KR101623725B1 - Electrode for dye-sensitized solar cell, resin composition for forming a shielding film of electrode for dye-sensitized solar cell, shielding film and forming method thereof, and dye-sensitized solar cell - Google Patents

Abstract

(PROBLEMS TO BE SOLVED BY THE INVENTION) A resin composition capable of accurately coating on a substrate having a step of a metal wiring and capable of forming a shield film having excellent corrosion resistance while maintaining high photoelectric conversion efficiency. Also provided is a resin composition capable of forming a shield film at a low cost by a relatively simple process such as a coating process and a heating process, and an electrode for a dye-sensitized solar cell having a shield film having this corrosion resistance and excellent in photoelectric conversion efficiency.
The present invention provides a dye-sensitized solar cell electrode comprising a shield film formed from a resin composition, wherein the resin composition is selected from the group consisting of [A] a carboxyl group, an epoxy group and a (meth) acryloyl group And a polymer having at least one kind of reactive functional group.

Description

TECHNICAL FIELD [0001] The present invention relates to an electrode for a dye-sensitized solar cell, a resin composition for forming a shielding film of an electrode for a dye-sensitized solar cell, a shielding film and a method for forming the shielding film, and a dye-sensitized solar cell OF ELECTRODE FOR DYE-SENSITIZED SOLAR CELL, SHIELDING FILM AND FORMING METHOD THEREOF, AND DYE-SENSITIZED SOLAR CELL}

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

The dye-sensitized solar cell has been developed by Grassell et al. In Switzerland and has attracted attention as a new type of solar cell because it has advantages such as high photoelectric conversion efficiency and low manufacturing cost (for example, Japan See, for example, JP-A-1-220380; M.Graetzel et al., Nature, (1991) 353, p. 737). The dye-sensitized solar cell includes a working electrode having an oxide semiconductor porous film on which a photosensitizing dye made of fine oxide semiconductor particles is supported on a transparent electrode substrate, a counter electrode formed opposite to the working electrode, and a counter electrode formed between the working electrode and the counter electrode And an electrolyte layer (charge transfer layer) formed by filling an electrolyte solution in the electrolyte layer. In such a dye-sensitized solar cell, oxide semiconductor fine particles are increased or decreased by the photosensitizing dye absorbing incident light such as sunlight and function as a photoelectric conversion element for converting light energy into electric power.

As the transparent electrode substrate used in the dye-sensitized solar cell, a transparent conductive film such as tin-doped indium oxide (ITO) or fluorine-doped tin oxide (FTO) can be used as a transparent electrode substrate in a substrate of a high strain point glass It is common to form the film on the surface. The tin-doped indium oxide (ITO) and the fluorine-doped tin oxide (FTO) are preferably used from the viewpoints of transparency, resistance to corrosion by an electrolytic solution, ease of film formation and the like. However, the resistivity of ITO or FTO is on the order of 10 ^-4 [Ω · cm] and is about 100 times larger than that of metal such as silver or gold. In such a case, this causes a decrease in the photoelectric conversion efficiency.

As a method of lowering the resistance of the transparent electrode substrate, it is conceivable to increase the thickness of the transparent conductive film (ITO, FTO or the like). However, when the film thickness is enough to sufficiently lower the resistance value, the light absorption by the transparent conductive film becomes large Throw away. In this case, since the transmission efficiency of the incident light in the transparent conductive film is remarkably lowered, the photoelectric conversion efficiency is likely to be lowered. As a solution to this problem, studies have been made to reduce the resistance of the transparent electrode substrate by forming a metal wiring on the surface of the transparent electrode substrate to such an extent that the aperture ratio is not significantly deteriorated (JP-A-2003-203681 See also

However, in this case, the corrosion of the metal wiring due to the electrolytic solution occurs, and the resistance of the transparent electrode substrate increases with the lapse of time, resulting in a decrease in the photoelectric conversion efficiency. Therefore, when the metal wiring is formed on the surface of the transparent electrode substrate, it is necessary that at least the surface portion of the metal wiring is protected by any shielding layer. This shielding layer can closely coat the metal wiring and is required to have excellent corrosion resistance to the electrolyte constituting the electrolyte layer.

In view of the above situation, Japanese Unexamined Patent Publication (Kokai) No. 2005-197176 discloses an acrylic resin composition containing conductive particles (ITO, ATO, ZnO and the like) in order to protect metal wiring formed on an electrode for a dye-sensitized solar cell from corrosion by an electrolytic solution Discloses a technique for forming an organic film made of a transparent resin such as a resin, a polyester resin, or a polyurethane resin on the uppermost layer of the electrode. However, since the conductive particles are dispersed unevenly in the transparent resin solution, it is difficult to form a coating film having a uniform thickness on the substrate having the stepped portion of the metal wiring. As a result, there is a problem that the photoelectric conversion efficiency is lowered because the organic film is defective or the organic film is formed to the portion where no metal wiring exists.

Japanese Patent Laid-Open No. 2005-197176 discloses a method of forming an organic film made of a transparent resin such as an acrylic resin, a polyester resin or a polyurethane resin so as to cover a surface portion of a metal wiring formed on an electrode for a dye-sensitized solar cell Technology is disclosed. However, it is very difficult to apply the resin composition precisely to only the portion where the metal wiring exists, by screen printing or gravure printing, with respect to the substrate having the stepped portion of the metal wiring. Even in the case of adopting such a coating method, there is also a problem that the organic film is partially broken in the metal wiring, or the organic film is formed in an unnecessary part where no metal wiring is present, and the photoelectric conversion efficiency is lowered.

Accordingly, it is an object of the present invention to provide a dye-sensitized solar cell which can accurately coat a substrate having a step of a metal wiring and can form a shielding film having excellent corrosion resistance while maintaining high photoelectric conversion efficiency Development of a film-forming composition is strongly desired. Further, a substrate having a step of a metal wiring in a dye-sensitized solar cell is coated on a substrate by a coating method such as a bar coating method, a spin coating method, a slit die method, and the like, A resin composition which can be formed is not known.

Japanese Unexamined Patent Publication No. 1-220380 Japanese Laid-Open Patent Publication No. 2003-203681 Japanese Patent Application Laid-Open No. 2005-197176

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

SUMMARY OF THE INVENTION The present invention has been made based on the above-described circumstances, and it is an object of the present invention to provide an electrode for a dye-sensitized solar cell having a metal wiring layer formed on a substrate, which can be accurately applied onto a substrate having a step of metal wiring, And which is capable of forming a shield film having excellent corrosion resistance against corrosion caused by an electrolytic solution, while maintaining the above composition. Another object of the present invention is to provide a resin composition capable of forming a shield film at a low cost by a relatively simple process such as a coating process and a heating process, and an electrode for a dye-sensitized solar cell having a shield film having this corrosion resistance and excellent in photoelectric conversion efficiency.

According to an aspect of the present invention,

1. An electrode for a dye-sensitized solar cell comprising a shield film formed by a resin composition,

Wherein the resin composition comprises a shield film comprising a cured product of a resin composition containing a copolymer having at least one reactive functional group selected from the group consisting of a carboxyl group, an epoxy group and a (meth) acryloyl group And is a dye-sensitized solar cell electrode.

The formation of the shielding film using the resin composition can be performed at a low cost by only a relatively simple process such as a coating step and a heating step. The shielding film is excellent in corrosion resistance from the electrolyte solution and can be used for a dye sensitized solar cell using the shielding film. The electrode has excellent photoelectric conversion efficiency.

The resin composition preferably further contains a polymerizable compound having an ethylenically unsaturated double bond [B], and the polymerizable compound having an ethylenically unsaturated double bond as the [B] monofunctional (meth) acrylate , Bifunctional (meth) acrylate, and trifunctional or more (meth) acrylate. It is also preferable that the resin composition contains a [C] radiation-sensitive polymerization initiator, and the [C] radiation-sensitive polymerization initiator is preferably an O-acyloxime compound and / or an acetophenone compound. By using these compounds, it is possible to obtain a shield film excellent in the corrosion resistance of the metal wiring without defects of the film.

In addition, the resin composition according to the present invention is characterized in that,

[A] A curable resin composition for forming a shield film of an electrode for a dye-sensitized solar cell comprising a copolymer having at least one reactive functional group selected from the group consisting of a carboxyl group, an epoxy group and a (meth) acryloyl group. The resin composition can be suitably used as a shielding film-forming material of an electrode for a dye-sensitized solar cell.

The resin composition

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

[C] Radiation-sensitive polymerization initiator

May be further contained. When the resin composition is used for forming a shield film of an electrode for a dye-sensitized solar cell because of its high sensitivity to radiation, a shield film having a uniform thickness is formed only on a portion where metal wiring exists, . Therefore, the shielding film formed by using the resin composition effectively protects the metal wiring from corrosion by the electrolytic solution, and the dye-sensitized solar cell electrode using the shielding film can maintain high photoelectric conversion efficiency.

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

Therefore, the shield film formed using the resin composition and the dye-sensitized solar cell (photoelectric conversion element) having the shield film can be formed by exposure and development using the radiation-sensitive property so that the shield film is formed accurately only at the portion where the metal wiring exists And thus has a high photoelectric conversion efficiency.

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

(1) a step of forming a coating film of the curable resin composition such that at least a metal wiring layer is entirely covered with a laminate including a conductive substrate and a metal wiring layer on the front surface side of the conductive substrate, and

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

Lt; / RTI > This forming method requires only a relatively simple process of a coating step and a heating step, and a shield film can be formed at a low cost.

As a method of forming a shield film of an electrode for a dye-sensitized solar cell according to another aspect of the present invention,

(i) a step of forming a coating film of the radiation sensitive resin composition so that at least a metal wiring layer is entirely covered with a laminate including a conductive substrate and a metal wiring layer on the front surface side of the conductive substrate,

(ii) a step of irradiating only the portion of the coating film formed in the step (i) on the metal wiring layer,

(iii) a step of developing the coating film irradiated with the radiation in the step (ii)

(iv) a step of heating the developed coating film in the step (iii)

Lt; / RTI > Here, the " surface " of the conductive substrate means a surface on the side of the counter electrode in the dye-sensitized solar cell comprising the conductive substrate. A method of forming a shielding film of an electrode for a dye-sensitized solar cell using the resin composition having a radiation-sensitive property is a method in which a pattern is formed by exposure and development using radiation-sensitive properties, It is possible to easily form a pattern of the pattern. Therefore, according to this method, it is possible to form a shield film having sufficient resistance to corrosion by an electrolytic solution.

As described above, since the resin composition having the radiation-sensitive properties forms a pattern by exposure and development using radiation-sensitive properties, it is possible to form a pattern on a substrate having a step of a metal wiring in a dye- It is possible to form a shield film having a uniform thickness only in a portion where wiring exists. In addition, the above resin composition having radiation-sensitive properties can form a shield film precisely only at a portion of a metal wiring as described above, so that a shield film having sufficient corrosion resistance can be obtained. Therefore, the resin composition having radiation-sensitive properties can be suitably used as a material for forming a shield film of a dye-sensitized solar cell electrode. The resin composition having no radiation-sensitive property of the present invention is a resin composition capable of forming a shield film at a low cost by a relatively simple process such as a coating process and a heating process, and a resin composition having a shield film having corrosion resistance and having excellent photoelectric conversion efficiency An electrode for a sensitized solar cell can be provided.

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

(Mode for carrying out the invention)

Dye-sensitized solar cell

The dye-sensitized solar cell of the present invention mainly includes a conductive substrate, a working electrode stacked on the conductive substrate, a counter electrode disposed on the working electrode, and a charge transfer layer disposed between the electrodes . This working electrode has a metal wiring layer having a shielding film on its periphery (excluding a lower surface) and a porous oxide semiconductor layer arranged between the metal wiring layers.

As the conductive substrate, a substantially transparent material is used. The light transmittance of the conductive base material is preferably 50% or more, 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 its surface, a glass plate, an abrasive plate of ceramics such as titanium oxide or alumina, or a plastic sheet can be used. Examples of plastics for use in the plastic sheet include plastics such as triacetylcellulose, polyethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, syndiotactic polystyrene, polycarbonate, polyarylate, polyetherimide, polysulfone, Cyclic polyolefin, phenoxy resin, and brominated phenoxy resin.

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

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

The porous oxide semiconductor film is composed of a polymer of metal oxide fine particles showing semiconducting properties such as titanium oxide, tin oxide, tungsten oxide, zinc oxide, zirconium oxide, and niobium oxide. The porous oxide semiconductor film is a porous body having innumerable minute voids therein and having fine irregularities on its surface, and its thickness is 5 to 50 占 퐉. This porous oxide semiconductor film is typically formed in a portion where a metal wiring layer on a conductive substrate is not disposed.

The porous oxide semiconductor film can be formed, for example, by dispersing a colloidal solution or dispersion (using water and / or an organic solvent as a solvent) in which fine particles of the above metal oxide having an average particle diameter of 5 to 50 nm are dispersed, By a known application method such as printing, inkjet printing, roll coating, doctor coating, spray coating, etc., and sintering at 300 to 800 ° C. This porous oxide semiconductor film is supported with a photosensitizing dye.

As the photosensitizer, it is preferable that the dye has absorption in a visible light region and / or an infrared light region and has a lowest empty level than a conduction band of a semiconductor. Examples of the photosensitizing dye include azo dyes, quinone dyes, quinone imine dyes, quinaclidone dyes, squarylium dyes, cyanine dyes, cyanide dyes, merocyanine dyes, triphenyl dyes, A methane-based dye, a xanthene-based dye, a porphyrin-based dye, a perylene-based dye, an indigo-based dye, a phthalocyanine-based dye, a naphthalocyanine-based dye and a rhodamine-based dye. As the photosensitizing dye, a metal complex dye is also preferably used. Examples of the metal constituting the metal complex pigment include Cu, Ni, Fe, Co, V, Sn, Si, Ti, Ge, Cr, Zn, Ru, Mg, Al, Pb, Mn, In, Mo, Ag, Cd, Hf, Re, Au, Ac, Tc, Te, Nb, Sb, La, W, Pt, Ta, Ir, Pd, Os, Ga, Tb, Eu, Rb, Bi, Se, Rh, and the like. Examples of preferable metal complex pigments are metal phthalocyanine pigments, metal porphyrin pigments or ruthenium complex pigments, and ruthenium complex pigments are particularly preferable.

As the counter electrode, a single layer structure of a conductive material itself or a substrate having a counter electrode conductive film on its surface can be used as the conductive substrate. In the latter case, as the conductive material and substrate, the same materials as those of the above-described conductive substrate can be used. As the counter electrode, it is preferable to use one having a catalytic ability to perform an oxidation reaction of I ₃ ^- ions or the like and a reduction reaction of other redox ions at a sufficient rate. Examples of the counter electrode include a platinum electrode, a platinum-plated or platinum-deposited surface of a conductive material, rhodium metal, ruthenium metal, ruthenium oxide, carbon and the like.

The charge transporting layer is a layer containing a charge transporting material having a function of replenishing electrons to the oxidation enhancer dye. Examples of the charge transporting material constituting the charge transporting layer include an electrolyte solution such as a solvent in which a redox pair ion is dissolved or a room temperature molten salt containing a redox pair ion or a solution of a redox pair ion is impregnated in a polymer matrix or a low molecular weight gelling agent (Pseudo-solidified) electrolytes in a gel state.

Examples of the redox pair ion, I ^- / I ₃ ^- system, Br ^- / Br ₃ ^- one that contains a redox pair ion of the system, etc., ferrocyanide salts / Perry cyanates, ferrocene / Perry upon hydronium ions, cobalt complex A metal complex oxide such as a metal complex oxide; An organic redox system such as an alkylthiol-alkyl disulfide, a biologen dye, a hydroquinone / quinone, and the like; Sulfur compounds such as sodium polysulfide, alkyl thiol / alkyl disulfide, and the like. Examples of the solvent include carbonate compounds such as dimethyl carbonate, diethyl carbonate, ethylene carbonate and propylene carbonate; Heterocyclic compounds such as 3-methyl-2-oxazolidinone; Ether compounds such as dioxane and diethyl ether; Chain ethers such as ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether and polypropylene glycol dialkyl ether; Alcohols such as methanol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether and polypropylene glycol monoalkyl ether; And non-proton polar substances such as tetrahydrofuran, dimethyl sulfoxide and sulfolane. Examples of the molten salt electrolyte include electrolytes containing iodine salts such as pyridinium salts, imidazolium salts, and triazolium salts.

Examples of the method for forming the charge transfer layer between the working electrode and the counter electrode include a method in which the working electrode and the counter electrode are disposed facing each other and then the electrolyte is filled between both electrodes to form a charge transfer layer; A method of forming a charge transporting layer by dropping or applying an electrolytic solution on an electrode, and then overlapping the other electrode on the charge transporting layer can be used.

Such a dye-sensitized solar cell (photoelectric conversion element) has a high photoelectric conversion efficiency because a shield film is precisely formed only in a portion where metal wiring on a substrate is formed by exposure and development using the resin composition of the present invention.

Resin composition

The resin composition for shield film formation of an electrode for a dye-sensitized solar cell according to the present invention comprises (A) a copolymer having at least one reactive functional group selected from the group consisting of a carboxyl group, an epoxy group and a (meth) acryloyl group Hereinafter sometimes referred to as " [A] copolymer "). Further, a polymerizable compound having an ethylenically unsaturated double bond [B] (hereinafter sometimes referred to as "[B] polymerizable compound") and a radiation sensitive polymerization initiator [C] , It contains other optional components. Each component will be described below.

[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) acryloyl group. By having these reactive functional groups in the copolymer [A], it is possible to form a shield film excellent in corrosion resistance of the metal wiring without defects of the film. When the resin composition of the present invention is irradiated with radiation, the polymerization reactivity between the [A] copolymer and the polymerization reactivity between the [A] copolymer and the [B] polymerizable compound when exposed to a curing reaction As a result, a shield film having a desired shape can be easily formed.

A copolymer having a reactive functional group such as a carboxyl group or an epoxy group can be synthesized by copolymerizing a radically polymerizable monomer having these reactive functional groups with another radically polymerizable monomer. The copolymer having a (meth) acryloyl group can be synthesized by copolymerizing a radically polymerizable monomer having a hydroxyl group with another radically polymerizable monomer and then reacting with an isocyanate compound having a (meth) acryloyl group. The copolymer [A] may be obtained by copolymerizing a constituent unit derived from a radically polymerizable monomer having a reactive functional group such as a carboxyl group, an epoxy group or a (meth) acryloyl group with a constituent unit derived from these radical polymerizable monomers and other radically polymerizable monomers , Preferably from 10 to 90 mass%, particularly preferably from 20 to 80 mass%, based on the total of the units. When the content of the constituent unit derived from the radical polymerizable monomer having a reactive functional group in the [A] copolymer is 10 to 90% by mass, when the resin composition of the present invention is radiation sensitive, the curing reactivity during exposure can be increased have.

As examples of the radically polymerizable monomer having a carboxyl group,

Acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid And the like;

Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid;

And the acid anhydrides of the above-mentioned dicarboxylic acids.

As examples of the radically polymerizable monomer having an epoxy group,

4-methacryloyloxymethyl-2-cyclohexyl-1,3-dioxolane. Glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxybutyl acrylate, 6,7-epoxyhexyl acrylate, acrylate-3,4-epoxycyclohexyl acrylate, Acrylic acid epoxy alkyl esters such as hexylmethyl;

Glycidyl methacrylate, 2-methylglycidyl methacrylate, methacrylic acid-3,4-epoxybutyl, methacrylic acid-6,7-epoxyheptyl, methacrylic acid-3,4- Methacrylic acid epoxyalkyl esters such as hexyl and methacrylic acid-3,4-epoxycyclohexylmethyl;

? -alkylacrylic acid epoxyalkyl esters such as glycidyl? -ethyl acrylate, glycidyl? -n-propyl acrylate, glycidyl? -n-butyl acrylate and? -ethylacrylic acid-6,7-epoxyheptyl;

glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether;

3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) oxetane, 3- (Methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (Methacryloyloxymethyl) oxetane, 3-ethyl-3- (methacryloyloxymethyl) oxetane, and other oxetanyl groups;

3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) Acryloyloxyethyl) oxetane, oxetanyl group-containing acrylate esters such as 3- (acryloyloxyethyl) -3-ethyloxetane and 2-ethyl-3- (acryloyloxyethyl) have.

Among these radically polymerizable monomers having an epoxy group, glycidyl methacrylate, 2-methylglycidyl methacrylate, methacrylic acid-3,4-epoxycyclohexyl, methacrylic acid-3,4- (Methacryloyloxymethyl) oxetane, 3-methyl-3- (methacryloyloxymethyl) oxetane and 3-ethyl-3- (methacryloyloxymethyl) oxetane, the copolymerization reactivity with other radically polymerizable monomers, From the viewpoint of developability when the resin composition of the present invention is radiation-sensitive.

As examples of the radically polymerizable monomer having a hydroxyl group,

Acrylic acid hydroxyalkyl esters such as acrylic acid-2-hydroxyethyl ester, acrylic acid-3-hydroxypropyl ester, acrylic acid-4-hydroxybutyl ester, and acrylic acid-4-hydroxymethyl-cyclohexylmethyl ester;

2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, methacrylic acid-5-hydroxypentyl ester, methacrylic acid- Hydroxyethyl methacrylate, hydroxyhexyl ester, methacrylic acid-4-hydroxymethyl-cyclohexylmethyl ester, and the like.

Among these radically polymerizable monomers having hydroxyl groups, from the viewpoint of copolymerization reactivity with other radically polymerizable monomers and reactivity with isocyanate compounds having a (meth) acryloyl group, acrylic acid-2-hydroxyethyl ester, acrylic acid-3 Hydroxypropyl esters, acrylic acid-4-hydroxybutyl esters, methacrylic acid-2-hydroxyethyl esters, methacrylic acid-4-hydroxybutyl esters, 4-hydroxymethyl-cyclohexylmethyl acrylate, Methacrylic acid-4-hydroxymethyl-cyclohexylmethyl ester is preferred.

Examples of the isocyanate compound having a (meth) acryloyl group for reacting with a copolymer of a radically polymerizable monomer having a hydroxyl group and other radically polymerizable monomers include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl Acrylic acid derivatives such as isocyanate and methacrylic acid derivatives. Examples of commercially available products of 2-acryloyloxyethyl isocyanate include Karenz AOI (manufactured by Showa Denko K.K.) and 2-methacryloyloxyethyl isocyanate commercially available products such as Carlene MOI Manufactured by K.K.).

Examples of other radically polymerizable monomers that are copolymerized with a radically polymerizable monomer having a reactive functional group such as a carboxyl group, an epoxy group,

Acrylic acid alkyl esters such as methyl acrylate and i-propyl acrylate;

Methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and t-butyl methacrylate;

Acrylic acid-tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, acrylic acid -2- (tricyclo [5.2.1.0 ^2,6 ] decan-8- yloxy Acrylic acid alicyclic esters such as ethyl and isobornyl acrylate;

2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 2- (tricyclo [5.2.1.0 ^{2, 6} ] decan-8-yloxy) ethyl methacrylate, isobornyl methacrylate, and other methacrylic acid alicyclic esters;

Aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate, and aralkyl esters of acrylic acid;

Aralkyl esters of methacrylic acid and aryl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate;

Dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

Unsaturated heterocyclic 5-membered methacrylic acid esters containing one oxygen atom such as tetrahydrofuranyl methacrylate, tetrahydrofurfuryl methacrylate, tetrahydrofuryl methacrylate, and tetrahydropyran-2-methyl methacrylate, and unsaturated complex 6-membered methacrylic acid esters ;

4-methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-methacryloyloxymethyl- Methacryloyloxyethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methacryloyloxyethyl-2-cyclohexyloxy- Ethyl-2-methyl-2-isobutyl-1,3-dioxolane, and other unsaturated heterocyclic 5-membered methacrylic acid esters containing two oxygen atoms;

Acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl- Dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-acryloyloxymethyl- Cyclohexyl-1,3-dioxolane, 4-acryloyloxyethyl-2-methyl-2-ethyl-1,3- Dioxolane, 4-acryloyloxypropyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxybutyl- An unsaturated complex 5-membered ring acrylate ester containing two oxygen atoms;

Vinyl aromatic compounds such as styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and 4-isopropenylphenol;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- N-substituted maleimides such as 6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

Conjugated diene-based compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene;

And other unsaturated compounds such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, and vinyl acetate.

Of these other radical polymerizable monomers, styrene, 4-isopropenylphenol, methacrylic tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, methacrylic acid tetrahydrofurfuryl, 1,3-butadiene , 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, N-cyclohexylmaleimide, N-phenylmaleimide and benzyl methacrylate. From the viewpoint of copolymerization reactivity with the radically polymerizable monomer and from the viewpoint of developability when the resin composition of the present invention is irradiated with radiation.

The polystyrene reduced number average molecular weight (hereinafter referred to as "Mn") of the copolymer [A] by GPC (gel permeation chromatography) is preferably 2 × 10 ^{3 to} 1 × 10 ⁵ , more preferably 5 × 10 ^{3 to} 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 sensitive to radiation, the curing reactivity upon exposure can be improved.

The molecular weight distribution " Mw / Mn " (here, " Mw " is the polystyrene reduced weight average molecular weight of the copolymer measured by gel permeation chromatography) of the copolymer [A] More preferably 3.0 or less. When the Mw / Mn of the copolymer is 5.0 or less, when the resin composition of the present invention is radiation sensitive, it is possible to form a shield film of a desired shape more accurately at the time of development.

Examples of the solvent used in the polymerization reaction for producing the copolymer [A] include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol mono Alkyl ether acetates, propylene glycol monoalkyl ether propionates, aromatic hydrocarbons, ketones, and other esters.

As these solvents,

Examples of alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like;

As the ethers, for example, tetrahydrofuran and the like;

As the glycol ether, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like;

As the ethylene glycol alkyl ether acetate, for example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate and the like;

As the diethylene glycol alkyl ether, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like;

As the propylene glycol monoalkyl ether, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like;

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 and the like;

Examples of the propylene glycol monoalkyl ether propionate include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, and propylene glycol monobutyl ether propionate;

As the aromatic hydrocarbons, for example, toluene, xylene and the like;

As the ketone, for example, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and the like;

Examples of other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy- Hydroxypropionate, propyl 3-hydroxypropionate, propyl 3-hydroxypropionate, propyl 3-hydroxypropionate, propyl 3-hydroxypropionate, propyl 3-hydroxypropionate, Propyl methoxyacetate, butyl hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethyl ethoxyacetate, ethoxyacetic acid Propyl, butyl ethoxyacetate, methyl propoxyacetate, propoxyacetic acid Butoxy propionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, butyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, propoxypropionate, propoxyacetate, Propoxy propionate, propyl propionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, Ethyl, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, 3- Esters such as ethyloxy propionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate and butyl 3- Respectively.

Of these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate and butyl methoxyacetate are preferable, and diethylene glycol dimethyl ether, diethylene glycol ethyl methyl Ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and butyl methoxyacetate are preferable.

As the polymerization initiator used in the polymerization reaction for producing the copolymer [A], those generally known as radical polymerization initiators can be used. As the radical polymerization initiator, for example,

(2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethyl Azo compounds such as valeronitrile);

Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane; And hydrogen peroxide.

When a peroxide is used as the radical polymerization initiator, the peroxide may be used as a redox type initiator together with a reducing agent.

In the polymerization reaction for producing the copolymer [A], a molecular weight modifier may be used to adjust the molecular weight. As specific examples of the molecular weight adjuster,

Halogenated hydrocarbons such as chloroform and carbon tetrabromide;

mercaptans such as n-hexylmercaptan, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan and thioglycolic acid;

Xantogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide;

Terpinolene, alpha -methylstyrene dimer, and the like.

[B] Polymerizable  compound

[B] The polymerizable compound is suitably used in the resin composition of the present invention. Preferable examples of the [B] polymerizable compound include monofunctional (meth) acrylate, bifunctional (meth) acrylate, and trifunctional or more (meth) acrylate. By using these compounds, the polymerization reactivity between the compounds of the polymerizable compound [B] and the polymerization reactivity between the [A] copolymer and the [B] polymerizable compound when the resin composition of the present invention is radiation- It is possible to obtain a shield film having an accurate shape and excellent corrosion resistance.

Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl And 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate. Examples of commercially available products of these monofunctional (meth) acrylates include Aronix M-101, M-111, M-114 (manufactured by Toagosei Kogyo K.K.), KAYARAD TC-110S, Nippon Kayaku Co., Ltd.), Viscoat 158, and 2311 (manufactured by Osaka Yuki Kagaku Kogyo K.K.).

Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorenedi (meth) acrylate, and the like. Examples of commercially available products of these bifunctional (meth) acrylates include Aronix M-210, M-240, M-6200 (manufactured by Toagosei Kogyo K.K.), KAYARAD HDDA, 604 (manufactured by Nippon Kayaku Co., Ltd.), Viscot 260, Copper 312 and Copper 335 HP (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.).

Examples of the trifunctional or more (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, succinic acid mono- [3- (3- (meth) acryloyloxy- (Acryloyloxymethyl-propoxy) -2,2-bis- (meth) acryloyloxymethyl-propyl] ester. Examples of commercial products of these trifunctional or more (meth) acrylates include Aronix M-309, M-400, M-405, M-450, M-7100, M- 20, DPCA-30, DPCA-60, DPCA-120, DPCA-120 (manufactured by Nippon Kayaku K.K.), Viscoat 295, Copper DPCA- 300, copper 360, copper GPT, copper 3PA, copper 400 (manufactured by Osaka Yuki Kagakuko Kogyo Co., Ltd.), and the like.

Of these polymerizable compounds having ethylenically unsaturated double bonds, trifunctional or more (meth) acrylates are preferably used from the viewpoint of improving the curability of the resin composition. Among them, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, succinic acid mono- [3- (3-acryloyloxy- -Acryloyloxymethyl-propoxy) -2,2-bis-acryloyloxymethyl-propyl] ester is particularly preferred. These ethylenically unsaturated double bond-containing polymerizable compounds may be used alone or in combination of two or more.

The amount of the [B] polymerizable compound in the resin composition is preferably 50 to 300 parts by mass, more preferably 60 to 250 parts by mass based on 100 parts by mass of the [A] copolymer. When the amount of the polymeric compound [B] used is 50 to 300 parts by mass, a resin composition in which characteristics of the formed shielding film, such as adhesion to a substrate and corrosion resistance to an electrolytic solution, are balanced to a higher level can be obtained.

[C] Sensitizing radiation property  polymerization Initiator

The [C] radiation-sensitive polymerization initiator is suitably 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 active species capable of initiating polymerization of the [B] polymerizable compound in response to radiation. Examples of such [C] radiation-sensitive polymerization initiators include O-acyloxime compounds, acetophenone compounds, and imidazole compounds.

Examples of the O-acyloxime compound used as the radiation-sensitive polymerization initiator include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- Oxime-1-onoxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) (9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethan- -9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1 -9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyl Oxime), ethanone- 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H- Ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} - (9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole Yl] -1- (O-acetyloxime).

Preferable examples of these O-acyloxime compounds include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- -1- (9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol- Methyl-4- (2,2-dimethyl-1,3-dioxoranyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O- ). These O-acyloxime compounds may be used alone or in combination of two or more.

Examples of the acetophenone compound used as the radiation-sensitive polymerization initiator include an? -Amino ketone compound and? -Hydroxy ketone compound.

Examples of the? -amino ketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) (4-morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one.

Examples of the? -hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, and the like.

Among these acetophenone compounds,? -Amino ketone compounds are preferable, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one is particularly preferred. These acetophenone compounds may be used alone or in admixture of two or more.

Examples of the imidazole compound used as the radiation-sensitive polymerization initiator include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1 , 2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, and the like.

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

In the resin composition of the present invention, when a nonimidazole compound is used as the radiation-sensitive polymerization initiator [C], an aliphatic or aromatic compound having a dialkylamino group (hereinafter referred to as " ) Can be added.

Examples of such amino-group sensitizers include 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone. Of these amino-based sensitizers, 4,4'-bis (diethylamino) benzophenone is particularly preferable. These amino-based sensitizers may be used alone or in combination of two or more.

When a nonimidazole compound and an amino-based sensitizer are used in combination, a thiol compound can be added as a hydrogen radical donating agent. The imidazole compound is increased or decreased by the amino-group sensitizer to cleave and generate an imidazole radical. However, the imidazole compound itself may not exhibit high polymerization initiating ability. However, by adding a thiol compound to a system in which a nonimidazole compound and an amino-based sensitizer coexist, a hydrogen radical is donated from an imidazole radical thiol compound. As a result, imidazole radicals are converted into neutral imidazoles, and a component having a sulfur radical having a high polymerization initiating ability is generated, whereby when the resin composition of the present invention is irradiated with radiation, the curing reactivity at the time of exposure is increased As a result, a shield film having a desired shape can be easily formed.

As examples of such thiol compounds,

Aromatic thiol compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, and 2-mercapto-5-methoxybenzothiazole;

Aliphatic monothiol compounds such as 3-mercaptopropionic acid and methyl 3-mercaptopropionate;

And aliphatic thiol compounds having two or more functionalities such as pentaerythritol tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate). Among these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.

In the resin composition, when the nonimidazole compound is used in combination with the amino-based sensitizer, the amount of the amino-based sensitizer is preferably 0.1 to 50 parts by mass based on 100 parts by mass of the non-imidazole compound, Is from 1 to 20 parts by mass. When the amount of the amino-based sensitizer is in the range of 0.1 to 50 parts by mass, the curing reactivity during exposure can be further enhanced when the resin composition of the present invention is irradiated with radiation.

When a non-imidazole compound, an amino-based sensitizer and a thiol compound are used in combination, the amount of the thiol compound to be added is preferably 0.1 to 50 parts by mass, more preferably 1 to 100 parts by mass, To 20 parts by mass. By setting the addition amount of the thiol compound to 0.1 to 50 parts by mass, the curing reactivity at the time of exposure is further improved, and it becomes easier to obtain a shield film having a desired shape.

[C] The radiation sensitive polymerization initiator preferably contains at least one member selected from the group consisting of an O-acyloxime compound and an acetophenone compound, and is selected from the group consisting of an O-acyloxime compound and an acetophenone compound More preferably at least one kind thereof, and a nonimidazole compound.

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

The ratio of the O-acyloxime compound and the acetophenone compound in the radiation-sensitive polymerization initiator of the [C] radiation-sensitive polymerization initiator is preferably in the range of , Preferably not less than 40 mass%, more preferably not less than 45 mass%, and particularly preferably not less than 50 mass%. By using an O-acyloxime compound and an acetophenone compound in such a ratio, a high curing reactivity can be obtained even at a low exposure dose, and as a result, a shield film having a more accurate shape can be formed.

Other optional components

The resin composition of the present invention may contain, in addition to the above-mentioned [A] copolymer, [B] polymerizable compound and [C] radiation-sensitive polymerization initiator, , [H] surfactants, and the like.

In the resin composition of the present invention, a [G] adhesion aid may be used to improve the adhesion between the formed shield film and the substrate. As such an adhesion auxiliary agent, a functional silane coupling agent is preferably used. Examples of the functional silane coupling agent include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group or an epoxy group. Specific examples of the functional silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxy Silane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

The [G] adhesion aid may be used alone or in combination of two or more. The amount of the [G] adhesion aid to be used is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass, based on 100 parts by mass of the [A] copolymer. By setting the amount of the [G] adhesion auxiliary agent to 0.1 to 30 parts by mass, the adhesion of the formed shielding film to the base material can be maintained at a sufficiently high level.

In the resin composition of the present invention, a [H] surfactant may be used in order to further improve the coating property upon forming a coating film. Examples of preferred surfactants include fluorinated surfactants, silicone surfactants and nonionic surfactants.

Examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octa Ethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di , 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, and other fluoroethers; Sodium perfluorododecylsulfonate; Fluoroalkanes such as 1,1,2,2,8,8,9,9,10,10-decafluorododecane and 1,1,2,2,3,3-hexafluorodecane; Sodium fluoroalkylbenzenesulfonate; Fluoroalkyloxyethylene ethers; Fluoroalkylammonium iodides; Fluoroalkyl polyoxyethylene ethers; Perfluoroalkyl polyoxyethanols; Perfluoroalkyl alkoxylates; Fluorine-based alkyl esters and the like.

Examples of commercially available products of these fluorinated surfactants include BM-1000, BM-1100 (manufactured by BM CHEMIE), Megaface F142D, F172, F173, F183 (manufactured by Dainippon Ink and Chemicals, Incorporated) Surflon S-112, S-113, S-131 (manufactured by Sumitomo 3M Limited), Fluorad FC-135, FC-170C, FC-430, FC-431 , S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105 and SC- Ltd.) and FTX-218 (manufactured by NEOS Co., Ltd.).

Examples of the silicone surfactant include SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57 and DC- 190 (manufactured by Toray Dow Corning Toray Silicone Co., ), KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Eftop EF301, EF303 and EF352 (manufactured by Shin-Aichi Kasei Kogyo Co., Ltd.).

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

Examples of polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether. Examples of polyoxyethylene aryl ethers include polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Examples of polyoxyethylene dialkyl esters include polyoxyethylene dilaurate and polyoxyethylene distearate. Examples of the (meth) acrylic acid copolymer are commercially available trade names such as Polyflow No. 57 and No. 90 (manufactured by Kyoeisha Chemical Co., Ltd.).

[H] Surfactants may be used alone or in combination of two or more. The amount of the [H] surfactant used is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass based on 100 parts by mass of the [A] copolymer. When the amount of the surfactant used is from 0.01 to 5 parts by mass, occurrence of film roughening on the surface of the formed shield film is suppressed, and a uniform coating film can be formed.

Resin composition

The resin composition of the present invention can be obtained by copolymerizing the above-mentioned copolymer [A], the polymerizable compound [B], the radiation sensitive polymerization initiator [C] and optional components ([G] adhesion auxiliary agent and / or [H] ) Are uniformly mixed. Usually, the resin composition is preferably dissolved in a suitable solvent and stored in a solution state and used. The 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 optional components in a predetermined ratio, for example, in a solvent.

As the solvent used for preparing the resin composition, the above-mentioned [A] copolymer, [B] polymerizable compound and [C] radiation-sensitive polymerization initiator and optional components ([G] adhesion aid and / or [H] Is not particularly limited as long as it uniformly dissolves each component of the water-soluble polymer (e.g. Examples of such a solvent include the same solvents as those exemplified as solvents that can be used for preparing the [A] copolymer.

Examples of such solvents include alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters, diethylene glycol alkyl ethers, propylene glycol ethers, and the like, from the viewpoints of solubility of each component, Glycol monoalkyl ether, propylene glycol monoalkyl ether acetate are preferably used. Of these, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether , Diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl 2- or 3-methoxypropionate, ethyl 2- or 3-ethoxypropionate and butyl methoxyacetate are particularly preferably used have.

In addition, in order to increase the in-plane uniformity of the film thickness of the formed coating film, a high boiling point solvent may be used together with the above solvent. Examples of the solvent having a high boiling point which can be used in combination with the solvent include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, But are not limited to, methyl pyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, , Diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like. Among these high-boiling solvents, N-methylpyrrolidone,? -Butyrolactone and N, N-dimethylacetamide are preferable.

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

When the resin composition is prepared in the form of a solution, the total amount of the components other than the solvent in the solution (i.e., the total amount of the [A] copolymer, the [B] polymerizable compound, the radiation sensitive polymerization initiator [C] Is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass, and still more preferably from 15 to 35% by mass, although it can be arbitrarily set depending on the purpose of use and the desired film thickness. The solution of the resin composition thus prepared may be filtered for use with a millipore filter having a pore size of about 0.2 탆 or the like and then used for use.

Of a dye-sensitized solar cell electrode Shielded membrane  formation

Next, a method of forming the shield film of the present invention using the above resin composition will be described. As the method for forming the shield film,

(1) a step of forming a coating film of the resin composition having no radiation-sensitive property such that at least a metal wiring layer is entirely covered with a laminate including a conductive substrate and a metal wiring layer on the front surface side of the conductive substrate, and

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

In this order.

(1) Process for forming a coating film of a resin composition

In this step, a solution of the resin composition of the present invention is applied onto a laminate including a conductive substrate and a metal wiring layer on the front surface side of the conductive substrate, and then the coated surface is heated (prebaked) to form a coated film. The application is performed so that at least the entire metal wiring layer on the front surface side of the conductive substrate is covered. The conditions for the prebaking vary depending on the kind of each component and the blending ratio, and preferably about 70 to 110 DEG C for about 1 to 10 minutes. The thickness of the coating film after pre-baking is preferably 0.1 to 5.0 탆, and more preferably 0.3 to 2.0 탆 or so.

The solid content concentration of the resin composition solution used for coating is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, and still more preferably 15 to 35 mass%. The method of applying the composition solution is not particularly limited and suitable methods such as spraying, roll coating, spin coating (coating method), slit die coating, bar coating, inkjet coating and the like are employed . Of these coating methods, a bar coating method or a slit die coating method is particularly preferable. By applying the composition solution by a bar coating method or a slit die coating method, a shielding film free from defects can be formed even on a substrate having a stepped portion of the metal wiring layer.

(2) Heating process

After the above step (1), the coated film is subjected to a heat treatment (post-baking treatment) by a suitable heating apparatus such as a hot plate or a clean oven. The heating temperature is preferably about 150 to 250 DEG C, and the heating time is preferably about 5 to 30 minutes in the case of using a hot plate and about 30 to 90 minutes in the case of using a clean oven. In this manner, a shield film having a desired shape can be formed on the dye-sensitized solar cell electrode.

As described above, a shield film can be formed on a substrate in a dye-sensitized solar cell electrode by forming a shield film by a film forming process and a heating process using the resin composition. This forming method requires only a relatively simple process of the coating step and the heating step, and a shielding film can be formed at a low cost.

As another method for forming a shielding film of an electrode for a dye-sensitized solar cell of the present invention, there is a method for forming a shield film of (i) a laminated body having a conductive substrate and a metal wiring layer on the surface side of the conductive substrate, A step of forming a coating film of the resin composition having radiation properties,

(ii) a step of irradiating only the portion of the coating film formed in the step (i) on the metal wiring layer,

(iii) a step of developing the coating film irradiated with the radiation in the step (ii)

(iv) a step of heating the developed coating film in the step (iii)

In this order.

(i) Sensitizing radiation  A step of forming a coating film of the resin composition having

In this step, a solution of the resin composition having radiation-sensitive properties is applied onto a laminate including a conductive substrate and a metal wiring layer on the front surface side of the conductive substrate, and then the coated surface is heated (prebaked) . The application is performed so that at least the whole of the metal wiring layer on the front surface side of the conductive substrate is covered. The conditions for the prebaking vary depending on the kind of each component and the blending ratio, and preferably about 70 to 110 DEG C for about 1 to 10 minutes. The thickness of the coating film after pre-baking is preferably 0.1 to 5.0 탆, and more preferably 0.3 to 2.0 탆 or so.

The solid concentration of the composition solution used for coating is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, and still more preferably 15 to 35 mass%. The method of applying the composition solution is not particularly limited and suitable methods such as spraying, roll coating, spin coating (coating method), slit die coating, bar coating, inkjet coating and the like are employed . Of these coating methods, a bar coating method or a slit die coating method is particularly preferable. By applying the composition solution by a bar coating method or a slit die coating method, a shielding film free from defects can be formed even on a substrate having a stepped portion of the metal wiring layer.

( ii ) Step of irradiating the coating film with radiation

Subsequently, only the portion of the coating film formed in the above-described step (i) on the metal wiring layer is exposed through a photomask having a predetermined pattern. Examples of the radiation used for exposure include visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like. Among these radiation, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation including ultraviolet radiation having a wavelength of 365 nm is particularly preferable.

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

( iii ) Development Process

Subsequently, in the step (ii), the coated film irradiated with the radiation is developed to remove the non-irradiated portion of the radiation to form a predetermined pattern. As the developing solution used for the development, an aqueous solution of an alkali (basic substance) is preferably used. Examples of the alkali which can be used include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia; Quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and the like. A water-soluble organic solvent such as methanol, ethanol and the like or a surfactant may be added in an appropriate amount to the above-mentioned alkali aqueous solution.

As the developing method, any of a puddle 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, water washing is performed for 30 to 90 seconds, and then air is blown with, for example, compressed air or compressed nitrogen to form a desired pattern.

( iv ) Heating process

After the developing step (iii), the patterned coating film is subjected to heat treatment (post-baking treatment) by a suitable heating apparatus such as a hot plate or a clean oven. The heating temperature is preferably about 150 to 250 DEG C, and the heating time is preferably about 5 to 30 minutes in the case of using a hot plate and about 30 to 90 minutes in the case of using a clean oven. In this manner, a shield film having a desired shape can be formed on the dye-sensitized solar cell electrode.

As described above, the resin composition having the radiation-sensitive properties is used to form a pattern by a coating film forming process, a radiation irradiation process (exposure process), a development process, and a heating process, whereby a metal wiring layer The shielding film having a uniform thickness can be formed only on the portion where the metal wiring exists. According to this method, it is possible to form a shield film precisely only in the portion where the metal wiring exists, and it is possible to reliably prevent the shield film from being erroneously formed on the conductive substrate or the oxide semiconductor layer. Therefore, There is no. In addition, the metal wiring having the shield film thus formed can exhibit high corrosion resistance to the electrolytic solution because there is no defect of the shield film.

(Example)

Hereinafter, the present invention will be described more specifically with reference to Synthesis Examples and Examples, but the present invention is not limited to the following Examples. The number-average molecular weight and the molecular weight distribution (Mw / Mn) measured in the following were measured using a GPC chromatograph "HLC-8020" (TSKgel α-M 1, TSKgel α-2500 1) manufactured by TOSOH CORPORATION Was measured by a gel permeation chromatography (GPC) method under the conditions of a flow rate of 1.0 milliliter / minute and elution solvent: N, N-dimethylformamide and a column temperature of 35 ° C.

Preparation of Copolymer

[Synthesis Example 1]

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 placed. Subsequently, 40 parts by mass of glycidyl methacrylate, 18 parts by mass of styrene, 20 parts by mass of methacrylic acid, and 22 parts by mass of N-cyclohexylmaleimide were charged, and after nitrogen replacement, gentle stirring was started. The solution temperature was raised to 70 占 폚, and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-1). The solid content concentration of the obtained polymer solution was 33.1% by mass. The resulting copolymer had a number average molecular weight of 7,000 and a molecular weight distribution (Mw / Mn) of 2.

[Synthesis Example 2]

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

[Synthesis Example 3]

5 parts by mass of 2,2'-azobisisobutyronitrile and 250 parts by mass of butyl methoxyacetate were placed in a flask equipped with a stirrer, a cooling tube and a stirrer, and then 18 parts by mass of methacrylic acid, 5.2 parts by mass of methacrylic acid tricyclo [5.2. 1.0, ^2,6 ] decan-8-yl, 5 parts by mass of styrene, 30 parts by mass of methacrylic acid-2-hydroxyethyl ester and 22 parts by mass of benzyl methacrylate were charged and replaced with nitrogen, , The temperature of the solution was raised to 80 占 폚, and this temperature was maintained for 5 hours to polymerize to obtain a polymer solution containing the copolymer (? -1) at a solid concentration of 28.8 mass%.

Then, 14 parts by mass of 2-methacryloyloxyethyl isocyanate ("CALENSE MOI" manufactured by Showa Denko KK) and 4 parts by mass of 4-methoxyphenol 0.1 were added to the polymer solution containing the copolymer (? -1) Followed by stirring at 40 ° C for 1 hour and further at 60 ° C for 2 hours. The progress of the reaction between the isocyanate group derived from 2-methacryloyloxyethyl isocyanate and the hydroxyl group of the copolymer (? -1) was confirmed by IR (infrared absorption) spectrum. In the IR spectrum of the polymer solution containing the original copolymer (? -1), the solution after 1 hour of reaction, and the solution after further reaction at 60 ° C for 2 hours at 40 ° C, 2-methacryloyloxyethyl The peak near 2270 cm ^-1 derived from the isocyanate group of isocyanate was confirmed to be decreased. By this reaction, a polymer solution containing a copolymer (A-3) having a solid concentration of 30.0 mass% was obtained. The resulting copolymer had a number average molecular weight of 7,000 and a molecular weight distribution (Mw / Mn) of 2.

[Comparative Synthesis Example 1]

A cooling tube and a flask equipped with a stirrer were charged with 5 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 10 parts by mass of styrene and 90 parts by mass of methyl methacrylate were charged, and after nitrogen replacement, gentle stirring was started. The solution temperature was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (a-1). The solid concentration of the obtained polymer solution was 34.0 mass%. The resulting copolymer had a number average molecular weight of 8,500 and a molecular weight distribution (Mw / Mn) of 2.

Preparation of resin composition

[Example 1]

(B-1) as a polymerizable compound (B-1) as a polymer [A] copolymer in an amount of 100 parts by mass (solid content) 100 parts by mass of pentaerythritol hexaacrylate ("KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.) as the polymerization initiator, (C-1) 2-dimethylamino- (Irgacure 379, manufactured by Chiba Specialty Chemicals Co., Ltd.), 20 parts by mass of [G] -1- (4-morpholin- 10 parts by mass of (G-1)? -Glycidoxypropyltrimethoxysilane as the adhesion assisting agent and 0.2 parts by mass of "FTX-218" manufactured by Neos, which is a surfactant (H-1) Propyleneglycol monomethyl ether acetate was further added so as to have a solid content concentration of 22 mass%, and then millipore filter Filtered to prepare a resin composition solution (S-1).

[Examples 2 to 13, Comparative Example 1]

(S-2) to (S (2)) of the resin composition were obtained in the same manner as in Example 1, except that the kinds and amounts as shown in Table 1 were used as the components [A] to [ -13) and (s-1) were prepared.

Fabrication of electrode substrate for dye-sensitized solar cell

1, an electrode substrate of a dye-sensitized solar cell was prepared.

(1) Construction of transparent conductive substrate

A saturated aqueous solution of ammonium fluoride was added and dissolved in an ethanol solution of tin (IV) chloride pentahydrate to prepare a raw material liquid for FTO (fluorine-doped tin oxide) film. Subsequently, the substrate 1 was placed on a heater plate of 350 DEG C so that the back surface of the substrate 1 (high-strain glass) was in contact with the substrate 1, and the raw material liquid for the FTO film was irradiated onto the substrate 1 by using a spray nozzle while heating with a heater plate for one hour. To form a transparent conductive film 2 (film thickness: 0.05 to 5 m) made of FTO. Thus, a transparent conductive substrate having a transparent conductive film 2 formed on the surface of the substrate 1 was obtained (see Fig. 1 (a)). The film thickness of the transparent conductive film 2 was 0.2 탆.

(2) Formation of metal wiring layer

A screen printing apparatus ("HR-320" manufactured by Nyun-Shimitsu Kikai Kikai Kikai Co., Ltd.) was used to form a transparent conductive film on the transparent conductive substrate on which the transparent conductive film 2 was formed in (1) (Having a volume resistivity after sintering of 3 x 10 < ^-6 > [OMEGA .cm]) of a silver paste was formed on the surface of the substrate. The metal wiring layer 3 was formed so as to have a circuit width (design value) of 300 mu m, a thickness of 10 mu m, and a thickness of 10 mu m. Mu m, and was formed into a shape extending in a lattice form from the current collector terminal (see Fig. 1 (b)).

(3) Formation of Porous Oxide Semiconductor Layer

A titanium oxide paste (ethanol dispersion with a solid content of 20% by mass) was applied between the metal wiring layers 3 on the transparent conductive substrate on which the transparent conductive film 2 was formed by the same screen printing as in the above (2). Subsequently, the resultant structure was baked at 450 DEG C for one hour to form a porous oxide semiconductor layer 4 between the lattice-shaped metal wiring layers 3 (see Fig. 1 (c)).

(4) Shield film formation of metal wiring layer

The solution of the resin composition of Example 1 ((1)) was applied to the entire surface of the laminate prepared in the above (3) using an automatic coating device for coating a bar (PI-1210 automatic coating device I of a tester manufactured by TESAN SANGYO KABUSHIKI KAISHA) S-1) (see Fig. 1 (d)). Subsequently, the solvent was volatilized and dried at 90 DEG C for 5 minutes. Ultraviolet rays from high-pressure mercury or the like were irradiated through a photomask having the same design size as the lattice-like plate used in the above (2) so that the exposure amount at 365 nm was 1,000 J / m 2. The film thickness of the coated film after exposure was 0.6 탆. Subsequently, this coating film was developed with an aqueous solution of potassium hydroxide and further baked in a clean oven at 180 DEG C for 1 hour. Thus, an electrode substrate 7 having a shield film 6 was formed on the surface of the metal wiring layer 3 in the lattice shape (see Fig. 1 (e)). The thickness of the shield film 6 was 0.5 mu m. Hereinafter, this electrode substrate is referred to as " sample electrode substrate 1 ".

(S-2) to (S-12) of the resin compositions of Examples 2 to 12 were used instead of the solution (S-1) of the resin composition of Example 1, ) To (4) were carried out to prepare an electrode substrate. These electrode substrates are referred to as " sample electrode substrate 2 " to " sample electrode substrate 12 ". (S-13) of the resin composition of Example 13 was used instead of the solution (S-1) of the resin composition of Example 1, and the exposure step and the developing step were not carried out. To prepare an electrode substrate. 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 Chemical Co., Ltd.) were dispersed in 100 parts by mass of the solution (s-1) of the resin composition of Comparative Example 1 to obtain ITO fine particles To prepare a resin composition solution. (1) to (4) were carried out in the same manner as described above, except that the resin composition solution containing ITO fine particles was used in place of the solution (S-1) of the resin composition of Example 1, A substrate was prepared. This electrode substrate is referred to as " comparative sample electrode substrate 1 ". In addition, since the resin composition of Comparative Example 1 has no radiation-sensitive properties, the exposure and development in the step (4) are omitted.

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

In Table 1, the abbreviations denoting the respective compounds indicate the following.

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

B-2: Synthesis of succinic acid mono- [3- (3-acryloyloxy-2,2-bisacryloyloxymethylpropoxy) -2,2-bisacryloyloxymethyl-

C-1: 2-Dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (available from Ciba Specialty Chemicals, "Irgacure 379")

C-2: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O- acetyloxime) (Chiba Specialty Chemicals Co., Irgacure OX02 " manufactured by Kao Corporation)

G-1:? -Glycidoxypropyltrimethoxysilane

H-1: Fluorine-based surfactant ("FTX-218" manufactured by NEOS Corporation)

Preparation of dye-sensitized solar cell

Using the above-described sample electrode substrates 1 to 13 and comparative sample electrode substrates 1 and 2, a dye-sensitized solar cell (photoelectric conversion element) was produced by the following method according to the procedure shown in Fig.

(a) adsorption of a photosensitizing dye

Each of the sample electrode substrates 1 to 13 and the comparative sample electrode substrates 1 and 2 was immersed in an acetonitrile / t-butanol solution (mass ratio 1: 1) of a photosensitivity dye ruthenium bipyridine complex (N719 dye) The substrate was immersed at 25 占 폚 for 24 hours or more to adsorb the photosensitivity dye on the surface of the porous oxide semiconductor layer of the sample electrode substrate to obtain a working electrode having the porous oxide semiconductor layer 8 carrying the photosensitizing dye f).

(b) adhesion of counter electrode and injection of electrolyte solution

A platinum layer having a sputter-formed Ti foil on its surface was used as the counter electrode 9, and this was overlapped on the working electrode in (a) above. The iodine electrolytic solution 10 was injected into the syringe from the gap between the working electrode and the counter electrode in a circulating tablet glove box filled with an inert gas. As the iodine electrolytic solution 10, 0.5M of 1,2-dimethyl-3-propylimidazolium iodide and 0.05M of iodine were dissolved in methoxyacetonitrile, and an appropriate amount of lithium iodide and 4-t -Butylpyridine was added (see Fig. 2 (g)).

(c) bag

The positive electrode was sealed with a hot press at 120 DEG C by using an adhesive film 11 ("Surlyn" manufactured by DuPont) to prevent the electrolyte from flowing down from the sample prepared in (b) (Corresponding to each of the sample electrode substrates 1 to 13 and the comparative sample electrode substrate 1) (see Fig. 2 (h)).

Evaluation of dye-sensitized solar cells

(I) Confirmation of absence of shield film on the sample electrode substrate

The sample electrode substrates 1 to 13 and the comparative sample electrode substrate 1 having a shield film on the metal wire were observed with naked eyes under the sodium lamp to observe the appearance of the shield film surface. The portion where the shield film was not formed was regarded as a defect of the shield film, and the presence or absence of the defect was evaluated. The case where the shield film was not defected was rated as & cir &, and the case where the shield film was confirmed to be defective was evaluated as " X ". The results are shown in Table 1.

(II) Measurement of photoelectric conversion efficiency (?)

The output characteristics of the dye-sensitized solar cell were measured in accordance with the method of measuring the output of a silicon crystal solar cell of JIS C8913: 1998. An air mass filter equivalent to AM 1.5G was combined with a 300W solar simulator ("YSS-80" manufactured by Yamashita Tenso Co., Ltd.), and the light amount was adjusted to 100 mW / ("HSV-100" manufactured by Hokuto Chemical Co., Ltd.) while irradiating light to the dye-sensitized solar cell (corresponding to each of the sample electrode substrates 1 to 13 and the comparative sample electrode substrates 1 and 2) (Voc (unit V), short-circuit current (Isc; unit mA / cm 2), and fill factor (FF (unitless)) obtained from the I-V curve characteristic are derived by measuring the I- did. The short circuit current density Jsc (unit mA / cm 2) and the photoelectric conversion efficiency? (Unit%) were calculated using the following equations (1) and (2). If the value of the photoelectric conversion efficiency thus calculated is 4% or more, corrosion of the metal wiring does not occur, and the iodine electrolyte solution is not discolored, so that the photoelectric conversion efficiency is good. The results are shown in Table 1. Here, AM1.5G indicates the distance through which the sunlight passes through the atmosphere. AM1.0G, the distance that the sunlight passes directly under the equator, is the standard, and AM1.5G corresponds to the value in Tokyo.

(III) Evaluation of Corrosion Resistance of Metal Wiring Having a Shield Film

Immediately after the measurement of the photoelectric conversion efficiency (?) Of the above (II), the appearance of the metal wiring having the shield film was inspected. The metal wiring was observed with naked eyes to confirm the corrosion and the discoloration of the wiring. When there was no change, it was evaluated as " good /? &Quot;, and when it was changed (corrosion or discoloration), it was evaluated as " defective / x ". The results are shown in Table 1.

As is evident from the results shown in Table 1, the dye-sensitized solar cells (Examples 1 to 12) having a shield film formed using the resin composition having the radiation-sensitive properties were prepared by using the resin composition of the prior art Compared with the dye-sensitized solar cell having the shield film (Comparative Example 1) and the dye-sensitized solar cell having no shield film (Comparative Example 2), the photoelectric conversion efficiency was good, the shield film was not defected at all, It was found that it has a high corrosion resistance to an electrolytic solution. 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 auxiliary agent and / or the [H] surfactant as optional components. From the results of Examples 4 to 12, it was also found that good characteristics can be obtained even when various kinds of [A] to [C] are used. By using the resin composition having the radiation-sensitive properties as described above, it is possible to form a shield film precisely only on the portion where the metal wiring exists on the substrate having the stepped portion of the metal wiring in the dye-sensitized solar cell electrode, High corrosion resistance can be obtained while maintaining photoelectric conversion efficiency. It is also understood from the results of Example 13 that the shield film formed by using the resin composition having no radiation-sensitive property of the present invention has no defect and has high corrosion resistance to the electrolytic solution, It was found that the photoelectric conversion efficiency was also good in batteries.

≪ Industrial applicability >

In the resin composition having a radiation-sensitive property, a pattern is formed by exposure and development using radiation-sensitive properties. Therefore, on a substrate having a step of a metal wiring in a dye-sensitized solar cell electrode, It is possible to form a shield film having a uniform thickness only. In addition, the resin composition having a radiation-sensitive property can form a shield film precisely only at a portion of a metal wiring, and thus has no defect of a film and has sufficient corrosion resistance. The dye-sensitized solar cell electrode having this shield film has high photoelectric conversion efficiency. Therefore, the resin composition having a radiation-sensitive property can be suitably used as a material for forming a shield film of a dye-sensitized solar cell electrode. Further, the resin composition having no radiation-sensitive property of the present invention is a resin composition capable of forming a shield film at a low cost by only a relatively simple process such as a coating process and a heating process, and a resin composition having a shield film having corrosion resistance and having excellent photoelectric conversion efficiency An electrode for a sensitized solar cell can be provided.

1: substrate
2: transparent conductive film
3: metal wiring layer
4: Porous oxide semiconductor layer
5:
6: shield film
7: Electrode substrate having a shield film
8: A porous oxide semiconductor layer carrying a photoimageable dye
9: opposite electrode
10: Iodine electrolyte solution
11: Adhesive film

Claims (13)

A laminate including a conductive substrate and a metal wiring layer on a front surface side of the conductive substrate; and a shield film formed so as to cover at least the entire metal wiring layer,
Wherein the shielding film is a cured product of a resin composition containing a copolymer having at least one reactive functional group selected from the group consisting of a carboxyl group, an epoxy group and a (meth) acryloyl group. Type solar cell. The method according to claim 1,
Wherein the resin composition further comprises a polymerizable compound having an ethylenically unsaturated double bond [B]. 3. The method of claim 2,
(B) the polymerizable compound having an ethylenically 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 more (meth) Type solar cell. The method according to claim 2 or 3,
Wherein the resin composition further comprises a [C] radiation-sensitive polymerization initiator. 5. The method of claim 4,
[C] An electrode for a dye-sensitized solar cell, wherein the radiation-sensitive radiation polymerization initiator is one or both of an O-acyloxime compound and an acetophenone compound. 1. A resin composition for forming a shield film formed so that at least a metal wiring layer is entirely covered with a laminate including a conductive substrate and a metal wiring layer on a front surface side of the conductive substrate,
[A] A resin composition for forming a shielding film for a dye-sensitized solar cell, comprising a copolymer having at least one reactive functional group selected from the group consisting of a carboxyl group, an epoxy group and a (meth) acryloyl group. The method according to claim 6,
[B] a polymerizable compound having an ethylenically unsaturated double bond,
[C] Radiation-sensitive polymerization initiator
By weight. 8. The method of claim 7,
Wherein the polymerizable compound having an ethylenically 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) . 8. The method of claim 7,
[C] The resin composition according to any one of the above items, wherein the radiation sensitive polymerization initiator is at least one of an O-acyloxime compound and an acetophenone compound. A shield film for an electrode for a dye-sensitized solar cell formed from the resin composition according to any one of claims 6 to 9. A dye-sensitized solar cell comprising the shield film according to claim 10. (1) a step of forming a coating film of the resin composition according to claim 6 so that at least a metal wiring layer is entirely covered with a laminate including a conductive substrate and a metal wiring layer on the front surface side of the conductive substrate,
(2) a step of heating the coating film formed in the step (1)
Of the electrode for a dye-sensitized solar cell. (i) a coating film of the resin composition according to any one of claims 7 to 9 is formed so that at least a metal wiring layer is entirely covered with a laminate including a conductive substrate and a metal wiring layer on the front surface side of the conductive substrate The process,
(ii) a step of irradiating only the portion of the coating film formed in the step (i) on the metal wiring layer,
(iii) a step of developing the coating film irradiated with the radiation in the step (ii)
(iv) a step of heating the developed coating film in the step (iii)
Of the electrode for a dye-sensitized solar cell.

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