JP2017050043A - Conductive pattern precursor and method for manufacturing conductive pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive material precursor from which a conductive material having excellent property for eliminating visibility of a sensor pattern can be obtained, and a method for manufacturing a conductive pattern using the conductive material precursor.SOLUTION: A conductive pattern precursor includes a base layer comprising at least a water-soluble polymer compound, a crosslinking agent and a metal sulfide on a support body, and a photosensitive resist layer on the base layer. The photosensitive resist layer is a quinone diazide-based positive photoresist layer; and the photosensitive resist layer comprises at least an acrylic resin and toluene sulfonamide.SELECTED DRAWING: None

Description

  The present invention relates to a conductive pattern precursor used for obtaining a conductive material having a conductive pattern composed of fine metal wires on a support. And a method for producing a conductive pattern using the conductive pattern precursor.

Conventionally, in applications such as a light-transmissive touch panel, an electromagnetic shielding material, and a heater, a thin film (transparent conductive material) made of a transparent conductive material such as tin oxide (SnO ₂ ), indium tin oxide (ITO), or zinc oxide (ZnO). Thin film) is used. Although these thin films are transparent, the sheet resistance value is 100 Ω / □ or more, and in recent years, studies are underway to replace this transparent conductive thin film with a mesh-like conductive pattern composed of fine metal wires. At present, from the viewpoint of pattern visibility (difficult visibility where the pattern is difficult to be seen), further fine pitch of the conductive pattern is required, the width of the fine metal wire is 5 μm or less, and the sheet resistance value is 100Ω / □ A conductive pattern having the following sufficient conductivity is required.

  As a method for forming a mesh-like conductive pattern composed of fine metal wires, a resist having a photosensitive resist layer provided on a metal foil and having a resist opening in an arbitrary pattern by a so-called photolithography method comprising a photo-sensitive and developing process After forming the pattern, a subtractive method is known in which the metal foil in the resist opening is dissolved and removed by etching, and the metal foil is processed into a desired pattern. There is an urgent need to thin metal foils (mainly copper foils) and photosensitive resist layers to be etched.

  Examples of those that do not require an etching step include JP-A-8-239773, JP-A-9-205270, JP-A-10-18044, and the like. Disclosed is a photosensitive sheet in which a base layer for electroless plating containing fine particles and a crosslinking agent is provided, a base metal layer is provided by electroless plating thereon, and a photosensitive resist layer is provided thereon. . However, it is necessary to go through complicated steps such as transfer of the plating layer to the insulating support and subsequent peeling of the plastic film, and productivity has not been improved.

  In JP-A No. 2002-134879, a metal pattern can be formed in an accurate shape by providing a catalyst layer that absorbs light of a specific wavelength for curing a plating resist on a base material. JP-A No. 2007-191731 Discloses that after forming a resist pattern on a catalyst layer formed by treatment with a tin compound, a copper compound, a palladium compound, or the like, an electroless plating treatment is performed. However, in the process of forming the catalyst layer, a plurality of immersion treatments are required, and a uniform metal thickness cannot be obtained due to uneven adhesion of the catalyst layer, and improvement has been demanded.

  In JP 2003-249790 A, a metal complex reducing layer is applied on a light-transmitting support, a resist pattern is formed thereon, and then the metal complex is brought into contact with the metal complex reducing layer using a spray or the like. Thus, it is disclosed to form a conductive pattern. However, since a heating and baking step is required, there is a problem that it is difficult to use a light-transmitting support such as a resin film. Japanese Patent Application Laid-Open No. 2011-35220 discloses that a patterning plating catalyst layer is formed on an easy plating resin layer by bringing a plating catalyst compound solution into contact with an easy plating resin layer printed in a pattern on a support. A technique for forming a metal pattern by providing and then performing electroless plating and / or electrolytic plating is disclosed. However, this method has a problem that it is difficult to obtain a conductive material that is fine and highly conductive.

  JP, 2014-197531, A (patent documents 1) is known as technology which forms a metal pattern by performing electroless plating in order to solve the above-mentioned problem. The publication uses a conductive pattern precursor having a base layer containing a water-soluble polymer compound, a crosslinking agent and a metal sulfide on a support and a photosensitive resist layer in this order, and electroless plating is applied to the resist openings. The method of doing is described. By this technique, a conductive material having good conductivity and excellent adhesion to the support can be obtained. However, in this method, when the resist image is removed after electroless plating, the metal deposited along the wall surface of the resist image portion remains together with the metal deposited on the base layer not covered with the resist image. There is a case where the sensor pattern is easily visually recognized, and improvement has been demanded.

  On the other hand, JP-A-2000-241974 (Patent Document 2) discloses benzenesulfonamide as a compound for adjusting the dissolution rate of a positive photosensitive composition containing a cresol novolak resin and improving the adhesion to a substrate. A compound having a sulfone group such as toluenesulfonamide is described. JP-A 2000-338660 (Patent Document 3) discloses a positive type capable of forming a high-definition pattern by sulfoamides having an aryl group or an aralkyl group. An electron beam resist composition is described.

JP 2014-197531 A JP 2000-241974 A JP 2000-338660 A

  An object of the present invention is to provide a conductive material precursor capable of obtaining a conductive material having excellent sensor pattern visibility (hard visibility) without remaining metal deposited along the wall surface of the resist image portion, and It is to provide a method for producing a conductive pattern using a conductive material precursor.

The above object of the present invention has been achieved by the following invention.
1. A conductive pattern precursor having an underlayer containing at least a water-soluble polymer compound, a crosslinking agent, and a metal sulfide on a support, and a photosensitive resist layer on the underlayer, the photosensitive resist A conductive pattern precursor, wherein the layer is a quinonediazide-based positive photoresist layer, and the photosensitive resist layer contains at least an acrylic resin and toluenesulfonamide.
2. After exposing the surface of the photosensitive resist layer of the conductive pattern precursor described in 1 to an arbitrary pattern, developing the resist image, forming a resist image, and performing electroless plating on the base layer not covered with the resist image A method for producing a conductive pattern, comprising forming a conductive pattern and then removing the resist image.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the electroconductive pattern using the electroconductive material precursor from which the electroconductive material excellent in the visibility (difficult visibility) of the sensor pattern is obtained, and this electroconductive material precursor is provided. be able to.

  The present invention is described in detail below. The conductive pattern precursor of the present invention has a base layer containing at least a water-soluble polymer compound, a crosslinking agent, and a metal sulfide on a support, and a photosensitive resist layer on the base layer. The photosensitive resist layer is a quinonediazide-based positive photoresist layer, and the photosensitive resist layer contains at least an acrylic resin and toluenesulfonamide.

  Examples of the support possessed by the conductive pattern precursor of the present invention include glass and resin film, but a resin film is suitably used in terms of excellent handleability. Specific examples of the resin film include polyester resins such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate), acrylic resins, epoxy resins, fluororesins, silicone resins, polycarbonate resins, diacetate resins, triacetate resins, polyarylate resins. And resin films made of polyvinyl chloride, polysulfone resin, polyether sulfone resin, polyimide resin, polyamide resin, polyolefin resin, cyclic polyolefin resin, and the like. The thickness of these supports is preferably 20 to 300 μm. In addition, when light transmittance is required for the conductive material having a conductive pattern, the support is preferably a transparent support, and the total light transmittance of the transparent support is preferably 80% or more, 85% or more is more preferable. In the present invention, the support may have an easy-adhesion layer, a hard coat layer (HC layer) for the purpose of scratch resistance, or an anti-reflection layer (AR layer) for the purpose of reducing the reflectance. Etc.) may be known.

The underlayer of the conductive pattern precursor of the present invention contains at least a water-soluble polymer compound, a crosslinking agent, and a metal sulfide. Examples of such water-soluble polymer compounds include water-soluble anionic polymer compounds, nonionic polymer compounds, and amphoteric polymer compounds. The anionic polymeric compounds, naturally occurring compounds, or can be used in any of the synthesized compounds, for example, -COO ^- group, -SO ₃ ^- include those having a group. Specific anionic natural polymer compounds include gum arabic, alginic acid, pectin, etc., and semi-synthetic products include carboxymethylcellulose, gelatin derivatives represented by phthalated gelatin, sulfated starch, sulfated cellulose, lignin sulfone. An acid etc. are mentioned. Synthetic products include maleic anhydride (including hydrolyzed) copolymers, acrylic acid (including methacrylic acid) polymers and copolymers, vinyl benzene sulfonic acid polymers and copolymers. And carboxy-modified polyvinyl alcohol. Examples of nonionic polymer compounds include polyvinyl alcohol, hydroxyethyl cellulose, and methyl cellulose. Examples of amphoteric polymer compounds include gelatin.

  Among the above-mentioned water-soluble polymer compounds, gelatin, gelatin derivatives, and polyvinyl alcohol are preferable. Particularly, when polyvinyl alcohol is used, in addition to excellent adhesion to the metal layer described later, conductivity having particularly excellent conductivity. A pattern can be obtained. Polyvinyl alcohol is preferably completely or partially saponified polyvinyl alcohol from the viewpoint of film formation and film toughness of the underlayer, and particularly preferably polyvinyl alcohol having a saponification degree of 80% or more. Moreover, 500-6000 are preferable and, as for the average degree of polymerization of polyvinyl alcohol, 1000-5000 are more preferable. The polyvinyl alcohol used in the present invention includes, in addition to general polyvinyl alcohol, cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, and other polyvinyl alcohol derivatives. Polyvinyl alcohol may be used alone or in combination of two or more.

In the present invention, the water solubility of the water-soluble polymer compound means that the amount dissolved in water at 25 ° C. is at least 0.5% by mass, preferably the amount dissolved is 5% by mass or more. The content of the water-soluble polymer compound in the underlayer of the present invention is preferably 1 to 1000 mg, more preferably 5 to 200 mg, per 1 m ² as a solid content. In the present invention, the underlayer may contain a urethane polymer latex together with a water-soluble polymer compound for the purpose of improving the adhesion of the conductive pattern to the support.

  The above urethane polymer latex is also referred to as urethane polymer emulsion, polyurethane latex, polyurethane emulsion, aqueous urethane resin, and the like, and the urethane polymer latex contains urethane polymer fine particles synthesized from polyol and polyisocyanate. Examples of the polyol to be used include polyether polyol, polyester polyol, polycarbonate polyol, and acrylic polyol. The average particle size of the urethane polymer fine particles in the urethane polymer latex is preferably 0.01 to 0.3 μm, more preferably 0.01 to 0.1 μm. The urethane polymer latex is an aqueous dispersion of urethane polymer fine particles at the stage of the coating liquid used when applying the undercoat layer on the support, but the undercoat layer is dried after application to form a solid coating film. Therefore, the urethane polymer latex in the undercoat layer does not need to maintain the state of the aqueous dispersion or the particle shape of the urethane polymer fine particles.

  As the crosslinking agent contained in the underlayer, a water-soluble crosslinking agent having a solubility in water at 25 ° C. of 0.5% by mass or more is preferable. For example, inorganic compounds such as chromium alum, formaldehyde, glyoxal, malonaldehyde, Aldehydes such as glutaraldehyde, N-methylol compounds such as urea and ethyleneurea, aldehyde equivalents such as mucochloric acid and 2,3-dihydroxy-1,4-dioxane, 2,4-dichloro-6-hydroxy-s- Compounds having active halogen such as triazine salt, 2,4-dihydroxy-6-chloro-s-triazine salt, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, polyethylene glycol di Glycidyl Compounds having two or more epoxy groups in the molecule such as ether and polypropylene glycol diglycidyl ether, divinyl sulfone, divinyl ketone, N, N, N-triacryloylhexahydrotriazine, ethyleneimino group which is an active three-membered ring Compounds having two or more, such as cross-linking agents described in chapters 2, 6, 7, 5, 2, 9 and 3 of "Chemical Reaction of Polymer" (Nobu Okawara 1972, Chemical Dojinsha) A known cross-linking agent for polymer can be used. In particular, when polyvinyl alcohol is used as the water-soluble polymer compound contained in the underlayer, it is preferable to use a polyvalent aldehyde compound as a crosslinking agent. When a polyvalent aldehyde compound is used as the cross-linking agent, it is possible to obtain a conductive pattern having particularly excellent conductivity.

  Representative examples of polyvalent aldehyde compounds include, for example, glyoxal, malonaldehyde, glutaraldehyde, succinaldehyde, heptane dial, octane dial, nonane dial, decandial, dodecandial, 2,4-dimethylheptane dial, 4- Acetal compounds in which aliphatic dialdehydes such as methylhexane dial and aromatic dialdehydes such as terephthalaldehyde and phenylmalondialdehyde, and alcohols such as methanol, ethanol, propanol, ethylene glycol and propylene glycol have reacted with them, And trialdehyde compounds such as N, N ′, N ″-(3,3 ′, 3 ″ -trisulfomilethyl) isocyanurate. Particularly preferable polyvalent aldehyde compounds are dialdehyde compounds, and glutaraldehyde and glyoxal are particularly preferable. A polyvalent aldehyde compound may be used individually by 1 type, and may use 2 or more types together. The content of the crosslinking agent in the underlayer is preferably 1 to 200% by mass with respect to the content of the water-soluble polymer compound.

The metal sulfide contained in the underlayer is mainly heavy metal sulfide fine particles (particle size is about 1 to several tens of nm). Representative examples of metal sulfides include, for example, colloidal particles such as gold and silver, metal sulfides obtained by reacting sulfides with water-soluble salts such as palladium, zinc and tin, among which sulfides. Palladium is preferred. The content of the metal sulfide in the underlayer is preferably 0.1 to 10 mg per 1 m ² of the conductive pattern precursor as a solid content.

  The underlayer can be applied to the support by a known application method such as dip coating, slide coating, curtain coating, bar coating, air knife coating, roll coating, gravure coating, slit die coating, spray coating, etc. However, air knife coating, gravure coating (particularly small-diameter gravure coating), and slit die coating are preferred from the viewpoint of uniformly applying the underlayer. Various coating aids such as thickeners and surfactants can also be used in accordance with the coating method. The underlayer of the present invention is desirably heated at a temperature of 30 to 50 ° C. for 3 to 7 days after the formation of the film in order to promote the crosslinking of the film.

  The conductive material precursor of the present invention has a photosensitive resist layer on the base layer provided on the support, and is between the support and the base layer or between the base layer and the photosensitive resist layer. There is no metal layer in between. From the viewpoint of forming a fine pitch conductive pattern, the photosensitive resist layer in the present invention is preferably a photosensitive resist layer formed by applying a photosensitive liquid resist on the underlayer. A positive photosensitive resist layer is preferred in order to prevent temporal changes in the photosensitive performance due to contact with the photosensitive resist layer.

  As the positive photosensitive resist layer, a water-treatable part that can be dissolved and removed with a developer mainly composed of an alkaline aqueous solution is preferably used as the photosensitive and soluble part, and in the present invention, a quinonediazide positive type is used. Use photoresist. The quinonediazide-based positive photoresist contains an alkali-soluble resin and a photosensitizing agent that is a photolytic component. The alkali-soluble resin is preferably a cresol novolac resin, and the photosensitizer is preferably a naphthoquinone diazide sulfonic acid ester.

  The cresol novolac resin may be, for example, a cresol novolac resin containing each of an ortho form, a para form, and a meta form alone, or a cresol novolak resin in which two or more kinds thereof are mixed regardless of their ratio. Also good.

  Naphthoquinone diazide sulfonic acid ester can be easily produced by esterifying naphthoquinone diazide sulfonic acid and a compound having a phenolic hydroxyl group according to a conventional method.

  Examples of the compound having a phenolic hydroxyl group include novolak resins such as phenol novolak resins and cresol novolak resins, polyhydroxybenzophenones such as tetrahydroxybenzophenone and trihydroxybenzophenone, hydroxystyrene, alkyl gallate, and trihydroxybenzene monoethers. , 2 ', 4,4'-tetrahydroxydiphenylmethane, 4,4'-dihydroxyphenylpropane, 4,4'-dihydroxydiphenylsulfone, 2,2'-dihydroxy-1,1-naphthylmethane, 2-hydroxyfluorene, 2-hydroxyphenanthrene, polyhydroxyanthraquinone, purpurogallin and its derivatives, phenyl-2,4,6-trihydroxybenzoic acid ester, trisphenol, etc. It is.

  The naphthoquinone diazide sulfonic acid ester in the photosensitive resist layer of the present invention is preferably contained in a proportion of 10 to 50 parts by mass with respect to 100 parts by mass of the cresol novolac resin, and contained in a proportion of 15 to 40 parts by mass. More preferably. The photosensitive resist layer of this blending amount is particularly excellent in plating resistance and adhesion with the underlayer.

  As the acrylic resin contained in the photosensitive resist layer of the present invention, those known as acrylic resins can be used. Here, the acrylic resin refers to polymers and copolymers of acrylic acid and derivatives thereof such as esters thereof, and methacrylic acid derivatives such as methyl methacrylate. The acrylic resin in the photosensitive resist layer is preferably contained at a ratio of 15 parts by mass or more with respect to 100 parts by mass of the cresol novolac resin. The upper limit is preferably 45 parts by mass or less. By setting it as such a range, it becomes possible to obtain the electroconductive material especially excellent in the visibility of a pattern (difficult visibility that a pattern is hard to be visually recognized).

  The toluenesulfonamide in the photosensitive resist layer of the present invention is preferably contained in a proportion of 7 parts by mass or more with respect to 100 parts by mass of the cresol novolac resin. Moreover, it is preferable that an upper limit is 21 mass parts or less. By setting it as such a range, it becomes possible to obtain the electroconductive material especially excellent in the visibility of a pattern (difficult visibility that a pattern is hard to be visually recognized). In addition, although toluenesulfonamide has structural isomers such as ortho, para, and meta isomers, the structure of toluenesulfonamide is not limited in the present invention, and a mixture thereof may be used.

  In addition, the positive photosensitive resist layer may contain other known leveling agents, dyes, pigments, stabilizers and the like.

  The photosensitive resist layer of the present invention is preferably provided by coating on the above-described underlayer. In such coating, the quinonediazide positive photoresist is dissolved in a suitable solvent to form a coating solution. As examples of such a solvent, any solvent used in this field can be used. Examples of such a solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, and methyl isoamyl ketone; ethylene glycol or monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether of ethylene glycol monoacetate; diethylene glycol Or monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether of diethylene glycol monoacetate; monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether of propylene glycol or propylene glycol monoacetate, etc. Polyhydric alcohols and their derivatives and ethers; Rings such as dioxane Ethers; and ethyl acetate, butyl acetate, methyl lactate, can be mentioned esters such as ethyl lactate. These solvents may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The film thickness of the photosensitive resist layer is preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 3 μm or less. The lower limit is preferably 0.5 μm or more from the viewpoint of securing necessary resist performance and uniform coating.

  The photosensitive resist layer of the present invention can be applied in the same manner as the underlayer, for example, dip coating, slide coating, curtain coating, bar coating, air knife coating, roll coating, gravure coating, slit die coating. However, from the viewpoint of uniformly applying the photosensitive resist layer, air knife coating, gravure coating (particularly small-diameter gravure coating), and slit die coating are preferable. Various coating aids such as thickeners and surfactants can also be used in accordance with the coating method. The photosensitive resist layer is preferably dried at 60 to 150 ° C. after coating.

  Next, the manufacturing method of the electroconductive material of this invention is demonstrated. In the method for producing a conductive material of the present invention, the photosensitive resist layer surface of the conductive material precursor described above is exposed with an arbitrary pattern, developed, and after forming an exposed pattern-like resist image, electroless plating is performed. By carrying out the process, a metal layer is preferentially formed on the base layer not covered with the resist image, and then the resist image is removed. Examples of the pattern exposure method for obtaining a conductive pattern include a method in which a photosensitive resist layer surface and a photomask having an arbitrary pattern are in close contact with each other and exposed. There is also a method of scanning exposure of the photosensitive resist layer surface in an arbitrary pattern using a laser beam in the photosensitive region of the photosensitive resist layer. Here, the arbitrary pattern is an example of a transparent electrode for a touch panel having a metal mesh pattern and a peripheral trace wiring pattern, and the repeating unit is designed according to the purpose and required performance. The repeating unit is square, rhombus, regular hexagon, etc. A mesh pattern consisting of, a peripheral trace wiring pattern, and the like are exemplified. As for the line width of the metal mesh pattern, a metal fine line having a line width of 1 to 50 μm is preferably used in consideration of conductivity, light transmittance, and the like. The pitch (length of the repeating unit) is preferably set to 100 to 1000 μm for the same reason. Further, as the peripheral trace wiring, the line & space (line width of a plurality of trace wirings and the interval between the trace wirings) is preferably set to 10 to 200 μm. In exposing such an arbitrary pattern, it is preferable to perform parallel light exposure using a parallel light source with a photomask in close contact, particularly when a fine pattern having a line width of 10 μm or less is exposed. The method for producing a conductive material according to the present invention is particularly suitable for producing a pattern of such fine metal wires having a line width of 10 μm or less. About development of a resist layer after exposure, it is preferable to use alkaline aqueous solution from a viewpoint of environmental load reduction. By developing the photosensitive resist layer exposed to an arbitrary pattern, a base layer appears in the area where the photosensitive resist layer is dissolved and removed, and a resist image having an arbitrary pattern is formed.

  Examples of the alkaline aqueous solution include inorganic alkalis such as sodium carbonate, sodium hydroxide, potassium hydroxide, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, di- Secondary amines such as n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium such as tetramethylammonium hydroxide and tetraethylammonium hydroxide An alkaline aqueous solution containing a cyclic amine such as a salt, pyrrole or piperidine can be used. Furthermore, an appropriate amount of alcohols and surfactants can be added to the alkaline aqueous solution, and an alkaline aqueous solution having a pH of 11 to 14 can be exemplified. By developing the photosensitive resist layer exposed to an arbitrary pattern, a resist pattern having a resist opening in which the underlying layer is exposed in an arbitrary pattern can be formed on the underlying layer. Moreover, in order to improve the elution property at the time of development and to make it easy to form a resist pattern, the conductive pattern precursor may be heated at 60 to 150 ° C. before development.

  In the conductive pattern manufacturing method of the present invention, the resist pattern obtained as described above is subjected to electroless plating treatment, so that a metal is preferentially laminated on the base layer of the resist opening, thereby providing a conductive metal. Form a pattern. As the electroless plating treatment, a known plating method such as a copper plating method, a nickel plating method, a galvanizing method, a tin plating method, or a silver plating method can be used. Silver plating is particularly preferred.

  As an electroless silver plating method, a conductive pattern in which a resist pattern having the above-mentioned arbitrary pattern is formed by using two solutions of an ammoniacal silver nitrate solution containing silver nitrate and ammonia and a reducing agent solution containing a reducing agent and a strong alkali component. There is a method in which metallic silver is deposited by applying the mixture so as to be mixed on the surface of the precursor, causing a redox reaction.

  Examples of the reducing agent solution include reducing agents such as aldehyde compounds such as glucose and glyoxal, hydrazine compounds such as hydrazine sulfate, hydrazine carbonate or hydrazine hydrate, and strong alkali components represented by sodium hydroxide. Such a reducing agent solution may contain sodium sulfite, sodium thiosulfate, or the like.

  Several additives can be added to the ammoniacal silver nitrate solution in order to increase the deposition rate of metallic silver in the electroless silver plating process. For example, monoethanolamine, tris (hydroxymethyl) aminomethane, 2-amino-2-hydroxymethyl-1,3-propanediol, 1-amino-2-propanol, 2-amino-1-propanol, diethanolamine, diisopropanol Examples include amino alcohol compounds such as amine, triethanolamine and triisopropanolamine, amino acids such as glycine, alanine and sodium glycine, and salts thereof, but are not particularly limited.

  As a method for applying two solutions of the ammoniacal silver nitrate solution and the reducing agent solution so as to be mixed on the surface of the conductive pattern precursor on which an arbitrary pattern is formed, two kinds of aqueous solutions are mixed in advance. , Spraying this mixed liquid onto the surface of the conductive pattern precursor on which the resist pattern is formed using a spray nozzle, slit nozzle, spray gun, etc., mixing two types of aqueous solutions in the spray gun head, and immediately discharging A method of spraying using a concentric spray gun having a structure for spraying, a method of spraying two types of aqueous solutions by spraying each spray gun from a double-head spray gun having two spray nozzles, and two different sprays of two types of aqueous solutions There are a method of spraying simultaneously using a gun, a method of arranging two slit nozzles and spraying two kinds of aqueous solutions in order. . These can be arbitrarily selected according to the situation.

  In the conductive pattern manufacturing method of the present invention, the electroless plating treatment time is preferably 5 to 300 seconds. Thereby, the thickness of the metal laminated | stacked on the base layer of a resist opening part is about 0.1-1 micrometer. When the conductive pattern precursor of the present invention is used, plating proceeds rapidly and a stable metal layer can be obtained in a short time. Furthermore, firing by heat treatment is not necessary, and sufficient conductivity can be obtained only by ordinary natural drying.

  In the conductive pattern manufacturing method of the present invention, the resist image is removed after the electroless plating treatment. Before the removal treatment, in order to improve the swelling / dissolution of the resist pattern, the resist pattern may be exposed to light having a wavelength capable of exposing the photosensitive resist layer. The removal process is a process of spraying a removal treatment liquid made of an organic solvent and / or an alkaline aqueous solution that swells the resist pattern by spraying, swelling and dissolving the resist pattern, and removing the resist pattern. From the viewpoint of reducing environmental burden, it is preferable to use an alkaline aqueous solution as the removal treatment liquid. Examples of the alkaline aqueous solution include inorganic alkalis such as sodium carbonate, sodium hydroxide, potassium hydroxide, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and diamine. Secondary amines such as n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary compounds such as tetramethylammonium hydroxide and tetraethylammonium hydroxide An alkaline aqueous solution containing a cyclic amine such as an ammonium salt, pyrrole, or piperidine can be used. Furthermore, an appropriate amount of alcohols and surfactants can be added to the alkaline aqueous solution, and an alkaline aqueous solution having a pH of 11 to 14 can be exemplified.

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

<< Production of Conductive Pattern Precursor 1 >>
As a support, a 75 μm thick polyethylene terephthalate film (Lumirror U34 manufactured by Toray Industries, Inc.) was used. The total light transmittance of the support was measured using a double beam haze computer manufactured by Suga Test Instruments Co., Ltd. and found to be 92.4%. The following palladium sulfide sol was prepared, and a coating liquid for the underlayer 1 was prepared using the palladium sulfide sol. The coating apparatus uses an oblique gravure roll having a diameter of 60 mm, an oblique line angle of 45 degrees, a line number of 90 lines / inch, and a groove depth of 110 μm. Later, it was heated in a heating chamber at 40 ° C. for 1 week.

<Preparation of palladium sulfide sol>
Liquid A Palladium chloride 5g
48g of hydrochloric acid
1000g of distilled water
B liquid sodium sulfide 8.6g
1000g of distilled water
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.

<Underlayer coating solution / per 1 m ² >
PVA217 (polyvinyl alcohol manufactured by Kuraray Co., Ltd., saponification degree 88%, polymerization degree 1700) 12 mg
Taipol NPS-436 (surfactant manufactured by Taiko Yushi Chemical Co., Ltd.)
12mg
1N sodium hydroxide 110mg
Glutaraldehyde 18mg
The palladium sulfide sol 0.4mg

  The photosensitive resist 1 having the following composition is applied on the underlayer thus obtained by reverse rotation and kiss touch using the above-described oblique gravure roll, and dried at 90 ° C. for 2 minutes. A conductive pattern precursor 1 was obtained by providing a .5 μm positive photosensitive resist layer.

<Manufacture of o-cresol novolac resin>
A 2 liter four-necked flask equipped with a stirrer and a reflux condenser was charged with 756 g of o-cresol, 369 g of 37% formalin and 7.52 g of p-toluenesulfonic acid monohydrate as a reaction catalyst, and these were stirred and mixed. While raising the temperature to the reflux temperature, the reaction was continued for 12 hours under reflux.

  Next, liquid removal was started, the temperature was raised to 230 ° C. to perform concentration, and further, the temperature was raised to 240 ° C. at a reduced pressure of 2 kPa to perform concentration. The fraction was distilled off to obtain 600 g of o-cresol novolac resin. The obtained o-cresol novolak resin had a weight average molecular weight (polystyrene equivalent weight average molecular weight by high performance liquid chromatography) of 12,000.

<Preparation of photosensitive resist 1>
100 g of o-cresol novolac resin
Naphthoquinonediazide sulfonate ester of 2,3,4-trihydroxybenzophenone
30g
AR-7490 (Acrylic resin manufactured by Koyo Chemical Industries, solid content 45%)
40g
9.25 g of p-toluenesulfonamide
350 g of propylene glycol monomethyl ether acetate

<< Preparation of Conductive Pattern Precursor 2 >>
A conductive pattern precursor 2 was obtained in the same manner as the conductive pattern precursor 1 except that a photosensitive resist 2 comprising the following was used instead of the photosensitive resist 1 in the preparation of the coating solution for the underlayer. .

<Preparation of photosensitive resist 2>
100 g of o-cresol novolac resin
Naphthoquinonediazide sulfonate ester of 2,3,4-trihydroxybenzophenone
30g
AR-7490 (Acrylic resin manufactured by Koyo Chemical Industries, solid content 45%)
80g
18.5 g of p-toluenesulfonamide
350 g of propylene glycol monomethyl ether acetate

<< Preparation of Conductive Pattern Precursor 3 >>
A conductive pattern precursor 3 was obtained in the same manner as the conductive pattern precursor 1 except that a photosensitive resist 3 comprising the following was used instead of the photosensitive resist 1 in the preparation of the coating liquid for the underlayer. .

<Preparation of photosensitive resist 3>
100 g of o-cresol novolac resin
Naphthoquinonediazide sulfonate ester of 2,3,4-trihydroxybenzophenone
30g
350 g of propylene glycol monomethyl ether acetate

<< Preparation of Conductive Pattern Precursor 4 >>
A conductive pattern precursor 4 was obtained in the same manner as the preparation of the conductive pattern precursor 1 except that the photosensitive resist 4 comprising the following was used instead of the photosensitive resist 1 in the preparation of the coating liquid for the underlayer. .

<Preparation of photosensitive resist 4>
100 g of o-cresol novolac resin
Naphthoquinonediazide sulfonate ester of 2,3,4-trihydroxybenzophenone
30g
AR-7490 (Acrylic resin manufactured by Koyo Chemical Industries, solid content 45%)
40g
350 g of propylene glycol monomethyl ether acetate

<< Production of Conductive Pattern Precursor 5 >>
A conductive pattern precursor 5 was obtained in the same manner as the preparation of the conductive pattern precursor 1 except that the photosensitive resist 5 comprising the following was used instead of the photosensitive resist 1 in the preparation of the coating solution for the underlayer. .

<Preparation of photosensitive resist 5>
100 g of o-cresol novolac resin
Naphthoquinonediazide sulfonate ester of 2,3,4-trihydroxybenzophenone
30g
9.25 g of p-toluenesulfonamide
350 g of propylene glycol monomethyl ether acetate

<< Production of Conductive Pattern Precursor 6 >>
A conductive pattern precursor 6 was obtained in the same manner as the preparation of the conductive pattern precursor 1 except that the photosensitive resist 6 comprising the following was used instead of the photosensitive resist 1 in the preparation of the coating liquid for the underlayer. .

<Preparation of photosensitive resist 6>
100 g of o-cresol novolac resin
Naphthoquinonediazide sulfonate ester of 2,3,4-trihydroxybenzophenone
30g
AR-7490 (Acrylic resin manufactured by Koyo Chemical Industries, solid content 45%)
40g
o-Toluenesulfonamide / p-toluenesulfonamide mixture
9.25g
350 g of propylene glycol monomethyl ether acetate

<Preparation of conductive pattern>
Each of the conductive pattern precursors 1 to 6 obtained as described above is formed of a square having a line width of 3 μm (translucent portion) and a line interval pitch of 300 μm (light-shielding portion) on the photosensitive resist layer surface. Vacuum-adhering a glass mask having a mask image having a mesh pattern and a mask image composed of a line / space image in which fine lines are arranged in parallel with a line width of 10 μm (translucent part), a line interval of 10 μm (light-shielding part) Then, the light (ultra-high pressure mercury lamp) having a wavelength in the photosensitive region of the photosensitive resist layer was collected and subjected to parallel light exposure through a collimator lens. Each of the conductive material precursors 1 to 6 after the exposure uses a 1% by mass sodium carbonate (pH = 11.8) aqueous solution having a liquid temperature of 30 ° C. as a developer, and the developer is used as a photosensitive resist layer by a shower method. Development was performed by spraying for 30 seconds to obtain a resist image.

  Next, after cleaning the front and back surfaces with deionized water and blowing off the deionized water with compressed air, an ammoniacal silver nitrate solution and a reducing agent solution having the following composition are simultaneously sprayed for 16 seconds with a double-head spray gun. Silver plating treatment was performed, and a silver image was formed in the groove portion where the underlayer of the resist opening was exposed. The deposition of metallic silver due to the electroless silver plating treatment was recognized not only on the underlayer not covered with the resist image but also on the wall surface of the resist image. Then, it was washed thoroughly with deionized water and allowed to dry naturally. The spraying amount per one double-head spray gun was 240 ml / min, and the electroless plating treatment time was approximately 16 seconds.

<Ammonia silver nitrate solution>
D liquid silver nitrate 20g
1000g of deionized water
E liquid 28% ammonia aqueous solution 100g
Monoethanolamine 5g
1000g of deionized water
Liquid D and liquid E were mixed at a ratio of 1: 1 to prepare an ammoniacal silver nitrate solution.

<Reducing agent solution>
10g of hydrazine sulfate
Monoethanolamine 5g
Sodium hydroxide 10g
A reducing agent solution was prepared by dissolving in 1000 g of deionized water.

  Next, the resist pattern is dissolved and removed by spraying a 5% aqueous sodium hydroxide solution having a pH of 13.8 for 60 seconds by a shower method, washed with water, and then naturally dried. 6 obtained conductive patterns 1-6.

<Pattern visibility (difficult visibility)>
About the obtained electroconductive patterns 1-6, it observed visually from the place 30 cm away from the pattern, and evaluated from the following viewpoints. The results are shown in Table 1. In the present invention, the evaluation from the following viewpoints is considered to be effective.

○: Not visually recognized as a mesh pattern.
(Triangle | delta): Presence of silver is scattered in a mesh pattern part.
X: The presence of silver is recognized in the mesh pattern portion and is visually recognized as a mesh pattern.

  About the obtained conductive patterns 1-6, when the conductive pattern was observed with a confocal microscope (OPTELICS C130 manufactured by Lasertec), the resist image was covered with the one that was not effective in the present invention. It was confirmed that the metal deposited along the wall surface of the resist image portion remained together with the metal deposited on the underlying layer.

  From the above results, a conductive material precursor from which a conductive material excellent in sensor pattern visibility (difficult visibility) was obtained in the present invention, and a conductive pattern using the conductive material precursor were obtained. .

Claims (2)

  A conductive pattern precursor having an underlayer containing at least a water-soluble polymer compound, a crosslinking agent, and a metal sulfide on a support, and a photosensitive resist layer on the underlayer, the photosensitive resist A conductive pattern precursor, wherein the layer is a quinonediazide-based positive photoresist layer, and the photosensitive resist layer contains at least an acrylic resin and toluenesulfonamide.   The photosensitive resist layer surface of the conductive pattern precursor according to claim 1 is exposed to an arbitrary pattern, developed to form a resist image, and then an electroless plating is performed to form an undercoat layer that is not covered with the resist image A method for producing a conductive pattern, comprising forming a conductive pattern on the substrate and then removing the resist image.