation of a masking film for a dye-sensitized solar cell electrode

Next, a method of forming the masking film of the present invention using the above resin composition will be described. The method for forming the masking film is a method for forming a masking film for an electrode for a dye-sensitized solar cell, which in turn comprises:

(1) A coating film of the resin composition of claim 6 is formed on a laminate having a conductive substrate and a metal wiring layer on the surface side of the conductive substrate so as to cover at least the entire metal wiring layer A step of,

(2) A step of heating the coating film formed in the step (1).

(1) Step of forming a coating film of a resin composition on a substrate

In this step, a solution of the resin composition of the present invention is applied onto a laminate having a conductive substrate and a metal wiring layer on the surface side of the conductive substrate, and then the coated surface is heated (prebaked). A coating film is formed. The coating is performed at least to the entire metal wiring layer covering the surface side of the conductive substrate. The prebaking conditions vary depending on the type and blending ratio of each component, and are preferably about 1 to 10 minutes at 70 to 110 °C. The film thickness after pre-baking of the coating film is preferably from 0.1 to 5.0 μm, and more preferably from about 0.3 to 2.0 μm.

The solid content concentration of the composition solution used in the coating is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, still more preferably 15 to 35% by mass. The coating method of the composition solution is not particularly limited, and for example, a suitable 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 inkjet coating method can be employed. Among these coating methods, a bar coating method or a slit die coating method is particularly preferred. By coating the composition solution by a bar coating method or a slit die coating method, a defect-free masking film can be formed even for a substrate having a metal wiring layer height difference.

(2) Heating step

After the step (1), the coating film is subjected to heat treatment (post-baking treatment) by a suitable heating means such as a hot plate or a clean oven. The heating temperature is preferably about 150 to 250 ° C. 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 manner, a masking film having a desired shape can be formed on the electrode for a dye-sensitized solar cell.

As described above, by using the resin composition and forming the mask film by the coating film forming step and the heating step, a mask film can be formed on the substrate of the electrode for dye-sensitized solar cells. This formation method requires only a relatively simple step of the coating step and the heating step, so that the mask film can be formed at low cost.

The method for forming a masking film of the electrode for a dye-sensitized solar cell of the present invention includes (1') a layered body having a conductive substrate and a metal wiring layer on the surface side of the conductive substrate, in order to have a step of exposing the coating film of the resin composition to at least the entire surface of the metal wiring layer

(3) a step of irradiating only a portion of the coating film formed in the step (1') on the metal wiring layer,

(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).

(1') Step of forming a coating film having a radiation-sensitive resin composition on a substrate

In this step, a solution having a radiation-sensitive resin composition is applied onto a laminate having a conductive substrate and a metal wiring layer on the surface side of the conductive substrate, and then the coated surface is heated (prebaking) ), and a coating film is formed. The coating is performed at least to the entire metal wiring layer covering the surface side of the conductive substrate. The prebaking conditions vary depending on the type and blending ratio of each component, and are preferably about 1 to 10 minutes at 70 to 110 °C. The film thickness after pre-baking of the coating film is preferably from 0.1 to 5.0 μm, and more preferably from 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 still more preferably 15 to 35% by mass. The coating method of the composition solution is not particularly limited, and for example, a suitable 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 inkjet coating method can be employed. Among these coating methods, a bar coating method or a slit die coating method is particularly preferred. By coating the composition solution by a bar coating method or a slit die coating method, a defect-free masking film can be formed even for a substrate having a metal wiring layer step.

(3) Step of irradiating the coating film with radiation

Next, only a portion of the coating film formed in the above step (1') laminated on the metal wiring layer is exposed by a mask having a predetermined pattern. Examples of the radiation used in the exposure include visible light rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like. Among these radiations, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation containing ultraviolet rays having a wavelength of 365 nm is particularly preferable.

The exposure amount is a value obtained by measuring the intensity at a wavelength of 365 nm in the radiation using an illuminometer ("OAI model 356" manufactured by Optical Associates Inc.), and is preferably 100 to 10,000 J/m ² , and more preferably 500 to 3,000 J. /m ² .

(4) Development step

Next, the coating film irradiated with radiation in the step (3) is developed, and the non-irradiated portion of the radiation is removed to form a predetermined pattern. As the developing solution used for development, an aqueous solution of an alkali (basic substance) can be preferably used. Examples of the base which can be used include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and ammonia; tetramethylammonium hydroxide and tetraethylammonium hydroxide. Ammonium salts, etc. The aqueous alkali solution may be added by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant.

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

(2') heating step

After the development step of the above (4), the patterned coating film is subjected to heat treatment (post-baking treatment) by a suitable heating means such as a hot plate or a clean oven. The heating temperature is preferably about 150 to 250 ° C. 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 manner, a masking film having a desired shape can be formed on the electrode for a dye-sensitized solar cell.

As described above, the resin composition having the radiation sensitivity can be formed into a pattern by the coating film forming step, the radiation irradiation step (exposure step), the development step, and the heating step, and can be used in the electrode for dye-sensitized solar cells. On the substrate having the metal wiring step difference, a mask film having a uniform thickness is formed only on the portion where the metal wiring is present. According to this method, it is possible to accurately form the mask film only on the portion where the metal wiring exists, and to surely prevent the mask film from being erroneously formed on the conductive substrate or the oxide semiconductor layer, so that no mask film is formed on the metal wiring. Defect. Further, since the metal wiring having the mask film thus formed does not have a defect of the mask film, it is possible to exhibit high corrosion resistance to the electrolytic solution.

Example

Hereinafter, the present invention will be specifically described by way of Synthesis Examples and Examples, but the present invention is not limited to the following examples. In addition, the number average molecular weight and molecular weight distribution (Mw/Mn) measured below were GPC chromatograph "HLC-8020" (1 TsKgel α-M, 1 TsKgel α-2500) manufactured by Tosoh Co., Ltd., The measurement was carried out by gel permeation chromatography (GPC) under the conditions of flow rate: 1.0 ml/min, elution solvent: N,N-dimethylformamide, and column temperature: 35 °C.

Copolymer manufacturing [Synthesis Example 1]

Into a flask having a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were added. Further, 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 continuously added, and after nitrogen substitution, slow stirring was started. The temperature of the solution was raised to 70 ° C, and the 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 obtained copolymer had a number average molecular weight of 7,000 and a molecular weight distribution (Mw/Mn) of 2.

[Synthesis Example 2]

In a flask having a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were added. Further adding 40 parts by mass of 3-(methacryloxyethyl)oxetane, 10 parts by mass of styrene, 30 parts by mass of methacrylic acid, and 20 parts by mass of N-cyclohexylmaleimide, and After the nitrogen exchange, slow stirring was started. The temperature of the solution was raised to 70 ° C, and the 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 obtained copolymer had a number average molecular weight of 7,300 and a molecular weight distribution (Mw/Mn) of 2.

[Synthesis Example 3]

In a flask having a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobisisobutyronitrile and 250 parts by mass of butyl methoxyacetate were added, and 18 parts by mass of methacrylic acid and 25 parts by mass of A were continuously added. Tricyclohexyl acrylate [5.2.1.0 ^2,6 ]癸-8-yl ester, 5 parts by mass of styrene, 30 parts by mass of 2-hydroxyethyl methacrylate and 22 parts by mass of benzyl methacrylate, and replaced by nitrogen Thereafter, the temperature of the solution was raised to 80 ° C while stirring slowly, and the temperature was maintained for 5 hours to carry out polymerization to obtain a polymer solution containing a copolymer (β-1) having a solid concentration of 28.8% by mass.

Next, 14 parts by mass of 2-methylpropenyloxyethyl isocyanate ("Karenz MOI" manufactured by Showa Denko Co., Ltd.) and 0.1 part of 4- in the polymer solution containing the copolymer (β-1) were added. The methoxyphenol was stirred at 40 ° C for 1 hour and further stirred at 60 ° C for 2 hours to carry out a reaction. The progress of the reaction from the isocyanate group of 2-methylpropenyloxyethyl isocyanate and the hydroxyl group of the copolymer (β-1) was confirmed by IR (infrared absorption) spectrum. It was confirmed from the respective IR spectra of the solution containing the copolymer (β-1), the solution after 1 hour of reaction, the reaction at 40 ° C for 1 hour, and the reaction at 60 ° C for 2 hours. The peak of the isocyanate group derived from 2-methylpropenyloxyethyl isocyanate was reduced around 2270 cm ^-1 . By this reaction, a polymer solution containing the copolymer (A-3) having a solid concentration of 30.0% by mass was obtained. The obtained copolymer had a number average molecular weight of 7,000 and a molecular weight distribution (Mw/Mn) of 2.

[Comparative Synthesis Example 1]

In a flask having a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were added. 10 parts by mass of styrene and 90 parts by mass of methyl methacrylate were continuously added, and after nitrogen substitution, slow stirring was started. The temperature of the solution was raised to 70 ° C, and the 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 34.0% by mass. The obtained copolymer had a number average molecular weight of 8,500 and a molecular weight distribution (Mw/Mn) of 2.

Modification of resin composition [Example 1]

The polymer solution (corresponding to 100 parts by mass of the copolymer (solid content)) of the copolymer (A-1) of Synthesis Example 1 was added as [A] copolymer, 100 parts by mass (B-1) dioxon Tetraol hexaacrylate ("KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.) as [B] polymerizable compound, 20 parts by mass of (C-1) 2-dimethylamino-2-(4-methyl) Benzyl)-1-(4-morpholinyl-4-yl-phenyl)-1-butanone ("Irgacure 379" manufactured by Ciba Specialty Chemicals Co., Ltd.) as [C] radiation sensitive polymerization initiator, 10.0 mass (G-1) γ-glycidoxypropyltrimethoxydecane as [G] adhesion aid, 0.2 parts by mass of (H-1) surfactant (unit) NEOS "FTX-218" as [ H] a surfactant, and further added propylene glycol monomethyl ether acetate to have a solid content concentration of 22% by mass, and then filtered using a micropore filter having a pore diameter of 0.5 μm to prepare a solution of the resin composition (S- 1).

[Examples 2 to 13 and Comparative Example 1]

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

Fabrication of electrode substrate for dye-sensitized solar cell

An electrode substrate of a dye-sensitized solar cell was produced in the order shown in Fig. 1 .

(1) Production of transparent conductive substrate

A saturated aqueous solution of ammonium fluoride was added to an ethanol solution of tin (IV) chloride pentahydrate and dissolved to prepare a raw material liquid for FTO (fluorinated tin oxide) film. Next, the substrate 1 (high strain point glass) was placed on a hot plate at 350 ° C, and the inside was connected to a hot plate, and while heating with a hot plate for 1 hour, the FTO film was sprayed with a spray nozzle to the raw material liquid. On the surface of the substrate 1, a transparent conductive film 2 (film thickness: 0.05 to 5 μm) formed by FTO was formed. A transparent conductive substrate on which the transparent conductive film 2 was formed on the surface of the substrate 1 obtained above was obtained (see Fig. 1(a)). The film thickness of the transparent conductive film 2 was 0.2 μm.

(2) Formation of metal wiring layer

In the transparent conductive substrate on which the transparent conductive film 2 is formed in the above (1), a grid-shaped stencil is used, and silver for printing is formed by a screen printing apparatus ("HR-320" manufactured by NEWLONG Precision Industries Co., Ltd.). a coating film of a grid pattern of a paste (volume resistivity after sintering of 3 × 10 ^-6 [Ω‧cm]). Then, it was allowed to stand at 25 ° C for 10 minutes, and then dried at 130 ° C for 10 minutes. Further, it is baked at a maximum temperature of 510 ° C for 2 hours, thereby forming a lattice-shaped metal wiring layer 3 formed of silver. Here, the metal wiring layer 3 is formed to have a circuit width (design value) of 300 μm and a film thickness of 10 μm, and A shape in which the collector terminals are stretched in a lattice shape (see Figure 1(b)).

(3) Formation of a porous oxide semiconductor layer

A titanium oxide paste (an ethanol dispersion having a solid content of 20% by mass) is formed between the metal wiring layers 3 on the transparent conductive substrate on which the transparent conductive film 2 is formed by the same screen printing as in the above (2). Coating. Next, the film was fired at 450 ° C for 1 hour to form a porous oxide semiconductor layer 4 between the grid-like metal wiring layers 3 (see Fig. 1(c)).

(4) Formation of a masking film of the metal wiring layer

The resin composition of Example 1 was formed on the entire surface of the layered body produced in the above (3) by using an automatic coating apparatus for a bar coating (PI-1210 automatic coating apparatus type I manufactured by TESTER Industries Co., Ltd.). The coating film 5 of the solution (S-1) (see Fig. 1(d)) was then evaporated and dried at 90 ° C for 5 minutes. The photoreceptor having the same design dimensions as the lattice-shaped stencil used in the above (2) was irradiated with ultraviolet rays by a high pressure mercury lamp, and the exposure amount at 365 nm was 1,000 J/m ² . The film thickness after the exposure was 0.6 μm. Next, the coating film was developed with an aqueous potassium hydroxide solution, and further fired at 180 ° C for 1 hour using a clean oven. Thereby, the electrode substrate 7 having the shielding film 6 is formed on the surface of the lattice-shaped metal wiring layer (see FIG. 1(e)). The film thickness of the masking film 6 was 0.5 μm. Hereinafter, the electrode substrate will be referred to as "sample electrode substrate 1".

(1) to (4) were carried out in the same manner as described above except that the resin composition solutions (S-2) to (S-12) of Examples 2 to 12 were used instead of the resin composition solution (S-1) of Example 1. The step of manufacturing an electrode substrate. These electrode substrates are referred to as "sample electrode substrate 2" to "sample electrode substrate 12". Further, an electrode substrate was produced in the same manner as above except that the resin composition solution (S-13) of Example 13 was used instead of the resin composition solution (S-1) of Example 1, and the exposure step and the development step were not performed. 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 Mine Co., Ltd.) were dispersed in 100 parts by mass of the resin composition solution (s-1) of Comparative Example 1, and a resin composition containing ITO fine particles was prepared. Solution. An electrode substrate was produced by performing the procedures of (1) to (4) in the same manner as described above except that the resin composition solution containing the ITO fine particles was used instead of the resin composition solution (S-1) of Example 1. 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 a susceptibility to radiation, the exposure and development in the step (4) above are omitted.

The steps (1) to (3) described above were carried out, and the electrode substrate (Comparative Example 2) was produced without performing the above step (4) (formation of a mask film). Such an electrode substrate having no masking film is referred to as "comparative sample electrode substrate 2".

In addition, in Table 1, the abbreviation of each compound shows the following.

B-1: dipentaerythritol hexaacrylate ("KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.)

B-2: succinic acid mono [3-(3-propenyloxy-2,2-di-propenyloxymethyl-propoxy)-2,2-di-propenyloxymethyl-propyl Ester

C-1: 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinyl-4-yl-phenyl)-1-butanone (manufactured by Ciba Specialty Chemicals Co., Ltd.) "Irgacure 379")

C-2: Ethyl-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-acetyl) (Ciba specialty) "Irgacure OX02" manufactured by Chemicals)

G-1: γ-glycidoxypropyltrimethoxydecane

H-1: Production of a dye-sensitized solar cell with a fluorine-based surfactant ("FTX-218" manufactured by NEOS)

Using the sample electrode substrates 1 to 13 and the comparative sample electrode substrates 1 to 2, a dye-sensitized solar cell (photoelectric conversion element) was produced in the following manner in the order shown in Fig. 2 .

(a) Adsorption of photosensitizing pigments

Acetonitrile/tertiary butanol of the photo-sensitized dye-bipyridine complex (N719 dye) at a concentration of 5 mass% on each of the sample electrode substrates 1 to 13 and the comparative sample electrode substrates 1 and 2 In the solution (quality ratio 1:1), the film is immersed at 25 ° C for 24 hours or more, whereby the photosensitizing dye is adsorbed on the surface of the porous oxide semiconductor layer of the sample electrode substrate to form a light-sensitized load. The working electrode of the porous oxide semiconductor layer 8 of the pigment (see Fig. 2(a)).

(b) application of the counter electrode and the injection of the electrolyte solution

A platinum layer having a sputter-formed Ti foil on its surface was used as the counter electrode 9, and was superposed on the working electrode fabricated in the above (a). The iodine electrolyte solution 10 was injected from the gap between the working electrode and the counter electrode using a dropping pipette in a circulating refining glove type working box filled with an inert gas. As the iodine electrolyte solution 10, 0.5 M of 1,2-dimethyl-3-propylimidazolium iodide and 0.05 M of iodine were dissolved in methoxyacetonitrile, and an appropriate amount of lithium iodide and 4- were further added. Material obtained from tertiary butyl pyridine (see Figure 2(b)).

(c) sealed

The adhesive film 11 ("Surlyn" manufactured by Dupont Co., Ltd.) was used, and the two electrodes were bonded together by a hot press at 120 ° C to seal, so that the electrolyte was not from the sample prepared in the above (b). By overflowing, a dye-sensitized solar cell (a solar cell corresponding to the sample electrode substrates 1 to 13 and the comparative sample electrode substrate 1) was produced (see Fig. 2(c)).

Evaluation of dye-sensitized solar cells (I) Confirming whether or not the mask film on the sample electrode substrate is defective

With respect to the sample electrode substrates 1 to 13 and the comparative sample electrode substrate 1 having a shielding film on the metal wiring, the appearance of the surface of the masking film was observed under a sodium lamp by the naked eye. The defect in which the portion where the mask film was not formed was used as a mask film was evaluated for the presence or absence of the defect. The case where there is no mask film defect is denoted by ○, and the case where the mask film defect is confirmed is denoted by ×. The results are shown in Table 1.

(II) Determination 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 a twin crystal solar cell of JIS C8913:1998. The air mass filter equivalent to AM1.5G is combined with a 300W solar simulator ("YSS-80" manufactured by Yamashita Denso Co., Ltd.) and adjusted to 100mW/cm ² by two reference Si solar cells. The amount of light is used as a light source for measurement, and a potentiostat is used for light-irradiating solar cells (solar cells corresponding to the sample electrode substrates 1 to 13 and the comparative sample electrode substrates 1 to 2, respectively). "HSV-100" manufactured by Hokuto Electric Co., Ltd., measuring the IV curve characteristics, and deriving the open voltage (Voc; unit V), short-circuit current (Isc; unit mA/cm ² ) obtained from the characteristics of the IV curve, and duty Factor (FF; no unit). Then, using the following formulas (1) and (2), the short-circuit current density (Jsc; unit mA/cm ² ) and the photoelectric conversion efficiency (η; unit %) were calculated. When the value of the photoelectric conversion efficiency calculated in this way is 4% or more, it is considered that corrosion of the metal wiring is not generated, and the iodine electrolyte solution is not discolored, and the photoelectric conversion efficiency is good. The results are shown in Table 1. In addition, AM 1.5G described here indicates the distance of sunlight by the atmosphere. The solar light directly below the equator is based on the distance AM1.0G of the atmosphere, and AM1.5G is equivalent to the value in Tokyo.

(III) Evaluation of Corrosion Resistance of Metal Wiring with Masking Film

Immediately after the measurement of the photoelectric conversion efficiency (η) of the above (II), the appearance inspection of the metal wiring having the mask film was performed. When the metal wiring was observed with the naked eye, the corrosion and the discoloration of the wiring were confirmed, and the change was evaluated as "good/○", and the change (corrosion or discoloration) was observed as "failed/x". The results are shown in Table 1.

As is clear from the results shown in Table 1, a dye-sensitized solar cell (Examples 1 to 12) containing a masking film formed by using the resin composition having a radiation sensitivity, and a resin composition using the prior art were contained. The dye-sensitized solar cell (Comparative Example 1) of the formed masking film and the dye-sensitized solar cell (Comparative Example 2) having no masking film were excellent in photoelectric conversion efficiency, and there was no defect of the masking film at all. And 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 the [G] adhesion aid and/or [H] surfactant as an optional component. Further, from the results of Examples 4 to 12, it was found that good characteristics can be obtained when various [A] to [C] are used. By using the resin composition having a radiation-sensing property, it is possible to accurately form a mask film on a portion having a metal wiring difference in the electrode for dye-sensitized solar cells, and to form a mask film only on the portion where the metal wiring exists. Excellent photoelectric conversion efficiency can be maintained while achieving high corrosion resistance. Further, from the results of Example 13, it is understood that the masking film formed by using the resin composition having no radiation sensitivity of the present invention has no defects at all, and has high corrosion resistance to the electrolytic solution, and is increased in pigmentation with the shielding film. For a sensitive solar cell, it has good photoelectric conversion efficiency.

Industrial applicability

In the resin composition having a radiation-sensitive linearity, since the pattern is formed by radiation exposure and development, it is possible to have metal wiring only on the substrate having the metal wiring difference in the dye-sensitized solar cell electrode. On the portion, a mask film having a uniform thickness is formed. Further, since the resin composition having a radiation-sensitive property can accurately form a mask film only at the position of the metal wiring, there is no film defect and sufficient corrosion resistance. The electrode for a dye-sensitized solar cell having the masking film has high photoelectric conversion efficiency. Therefore, the resin composition having a radiation-sensing property can be preferably used as a material for forming a masking film for an electrode for a dye-sensitized solar cell. Further, the present invention does not have a radiation-sensitive resin composition, and can provide a resin composition capable of forming a mask film at a low cost by only a relatively simple step of a coating step and a heating step, and contains the corrosion-resistant composition. An electrode for a dye-sensitized solar cell having excellent photoelectric conversion efficiency of a masking film.

1. . . Substrate

2. . . Transparent conductive film

3. . . Metal wiring layer

4. . . Porous oxide semiconductor layer

5. . . Coating film

6. . . Masking film

7. . . Electrode substrate

8. . . Porous oxide semiconductor layer

9. . . Electrode

10. . . Iodine electrolyte solution

11. . . Adhesive film

DRAWINGS

Fig. 1 is a schematic cross-sectional view showing each stroke of a method (Example) of producing an electrode substrate of a dye-sensitized solar cell having a masking film of the present invention.

Fig. 2 is a schematic cross-sectional view showing the steps of a method (Example) for producing a dye-sensitized solar cell using the electrode substrate of Fig. 1.

1. . . Substrate

2. . . Transparent conductive film

3. . . Metal wiring layer

4. . . Porous oxide semiconductor layer

5. . . Coating film

6. . . Masking film

7. . . Electrode substrate

Claims (12)

An electrode for a dye-sensitized solar cell, characterized by having a masking film formed of a cured product of a resin composition containing [A] having a carboxyl group, an epoxy group, and a (meth) propylene group. A copolymer of at least one reactive functional group in the group consisting of fluorenyl groups, and [B] a polymerizable compound having an ethylenically unsaturated double bond. An electrode for a dye-sensitized solar cell according to the first aspect of the invention, wherein [B] a polymerizable compound having an ethylenically unsaturated double bond is selected from the group consisting of a monofunctional (meth) acrylate and a bifunctional (methyl) group. At least one of the group consisting of an acrylate and a trifunctional or higher (meth) acrylate. The electrode for a dye-sensitized solar cell according to claim 1 or 2, wherein the resin composition further contains a [C] radiation-sensitive polymerization initiator. The electrode for a dye-sensitized solar cell according to the third aspect of the invention, wherein the [C] radiation-sensitive polymerization initiator is an O-mercaptopurine compound and/or an acetophenone compound. A resin composition for forming a masking film for an electrode for a dye-sensitized solar cell, comprising [A] at least one reaction having a group selected from the group consisting of a carboxyl group, an epoxy group, and a (meth)acryl fluorenyl group; A functional group-based copolymer and [B] a polymerizable compound having an ethylenically unsaturated double bond. The resin composition of claim 5, further comprising: [C] a radiation-sensitive polymerization initiator. Such as the resin composition of claim 6 of the patent scope, wherein [B] has ethylene The polymerizable compound of the unsaturated double bond is at least one selected from the group consisting of a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, and a trifunctional or higher (meth) acrylate. . The resin composition of claim 6 or 7, wherein the [C] radiation-sensitive polymerization initiator is an O-mercaptopurine compound and/or an acetophenone compound. A masking film for an electrode for a dye-sensitized solar cell, which is formed by a resin composition according to any one of claims 5 to 8. A dye-sensitized solar cell having a masking film as in claim 9 of the patent application. A method for forming a masking film for an electrode for a dye-sensitized solar cell, comprising: (1) forming a laminated body having a conductive substrate and a metal wiring layer on a surface side of the conductive substrate, as in Patent Application No. 5 The step of coating the coating film of the resin composition so as to cover at least the entirety of the metal wiring layer, and (2) the step of heating the coating film formed in the step (1). A method for forming a masking film for an electrode for a dye-sensitized solar cell, comprising: (1') forming a laminate having a conductive substrate and a metal wiring layer on a surface side of the conductive substrate, as described in the patent application scope The coating film of the resin composition of any one of 6 to 8 so as to cover at least the entirety of the metal wiring layer, (3) a step of irradiating only a portion of the coating film formed in the step (1') on the metal wiring layer, and (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).