JP2022146254A - Laminate material - Google Patents

Abstract

To provide a laminate material that has a functional layer having high adhesion to a conductive metal oxide layer, and has excellent optical transparency.SOLUTION: A laminate material has, on an optical transparent support, a conductive metal oxide layer and a functional layer in the stated order. The functional layer has at least an elemental metal (excluding elements of group 1 and group 2) and/or a metal compound (excluding elements of group 1 and group 2), a polyvinyl alcohol and/or hydroxypropyl cellulose, a crosslinker, and polyvinylpyrrolidone.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a laminated material that can be used for the production of conductive materials and functional materials that apply light-transmitting metal oxide films, such as dye-sensitized solar cells.

Light-transmitting electrodes are used in liquid crystal displays, electroluminescence displays (EL displays), plasma displays, electrochromic displays, solar cells, touch panels, electronic paper, and the like. In particular, in recent years, attention has been focused on a light-transmitting electrode having a conductive metal oxide film (hereinafter also referred to as a conductive metal oxide layer) using a foldable light-transmitting film as a support. As a widely applied light-transmitting electrode using a light-transmitting film as a support, at least one surface of a light-transmitting film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) is coated with indium-tin. A conductive metal oxide film formed by forming a conductive metal oxide represented by composite oxide (ITO) by a dry process such as a vacuum deposition method or a sputtering method can be mentioned. However, since the conductivity of a thin ITO film is by no means sufficient, a large voltage drop may be a problem in a device with a large area. As a method for solving such a problem, a method of increasing the film thickness of the ITO film or a method of heat-treating the ITO film are generally used.

However, in the method of increasing the thickness of the ITO film, there is a problem that the productivity is lowered, and the ITO film becomes yellow, and the ITO film is weak against bending, so that cracks occur to impair the conductivity. Further, in the method of heat-treating an ITO film, when a light-transmitting film is used as a support, heat-treating at a high temperature cannot be performed, so there is a problem that it is difficult to obtain high conductivity.

On the other hand, it is also known to use a grid electrode consisting of a metal part having openings as a light-transmitting electrode. A method for producing a conductive material having a network-patterned silver thin film with high surface resistivity from a conductive material precursor is described. However, when a metal part having an opening is used as an electrode of an inorganic EL display, for example, there is a problem that light is emitted only above the metal part because no potential is applied to the opening.

In order to solve such problems, it is also known to use a light-transmitting conductive metal oxide film and a metal portion having an opening in combination. A photovoltaic element having a grid-like collecting electrode is described thereon, and Patent Document 3 describes a solar cell electrode film having a striped or mesh-like metal electrode on a transparent electrode thin film, and Patent Document 4. describes an EL display device in which a plurality of anode lines including a transparent electrode film and a plurality of cathode lines including a metal layer sandwich a light-emitting medium and cross each other. In each of these publications, a light-transmitting conductive metal oxide film and a metal part having an opening are provided in this order on a support.

However, a conductive metal oxide film typified by an ITO film is difficult to obtain sufficient adhesion between a metal pattern and a polymer compound. In the method of forming a metallic silver pattern on an ITO film by the method, it is necessary to form a physical development nucleus layer (functional layer) with good adhesion on the ITO film.

In Patent Document 5, a transition metal thin film layer is generated by applying a solution in which a transition metal compound containing an organic anion species and a transition metal cation species is dissolved in an organic solvent to the surface of an ITO film and performing heat treatment. Then, a fine metal pattern (functional layer) with excellent adhesion is formed by applying a dispersion liquid of fine metal particles to the surface of this transition metal thin film layer and heating and baking it.

Patent Document 6 describes a method of applying a coating liquid using titanium dioxide and a polymer compound such as polyvinylpyrrolidone as a binder onto the ITO film in order to form a titanium dioxide layer (functional layer) on the ITO film. It is Further, in Patent Document 7, after coating and drying a dispersion containing a polymer component, titanium oxide particles, a water-soluble polar solvent, and optionally a water-soluble polymer, water, and a cross-linking agent on an ITO film, A method for forming a laminated material having a titanium oxide-containing porous film (functional layer) by immersion and drying is described. A method of coating a physical development nucleus layer coating solution (functional layer coating solution) containing a cross-linking agent that reacts with active hydrogen is described.

JP 2009-245748 A JP-A-6-140646 JP 2009-99574 A JP-A-10-162961 JP 2005-293937 A JP 2011-222532 A JP 2013-136216 A JP 2005-250169 A

In Patent Document 5, a transition metal thin film layer having high adhesion to a conductive metal oxide film can be obtained, but there is room for improvement in light transmittance. In addition, the functional layers described in Patent Documents 6 and 7 may not provide sufficient adhesion, and the technology described in Patent Document 8 may not provide sufficient adhesion of the functional layer. was sought.

Accordingly, the problem to be solved by the present invention is to provide a laminate material having a conductive metal oxide layer and a functional layer having high adhesion and having excellent light transmittance.

The object of the present invention has been achieved by the following means.
A conductive metal oxide layer and a functional layer are provided in this order on a light-transmitting support, and the functional layer comprises at least a single metal (excluding group 1 and group 2 elements) and/or a metal (group 1 and 2 A laminate material, characterized in that it contains a compound, polyvinyl alcohol and/or hydroxypropyl cellulose, a cross-linking agent, and polyvinylpyrrolidone.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a laminate material having a functional layer that has high adhesion to a conductive metal oxide layer and excellent light transmittance.

The laminate material of the present invention has a conductive metal oxide layer and a functional layer in this order on a light-transmitting support.

As the light-transmitting support possessed by the lamination material of the present invention, any light-transmitting support having a total light transmittance of preferably 50% or more, more preferably 70% or more, and still more preferably 85% or more can be used. Available. Examples of light-transmitting supports include polyester resins such as polyethylene terephthalate, diacetate resins, triacetate resins, acrylic resins, polycarbonate resins, polyvinyl chloride resins, polyimide resins, polyvinylidene fluoride resins, cellophane, celluloid, and cycloolefins. , glass and the like. Furthermore, in the present invention, the light-transmitting support may have an easy-adhesion layer.

The conductive metal oxide layer of the laminate material of the present invention is not particularly limited, but it is preferably light-transmitting because it is often used as a light-transmitting electrode. Conductive metal oxide layers having optical transparency include, for example, tin oxide, indium-tin mixed tin oxide (ITO), antimony-tin mixed oxide (ATO), zinc oxide, indium-zinc mixed oxide ( IZO), antimony-zinc mixed oxide (AZO), and the like, containing at least one selected from conductive metal oxide particles. Moreover, these may be used alone, or may be used in combination. The surface resistivity with the conductive metal oxide layer is at least 10 ⁷ Ω/□ or less, preferably 10 ⁵ Ω/□ or less, and more preferably 10 ⁴ Ω/□ or less.

Furthermore, in the present invention, a commercially available product in which a conductive metal oxide layer is formed on the above-described light-transmitting support can also be used. film), glass with an ITO film (manufactured by Geomatec Co., Ltd.), and the like. The shape of the conductive metal oxide particles contained in the conductive metal oxide layer of the present invention is not particularly limited. It is preferable because it is easy to obtain a relatively low surface resistance value.

The functional layer of the present invention contains a metal (excluding group 1 and group 2 elements) and/or a metal compound (excluding group 1 and group 2 elements) and is in contact with the conductive metal oxide layer. Preferred simple metals (excluding Groups 1 and 2 elements) and/or metal compounds (excluding Groups 1 and 2 elements) contained in the functional layer of the present invention vary depending on the application of the laminated material of the present invention. However, the simple metal is preferably a metal of Groups 9 to 14, such as gold, silver, copper, palladium, rhodium, aluminum, etc. As the metal compound, a metal compound containing a metal of Group 9 to 14 is used. Examples include sulfides such as palladium sulfide and silver sulfide, tin oxide, aluminum oxide (alumina), and metal oxides such as ITO. In addition, transition metals, their oxides, sulfides, salts such as phosphorus oxoacid compounds and sulfate compounds, transition metal complexes such as copper phthalocyanine, and the like can be contained depending on the application. The preferred content of the metal (excluding group 1 and group 2 elements) and/or metal compound (excluding group 1 and group 2 elements) contained in the functional layer varies depending on the application, but the solid content is 10 per 1 m ² ~2000 mg is suitable.

The functional layer of the laminated material of the present invention includes, in addition to a single metal (excluding group 1 and group 2 elements) and/or a metal (excluding group 1 and group 2 elements) compound, polyvinyl alcohol and/or hydroxypropyl cellulose, crosslinked agent, and polyvinylpyrrolidone.

The polyvinyl alcohol contained in the functional layer is a compound having a polyvinyl alcohol moiety. For example, known polyvinyl alcohols including modified compounds obtained by partially acetalizing polyvinyl alcohol can be used.

The hydroxypropyl cellulose contained in the functional layer is a cellulose derivative having a hydroxypropyl group. Known hydroxypropyl celluloses can be used, including compounds in which hydroxypropyl groups are continuously bonded to groups. In addition, although the method for forming a functional layer in the present invention is not particularly limited, a method for forming a film by applying an aqueous solution or an aqueous dispersion is practically preferable. The degree is preferably 3 or more.

The cross-linking agent contained in the functional layer of the present invention is a compound that enhances film strength by linking the polymer chains of polyvinyl alcohol and hydroxypropyl cellulose described above. The type of cross-linking agent is not limited, but it is preferably a compound that forms a cross-linked structure with a polymer such as polyvinyl alcohol or hydroxypropyl cellulose coexisting in the functional layer. cross-linking agent, aldehyde-based cross-linking agent, carbodiimide-based cross-linking agent, organic titanium-based cross-linking agent, and the like. Among these, an isocyanate-based cross-linking agent that rapidly reacts with polyvinyl alcohol or hydroxypropyl cellulose is particularly preferable. is preferred. Commercially available products such as Duranate (registered trademark) WB40-80D manufactured by Asahi Kasei can be used as the water-dispersible polyisocyanate.

The polyvinylpyrrolidone contained in the functional layer of the present invention is a compound obtained by polymerizing vinylpyrrolidone, and if the vinylpyrrolidone unit is included in 50 mol% or more of the polymer structural units, it is a copolymer with a monomer other than vinylpyrrolidone. There may be. However, in order to form the functional layer by applying an aqueous solution or aqueous dispersion, it is preferable that the polyvinylpyrrolidone is water-soluble. Although the degree of polymerization of polyvinylpyrrolidone is not particularly limited, a Fikentscher K value of 80 to 100 is preferable. The K value can be measured by the method described in JIS K7367-2, and commercially available products with specified K values may be used as appropriate.

The ratio of the binder component (all polymers such as polyvinyl alcohol, hydroxypropylcellulose, polyvinylpyrrolidone, etc.) in the functional layer is not particularly limited, but a high-strength functional layer can be obtained by containing 0.1% by mass or more of the entire functional layer. preferred for

The ratio of each binder component in the functional layer is not particularly limited, but polyvinylpyrrolidone preferably accounts for 5 to 20 mass % of the total binder components.

Although the ratio of the cross-linking agent in the functional layer is not particularly limited, it is preferably 1 to 20 mass % with respect to the total binder component. If it is less than this range, sufficient film strength may not be obtained, and if it is more than this range, the haze of the film may increase.

The functional layer of the laminate material of the present invention comprises a metal (excluding group 1 and group 2 elements) and/or metal compounds, polyvinyl alcohol, hydroxypropyl cellulose, a cross-linking agent, polyvinylpyrrolidone, surfactant, Various compounds such as ultraviolet absorbers and pH adjusters may be included.

In forming the functional layer of the present invention, it is preferable to form a film by coating a coating solution containing each of the components described above. It is preferred to use water as the dispersing medium. In addition, the solvent or dispersion medium may contain an organic solvent miscible with water as long as water is the main component. The solid content concentration in the coating liquid is not particularly limited, but if the solid content concentration is high, the viscosity of the coating liquid increases and it becomes difficult to form a uniform layer, so it is preferably 20% by mass or less, more preferably 15% by mass. It is below. Although the lower limit varies depending on the coating liquid, it is preferably 0.1% by mass or more.

The use of the laminate material of the present invention is not particularly limited, and it can be used for the production of functional materials to which light-transmitting metal oxide layers are applied. Examples thereof include light-transmitting conductive materials such as light-transmitting substrates and light-transmitting electrodes, and functional materials such as electrodes for dye-sensitized solar cells. Specifically, a high refractive index light-transmitting electrode in which a functional layer containing zirconium oxide (zirconia) as a metal compound (excluding group 1 and group 2 elements) is laminated on a conductive metal oxide layer, and a conductive metal a functional layer containing palladium sulfide, metallic silver particles, aluminum oxide, etc. as a metal (excluding group 1 and group 2 elements) and/or a metal (excluding group 1 and 2 elements) compound on the oxide layer; A light-transmitting conductive material formed by a silver salt diffusion transfer method can be obtained from a silver salt photosensitive material in which a silver halide emulsion layer is laminated on a functional layer. It can be suitably used for a light-transmitting conductive material having a metal part with an opening formed by

In order to use the laminated material of the present invention to produce a light-transmitting conductive material having a metal portion (a metal portion having an opening) formed by the silver salt diffusion transfer method, a conductive material is formed as described above. A functional layer is provided on the metal oxide layer, and then a silver halide emulsion layer is provided on the functional layer to form a light-transmitting conductive material precursor, which can be obtained by exposing and developing the precursor. The light-transmitting conductive material obtained in this way can also be subjected to a plating treatment.

As the silver halide emulsion layer provided on the functional layer in the light-transmitting conductive material precursor, silver halide using the technology used in silver salt photographic film, photographic paper, printing plate-making film, emulsion mask for photomask, etc. The emulsion can also be used as it is.

For the formation of the silver halide grains used in the silver halide emulsion layer, forward mixing, reverse mixing, simultaneous mixing, etc. are described in Research Disclosure Items 17643 (December 1978) and 18716 (November 1979), 308119 ( December 1989) can be used. Among them, the so-called controlled double jet method, which is one of the simultaneous mixing methods and maintains a constant pAg in the liquid phase in which grains are formed, is preferable in that silver halide emulsion grains having a uniform grain size can be obtained. In the light-transmitting conductive material precursor of the present invention, the silver halide emulsion grains preferably have an average grain size of 0.25 μm or less, particularly preferably 0.05 to 0.2 μm. There is a preferable range for the halide composition of the silver halide emulsion grains used in the present invention, and the chloride content is preferably 80 mol % or more, particularly preferably 90 mol % or more.

In the production of silver halide emulsions, group 9 salts such as sulfites, lead salts, thallium salts, rhodium salts or their complex salts, iridium salts or their complex salts, etc. A salt of a metal element or a complex salt thereof may coexist. In addition, it can be sensitized with various chemical sensitizers, and methods commonly used in the art such as sulfur sensitization, selenium sensitization and noble metal sensitization can be used alone or in combination. In addition, the silver halide emulsion in the light-transmitting conductive material precursor used in the present invention can be dye-sensitized as necessary.

The ratio of the amount of silver halide to the amount of gelatin contained in the silver halide emulsion layer is preferably such that the mass ratio of silver halide (in terms of silver) to gelatin (silver/gelatin) is 1.2 or more. More preferably, it is 1.5 or more. The amount of silver halide contained in the silver halide emulsion layer is preferably 2 to 10 g/m ² in terms of silver.

Known photographic additives can be used in the silver halide emulsion layer for various purposes. These are described in Research Disclosure Items 17643 (December 1978) and 18716 (November 1979), 308119 (December 1989) or in the literature cited.

A light-transmitting conductive material precursor can be provided with a non-photosensitive layer between the silver halide emulsion layer and the functional layer or on the silver halide emulsion layer. These non-photosensitive layers are layers containing a water-soluble polymer as a main binder. Any water-soluble polymer can be selected as the water-soluble polymer as long as it easily swells with a developer and allows the developer to easily permeate the underlying silver halide emulsion layer or functional layer.

Specifically, gelatin, albumin, casein, polyvinyl alcohol and the like can be used. Particularly preferred water-soluble polymers are proteins such as gelatin, albumin and casein. The amount of binder in the non-photosensitive layer is preferably in the range of 20 to 100% by weight, more preferably 30 to 80% by weight, based on the total amount of binder in the silver halide emulsion layer.

These non-light sensitive layers optionally contain known photographic addenda such as those described in Research Disclosure Items 17643 (December 1978) and 18716 (November 1979), 308119 (December 1989). agents can be included. In addition, the film can be hardened with a cross-linking agent as long as it does not interfere with peeling of the silver halide emulsion layer after processing.

A non-sensitizing dye or pigment having an absorption maximum in the photosensitive wavelength region of the silver halide emulsion layer is preferably used in the light-transmissive conductive material precursor as an anti-halation or anti-irradiation agent for improving image quality. The antihalation agent is preferably contained in the above-described functional layer, an intermediate layer optionally provided between the functional layer and the silver halide emulsion layer, or a backing layer provided with a light-transmitting support interposed therebetween. can be made The anti-irradiation agent is preferably contained in the silver halide emulsion layer. The content of the non ^- sensitizing dyes or pigments can vary within a wide range as long as the desired effect is obtained. is desirable, and the absorbance at the maximum absorption wavelength is preferably 0.5 or more.

The exposure of the light-transmissive conductive material precursor will be described. The silver halide emulsion layer of the light-transmitting conductive material precursor is exposed imagewise (desired fine line pattern). There is a method of scanning exposure using a laser beam. In the method of exposing with laser light, for example, a blue semiconductor laser (also referred to as a violet laser diode) having an oscillation wavelength of 400 to 430 nm can be used.

The development of the light-transmissive conductive material precursor with a silver salt diffusion transfer developer will be described. The silver halide emulsion layer of the light-transmitting conductive material precursor imagewise exposed as described above undergoes physical development by processing with a silver salt diffusion transfer developing solution to form developable latent image nuclei. The silver halide which does not exist is dissolved by a soluble silver complex salt forming agent to form a silver complex salt, which is reduced on the functional layer to precipitate metallic silver, thereby obtaining a metal portion. On the other hand, silver halide having latent image nuclei capable of being developed is chemically developed in a silver halide emulsion layer to become blackened silver. After development, the unnecessary silver halide emulsion layer (including blackened silver), intermediate layer, protective layer, backing layer, etc. are removed to expose the metal part on the functional layer.

Methods for removing the silver halide emulsion layer and the backing layer after development processing include a method of removing by washing with water or a method of transferring and peeling to a release paper or the like. The removal by washing with water includes a method of removing while injecting a hot water shower using a scrubbing roller or the like, and a method of removing with the force of water while jetting hot water from a nozzle or the like. In the method of transferring and peeling off with a release paper or the like, excess alkali solution (developer for silver complex salt diffusion transfer) on the silver halide emulsion layer is squeezed out in advance with a roller or the like, and the silver halide emulsion layer and the like are separated from the release paper. This is a method in which the silver halide emulsion layer and the like are transferred to a release paper by bringing them into close contact with each other, followed by release. As the release paper, water-absorbent paper or non-woven fabric, or paper on which a water-absorbent void layer is formed by a fine particle pigment such as silica and a binder such as polyvinyl alcohol is used.

The developer for silver salt diffusion transfer development used in the development processing of the light-transmissive conductive material precursor will be described. The developer is an alkaline solution containing a soluble silver complex-forming agent and a reducing agent. The soluble silver complex salt-forming agent is a compound that dissolves silver halide to form a soluble silver complex salt. It is a compound for depositing silver.

Soluble silver complex salt forming agents used in the developer include thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, and sulfites such as sodium sulfite and potassium hydrogen sulfite. salts, oxazolidones, 2-mercaptobenzoic acid and its derivatives, cyclic imides such as uracil, alkanolamines, diamines, mesoionic compounds described in JP-A-9-171257, US Pat. No. 5,200,294 Thioethers, 5,5-dialkylhydantoins, alkyl sulfones, as described in the specification, as well as "The Theory of the Photographic Process (4th edition, p. 474-475)", T.W. H. James, the compounds described. These soluble silver complex salt forming agents can be used alone or in combination.

The reducing agents used in the developer are those known in the art of photographic development as described in Research Disclosure Items 17643 (December 1978) and 18716 (November 1979), 308119 (December 1989). A main drug can be used. For example, polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, chlorohydroquinone, ascorbic acid and its derivatives, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1- 3-pyrazolidones such as phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, paraphenylenediamine and the like. These reducing agents can be used alone or in combination.

The content of the soluble silver complex salt forming agent is preferably 0.001 to 5 mol, more preferably 0.005 to 1 mol per liter of developer. The content of the reducing agent is preferably 0.01 to 1 mol, more preferably 0.05 to 1 mol, per liter of developer.

The pH of the developer is preferably 10 or more, more preferably 11-14. Alkaline agents such as sodium hydroxide and potassium hydroxide and buffer agents such as phosphoric acid and carbonic acid are contained alone or in combination to adjust the pH to a desired value. Further, the developer of the present invention preferably contains a preservative such as sodium sulfite or potassium sulfite.

Further, the metal portion having openings obtained by the above developing treatment and washing treatment can be post-treated. Examples of post-treatment liquids include aqueous solutions of reducing substances, water-soluble phosphorous acid compounds, water-soluble halogen compounds, and the like. If such a post-treatment liquid is treated at 50 to 70° C., more preferably 60 to 70° C. for 10 seconds or more, preferably 30 seconds to 3 minutes, the conductivity will be improved, and even under high temperature and high humidity conditions. This is preferable because the surface resistivity does not fluctuate.

Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In addition, the percentages in the description are based on mass unless otherwise specified.

"Preparation of laminated material 1"
First, a palladium sulfide sol liquid was prepared as follows.

<Preparation of palladium sulfide sol>
A solution Palladium chloride 5g
Hydrochloric acid 40mL
Distilled water 1000mL
B liquid sodium sulfide 8.6g
Distilled water 1000mL
Liquid A and liquid B were mixed with stirring, and after 30 minutes, the mixture was passed through a column packed with an ion exchange resin to obtain a palladium sulfide sol having a palladium sulfide concentration of 0.17%.

Toyobo Co., Ltd. transparent conductive film Cosmo Crysta 300R (PET film with ITO film) (surface resistance 250 Ω / square, thickness 125 μm, total light transmittance 86%, haze 1.0%). Laminated material 1 was obtained by applying functional layer coating liquid 1 having the composition so that the WET coating amount was 12 g/m ² and drying.

<Functional layer coating solution 1>
60 g of palladium sulfide sol prepared as above
25-98R (silanol-modified polyvinyl alcohol manufactured by Kuraray Co., Ltd.) 9 mg
Polyvinylpyrrolidone K-90 (manufactured by Kishida Chemical Co., Ltd., K value 90) 1 mg
Duranate WB40-80D (isocyanate-based cross-linking agent manufactured by Asahi Kasei Corp.) 1 mg
Nikkor (registered trademark) BT-9
(Nonionic surfactant manufactured by Nikko Chemicals Co., Ltd.) 1 mg
Silicia 450 (silica manufactured by Fuji Silysia Chemical Co., Ltd.) 1.25 mg
1 g distilled water

"Preparation of laminated material 2"
Laminate material 2 was prepared in the same manner as in preparation of laminate material 1, except that functional layer coating liquid 1 was changed to functional layer coating liquid 2 below.

<Functional layer coating liquid 2>
60 g of palladium sulfide sol used in the production of laminated material 1
JP-05 (partially saponified polyvinyl alcohol manufactured by Japan Vie Poval Co., Ltd.) 9 mg
Polyvinylpyrrolidone K-90 1mg
Duranate WB40-80D 1mg
Nikkor BT-9 1mg
Silicia 450 1.25mg
1 g distilled water

"Preparation of laminated material 3"
A laminate material 3 was prepared in the same manner as in the preparation of the laminate material 1, except that the functional layer coating liquid 1 was changed to the following functional layer coating liquid 3.

<Functional layer coating solution 3>
60 g of palladium sulfide sol used in the production of laminated material 1
HPC M
(Hydroxypropyl cellulose manufactured by Nippon Soda Co., Ltd., molar substitution degree 7.8) 9 mg
Polyvinylpyrrolidone K-90 1mg
Duranate WB40-80D 1mg
Nikkor BT-9 1mg
Silicia 450 1.25mg
1 g distilled water

"Preparation of laminated material 4"
A laminate material 4 was prepared in the same manner as in the preparation of the laminate material 1, except that the functional layer coating liquid 1 was changed to the functional layer coating liquid 4 described below.

<Functional layer coating solution 4>
60 g of palladium sulfide sol used in the production of laminated material 1
25-98R 4.5mg
HPCM 4.5mg
Polyvinylpyrrolidone K-90 1mg
Duranate WB40-80D 1mg
Nikkor BT-9 1mg
Silicia 450 1.25mg
1 g distilled water

"Preparation of laminated material 5"
A laminate material 5 was prepared in the same manner as in the preparation of the laminate material 1, except that the functional layer coating liquid 1 was changed to the following functional layer coating liquid 5.

<Functional layer coating solution 5>
60 g of silver sol (silver concentration 0.5%) prepared by the method described in JP-A-2003-268423
HPCM 9mg
Polyvinylpyrrolidone K-90 1mg
Duranate WB40-80D 1mg
Nikkor BT-9 1mg
Silicia 450 1.25mg
1 g distilled water
"Preparation of laminated material 6"
A laminate material 6 was produced in the same manner as in the preparation of the laminate material 1, except that the functional layer coating liquid 1 was changed to the functional layer coating liquid 6 below.

<Functional layer coating liquid 6>
30 g of palladium sulfide sol used in the production of laminated material 1
30 g of silver sol used in the production of laminated material 5
HPCM 9mg
Polyvinylpyrrolidone K-90 1mg
Duranate WB40-80D 1mg
Nikkor BT-9 1mg
Silicia 450 1.25mg
1 g distilled water

"Preparation of laminated material 7"
Laminate material 7 was prepared in the same manner as in preparation of laminate material 1, except that functional layer coating liquid 1 was changed to functional layer coating liquid 7 below.

<Functional layer coating solution 7>
AS-200
(Nissan Chemical Co., Ltd. alumina sol, alumina concentration 10.5%) 60 g
HPCM 9mg
Polyvinylpyrrolidone K-90 1mg
Duranate WB40-80D 1mg
Nikkor BT-9 1mg
Silicia 450 1.25mg
1 g distilled water

"Preparation of laminated material 8"
Laminate material 8 was prepared in the same manner as in preparation of laminate material 1, except that functional layer coating liquid 1 was changed to functional layer coating liquid 8 below.

<Functional layer coating solution 8>
60 g of palladium sulfide sol used in the production of laminated material 1
Polyvinylpyrrolidone K-90 10mg
Duranate WB40-80D 1mg
Nikkor BT-9 1mg
Silicia 450 1.25mg
1 g distilled water

"Preparation of laminated material 9"
Laminate material 9 was prepared in the same manner as in preparation of laminate material 1, except that functional layer composition 1 was changed to functional layer composition 9 below.

<Functional layer coating solution 9>
60 g of palladium sulfide sol used in the production of laminated material 1
HPCM 9mg
Polyvinylpyrrolidone K-90 1mg
Nikkor BT-9 1mg
Silicia 450 1.25mg
1 g distilled water

"Preparation of laminated material 10"
A laminate material 10 was produced in the same manner as in the preparation of the laminate material 1, except that the functional layer coating liquid 1 was changed to the following functional layer coating liquid 10.

<Functional layer coating liquid 10>
60 g of palladium sulfide sol used in the production of laminated material 1
HPCM 9mg
Duranate WB40-80D 1mg
Nikkor BT-9 1mg
Silicia 450 1.25mg
1 g distilled water

<Adhesion of Functional Layer Provided on ITO Film>
Polyester Adhesive Tape No. 1 manufactured by Nitto Denko Corporation was applied to the surfaces of the functional layers of the laminate materials 1 to 10 described above. 31 was adhered so as not to contain air bubbles, and then the tape was peeled off vigorously to evaluate the adhesion of the functional layer to the ITO film surface. Adhesion was evaluated by visually observing the delamination state of the functional layer, with ◯ being no delamination, Δ being partial delamination, and × being full delamination. Table 1 shows the results.

"Preparation of light transmissive electrode 1"
An intermediate layer, a silver halide emulsion layer, and an outermost layer having the following compositions were provided in this order on the functional layers of Laminate Material 1 described above. A backing layer was provided on the opposite side of the light-transmitting support. The silver halide emulsion was prepared by a double-jet mixing method commonly used for photographic silver halide emulsions. This silver halide emulsion contained 95 mol % silver chloride and 5 mol % silver bromide and was prepared to have an average grain size of 0.15 μm. The silver halide emulsion thus obtained was subjected to gold-sulfur sensitization using sodium thiosulfate and chloroauric acid according to the usual method. The silver halide emulsion thus obtained contains 0.5 g of gelatin per g of silver.

<Intermediate layer composition/per 1 ^m2 >
0.5g gelatin
Nikkor BT-9 5mg

<Silver halide emulsion layer composition/per 1 m ² >
0.5g gelatin
Silver halide emulsion 3.0 g equivalent to silver 1-phenyl-5-mercaptotetrazole 3 mg
Nikkor BT-9 20mg

<Outermost layer composition/per ^1m2 >
1g gelatin
Amorphous silica mat agent (average particle size 3.5 μm) 10 mg
Nikkor BT-9 10mg

<Backing layer composition/per 1 ^m2 >
2g gelatin
Amorphous silica matting agent (average particle size 5 μm) 20 mg
Dye 1 200 mg
Nikkor BT-9 400mg

Laminated material 1 provided with the intermediate layer, silver halide emulsion layer, outermost layer, and backing layer was printed with a contact printer using a mercury lamp as a light source, through a resin filter that cuts light of 400 nm or less, with a fine line width of 20 μm and a lattice spacing. A positive transmission original with a mesh pattern of 250 μm was brought into close contact with the exposure.

Subsequently, the exposed laminated material 1 was immersed in a diffusion transfer developer having the following composition at 15°C for 90 seconds, and then the silver halide emulsion layer, intermediate layer, outermost layer and backing layer were removed by washing with hot water at 40°C. and dried. In this way, a mesh-like metal pattern (a metal portion having openings) having a thickness of 0.1 μm and a fine line width of 20 μm was obtained on the functional layer. The conductive material having the mesh-like metal pattern thus formed was post-treated at 60° C. for 60 seconds using a 3% sodium chloride aqueous solution. After that, it was washed with hot water at 35° C. for 30 seconds and dried to obtain a transparent electrode 1 .

<Diffusion transfer developer composition>
Potassium hydroxide 25g
18 grams of hydroquinone
1-phenyl-3-pyrazolidone 2g
Potassium sulfite 80g
N-methylethanolamine 15g
Potassium bromide 1.2g
The total amount was adjusted to 1000 mL with water, and the pH was adjusted to 12.2 with an 85% aqueous solution of phosphoric acid.

The surface resistivity of the light-transmitting electrode 1 formed with the mesh-like metal pattern obtained as described above was measured according to JIS K 7194 using a Lorestar GP/ESP probe manufactured by Dia Instruments. Further, the total light transmittance of the light transmissive electrode 1 was measured using a haze meter HZ-V3 manufactured by Suga Test Instruments Co., Ltd. Furthermore, the adhesion of the metal pattern was evaluated in the same manner as the evaluation of the adhesion of the functional layer described above. Table 2 shows the results.

In the same manner as in the production of the light-transmissive electrode 1, the laminate materials 2 to 10 are also provided with an intermediate layer, a halogenated emulsion layer, and an outermost layer on each functional layer in this order, followed by exposure, development, and post-treatment. After treatment, light transmissive electrodes 2 to 10 were produced. The surface resistivity and total light transmittance of the light-transmitting electrodes 2 to 10 were measured in the same manner as the light-transmitting electrode 1, and the adhesion of the metal pattern was evaluated. Table 2 shows the results.

Tables 1 and 2 show the effects of the present invention. As for the light-transmitting electrodes 8 to 10, the adhesion of the functional layer was not sufficient, so a metal pattern having sufficient adhesion could not be obtained.

Claims (1)

It has a conductive metal oxide layer and a functional layer in this order on a light-transmitting support, and the functional layer comprises at least a single metal (excluding group 1 and group 2 elements) and/or a metal (group 1 and 2 A lamination material containing a group element) compound, polyvinyl alcohol and/or hydroxypropyl cellulose, a cross-linking agent, and polyvinylpyrrolidone.