JPWO2015125661A1 - Reactive resin composition, circuit pattern and circuit board - Google Patents

Abstract

An object of the present invention is to reduce the variation in the contact resistance value at the interface with a circuit pattern for a film having a conductive material-containing layer, and to use the reactive resin composition to form a circuit pattern having stable conductivity. The reactive resin composition of the present invention comprises conductive fine metal particles (A), a photosensitive resin composition (C), an aprotic polar solvent or a nonpolar solvent (D ), And a reactive resin composition used for a film having a conductive material-containing layer, wherein the content of the aprotic polar solvent or the nonpolar solvent (D) is relative to the reactive resin composition And 0.2 to 15% by weight.

Description

The present invention relates to a reactive resin composition used for a film having a conductive material-containing layer. Furthermore, a circuit pattern formed using the reactive resin composition, and a circuit board (for example, a touch panel substrate, a display device substrate, or the like) formed on a film having the conductive material-containing layer. Information processing terminal device substrate, etc.).

In recent years, ITO (Indium Tin Oxide) is widely used as a transparent conductive material in touch panels, which are rapidly growing in demand due to the spread of smartphones and tablet-type terminals. Among them, ITO films are formed on films. The used substrate is widely used because it is lighter and less likely to be damaged than a glass substrate. Usually, as a technique for lowering the resistance value of the ITO film, a technique for crystallizing ITO by subjecting it to thermal (annealing) treatment is used. When a glass substrate is used, it is easy to lower the resistance value because heat (annealing) treatment can be performed at a high temperature. However, when a film is used, expansion and contraction due to heat occur. It is difficult to heat-treat at 150 ° C. or higher. Therefore, when a film is used, even if the resistance value is low, the limit value is about 100Ω. When the screen of a display or the like becomes large, a problem of signal delay occurs due to the high resistance value.

As a method for solving the problem of the ITO film, a transparent conductive film covered with a coating containing metal nanoparticles has been proposed. (Patent Document 1). This proposal is excellent in terms of transparency, low resistance, and reduction in the amount of metal used. A film covered with a coating containing metal nanoparticles is obtained by dispersing metal nanoparticles in a binder resin on the film. It is manufactured by coating. Since the metal nanoparticles are coated on the film in a state of being dispersed in the binder resin, the proportion of the metal nanoparticles present in the coating covering the film varies depending on the location, and some of them are covered with the binder resin. Will be. Therefore, since the contact resistance value at the interface between the film and the circuit pattern varies, further improvement is desired.

US Patent Application Publication No. 2007/0074316

An object of the present invention is to reduce the variation in the contact resistance value at the interface with a circuit pattern for a film having a conductive material-containing layer, and to use the reactive resin composition to form a circuit pattern having stable conductivity. Is to provide things.

The inventors of the present invention have made extensive studies to solve the above problems, and have conductive metal fine particles (A), a photosensitive resin composition (C), and an aprotic polar solvent or a nonpolar solvent (D). A reactive resin composition used for a film having a conductive material-containing layer, wherein the content of the aprotic polar solvent or the nonpolar solvent (D) is relative to the reactive resin composition By using a reactive resin composition characterized by being 0.2 to 15% by weight, the contact resistance value (hereinafter referred to as resistance value) at the interface between the film having the conductive material-containing layer and the circuit pattern is used. ) Was found to be reduced.

The present invention has been completed based on the above knowledge, and a reactive resin composition used for a film having a conductive material-containing layer, a circuit pattern formed using this reactive resin composition, and this circuit Provided is a circuit board in which a pattern is formed on a film having a conductive material-containing layer.

The reactive resin composition of the present invention is
Conductive fine metal particles (A);
A photosensitive resin composition (C);
Containing an aprotic polar solvent or a nonpolar solvent (D),
A reactive resin composition used for a film having a conductive material-containing layer,
Content of the said aprotic polar solvent or nonpolar solvent (D) is 0.2 to 15 weight% with respect to the reactive resin composition, It is characterized by the above-mentioned.

The reactive resin composition of the present invention contains an aprotic polar solvent or a nonpolar solvent (D).
By forming a circuit pattern using the reactive resin composition of the present invention containing such a solvent, there is little variation in the resistance value at the interface between the film having the conductive material-containing layer and the circuit pattern, and stable conductivity. A circuit pattern having characteristics can be obtained.

In the reactive resin composition of the present invention, the aprotic polar solvent or the nonpolar solvent (D) is an ether solvent, ketone solvent, amine solvent, amide solvent, nitro solvent, and aromatic carbonization. It is preferably at least one selected from the group consisting of hydrogen solvents.
When these solvents are used, the effects of the present invention are more suitably exhibited.

In the reactive resin composition of the present invention, the photosensitive resin composition (C) contains a binder polymer (c-1), a polymerizable compound (c-2), and an initiator (c-3). It is preferable.
When a photosensitive resin composition comprising such components is used, a circuit pattern can be suitably formed.

In the reactive resin composition of the present invention, the average particle size of the conductive fine metal particles (A) is preferably 0.1 μm or more and 10 μm or less.
When the average particle size of the metal fine particles (A) is within the above range, the intended conductivity can be more suitably obtained.

The circuit pattern of the present invention is formed using the reactive resin composition of the present invention.
Since the circuit pattern of the present invention is formed using the reactive resin composition of the present invention, there is little variation in resistance value at the interface between the film having the conductive material-containing layer and the circuit pattern, and stable conductivity. Have

The circuit board of the present invention is characterized in that the circuit pattern of the present invention is formed on a film having a conductive material-containing layer.
The circuit board of the present invention is a high-definition circuit board because variation in resistance value at the interface between the film having the conductive material-containing layer and the circuit pattern is reduced.

By using the reactive resin composition of the present invention, a variation in resistance value at the interface with the circuit pattern can be reduced and a circuit pattern having stable conductivity can be formed on the film having the conductive material-containing layer. Moreover, by using the reactive resin composition of the present invention, a high-definition electric wiring circuit pattern can be manufactured, and a high-definition electric wiring circuit board can be obtained.

FIG. 1A is a top view schematically showing a circuit for conductivity evaluation, and FIG. 1B is a cross-sectional view schematically showing a layer structure of the circuit for conductivity evaluation.

Hereinafter, the present invention will be described in detail.

Reactive resin composition used for film having conductive material-containing layer The reactive resin composition of the present invention comprises conductive fine metal particles (A), a photosensitive resin composition (C), and A reactive resin composition used for a film containing an aprotic polar solvent or a nonpolar solvent (D) and having a conductive material-containing layer, the aprotic polar solvent or the nonpolar solvent (D) The content of is 0.2 to 15% by weight with respect to the reactive resin composition.

By using the reactive resin composition of the present invention to form a circuit pattern on a film having a conductive material-containing layer, variation in resistance value at the interface between the film having the conductive material-containing layer and the circuit pattern can be achieved. A small circuit pattern having stable conductivity can be obtained. In the present invention, the variation in the resistance value is small, meaning that the film having the conductive material-containing layer is stripped so that unnecessary portions are peeled off by etching, and a reactive resin composition is provided at both ends of the film. A circuit pattern (film) is formed so as to contact the area, and the resistance value is measured with a digital multimeter at both ends of the film, and the difference between the maximum value and the minimum value of the five resistance values is an average value of five points. It means about 10% or less. If the resistance value is larger than 10%, the transmission of the signal (signal) is hindered. The resistance value measurement method in the present invention refers to a value obtained by measuring a resistance value [Ω] of a circuit pattern (film) formed on a film having a conductive material-containing layer with a digital multimeter.

Conductive metal fine particles (A)
The conductive metal fine particles (A) can be used without particular limitation as long as the average particle diameter is a metal powder having a particle size of 0.1 μm or more and 10 μm or less. For example, noble metals such as gold, silver, copper, and platinum group metals, single metal powders having high conductivity such as nickel and aluminum, or metal powders of these alloys can be exemplified. It is also possible to use a single metal powder or a combination of two or more metal powders of these alloys. Among these, gold, silver, copper, or a metal powder thereof is preferable in terms of conductivity, and silver or a metal powder thereof is more preferable.

The shape of the conductive metal 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, an irregular shape, and the like. From this point, a spherical shape is preferable. The average particle size of the metal powder is preferably in the range of 0.1 μm to 10 μm. When the metal powder having an average particle size in the above range is used, the effects of the present invention can be sufficiently obtained. The average particle diameter of the conductive fine metal particles (A) in the present invention is a value measured by a particle size distribution measuring device.

As the conductive metal fine particles (A) used in the present invention, those commercially available may be used, and 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 metal particles (A), the spray pyrolysis method described in Japanese Patent Publication No. 63-31522, the production method described in Japanese Patent Application Laid-Open No. 2002-20809, and Examples include the manufacturing method described in JP-A-2004-99992.

The content of the conductive fine metal particles (A) in the reactive resin composition of the present invention is preferably 62% by weight or more, and 64% by weight or more based on the total amount of the reactive resin composition. More preferably, it is more preferably 66% by weight or more, and particularly preferably 68% by weight or more. If it is the said range, there will be little dispersion | variation in resistance value in the interface of the film which has a conductive material content layer, and a circuit pattern, and will not interfere with transmission of a signal (signal).

The content of the conductive metal fine particles (A) is preferably 86% by weight or less, more preferably 84% by weight or less, and more preferably 82% by weight or less based on the total amount of the reactive resin composition. More preferred is 80% by weight or less. If it is in the above range, the sensitivity decreases due to a decrease in the amount of the resin in the reactive resin composition, the yield of circuit pattern formation is remarkably decreased, the adhesion with the film is decreased, the resolution is decreased, etc. The problem does not occur.
The content of the conductive fine metal particles (A) is 62 to 86% by weight, 62 to 84% by weight, 62 to 82% by weight, 62 to 80% by weight, 64% with respect to the total amount of the reactive resin composition. -86 wt%, 64-84 wt%, 64-82 wt%, 64-80 wt%, 66-86 wt%, 66-84 wt%, 66-82 wt%, 66-80 wt%, 68-86 The range of weight%, 68-84 weight%, 68-82 weight%, 68-80 weight% etc. is mentioned.

Photosensitive resin composition (C)
The photosensitive resin composition (C) constituting the reactive resin composition of the present invention can be used without particular limitation as long as adhesion with a film having a conductive material-containing layer is obtained.
The photosensitive resin composition (C) in the present invention refers to a composition that forms a corrosion-resistant image by light irradiation upon crosslinking reaction, polymerization reaction, or decomposition reaction. Furthermore, the photosensitive resin composition (C) includes those that are cured by light to obtain a cured product.

The photosensitive resin composition (C) used in the present invention exhibits any of the properties of polymerizability, crosslinkability, decomposability, and curability when irradiated with active energy rays such as electron beams, ultraviolet rays, and visible rays. If it is a thing, it can be used without a restriction | limiting in particular.

As the photosensitive resin composition (C), a compound that absorbs active energy rays (for example, a binder polymer (c-1) or a polymerizable compound (c-2) described later) undergoes a single reaction to polymerize, It is preferably one that crosslinks and cures. Further, the compound itself that has absorbed the active energy ray is not polymerized, crosslinked, cured, or the like, but other compounds contained in the photosensitive resin composition (C) (for example, an initiator (c-3) described later) It is preferably one that acts on a compound that absorbs active energy rays to polymerize, crosslink, cure, or the like. In addition, two or more kinds of compounds may be involved in that case. For example, a composition containing a polymerizable compound (c-2) and an initiator (c-3) can be exemplified.
The photosensitive resin composition (C) preferably contains a binder polymer (c-1), a polymerizable compound (c-2), and an initiator (c-3).

Moreover, in the reactive resin composition of this invention, in order to obtain high adhesiveness and electroconductivity with the film which has a conductive material content layer, content of the photosensitive resin composition (C) in a reactive resin composition Is preferably 10 parts by weight or more, more preferably 14 parts by weight or more with respect to 100 parts by weight of the conductive fine particles (A). Moreover, 60 weight part or less is preferable and 50 weight part or less is more preferable.

The content of the photosensitive resin composition (C) in the reactive resin composition is 10 to 60 parts by weight, 10 to 50 parts by weight, 14 to 100 parts by weight with respect to 100 parts by weight of conductive fine particles (A). The range of 60 weight part and 14-50 weight part can be illustrated. In addition, when there is too little content of the photosensitive resin composition (C) in a reactive resin composition, sufficient adhesiveness with the film which has a conductive material content layer will not be obtained, but the photosensitive resin composition (C). If the content of is too large, sufficient conductivity cannot be obtained.

Binder polymer (c-1)
The binder polymer (c-1) can be used without particular limitation as long as it does not cause separation, sedimentation, precipitation or the like even when mixed with other components of the photosensitive resin composition (C). What can maintain adhesiveness with the film which has a content layer can be used conveniently. Specifically, (meth) acrylate resin, epoxy resin, phenol resin, polyurethane, polystyrene, vinyl acetate polymer, polyamide, vinyl chloride-vinyl acetate copolymer, cellulose diacetate, polychlorethylene, nitrocellulose, tetron, etc. The polymer etc. which have the structure of 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 photosensitive resin composition (C). 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 (c-1) having excellent resolution in development processing after curing with active energy rays. Is preferred. As an alkali-soluble binder polymer, a homopolymer obtained by polymerizing an ethylenically unsaturated monomer having one or more carboxyl groups, or a copolymer, 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 (c-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.

Moreover, as a binder polymer (c-1), 1 type or 2 types or more of the ethylenically unsaturated monomer which has a 1 or more carboxyl group, and 1 type of the ethylenically unsaturated monomer copolymerizable with it 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 (c-1). Good.

Further, as the binder polymer (c-1), it is also possible to use a polymer that crosslinks by a photodimerization reaction 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, and specifically include a polyvinyl cinnamate and a maleimide skeleton. Examples thereof include Aronix UVT-302 (Toagosei) which is a polymer.

The binder polymer (c-1) used in the photosensitive resin composition (C) has a number average molecular weight in order to improve the balance between developability and performance such as adhesion between the formed circuit pattern and the film. The thing of the range of 2,000-500,000 is preferable, and the thing of the range of 4,000-100,000 is especially preferable.
Moreover, the usage-amount of the binder polymer (c-1) in the photosensitive resin composition (C) should be the range of 30 to 80 weight% with respect to the whole quantity of the photosensitive resin composition (C), for example. Preferably, it is 40 to 75% by weight.
In addition, the number average molecular weight of binder polymer (c-1) is the value of polystyrene conversion by gel permeation chromatography (GPC). For example, the model: Showdex (manufactured by Showa Denko KK), column: KF-805L, KF-803L, and KF-802 (manufactured by Showa Denko KK), using THF as an eluent, standard This was performed using polystyrene as a sample. In addition, what is necessary is just to select suitably the measurement conditions of the number average molecular weight of binder polymer (c-1) according to the physical property of a polymer.

Polymerizable compound (c-2)
As the polymerizable compound (c-2), a radical polymerizable compound can be exemplified, and among them, the reactivity is high and the sensitivity to light of the photosensitive resin composition can be increased. ) Acrylate 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 thereof include la (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like. 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. Moreover, the polymeric compound (c-2) can use what was mentioned above individually or in combination of 2 or more types as appropriate.

Moreover, the usage-amount of the polymeric compound (c-2) in the photosensitive resin composition (C) is 20 with respect to 100 weight part of binder polymers (c-1) contained in the photosensitive resin composition (C). It should just be the range of -55 weight part, and the range of 25-50 weight part is preferable.

Initiator (c-3)
The initiator (c-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 polymerization reaction, a crosslinking reaction, a curing reaction, and the like. In general, ultraviolet rays are preferably used as active energy rays used in the reaction from the viewpoint of cost. Therefore, as the initiator (c-3), there are a wide variety of types, and radical photopolymerization initiators that are excellent in reactivity with monomers are preferable.

Specific examples of the initiator (c-3) 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 -Diphenylethane-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-ethyl-6- (2-methylbenzoyl) -9H- carbazol-3-yl] -, can be exemplified 1- (O-acetyl oxime) or the like. 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.

The usage-amount of the initiator (c-3) in the photosensitive resin composition (C) is 1-10 weight part with respect to 100 weight part of binder polymers (c-1) contained in the photosensitive resin composition (C). The range of 2 to 8 parts by weight is more preferable.

Aprotic polar solvent or nonpolar solvent (D)
In the reactive resin composition of the present invention, in addition to the organic solvent (E) described later, by containing an aprotic polar solvent or a nonpolar solvent (D), a film having a conductive material-containing layer is provided. When the pattern is formed, there is little variation in the resistance value at the interface between the film having the conductive material-containing layer and the circuit pattern, and stable conductivity can be obtained. The content of the aprotic polar solvent or the nonpolar solvent (D) may be 0.2% by weight or more with respect to the reactive resin composition, and is preferably 0.5% by weight or more. The content of the aprotic polar solvent or the nonpolar solvent (D) may be 15% by weight or less with respect to the reactive resin composition, and is preferably 10% by weight or less, and 7% by weight. More preferably, it is more preferably 5% by weight or less.
The content of the aprotic polar solvent or the nonpolar solvent (D) is, for example, 0.2 to 15% by weight, 0.2 to 10% by weight, or 0.2 to 7% by weight with respect to the reactive resin composition. %, 0.2-5 wt%, 0.5-15 wt%, 0.5-10 wt%, 0.5-7 wt%, 0.5-5 wt%, and the like.
When the content of the aprotic polar solvent or the nonpolar solvent (D) is less than 0.2% by weight, the effect of including the solvent (D) is not sufficiently exhibited. On the other hand, when the content of the aprotic polar solvent or the nonpolar solvent (D) exceeds 15% by weight, the viscosity of the reactive resin composition becomes too low to make it difficult to form a circuit pattern, and the resolution of the circuit pattern is reduced. It will decline.
The content of the aprotic polar solvent or the nonpolar solvent (D) when a plurality of aprotic polar solvents or nonpolar solvents are contained is determined as the total content of the respective solvents.

The aprotic polar solvent or the nonpolar solvent (D) is not particularly limited, but of the aprotic polar solvent or the nonpolar solvent (D), the aprotic polar solvent is 1-chlorobutane. Halogen solvents such as chlorobenzene, 1,1-dichloroethane, 1,2-dichloroethane, chloroform, 1,1,2,2-tetrachloroethane; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane; methyl ethyl ketone Ketone solvents such as (MEK), acetone and cyclohexanone; acetate solvents such as propylene glycol monomethyl ether acetate (PGMEA); lactone solvents such as γ-butyrolactone; carbonate solvents such as ethylene carbonate and propylene carbonate; triethylamine; Amine solvents such as lysine; nitrile solvents such as acetonitrile; N, N′-dimethylformamide (DMF), N, N′-dimethylacetamide (DMAc), tetramethylurea, 2-pyrrolidone, N-methyl-2- Amido solvents such as pyrrolidone (NMP); Nitro solvents such as nitromethane and nitrobenzene; Sulfide solvents such as dimethyl sulfoxide (DMSO) and sulfolane; Phosphoric acids such as hexamethylphosphoric acid amide and tri-n-butyl phosphate Examples include solvents selected from the group consisting of solvents and combinations thereof. Examples of the nonpolar solvent include a solvent selected from the group consisting of aromatic hydrocarbon solvents such as toluene and xylene, and combinations thereof.
The aprotic polar solvent or nonpolar solvent (D) is at least selected from the group consisting of ether solvents, ketone solvents, amine solvents, amide solvents, nitro solvents, and aromatic hydrocarbon solvents. One is preferred.

As the aprotic polar solvent or nonpolar solvent (D), diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone (MEK), acetone, cyclohexanone, triethylamine, pyridine, acetonitrile, N, N′-dimethylformamide (DMF), N, N′-dimethylacetamide (DMAc), tetramethylurea, 2-pyrrolidone, N-methyl-2-pyrrolidone (NMP), at least one selected from the group consisting of toluene and xylene is preferred, 2-pyrrolidone, tetrahydrofuran, toluene, cyclohexanone or N-methyl-2-pyrrolidone is more preferred.

Other components The reactive resin composition of the present invention includes conductive metal fine particles (A), a photosensitive resin composition (C), an aprotic polar solvent, or a nonpolar solvent (D). In addition, additives such as an organic solvent (E), a leveling agent, a thickener, a suspending agent, a coupling agent for improving adhesion, and an antifoaming agent may be included.

Organic solvent (E)
Examples of the organic solvent (E) used in the present invention include alcohols or acetate esters (such as butyl carbitol acetate).

As the organic solvent (E), those described above can be used alone or in appropriate combination of two or more. In addition, the organic solvent (E) in this invention means the organic solvent which can be added to a reactive resin composition separately from the aprotic polar solvent or organic solvent (D) mentioned above.

The amount of the organic solvent (E) used in the reactive resin composition of the present invention may be appropriately adjusted so that the viscosity of the reactive resin composition is in the range of about 10 to 1000 dPa · s, and is 100 to 500 dPa · s. It is preferable to prepare so that it may become this range.

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 Illustrative examples include acid alkyl copolymers, graft copolymers of polyoxyalkylene monoalkyl or alkenyl ether, and lecithin.

The addition amount of the leveling agent is preferably 0.1% by weight or more based on the total amount of the reactive 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 reactive resin composition. If it is this range, adhesiveness fall with the film which has a conductive material content layer, a printable deterioration, etc. will not occur. Moreover, the effect of the leveling agent does not increase any further if it is increased further.

As a thickener, if a higher viscosity is required, various polymers such as vinyl chloride / vinyl acetate copolymer resins, polyester resins, acrylic resins, polyurethane resins, polysaccharides such as carboxymethylcellulose, sugars such as dextrin palmitate Metal soaps such as fatty acid esters and zinc octylate, swelling 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 reactive 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 3% by weight or less with respect to the total amount of the reactive resin composition. If it is this range, deterioration of printability will not occur.

As the precipitation inhibitor, for example, commercially available products such as long-chain polyamides, phosphates of long-chain polyamides, polyamides, unsaturated polycarboxylic acids, and tertiary amino group-containing polymers can be used.

The addition amount of the precipitation inhibitor is preferably 0.1% by weight or more based on the total amount of the reactive resin composition. If it is this range, the effect of a precipitation inhibitor will fully be acquired. Moreover, the addition amount of the precipitation inhibitor is preferably 3% by weight or less with respect to the total amount of the reactive resin composition. Within this range, printability deterioration due to 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, Epoxys such as-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane Group-containing alkoxysilane compounds, alkoxysilane compounds having a styryl group such as p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxyp Alkoxysilane compounds having a methacryloxy group such as pyrmethyldiethoxysilane 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- Aminopro Alkoxysilane compounds having amino groups such as hydrochloride of rutrimethoxysilane, 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 alkoxysilane compounds having an isocyanate group such as ethoxysilane, and alkoxysilane compounds having an imidazole group such as imidazolesilane.

The addition amount of the coupling agent is preferably 0.1% by weight or more based on the total amount of the reactive 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 3% by weight or less with respect to the total amount of the reactive 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 a functional polymer, polysiloxane, foam-breaking polysiloxane, polymethylalkylsiloxane, polyether-modified polysiloxane, and paraffinic mineral oil.

The addition amount of the antifoaming agent is preferably 0.1% by weight or more with respect to the total amount of the reactive resin composition. If it is this range, the effect of an antifoamer is fully acquired. Further, the addition amount of the antifoaming agent is preferably 3% by weight or less with respect to the total amount of the reactive resin composition. If it is this range, the adhesive fall with a film, 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.

Method for producing reactive resin composition The reactive resin composition of the present invention comprises conductive fine particles (A), a photosensitive resin composition (C), and an aprotic polar solvent or nonpolar. It can manufacture by mixing or knead | mixing a solvent (D) and the other component added as needed.
The mixing or kneading method of these components is not particularly limited as long as each component can be uniformly dispersed or mixed in the reactive resin composition. Examples of such a method include a method using a mechanical stirrer, magnetic stirrer, ultrasonic disperser, planetary mill, ball mill, planetary mixer, or three rolls. A method using a planetary mill is preferable from the viewpoint of easy handling, and a method using three rolls is preferable from the viewpoint of uniform dispersion, and two or more methods may be combined.

Circuit pattern and circuit pattern manufacturing method The circuit pattern of the present invention is formed using the reactive resin composition of the present invention.
In forming a circuit pattern on a film having a conductive material-containing layer, the reactive resin composition of the present invention is formed on the film having a conductive material-containing layer by using a printing method such as screen printing. Thereafter, an active energy ray is irradiated to react the photosensitive resin composition (C) to obtain a circuit pattern. Also, the reactive resin composition is applied by a printing method such as screen printing, and the reactive resin composition is cured by irradiating active energy rays through a film mask pattern or glass mask pattern formed of PET or the like. The circuit pattern can be obtained by using a photolithographic technique for equalizing, then removing an unexposed portion using a developer, and removing the solvent by drying.

As a method for producing the circuit pattern of the present invention, the step of preparing the above-described reactive resin composition of the present invention (preparation step) and the coating of the reactive resin composition on the film having the conductive material-containing layer are applied. A process (application process) and a process of irradiating an active energy ray to the coating film of the reactive resin composition through a film or a negative mask corresponding to the circuit pattern to be formed to cure the coating film (exposure process) ), And a method including a step (developing step) of dissolving, removing, and drying the unexposed portion on the film with a developer.

In the coating step, the reactive resin composition of the present invention prepared in the above preparation step is coated on a film having a conductive material-containing layer and dried by a coating method such as a screen printing method, a bar coater, or a blade coater. . The drying temperature in the coating step is preferably 60 to 120 ° C., and the drying time is preferably 5 to 60 minutes. Moreover, the thickness of the coating film on the film having the conductive material-containing layer is not particularly limited, but it is preferably more than 1 μm and less than 30 μm, more preferably more than 5 μm and less than 15 μm.

In the exposure process, the active energy rays are irradiated to the coating film applied on the film having the conductive material-containing layer through a film or negative mask corresponding to the circuit pattern to be formed, and the irradiated portion is polymerized, crosslinked, and cured. Make them equal. Examples of the active energy rays to be irradiated include ultraviolet rays, electron beams, and X-rays, and among them, 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. Examples of the exposure method include contact exposure with a mask, proximity exposure, and projection exposure.

In the development step, a target 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 reactive resin composition 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 photosensitive resin composition (C), an aqueous alkali metal solution such as sodium hydroxide and sodium carbonate, an organic alkaline aqueous solution such as monoethanolamine and diethanolamine, etc. Can be used. Further, since the original purpose of “development” is to remove the unexposed portion of the reactive resin composition, the solubilization here does not mean to dissolve all of the reactive resin composition. It is sufficient that at least one component constituting the reactive 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 in photolithography can be used without any particular limitation. Specifically, a dip method in which a film having a conductive material-containing layer formed with a cured coating film is immersed in a developer, a spray method in which the developer is sprayed on the entire surface of the film, and the developer and this film are placed in a container. The barrel method etc. which are processed can be illustrated. What is necessary is just to determine a image development system suitably according to the property of the reactive resin composition to be used. In addition, although the development method varies depending on the shape of the film having a conductive material-containing layer, which is a target for forming a circuit pattern, etc., when an unnecessary coating film (unexposed portion) on the film having a conductive material-containing layer is removed A method of washing the coating surface with a uniform pressure by a spray method is preferable in that the resolution can be improved.

The circuit pattern is dried after washing with water and acid neutralization to remove unnecessary developer. The drying temperature is preferably 40 to 100 ° C., and the drying time is preferably 5 to 30 minutes. Further, in order to further enhance the adhesion between the circuit pattern and the film having the conductive material-containing layer, after baking may be further performed after the development step, if necessary. The temperature at this time is preferably 100 to 150 ° C., and the time is preferably 5 to 100 minutes.

By passing through the said process, a circuit pattern can be formed on the film which has a conductive material content layer using the reactive resin composition of this invention.

Film having a conductive material-containing layer The film having a conductive material-containing layer that can be used in the present invention is not particularly limited, and the material, shape, structure, thickness and the like are appropriately selected from known ones. can do. The film having a conductive material-containing layer refers to a film having a layer containing a conductive material on the film (the film is covered with a layer containing a conductive material). In addition, the thickness of the conductive material-containing layer on the film can be used without particular limitation as long as it has a thickness that provides the desired conductivity.

As the film, for example, a polyester resin film such as polyethylene terephthalate (PET), polyethylene naphthalate, modified polyester, a polyethylene (PE) resin film, a polypropylene (PP) resin film, a polystyrene resin film, a polyolefin resin such as a cyclic olefin resin, etc. Resin films, vinyl resin films such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin films, polysulfone (PSF) resin films, polyether sulfone (PES) resin films, polycarbonate (PC) resin films , Polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (TAC) resin film, etc. Films such as polyethylene terephthalate (PET), polycarbonate (PC), polystyrene (PS), and polyvinylidene chloride (PVDC) are preferable, and polyethylene terephthalate (PET). A polycarbonate (PC) film is more preferable.

The conductive material contained in the conductive material-containing layer of the film having the conductive material-containing layer can be used without particular limitation as long as it can be used for the layer covering the film. For example, a nonmetallic conductive material or a metallic conductive material can be exemplified.

Examples of the nonmetallic conductive material include carbon nanowires, carbon nanotubes, carbon nanocoils, carbon nanofibers, graphene, fullerenes, and the like. Among these, carbon nanotubes and graphene are preferable.

Examples of the carbon nanotube include single-walled or multi-walled carbon nanotubes, and the single-walled carbon nanotubes preferably have a diameter of 1 nm to 20 nm. Further, it is also possible to use one in which one to several (for example, 10) are bundled. A multi-walled carbon nanotube in which a plurality of single-walled carbon nanotubes are stacked in a nested manner can also be used. The diameter of the multi-walled carbon nanotube is preferably 150 to 200 nm, for example.

Examples of graphene include a sheet in which carbon atoms form a hexagonal network in the form of a honeycomb, and has a characteristic of being thin with one atom and having high mobility electrons on the sheet.

The metallic conductive material is not particularly limited as long as conductivity is obtained, but a conductive material having a diameter of 100 nm or less is preferable. Examples of the conductive material having a diameter of 100 nm or less include metal nanorods and metal nanowires. Among these, metal nanowires are preferable.

Examples of metal species of the metallic conductive material include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, and titanium. Bismuth, antimony, lead, alloys thereof, and the like. Among these, copper, silver, gold, platinum, palladium, nickel, and alloys thereof are preferable from the viewpoint of excellent conductivity, and those mainly containing silver or alloys of silver and metals other than silver are more preferable. In addition, containing said silver mainly means containing 50 mass% or more of silver in metal nanowire, Preferably it contains 90 mass% or more. Moreover, platinum, osmium, palladium, iridium, etc. are mentioned as a metal used with the said alloy with silver. These may be used alone or in combination of two or more.

There is no restriction | limiting in particular as a shape of metal nanowire, According to the objective, it can select suitably, For example, it can take arbitrary shapes, such as a column shape, a rectangular parallelepiped shape, and a column shape in which a section becomes a polygon, but it is high. For applications that require transparency, a cylindrical shape and a cross-sectional shape with rounded polygonal corners are preferred.

The thickness of the film having the conductive material-containing layer is not particularly limited, but is preferably in the range of 0.005 to 1 μm.

As the film having the conductive material-containing layer, a commercially available film may be used, or a manufactured film may be used. As a specific method for producing a film having a conductive material-containing layer, a method for producing a film having a conductive material-containing layer described in JP2013-924A is described in JP2011-086413A. A manufacturing method etc. can be illustrated.

The circuit board of the present invention is characterized in that the circuit pattern of the present invention is formed on a film having a conductive material-containing layer.
The circuit pattern of the present invention is produced by forming the circuit pattern of the present invention on the film having the conductive material-containing layer by the above-described method for producing a circuit pattern of the present invention.
The circuit board of the present invention can be used as an electric wiring circuit board such as a touch panel substrate, a display device substrate, and an information processing terminal device substrate.

Hereinafter, the reactive resin composition using the thermosetting resin composition (B) in place of the photosensitive resin composition (C) will be described.
A thermosetting resin composition (B) means what a polymerization reaction advances by attaching | subjecting heat processing.

Thermosetting resin composition (B)
The thermosetting resin composition (B) contains a thermosetting compound (b-1) and a curing agent (b-2). Examples of the thermosetting compound (b-1) include thermosetting resins such as epoxy resins, phenol resins, polyimide resins, polyurethane resins, alkyd resins, melamine resins, silicone resins, urea resins and the like. be able to. Among these, an epoxy resin is preferable from the viewpoint of easy handling and adhesion to a film having low heat resistance.

Moreover, in order to obtain high adhesiveness with a film having a conductive material-containing layer, and conductivity, the content of the thermosetting resin composition (B) in the reactive resin composition is the amount of the thermosetting resin used. What is necessary is just to select suitably according to a property. In addition, when there is too little content of the thermosetting resin composition (B) in a reactive resin composition, sufficient adhesiveness with the film which has a conductive material content layer will not be obtained, but a thermosetting resin composition ( When there is too much content of B), the metal fine particles (A) which have electroconductivity will be inhibited, and sufficient electroconductivity will not be obtained.

Thermosetting compound (b-1)
The thermosetting compound (B-1) in the thermosetting resin composition (B) has an epoxy group that provides high adhesion in terms of adhesion to a film having a conductive material-containing layer. Compounds are preferred. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol type epoxy resin such as bisphenol S type epoxy resin, hydrogenated bisphenol A, hydrogenated bisphenol F and other hydrogenated Bisphenol type epoxy resin, phenol novolak type epoxy resin, novolak type epoxy resin such as cresol novolak type epoxy resin, alkyl diphenol type epoxy resin such as tert-butyldiphenylglycidyl ether and methyldiphenylglycidyl ether, triglycidyl-p-aminophenol And polyfunctional glycidyl amine resins such as triglycidyl isocyanurate, polyfunctional glycidyl ether resins such as triphenyl glycidyl ether methane, and alicyclic ethers. Carboxymethyl resins, epoxy acrylates, oxetanes, urethane-modified, siloxane-modified, imide-modified, naphthalene-modified, can be exemplified acrylic-modified compounds having an epoxy group of various modified products of such vinyl-modified. Among them, a compound having an epoxy group having a linear bifunctional skeleton having a glycidyl group at the terminal is preferable from the viewpoint of compatibility with a solvent, and a bisphenol A type, bisphenol F type, or alkyldiphenol type skeleton is preferable. More preferably, the compound is at least one selected from compounds having an epoxy group.

The content of the thermosetting compound (b-1) in the thermosetting resin composition (B) is 0.1 to 50 parts by weight with respect to 100 parts by weight of the conductive metal fine particles (A). It is preferable that it is the range of these. If it is the said range, when it hardens | cures, sufficient adhesiveness with the film which has a conductive material content layer will be obtained.

Curing agent (b-2)
The curing agent (b-2) in the thermosetting resin composition (B) is usually a thermosetting resin curing agent as long as it is compatible with the thermosetting compound (b-1) used. A known curing agent can be used as appropriate. Specific examples include phenolic curing agents, acid anhydride curing agents, curing agents such as dicyandiamide, diamine curing agents, imidazole curing agents, tertiary amine curing agents, and phosphine curing agents. can do. Only 1 type may be used for the said hardening | curing agent, and it is also possible to use 2 or more types in combination.

The curing agent (b-2) is generally an addition polymerization type curing agent (i) that is a curing agent that reacts in an equivalent amount with the thermosetting compound (b-1), for example, phenols, acid anhydrides. , An ionic polymerization type curing agent (ii) that is a curing agent that reacts in a small amount with a thermosetting compound (b-1) and a curing agent of an amine such as dicyandiamide or diamine. It can be classified into curing agents such as secondary amines or phosphines. Moreover, you may use together hardening accelerators, such as imidazole, organic phosphonium, DBU (azabicycloundecene), as a regulator of hardening rate.

Examples of the addition polymerization type curing agent (i) include chain aliphatic polyamines such as diethylenetriamine and diethylaminopropylamine, cyclic aliphatic polyamines such as N-aminoethylpiverazine and isophoronediamine, and aromatic polyamines such as xylenediamine. , Polyamides, acid anhydrides such as methyltetrahydrophthalic anhydride and hexahydrophthalic anhydride, phenols such as dicyclopentadiene and triphenylalkyl, thiols such as liquid polymercaptan and polysulfide resin, boron trifluoride-amine complex And a curing agent such as dicyandiamide.

Examples of the ionic polymerization type curing agent (ii) include a cation polymerization type or an anion polymerization type. Specifically, examples of the anion polymerization type include benzyldimethylamine and 2,4,6-tris (dimethyl). Examples thereof include secondary or tertiary amines such as (aminomethyl) phenol, and imidazoles such as 2-methylimidazole and 1-cyanoethyl-2-methylimidazole. Examples of the cationic polymerization type include onium salts such as sulfonium and iodonium.

When an addition polymerization curing system is used, the curing agent (b-2) is generally an addition polymerization type (i) acid anhydride that does not undergo a curing reaction at room temperature (near storage temperature) and exhibits relatively fast curing properties. Things are preferred. By using the addition polymerization type (i) curing agent, the curing start temperature of the thermosetting resin composition (B) can be controlled. Moreover, the addition amount of the hardening | curing agent (b-2) in the thermosetting resin composition (B) in the case of using the addition polymerization type (i) hardening | curing agent is the compound (b-1) which has thermosetting property. On the other hand, a range of 0.9 to 1.1 equivalents is preferable, and a range of 0.95 to 1.05 equivalents is more preferable. In addition, when there is too little addition amount of a hardening | curing agent (b-2), many unreacted compounds of the compound (b-1) which has thermosetting will remain, and adhesiveness with a film will be impaired. Moreover, when there is too much addition amount, many unreacted hardening | curing agents of a hardening | curing agent (b-2) remain | survive, and adhesiveness with a film will be impaired. Furthermore, the curing start temperature can be easily controlled by adding a small amount of a curing accelerator to the composition containing the thermosetting compound (b-1) and the ionic polymerization type curing agent (ii). it can.

When a homopolymerization curing system is used, an imidazole that is an ionic polymerization type curing agent (ii) is preferable as the curing agent (b-2). When the ion polymerization type curing agent (ii) is used, the weight ratio of the thermosetting compound (b-1) / curing agent (b-2) in the thermosetting resin composition (B) is 100 / The range is preferably from 0.1 to 100/10, and more preferably from 100/1 to 100/5.

Method for producing circuit pattern in case of using reactive resin composition containing thermosetting resin composition (B) In forming circuit pattern on film having conductive material-containing layer, thermosetting resin composition When the reactive resin composition containing the product (B) is used, the reactive resin composition is applied onto the film by various means such as screen printing, transfer printing, dipping, brush coating, and coating using a dispenser. The reactive resin composition applied on the film is heat-treated by a known method, and the thermosetting resin composition (B) is cured to obtain a circuit pattern.

As a method for producing a circuit pattern in the case of using a reactive resin composition containing a thermosetting resin composition (B), a film having a process (preparation process) for preparing a reactive resin composition and a conductive material-containing layer A method of forming a circuit pattern on the film (circuit forming step), and a step of curing the circuit pattern by performing heat treatment on the circuit pattern formed on the film having the conductive material-containing layer (curing step). Can be illustrated.

In the preparation step, the conductive fine metal particles (A), the thermosetting resin composition (B), and the aprotic polar solvent or nonpolar solvent (D) 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 reactive resin composition. Examples of such a method include a method using a mechanical stirrer, magnetic stirrer, ultrasonic disperser, planetary mill, ball mill, planetary mixer, or three rolls. A method using a planetary mill is preferable from the viewpoint of easy handling, and a method using three rolls is preferable from the viewpoint of uniform dispersion, and two or more methods may be combined.

Examples of the method for forming a circuit pattern in the circuit forming step include a discharge method and a printing method. Examples of the discharge method include an inkjet method and a dispensing method. Examples of the printing method include screen printing, and rotary printing such as flexographic printing, offset printing, gravure printing, and gravure offset printing. .

In the curing step, the circuit pattern formed on the film having the conductive material-containing layer is subjected to heat treatment, whereby the thermosetting resin composition (B) is cured and a circuit pattern is obtained. Any heat treatment method may be used as long as the formed circuit pattern can be efficiently heated, such as heating in a drying furnace in which air heated or circulated in a desired atmosphere is circulated or convected, infrared Examples thereof include a heating method using electromagnetic waves such as a heater, and a method of heating a heated metal or ceramic in contact with the film. What is necessary is just to select the curing temperature in the case of heat processing suitably according to the thermosetting resin composition (B) to be used, the organic solvent (E), and the heat-resistant temperature of a film, For example, it is preferable to set it as 70 degreeC or more. Moreover, it is preferable to set it as 130 degrees C or less, and it is more preferable to set it as 120 degrees C or less especially. The curing time is preferably 10 to 150 minutes. Sufficient adhesion with the film having the conductive material-containing layer can be obtained by performing the curing reaction in the above range.

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

(1) Reactive resin composition materials The materials used in Examples and Comparative Examples described below are described below.

Conductive metal fine particles (A)
Conductive metal fine particles; silver fine particles M (granular, average particle size 1.1 μm)
The average particle diameter of the conductive fine metal particles is a value measured by a particle size distribution measuring device.

Photosensitive resin composition (C)
(Binder polymer: c-1)
Binder polymer P: Acrylic polymer AA-6 (number average molecular weight 6,000, manufactured by Toa Gosei Co., Ltd.)

(Polymerizable compound: c-2)
Polymerizable compound R: Light acrylate PE-3A (pentaerythritol triacrylate, manufactured by Kyoeisha Chemical Co., Ltd.)

(Initiator: c-3)
Photopolymerization initiator I: Irgacure 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, manufactured by BASF)

(Aprotic polar solvent or nonpolar solvent; D)
Solvent S1: N-methyl-2-pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.)
Solvent S2: 2-pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.)
Solvent S3: Tetrahydrofuran (Wako Pure Chemical Industries, Ltd.)
Solvent S4: Toluene (Wako Pure Chemical Industries, Ltd.)
Solvent S5: Cyclohexanone (Wako Pure Chemical Industries, Ltd.)

(Organic solvent; E)
Organic solvent S: Butyl carbitol acetate (manufactured by Wako Pure Chemical Industries, Ltd.)

The reactive resin compositions used in Examples and Comparative Examples have the same amount of components other than the aprotic polar solvent or the nonpolar solvent (D). Table 1 shows the composition of components other than the aprotic polar solvent or the nonpolar solvent (D).
In Examples 1 to 5, an aprotic polar solvent or an apolar solvent (D) is added, and in Comparative Example 1, an aprotic polar solvent or an apolar solvent (D) is not added.

(2) Electric wiring circuit pattern formation
Examples 1 to 5 and Comparative Example 1
(I) Reactive resin composition preparation step According to the composition shown in Table 1, each component was weighed so that the total weight of the reactive resin composition was 100 g. Awatori Netaro AR-100) was used for a total of 10 minutes. At this time, kneading was stopped every other minute so that the reactive resin composition did not have too much heat. Then, it knead | mixed using the three rolls and produced the paste-like reactive resin composition. Further, for the composition, an aprotic polar solvent or a nonpolar solvent (solvent S1: N-methyl-2-pyrrolidone (Example 1), solvent S2: 2-pyrrolidone (Example 2), solvent S3: tetrahydrofuran (Example 3), Solvent S4: Toluene (Example 4), Solvent S5: Cyclohexanone (Example 5)) were added to prepare a reactive resin composition. Moreover, the thing which does not add an aprotic polar solvent or a nonpolar solvent was made into the comparative example 1.
The amount of the aprotic polar solvent or the nonpolar solvent added was 1% by weight with respect to the reactive resin composition.

(Ii) Coating step and exposure step A silver nanowire PET film (having a layer containing silver nanowires on a PET film) having a thickness of 50 μm is used as a substrate, and the above-mentioned surface on the silver nanowire-treated surface side The reactive resin composition was uniformly applied by screen printing and dried at 70 ° C. for 10 minutes to obtain a coating film having a coating thickness of 7 μm. Subsequently, the photomask on which the circuit shown in FIG. 1 was drawn was brought into close contact with the coating film, and ultraviolet rays were irradiated using a metal halide lamp to cure the reactive resin composition.
FIG. 1A is a top view schematically showing a circuit for conductivity evaluation, and FIG. 1B is a cross-sectional view schematically showing a layer structure of the circuit for conductivity evaluation.

(Iii) Development step and evaluation thereof Next, an unexposed portion was removed using a 0.5% aqueous sodium carbonate solution as a developer, and unnecessary developer was removed by washing with water. Then, it dried for 10 minutes at 120 degreeC with the warm air dryer, the water | moisture content was removed, and the circuit was obtained.

(3) Evaluation of physical properties For the obtained circuit, the degree of variation in resistance value at the interface where the silver nanowire PET film and the cured coating of the reactive resin composition are in contact was evaluated.

(Measurement of resistance value)
As the evaluation circuit, the one shown in FIGS. 1A and 1B was used.
In the evaluation circuit shown in FIGS. 1A and 1B, a silver nanowire layer 2 is provided on a PET film 1, and circuit patterns 3a and 3b are drawn thereon.
Both ends of the circuit shown in FIG. 1 (a) are circuit patterns 3a and 3b formed using a reactive resin composition, and the central band-like portion is the lower silver nanowire layer 2.
That is, the current when measuring the resistance value flows through the path of the circuit pattern 3a-silver nanowire layer 2-circuit pattern 3b.
Resistance values at both ends of the reactive resin composition were measured using a digital multimeter (model number: KU-2608, manufactured by Kaise Corporation). The film thickness of the reactive resin composition is measured using a digimatic micrometer (model number: MDC-SB, manufactured by Mitutoyo Corporation) to avoid the influence of the thickness of the reactive resin composition on the resistance value. Was selected for evaluation. The average resistance value represents the average value of the five circuits, and the maximum and minimum resistance values represent the maximum value and the minimum value of the resistance values in the five circuits.

(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 circuit peeling was confirmed. The case where the coating film was not peeled off was indicated as “◯”, and the case where it was peeled off was indicated as “X”.

Table 2 shows the evaluation results of the examples and comparative examples.

From the results of Table 2, it was confirmed that by adding the aprotic polar solvent or the nonpolar solvent (D), the variation in the resistance value becomes smaller than that of the additive-free solvent.

Examples 6 to 8 and Comparative Example 2
In the process of preparing the reactive resin composition in Example 1, the addition amount of N-methyl-2-pyrrolidone, which is an aprotic polar solvent, was 0.1% by weight (Comparative Example 2), 5% by weight (Example 6). ) Changed to 10% by weight (Example 7) and 15% by weight (Example 8), applied to a film substrate, exposed and developed, and reacted with the silver nanowire PET film by the measurement method described above. The degree of variation in resistance value at the interface with which the cured film of the resin composition is in contact was evaluated. The results are shown in Table 3 together with the results of Example 1 in which the addition amount of N-methyl-2-pyrrolidone which is an aprotic polar solvent is 1% by weight.

比較例２に示すように、非プロトン性極性溶媒又は無極性溶媒（Ｄ）の添加量０．１重量％では抵抗値のばらつきが大きく効果が低かった。実施例１及び６〜８に示すように、非プロトン性極性溶媒又は無極性溶媒（Ｄ）添加量が１〜１５重量％であると抵抗値のばらつきが小さくなった。

As shown in Comparative Example 2, when the addition amount of the aprotic polar solvent or the nonpolar solvent (D) was 0.1% by weight, the resistance value varied greatly and the effect was low. As shown in Examples 1 and 6 to 8, when the addition amount of the aprotic polar solvent or the nonpolar solvent (D) was 1 to 15% by weight, the variation in resistance value became small.

The present invention can be effectively used in the field of manufacturing various electric wiring circuit boards.

DESCRIPTION OF SYMBOLS 1 PET film 2 Silver nanowire layer 3a, 3b Circuit pattern

Claims (6)

Conductive fine metal particles (A);
A photosensitive resin composition (C);
Containing an aprotic polar solvent or a nonpolar solvent (D),
A reactive resin composition used for a film having a conductive material-containing layer,
The reactive resin composition, wherein the content of the aprotic polar solvent or the nonpolar solvent (D) is 0.2 to 15% by weight with respect to the reactive resin composition. The aprotic polar solvent or nonpolar solvent (D) is at least selected from the group consisting of ether solvents, ketone solvents, amine solvents, amide solvents, nitro solvents, and aromatic hydrocarbon solvents. The reactive resin composition according to claim 1, which is one type. The said photosensitive resin composition (C) contains a binder polymer (c-1), a polymeric compound (c-2), and an initiator (c-3). Reactive resin composition. The reactive resin composition according to any one of claims 1 to 3, wherein the conductive fine metal particles (A) have an average particle size of 0.1 µm or more and 10 µm or less. A circuit pattern formed using the reactive resin composition according to claim 1. 6. A circuit board, wherein the circuit pattern according to claim 5 is formed on a film having a conductive material-containing layer.

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