TWI578099B - Photocurable resin composition containing metal particle and use thereof - Google Patents

Description

Photocurable resin composition containing metal microparticles and utilization thereof

The present invention relates to a photocurable resin composition containing metal fine particles. And a method for producing an electrical wiring circuit pattern using the photocurable resin composition containing the metal fine particles, a substrate for a touch panel, a substrate for a display device, a substrate for an information processing terminal device, and the like. The electrical wiring circuit forms a substrate.

In recent years, in terms of circuit materials and displays, demands for miniaturization, high density, high precision, and high reliability have been increasing, and improvement in pattern processing technology has been desired. In particular, the miniaturization of the conductive circuit pattern is indispensable for miniaturization and high density, and various methods have been proposed.

A method of forming an electrical wiring circuit pattern on a substrate is known as a printing method and a photolithography method.

In order to form a high-precision circuit pattern by a printing method, it is necessary to increase the viscosity of the conductive paste in order to suppress penetration of the circuit at the time of printing. However, if the viscosity of the conductive paste is increased, for example, in the screen printing method, the productivity is lowered due to clogging of the stencil, so that it is difficult to perform high precision. . Moreover, in general, the limit of the line & space corresponding to the mass production step is 200 μm.

Further, although the photolithography method can correspond to a high-precision circuit pattern, in order to improve the adhesion between the circuit and the substrate, it is necessary to perform metal sputtering on the entire surface of the substrate. Further, it is necessary to have a plurality of steps such as a resist film, pattern exposure, development, etching, and photoresist peeling, and the productivity is inferior to the printing method. Moreover, the pinholes generated by the sputtering step have a problem of lowering the yield.

In order to improve the above problems, development of a photocurable resin composition containing metal fine particles has been prevailing.

Patent Document 1 discloses that a metal colloidal particle and a polymer dispersing agent for dispersing it and a composition of a photoradical initiator and a solvent are coated on a substrate, and patterned by photolithography. And heating to show the conductivity. However, since the above method is required to perform baking treatment at 200 ° C or higher in order to obtain conductivity, the substrate used for circuit pattern formation is limited to heat resistance such as glass and ceramics.

Recently, a conductive paste for low-temperature firing of a plastic substrate has been developed, and a heat treatment at a relatively low temperature of about 120 ° C has been developed to obtain conductivity (Patent Document 2). However, the heat treatment time takes 60 minutes, etc., and in order to mass-produce with industrial specifications, it cannot be satisfied from the viewpoint of productivity.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-140330

[Patent Document 2] Japanese Patent No. 3218767

An object of the present invention is to provide a photocurable resin composition containing metal fine particles which can form a high-precision circuit pattern on a film substrate and which is a circuit pattern having a low electric resistance. Furthermore, an object of the present invention is to provide a method of manufacturing a high-precision and low-resistance electrical wiring circuit pattern on a film substrate, and an electrical wiring circuit board obtained by the method.

In order to solve the above problems, the inventors of the present invention have found that a photocurable resin composition containing metal fine particles contains a metal containing conductive particles (A) and a photocurable resin composition (B). The photocurable resin composition of the microparticles, wherein the content of the conductive metal microparticles (A) in the resin composition is in the range of 62 to 86% by weight, and the conductive microparticles (A) have: (i) a resin having a 50% average particle diameter of 0.1 to 5 μm, (ii) a knocking degree of 2.5 g/cm ³ or less, and (iii) a BET specific surface area of 1.5 m ² /g or less, by using the resin having the above physical properties The composition, that is, the high-precision electrical wiring circuit pattern having high conductivity, excellent adhesion, and excellent resolution can be formed on a film substrate such as a PET film which does not have high heat resistance without lowering productivity.

According to the present invention, the present invention provides a photocurable resin composition containing metal fine particles, a method for producing an electrical wiring circuit pattern using the same, and an electric wiring manufactured by the method. Road substrate.

(1) A photocurable resin composition containing metal fine particles, which comprises a photocurable resin composition containing fine particles (A) and a photocurable resin composition (B) containing metal fine particles, and the composition In the photocurable resin composition of the metal fine particles, the content of the conductive fine particles (A) is in the range of 62 to 86% by weight with respect to the total amount of the composition, and the conductive fine particles (A) have The following physical properties: (i) 50% average particle diameter is 0.1 to 5 μm, (ii) knocking degree is 2.5 g/cm ³ or less, and (iii) BET specific surface area is 1.5 m ² /g or less.

(2) The photocurable resin composition containing metal fine particles according to (1), wherein the photocurable resin composition (B) is contained in an amount of 15 to 60 with respect to 100 parts by weight of the conductive fine particles (A). The range of parts by weight.

(3) The photocurable resin composition containing metal fine particles according to (1) or (2), wherein the conductive fine particles (A) are silver or an alloy containing silver.

(4) The photocurable resin composition containing metal fine particles according to any one of (1) to (3), wherein the photocurable resin composition (B) contains an alkali-soluble resin.

(5) The photocurable resin composition containing metal fine particles according to any one of (1) to (4), wherein the photocurable resin composition (B) contains photopolymerization having an O-fluorenyl fluorene structure Starter.

(6) A method of manufacturing an electrical wiring circuit pattern comprising the steps of: coating a polyethylene terephthalate (PET) film with indium tin oxide (ITO), zinc oxide (ZnO) or silver nanoparticles Transparent conductive film substrate The coating step of coating the photocurable resin composition containing the metal fine particles according to any one of (1) to (5); and containing the metal via a film or a mask corresponding to the electric wiring circuit pattern to be formed The coating film of the photocurable resin composition of the microparticles is irradiated with an activation energy ray to cure the coating film; the developing step of dissolving, removing and drying the unexposed portion of the coating film with a developing solution.

(7) An electric wiring circuit board manufactured by using the method of manufacturing an electric wiring circuit pattern of (6).

A photocurable resin composition containing metal fine particles according to the present invention, which comprises a photocurable resin composition containing fine particles (A) and a photocurable resin composition (B) containing metal fine particles, In the resin composition, the content of the conductive fine particles (A) is in the range of 62 to 86% by weight, and the conductive fine particles (A) have: (i) 50% average particle diameter of 0.1 to 5 μm, (ii) physical properties of knocking tightness of 2.5 g/cm ³ or less and (iii) BET specific surface area of 1.5 m ² /g or less, and formation of conductivity on a film substrate having low heat resistance by using the resin composition An electrical circuit pattern that is excellent in adhesion and excellent in adhesion. Further, even if the photocurable resin composition containing metal fine particles as in the prior art is not subjected to heat treatment, conductivity can be exhibited. Further, by using the resin composition of the present invention, a high-precision electrical wiring circuit pattern can be manufactured, and a highly precise electrical wiring circuit board can be obtained.

[Formation of the Invention]

Hereinafter, the present invention will be described in detail.

(1) Photocurable resin composition containing metal fine particles

The photocurable resin composition containing metal fine particles of the present invention contains a composition of conductive fine particles (A) and photocurable resin composition (B). Preferably, the conductive fine particles (A) are uniformly dispersed in the photocurable resin composition (B). Further, a coating film can be formed on the substrate, and the portion irradiated with the active energy ray (exposed portion) is polymerized and insoluble in the developer, and the portion (unexposed portion) not irradiated with light can be dissolved in the developer.

In the photocurable resin composition containing metal fine particles of the present invention, the content of the conductive metal fine particles (A) is 62% by weight or more based on the total amount of the photocurable resin composition containing the metal fine particles. More preferably, it is 64% by weight or more, more preferably 65% by weight or more, and still more preferably 66% by weight or more. As in the above range, the resistance value of the electrical wiring circuit pattern is sufficiently low in practical use, and does not hinder the transmission of signals (signals).

The content of the conductive metal fine particles (A) may be 86% by weight or less based on the total amount of the photocurable resin composition containing the metal fine particles, preferably 84% by weight or less, and 83% by weight or less. More preferably, it is more preferably 82% by weight or less. In the above range, the sensitivity is lowered by the decrease in the amount of the photosensitive resin, the formation yield of the circuit pattern is remarkably lowered, or the adhesion to the substrate is lowered, and the resolution is lowered.

The content of the conductive metal fine particles (A) is preferably in the range of about 62 to 86% by weight, preferably about 64 to 84% by weight, based on the total amount of the photocurable resin composition containing the metal fine particles. More preferably, it is about 65 to 83% by weight, more preferably about 66 to 82% by weight.

When the photopolymerization initiator is used, the content of the conductive metal microparticles (A) in the photocurable resin composition containing the metal microparticles of the present invention is relative to the metal microparticles containing the metal microparticles. The total amount of the photocurable resin composition is preferably 70% by weight or more, more preferably 75% by weight or more. It is preferably 83% by weight or less.

When the photopolymerization initiator is used, the content of the conductive metal microparticles (A) in the case of using the O-indenyl ruthenium structure is as follows, and the total amount of the photocurable resin composition containing the metal microparticles is as follows. Range: preferably from 70 to 83% by weight, more preferably from 75 to 83% by weight.

In the photocurable resin composition containing metal fine particles, the content of the photocurable resin composition (B) is 15 parts by weight or more based on 100 parts by weight of the conductive fine particles (A) (for example, 20.5 parts by weight). The above) is preferably more preferably 18 parts by weight or more. Further, it is preferably 60 parts by weight or less (e.g., 53.9 parts by weight or less), more preferably 50 parts by weight or less, still more preferably 45 parts by weight or less.

In the photocurable resin composition containing metal fine particles, the content of the photocurable resin composition (B) is, for example, in the following range: from 15 to 60 parts by weight based on 100 parts by weight of the conductive fine particles (A). (e.g., 20.5 to 53.9 parts by weight) is preferably 18 to 50 parts by weight, more preferably 18 to 45 parts by weight.

Photocurable resin group containing metal microparticles of the present invention The product may contain, in addition to the conductive fine particles (A) and the photocurable resin composition (B), a leveling agent, a tackifier, an anti-precipitating agent, a coupling agent for improving adhesion, and an antifoaming agent. An additive for a photocurable resin composition containing metal fine particles.

Examples of the leveling agent include, for example, a polyether modified polydimethyl siloxane, a polyester modified polydimethyl siloxane, a polyester modified methyl alkyl polyoxy siloxane, a polyether modified product. Polymethylalkyl sulfoxane, aralkyl modified polymethyl alkyl decane, polyester modified hydroxyl-containing polydimethyl siloxane, polyether ester modified hydroxyl-containing polydimethyl a siloxane, an acrylic copolymer, a methacrylic copolymer, a polyether modified polymethylalkyl siloxane, an alkyl acrylate copolymer, an alkyl methacrylate copolymer, an acrylic acid, an alkyl acrylate copolymer A conventionally grafted copolymer of polyalkylene monoalkyl or alkenyl ether, lecithin or the like.

The amount of the leveling agent to be added is preferably 0.1% by weight or more based on the total amount of the photocurable resin composition containing the metal fine particles. As in this range, the effect of the leveling agent can be sufficiently obtained. Further, the amount of the leveling agent to be added is preferably 3% by weight or less based on the photocurable resin composition containing the metal fine particles. If it is this range, the fall of adhesiveness, the deterioration of printability, etc. are not caused. Moreover, even if it is increased above this range, the effect of the leveling agent is not improved.

When the tackifier requires high viscosity, various polymers such as vinyl chloride-vinyl acetate copolymer resin, polyester resin, acrylic resin, and polyurethane resin can be used; Sugar; fatty acid esters such as dextrin palmitate; metal soaps such as zinc octoate; swelling clay minerals such as bentonite; lavender oil, petroleum by distillation Mineral volatile oil, etc.

The amount of the tackifier added is preferably 0.1% by weight or more based on the total amount of the photocurable resin composition containing the metal fine particles. As in this range, the effect of the tackifier can be sufficiently obtained. Further, the amount of the tackifier added is preferably 5% by weight or less based on the total amount of the photocurable resin composition containing the metal fine particles. If it is within this range, deterioration of printability or the like is not caused.

As the anti-precipitation agent, for example, a commercially available product such as a long-chain polyamine-based, a long-chain polyamine-based phosphate, a polyamine-based, an unsaturated polycarboxylic acid, or a tertiary amino group-containing polymer can be used.

The amount of the anti-precipitating agent to be added is preferably 0.1% by weight or more based on the total amount of the photocurable resin composition containing the metal fine particles. As in this range, the effect of the anti-precipitating agent can be sufficiently obtained. Further, the amount of the anti-precipitating agent to be added is preferably 3% by weight or less based on the total amount of the photocurable resin composition containing the metal fine particles. Within this range, deterioration of printability or the like is not caused by an excessive viscosity-increasing effect. Moreover, even if it is increased above this range, the effect of the anti-precipitant is not improved.

The coupling agent for improving the adhesion is preferably an alkoxydecane compound having a reactive functional group, and examples thereof include ethylene having trivinyl decane, vinyl trimethoxy decane, and vinyl triethoxy decane. Alkoxy decane compound; 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyl An alkoxy decane compound containing an epoxy group such as methyl diethoxy decane or 3-glycidoxy propyl triethoxy decane; a styryl alkoxydecane compound such as an alkenyltrimethoxydecane; 3-methacryloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane An alkoxydecane compound having a methacryloxycarbonyl group such as 3-methacryloxypropylmethyldiethoxydecane or 3-methylpropenyloxypropyltriethoxydecane; An alkoxydecane compound having an acryloxy group such as acryloxypropyltrimethoxydecane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N -2-(Aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyl Trimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxyindolyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3- An alkoxydecane compound having an amine group such as an aminopropyltrimethoxydecane and a hydrochloride salt of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxydecane; a ureido-based alkoxydecane compound such as 3-ureidopropyltriethoxydecane; 3-chloropropyl Alkoxydecane compound having a chloropropyl group such as methoxy decane; alkoxy decane compound having a mercapto group such as 3-mercaptopropylmethyldimethoxydecane and 3-mercaptopropyltrimethoxydecane; Alkoxydecane compound having a sulfur group such as triethoxymercaptopropyl)tetrasulfide; an alkoxydecane compound having an isocyanate group such as 3-isocyanatepropyltriethoxydecane; imidazolium or the like having an imidazolyl group Alkoxydecane compounds and the like.

The amount of the coupling agent added is preferably 0.1% by weight or more based on the total amount of the photocurable resin composition containing the metal fine particles. As in this range, the effect of the coupling agent can be sufficiently obtained. Further, the amount of the coupling agent added is relative to the photocurable resin composition containing the metal fine particles. The total amount is preferably 5% by weight or less. As far as this range is concerned, no decrease in resolution is caused. Moreover, even if it is increased above this range, the effect of the coupling agent is not improved.

Examples of the antifoaming agent include polyfluorene oxide resin, polyfluorene oxide solution, special antifoaming agent without polyoxymethylene, alkyl acrylate copolymer, alkyl methacrylate copolymer, and alkyl vinyl group. Ether, acrylic copolymer, antifoaming polymer, polyoxyalkylene oxide, antifoaming polyoxyalkylene oxide, polymethylalkyl siloxane, polyether modified polyoxy siloxane, alkane mineral oil, etc. Traditional things.

The amount of the antifoaming agent added is preferably 0.01% by weight or more based on the total amount of the photocurable resin composition containing the metal fine particles. As is within this range, the effect of the antifoaming agent can be sufficiently obtained. Further, the amount of the antifoaming agent added is preferably 1% by weight or less based on the total amount of the photocurable resin composition containing the metal fine particles. Within this range, the adhesion is not lowered, the dispersibility of the composition is deteriorated, and the like. Moreover, even if it is increased above this range, the effect of the antifoaming agent will not be improved.

In the formation of the electric wiring circuit pattern, the photocurable resin composition containing the metal fine particles of the present invention is uniformly applied onto the substrate, and the coating film is adhered to the mask pattern, and the active energy ray is irradiated to cause the light containing the metal microparticles. The curable resin composition is hardened. Further, an electric wiring circuit pattern can be obtained by removing the unexposed portion by using a developing solution. As the electrical wiring circuit pattern, a circuit pattern such as a flexible circuit board, a touch panel substrate, or a display device substrate can be used.

Conductive metal particles (A)

The conductive metal fine particles (A) used in the photohardenable resin composition containing metal fine particles of the present invention have: (i) 50% average particle diameter of 0.1 to 5 μm, and (ii) knocking degree of 2.5. The physical properties of g/cm ³ or less and (iii) BET specific surface area of 1.5 m ² /g or less are not particularly limited as long as they are electrically conductive.

(i) The 50% average particle diameter may be 0.1 μm or more (for example, more than 0.1 μm), and preferably 0.3 μm or more. If it is within this range, there is no problem that the contact area between the particles is too small to lower the conductivity. Further, since the nano metal of less than 0.1 μm absorbs light by absorption by the plasmonic material, the photocurable resin composition containing the metal fine particles cannot be formed by a circuit using exposure.

Further, the 50% average particle diameter may be 5 μm or less (for example, less than 5 μm), and preferably 3 μm or less. If it is within the above range, it does not cause a decrease in resolution.

In terms of 50% average particle diameter, it is preferably more than 0.1 μm and less than 5 μm, or about 0.3 to 5 μm, more preferably about 0.3 to 3 μm.

The 50% average particle diameter in the present invention means an intermediate value (central value) when all of the conductive fine particles contained in the whole or a part of the composition are arranged in a particle size. The 50% average particle diameter in the present invention is a value measured by a micro track method (laser diffraction/scattering method).

(ii) The knocking degree may be 2.5 g/cm ³ or less (for example, less than 2.5 g/cm ³ ). When the light transmittance is not deteriorated, the curing of the photocurable resin composition (B) component is sufficient, and as a result, the photocurable resin composition containing the metal fine particles is adhered to the substrate. Sex, and the resolution becomes sufficient.

The knocking degree in the present invention means that after the conductive powder is filled into the container, tapping (moving the container to the top and allowing the container to fall freely), breaking the gap between the conductive powders, and filling the conductive powder tightly The apparent density and the knocking degree are measured by, for example, charging a conductive powder and filling a 30 mL measuring cylinder, tapping the sensor 100 times after tapping the sensor, and then measuring the volume of the conductive powder. The knocking degree D [g/cm ³ ] can be obtained by the following formula (1) from the mass W [g] in the measuring cylinder and the volume V [cm ³ ] after tapping.

D=W/V (1)

(iii) The BET specific surface area is 1.5 m ² /g or less (for example, less than 1.5 m ² /g), preferably 1.3 m ² /g or less. When the specific surface area of the metal fine particles is large, the binder resin penetrates into the pores, and this portion serves as a so-called binder resin which reduces the adhesion imparting action and the photosensitivity improving effect. In the present invention, the BET specific surface area is in the above range, so that a large amount of the binder resin is not required in the photocurable resin composition (B), and as a result, the electric resistance value of the electric wiring circuit pattern is not increased.

The BET method refers to a method of low temperature and low humidity physical adsorption using an inert gas. The BET specific surface area in the present invention is a value measured by a method in which a known molecule having an adsorption-occupying area is adsorbed at a temperature of liquid nitrogen on the surface of the powder particle, and the specific surface area of the sample is determined.

The shape of the conductive fine particles (A) is not particularly limited as long as it is a conductive property for the purpose, and examples thereof include a spherical shape, a chip shape, a granular shape, a rod shape, and a linear shape. Among them, in the case where the dispersibility in the photocurable resin composition containing metal fine particles is good, it is preferred that the particles are in a granular form.

Examples of the conductive fine particles (A) include noble metals such as gold, silver, copper, and platinum group metals, and gold having high conductivity such as nickel and aluminum. A monomeric metal such as a genus or a fine particle containing an alloy of the monomeric metals. Further, the metal fine particles of the monomer or the metal fine particles of the alloy may be used in combination of two or more kinds. Among them, since the conductivity is good, it is preferable to use gold, silver, copper or metal fine particles containing the alloy, and metal fine particles of silver or an alloy containing silver are more preferable.

The conductive fine particles (A) can be used commercially, and those produced by a vapor phase method or a liquid phase chemical reduction method can also be used. Specific examples of the production method of the conductive fine particles (A) include a spray pyrolysis method described in Japanese Patent Publication No. Sho 63-31522, and a metal oxide or metal hydroxide described in JP-A-2011-12290. A method of heating and reducing by irradiating a microwave with a microwave; a method of obtaining a reduced body by thermal decomposition of a metal complex compound described in JP-A-2010-265543; and a method for reducing metal ions described in JP-A-2010-77472 The production method described in Japanese Laid-Open Patent Publication No. 2002-20809, and the production method described in JP-A-2004-99992.

Photocurable resin composition (B)

The photocurable resin composition (B) used in the present invention can be used as long as it exhibits photocurability by irradiation with an active energy ray such as an electron beam, ultraviolet light or visible light, and is not particularly limited.

The photocurable resin composition (B) is generally a compound that absorbs an active energy ray (for example, a binder polymer (b-1) or a polymerizable compound (b-2) described below), for example, to cause a reaction by a monomer. Hardened. Further, although the compound which absorbs the active energy ray itself is not hardened, the other compound contained in the photocurable resin composition (for example, the photocurable initiator (b-3) described below) is an absorption activation energy. The compound of the ray acts and hardens can. Further, the types of the compounds involved at this time may be two or more. For example, a composition comprising a polymerizable compound and a photopolymerization initiator may be exemplified.

The photocurable resin composition (B) may preferably be a binder polymer (b-1), a polymerizable compound (b-2), and a photopolymerization initiator (b-3). In addition, in the photocurable resin composition (B), an additive for a photocurable resin other than a solvent or a photopolymerization initiator may be blended as needed.

Adhesive polymer (b-1)

When the binder polymer (b-1) is mixed with other components of the photocurable resin composition (B), it is not particularly limited and can be used without causing separation, sedimentation, precipitation, etc., and can be maintained with the substrate. Adhesives are available. For example, when the substrate is a polyethylene terephthalate (PET) film, the binder polymer (b-1) may have a solubility parameter (SP value) of the PET film of approximately 11.3, specifically For example, (meth) acrylate resin, epoxy resin, phenol resin, polyurethane, polystyrene, vinyl acetate polymer, polyamine, vinyl chloride-vinyl acetate copolymer, fiber Diacetate, polyvinyl chloride, nitrocellulose, and a polymer having a structure such as tetoron. Among them, (meth) acrylate resin, epoxy resin, cellulose diacetate, and polystyrene are preferred, and (meth) acrylate resin and polystyrene are more preferable.

In addition, as a developing solution of the photolithography method using the photocurable resin composition (B), an alkaline solution such as a metal alkali aqueous solution or an organic alkali aqueous solution is generally used. Therefore, the binder polymer (b-1) excellent in resolution in the development treatment after hardening by activation of energy rays is soluble in alkali The resin is preferably used, and for example, an alkali-soluble binder polymer having a carboxyl group or a sulfo group in the molecule can be used. The alkali-soluble binder polymer may, for example, be a homopolymer or a copolymer obtained by polymerizing an ethylenically unsaturated monomer having one or more carboxyl groups, or an ethylenically unsaturated monomer having one or more carboxyl groups. And a copolymer obtained by polymerizing an ethylenically unsaturated monomer copolymerizable therewith.

The ethylenically unsaturated monomer having one or more carboxyl groups may, for example, be (meth)acrylic acid, cinnamic acid, fumaric acid, itaconic acid, crotonic acid, ethylene acetic acid, maleic acid, etc., wherein (methyl) ) Acrylic is preferred. As the binder polymer (b-1), one type or two or more types of polymerized polymers of these monomers can be used.

The ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated monomer having one or more carboxy groups may, for example, be a (meth) acrylate-based unsaturated monomer or a glycol ester-based (meth) acrylate. , propylene glycol (meth) acrylate, butane diol mono (meth) acrylate, glycerol mono (meth) acrylate, (meth) acrylamide unsaturated monomer, N-substituted Malayan Amines, etc.

Specific examples of the ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated monomer having one or more carboxyl groups may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, or (methyl). Isobutyl acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, (meth) propylene Indoleamine, N-methyl(meth)acrylamide, N-cyclohexylmaleimide, and the like. Further, examples thereof include styrene, α-methylstyrene, vinyl ether, vinylpyrrolidone, and (meth)acrylonitrile.

In addition, one or two or more kinds of ethylenically unsaturated monomers having one or more carboxyl groups and one or more types copolymerizable therewith can be used as the binder polymer (b-1). The copolymer obtained by copolymerizing the ethylenically unsaturated monomers.

The reaction conditions and the composition ratio of each monomer component in the case of obtaining a copolymer can be appropriately selected depending on the physical properties (number average molecular weight, glass transition temperature, and the like) of the binder polymer (b-1).

The binder polymer (b-1) may also be a polymer which is crosslinked by photodimerization reaction or the like by irradiation with an active energy ray. Examples of such a polymer can be exemplified by having a cinnamic acid skeleton, a maleimine skeleton, a styrene skeleton, an anthracene skeleton or a pyridyl group. Specific examples of the polymer such as a skeleton include Aronix UVT-302 (East Asia Synthetic) having a polymer of a polyethyl cinnamate and a polymer having a maleic imine skeleton.

The binder polymer (b-1) used in the photocurable resin composition (B) of the present invention has a good balance between developability and adhesion between the formed circuit pattern and the substrate. The number average molecular weight is preferably in the range of about 2,000 to 500,000, and particularly preferably in the range of about 4,000 to 100,000.

The amount of the binder polymer (b-1) used in the photocurable resin composition (B) is, for example, about 20 to 65 wt%, based on the total amount of the photocurable resin composition (B). can.

Polymeric compound (b-2)

The polymerizable compound (b-2) is exemplified by a radical polymerizable compound, and a polyfunctional (meth) acrylate compound is preferred because it has high reactivity and can improve the sensitivity of the resin composition to light. Specific examples Such as: polyethylene glycol di (meth) acrylate (extension of the number of 2 to 14), trimethylolpropane di (meth) acrylate, trimethylolpropane tri (methyl) Acrylate, di-trimethylolpropane tetra(meth)acrylate, trimethylolpropane ethoxy tris(meth)acrylate, trimethylolpropane propoxytri(meth)acrylate, Trimethylolpropane ethylene glycol adduct triacrylate, tetramethylol methane tri(meth)acrylate, tetramethylol methane tetra(meth)acrylate, polypropylene glycol di(meth)acrylate (the number of propyl groups is 2 to 14), neopentyl alcohol tri (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa(meth) acrylate, etc., wherein polyethylene glycol di(meth)acrylate (the number of ethyl groups is 2 to 14), trimethylolpropane tris(methyl) Acrylate, trimethylolpropane ethylene glycol adduct triacrylate, and neopentyl alcohol tri(meth)acrylate are preferred.

The polymerizable compound (b-2) may be used singly or in combination of two or more kinds as appropriate.

In addition, the amount of the polymerizable compound (b-2) used in the photocurable resin composition (B) is 100% with respect to the binder polymer (b-1) contained in the photocurable resin composition (B). The parts by weight may be in the range of about 10 to 150 parts by weight, more preferably in the range of about 15 to 65 parts by weight.

Photopolymerization initiator (b-3)

The photopolymerization initiator (b-3) is used as it is an initiator having an absorption band at the wavelength of the active energy ray and generates a hardening (polymerization) reaction, and is not particularly limited. Generally, in terms of the active energy ray used in the hardening reaction, ultraviolet rays are suitable from the viewpoint of cost. Therefore, the photopolymerization initiator is abundant in kind, and photo-radical polymerization excellent in reactivity with a monomer is obtained. The initiator is preferred.

Specific examples of the photoradical polymerization initiator may, for example, be benzoin, acetophenone, 2-methylhydrazine, 2,4-dimethylthiaxanone, 2,4-diethylthiazepine Anthrone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diisopropylthiaxanone, diphenylketone, 4-benzylindolyl-4'- Methyl diphenyl sulfide, 2,4-diisopropyloxene, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1 , 2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4- (2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl) -Benzyl)-benzyl]phenyl]-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Phenyl)phenyl]-1-butanone, 2,4,6-trimethylbenzylidene-diphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenyl Phosphonium oxide, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylindenyl), ethyl ketone, 1-[9-ethyl-6-( 2-methylbenzylindenyl)-9H-indazol-3-yl]-, 1-(O-ethenylhydrazine) and the like. Among them, in the point of sensitivity to light, 2,4,6-trimethylbenzylidene-diphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-benzene Phosphine oxide, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylindenyl), ethyl ketone, 1-[9-ethyl-6- (2-methylbenzylindenyl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) is preferred as 1,2-octanedione, 1-[4-( Phenylthio)-, 2-(O-benzylindolyl), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-indazol-3-yl]- , 1-(O-ethinyl) is more preferred.

Also, the binder polymer (b-1) is using an alkali soluble tree In the case of a fat, the photopolymerization initiator (b-3) is preferably a photopolymerization initiator having an O-fluorenylfluorene structure.

The photopolymerization initiator (b-3) used in the photocurable resin composition (B) is used in an amount relative to the binder polymer (b-1) 100 contained in the photocurable resin composition (B). The parts by weight may be in the range of about 1 to 20 parts by weight, more preferably in the range of about 2 to 15 parts by weight.

Other additives

In the photocurable resin composition (B) of the present invention, photocuring properties such as a solvent, a polymerization inhibitor, a photopolymerization accelerator, and a sensitizer can be added as long as the effects of the present invention are not affected. An additive for a resin composition.

Solvent

The photocurable resin composition (B) of the present invention may contain a solvent as needed. The solvent is, for example, a liquid medium of the binder polymer (b-1), the polymerizable compound (b-2), and the photopolymerization initiator (b-3) in the photocurable resin composition (B). Use without special restrictions. Further, each component in the photocurable resin composition (B) does not necessarily have to be completely dissolved in the solvent, and the photocurable resin composition (B) of the present invention as a whole may be uniformly dispersed or maintained. The solvent in a dissolved state may not necessarily have the ability to dissolve all of the above components.

The solvent used in the present invention may, for example, be linear, branched, secondary or plural such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol or ethylene glycol. Alcohols; ketones such as methyl ethyl ketone, cyclohexanone, isophorone; aromatic hydrocarbons such as toluene and xylene; Swasol series (made by Maruzen Petrochemical Co., Ltd.), Solvesso series (Exxon chemistry) Company-made) petroleum-based aromatic mixed solvents, cellosolve such as cellosolve and butyl cellosolve; carbitol such as carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether Propylene glycol alkyl ethers such as propylene glycol dimethyl ether; polypropylene glycol alkyl ethers such as dipropylene glycol monomethyl ether and dipropylene glycol dimethyl ether; ethyl acetate, butyl acetate, fibrin acetate, butyl cellulolytic B Acetate such as acid ester, butyl carbitol acetate or propylene glycol monomethyl ether acetate; N-methylpyrrolidone and dialkyl glycol ether.

The solvent may be used singly or in combination of two or more kinds as appropriate.

The amount of the solvent used in the photocurable resin composition (B) can be appropriately adjusted so that the viscosity of the photocurable resin composition containing the metal fine particles is about 10 to 1000 dpa. The range of S can be adjusted to be about 100 to 500 dpa. The range of S is better.

(2) Manufacturing method of electrical wiring circuit pattern

The method for producing an electric wiring circuit pattern according to the present invention includes the step of forming an electric circuit pattern on a substrate by using the photocurable resin composition containing metal fine particles of the present invention described above, and the method includes the following steps Method for preparing a photocurable resin composition containing metal fine particles of the present invention described above; a step of applying the photocurable resin composition containing metal fine particles on a substrate (coating step); a film or a mask corresponding to the wiring circuit pattern, a step of irradiating the coating film of the photocurable resin composition containing the metal fine particles coated on the substrate with an active energy ray to cure the coating film (exposure step); The unexposed portion is a step of dissolving, removing, and drying the developing solution (developing step).

Photocurable resin group containing metal microparticles of the present invention In the preparation step of the product, the method of mixing or kneading the conductive fine particles (A), the photocurable resin composition (B), and other components added as needed is to contain the respective components in the metal microparticles. The method of uniformly dispersing and mixing the photocurable resin composition can be carried out without particular limitation. In such a method, a method such as a mechanical stirrer, a magnetic stirrer, an ultrasonic disperser, a planetary mill, a ball mill or a three-roll mill can be exemplified. It is preferable to use a planetary rolling mill from the point of easy operation, and it is preferable to use a three-roll mill by a point which can be uniformly dispersed, or a combination of two or more methods.

In addition, the photocurable resin composition (B) may be separately prepared, mixed with the conductive fine particles (A) and other components to prepare a photocurable resin composition containing metal fine particles, or may be electrically conductive. The fine particles (A), the photocurable resin composition (B), and other components are simultaneously mixed to prepare a photocurable resin composition containing metal fine particles.

In the coating step, the photocurable resin composition containing the metal fine particles prepared in the above-described preparation step is applied to a glass substrate, a ceramic substrate, a film-like resin substrate, or the like by a coating method such as screen printing, bar coating or blade coating. And let it dry.

In the method of the present invention, even if a film-like resin substrate having low heat resistance is used, a circuit pattern having high conductivity, high adhesion, and high precision can be formed. Therefore, a film-shaped resin substrate can be applied. Examples of the film-like resin substrate include a substrate having low heat resistance such as polyethylene terephthalate (PET), polycarbonate (PC), polystyrene (PS), or polyvinylidene chloride (PVDC). From the viewpoint of good adhesion of circuit patterns, it is possible to apply a substrate surface to facilitate handling. Also, the film may be coated with ITO (indium tin oxide) A transparent conductive film made of ZnO (zinc oxide) or silver nanowire.

In the coating step, the drying temperature can be set to about 60 to 120 ° C, and the drying time is set to about 5 to 60 minutes.

The thickness of the coating film on the substrate is not particularly limited, and is preferably about 1 to 30 μm (for example, more than 1 μm and less than 30 μm), more preferably about 5 to 15 μm (for example, more than 5 μm and less than 15 μm).

In the exposure step, the coating film coated on the substrate is irradiated with an active energy ray to cure the irradiated portion via a film or a mask corresponding to the electrical wiring circuit pattern to be formed. The active energy ray to be irradiated can be exemplified by ultraviolet rays, electron beams, and X-rays, and among them, ultraviolet rays are preferred. The light source can be used: low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, halogen lamps, and black lamps. Further, the exposure method can be exemplified by adhesion exposure to a mask, proximity exposure, projection exposure, or the like.

The development step is to obtain a desired electrical wiring circuit pattern by using a developing solution to dissolve and remove the unhardened unexposed portion.

In the case of the developer, the unexposed portion of the photocurable resin composition containing the metal fine particles of the present invention can be used without being particularly limited. The developer used may be either aqueous or oily, regardless of the pH of the liquid. For example, when a compound having an acidic group is present in the photocurable resin composition (B), an aqueous solution of an organic alkali such as monoethanolamine or diethanolamine may be used in addition to a metal alkali aqueous solution such as sodium hydroxide or sodium carbonate. Further, the original purpose of "development" is to remove the unexposed portion of the photocurable resin composition containing the metal fine particles from the substrate. Therefore, the so-called soluble non-finishing means hardening the light containing the metal fine particles. It is sufficient that all of the resin composition is dissolved, and at least one component constituting the photocurable resin composition containing the metal fine particles can be melted to the extent that the unexposed portion is removed.

The developing method in the developing step can be used as the developing method used in the general photolithography method, and is not particularly limited. Specifically, for example, a method of immersing a substrate on which a cured coating film is formed in a developing solution, a spraying method in which a developing solution is sprayed on the substrate, a developing solution in which a developing solution is filled in the container, and a rotating method in which the substrate is processed can be exemplified. Wait. The development method can be appropriately determined depending on the properties of the photocurable resin composition containing metal fine particles used. Further, the development method differs depending on the shape of the substrate on which the circuit is formed, etc., but when the unnecessary coating film (unexposed portion) on the substrate is removed, the coating film adhesion surface is sprayed at a uniform pressure by spraying. Can improve the resolution and better.

The electric wiring circuit pattern is dried after water washing or acid neutralization in order to remove unnecessary developing solution. The drying temperature can be set at about 40 to 70 ° C, and the drying time can be set at about 5 to 30 minutes. Further, in order to further improve the adhesion between the electrical wiring circuit pattern and the substrate, post-baking may be performed after the development step as needed. The temperature at this time may be set at about 100 to 150 ° C, and the time may be set at about 5 to 100 minutes.

After the above steps, the electrical wiring circuit pattern can be formed on various substrates by using the photocurable resin composition containing metal fine particles of the present invention.

According to the method of manufacturing the electrical wiring circuit pattern of the present invention described above, an electrical wiring circuit board such as a substrate for a touch panel, a substrate for a display device, or a substrate for an information processing terminal device can be manufactured.

[Examples]

Hereinafter, the present invention will be further specifically described by way of examples. However, the invention is not limited to this.

(1) A material of a photocurable resin composition containing metal fine particles

The materials used in the following examples and comparative examples are explained below.

Metal particles (electromagnetic particles) (A)

Metal microparticles M1: silver microparticles (granular; 50% average particle diameter 0.7 μm, knock tightness 1.4 g/cm ³ , BET specific surface area 1.3 m ² /g)

Metal microparticles M2: silver microparticles (granular; 50% average particle diameter 0.4 μm, knock tightness 1.8 g/cm ³ , BET specific surface area 0.9 m ² /g)

Metal microparticles M3: silver microparticles (fragmented; 50% average particle diameter 3.0 μm, knock tightness 2.9 g/cm ³ , BET specific surface area 0.9 m ² /g)

Metal microparticles M4: silver microparticles (spherical; 50% average particle diameter 2.7 μm, knock tightness 4.4 g/cm ³ , BET specific surface area 0.4 m ² /g)

Metal microparticles M5: silver microparticles (granular; 50% average particle diameter 0.9 μm, knock tightness 1.5 g/cm ³ , BET specific surface area 1.8 m ² /g)

Metal microparticles M6: silver microparticles (fragmented; 50% average particle diameter 7.6 μm, knock tightness 5.5 g/cm ³ , BET specific surface area 0.4 m ² /g)

The 50% average particle diameter of the above metal fine particles is a value measured by (micro tracking method), and the knocking degree and the BET specific surface area are values measured by the above method.

Photocurable resin composition (B) (Binder polymer: b-1)

Adhesive polymer P1: acrylic polymer AA-6 (quantitative average molecular weight) 6,000; manufactured by East Asia Synthetic Co., Ltd.)

Adhesive polymer P2: Acrylic polymer AS-6 (quantitative average molecular weight 6,000; manufactured by Toagosei Co., Ltd.)

(Polymerizable compound: b-2)

Polymerizable compound R1: A-200 (polyethylene glycol #200 diacrylate; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

Polymerizable compound R2: Light Acrylate PE3A (neopentitol tris(meth)acrylate; manufactured by Kyoeisha Chemical Co., Ltd.)

(Photopolymerization initiator: b-3)

Photopolymerization initiator I1: bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (manufactured by BASF Corporation)

Photopolymerization initiator I2: ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) ) (manufactured by BASF)

(solvent)

Solvent S1: propylene glycol monomethyl ether (manufactured by Wako Pure Chemical Industries Co., Ltd.)

The composition of the photocurable resin composition containing metal fine particles used in the examples is shown in Table 1, and the composition of the photocurable resin composition containing metal fine particles used in the comparative examples is shown in Table 2. Further, the numerical values in Tables 1 and 2 indicate the ratio (% by weight) of each component with respect to the total amount of the composition.

(2) Formation of electrical wiring circuit patterns Examples 1 to 5 (i) Modulation step of photocurable resin composition containing metal fine particles

In the composition shown in Tables 1 and 2, the total weight of the photocurable resin composition containing the metal fine particles was 50 g, and the components were weighed separately. First, the planetary mill (Awatorinentaro AR manufactured by Thinky) was used. -100), a total of 5 minutes of mixing. At this time, the kneading is stopped every 1 minute to form a photocurable resin containing metal fine particles. The composition does not overheat. Then, this was kneaded by a three-roll mill to prepare a paste-like photocurable resin composition containing metal fine particles.

(ii) coating step and exposure step

The photocurable resin composition containing the metal fine particles was uniformly coated on the treated surface by a screen printing method using a PET film (manufactured by Teijin DuPont Film Co., Ltd.) having a thickness of 100 μm on one side as a substrate. The surface of the side was dried at 80 ° C for 10 minutes to obtain a coating film having a thickness of 10 μm. Then, the photomask on which the fine line pattern having a line space of 50/50 (μm) is drawn is adhered to the coating film, and ultraviolet rays are irradiated with a metal halide lamp to cure the photocurable resin composition containing the metal fine particles.

(iii) development steps and their evaluation

Next, 1% sodium carbonate was used in the developing solution to remove the unexposed portion, and the unnecessary developing solution was removed by washing with water. Then, it was dried at 50 ° C for 5 minutes to remove moisture, and an electrical wiring circuit pattern was obtained.

Example 6

A transparent conductive film substrate having a thickness of 100 μm in which an ITO film is formed by a sputtering deposition method using a polyester film containing a photo-curable resin composition containing metal fine particles as shown in Table 1 (ELECRYSTA manufactured by Nitto Denko Corporation) In addition to the PET film substrate (manufactured by Teijin DuPont Film Co., Ltd.) having a thickness of 100 μm on one side, the surface of the ITO film is coated with a paste-like photocurable resin composition containing metal fine particles. In the same manner as in Example 1, an electrical wiring circuit pattern was obtained.

Example 7

In addition to the photocurable resin composition containing metal fine particles prepared as shown in Table 1, a transparent conductive film substrate (manufactured by TORAY Film Processing Co., Ltd.) having a thickness of 100 μm of a silver nanowire was used instead of a single side having a thickness of 100 μm. The PET film substrate (manufactured by Teijin DuPont Film Co., Ltd.) which is easy to be processed, and the photocurable resin composition containing metal fine particles in the form of a paste on the silver nanowire surface are the same as those of the first embodiment. The method obtains an electrical wiring circuit pattern.

Example 8

Instead of using the photocurable resin composition containing metal fine particles formulated as shown in Table 1, and at the time of exposure, a photomask having a fine line pattern with a column pitch of 30/30 (μm) was used instead of the column pitch. An electrical wiring circuit pattern was obtained in the same manner as in Example 1 except for a 50/50 (μm) fine line pattern mask.

Comparative Examples 1 to 6

Using the photocurable resin composition containing metal fine particles prepared as shown in Table 2, a photocurable resin composition containing metal fine particles was prepared in the same manner as in Example 1 to form an electric wiring circuit pattern.

Comparative Example 7

A transparent conductive film substrate having a thickness of 100 μm of an ITO film formed by a sputter deposition method using a photocurable resin composition containing metal fine particles as shown in Table 2 (ELECRYSTA, manufactured by Nitto Denko Corporation) was used. In place of the photo-curable resin composition containing the metal fine particles in the form of a paste on the surface of the ITO film, instead of the PET film (manufactured by Teijin DuPont Film Co., Ltd.) having a thickness of 100 μm on one side, The same method of 1 gets electrical wiring Circuit pattern.

(3) Physical property assessment

The photocurable resin composition containing metal fine particles is evaluated for the minimum amount of ultraviolet radiation that can form an electrical wiring circuit pattern, and the obtained electrical wiring circuit pattern has a resolution of development, development, and adhesion to the substrate. It is measured or evaluated by the following method.

(Evaluation of sensitivity: the minimum amount of ultraviolet radiation)

On a substrate coated with a photocurable resin composition containing metal fine particles having a thickness of 10 μm, a photomask having a fine line pattern is adhered thereto, and irradiated with a halogen lamp at 100 to 1000 mJ/cm ² , and after development, a thin line pattern can be confirmed. The minimum amount of exposure of the exposure amount formed is used as the sensitivity.

(measurement of specific resistance)

The measurement of the specific resistance was carried out in accordance with JIS K7149 using a four-probe resistance meter Loresta AX (manufactured by Mitsubishi Chemical Analytech Co., Ltd.). When the specific resistance is below the measurement limit, it is represented by O.L. (Over Load).

(evaluation of resolution)

In the evaluation of the resolution, the circuit pattern after the development treatment was observed at an magnification of 100 times by an epi-illumination type optical microscope, and the presence or absence of the residue of the resin composition in the space portion and the presence or absence of breakage of the line portion were evaluated. It is confirmed that the residue of the resin-free composition and the line portion are not broken are indicated by ○; the residue of the resin composition and the disconnection of the line portion are indicated by ×.

(Assessment of adhesion)

The evaluation of the adhesion to the substrate is based on the JIS H8504 tape test. Method A peel test was performed. Check if the circuit pattern is peeled off. The peeling of the coating film is indicated by ○, and the peeling of the coating film is indicated by ×.

The evaluation results of the respective examples are shown in Table 3, and the evaluation results of the comparative examples are shown in Table 4.

In Examples 1 to 8, conductive silver particles having a physical property of 50% of an average particle diameter of 0.1 μm to 5 μm, a knocking degree of 2.5 g/cm ³ or less, and a BET specific surface area of 1.5 m ² /g or less were obtained. By using the total amount of the photocurable resin composition containing metal fine particles, it is used within the scope of the present invention to form an electrical wiring circuit pattern which is practically excellent in electrical conductivity, high resolution, and adhesion.

Further, the photosensitivity resin composition containing the metal fine particles used in Examples 1 to 8 has a good sensitivity, and in particular, in Example 5, by using a photopolymerization initiator having an O-fluorenylfluorene structure, In Example 4, which is otherwise the same, the sensitivity is about 2 times higher.

Moreover, as can be seen from the results of Examples 6 and 7, by using the present invention The photocurable resin composition containing the metal fine particles can obtain an electrical wiring circuit pattern having sufficient adhesion regardless of the type of the substrate.

Further, when the 50% average particle diameter is more than 5 μm (Comparative Example 7), the knock tightness is more than 2.5 g/cm ³ (Comparative Examples 1, 2, 5, and 7), and the BET specific surface area is more than 1.5 m ² /g (Comparative Example) 6) When the content of the conductive fine particles (A) is out of the range of the present invention (Comparative Examples 3 and 4), there is a problem in any of sensitivity, specific resistance, resolution, and adhesion.

In Comparative Example 2, conductivity was not obtained when silver fine particles M4 were used. This is because M4 is a spherical metal fine particle, and the contact between the particles is small, and conductivity cannot be obtained. In Comparative Example 3, sufficient conductivity was not obtained. It is estimated that the content of the conductive metal fine particles (A) in the photocurable resin composition containing the metal fine particles is outside the range of the present invention, so that a large amount of photocurable resin or the like exists between the metal fillers to form an electric resistance. Therefore, conductivity cannot be obtained.

In Comparative Example 7, although a low specific resistance was exhibited, contact between a plurality of metal fine particles (short-circuit portion) was observed between the lines after development. When the average particle diameter of the metal fine particles is large, the particles are easily contacted, and it is considered that although high conductivity is obtained, the reverse side also exhibits a high probability of short circuit.

[Industrial availability]

The photocurable resin composition containing metal fine particles, the method for producing an electric wiring circuit pattern, and the electric wiring circuit substrate of the present invention can be effectively utilized in the field of manufacturing various electric wiring circuit boards.

Claims (7)

A photocurable resin composition containing metal fine particles, which comprises a photocurable resin composition containing fine particles (A) and a photocurable resin composition (B) containing metal fine particles, the light containing metal fine particles In the curable resin composition, the content of the conductive fine particles (A) is in the range of 62 to 86% by weight based on the total amount of the composition, and the conductive fine particles (A) have the following physical properties: (i) 50% average particle diameter is 0.1 to 5 μm, (ii) knocking degree is 2.5 g/cm ³ or less, and (iii) BET specific surface area is 1.3 m ² /g or less. The photocurable resin composition containing metal fine particles according to the first aspect of the invention, wherein the photocurable resin composition (B) is contained in an amount of 15 to 100 parts by weight of the conductive fine particles (A). A range of 60 parts by weight. The photocurable resin composition containing metal fine particles according to claim 1 or 2, wherein the conductive fine particles (A) are silver or a silver-containing alloy. The photocurable resin composition containing metal fine particles according to claim 1 or 2, wherein the photocurable resin composition (B) contains an alkali-soluble resin. The photocurable resin composition containing metal fine particles according to the first or second aspect of the invention, wherein the photocurable resin composition (B) contains a photopolymerization initiator having an O-fluorenylfluorene structure. A method of manufacturing an electrical wiring circuit pattern, comprising the steps of: Polyethylene terephthalate (PET) film coated on a transparent conductive film substrate made of indium tin oxide (ITO), zinc oxide (ZnO) or silver nanowires, coated as claimed in the first to a coating step of a photocurable resin composition containing metal fine particles according to any one of the items 5, and a photocurable resin composition containing metal fine particles, via a film or a mask corresponding to the electric wiring circuit pattern to be formed An exposure step of irradiating the coating film with an activation energy ray to harden the coating film; a developing step of dissolving, removing and drying the unexposed portion of the coating film with a developing solution. An electric wiring circuit board is manufactured by using the manufacturing method of the electric wiring circuit pattern of the sixth aspect of the patent application.