JP2012008065A - Electrode for biosensor and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrode for a biosensor that can be made in gross in fewer processes and has high measurement accuracy, and a manufacturing method thereof.SOLUTION: An electrode for a biosensor is made by electroplating an amorphous metal on a conductive silver pattern obtained by exposing and developing a silver halide photographic sensitive material formed on a base material.

Description

  The present invention relates to a biosensor electrode for detecting a specific component in a sample solution and a method for producing the same.

  Conventionally, a biosensor for measuring a blood glucose level of a specimen and a method for manufacturing the same have been proposed. A biosensor is obtained by immobilizing a biological substrate that causes a specific chemical reaction with a substrate to be quantified on an electrode. The substrate concentration can be quantified by converting the chemical reaction with the substrate into an electric current and measuring the response current value. Since this response current value depends on the substrate concentration and the electrode area, the accuracy of the electrode area must be high in order to measure accurately. Further, when the electrode itself reacts in the measurement, a dissolution current is generated, resulting in a measurement error. For this reason, there is a need for a biosensor electrode with a stable response current measurement and a method for producing the same, and a metal film formed on the entire surface by vapor deposition, sputtering, or metal foil adhesion on a substrate is slit with a laser or the like. Method of forming (for example, Patent Document 1), plating on a plating catalyst formed in a pattern by ink jet (for example, Patent Document 2), photolithography and etching of a metal film formed on the entire surface by plating or metal foil adhesion Various proposals have been made to form an electrode pattern with high accuracy, such as a method of forming a pattern by plating and plating on the pattern (for example, Patent Documents 3 and 4). However, it is difficult to control the high definition of the pattern by the inkjet method or the etching method, and it is preferable that the high definition pattern can be formed by a simpler method. In addition, these methods are methods of forming electrodes individually, and there are problems such as a long time for pattern formation and a complicated process.

Japanese Patent No. 3365184 JP 2008-45875 A JP 2004-4017 A JP 2002-189012 A

  Therefore, as a result of intensive studies to solve the above problems, the present inventor has reached the present invention.

  That is, an object of the present invention is to provide a biosensor electrode with a low coefficient of variation that can be formed in a batch, has high measurement accuracy, and provides a stable response current, and a method for manufacturing the same.

The object of the present invention is achieved by the following invention.
(1) A photosensitive silver material having at least a silver halide emulsion layer on a substrate is exposed to light and developed to produce a conductive silver pattern, and then an amorphous metal is electroplated on the conductive silver pattern. The electrode for biosensor obtained by this.
(2) The biosensor electrode according to the above (1), wherein the photographic material is a photographic material having a physical development nucleus layer and a silver halide emulsion layer in this order on a substrate.
(3) First step of producing a photographic light-sensitive material having a silver halide emulsion layer by continuously unwinding a roll-shaped substrate, applying a silver halide emulsion layer coating solution on the substrate, and drying it. A second step of exposing the continuously conveyed photographic photosensitive material, and a third step of developing the exposed photographic photosensitive material continuously conveyed to form a conductive silver pattern on the substrate. And a method for producing an electrode for a biosensor comprising at least a fourth step of plating an amorphous metal on the conductive silver pattern on the substrate by electrolytic plating and then winding it into a roll.

  According to the present invention, it is possible to produce a biosensor electrode with a low coefficient of variation that can be formed in a batch, has high measurement accuracy, and provides a stable response current.

FIG. 3 is a plan view showing a document pattern according to an embodiment of the present invention. FIG. 3 is a plan view showing a document pattern according to an embodiment of the present invention. The schematic side view of the plating apparatus used at the 4th process of this invention.

  The present invention relates to a biosensor obtained by a method of forming a conductive silver pattern by subjecting a silver halide photographic material containing at least one silver halide emulsion layer on a substrate to pattern exposure and development. It is an electrode and a method for manufacturing the electrode, and has both excellent accuracy of the conductive pattern and ease of production.

A method for producing a conductive silver pattern using a photographic material having at least a silver halide emulsion layer on a substrate will be described. As such a method, there is a method shown in the following (1), (2) or (3).
(1) A photographic light-sensitive material having at least a physical development nucleus layer and a silver halide emulsion layer on a substrate is exposed and subjected to development processing according to a silver salt diffusion transfer method, and then a silver halide emulsion layer that is no longer necessary is formed. At least a method of removing with water.
(2) A method in which a photographic material having at least a silver halide emulsion layer on a substrate is exposed, developed, and then fixed.
(3) After exposing a photographic light-sensitive material having at least a silver halide emulsion layer on a base material and carrying out a development treatment according to a hardening development method, at least the uncured silver halide emulsion layer which has become unnecessary is removed by washing with water. how to.

  The method (1) is, for example, the method described in JP-B-42-23745, the method (2) is, for example, the method described in JP-A-2004-221564, and the method (3) is For example, J. et al. Photo. Sci. Magazine No. 11 p 1, A. G. Tull (1963) or “The Theory of the Photographic Process (4th edition, p326-327)”, T. H. As described in James et al., A relief image is formed on a substrate according to a curing development method. The curing development method is to treat an uncured silver halide emulsion layer substantially free of a hardener prepared on a substrate with a developer containing a developing agent such as a polyhydroxybenzene, In this method, when the developing agent reduces the exposed silver halide, a water-soluble polymer compound such as gelatin is cross-linked by an oxidized compound generated from the developing agent itself, and is hardened in an image form. In the present invention, it is most preferable to use the method (1) because a biosensor electrode having a lower coefficient of variation is obtained when exposed to high temperature and high humidity for a long time.

  The method for producing the conductive silver patterns (1) to (3) will be described in more detail. Hereinafter, the method for producing the conductive silver pattern of (1) is abbreviated as type 1, the method of producing the conductive silver pattern of (2) is abbreviated as type 2, and the method of producing the conductive silver pattern of (3) is abbreviated as type 3. I will explain.

<Base material>
As a base material of the photographic photosensitive material used for types 1 to 3 of the present invention, a resin film having flexibility is preferably used in terms of excellent handleability. Specific examples of the resin film used for the substrate include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic resins, epoxy resins, fluororesins, silicone resins, polycarbonate resins, diacetate resins, Examples include triacetate resin, polyarylate resin, polyvinyl chloride, polysulfone resin, polyether sulfone resin, polyimide resin, polyamide resin, polyolefin resin, and cyclic polyolefin resin. The thickness of these resin films is preferably 50 to 300 μm.

<Easily adhesive layer>
When using a resin film as a base material, an easily bonding layer can be provided on a base material.

  The easy-adhesion layer provided on the resin film preferably contains various polymer latexes such as those used in the physical development nucleus layer described later. These polymer latexes use an aqueous dispersion, and the easy-adhesion layer is an aqueous coating. It is preferable to be formed by work. Among these, it is preferable to contain an aqueous dispersion of polyester latex, acrylic latex, and urethane latex from the viewpoint of weather resistance, and urethane latex from the viewpoint of adhesion to various materials, particularly non-yellowing urethane polycarbonate latex having high weather resistance. Is preferred. These polymer latexes preferably have an average particle size of 0.01 to 0.3 μm, more preferably 0.02 to 0.1 μm. These polymer latexes can be used by mixing a plurality of types of latexes. Polyester latex, acrylic latex, and urethane latex contain 30% by mass or more of the resin component in the easy-adhesion layer, preferably 50 It is at least mass%.

The easy adhesion layer on the resin film is preferably an easy adhesion layer containing a water-soluble polymer compound together with the polymer latex and further crosslinked with a crosslinking agent. Examples of such water-soluble polymer compounds include polyacrylic acid, polyacrylamide, polyvinyl alcohol, polyvinyl pyrrolidone, a copolymer of maleic anhydride and styrene, and proteins such as gelatin, albumin, casein, polylysine, carrageenan, Mucopolysaccharides such as hyaluronic acid, “chemical reaction of polymers” (Nobu Okawara, 1972, Chemical Dojinsha), chapter 2.6.4, aminated cellulose, polyethyleneimine, polyallylamine, polydiallylamine, allylamine and diallylamine Examples thereof include a polymer, a copolymer of diallylamine and maleic anhydride, and a copolymer of diallylamine and sulfur dioxide. Among these water-soluble polymer compounds, it is preferable to use proteins. The water-soluble polymer compound is preferably 40% by mass or less, more preferably 2 to 30% by mass of the resin component in the easy-adhesion layer. Moreover, it is preferable that the amount of resin components used for an easily bonding layer is 100 mg / m < ² > or more, and it is preferable that an upper limit is 2500 mg / m < ² >. More preferably 100-2000 mg / ^{m 2,} more preferably from 150~1000mg / ^{m 2.}

  Examples of the crosslinking agent include inorganic compounds such as chromium alum, aldehydes such as formaldehyde, glyoxal, malealdehyde, and glutaraldehyde, N-methylol compounds such as urea and ethylene urea, mucochloric acid, and 2,3-dihydroxy- Aldehyde equivalent such as 1,4-dioxane, 2,4-dichloro-6-hydroxy-s-triazine salt, compound having active halogen such as 2,4-dihydroxy-6-chloro-triazine salt, divinyl Sulfone, divinyl ketone, N, N, N-triacryloylhexahydrotriazine, compounds having two or more active three-membered ethyleneimino groups, compounds having two or more epoxy groups in the molecule, such as sorbitol Polyglycidyl ether and polyglycerol polyglycidyl ester Teru, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc., or in addition to these, “Polymer chemical reaction” (Nobu Okawara 1972, Kagaku Dojinsha) Known polymer cross-linking agents such as the cross-linking agents described in Chapters 6 and 7, Chapters 5 and 2, and 9 and 3 can also be included. Of these, a water-soluble crosslinking agent having two or more epoxy groups in the molecule or a vinylsulfone crosslinking agent is preferable. The vinyl sulfone crosslinking agent refers to a compound having at least two vinylsulfonyl groups in the molecule, and refers to a compound represented by the following general formula I or general formula II.

In the formula, L ¹ and L ² each represent a divalent linking group that may or may not be present. When present, it preferably represents an alkylene group having 1 to 5 carbon atoms, an arylene group, a carbamoyl group, a sulfamoyl group, oxygen, sulfur, an imino group and the like, and these may be combined. R ³ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 5 carbon atoms, an optionally substituted aryl group such as benzene or naphthalene, and among them, a hydrogen atom is preferable.

  In the formula, L is an m-valent group having at least one hydroxyl group, and m is 2-4. In general formula II, L is a 2- to 4-valent C1-C10 acyclic hydrocarbon group, a 5- or 6-membered heterocyclic group containing a nitrogen atom, an oxygen atom and / or a sulfur atom, 5 or Examples thereof include a 6-membered cyclic hydrocarbon group or a cycloalkylene group having 7 to 10 carbon atoms. The acyclic hydrocarbon group is preferably an alkylene group having 1 to 8 carbon atoms. Each group represented by L may have a substituent, or may be bonded to each other through a hetero atom (for example, a nitrogen atom, an oxygen atom and / or a sulfur atom), a carbonyl group or a carbamide group. Also good. L may be substituted with, for example, one or more alkyloxy groups having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group, a halogen atom such as a chlorine atom or a bromine atom, an acetoxy group, or the like.

  Specific examples of the compound of the general formula I are shown below, but are not limited thereto.

  Specific examples of the compound of the general formula II are shown below, but are not limited thereto.

  1-7 mass% is preferable with respect to the total resin component amount in an easily bonding layer, and, as for the addition amount of the crosslinking agent in an easily bonding layer, More preferably, it is 2-5 mass%.

  Furthermore, the easily adhesive layer can contain a matting agent such as silica, a lubricant, a pigment, a dye, a surfactant, an ultraviolet absorber and the like.

<Physical development nucleus layer>
The physical development nucleus layer included in the photographic photosensitive material used for Type 1 contains at least physical development nuclei. As the physical development nuclei, fine particles (having a particle size of about 1 to several tens of nm) made of heavy metals or sulfides thereof are used. Examples thereof include metal colloids such as gold and silver, metal fluids obtained by mixing water-soluble salts such as palladium and zinc and sulfides, and the like. The fine particle layer of these physical development nuclei can be provided on the substrate or the easy-adhesion layer by a coating method or an immersion treatment method. From the viewpoint of production efficiency, a coating method is preferably used. The content of physical development nuclei in the physical development nuclei layer is suitably about 0.1 to 10 mg / m ² in terms of solid content.

  The physical development nucleus layer preferably contains a water-soluble polymer compound. The amount of the water-soluble polymer compound added is preferably about 10 to 500% by mass relative to the physical development nucleus. Water-soluble polymer compounds include gelatin, gum arabic, cellulose, albumin, casein, sodium alginate, various starches, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, acrylamide, polyethylenimine, polyallylamine, polyvinylamine and vinylimidazole A coalescence or the like can be used.

  Further, the physical development nucleus layer may contain a polymer latex. The polymer latex is preferably water-based coated using an aqueous dispersion. As the polymer latex, various known latexes such as homopolymers and copolymers can be used. Homopolymers include polymers such as vinyl acetate, vinyl chloride, styrene, methyl acrylate, butyl acrylate, methacrylonitrile, butadiene, and isoprene. Copolymers include ethylene / butadiene copolymers and styrene / butadiene copolymers. Polymer, styrene / p-methoxystyrene copolymer, styrene / vinyl acetate copolymer, vinyl acetate / vinyl chloride copolymer, vinyl acetate / diethyl maleate copolymer, methyl methacrylate / acrylonitrile copolymer, methyl methacrylate・ Butadiene copolymer, methyl methacrylate / styrene copolymer, methyl methacrylate / vinyl acetate copolymer, methyl methacrylate / vinylidene chloride copolymer, methyl acrylate / acrylonitrile copolymer, methyl acrylate / butadiene Copolymer, methyl acrylate / styrene copolymer, methyl acrylate / vinyl acetate copolymer, acrylic acid / butyl acrylate copolymer, methyl acrylate / vinyl chloride copolymer, butyl acrylate / styrene copolymer, polyester, various There are urethane, etc.

  Further, the physical development nucleus layer preferably contains a cross-linking agent (hardener) of the water-soluble polymer compound described above. Examples of the crosslinking agent for the water-soluble polymer compound include the same crosslinking agents as those contained in the aforementioned easy-adhesion layer, but preferably glyoxal, glutaraldehyde, 3-methylglutaraldehyde, succinaldehyde, adipone Dialdehydes such as aldehydes, and a more preferred crosslinking agent is glyoxal. The crosslinking agent preferably contains 0.1 to 30% by mass, particularly 1 to 20% by mass, based on the water-soluble polymer compound contained in the physical development nucleus layer.

  The physical development nucleus layer can be applied by an application method such as dip coating, slide coating, curtain coating, bar coating, air knife coating, roll coating, gravure coating, spray coating and the like.

<Silver halide emulsion layer>
The silver halide emulsion layer of the photographic light-sensitive material used in types 1 to 3 of the present invention is a silver halide photographic film relating to silver halide, photographic paper, a film for printing plate making, a photomask emulsion mask, etc. It can also be used as it is in the invention.

  The halide contained in the silver halide emulsion may be any of chloride, bromide, iodide and fluoride, or a combination thereof. For the formation of silver halide emulsion grains, methods well known in the art such as forward mixing, reverse mixing, and simultaneous mixing are used. In particular, it is preferable to use a so-called controlled double jet method in which a pAg in a liquid phase in which grains are formed is kept constant, which is one of the simultaneous mixing methods, from the viewpoint of obtaining silver halide emulsion grains having a uniform grain size. In the present invention, the average grain size of preferable silver halide emulsion grains is 0.25 μm or less, particularly preferably 0.05 to 0.2 μm. There is a preferred range in the halide composition of the silver halide emulsion of the photographic light-sensitive material used for Type 1, and it is preferable that the chloride is contained in an amount of 80 mol% or more, and particularly that 90 mol% or more is a chloride. .

  The shape of the silver halide grains is not particularly limited. For example, the shape can be various shapes such as a spherical shape, a cubic shape, a flat plate shape (hexagonal flat plate shape, triangular flat plate shape, quadrangular flat plate shape, etc.) Can be.

  In the production of silver halide emulsions, group VIII such as sulfite, lead salt, thallium salt, rhodium salt or complex thereof, iridium salt or complex thereof, in the process of silver halide grain formation or physical ripening, if necessary A metal element salt or a complex salt thereof may coexist. Further, it can be sensitized by various chemical sensitizers, and methods commonly used in the art such as sulfur sensitization method, selenium sensitization method and noble metal sensitization method can be used alone or in combination.

  The silver halide emulsion can be spectrally sensitized as necessary. Further, the silver halide emulsion does not necessarily have to be negative photosensitive, and may be a direct reversal emulsion having positive sensitivity if necessary. Thereby, a negative type can be converted into a positive type, and a positive type can be converted into a negative type. Direct inversion emulsions can be prepared by the methods described in JP-A-8-17120 and JP-A-8-202041.

The amount of silver applied to the silver halide emulsion layer is at least 0.01 g (in terms of silver nitrate) / m ² in order to form a conductive silver pattern. The preferred coated silver amount is 2.0 to 4.0 g (in terms of silver nitrate) / m ^{2. If} the coated silver amount is too much, a long development time is required, or the silver halide emulsion on the side closer to the substrate. The upper limit should be about 5.0 g (in terms of silver nitrate) / m ² because there is a problem that the photosensitivity of the grains decreases.

  The silver halide emulsion layer contains a binder. Examples of the binder include natural polymers, water-soluble synthetic polymers, and water-insoluble synthetic polymers.

  Natural polymers include proteins such as gelatin, casein and albumin, polysaccharides such as starch and dextrin, cellulose and its derivatives (eg, carboxymethylcellulose, hydroxylpropylcellulose, methylcellulose), alginic acid, carrageenan, fucoidan, chitosan, hyaluronic acid, etc. Among these, gelatin is the most preferred natural polymer. Natural polymers modified by a known method such as succinylated gelatin can also be used.

  Examples of the water-soluble synthetic polymer include polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polyvinyl methyl ether, polyethylene oxide, polyvinyl amine, polylysine, and polyacrylic acid. Moreover, these graft polymerization polymers etc. can also be used.

  As the polymer latex as the water-insoluble synthetic polymer, various known latexes such as a homopolymer and a copolymer can be used. Homopolymers include vinyl acetate, vinyl chloride, styrene, methyl acrylate, butyl acrylate, methacrylonitrile, butadiene, and isoprene. Copolymers include ethylene / butadiene, styrene / butadiene, and styrene / p-methoxystyrene. , Styrene / vinyl acetate, vinyl acetate / vinyl chloride, vinyl acetate / diethyl maleate, methyl methacrylate / acrylonitrile, methyl methacrylate / butadiene, methyl methacrylate / styrene, methyl methacrylate / vinyl acetate, methyl methacrylate / vinylidene chloride, methyl acrylate / acrylonitrile , Methyl acrylate / butadiene, methyl acrylate / styrene, methyl acrylate / vinyl acetate, acrylic acid / butyl acrylate, methyl Acrylate-vinyl chloride, butyl acrylate-styrene and the like. The average particle size of the polymer latex used in the present invention is preferably 0.01 to 1.0 μm, more preferably 0.05 to 0.8 μm.

  The silver halide emulsion layer can contain a crosslinking agent. Examples of such crosslinking agents include inorganic compounds such as chromium alum, aldehydes such as formalin, glyoxal, malealdehyde, and glutaraldehyde, N-methylol compounds such as urea and ethylene urea, mucochloric acid, and 2,3-dihydroxy. Aldehyde equivalents such as 1,4-dioxane, active halogen compounds such as 2,4-dichloro-6-hydroxy-s-triazine salt and 2,4-dihydroxy-6-chloro-triazine salt, divinyl sulfone , Divinyl ketone, N, N, N-triacroyl hexahydrotriazine, compounds having two or more active three-membered ethyleneimino groups and epoxy groups in the molecule, and dialdehyde as a polymer hardener One or more of various compounds such as starch can be used. As the amount of the crosslinking agent, in the type 2 photographic light-sensitive material, 0.1 to 30% by mass of the silver halide is based on the water-soluble polymer compound such as a natural polymer or a water-soluble synthetic polymer contained in the silver halide emulsion layer. It is preferably contained in the emulsion layer, particularly 1 to 20% by mass. On the other hand, the photographic light-sensitive materials used for Type 1 and Type 3 remove at least the silver halide emulsion layer that is no longer necessary after development in the development process by washing with water. It is necessary to use in.

  The silver halide emulsion layer may contain a developing agent contained in a developer described later. As the developing agent, a developing agent known in the field of photographic development can be used. For example, polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, chlorohydroquinone, 1-phenyl-4,4-dimethyl- 3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone , 3-pyrazolidones such as 1-p-chlorophenyl-3-pyrazolidone, paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, paraphenylenediamine and the like, and two or more of these can be used in combination. . The silver halide emulsion layer of the type 3 photographic light-sensitive material preferably contains a benzene having a hydroxyl group substituted at least at the 1,2-position or 1,4-position of the benzene nucleus, among the developing agents described above. . These developing agents may be dissolved in the coating solution or contained in each layer, or may be dissolved in an oil dispersion and contained in each layer.

  In the silver halide emulsion layer, known photographic additives can be used for various purposes. These are described in Research Disclosure Item 17643 (December 1978) and 18716 (November 1979), 308119 (December 1989) or cited. Moreover, various coating aids, such as surfactant and a thickener, can be contained.

The silver halide emulsion layer possessed by the type 3 photographic light-sensitive material preferably contains a swelling inhibitor. The swelling inhibitor in the present invention can suppress the swelling of the water-soluble polymer compound during the development processing of the photographic light-sensitive material and obtain good image quality. Whether or not it acts as a swelling inhibitor was determined by adding a swelling inhibitor to a 5% by weight gelatin aqueous solution at pH 3.5 to 0.35 mol / L to determine whether gelatin precipitation occurred. Any chemical that causes precipitation will act as a swelling inhibitor. Specific examples of the swelling inhibitor include inorganic salts such as sodium sulfate, lithium sulfate, calcium sulfate, magnesium sulfate, sodium nitrate, calcium nitrate, magnesium nitrate, zinc nitrate, magnesium chloride, sodium chloride, manganese chloride, and magnesium phosphate. Or, for example, benzenesulfonic acid, diphenylsulfonic acid, 5-sulfosalicylic acid, p-toluenesulfonic acid, phenol disulfonic acid, α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, 1,5-naphthalenedisulfonic acid, 1-hydroxy- Sulfonic acids such as 3,6-naphthalenedisulfonic acid and dinaphthylmethanesulfonic acid, for example, polyvinyl benzene sulfonic acid, a copolymer of maleic anhydride and vinyl sulfonic acid, and a polymer precipitant such as polyvinyl acrylamide. And the compounds used. These swelling inhibitors may be used alone or in combination, but it is preferable to use inorganic salts, particularly sulfates. The preferred content of the swelling inhibitor 0.01 to 10 g / ^{m 2,} more preferably from 0.03~2g / ^{m 2.}

  Further, the silver halide emulsion layer of the type 3 photographic light-sensitive material can further contain an electroless plating catalyst, a conductive substance, and the like.

<Other constituent layers>
The photosensitive materials used for types 1 to 3 of the present invention can be provided with non-photosensitive layers such as a backing layer and an over layer, if necessary. In the photographic light-sensitive material of the present invention, in addition to the effect of protecting the overlayer from scratches on the silver halide emulsion layer, for example, in the type 1 photographic light-sensitive material, silver in the photographic light-sensitive material diffuses out of the system by development processing. This has the effect of suppressing the deposition and increasing the efficiency of silver deposition on the physical development nuclei. Accordingly, the over layer is preferably provided on the silver halide emulsion layer. These non-photosensitive layers are layers mainly composed of a water-soluble polymer compound, and natural polymers and water-soluble synthetic polymers contained in the above-described silver halide emulsion layer can be used. The amount of the water-soluble polymer compound in the non-photosensitive layer varies depending on each application, but is preferably in the range of 0.001 to 10 g / m ² . In addition, a crosslinking agent of a water-soluble polymer compound can be used for these non-photosensitive layers. In the type 1 and type 3 development processing of the present invention, at least the unnecessary silver halide emulsion layer is removed by washing with water. Therefore, when a water-soluble polymer compound crosslinking agent is used in the non-photosensitive layer in type 1 and type 3 photographic light-sensitive materials, it should be used within a range that does not hinder the removal of the silver halide emulsion layer after washing with water. desirable.

In the case of the photographic light-sensitive material used in types 1 and 3 of the present invention, it is preferable to provide a water washing removal promoting layer as a non-photosensitive layer. In this case, the water washing removal promoting layer is provided for the purpose of facilitating removal of unnecessary silver halide emulsion layers. It is preferably provided between the material or the easy-adhesion layer and the silver halide emulsion layer. The water washing removal promoting layer uses a water-soluble polymer compound as a binder. Preferred binders include, for example, gelatin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polysaccharides such as starch, cellulose and its derivatives, polyethylene oxide. , Polyvinylamine, chitosan, polylysine, polyacrylic acid, polyalginic acid, polyhyaluronic acid, carboxycellulose and the like. Moreover, it is not preferable to use a water-soluble polymer compound crosslinking agent for the water washing removal promoting layer. The coating amount of the water-soluble polymer compound is preferably 1.0 g / m ² or less. If the coating amount of the water-soluble polymer compound is too large, for example, in the type 1 photographic material, the distance between the physical development nucleus layer and the silver halide emulsion layer becomes long. About 0.1 to 0.6 g / m ² is preferable because there are problems such as a decrease in the amount of precipitation and a decrease in image quality.

In each of the above-described constituent layers, it is preferable to use a non-sensitizing dye or pigment having an absorption maximum in the photosensitive wavelength region of the silver halide emulsion as a halation for improving image quality or an irradiation prevention agent. The antihalation agent is preferably used in the above-mentioned backing layer or a layer provided between a silver halide emulsion layer such as an adhesive layer, a physical development nucleus layer, and a water removal promoting layer and a substrate. You may divide and use for the above layer. The irradiation inhibitor is preferably used in a silver halide emulsion layer. The addition amount of these non-sensitizing dyes or pigments can vary over a wide range as long as the desired effect is obtained, but is preferably in the range of about 0.01 to about 1 g / m ² . If necessary, it may contain known photographic additives, surfactants, matting agents, lubricants, developing agents similar to the above-described silver halide emulsion layers, and the like.

<Exposure>
In the method of forming type 1 to 3 conductive silver patterns, the above-described photographic photosensitive material is exposed and then developed. As an exposure method, scanning exposure is performed using a method in which a transparent original and a silver halide emulsion layer are in close contact with each other, or various laser beams, for example, a blue semiconductor laser (also referred to as a violet laser diode) having an oscillation wavelength of 400 to 430 nm. There are ways to do this.

<Development processing>
For type 1 development processing, the silver halide in the image forming part is dissolved, diffused, reduced on the physical development nuclei, and precipitated, and the silver halide layer that has become unnecessary is washed with water. There is a water washing removal process to remove. In this case, when a negative type silver halide emulsion is used for the photographic light-sensitive material, a portion not irradiated with light by exposure becomes a portion for forming an image, and when a positive type silver halide emulsion is used, A portion irradiated with light becomes a portion where an image is formed by exposure.

  In the type 2 development processing, when the negative type silver halide emulsion is used as a photographic light-sensitive material, a development processing step for reducing the portion of the silver halide irradiated with light by exposure, and light irradiation are performed. There is a fixing processing step for dissolving and removing a portion of silver halide that is not present. On the other hand, when a positive type silver halide emulsion is used for the photographic light-sensitive material, a development processing step for reducing the portion of the silver halide that has not been irradiated with light by the exposure, and a portion of the silver halide that has been irradiated with the light, There is a fixing process for dissolving and removing.

  The type 3 development processing includes a development processing step of reducing the silver halide in the portion where the image is formed and simultaneously hardening the water-soluble polymer compound, and a water washing removal step of washing away the uncured portion which is an unnecessary portion. In this case, when a negative type silver halide emulsion is used for the photographic light-sensitive material, a portion irradiated with light by exposure becomes a portion for forming an image. When a positive type silver halide emulsion is used, exposure is performed. The portion that is not irradiated with light is the portion that forms an image.

  In any of the above-described methods of types 1 to 3, an acidic aqueous solution containing, for example, acetic acid or citric acid is used between the development processing step and the water washing removal step or between the development processing and the fixing processing. A development stop process may be performed.

<Developer>
When each constituent layer of the photographic light-sensitive material contains a developing agent, the developer used in the above-described types 1 to 3 does not necessarily need to contain a developing agent, and the developer is a latent image nucleus that can be developed. It contains an alkaline agent for enabling reduction of silver halide having Examples of the alkaline agent include potassium hydroxide, sodium hydroxide, lithium hydroxide, tribasic sodium phosphate, and various amine compounds. The pH of the developer used for Type 1 and Type 3 is preferably 10 or more, and more preferably in the range of 11-14. The pH of the developer used for Type 2 is preferably 9 or more, and more preferably 10 or more.

  When each constituent layer of the photographic light-sensitive material does not contain a developing agent in an amount that enables reduction of silver halide having latent image nuclei that can be developed, the developer used for the above-described development processes of types 1 to 3 Contains a developing agent. As the developing agent contained in the type 1 and type 2 developers, for example, hydroquinone, catechol, pyrogallol, methylhydroquinone, polyhydroxybenzenes such as chlorohydroquinone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-p Examples include 3-pyrazolidones such as -chlorophenyl-3-pyrazolidone, paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, paraphenylenediamine, ascorbic acid, and the like, and two or more of these may be used in combination. The developer used for Type 3 contains a hardened developing agent. Examples of the hardened developing agent include hydroquinone, catechol, chlorohydroquinone, pyrogallol, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,3-dimethylhydroquinone, 2,3-dibromohydroquinone, 1 , 4-dihydroxy-2-acetophenone, 2,5-dimethylhydroquinone, 4-phenylcatechol, 4-t-butylcatechol, 4-s-butylpyrogalol, 4,5-dibromocatechol, 2,5-diethylhydroquinone, 2 , 5-dibenzoylaminohydroquinone and other polyhydroxybenzenes such as N-methyl-p-aminophenol, p-aminophenol, 2,4-diaminophenol, p-benzyla Aminophenol compounds such as nophenol, 2-methyl-p-aminophenol, 2-hydroxymethyl-p-aminophenol, and others such as JP 2001-215711 A, JP 2001-215732 A, Examples of known hardened developing agents described in JP-A-2001-312031 and JP-A-2002-62664 include benzene having a hydroxyl group substituted at least at the 1,2-position or 1,4-position of the benzene nucleus. Is preferred. The amount of the developing agent and the hardened developing agent used is preferably 1 to 100 g / L.

  Developers used for type 1 to 3 development processes are preservatives represented by sodium sulfite and potassium sulfite, and carbonates and phosphates for maintaining the pH of the developer in the preferred range. It is preferable to contain a buffering agent. Further, an antifoggant added such that bromide ions, benzimidazole, benzotriazole, 1-phenyl-5-mercaptotetrazole, and the like can be added so that silver halide grains having no development nucleus are not reduced. However, in the type 3 developer, the preservative has an action of stopping the curing reaction by the curing development, and therefore it is preferable to keep the amount used at least 20 g / L or less, preferably 10 g / L or less.

  Type 1 developer contains a soluble silver complex salt-forming agent as an essential component for diffusion transfer development. In the type 2 and type 3 developers, the soluble silver complex salt forming agent is not an essential component, but can be preferably used because the conductivity of the silver image obtained by containing the soluble silver complex salt forming agent is further improved. Specific examples of soluble silver complex forming agents include thiosulfates such as ammonium thiosulfate and sodium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, and sulfites such as sodium sulfite and potassium hydrogen sulfite. Thioethers such as 1,10-dithia-18-crown-6,2,2'-thiodiethanol, oxazolidones, 2-mercaptobenzoic acid and its derivatives, cyclic imides such as uracil, alkanolamines, diamines, JP-A-9-171257 discloses mesoionic compounds, 5,5-dialkylhydantoins, alkylsulfones, and other “The Theory of the Photographic Process (4th edition, p474-475)”, T. et al. H. Examples include compounds described in James. Of these soluble silver complex salt forming agents, alkanolamines are particularly preferred. Examples of the alkanolamine include N- (2-aminoethyl) ethanolamine, diethanolamine, N-methylethanolamine, triethanolamine, N-ethyldiethanolamine, diisopropanolamine, ethanolamine, 4-aminobutanol, N, N- Examples include dimethylethanolamine, 3-aminopropanol, and 2-amino-2-methyl-1-propanol. These soluble silver complex salt forming agents can be used alone or in combination. The amount of the soluble silver complex salt forming agent is 0.1 to 40 g / L, preferably 1 to 20 g / L.

  Type 3 developers can contain swelling inhibitors. Examples of the swelling inhibitor include the same swelling inhibitors as those contained in the photographic material. The content of a preferred swelling inhibitor is 50 to 300 g / L, preferably 100 to 250 g / L.

<Development processing conditions>
The processing temperature in the type 1 developer is preferably 15 ° C. to 30 ° C., and the range of 18 ° C. to 23 ° C. is preferred in order to prevent the silver halide emulsion layer from eluting into the developer. The development time is preferably 120 seconds or less in consideration of production efficiency. The processing temperature in the type 2 developer is usually selected between 15 ° C. and 45 ° C., more preferably 25 ° C. to 40 ° C. The development time is preferably 120 seconds or less in consideration of production efficiency. Further, the processing temperature in the type 3 developer is preferably 2 ° C to 30 ° C, more preferably 10 ° C to 25 ° C. The development time is 5 seconds to 30 seconds, preferably 5 seconds to 20 seconds.

The method of supplying the developer to the photographic photosensitive material after exposure may be an immersion method or a coating method. In the dipping method, for example, the exposed photographic light-sensitive material is conveyed in a developing solution stored in a large amount in a tank, and the coating method is, for example, a developing solution on a silver halide emulsion layer. About 40 to 120 ml per 1 m ² . In particular, when a type 3 developer (cured developer) is used, it is preferable to use a coating method and avoid repeated use of cured development.

<Washing removal process>
The water washing removal in the type 1 and type 3 development processes is a process of removing each constituent layer such as a silver halide emulsion layer which becomes unnecessary after the development process, and exposing the silver image on the substrate. Accordingly, water is the main component of the water removal treatment liquid. In addition, the treatment liquid may contain a buffer component, and may contain a preservative for the purpose of preventing the removed gelatin from being spoiled.

  As a water washing removal method, a treatment method can be used alone or in combination with a shower method, a slit method, or the like using a scrubbing roller or the like. Also, a plurality of showers and slits can be provided to increase the removal efficiency. Moreover, you may use the method of carrying out transfer peeling to a release paper etc. instead of water washing removal. As a method of transferring and peeling with release paper, etc., excess developer on the silver halide emulsion layer is squeezed out beforehand with a roller, etc., and the silver halide emulsion layer and the release paper are brought into close contact with each other to remove the silver halide emulsion layer etc. This is a method of transferring from a plastic resin film to release paper and peeling. As the release paper, water-absorbing paper or non-woven fabric, or paper having a water-absorbing void layer formed of fine pigment such as silica and binder such as polyvinyl alcohol on the paper is used.

<Fixing process>
The fixing process in Type 2 is performed for the purpose of removing and stabilizing the silver salt in the non-image area. The fixing process can be performed by using a fixing process technique used in known silver salt photographic film, photographic paper, film for printing plate making, emulsion mask for photomask, etc. And a fixing solution described in p321. Among them, a fixing solution containing a desilvering agent other than thiosulfate is preferable. In this case, as a desilvering agent, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, sulfites such as sodium sulfite and potassium bisulfite, 1,10-dithia-18-crown-6, 2,2 ′ -Thioethers such as thiodiethanol, oxazolidones, 2-mercaptobenzoic acid and derivatives thereof, cyclic imides such as uracil, alkanolamines, diamines, mesoionic compounds described in JP-A-9-171257, 5,5 -Dialkylhydantoins, alkylsulfones, and others "The Theory of the Photographic Process (4th edition, p474-475)", T. et al. H. Examples include compounds described in James.

  Among these desilvering agents, alkanolamine is particularly preferable. As the alkanolamine, the same compounds as those used as the soluble silver complex forming agent described in the developer can be used. Further, thiocyanate has a high desilvering ability, but it is not preferable to use it from the viewpoint of safety to the human body. These desilvering agents can be used alone or in combination. Further, the amount of desilvering agent is preferably 1 to 500 g / L, more preferably 10 to 300 g / L in total of the desilvering agent.

  In addition to the desilvering agent, the fixing solution may contain sulfite and bisulfite as preservatives, and acetic acid, borate amine, phosphate and the like as pH buffering agents. In addition, water-soluble aluminum (for example, aluminum sulfate, aluminum chloride, potassium alum) as a hardener, dibasic acid (for example, tartaric acid, potassium tartrate, sodium tartrate, etc.) or tribasic acid ( Acid sodium, lithium citrate, potassium citrate and the like). The preferred pH of the fixing solution varies depending on the type of desilvering agent, and in particular when the amine is used, it is 8 or more, preferably 9 or more. The fixing processing temperature is usually selected between 10 ° C. and 45 ° C., more preferably 18 ° C. to 30 ° C.

  In the type 3 of the present invention, there can be used a method of developing the photographic photosensitive material using a second developer containing a silver halide solvent after development with a developer. By this method, the silver in the relief image cured by the first development process can be increased (compensated) by the second development process. The second development step may be before or after the washing removal step of the silver halide emulsion layer, but since the silver halide in the non-image area can also be used as a silver supply source, before the washing removal. It is preferable to carry out. Further, silver can be further increased in the second developing step by further supplying silver ions such as adding a silver salt to the second developing solution.

  Next, the amorphous metal electroplating of the present invention will be described. In general, alloy plating is used to form an amorphous metal by electrolytic plating. Alloy plating is a method in which two or more metals or metals and non-metals are simultaneously deposited from one plating bath. The ease of metal deposition from the metal salt in the plating bath is electrochemically dependent on the standard electrode potential. Since the electrolytic plating of metal is performed at a constant potential, a plurality of metals are deposited together in the alloy plating bath, and the standard electrode potential needs to be close to be alloy plating. Even if the standard electrode potential is far away, there are cases where the potential can be made closer by changing the bath composition or changing the plating conditions such as current density. However, there are cases where the metal precipitates without following the theory of electrochemistry as described above, and the case where the base metal is preferentially precipitated, and the metal ion that cannot be electrodeposited alone, In some cases, other metals are precipitated and are induced. Tungsten, molybdenum, phosphorus, sulfur, boron, etc. that are not electrodeposited alone from an aqueous solution are induced by electrodeposition of iron group transition metals such as nickel, cobalt, iron, chromium, etc. There are many examples. Such a film preparation method is called induced eutectoid alloy plating, and an amorphous structure is formed when the content of induced eutectoid components increases. Moreover, a plating metal component composition can be changed with plating conditions, such as a plating bath composition, temperature, and a current density. The combination of the plating elements is mainly two types (binary) or three types (ternary). However, the management of the plating bath becomes more complicated as the number of elements increases, so binary alloys are preferable in terms of liquid management. . As combinations in binary alloy plating, Ni—W, Co—W, Fe—W, Cr—W, Ni—Mo, Co—Mo, Fe—Mo, Cr—Mo, Ni—Sn, Zn—Ni, Ni-P, Fe-P, Co-P, Pd-P, Ni-B, Cr-C, Ni-S, Co-S, etc. are mentioned.

  The determination of the crystallinity of the plated metal can be performed by performing X-ray diffraction measurement with an X-ray diffractometer. Since a crystalline metal has a peak at a diffraction angle unique to a metal species, it can be said to be amorphous if this unique metal crystal peak is not detected.

  Of the binary alloy plating, a nickel alloy is preferable from the viewpoint of the response current linearity and coefficient of variation obtained. Among nickel alloys, nickel phosphorus plating is particularly preferable because of the ease of management of the plating bath and the ease of forming a plating film with respect to the plating conditions. Hereinafter, electrolytic nickel phosphorus plating will be described.

  Electrolytic nickel phosphorus plating is basically structured by introducing phosphorous acid as a reducing agent into an electrolytic nickel plating bath. As the nickel source of the plating solution, known ones such as nickel sulfate, nickel chloride, nickel sulfamate, nickel phosphite, which are water-soluble nickel salts, can be used. Moreover, you may use these 2 types or more in mixture. The amount used is preferably in the range of 0.1 to 2 mol / l as nickel ions. If the ion concentration is too low, the current density at the time of plating cannot be increased and the time becomes longer, so that the working efficiency is lowered. On the other hand, if the ion concentration is too high, there will be an adverse effect on the plating due to the precipitation of nickel phosphite and the increase in liquid viscosity.

  As the phosphorus source of the electrolytic nickel phosphorus plating solution preferably used in the present invention, at least one of phosphorous acid and phosphite is used. Examples of the phosphite include sodium phosphite, ammonium phosphite, potassium phosphite, sodium hydrogen phosphite and the like. The amount used is preferably in the range of 0.1 to 3 mol / l as phosphite ion. If the ion concentration is too low, the current density dependency of the phosphorus content in the plating film increases, making it difficult to obtain a plating film having a uniform composition. On the other hand, when the ion concentration is too high, the plating deposition rate is lowered and the working efficiency is lowered.

  Citric acid or citrate is used for the electrolytic nickel phosphorus plating solution preferably used in the present invention. Citrate ions have the effect of complexing nickel ions to increase the phosphorus content in the plating film, maintaining a constant plating composition at a wide current density, and improving plating coverage. Examples of the citrate include sodium citrate, trisodium citrate, potassium citrate, and ammonium citrate. The amount of citrate ions used is usually in the range of 0.1 to 3 times the molar ratio of nickel ions.

  The nickel phosphorus plating solution used in the present invention may contain boric acid, a brightener (such as saccharin and butynediol), a pit inhibitor (such as sodium lauryl sulfate), and the like, in the same manner as known nickel plating solutions. .

  The pH range of the nickel phosphorus plating solution used in the present invention is preferably 2 to 5. If the pH is less than 2, the electrodeposition rate is remarkably slowed due to a decrease in current efficiency due to hydrogen generation. On the other hand, when the pH exceeds 5, precipitates are formed by phosphate ions and nickel ions oxidized at the anode, making it difficult to form a stable plating film. The pH of the plating solution can be appropriately adjusted with an alkali such as sodium hydroxide or ammonium hydroxide, or an acid such as sulfuric acid or hydrochloric acid, depending on the composition of the solution.

The current density of the nickel-phosphorus plating used in the present invention, 0.1~30A / dm ² is preferred. If the current density is too high, it is difficult to keep the plating solution concentration constant with normal stirring.

  The temperature of the nickel phosphorus plating solution used in the present invention is preferably 40 to 80 ° C. When the plating bath temperature is too low, the current density dependency of the phosphorus content in the plating film increases, and it becomes difficult to obtain a plating film having a uniform composition.

  The biosensor electrode of the present invention can produce a large number of electrodes in a mass by a roll-to-roll method. In the present invention, the roll-to-roll method refers to a long base material wound in a roll shape, for example, a film, which is processed on the base material while being intermittently or continuously conveyed, and again into a roll. It is a winding method. The method for producing an electrode for a biosensor according to the present invention comprises a roll-shaped substrate continuously unwound, a silver halide emulsion layer coating solution coated on the substrate, and dried to have a silver halide emulsion layer. The first step for producing the photosensitive material, the second step for exposing the continuously conveyed photographic photosensitive material, the exposed photographic photosensitive material that has been continuously conveyed is developed, and conductive on the substrate. It includes at least a third step of forming a silver pattern and a fourth step of plating the conductive silver pattern on the substrate with an amorphous metal by electrolytic plating and then winding it into a roll. These first to fourth steps may be further wound up as needed during the step or after each step, but may be performed continuously from the first step to the fourth step. is there.

  In the first step, a roll-shaped substrate is unwound and continuously conveyed, and a silver halide emulsion coating solution is applied by a coating head. The substrate on which the coating liquid is provided passes through the cooling zone and the drying zone, takes a photographic material, and is wound up as necessary.

  The second step can be performed using, for example, a continuous exposure apparatus described in JP-A-2007-225884. The apparatus has a continuous exposure unit that exposes the photosensitive material produced in the first step while conveying it, and a winding unit that winds the photosensitive material that has been exposed in a roll shape. The continuous exposure unit consists of a transparent cylindrical body and an in-cylinder light source. A pattern mask is provided between the outer periphery of the transparent cylinder and the photographic photosensitive material, and the photographic photosensitive material is wrapped around and conveyed to be exposed from the light source provided in the center. Thus, continuous pattern exposure can be performed. The pattern mask is a collection of a large number of individual electrodes, and is connected at a power feeding portion in order to perform plating in a later electrolytic plating process.

  The third step can be performed using, for example, a processing apparatus described in JP-A-2006-190535. The apparatus is a conductive silver produced by processing and drying, an unwinding shaft for holding the roll-shaped exposed photographic photosensitive material obtained in the second step, a developing unit, a rinsing or fixing unit, a drying unit, A conductive silver pattern can be obtained by having a winding shaft for winding the pattern in a roll shape and continuously conveying the pattern.

  For example, the fourth step can be performed by an apparatus as shown in FIG. The base material having a roll-shaped conductive silver pattern produced in the third step is unwound from the unwinding portion 1, the conductive silver pattern is brought into contact with the power supply roll 6 (cathode), and the plating solution 4 is charged. Carry into the liquid tank 3. An anode plate 5 is provided in the plating solution 4 so as to face the conductive silver pattern, and amorphous metal is deposited on the conductive silver pattern while being continuously conveyed in the plating solution 4. After being unloaded from the plating solution tank 3, it is wound by the winder 2 through a water washing step and a drying step (not shown) to form a roll sensor electrode assembly.

  Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to these examples.

Example 1
Examples of the present invention are shown below. First, a conductive silver pattern was prepared by a photographic material method.
<Photosensitive material system>
A white polyethylene terephthalate film having a thickness of 100 μm was used as the substrate. A physical development nucleus layer coating solution containing palladium sulfide prepared as described below was applied to a roll-shaped substrate around which 1000 m of the substrate was wound up, dried, and wound up once.

<Preparation of palladium sulfide sol>
Liquid A 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 30 minutes later, the solution was passed through a column filled with an ion exchange resin to obtain palladium sulfide sol.

<Preparation of physical development nucleus layer coating solution / per 1 m ² >
The palladium sulfide sol (as solid content) 0.4mg
Glyoxal aqueous solution (40% aqueous solution) 0.08 ml
Polyethyleneimine 50mg
(Epomin SP-200 (active ingredient about 100%): manufactured by Nippon Shokubai Co., Ltd.)
Surfactant (S-1) 10mg

  Subsequently, a water washing removal promoting layer 1, a silver halide emulsion layer 1, and an outermost layer 1 having the following composition were coated on the physical development nucleus layer in a roll-to-roll manner in order from the side closer to the substrate. The silver halide emulsion was prepared by a general double jet mixing method for photographic silver halide emulsions. This silver halide emulsion was prepared with 95 mol% of silver chloride and 5 mol% of silver bromide, and 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 a conventional method. The silver halide emulsion thus obtained contains 0.5 g of gelatin per gram of silver.

<Water-washing removal promoting layer 1 composition / 1 m ² >
Gelatin 0.5g
Surfactant (S-1) 5mg

<Silver halide emulsion layer 1 composition / m ² >
Gelatin 0.5g
Silver halide emulsion 3.0g Silver equivalent 1-Phenyl-5-mercaptotetrazole 3.0mg
Surfactant (S-1) 20mg

<Outermost layer 1 composition / per 1 m ² >
1g of gelatin
Amorphous silica matting agent (average particle size 3.5μm) 10mg
Surfactant (S-1) 10mg

  The photographic light-sensitive material thus obtained is continuously conveyed in a roll-to-roll manner using the apparatus shown in FIG. 1 described in Japanese Patent Application Laid-Open No. 2007-225884, and light of 400 nm or less is cut using a mercury lamp as a light source. A large number of patterns in FIG. 1 were exposed at one time by exposing through a resin filter through a document on which the patterns in FIG. 1 were integrated.

  Subsequently, the following diffusion transfer developer was prepared. Thereafter, the previously exposed photographic photosensitive material is continuously conveyed by a roll-to-roll method using the apparatus shown in FIG. 1 described in JP-A-2006-190535, and immersed in the following developer at 20 ° C. for 90 seconds. Subsequently, the silver halide emulsion layer and the non-light-sensitive layer were washed away with warm water at 40 ° C. and dried. Thus, the electroconductive silver pattern base material roll which has many patterns of FIG. 1 was obtained.

<Diffusion transfer developer>
Potassium hydroxide 25g
Hydroquinone 18g
1-phenyl-3-pyrazolidone 2g
Potassium sulfite 80g
N-methylethanolamine 15g
Potassium bromide 1.2g
Bring the total volume to 1000 mL with water
Adjust to pH = 12.2.

  Using the apparatus shown in FIG. 3, the following electroplating treatment of the following <A-1> to <A-5> is continuously conveyed to the conductive silver pattern obtained as described above by the roll-to-roll method. The electrode for sensors was produced. Details of each sample obtained are shown in Table 1.

<A-1>
Nickel phosphorus plating was performed using a nickel plate as an anode at a temperature of 60 ° C. and a current density of 2 A / dm ² using the following nickel phosphorus plating solution.

<Prescription of nickel phosphorus plating solution>
Nickel sulfate hexahydrate 250g / L
Nickel chloride hexahydrate 77g / L
Boric acid 77g / L
Trisodium citrate dihydrate 322g / L
Phosphorous acid 205g / L
pH = 2.5

<A-2>
Nickel plating was performed using a nickel plate as an anode at a temperature of 45 ° C. and a current density of 4 A / dm ² using the following nickel plating solution.

<Prescription of nickel plating solution>
Nickel sulfate hexahydrate 240g / L
Nickel chloride hexahydrate 45g / L
Boric acid 30g / L
pH = 4.5

<A-3>
Nickel tin plating was performed using a nickel plate as an anode at a temperature of 50 ° C. and a current density of 0.5 A / dm ² using the following nickel tin plating solution.

<Prescription of nickel tin plating solution>
Nickel chloride hexahydrate 30g / L
Stannous chloride 30g / L
Potassium pyrophosphate 200g / L
Glycine 20g / L
Ammonia water (28%) 5ml / L
pH = 8.0

<A-4>
Nickel tungsten plating was performed using a nickel plate as an anode at a temperature of 60 ° C. and a current density of 2.5 A / dm ² using the following nickel tungsten plating solution.

<Prescription of nickel tungsten plating solution>
Nickel sulfate hexahydrate 27g / L
Sodium tungstate dihydrate 53g / L
Trisodium citrate dihydrate 300g / L
pH = 6.0

<A-5>
Using the following tin-zinc plating solution, tin zinc plating was performed using a 75% tin and 25% zinc alloy plate for the anode at a temperature of 50 ° C. and a current density of 5.0 A / dm ² .

<Tin zinc plating solution prescription>
Stannous sulfate 36g / L
Zinc sulfate 17g / L
Citric acid 100g / L
Ammonium sulfate 80g / L
pH = 5.5

  Separately from the photographic light sensitive material method, a conductive silver pattern was prepared by the following two methods.

<Etching method>
A silver film was formed on the entire surface of a white polyethylene terephthalate film having a thickness of 100 μm by vapor deposition. On this silver film, a positive photosensitive resist containing a cresol novolak resin and naphthoquinone diazide sulfonate was applied and dried. Next, the resist layer surface is brought into close contact with a document on which the pattern of FIG. 1 is integrated, light having a wavelength in the resist photosensitive area (ultra-high pressure mercury lamp) is collected, and parallel light exposure is performed through a collimator lens at a time. A number of the patterns of FIG. 1 were exposed. The exposed sheet was developed for 40 seconds while rocking in a 1% aqueous sodium carbonate solution at 30 ° C. to obtain a resist pattern on the silver thin film layer.

  A portion of the silver thin film having the resist pattern, which is not shielded by the resist, was removed by immersing in a bleach-fixing solution PSA-2 for color printing paper manufactured by Mitsubishi Paper Industries, Inc. while shaking at 40 ° C. for 30 seconds. . Thereafter, a 3% sodium hydroxide aqueous solution at 40 ° C. was sprayed on to remove and remove the resist, washed with water, and dried to produce a conductive silver pattern.

  The substrate having a conductive silver pattern obtained as described above was subjected to the above-described electrolytic plating treatment <A-1> to produce a sensor electrode.

<Inkjet method>
50 ml of an inducer containing a palladium catalyst (OPC-50; manufactured by Okuno Pharmaceutical Co., Ltd.), 50 ml of water, and 100 ml of glycerin were mixed to prepare an ink having a viscosity of 15 mPas (temperature 25 ° C.). Using this ink, the pattern of FIG. 1 was drawn on a white polyethylene terephthalate film having a thickness of 100 μm by an inkjet apparatus, dried at 40 ° C. for 6 minutes, and then washed with water. This obtained the printing pattern on the base material.

  As an ink jet device, an ink jet type coating device (MJP-1500V) manufactured by Microjet Co., Ltd. was used.

  Printing is performed by immersing the substrate 1 on which the printing pattern is formed in the first pretreatment liquid (temperature 25 ° C.) for 5 minutes and then immersing in the second pretreatment liquid (temperature 25 ° C.) for 1 minute. A treatment for reducing the palladium nucleus in the pattern 3 to facilitate the deposition of electroless plating was performed. The first pretreatment liquid and the second pretreatment liquid are as follows.

<First pretreatment liquid>
OPC-150 Cryster MU (Okuno Pharmaceutical Co., Ltd.) 150ml
1000ml of water
<Second pretreatment liquid>
OPC-150 Cryster MU (Okuno Pharmaceutical Co., Ltd.) 30ml
1000ml of water
Then, it was immersed in an autocatalytic electroless silver plating solution (Okuno Pharmaceutical Co., Ltd. Muden Silver KSS bath) at 35 ° C. for 15 minutes to obtain a conductive silver pattern having a thickness of 0.1 μm.

  The electroconductive silver pattern obtained as described above was subjected to the above-described electrolytic plating treatment <A-1> to produce a sensor electrode.

  Sensor electrodes prepared using the above-described photographic material method, etching method, and inkjet method were individually cut, and the following reagent layers were formed thereon.

<Reagent layer formation>
An aqueous solution containing an enzyme (glucose oxidase), a mediator (potassium ferricyanide), and a hydrophilic polymer (carboxymethylcellulose) was dropped onto the sensor electrode and dried to prepare a sensor electrode.

<Plating metal crystallinity>
The metal crystal corresponding to the plated metal film formed by using the Rigaku X-ray diffractometer MiniFlex without using the pattern of FIG. It was confirmed whether a peak was detected. MiniFlex uses CuKα rays as a light source, and its output is 30 kV, 15 mA. The measurement method uses a step scanning method, the data sampling interval is 0.01 °, and the measurement time of one data point is 1 second. If no metal crystal peak was detected, it was judged as amorphous. The results are shown in Table 1.

<Evaluation of response current linearity>
With the sensor electrode obtained as described above, whole blood was used to determine the relationship between the glucose concentration and the response current. The whole blood was introduced into the electrode part, the reaction was allowed to proceed for 5 seconds, a potential of 0.2 V was applied, and the current value 10 seconds after the application was measured. The measured current value was linearly regressed with respect to the glucose concentration to obtain a regression constant. The results are shown in Table 1 with a regression constant of 0.95 or more as “◯” as good response current linearity and a value of less than 0.95 as “x”.

  As a result, the linearity of the response current was not obtained with the electrodes of Samples 2 and 3. In the electrodes of Samples 1 and 4 to 8, response current linearity was obtained. Table 1 also shows the upper limit value of the coefficient of variation (n = 5) of the response current at each concentration in samples other than Samples 2 and 3. The coefficient of variation of the obtained data was 4% to 5% or less at any density in the samples (samples 1, 4 to 6) in which the pattern was prepared by the photographic photosensitive material method. On the other hand, in the sample in which the pattern was produced by the etching method and the ink jet method, it was 8% or less, and the measurement accuracy was inferior to that of the photographic material method.

(Example 2)
In the photographic light-sensitive material system, each of <Type 1>, <Type 2>, and <Type 3> is used, and a conductive silver pattern base material is produced on a white polyethylene terephthalate film having a thickness of 100 μm in the same manner as in Example 1. did.

<Type 1>
Sample No. 1 was produced.

<Type 2>
The following silver halide emulsion layer 2 was coated on a roll-shaped substrate obtained by winding 1000 m of a white polyethylene terephthalate film having a thickness of 100 μm. The silver halide emulsion was prepared by a general double jet mixing method for photographic silver halide emulsions. This silver halide emulsion was prepared such that silver chloride was 40 mol% and silver bromide 60 mol%, and the average grain size was 0.15 μm. The silver halide emulsion thus obtained was subjected to gold sulfur sensitization using sodium thiosulfate and chloroauric acid according to a conventional method. The silver halide emulsion thus obtained contains 1 g of gelatin per 3 g of silver.

<Silver halide emulsion layer 2 composition / 1 m ² >
1g of gelatin
Silver halide emulsion 3.0g Silver equivalent 1-Phenyl-5-mercaptotetrazole 3.0mg
Surfactant (S-1) 20mg
Glyoxal (40% aqueous solution) 50mg

  The photographic light-sensitive material thus obtained was exposed in the same manner as in Example 1 except that the pattern original was changed to FIG.

  Subsequently, using the same apparatus as in Example 1, the film was immersed in a direct developer solution B having the following formulation at 30 ° C. for 30 seconds, and then immersed in a 2% acetic acid solution at 20 ° C. for 30 seconds to stop treatment.

<Direct developer b>
Sodium sulfite 70g / L
Hydroquinone 18g / L
1-phenyl-3-pyrazolidone 0.7 g / L
Potassium carbonate 30g / L
Potassium bromide 3g / L
N- (2-aminoethyl) ethanolamine 3 g / L
Sodium hydroxide pH = 10.5

  The photographic light-sensitive material that had been developed and stopped was immersed in the following fixing solution at 20 ° C. for 180 seconds.

<Fixing solution formulation>
N- (2-aminoethyl) ethanolamine 250 g
The pH is adjusted to 10.5 with 5N aqueous sodium hydroxide solution, and water is added to make the total volume 1L.

<Type 3>
The silver halide emulsion layer 3 was coated on a roll-shaped substrate obtained by winding 1000 m of a white polyethylene terephthalate film having a thickness of 100 μm. The silver halide emulsion was prepared by a general double jet mixing method for photographic silver halide emulsions. This silver halide emulsion was prepared such that silver chloride was 40 mol% and silver bromide 60 mol%, and the average grain size was 0.15 μm. Further, by using low molecular weight gelatin having a molecular weight of 10,000 or less as a part of the protective binder of the silver halide emulsion, the low molecular weight gelatin is removed at the time of washing and removing in the desalting process after mixing. The silver halide emulsion thus obtained was subjected to gold sulfur sensitization using sodium thiosulfate and chloroauric acid according to a conventional method. The silver halide emulsion thus obtained contains 0.5 g of gelatin per 3 g of silver.

<Silver halide emulsion layer 3 composition / 1 m ² >
Gelatin 1.0g
Silver halide emulsion 3.0g Silver equivalent 1-Phenyl-5-mercaptotetrazole 3.0mg
Surfactant (S-1) 20mg
4-Phenylcatechol 20mg
Sodium sulfate 0.05g

  The photographic light-sensitive material thus obtained was exposed in the same manner as in Example 1 except that the pattern original was changed to FIG.

  Subsequently, using the same apparatus as in Example 1, it was cured by developing at 23 ° C. for 10 seconds with a developer having the following formulation, then treated at 25 ° C. for 40 seconds with the following second developer, and then treated at 35 ° C. The water was removed by washing with warm water.

<Developer>
Sodium hydroxide 20g
Potassium bromide 1g
Sodium sulfite 1g

<Second developer>
25g of tripotassium phosphate
Hydroquinone 18g
1-phenyl-3-pyrazolidone 2g
Potassium sulfite 50g
N-methylethanolamine 10g
Potassium bromide 0.5g
Bring the total volume to 1000 mL with water
Add phosphoric acid and adjust to pH = 10.5.

  The roll-shaped base material having the three types of conductive silver patterns (samples 1, 9, and 10) obtained as described above was used in <A-1> in Example 1 using the apparatus shown in FIG. Plating treatment was performed to produce a sensor electrode. The plating conditions are the same as in Sample 1. The produced electrode was exposed to a wet heat condition of 60 ° C. and 90% RH for 1000 hours. A reagent layer was formed on the exposed electrode in the same manner as in Example 1, and the response current linearity was evaluated. The results are shown in Table 2.

  As a result, good response current linearity was obtained in any of the production methods of types 1 to 3. The coefficient of variation was the best when the conductive silver pattern prepared by the method of <Type 1> was used.

B Substrate part E1 Working electrode part E2 Counter electrode part 1 Unwinding part 2 Winding part 3 Plating solution tank 4 Plating solution 5 Anode plate 6 Feeding roll

Claims (3)

  A photosensitive silver material having at least a silver halide emulsion layer on a substrate is exposed and developed to produce a conductive silver pattern, and then obtained by electroplating an amorphous metal on the conductive silver pattern. Electrode for biosensor.   2. The biosensor electrode according to claim 1, wherein the photographic material is a photographic material having a physical development nucleus layer and a silver halide emulsion layer in this order on a substrate.   A first step of continuously producing a photographic light-sensitive material having a silver halide emulsion layer by continuously unwinding a roll-like substrate, coating a silver halide emulsion layer coating solution on the substrate, and drying it. A second step of exposing the conveyed photographic material, a third step of developing the exposed photographic material continuously conveyed to form a conductive silver pattern on the substrate, and A method for producing an electrode for a biosensor comprising at least a fourth step of plating an amorphous metal on an electroconductive silver pattern on a substrate by electrolytic plating and then winding it into a roll.

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