JP6079645B2 - Photocurable resin composition containing fine metal particles and use thereof - Google Patents

Description

  The present invention relates to a photocurable resin composition containing metal fine particles. Furthermore, a method for manufacturing an electric wiring circuit pattern using the photocurable resin composition containing metal fine particles, and an electric wiring such as a touch panel substrate, a display device substrate, and an information processing terminal device substrate obtained by the manufacturing method The present invention relates to a circuit forming substrate.

  In recent years, demands for miniaturization, high density, high definition, and high reliability are increasing in circuit materials and displays, and accordingly, improvement of pattern processing technology is desired. In particular, since miniaturization of the conductive circuit pattern is an indispensable requirement for miniaturization and high density, various methods have been proposed.

  As a method for forming an electric wiring circuit pattern on a substrate, a printing method and a photolithography method are widely known.

  In order to form a high-definition circuit pattern by the printing method, it is necessary to increase the viscosity of the conductive paste in order to suppress the bleeding of the circuit during printing. However, when the viscosity of the conductive paste is increased, for example, in the screen printing method, there is a problem that the plate is clogged and the productivity is lowered, so that high definition is difficult. In general, the line and space that can be used for mass production is limited to 200 μm.

  The photolithography method can cope with a high-definition circuit pattern, but it is necessary to sputter metal over the entire surface of the substrate in order to improve the adhesion between the circuit and the substrate. Furthermore, many processes such as resist coating, pattern exposure, development, etching, and resist stripping are necessary, and the productivity is inferior to the printing method. In addition, a decrease in yield due to pinholes generated in the sputtering process has been regarded as a problem.

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

  In Patent Document 1, a composition containing metal colloid particles, a polymer dispersant for dispersing the metal colloid particles, a photo radical generator, and a solvent is applied on a substrate, patterned by a photolithography method, and further heated. Describes a method for developing conductivity. However, the above method requires baking at 200 ° C. or higher in order to obtain conductivity, and the substrate used for forming the circuit pattern is limited to a heat resistant material such as glass or ceramics.

  Recently, a low-temperature firing type conductive paste for plastic substrates has been developed, and a paste capable of obtaining conductivity by heat treatment at a relatively low temperature of about 120 ° C. has been developed (Patent Document 2). However, in order to mass-produce on an industrial scale, for example, it takes 60 minutes or more for the heat treatment time, it was not satisfactory in terms of productivity.

JP 2003-140330 A Japanese Patent No. 3218767

  An object of the present invention is to provide a photocurable resin composition containing metal fine particles that can form a high-definition circuit pattern on a film substrate and is suitable for obtaining a low-resistance circuit pattern. Furthermore, the objective of this invention is providing the manufacturing method of the high-definition and low-resistance electrical wiring circuit pattern on a film substrate, and the electrical wiring circuit board obtained by the method.

The present inventors have repeated research to solve the above problems, and are a metal fine particle-containing photocurable resin composition containing conductive fine particles (A) and a photocurable resin composition (B), In this resin composition, the content of conductive fine metal particles (A) is in the range of 62 to 86% by weight, and the conductive fine particles (A) are (i) 50% average particle size is 0.1. By using a resin composition having a physical property of ˜5 μm, (ii) tap density of 2.5 g / cm ³ or less, and (iii) BET specific surface area of 1.5 m ² / g or less, productivity is improved. It has been found that a high-definition electric wiring circuit pattern having high conductivity and excellent adhesion and resolution can be formed on a film substrate such as a PET film that does not have high heat resistance without being lowered.
The present invention has been completed based on these findings, and includes the following metal fine particle-containing photocurable resin composition, a method for producing an electric wiring circuit pattern using the same, and an electric wiring circuit produced by this method. Providing a substrate.

Item 1. A metal fine particle-containing photocurable resin composition containing conductive fine particles (A) and a photocurable resin composition (B), wherein the content of conductive fine particles (A) in the composition is , In the range of 62 to 86% by weight with respect to the total amount of the metal fine particle-containing photocurable resin composition,
Conductive fine particles (A)
(I) 50% average particle size is 0.1-5 μm,
(Ii) the tap density is 2.5 g / cm ³ or less,
(Iii) A BET specific surface area of 1.5 m ² or less,
A metal fine particle-containing photocurable resin composition characterized by having the following physical properties:
Item 2. Item 2. The metal fine particles according to Item 1, wherein the content of the photocurable resin composition (B) is in the range of 15 to 60 parts by weight with respect to 100 parts by weight of the conductive fine particles (A). Containing photocurable resin composition.
Item 3. Item 3. The photocurable resin composition containing metal fine particles according to Item 1 or 2, wherein the conductive fine particles (A) are silver or an alloy containing the same.
Item 4. Item 4. The photocurable resin composition containing metal fine particles according to any one of Items 1 to 3, wherein the photocurable resin composition (B) contains an alkali-soluble resin.
Item 5. Item 5. The photocurable resin composition containing metal fine particles according to any one of Items 1 to 4, wherein the photocurable resin composition (B) contains a photopolymerization initiator having an O-acyloxime structure.
Item 6. Item 6. The light containing metal fine particles according to any one of Items 1 to 5, on a transparent conductive film substrate in which a polyethylene terephthalate (PET) film is coated with indium tin oxide (ITO), zinc oxide (ZnO), or silver nanowires. The coating layer of the photocurable resin composition containing metal fine particles is irradiated with active energy rays through a coating process for applying the curable resin composition and a film or mask corresponding to the electric wiring circuit pattern to be formed. A method for producing an electrical wiring circuit pattern, comprising: an exposure step of curing the coating film; and a development step of dissolving, removing, and drying the unexposed portion of the coating film using a developer.
Item 7. Item 7. An electric wiring circuit board manufactured using the method for manufacturing an electric wiring circuit pattern according to Item 6.

According to the present invention, there is a metal fine particle-containing photocurable resin composition containing conductive fine particles (A) and a photocurable resin composition (B), and the conductive metal in the resin composition. The content of the fine particles (A) is in the range of 62 to 86% by weight, the conductive fine particles (A) are (i) a 50% average particle size is 0.1 to 5 μm, and (ii) a tap density is 2. By using a resin composition having physical properties of 5 g / cm ³ or less and (iii) a BET specific surface area of 1.5 m ² / g or less, it has excellent conductivity on a film substrate with low heat resistance. An electric circuit pattern having excellent adhesion can be formed. Moreover, electroconductivity can be expressed even if it does not heat-process like the conventional metal microparticle containing photocurable resin composition. Moreover, by using the resin composition of the present invention, a high-definition electric wiring circuit pattern can be produced, and a high-definition electric wiring circuit board can be obtained.

  Hereinafter, the present invention will be described in detail.

(1) Metal fine particle-containing photocurable resin composition The metal fine particle-containing photocurable resin composition of the present invention is a composition containing conductive fine particles (A) and a photocurable resin composition (B). is there. Preferably, the conductive fine particles (A) are uniformly dispersed in the photocurable resin composition (B). In addition, the portion where the coating film can be formed on the substrate and the active energy ray is irradiated (exposed portion) is polymerized and becomes insoluble in the developer, and the portion not irradiated with light (non-exposed portion) May be any that dissolves in the developer.

The content of the conductive metal fine particles (A) in the metal fine particle-containing photocurable resin composition of the present invention is 62% by weight or more with respect to the total amount of the metal fine particle-containing photocurable resin composition. It is preferably 64% by weight or more, more preferably 65% by weight or more, and even more preferably 66% by weight or more. If it is the said range, the resistance value of an electrical wiring circuit pattern will become low enough practically, and will not interfere with transmission of a signal (signal).
Further, the content of the conductive metal fine particles (A) may be 86% by weight or less, preferably 84% by weight or less, and 83% by weight with respect to the total amount of the metal fine particle-containing photocurable resin composition. Is more preferable, and 82% by weight or less is even more preferable. If it is in the above range, the sensitivity is lowered due to a decrease in the amount of the photosensitive resin, and the yield of circuit pattern formation is remarkably lowered, the adhesion to the substrate is lowered, and the resolution is not lowered. .
The content of the conductive metal fine particles (A) is about 62 to 86% by weight, preferably about 64 to 84% by weight, and more preferably about 62% by weight, based on the total amount of the metal fine particle-containing photocurable resin composition. A range of 65 to 83% by weight, even more preferably about 66 to 82% by weight is mentioned.

When a photopolymerization initiator having an O-acyloxime structure is used, the content of the conductive metal fine particles (A) in the photocurable resin composition containing metal fine particles of the present invention is the same as that of the light containing metal fine particles. 70 weight% or more is preferable with respect to the whole quantity of curable resin composition, and 75 weight% or more is more preferable. Moreover, 83 weight% or less is preferable.
The content of the conductive metal fine particles (A) when using a photopolymerization initiator having an O-acyloxime structure is preferably relative to the total amount of the metal fine particle-containing photocurable resin composition. The range is about 70 to 83% by weight, more preferably about 75 to 83% by weight.

The content of the photocurable resin composition (B) in the metal fine particle-containing photocurable resin composition is 15 parts by weight or more (for example, 20.5) with respect to 100 parts by weight of the conductive fine particles (A). Parts by weight or more) is preferable, and 18 parts by weight or more is more preferable. Moreover, 60 parts by weight or less (for example, 53.9 parts by weight or less) is preferable, 50 parts by weight or less is more preferable, and 45 parts by weight or less is even more preferable.
The content of the photocurable resin composition (B) in the metal fine particle-containing photocurable resin composition is preferably about 15 to 60 parts by weight with respect to 100 parts by weight of conductive fine particles (A) ( For example, the range is 20.5 to 53.9 parts by weight), more preferably about 18 to 50 parts by weight, and still more preferably about 18 to 45 parts by weight.

  In addition to the conductive fine particles (A) and the photocurable resin composition (B), the metal fine particle-containing photocurable resin composition of the present invention has a leveling agent, a thickener, a suspending agent, and improved adhesion. In addition, a metal fine particle-containing photocurable resin composition such as a coupling agent and an antifoaming agent may be included.

Examples of the leveling agent include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, polyester-modified methylalkylpolysiloxane, polyether-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyester-modified hydroxyl group-containing polydimethylsiloxane, Polyethersiloxane modified with hydroxyl group-containing polydimethylsiloxane, acrylic copolymer, methacrylic copolymer, polyether-modified polymethylalkylsiloxane, alkyl acrylate ester copolymer, alkyl methacrylate ester copolymer, acrylic acid, acrylic Examples of known alkyl copolymers, grafted copolymers of polyoxyalkylene monoalkyl or alkenyl ether, and lecithin Door can be.
The addition amount of the leveling agent is preferably 0.1% by weight or more with respect to the total amount of the metal fine particle-containing photocurable resin composition. If it is this range, the effect of a leveling agent will fully be acquired. Moreover, the addition amount of the leveling agent is preferably 3% by weight or less with respect to the photocurable resin composition containing metal fine particles. If it is this range, adhesiveness fall, printability deterioration, etc. will not occur. Moreover, the effect of the leveling agent does not increase any further if it is increased further.

When thickening is required, thickeners include various polymers such as vinyl chloride / vinyl acetate copolymer resins, polyester resins, acrylic resins, polyurethane resins, polysaccharides such as carboxymethyl cellulose, sugars such as dextrin palmitate, etc. Fatty acid esters, metal soaps such as zinc octylate, swellable clay minerals such as smectite, spike lavender oil, mineral petrol obtained by distilling petroleum, and the like can be used.
The addition amount of the thickener is preferably 0.1% by weight or more with respect to the total amount of the metal fine particle-containing photocurable resin composition. If it is this range, the effect of a thickener will fully be acquired. Further, the addition amount of the thickener is preferably 5% by weight or less with respect to the total amount of the metal fine particle-containing photocurable resin composition. Within this range, printability does not deteriorate.

As the precipitation inhibitor, for example, a commercially available product such as a long-chain polyamide, a phosphate of a long-chain polyamide, a polyamide-based, an unsaturated polycarboxylic acid, or a tertiary amino group-containing polymer can be used.
The addition amount of the precipitation inhibitor is preferably 0.1% by weight or more with respect to the total amount of the metal fine particle-containing photocurable resin composition. If it is this range, the effect of a precipitation inhibitor will be fully acquired. Moreover, the addition amount of the precipitation inhibitor is preferably 3% by weight or less with respect to the total amount of the metal fine particle-containing photocurable resin composition. Within this range, printability deterioration due to an excessive thickening effect does not occur. Moreover, even if it increases more than this, the effect of a precipitation inhibiting agent does not become high any more.

As a coupling agent for improving adhesion, an alkoxysilane compound having a reactive functional group is preferable. For example, an alkoxysilane compound having a vinyl group such as vinyltrichlorosilane, vinyltrimethoxysilane, and vinyltriethoxysilane, 2 Epoxy groups such as-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane , Alkoxysilane compounds having a styryl group such as p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypro Alkoxysilane compounds having a methacryloxy group such as rumethyldiethoxysilane and 3-methacryloxypropyltriethoxysilane, alkoxysilane compounds having an acryloxy group such as 3-acryloxypropyltrimethoxysilane, N-2 (aminoethyl) 3 -Aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltri Ethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N- (vinylbenzyl) -2-aminoethyl-3- Aminopropy Alkoxysilane compounds having amino groups such as hydrochloride of trimethoxysilane, alkoxysilane compounds having ureido groups such as 3-ureidopropyltriethoxysilane, alkoxysilane compounds having chloropropyl groups such as 3-chloropropyltrimethoxysilane Alkoxysilane compounds having a mercapto group such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, alkoxysilane compounds having a sulfide group such as bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltri Examples include an alkoxysilane compound having an isocyanate group such as ethoxysilane and an alkoxysilane compound having an imidazole group such as imidazolesilane.
The addition amount of the coupling agent is preferably 0.1% by weight or more with respect to the total amount of the metal fine particle-containing photocurable resin composition. If it is this range, the effect of a coupling agent will fully be acquired. Moreover, the addition amount of the coupling agent is preferably 5% by weight or less with respect to the total amount of the metal fine particle-containing photocurable resin composition. If it is this range, resolution will not fall. Moreover, even if it increases more, the effect of a coupling agent does not become high any more.

Examples of antifoaming agents include silicone resins, silicone solutions, special foam breakers that do not contain silicone, alkyl acrylate ester copolymers, alkyl methacrylate ester copolymers, alkyl vinyl ethers, acrylic copolymers, and bubble breakers. Examples thereof include known polymers such as water-soluble polymers, polysiloxanes, foam-breaking polysiloxanes, polymethylalkylsiloxanes, polyether-modified polysiloxanes, and paraffinic mineral oils.
The addition amount of the antifoaming agent is preferably 0.01% by weight or more with respect to the total amount of the metal fine particle-containing photocurable resin composition. If it is this range, the effect of an antifoamer is fully acquired. Moreover, the addition amount of the antifoaming agent is preferably 1% by weight or less with respect to the total amount of the metal fine particle-containing photocurable resin composition. If it is this range, the adhesive fall, the deterioration of the dispersibility of a composition, etc. will not occur. Moreover, even if it increases more, the effect of an antifoamer does not become high any more.

  In forming an electric wiring circuit pattern, the metal fine particle-containing photocurable resin composition of the present invention is uniformly applied on a substrate, a mask pattern is adhered to the coating film, active energy rays are irradiated, The fine particle-containing photocurable resin composition is cured. Furthermore, an electrical wiring circuit pattern is obtained by removing an unexposed part using a developing solution. The said electrical wiring circuit pattern can be used as circuit patterns, such as a flexible circuit board, a board | substrate for touch panels, a board | substrate for display apparatuses, for example.

Conductive fine particles (A)
The conductive fine particles (A) used in the photocurable resin composition containing metal fine particles of the present invention are:
(I) 50% average particle size is 0.1-5 μm,
(Ii) the tap density is 2.5 g / cm ³ or less, and (iii) the BET specific surface area is 1.5 m ² / g or less,
As long as it has the above physical properties and conductivity, it can be used without particular limitation.

(I) The 50% average particle diameter should just be 0.1 micrometer or more (for example, more than 0.1 micrometer), and 0.3 micrometer or more is preferable. If it is the said range, the contact area between particle | grains will not be too small, and electroconductivity will not fall. In addition, since nanometals of less than 0.1 μm absorb light by plasmon absorption, a photocurable resin composition containing such metal fine particles cannot form a circuit by exposure.
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 the said range, the fall of resolution will not be caused.
The 50% average particle size preferably includes 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 a median value (median value) when all the conductive fine particles contained in the whole or part of the composition are arranged in the size of the particle diameter. The 50% average particle diameter in the present invention is a value measured by a microtrack method (laser diffraction / scattering method).

(Ii) The tap density may be 2.5 g / cm ³ or less (for example, less than 2.5 g / cm ³ ). Within the above range, the light transmittance is not deteriorated, and the curing of the photocurable resin composition (B) component becomes sufficient. As a result, the adhesion between the metal fine particle-containing photocurable resin composition and the substrate, And the resolution is sufficient.
In the present invention, the tap density is determined by filling the container with conductive powder, and then tapping (moving the container upward and then allowing the container to fall freely) to break the gap between the conductive powders, It means the apparent bulk density when filling, tap density measurement method, for example, put conductive powder into the upper limit of 30mL graduated cylinder, set to tap dancer and tap 100 times, then measure the volume of conductive powder To do. The tap density D [g / cm ³ ] can be obtained by the following formula (1) from the mass W [g] in the graduated cylinder and the volume V [cm ³ ] after tapping.
D = W / V (1)

(Iii) The BET specific surface area may be 1.5 m ² / g or less (for example, less than 1.5 m ² / g), and preferably 1.3 m ² / g or less. When the specific surface area of the metal fine particles is large, the binder resin enters into the pores, and accordingly, the action of the binder resin such as an adhesion providing action and a photosensitivity improving action is reduced. In the present invention, since the BET specific surface area is in the above range, a large amount of binder resin in the photocurable resin composition (B) is not required, and as a result, the resistance value of the electric wiring circuit pattern is reduced. There is no going up.
The BET method means a method using low temperature and low humidity physical adsorption of an inert gas. The BET specific surface area in the present invention is a value measured by a method in which a molecule having a known adsorption occupation area is adsorbed on the powder particle surface at the temperature of liquid nitrogen and the specific surface area of the sample is obtained from the amount.

  The shape of the conductive fine particles (A) is not particularly limited as long as the desired conductivity can be obtained, and examples thereof include a spherical shape, a flake shape, a granular shape, a rod shape, and a wire shape. . Among these, granular materials are preferable in that the dispersibility in the photocurable resin composition containing metal fine particles is good.

  Examples of the conductive fine particles (A) include noble metals such as gold, silver, copper, and platinum group metals, or simple metals such as highly conductive metals such as nickel and aluminum, or alloys containing these simple metals. Examples of such fine particles can be given. In addition, a single metal fine particle or a metal fine particle of these alloys may be used in combination of two or more. Among these, gold, silver, copper, or metal fine particles of an alloy containing them are preferable, and silver or metal fine particles of an alloy containing the same are more preferable because conductivity is improved.

  As the conductive fine particles (A), those commercially available may be used, or those produced by a gas phase method or a liquid phase chemical reduction method may be used. As a specific method for producing the conductive fine particles (A), the spray pyrolysis method described in JP-B-63-31522, the metal oxide described in JP2011-12290, or the metal water A method of heating and reducing oxides by irradiating them with microwaves, a method of thermally decomposing a metal complex compound described in JP 2010-265543 A and obtaining a reduced product, a metal ion described in JP 2010-77472 A Examples thereof include a method for reducing bisphenol with a polyhydric alcohol, a production method described in JP-A No. 2002-20809, and a production method described in JP-A No. 2004-99992.

Photocurable resin composition (B)
The photocurable resin composition (B) used in the present invention can be used without particular limitation as long as it exhibits photocurability when irradiated with active energy rays such as electron beams, ultraviolet rays, and visible rays. .
As a photocurable resin composition (B), the compound (for example, binder polymer (b-1) mentioned later, or polymeric compound (b-2) mentioned later) reacted normally by the active substance was absorbed. As long as it hardens. Moreover, although the compound itself which absorbed active energy rays does not harden | cure, the other compound (for example, photocurable initiator (b-3) mentioned later) contained in a photocurable resin composition is active energy rays. It may be cured by acting with the absorbed compound. In addition, two or more kinds of compounds may be involved in that case. For example, a composition containing a polymerizable compound and a photopolymerization initiator can be exemplified.
The photocurable resin composition (B) preferably contains a binder polymer (b-1), a polymerizable compound (b-2), and a photopolymerization initiator (b-3). Furthermore, you may mix | blend the additive for photocurable resins other than a solvent and a photoinitiator with a photocurable resin composition (B) as needed.

Binder polymer (b-1)
The binder polymer (b-1) can be used without particular limitation as long as it does not cause separation, sedimentation or precipitation even when mixed with the other components (B) in the photocurable resin composition. Those that can maintain the adhesion to the substrate can be suitably used. For example, when a polyethylene terephthalate (PET) film is used as the substrate, the binder polymer (b-1) may have any value close to the solubility parameter (SP value) 11.3 of the PET film. (Meth) acrylate resin, epoxy resin, phenol resin, polyurethane, polystyrene, vinyl acetate polymer, polyamide, vinyl chloride-vinyl acetate copolymer, cellulose diacetate, polychlorethylene, nitrocellulose, and tetron The polymer which has can be illustrated. Among these, (meth) acrylate resin, epoxy resin, cellulose diacetate, and polystyrene are preferable, and (meth) acrylate resin and polystyrene are more preferable.

  Moreover, alkaline solutions, such as metal alkali aqueous solution and organic alkali aqueous solution, are normally used as a developing solution of the photolithography method using the photocurable resin composition (B). Therefore, an alkali-soluble resin, for example, an alkali-soluble binder polymer having a carboxyl group or a sulfone group in the molecule is used as the binder polymer (b-1) having excellent resolution in development processing after curing with active energy rays. Is preferred. As an alkali-soluble binder polymer, a monopolymer or 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 a polymer and an ethylenically unsaturated monomer copolymerizable therewith.

  Examples of the ethylenically unsaturated monomer having one or more carboxyl groups include (meth) acrylic acid, cinnamic acid, fumaric acid, itaconic acid, crotonic acid, vinyl acetic acid, and maleic acid. Of these, (meth) acrylic acid is preferred. As the binder polymer (b-1), a polymer obtained by polymerizing one or more of these monomers can be used.

Examples of the ethylenically unsaturated monomer that can be copolymerized with an ethylenically unsaturated monomer having one or more carboxyl groups include (meth) acrylic ester unsaturated monomers, ethylene glycol ester (meth) Examples include acrylate, propylene glycol (meth) acrylate, butylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, (meth) acrylamide unsaturated monomer, N-substituted maleimide and the like.
Specific examples of the ethylenically unsaturated monomer copolymerizable with an ethylenically unsaturated monomer having one or more carboxyl groups include methyl (meth) acrylate, ethyl (meth) acrylate, and isobutyl (meth) acrylate. , Cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, N-cyclohexylmaleimide, etc. Can do. Moreover, styrene, (alpha) -methylstyrene, vinyl ether, vinyl pyrrolidone, (meth) acrylonitrile, etc. are mentioned.

In addition, as the binder polymer (b-1), one or more ethylenically unsaturated monomers having one or more carboxyl groups and one kind of ethylenically unsaturated monomers copolymerizable therewith. Alternatively, a copolymer obtained by copolymerizing two or more types in combination can be used.
The reaction conditions for obtaining the copolymer and the composition ratio of each monomer component may be appropriately selected according to the physical properties (number average molecular weight, glass transition temperature, etc.) of the target binder polymer (b-1). Good.

  Further, as the binder polymer (b-1), it is also possible to use a polymer that crosslinks by a photodimerization reaction or the like by irradiation with active energy rays. Examples of such a polymer include a polymer having a cinnamic acid skeleton, a maleimide skeleton, a styrene skeleton, an anthracene skeleton, or a pyrazine skeleton. Specifically, a polymer having a polyvinyl cinnamate and a maleimide skeleton And Aronics UVT-302 (Toagosei Co., Ltd.).

The binder polymer (b-1) used in the photocurable resin composition (B) of the present invention has a good balance between developability and performance such as adhesion between the circuit pattern to be formed and the substrate. The number average molecular weight is preferably in the range of about 2,000 to 500,000, particularly preferably in the range of about 4,000 to 100,000.
Moreover, the usage-amount of the binder polymer (b-1) in a photocurable resin composition (B) is the range of about 20 to 65 weight% with respect to the whole quantity of a photocurable resin composition (B), for example. I just need it.

Polymerizable compound (b-2)
As the polymerizable compound (b-2), a radical polymerizable compound can be exemplified, among which a polyfunctional (meth) acrylate is high in that the reactivity is high and the sensitivity of the resin composition to light can be increased. Compounds are preferred. Specifically, polyethylene glycol di (meth) acrylate (having 2 to 14 ethylene groups), trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) Acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane propoxytri (meth) acrylate, trimethylolpropane ethylene glycol adduct triacrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, Polypropylene glycol di (meth) acrylate (having 2 to 14 propylene groups), pentaerythritol tri (meth) acrylate, pentaerythritol Examples include la (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Among them, polyethylene glycol di (meth) acrylate (having 2 to 14 ethylene groups) ), Trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene glycol adduct triacrylate, and pentaerythritol tri (meth) acrylate are preferred.
A polymeric compound (b-2) can be used individually or in combination of 2 or more types as appropriate.

  Moreover, the usage-amount of the polymeric compound (b-2) in a photocurable resin composition (B) is 100 weight part of binder polymers (b-1) contained in a photocurable resin composition (B). About 10 to 150 parts by weight, and preferably about 15 to 65 parts by weight.

Photopolymerization initiator (b-3)
The photopolymerization initiator (b-3) can be used without particular limitation as long as it has an absorption band at the wavelength of the active energy ray and generates a starting species for the curing (polymerization) reaction. In general, ultraviolet rays are preferably used as the active energy ray used for the curing reaction from the viewpoint of cost. Therefore, as the photopolymerization initiator, a variety of photopolymerization initiators that are excellent in reactivity with the monomer are preferable.
Specific examples of the radical photopolymerization initiator include benzoin, acetophenone, 2-methylanthraquinone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diisopropylthioxanthone. Benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 2,4-diisopropylxanthone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenyl Ethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2 -Hydroxy-2-methyl-1- Lopan-1-one, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one, 2-methyl-1 -(4-Methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2- [(4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethyl) Benzoyl) -phenylphosphine oxide, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime), ethanone, 1- [9-e -6- (2-methylbenzoyl) -9H- carbazol-3-yl] -, and the like can be exemplified 1-(O-acetyl oxime). Of these, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1,2-octanedione, 1- [ 4- (phenylthio)-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyl) Oxime), 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl]-, 1- (O-acetyloxime) is more preferred.

  Moreover, when using alkali-soluble resin as a binder polymer (b-1), it is preferable to use the photoinitiator which has O-acyl oxime structure as a photoinitiator (b-3).

  The usage-amount of the photoinitiator (b-3) in a photocurable resin composition (B) is with respect to 100 weight part of binder polymers (b-1) contained in a photocurable resin composition (B). It may be in the range of about 1 to 20 parts by weight, and more preferably in the range of about 2 to 15 parts by weight.

Other Additives The photocurable resin composition (B) of the present invention may be added to a solvent, a polymerization inhibitor, a photopolymerization accelerator, and a sensitizer as long as they do not affect the effects of the present invention. The additive for photocurable resin compositions, such as, can be added.

Solvent The photocurable resin composition (B) of the present invention may contain a solvent, if necessary. The solvent is a liquid medium that can dissolve the binder polymer (b-1), the polymerizable compound (b-2), and the photopolymerization initiator (b-3) in the photocurable resin composition (B). If there is, it can be used without any particular limitation. Each component in the photocurable resin composition (B) does not need to be completely dissolved in the solvent, and the photocurable resin composition (B) of the present invention is uniformly dispersed or dissolved as a whole. The ability to dissolve all the above components is not necessarily required as long as the solvent can maintain such a state.

As the solvent used in the present invention, for example, linear, branched, secondary or polyhydric alcohols such as ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-butyl alcohol, hexanol and ethylene glycol, methyl ethyl ketone, Ketones such as cyclohexanone and isophorone, aromatic hydrocarbons such as toluene and xylene, petroleum aromatic mixed solvents such as Swazol series (manufactured by Maruzen Petrochemical Co., Ltd.), Solvesso series (manufactured by Exxon Chemical Co., Ltd.), Cellosolves such as cellosolve and butylcellosolve, carbitols such as carbitol, ethylcarbitol, and butylcarbitol, propylene such as propylene glycol monomethyl ether and propylene glycol dimethyl ether Polypropylene glycol alkyl ethers such as glycol alkyl ethers, dipropylene glycol monomethyl ether and dipropylene glycol dimethyl ether, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate , N-methylpyrrolidone, and dialkyl glycol ethers.
A solvent can be used individually or in combination of 2 or more types as appropriate.

  The amount of the solvent used in the photocurable resin composition (B) may be suitably adjusted so that the viscosity of the metal fine particle-containing photocurable resin composition is in the range of about 10 to 1000 dpa · S, and about 100 to 500 dpa. -It is preferable to prepare so that it may become the range of S.

(2) Method for Producing Electric Wiring Circuit Pattern The method for producing an electric wiring circuit pattern of the present invention forms an electric circuit pattern on a substrate using the above-described metal fine particle-containing photocurable resin composition of the present invention. For example, a step of preparing the above-described metal fine particle-containing photocurable resin composition of the present invention, and a step of applying the metal fine particle-containing photocurable resin composition to a substrate (application step). And irradiating the coating film of the photocurable resin composition containing metal fine particles applied on the substrate through a film or negative mask corresponding to the electric wiring circuit pattern to be formed, and curing the coating film A method including a step of exposing (developing step) and a step of dissolving, removing and drying the unexposed portion on the substrate using a developer (development step) can be exemplified.

In the step of preparing the metal fine particle-containing photocurable resin composition of the present invention, the conductive fine particles (A), the photocurable resin composition (B), and other components added as necessary The mixing or kneading method is not particularly limited as long as each component can be uniformly dispersed or mixed in the photocurable resin composition containing metal fine particles. Examples of such a method include a method using a mechanical stirrer, a magnetic stirrer, an ultrasonic disperser, a planetary mill, a ball mill, or a three roll. A method using a planetary mill is preferable in terms of easy handling, and a method using three rolls is preferable in terms of uniform dispersion, and two or more methods may be combined.
In addition, a photocurable resin composition containing metal fine particles may be prepared by mixing the photocurable resin composition (B) separately prepared, conductive fine particles (A), and other components. Alternatively, the metal fine particle-containing photocurable resin composition may be prepared by simultaneously mixing the conductive fine particles (A), the photocurable resin composition (B), and other components.

In the application step, the metal fine particle-containing photocurable resin composition prepared in the preparation step is applied by a coating method such as a screen printing method, a bar coater, or a blade coater, and a glass substrate, a ceramic substrate, or a film-like resin substrate. Apply to dry.
Since the method of the present invention can form a highly conductive, highly adhesive and high-definition circuit pattern even when a film-like resin substrate having low heat resistance is used, the film-like resin substrate can be suitably used. Examples of the film-like resin substrate include substrates having low heat resistance such as polyethylene terephthalate (PET), polycarbonate (PC), polystyrene (PS), polyvinylidene chloride (PVDC), and adhesion of circuit patterns. However, it is preferable to use a substrate whose surface is subjected to an easy adhesion treatment. A transparent conductive film in which ITO (indium tin oxide), ZnO (zinc oxide), or silver nanowire is coated on the film can also be used.
The drying temperature in the coating process may be about 60 to 120 ° C., and the drying time may be about 5 to 60 minutes.

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

  In the exposure step, active energy rays are irradiated to the coating film applied on the substrate through a film or negative mask corresponding to the electric wiring circuit pattern to be formed, and the irradiated portion is cured. Examples of active energy rays to be irradiated include ultraviolet rays, electron beams, and X-rays, and among these, ultraviolet rays are preferable. As the light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, a black light, or the like can be used. Further, examples of the exposure method include contact exposure with a mask, proximity exposure, and projection exposure.

In the development step, a target electric wiring circuit pattern can be obtained by dissolving and removing unexposed portions that have not been cured using a developer.
Any developer can be used without particular limitation as long as it can solubilize the unexposed portion of the photocurable resin composition containing metal fine particles of the present invention. The developer used may be either aqueous or oily, and the pH of the solution is not limited. For example, when a compound having an acidic group is present in the photocurable resin composition (B), an organic alkali aqueous solution such as monoethanolamine and diethanolamine in addition to a metal alkali aqueous solution such as sodium hydroxide and sodium carbonate, etc. Can be used. Further, since the original purpose of “development” is to remove the unexposed portion of the photocurable resin composition containing metal fine particles from the substrate, the solubilization referred to here is the photocurable resin composition containing metal fine particles. It is not necessary to dissolve all of the above, and it is sufficient that at least one component constituting the metal fine particle-containing photocurable resin composition can be solubilized to such an extent that an unexposed portion can be removed.

  As a developing method in the developing step, any developing method usually used for photolithography can be used without any particular limitation. Specifically, a dip method in which a substrate on which a cured coating film is formed is immersed in a developer, a spray method in which the developer is sprayed on the entire surface of the substrate, a barrel method in which the developer and this substrate are placed in a container, and the like are processed. Can be illustrated. The development method may be appropriately determined according to the properties of the metal fine particle-containing photocurable resin composition to be used. In addition, although the development method differs depending on the shape of the substrate forming the circuit, etc., when removing an unnecessary coating film (unexposed part) on the substrate, a method of washing the coating film adhesion surface with a uniform pressure by a spray method, This is preferable in that the resolution can be improved.

  The electrical wiring circuit pattern is dried after washing with water and acid neutralization to remove unnecessary developer. The drying temperature may be about 40 to 70 ° C., and the drying time may be about 5 to 30 minutes. Further, in order to further enhance the adhesion between the electric wiring circuit pattern and the substrate, after-baking may be further performed after the development step, if necessary. The temperature at this time may be about 100 to 150 ° C., and the time may be about 5 to 100 minutes.

  By passing through the above steps, electrical wiring circuit patterns can be formed on various substrates using the photocurable resin composition containing metal fine particles of the present invention.

  Electrical wiring circuit boards such as a touch panel substrate, a display device substrate, and an information processing terminal device substrate can be manufactured by the above-described method for manufacturing an electrical wiring circuit pattern of the present invention.

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

(1) Material of metal fine particle containing photocurable resin composition The material used by the below-mentioned Example and comparative example is demonstrated below.
Metal fine particles (conductive fine particles) (A)
Metal fine particles M1: Silver fine particles (granular, 50% average particle size 0.7 μm, tap density 1.4 g / cm ² , BET specific surface area 1.3 m ² / g)
Metal fine particles M2: Silver fine particles (granular, 50% average particle size 0.4 μm, tap density 1.8 g / cm ² , BET specific surface area 0.9 m ² / g)
Metal fine particles M3: Silver fine particles (flakes, 50% average particle size 3.0 μm, tap density 2.9 g / cm ² , BET specific surface area 0.9 m ² / g)
Metal fine particles M4: Silver fine particles (spherical, 50% average particle size 2.7 μm, tap density 4.4 g / cm ² , BET specific surface area 0.4 m ² / g)
Metal fine particles M5: Silver fine particles (granular, 50% average particle size 0.9 μm, tap density 1.5 g / cm ² , BET specific surface area 1.8 m ² / g)
Metal fine particles M6: Silver fine particles (flakes, 50% average particle size 7.6 μm, tap density 5.5 g / cm ² , BET specific surface area 0.4 m ² / g)
The 50% average particle diameter of the metal fine particles is a value measured by (Microtrack method), and the tap density and the BET specific surface area are values measured by the above-described methods.

Photocurable resin composition (B)
(Binder polymer: b-1)
Binder polymer P1: Acrylic polymer AA-6 (number average molecular weight 6,000, manufactured by Toa Gosei Co., Ltd.)
Binder polymer P2: Acrylic polymer AS-6 (number average molecular weight 6,000, manufactured by Toa Gosei Co., Ltd.)
(Polymerizable compound: b-2)
Polymerizable compound R1: A-200 (polyethylene glycol # 200 diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Polymerizable compound R2: Light acrylate PE3A (pentaerythritol tri (meth) acrylate, manufactured by Kyoeisha Chemical)
(Photopolymerization initiator: b-3)
Photoinitiator I1: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (BASF)
Photoinitiator I2: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (manufactured by BASF)
(solvent)
Solvent S1: Propylene glycol monomethyl ether (Wako Pure Chemical Industries, Ltd.)

  The composition of the metal fine particle-containing photocurable resin composition used in the examples is shown in Table 1, and the composition of the metal fine particle-containing photocurable resin composition used in the comparative example is shown in Table 2. In addition, the numerical value in Table 1 and Table 2 shows the ratio (weight%) of each component with respect to the whole quantity of a composition.

(2) Electric wiring circuit pattern formation
Examples 1-5
(I) Preparation process of metal fine particle-containing photocurable resin composition According to the composition shown in Tables 1 and 2, each component was weighed so that the total weight of the metal fine particle-containing photocurable resin composition was 50 g. First, this was kneaded for a total of 5 minutes using a planetary mill (Shinky Awatori Nertaro AR-100). At this time, kneading was stopped every other minute so that the metal fine particle-containing photocurable resin composition did not have too much heat. Subsequently, this was kneaded using three rolls to prepare a paste-like fine metal particle-containing photocurable resin composition.

(Ii) Coating process and exposure process 100 μm thick single-sided easy-adhesion-treated PET film (Teijin DuPont Films Co., Ltd. O3) is used as a substrate, and the above-mentioned metal fine particle-containing photocurable resin composition on the treated surface side surface Was uniformly applied by screen printing and dried at 80 ° C. for 10 minutes to obtain a coating film having a coating thickness of 10 μm. Subsequently, a photomask on which a fine line pattern with a line / space of 50/50 (μm) is adhered is closely adhered to the coating film, and ultraviolet rays are irradiated using a metal halide lamp to cure the photocurable resin composition containing metal fine particles. I let you.

(Iii) Development step and its evaluation Next, a 1% aqueous sodium carbonate solution was used as a developer to remove unexposed portions, and unnecessary developer was removed by washing with water. Thereafter, drying was performed at 50 ° C. for 5 minutes to remove moisture, and an electric wiring circuit pattern was obtained.

Example 6
Using a photocurable resin composition containing metal fine particles of the composition shown in Table 1, instead of a PET film substrate (O3 manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 100 μm on one side, a sputter deposition method on a polyester film Example: A transparent conductive film substrate having a thickness of 100 μm (ELECTRYSTA manufactured by Nitto Denko Corporation) with an ITO film formed thereon was used, and a paste-like fine metal particle-containing photocurable resin composition was applied to the ITO film surface. 1 was used to obtain an electric wiring circuit pattern.

Example 7
Silver nanowires were used instead of the PET film substrate (O3 manufactured by Teijin DuPont Films, Inc.) having a thickness of 100 μm and a single-sided easy-adhesion treatment using the metal fine particle-containing photocurable resin composition having the composition shown in Table 1. A transparent conductive film substrate (manufactured by Toray Film Processing Co., Ltd.) having a thickness of 100 μm was used, and the same as in Example 1 except that a paste-like fine metal particle-containing photocurable resin composition was applied to the silver nanowire surface. An electric wiring circuit pattern was obtained by this method.

Example 8
Using the photocurable resin composition containing metal fine particles having the composition shown in Table 1, a line / space of 30 instead of a photomask on which a fine line pattern having a line / space of 50/50 (μm) was drawn at the time of exposure. An electric wiring circuit pattern was obtained in the same manner as in Example 1 except that a photomask on which a thin line pattern of / 30 (μm) was drawn was used.

Comparative Examples 1-6
Using the metal fine particle-containing photocurable resin composition having the composition shown in Table 2, a metal fine particle-containing photocurable resin composition was prepared in the same manner as in Example 1 to form an electric wiring circuit pattern.

Comparative Example 7
Using a photocurable resin composition containing metal fine particles having the composition shown in Table 2, instead of a PET film substrate (O3 manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 100 μm on one side, a sputter deposition method is applied to a polyester film. Example: A transparent conductive film substrate having a thickness of 100 μm (ELECTRYSTA manufactured by Nitto Denko Corporation) with an ITO film formed thereon was used, and a paste-like fine metal particle-containing photocurable resin composition was applied to the ITO film surface. 1 was used to obtain an electric wiring circuit pattern.

(3) Evaluation of physical properties For the photocurable resin composition containing fine metal particles, the minimum amount of ultraviolet irradiation that can form an electric wiring circuit pattern was evaluated, and the electric wiring circuit pattern thus obtained had a specific resistance, resolution by development, substrate Was measured or evaluated by the following method.
(Evaluation of sensitivity: minimum amount of UV irradiation)
A photomask on which a fine line pattern is drawn is adhered to a photocurable resin composition containing metal fine particles coated to a thickness of 10 μm on a substrate, and irradiated with 100 to 1000 mJ / cm ² of ultraviolet rays using a metal halide lamp. The minimum exposure amount at which the formation of a fine line pattern was confirmed later was defined as sensitivity.

(Measurement of specific resistance)
The specific resistance was measured according to JIS K7149 using a four-point probe resistivity meter Loresta-AX (manufactured by Mitsubishi Chemical Analytech Co., Ltd.). The specific resistance is below the measurement limit. L. Shown as (Over Load).

(Resolution evaluation)
The evaluation of the resolution was carried out by observing the circuit pattern after the development processing at a magnification of 100 using an epi-illumination type optical microscope, and evaluating the presence or absence of the resin composition residue in the space portion and the presence or absence of disconnection in the line portion. Resin composition residue and those in which no disconnection of the line portion was confirmed are indicated as ◯, and those confirmed are indicated as ×.

(Evaluation of adhesion)
For evaluation of adhesion to the substrate, a peel test was performed according to the JIS H8504 tape test method. The presence or absence of peeling of the circuit pattern was confirmed. The case where the coating film was not peeled off is indicated by ◯, and the case where the coating film was peeled off is indicated by ×.

Table 3 shows the evaluation results of the examples, and Table 4 shows the evaluation results of the comparative examples.

In Examples 1 to 8, the conductivity satisfying the physical properties of 50% average particle size of 0.1 μm to 5 μm, tap density of 2.5 g / cm ³ or less, and BET specific surface area of 1.5 m ² / g or less. By using the silver fine particles having the metal fine particle-containing photocurable resin composition within the scope of the present invention with respect to the total amount of the metal fine particle-containing photocurable resin composition, an electric wiring circuit pattern having practically sufficient conductivity, high resolution, and adhesion can be obtained. Been formed.
Moreover, although the metal microparticle containing photocurable resin composition used in Examples 1-8 had good sensitivity, in particular, in Example 5, a photopolymerization initiator having an O-acyloxime structure was used. Thus, compared with Example 4 in which the other conditions were the same, the sensitivity could be increased approximately twice.
In addition, from the results of Examples 6 and 7, by using the photocurable resin composition containing metal fine particles of the present invention, an electric wiring circuit pattern having sufficient adhesion was obtained regardless of the type of substrate. I understand.

On the other hand, when the 50% average particle size is larger than 5 μm (Comparative Example 7), when the tap density is larger than 2.5 g / cm ³ (Comparative Examples 1, 2, 5, and 7), the BET specific surface area is 1. When it is larger than 5 m ² / g (Comparative Example 6) or when the content of conductive metal fine particles (A) is not within the scope of the present invention (Comparative Examples 3 and 4), the sensitivity, specific resistance, resolution, There was a problem with one of the adhesions.

When the silver fine particles M4 were used in Comparative Example 2, conductivity was not obtained. It is presumed that the conductivity was not obtained because M4 is a spherical metal fine particle and there are few contacts between the particles. In Comparative Example 3, sufficient conductivity was not obtained. This is because the content of the conductive metal fine particles (A) in the metal fine particle-containing photocurable resin composition is outside the scope of the present invention, and therefore, a large amount of photocurable resin or the like exists between the metal fillers. Therefore, it is presumed that resistance is obtained and conductivity cannot be obtained.
Comparative Example 7 showed a low specific resistance, but many metal fine particle contacts (short-circuit portions) were observed between the lines after development. When the average particle size of the metal fine particles is large, the particles are easily brought into contact with each other, and high conductivity is obtained. On the other hand, it is considered that the probability that the circuit is short-circuited is high.

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

Claims (5)

It is a photocurable resin composition containing metal fine particles for a film-like resin substrate, which contains conductive fine particles (A) and a photocurable resin composition (B), and conductive fine particles (A ) Is in the range of 62 to 86% by weight with respect to the total amount of the metal fine particle-containing photocurable resin composition for a film-like resin substrate ,
Conductive fine particles (A)
(I) 50% average particle size is 0.1-5 μm,
(Ii) the tap density is 2.5 g / cm ³ or less,
(Iii) BET specific surface area is 1.3 m ² / g or less,
Has the physical properties of
The photocurable resin composition (B) contains a binder polymer (b-1), a polymerizable compound (b-2) and a photopolymerization initiator (b-3),
The binder polymer (b-1) is an alkali-soluble resin.
A photocurable resin composition containing metal fine particles for a film-like resin substrate . The film according to claim 1, wherein the content of the photocurable resin composition (B) is in the range of 15 to 60 parts by weight with respect to 100 parts by weight of the conductive fine particles (A). A photocurable resin composition containing fine metal particles for a resin-like resin substrate . The photocurable resin composition containing metal fine particles for a film-form resin substrate according to claim 1 or 2, wherein the conductive fine particles (A) are silver or an alloy containing the same. The photocurable resin composition (B) contains a photopolymerization initiator having an O-acyloxime structure, and the metal fine particle-containing light for a film-form resin substrate according to any one of claims 1 to 3 Curable resin composition. The film-like resin according to any one of claims 1 to 4, wherein the transparent conductive film substrate is formed by coating a polyethylene terephthalate (PET) film with indium tin oxide (ITO), zinc oxide (ZnO), or silver nanowires. a coating step of coating a substrate metal particle-containing photo-curable resin composition, through a corresponding film or mask on an electric wiring circuit pattern to be formed, the film-like resin substrate metal particle-containing photo-curable resin composition An electric wiring circuit including an exposure process for irradiating an active energy ray to a coating film to cure the coating film, and a development process for dissolving, removing, and drying unexposed portions of the coating film using a developer. Pattern manufacturing method.