JP2016184084A - Photosensitive conductive ink and use of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive conductive paste having excellent developability with a diluted alkali aqueous solution, a cured product of the paste, and a laminate with a conductive pattern.SOLUTION: A photosensitive conductive ink is provided, which comprises: a component (A) having an acidic functional group, an acid value of 5-200 (mgKOH/g), and a number average molecular weight of 2,000 or more; a compound (B) having a functional group that can neutralize at least a part of the acidic functional group in the component (A); conductive particles (C); a photopolymerization initiator (D); and a monomer (E) having an active energy ray-reactive functional group and a number average molecular weight of less than 2,000.SELECTED DRAWING: None

Description

  The present invention relates to a conductive ink excellent in photosensitivity to active energy rays and developability, and a laminate with a conductive pattern obtained using the conductive ink.

  Etching methods and printing methods are known as means for forming thin parts for electronic parts, electromagnetic wave shields, or means for forming conductive circuits. The etching method is a method of dissolving or removing the surface or shape of a metal chemically or electrochemically, and is a processing technique in a broad sense including the surface treatment. Etching is mainly performed in order to obtain a desired pattern shape on the metal film. However, since the process is generally complicated and the waste liquid treatment is necessary in the subsequent process, it is expensive and problematic. In addition, since the conductive circuit formed by the etching method is formed of a metal material such as aluminum or copper, there is a problem that the conductive circuit is weak against physical impact such as bending.

  As a technique for solving these problems and forming a conductive circuit at a lower cost, conductive ink is attracting attention. A conductive circuit can be easily formed by printing using conductive ink. In addition, electronic components can be expected to be smaller and lighter, improve productivity, and reduce costs. For this reason, research and development on printable conductive ink has been energetically performed, and many proposals have been made.

  Patent Document 1 discloses the use of an acrylic copolymer having a carboxyl group and an ethylenically unsaturated group in the side chain as a photosensitive conductive paste for forming a conductor pattern on a ceramic circuit board. Yes. Since it is for a ceramic circuit board, after pattern formation, the organic substance such as the acrylic copolymer contained in the paste is completely oxidized and evaporated, held at 400 to 550 ° C. for 1 to 3 hours, and then 600 to Baking at 1000 ° C. forms a circuit pattern.

  Patent Document 2 discloses a photocurable thermosetting conductive composition that contains an organic binder (B) and (E) a thermosetting resin and does not require firing.

  Patent Documents 3 and 4 propose an epoxy resin having a carboxyl group and an ethylenically unsaturated group in the side chain as the photosensitive resin of the photosensitive paste.

In addition, although it is not an example of conductive ink, Patent Document 5 discloses a second grade as a photopolymerizable composition for forming a printing plate that can be developed with warm water at 40 ° C. for about 2 minutes. Alternatively, a photopolymerizable composition containing a vinyl compound having a tertiary nitrogen atom is disclosed.
Patent Document 6 discloses the formation of a color filter in which at least a part of the carboxyl group in the hydrophilic resin (A) having a carboxyl group is neutralized with a super strong basic compound (E) in order to improve color purity. A photosensitive resin composition is disclosed.

JP 05-271576 A JP 2003-162921 A JP 2010-95597 A JP 2010-195860 A Japanese Patent Laid-Open No. 61-22339 JP 2010-102169 A

However, the photosensitive conductive inks described in Patent Documents 1 to 4 have insufficient developability.
The inventions described in Patent Documents 5 and 6 relate to a composition for forming a printing plate or a color filter, and not a conductive ink.

  An object of this invention is to provide the photosensitive electrically conductive paste excellent in the image development by dilute alkaline aqueous solution, its hardened | cured material, and a laminated body with a conductive pattern.

In order to solve the above-mentioned problems, the present inventors have intensively studied and as a result, a component (A) having an acidic functional group and a functional group capable of neutralizing at least a part of the acidic functional group in the component (A). The present inventors have found that a photosensitive conductive ink containing a compound (B) having a salt that solves the above-mentioned problems, and has completed the present invention.
That is, the present invention has a component (A) having an acidic functional group, an acid value of 5 to 200 (mgKOH / g), and a number average molecular weight of 2,000 or more, and the acidity in the component (A). A compound (B) having a functional group capable of neutralizing at least a part of the functional group, a conductive particle (C), a photopolymerization initiator (D) and an active energy ray-reactive functional group, and having a number average molecular weight The present invention relates to a photosensitive conductive ink containing a monomer (E) that is less than 2,000.

In the present invention, the compound (B) is preferably an organic base having a boiling point of 200 ° C. or less, and is preferably a quaternary ammonium salt.
Furthermore, in this invention, it is preferable that content of a compound (B) is an quantity which can neutralize 5-95% of the acidic functional groups which a component (A) has.

In the present invention, the number average molecular weight of the component (A) is preferably 2,000 or more and 1,000,000 or less.
The component (A) is preferably a component (A1) having an active energy ray-reactive functional group, and the active energy ray-reactive functional group equivalent of the component (A1) is 300 to 5000 (g / mol). It is preferable.

The component (A) is a group consisting of a phenoxy resin, an acrylic resin, a urethane resin, a polyester resin, a polyolefin resin, a urea resin, a urethane urea resin, an epoxy resin, a polyamide resin, and a polyimide resin. It is preferable that it is at least one selected from more.
Moreover, it is preferable that the acidic functional group which the said component (A) has is at least 1 chosen from the group which consists of a carboxyl group, a sulfo group, a phosphoric acid group, and a phenolic hydroxyl group.

  In this invention, it is preferable that content of electroconductive particle (C) is 60-95 mass% in solid content of 100 mass% of photosensitive conductive ink.

Furthermore, the present invention relates to a component (A) having an acidic functional group, an acid value of 5 to 200 (mgKOH / g), and a number average molecular weight of 2,000 or more. A neutralized product (AB) obtained by neutralizing with a compound (B) having a functional group capable of neutralizing at least a part of the group,
The present invention relates to a photosensitive conductive ink containing a monomer (E) having conductive particles (C), a photopolymerization initiator (D) and an active energy ray-reactive functional group and having a number average molecular weight of less than 2,000.

Furthermore, the present invention provides the component (A) having an acidic functional group with an acid value of 5 to 200 (mgKOH / g) and a number average molecular weight of 2,000 or more. Compound (B) having a functional group capable of neutralizing at least a part of the functional group, to obtain a neutralized product (AB) of the component (A),
Next, the neutralized product (AB), conductive particles (C), photopolymerization initiator (D), and monomer (B) having an active energy ray-reactive functional group and a number average molecular weight of less than 2,000 The present invention relates to a method for producing a photosensitive conductive ink to be mixed.

  The present invention relates to a cured product obtained by curing the photosensitive conductive ink of the present invention.

Moreover, this invention is a laminated body with a conductive pattern which comprises the base material and the conductive pattern formed on the said base material, Comprising: The said conductive pattern is formed with the photosensitive conductive ink of the said this invention. It is related with the laminated body with a conductive pattern.
It is preferable to further include an insulating layer laminated so as to cover the conductive pattern.
Moreover, it is preferable that the said laminated body with a conductive pattern is electrically connected with the said conductive pattern, and the other conductive pattern which has a predetermined pattern is further provided between the said base material and the said conductive pattern.
The other conductive film is preferably a transparent conductive film mainly composed of indium oxide doped with tin.
Furthermore, it is preferable that the laminated body with a conductive pattern of this invention is used for a touch screen panel use.

  According to the present invention, it is possible to provide a photosensitive conductive paste excellent in developability with a dilute alkaline aqueous solution, a cured product thereof, and a laminate with a conductive pattern.

It is a schematic sectional block diagram of the principal part of an example of the resistive film type touch screen panel which applied the conductive ink of this invention to the wiring structure, and is equivalent to the AA 'cut line of FIG. It is a perspective view which shows the lamination | stacking state of a suitable resistive film type touch screen panel by applying the conductive ink of this invention to a wiring structure.

  Hereinafter, embodiments of the present invention will be described in detail. In addition, as long as it agree | coincides with the meaning of this invention, other embodiment can also belong to the category of this invention. In the present specification, the description “any number A to any number B” means a range larger than the numbers A and A but smaller than the numbers B and B. In addition, the expression “(meth) acrylo” described in the present specification and claims includes both the compound read as “acrylo” and the compound read as “methacrylo”. The same definition applies to “(meth) acryl” and “(meth) acrylate”.

[Photosensitive conductive ink]
The photosensitive conductive ink comprises a component (A) having an acidic functional group, a compound (B) having a functional group capable of neutralizing at least a part of the acidic functional group, conductive particles (C), a photopolymerization initiator ( D) and a monomer (E) having an active energy ray-reactive functional group.

[Component (A)]
The component (A) used in the present invention may be any compound having an acidic functional group, but preferably a phenoxy resin, an acrylic resin, a urethane resin, a polyester resin, a polyolefin resin, a urea resin, a urethane. Urea-based resins, epoxy-based resins, polyamide-based resins, and polyimide-based resins are preferable, and acrylic resins, urethane-based resins, and phenoxy-based resins are more preferable.

  Here, the phenoxy resin referred to in the present invention includes a resinous substance obtained by polymerizing bisphenols and an epoxy compound having two or more epoxy groups in the molecule, in addition to those synthesized from bisphenols and epichlorohydrin.

The number average molecular weight of a component (A) is 2000 or more, Preferably, it is 3000-1 million. When the number average molecular weight is small, viscosity at the time of coating, handling, and developability after photocuring can be improved. On the other hand, when the number average molecular weight is large, the heat resistance, heat resistance, etc. of the finally obtained coating film can be improved. In addition, by increasing the number average molecular weight, flexibility can be improved, and adhesion to a substrate for which it is difficult to ensure adhesion can be improved.
The acid value of a component (A) is 5-200 mgKOH / g, Preferably, it is 10-170 mgKOH / g. When the acid value of the component (A) is from 5 to 200 mgKOH / g, excellent developability is easily imparted.

  Although the acidic functional group of a component (A) is not specifically limited, Preferably they are a carboxyl group, a sulfo group, a phosphoric acid group, and a phenolic hydroxyl group, More preferably, they are a carboxyl group and a sulfo group.

Moreover, it is preferable that the component (A) in this invention has an ethylenically unsaturated group, It is preferable that the ethylenically unsaturated group equivalent is 300-5000 g / eq, More preferably, it is 300-3000 g / eq. It is. When the ethylenically unsaturated group equivalent is designed in a range close to 300 g / eq, the photosensitivity of the resulting coating film is increased, so that a good pattern shape can be easily obtained during development. On the other hand, when designing in a range close to 5000 g / eq, since it becomes an appropriate photocrosslinking point, adhesion to a base material that makes it difficult to ensure adhesion by increasing the flexibility of the finally obtained coating film, etc. Can be improved.
The “ethylenically unsaturated group equivalent” as used in the present invention is a theoretical value calculated from the weight of raw materials used during the synthesis of the resin, and the weight of the resin is the ethylenically unsaturated group present in the resin. It is divided by the number of groups and corresponds to the weight of the resin per mole of ethylenically unsaturated groups, that is, the reciprocal of the ethylenically unsaturated group concentration.

The solvent used for the synthesis | combination of a component (A) can be suitably selected according to a final use and the solubility of a reaction material.
For example, when it is used in the process of forming a fine pattern by photolithography after forming a rough pattern by screen printing, it is necessary to suppress ink solidification on the screen mesh due to solvent drying in the screen printing process. It is preferable to use the solvent. Examples of the high boiling point solvent in this case include ethylene glycol monohexyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, and dipropylene glycol monobutyl ether. Examples include dialkylene glycol monoalkylene ether compounds, trialkylene glycol monoalkylene ether compounds such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether.
In the present invention, these solvents may be used alone or in combination, if necessary, and may be used in combination. Or a solvent may be added.

[Compound capable of neutralizing acidic functional group (B)]
In the photosensitive conductive ink composition of the present invention, a compound (B) capable of neutralizing an acidic functional group is used in order to improve the developability of the resin. Examples of the basic compound (B) that can be used in the present invention include inorganic bases and organic bases.

  Inorganic bases include ammonia, alkali metal oxides, alkali metal hydroxides, alkali metal peroxides, alkali metal carbonates, alkali metal bicarbonates, alkaline earth metal oxides, alkaline earth metal hydroxides Products, alkaline earth metal peroxides, alkaline earth metal carbonates and the like.

Examples of the organic base include methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N-butylmethanolamine, N-methylethanolamine, N -Ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethyl Butanolamine, N-propylbutanolamine, N-butylbutanolamine, N, N-dimethylmethanolamine, N, N-diethylmethanolamine, N, N-dipropylmethanolamine N, N-dibutylmethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N, N-dibutylethanolamine, N, N-dimethylpropanolamine, N, N-diethylpropanolamine, N, N-dipropylpropanolamine, N, N-dibutylpropanolamine, N, N-dimethylbutanolamine, N, N-diethylbutanolamine, N, N-dipropylbutanolamine, N, N-dibutylbutanolamine, N-methyldimethanolamine, N-ethyldimethanolamine, N-propyldimethanolamine, N-butyldimethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanol Min, N-butyldiethanolamine, N-methyldipropanolamine, N-ethyldipropanolamine, N-propyldipropanolamine, N-butyldipropanolamine, N-methyldibutanolamine, N-ethyldibutanolamine, N -Propyldibutanolamine, N-butyldibutanolamine, N- (aminomethyl) methanolamine, N- (aminomethyl) ethanolamine, N- (aminomethyl) propanolamine, N- (aminomethyl) butanolamine, N -(Aminoethyl) methanolamine, N- (aminoethyl) ethanolamine, N- (aminoethyl) propanolamine, N- (aminoethyl) butanolamine, N- (aminopropyl) methanolamine, N- (aminopropyl) Ethanor Ruamine, N- (aminopropyl) propanolamine, N- (aminopropyl) butanolamine, N- (aminobutyl) methanolamine, N- (aminobutyl) ethanolamine, N- (aminobutyl) propanolamine, N- ( Aminobutyl) butanolamine, methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxybutylamine, butoxymethyl Amine, butoxyethylamine, butoxypropylamine, butoxybutylamine, methylamine, ethylamine, propylamine, butylamine N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tetramethylammonium hydroxide, tetraethylammonium Hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylethylenediamine, tetraethylethylenediamine, tetrapropylethylenediamine, tetrabutylethylenediamine, methylaminomethylamine, methylaminoethylamine, methylaminopropylamine, methylaminobutylamine , Ethylaminomethylamine, ethylaminoethylamine, ethylaminopropylamine, ethylamino Butylamine, propylaminomethylamine, propylaminoethylamine, propylaminopropylamine, propylaminobutylamine, butylaminomethylamine, butylaminoethylamine, butylaminopropylamine, butylaminobutylamine, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, Morpholine, methylmorpholine, diazabicycloocrane, diazabicyclononane, diazabicycloundecene, and tetramethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, tetramethylammonium borohydride as quaternary ammonium salts , Tetrabutylammonium borohydride and the like, but are not limited thereto. These can be used alone or in admixture of two or more.
From the viewpoint of improving the water resistance of a printing ink coating film obtained by printing a photosensitive conductive ink, for example, ammonia, triethylamine, morpholine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, N, It is preferable to use a volatile basic compound having a boiling point below 760 mmHg, such as N-diethylethanolamine, of 200 ° C. or less, and an organic basic compound is particularly preferable.

Examples of the timing for adding the neutralizing agent in the present invention include the synthesis of the component (A), the production of the photosensitive conductive ink, just before the printing operation, and the printing. Both are performed to neutralize the acidic functional group of component (A) and increase the solubility of the resin. Addition can be performed as many times as necessary.
The content of the compound (B) is preferably an amount capable of neutralizing 5% or more of the acidic functional groups of the component (A) from the viewpoint of solubility in a developer, and improves water resistance. From the standpoint, the amount is preferably an amount capable of neutralizing 95% or less of the acidic functional groups of the component (A).

[Conductive particles (C)]
Examples of the conductive particles used in the conductive ink of the present invention include gold, silver, copper, silver-plated copper powder, silver-copper composite powder, silver-copper alloy, amorphous copper, nickel, chromium, palladium, rhodium, ruthenium, Metal powder such as indium, silicon, aluminum, tungsten, morphbutene, platinum, inorganic powder coated with these metals, powder of metal oxide such as silver oxide, indium oxide, tin oxide, zinc oxide, ruthenium oxide, these Inorganic powders coated with metal oxides, carbon black, graphite and the like can be used. These conductive particles may be used alone or in combination of two or more. Among these conductive particles, silver is preferable because of its cost, high conductivity, and little increase in resistivity due to oxidation.

The shape of the conductive particles is not particularly limited as long as the above properties are satisfied, and an indeterminate shape, an aggregated shape, a scale shape, a microcrystalline shape, a spherical shape, a flake shape, and the like can be appropriately used. From the viewpoint of the printability of the high-definition pattern and the adhesiveness of the conductor pattern to the substrate, a spherical or small aggregate having a small particle size is preferable as a relatively small aggregate.
The D50 particle diameter of the conductive particles used in the conductive ink according to the present invention is 0.5 to 8 μm, preferably in the range of 1 to 5 μm, and more preferably in the range of 2 to 4 μm.
Further, BET specific surface area of 0.3 to 5 m ² / g, preferably in the range of 0.8~2.3m ² / g, still in the range of 0.8~2m ² / g preferable.

If the D50 particle diameter of the conductive particles is less than 0.5 μm, the dispersibility of the conductive particles deteriorates when the conductive ink is used, resulting in poor contact between the conductive particles, resulting in a large printed resistance value. There is a possibility. In addition, the cost of the conductive particles increases.
On the other hand, if the D50 particle diameter exceeds 8 μm, the printability of the high-definition pattern may be inferior.
In addition, the D50 particle diameter of the conductive particles was determined by measuring the cumulative particle size (D50) of the volume particle size distribution using a laser diffraction particle size distribution measuring device “SALAD-3000” manufactured by Shimadzu Corporation.

When the BET specific surface area of the conductive particles is less than 0.3 m ² / g, the contact point between the conductive particles decreases, and the contact resistance increases.
In addition, when the BET specific surface area exceeds 5 m ² / g, a large amount of resin is required to coat the surface of the conductive particles. Therefore, the wetness with respect to the epoxy resin as the binder resin is inferior. This is not preferable because the fluidity is deteriorated and the leveling property of the surface of the printed coating film is lowered. Moreover, since many resin is required to coat | cover the surface of electroconductive particle, the adhesiveness of the electroconductive pattern with respect to a base material also falls.
BET specific surface area is a method of adsorbing molecules whose adsorption occupation area is known to the powder particle surface at the temperature of liquid nitrogen, and obtaining the specific surface area of the sample from the amount, using low-temperature low-humidity physical adsorption of inert gas This is the BET method. The BET specific surface area is defined as a value calculated by using the following formula (1) as a surface area measured using a flow type specific surface area measuring device “Flowsorb II” manufactured by Shimadzu Corporation.
Formula (1) Specific surface area (m ² / g) = surface area (m ² ) / powder mass (g)

  The photosensitive conductive ink of the present invention preferably contains 60 to 95% by mass of conductive particles (C), more preferably 70 to 95% by mass, and more preferably 85 to 95% by mass in 100% by mass of the solid content of the ink. More preferably, the content is 95% by mass. The conductive particles are preferably 60% by mass or more from the viewpoint of the conductivity of the cured coating film, and preferably 95% by mass or less from the viewpoints of adhesion of the cured coating film to the substrate and mechanical strength.

[Photoinitiator (D)]
The photopolymerization initiator (D) is used for curing the photosensitive conductive ink with active energy rays. The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization by photoexcitation. For example, a monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, an acylphosphine oxide compound, an aminocarbonyl A compound etc. can be used. As the active energy ray, ultraviolet rays are preferable.

  Specific examples of the monocarbonyl compound include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 2-hydroxy-3- (4-benzoyl-phenoxy) -N, N, N-trimethyl-1- Propanamine hydrochloride, 4-benzoyl-N, N-dimethyl-n- [2- (1-oxo-2-propenyloxyethyl)] methammonium bromide, 2- / 4-iso-propylthioxanthone, 2, 4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9Hthioxanthone-2-yloxy) -N, N, N-trimethyl-1-propanamine hydrochloride, benzoylmethylene-3-methylnaphtho (1,2- ) Thiazoline, and the like.

  Examples of the dicarbonyl compound include 1,7,7-trimethyl-bicyclo [2.1.1] heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzene. Examples include acetate and 4-phenylbenzyl.

  Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- ( 4-Isopropylphenyl) 2-hydroxy-di-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one polymerization , Diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyla No-1- (4-morpholino-phenyl) butan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2- Morpholino-propanonyl) -9-butylcarbazole and the like.

  Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide.

Examples of aminocarbonyl compounds include methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-nbutoxyethyl-4- (dimethylamino) benzoate, isoamyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethyl benzoate, 4,4′-bis-4-dimethylaminobenzophenone, and the like.
In particular, in the present invention, when 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and thioxanthones are used in combination, the photosensitivity is very low, though it is inexpensive. It is particularly preferred because of its superiority.
These are not limited to the above-mentioned compounds, and any compounds can be used as long as they have the ability to initiate polymerization by ultraviolet rays. These can be used alone or in combination, and the amount used is not limited, but is preferably added in the range of 1 to 20 parts by mass with respect to 100 parts by mass of component (A). Moreover, a well-known organic amine can also be added as a sensitizer.

[Monomer (E) having an active energy ray-reactive functional group]
The photosensitive conductive ink of the present invention further contains an ethylenically unsaturated compound (E) having a number average molecular weight of less than 2000.
Examples of the ethylenically unsaturated compound (E) having a number average molecular weight of less than 2000 include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, cyclohexyl (meta ) Acrylates or monofunctional (meth) acrylates such as polyethylene glycol di (meth) acrylate;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol polyethylene glycol di (meth) acrylate, or neopentyl glycol modified trimethylol Bifunctional (meth) acrylates such as propanedi (meth) acrylate;
Trifunctional or more polyfunctional compounds such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or dipentaerythritol penta (meth) acrylate Functional (meth) acrylates; or
(Meth) acrylic acid adduct of 1,6-hexanediol diglycidyl ether, (meth) acrylic acid adduct of neopentyl glycol diglycidyl ether, (meth) acrylic acid adduct of glycerol diglycidyl ether, bisphenol A diglycidyl Examples include (meth) acrylic acid adducts of ether, (meth) acrylic acid adducts of bisphenol F type epoxy, and (meth) acrylic acid adducts of novolac type epoxy.

  Moreover, what modified | denatured the (meth) acrylate mentioned above further by (poly) alkylene oxide, (poly) caprolactone, etc. can also be used.

  Other examples include tris [2- (meth) acryloyloxyethyl)] isocyanurate or a reaction product of isocyanurate of diisocyanates and hydroxyalkyl (meth) acrylate.

In addition, vinyl ethers such as hydroxyethyl vinyl ether, ethylene glycol divinyl ether, or pentaerythritol trivinyl ether;
Unit cost monomers such as (meth) acrylic acid, styrene, or vinyl acetate; or
A monofunctional monomer having a nitrogen element such as (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, or acrylonitrile can also be used.

  Furthermore, what modified | denatured oligomers, such as a polyurethane, polyester, a methylol melamine resin, polydimethylsiloxane, or rosin, with the (meth) acryloyl group can also be used.

  Other examples include (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.

  In this invention, an ethylenically unsaturated compound (E) may be used individually by 1 type, and may use multiple together. The amount of the ethylenically unsaturated compound (E) used may be determined in consideration of the use of the photosensitive conductive ink of the present invention, and is not particularly limited. It is preferable to add in the ratio of 1-30 mass%. When the amount of the ethylenically unsaturated compound (E) used is more than 1% by mass, the effect of improving the sensitivity by adding the ethylenically unsaturated compound can be obtained. When it is less than 30% by mass, curing proceeds near the exposed surface and internal curing does not easily proceed, and a pattern having sufficient coating strength can be formed.

[Other additives]
In addition to the above, the photosensitive resin composition of the present invention includes, as an optional component, a solvent, a dye, a pigment, a flame retardant, an antioxidant, a polymerization inhibitor, a chain transfer agent, a leveling agent, and a humectant as long as the purpose is not impaired. Viscosity modifiers, antiseptics, antibacterial agents, antiblocking agents, ultraviolet absorbers, infrared absorbers, electromagnetic wave shielding agents, fillers, and the like can be added.

As described above, the photosensitive conductive ink of the present invention preferably contains 60 to 95% by weight, more preferably 70 to 95% by weight of conductive particles (C) in 100% by weight of the ink solid content. More preferably, the content is 85 to 95% by mass.
Therefore, as the photosensitive conductive ink, among the remaining 5 to 40% by mass of the ink solid content, the component (A) is 2 to 38% by mass, the photopolymerization initiator (D) is 0.1 to 5% by mass, It is preferable that the ethylenically unsaturated compound (E) is contained in an amount of 1 to 30% by mass. Among the remaining 5 to 30% by mass of the ink solid content, the component (A) is 4 to 28% by mass, and the photopolymerization initiator (D). It is more preferable that 0.5 to 4% by mass and 1 to 20% by mass of the ethylenically unsaturated compound (E) are contained, and among the remaining 5 to 15% by mass of the ink solid content, the component (A) is 4 to 13%. More preferably, it contains 1-3% by mass of the photopolymerization initiator (D) and 1-9% by mass of the ethylenically unsaturated compound (E).

The photosensitive conductive ink of the present invention can be applied to a metal, ceramics, glass, plastic, wood, slate or the like as a substrate, and is not particularly limited.
Specific types of plastic include polyester, polyolefin, polycarbonate, polystyrene, polymethyl methacrylate, triacetyl cellulose resin, ABS resin, AS resin, polyamide, epoxy resin, melamine resin, and the like. Examples of the shape of the substrate include a film sheet, a plate-like panel, a lens shape, a disk shape, and a fiber shape, but are not particularly limited.

The conductive ink of the present invention can be suitably applied particularly to screen printing, but may be applied to various conventionally known printing methods. In the screen printing method, it is preferable to use a fine mesh screen, particularly preferably a fine mesh screen of about 400 to 650 mesh, in order to cope with high definition of the conductive circuit pattern. At this time, the open area of the screen is preferably about 20 to 50%. The screen wire diameter is preferably about 10 to 70 μm.
Examples of the screen plate include polyester screens, combination screens, metal screens, and nylon screens. Moreover, when printing the thing of a highly viscous paste state, a high tension | tensile_strength stainless steel screen can be used.
The screen printing squeegee may be round, rectangular or square, and an abrasive squeegee can be used to reduce the attack angle (angle between printing plate and squeegee). Other printing conditions and the like may be appropriately designed according to conventionally known conditions.

The photosensitive conductive ink of the present invention can be cured by a known radiation curing method to obtain a cured product, and as active energy rays, electron beams, ultraviolet rays, and visible light of 400 to 500 nm can be used. A thermionic emission gun, a field emission gun, or the like can be used as the electron beam source to be irradiated. For example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used as a source (light source) for ultraviolet light and visible light of 400 to 500 nm. Specifically, an ultra-high pressure mercury lamp, a xenon mercury lamp, or a metal halide lamp is often used because of the point light source and the stability of luminance. The active energy dose to be irradiated, can be set appropriately in the range of 5~2000mJ / cm ^2, it is preferably in the range on the easy of 50~1000mJ / cm ² management process. Further, these active energy rays can be used in combination with heat by infrared rays, far infrared rays, hot air, high-frequency heating or the like.

  In order to increase exposure sensitivity by active energy rays, after applying and drying photosensitive conductive ink, water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to prevent polymerization inhibition by oxygen. After the film is formed, active energy rays can be irradiated from the composition application surface side.

  Furthermore, the photosensitive conductive ink of the present invention is irradiated with an active energy ray from the composition coated surface side through a photomask and immersed in a solvent or an alkaline developer, or sprayed with a developer by spraying or the like. It can be formed by removing the irradiated portion, that is, the uncured portion and developing. As the alkali developer, an aqueous solution such as sodium carbonate or sodium hydroxide is used, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. An antifoaming agent or a surfactant can also be added to the developer.

  Furthermore, the photosensitive conductive ink of this invention forms the coating film which is excellent in various durability and electroconductivity by heat-drying as a post-cure after pattern formation by radiation hardening / development. The post cure is preferably 30 to 2 hours at 100 to 200 ° C. Further, in order to further improve the resistance of the coating film, an active energy ray can be irradiated as necessary after post-curing. By irradiating active energy rays after post-cure, various durability, conductivity, etc. can be further improved.

The laminate with a conductive pattern according to the present invention can be suitably used particularly when a wiring structure is formed on a transparent electrode of a touch screen panel.
Here, an example in which the conductive ink of the present invention is applied to a resistive film type touch screen panel will be described with reference to FIGS. 1 and 2 are simple conceptual diagrams of the resistive touch screen panel, and the number of wirings, the wiring width, and the interval between the wirings are represented as conceptual diagrams. In FIG. 2, the laminated state of each substrate side is schematically shown with the viewpoint placed in the middle of the three layers, the position of the adhesive material 5, with the lower substrate 1 side looking down and the upper substrate 2 side looking up. .

The touch screen panel includes a lower substrate 1 and an upper substrate 2 made of a base material of glass or plastic film (polyethylene terephthalate film, polyethylene naphthalate film, acrylic resin film, polycarbonate film, or the like). Transparent electrodes 6 and 7 such as ITO are partially formed on the lower substrate 1 and the upper substrate 2, respectively. As a result, the lower substrate 1 and the upper substrate 2 and the transparent electrodes 6 and 7 are exposed.
Lower drive electrodes 13 and 14 made of the conductive ink pattern layer 3 are formed on both ends of the transparent electrode 6 on the lower substrate 1, respectively. The conductive ink layer 3 is covered with an insulating layer 4. As shown in FIG. 1, the conductive ink pattern layer 3 is in contact with the substrate 1, the transparent electrode 6 such as ITO, and the insulating layer 4.
Similarly, upper drive electrodes 9 and 10 made of the conductive ink layer 3 are formed on both ends of the transparent conductor 7 on the upper substrate 2.

  Specifically, the conductive ink of the present invention is used for the end of the transparent electrode 7 on the upper substrate 2 side, screen-printed, preliminary drying, exposure, development, and drying steps are performed in this order, and the low-resistance conductive ink. The pattern layer 3 is formed. Next, an insulating resist (not shown) is printed on the conductive ink layer 3 and the upper substrate 2 in the vicinity of the conductive ink pattern layer 3 and the end of the transparent electrode 7 by screen printing or the like. Then, it dries and hardens | cures, forms an insulating layer, and forms the laminated body with an insulating resist of this invention. The same applies to the lower substrate 1 side.

In order to prevent the transparent electrodes 6 and 7 from coming into contact with the transparent electrodes 6 and 7 at an appropriate place on the transparent electrode 6 provided on the lower substrate 1 except when the input is the original purpose, as shown in FIG. Small dot spacers 8 are provided at regular intervals at appropriate positions above.
(See FIG. 1), the insulating layer 4 on the lower substrate 1 side and the upper substrate 2, the lower substrate 1 and the upper substrate 2, and the lower substrate 1 and the upper substrate 2 side are insulated. The layers 4 are each bonded and laminated by the adhesive material 5. The adhesive material 5 can be arranged in a frame shape. In addition, as shown in FIG. 2, the drive electrodes 13 and 14 on the lower substrate 1 side and the upper drive electrodes 9 and 10 on the upper substrate 2 side may be formed to be orthogonal to each other in plan view. Furthermore, connection electrodes 11 and 12 are connected to the drive electrodes 9 and 10 on the upper substrate 2 side by a conductive adhesive, respectively. Similarly, the drive electrodes 13 and 14 on the lower substrate 1 side are connected to the connection electrodes 15 and 16 with a conductive adhesive, respectively.

  The touch screen panel in which the conductive ink pattern layer 3 is formed using the conductive ink of the present invention on each of the lower substrate 1 side and the upper substrate 2 side has good resistance value stability and can be used for various electronic devices over a long period of time. It can be used stably as a component for switching the functions of the above, and has excellent electrical characteristics.

  EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by mass”.

The measurement conditions for GPC are as follows.
<Measurement of number average molecular weight (Mn)>
For measurement of Mn, GPC (gel permeation chromatography) “HPC-8020” manufactured by Tosoh Corporation was used. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on the difference in molecular size. In the measurement of the present invention, “LF-604” (manufactured by Showa Denko KK: GPC column for rapid analysis: 6 mm ID × 150 mm size) is connected in series to the column, the flow rate is 0.6 ml / min, the column temperature. The determination was performed under the condition of 40 ° C., and the number average molecular weight (Mn) was determined in terms of polystyrene.

The acid value was measured according to JIS K0070.
<Measurement of acid value>
About 1 g of a sample is accurately weighed in a stoppered Erlenmeyer flask, and 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution is added and dissolved. To this was added a phenolphthalein test solution as an indicator and titrated with a 0.1N alcoholic potassium hydroxide solution. The end point was when the indicator retained a light red color for 30 seconds. The acid value was determined by the following formula (unit: mgKOH / g).
Acid value (mgKOH / g) = (5.611 × a × F) / S
However,
S: Sample collection amount (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

<Calculation of ethylenically unsaturated group equivalent>
In this invention, the ethylenically unsaturated group equivalent of the photosensitive resin (A) was calculated | required by following Formula. (Unit: g / mol)
Ethylenically unsaturated group equivalent (g / mol) = total solid content of raw material (g) / number of moles of charged ethylenically unsaturated group-containing compound (mol)

<Synthesis of Component (A)>
[Production Example 1]
Process 1
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube and thermometer, 43.2 parts of methyl methacrylate, 43.2 parts of styrene, 13.6 parts of methacrylic acid, diethylene glycol monoethyl ether as a solvent 100 parts of acetate and 1 part of azobisisobutyronitrile as a polymerization initiator were added and stirred at 80 ° C. for 2 to 6 hours under a nitrogen atmosphere to obtain an acrylic resin solution. The acid value was 88.64 mgKOH / g.

Process 2
Next, the nitrogen from the nitrogen introduction tube was stopped and switched to introduction of dry air into this flask, and while stirring, 13.39 parts of glycidyl methacrylate and 0.12 part of hydroquinone as a polymerization inhibitor were added at 80 ° C. The reaction was allowed for 8 hours. After completion of the reaction, diethylene glycol monoethyl ether acetate was added to this solution to adjust the solid content to 50% to obtain component (A).

[Production Examples 2 to 6]
Using the raw materials shown in Table 1, the same operations as in Production Example 1 were carried out to obtain Components (A) in Production Examples 2 to 6. Table 1 shows the number average molecular weight, acid value, and ethylenically unsaturated group equivalent of each component (A).

[Production Example 7]
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 48.5 parts of methyl methacrylate, 48.5 parts of styrene, 3 parts of methacrylic acid, and diethylene glycol monoethyl ether acetate 100 as a solvent And 1 part of azobisisobutyronitrile as a polymerization initiator were added and stirred at 80 ° C. for 2 to 6 hours under a nitrogen atmosphere to obtain component (A).

[Production Examples 8 to 12]
Using the raw materials shown in Table 1, the same operations as in Production Example 7 were performed to obtain Components (A) in Production Examples 8 to 12. Table 1 shows the number average molecular weight, ethylenically unsaturated group equivalent, acid value and the like of each component (A).

[Production Example 13]
Process 1
As an epoxy compound having two or more epoxy groups in a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet pipe, inlet pipe, and thermometer, jER825 (Mitsubishi Chemical Corporation, bisphenol A type epoxy compound, epoxy Equivalent 176 g / eq) 54.27 parts, EX830 (manufactured by Nagase ChemteX Corporation, polyethylene glycol diglycidyl ether, epoxy equivalent 268 g / eq) 82.63 parts, bisphenol A84 as a phenol compound having two or more phenolic OH groups .47 parts, 1.71 parts of triphenylphosphine (hereinafter referred to as TPP) as a catalyst, 1.71 parts of diazabicycloundenecene (hereinafter referred to as DBU), 100 parts of diethylene glycol monoethyl ether acetate as a solvent, and nitrogen flow Under stirring 80 reacted heated 12 hours ° C., to obtain a resin solution.

Process 2
Next, 14.07 parts of Rikacid TH (manufactured by Shin Nippon Rika Co., Ltd., tetrahydrophthalic anhydride) was added as an acid anhydride group-containing compound, and the mixture was reacted at 80 ° C. for 8 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, the mixture was cooled to room temperature to obtain a side chain hydroxyl group carboxyl group-containing resin. The acid value was 22.04 mgKOH / g.

Process 3
Next, the MOI (made by Showa Denko KK) was used as the compound (e) having an isocyanate group and an ethylenically unsaturated group while stirring and switching to introduction of dry air into the flask while switching to introduction of dry air and stirring. , Methacryloyloxyethyl isocyanate) 42.29 parts and 0.12 part of hydroquinone as a polymerization inhibitor were added and reacted at 40 ° C. for 8 hours. After completion of the reaction, diethylene glycol monoethyl ether acetate was added to this solution to adjust the solid content to 50% to obtain component (A).

[Production Examples 14 to 18]
By performing the same operations as in Production Example 13 using the raw materials shown in Table 1, Components (A) in Production Examples 14 to 18 were obtained. Table 1 shows the number average molecular weight, ethylenically unsaturated group equivalent, acid value and the like of each component (A).

[Production Example 19]
Process 1
As an epoxy compound having two or more epoxy groups in a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet pipe, inlet pipe, and thermometer, jER825 (Mitsubishi Chemical Corporation, bisphenol A type epoxy compound, epoxy Equivalent 176 g / eq) 54.27 parts, EX830 (manufactured by Nagase ChemteX Corporation, polyethylene glycol diglycidyl ether, epoxy equivalent 268 g / eq) 82.63 parts, bisphenol A 84. as a phenol compound having two or more phenolic hydroxyl groups. 47 parts, 1.71 parts of triphenylphosphine as a catalyst, 1.71 parts of diazabicycloundenecene, 100 parts of diethylene glycol monoethyl ether acetate as a solvent, heated to 80 ° C. with stirring in a nitrogen stream, and 12 hours React and let the resin solution It was.

Process 2
Next, 11.26 parts of Ricacid TH (manufactured by Shin Nippon Rika Co., Ltd., tetrahydrophthalic anhydride) was added as an acid anhydride group-containing compound, and the reaction was continued for 8 hours at 80 ° C. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, the mixture was cooled to room temperature to obtain component (A).

[Production Examples 20 to 24]
By performing the same operations as in Production Example 19 using the raw materials shown in Table 1, Components (A) in Production Examples 20 to 24 were obtained. Table 1 shows the number average molecular weight, ethylenically unsaturated group equivalent, acid value and the like of each component (A).

[Production Example 25]
In a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, PTG1000SN (manufactured by Hodogaya Chemical Co., Ltd., polytetramethylene glycol, hydroxyl value 110 mgKOH / g) 88.57 parts, dimethylol 38.41 parts of butanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 100 parts of diethylene glycol monoethyl ether acetate as a solvent were added, and the mixture was heated to 60 ° C. with stirring in a nitrogen atmosphere to be uniformly dissolved. Subsequently, 73.02 parts of isophorone diisocyanate was added to the flask, and the temperature was raised to 90 ° C. while stirring and reacted for 8 hours to obtain a urethane resin solution.

Process 2
Next, the nitrogen from the nitrogen introduction tube was stopped and switched to introduction of dry air, and 34.65 parts of glycidyl methacrylate and 0.12 part of hydroquinone as a polymerization inhibitor were added to the flask while stirring. The reaction was allowed to proceed for 8 hours to obtain a hydroxyl group-containing urethane resin solution.

Process 3
Next, 7.07 parts of Ricacid SA (manufactured by Shin Nippon Rika Co., Ltd., succinic anhydride) was added to the flask, and the mixture was further reacted for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, diethylene glycol monoethyl ether acetate was added to this solution to adjust the solid content to 50%, and component (A) was obtained.

[Production Examples 26 to 28]
By performing the same operations as in Production Example 26 using the raw materials shown in Table 1, Components (A) in Production Examples 26 to 28 were obtained. Table 1 shows the number average molecular weight, ethylenically unsaturated group equivalent, and acid value of each component (A).

[Production Example 29]
In a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, PTG1000SN (manufactured by Hodogaya Chemical Co., Ltd., polytetramethylene glycol, hydroxyl value 110 mgKOH / g) 144.22 parts, dimethylol 10.74 parts of butanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 100 parts of diethylene glycol monoethyl ether acetate as a solvent were charged, and the temperature was raised to 60 ° C. with stirring in a nitrogen atmosphere to dissolve uniformly. Subsequently, 45.04 parts of isophorone diisocyanate was added to the flask, and the temperature was raised to 90 ° C. with stirring and reacted for 8 hours. After completion of the reaction, diethylene glycol monoethyl ether acetate was added to this solution to obtain a component (A) which was adjusted to a solid content of 50%.

[Production Examples 30 to 32]
By performing the same operations as in Production Example 29 using the raw materials shown in Table 1, Components (A) in Production Examples 30 to 32 were obtained. Table 1 shows the number average molecular weight, ethylenically unsaturated group equivalent, and acid value of each component (A).

<Photosensitive conductive ink>
[Comparative Example 1]
14 parts by mass (7 parts by mass of solid content) of the component (A) obtained in Production Example 1, and spherical silver powder (D50 particle size 2.8 μm, specific surface area 0.36 m ² / g) as conductive particles (C) 86 parts by mass, IRGACURE 907 (manufactured by BASF Corporation, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one) as a photopolymerization initiator (D) was dissolved. After mixing 6 parts by mass of diethylene glycol monoethyl ether acetate and 4 parts by mass of Aronix M310 (manufactured by Toagosei Co., Ltd., trimethylolpropane PO-modified triacrylate) as a monomer (E) having an active energy ray-reactive functional group. A photosensitive conductive ink of Comparative Example was obtained by dispersing with three rolls.
About the obtained photosensitive conductive ink, developability and electroconductivity (volume resistance value) were evaluated by the method mentioned later. The results are shown in Table 2.

[Example 1]
With respect to 14 parts by mass (7 parts by mass of solid content) of the component (A) obtained in Production Example 1, 0.28 parts by mass of tetramethylammonium borohydride as a basic compound (B) (to a neutralization rate of 20%) Equivalent amount), and the conductive particles (C), photopolymerization initiator (D), active energy ray-reactive functional group-containing monomer (E) and the like are mixed with a disper and dispersed by a three-roll. The photosensitive conductive ink of the present invention was obtained.
About the obtained photosensitive conductive ink, developability etc. were evaluated by the method mentioned later. The results are shown in Table 2.

The neutralization rate here is a value represented by the following relational expression.
Neutralization rate (%) = 100 x (number of moles of basic functional group charged in basic compound (B) (mol)) x (base valence) / (number of moles of acidic functional group in component (A) (mol) )

[Examples 2-139], [Comparative Examples 2-36]
Except having used the component (A), the basic compound (B), and the ethylenically unsaturated compound (E) in the composition and amount (solid content) shown in Tables 2 to 4, the same manner as in Example 1 was performed. A photosensitive conductive ink was obtained and evaluated in the same manner.

[Compound (B) having a functional group capable of neutralization]
B1: Tetramethylammonium borohydride Boiling point: 205 ° C
B2: Tetramethylammonium hydroxide Boiling point: 140 ° C. (decomposition)
B3: Sodium hydroxide Boiling point: 1388 ° C
B4: N, N-dimethylaminoethanol Boiling point: 134 ° C
・ B5: Triethylamine Boiling point: 90 ° C

[Ethylenically unsaturated compound (E)]
・ Aronix M310 (manufactured by Toagosei Co., Ltd., trimethylolpropane PO-modified triacrylate)
A-200 (manufactured by Shin-Nakamura Chemical Co., Ltd., polyethylene glycol diacrylate)
R-167 (Nippon Kayaku Co., Ltd., 1,6-hexanediol diepoxy acrylate)

<Evaluation as photosensitive conductive ink>

[Developability]
The photosensitive conductive ink was applied to a glass substrate by screen printing and then dried at 70 ° C. for 15 minutes to obtain a coating film. When the film thickness was measured, the film thickness was 8 to 10 μm. Without irradiating ultraviolet rays, spray the unexposed film with 0.5% sodium carbonate aqueous solution with a spray pressure of 0.2MPa using a spin developer, and the dry film of photosensitive conductive ink disappears. Time was measured. The measurement time was divided by the measured film thickness, and the time per unit film thickness (seconds / μm) was taken as the development speed.
The film thickness was measured using a MH-15M type measuring instrument manufactured by Sendai Nikon.

[Development time reduction rate]
The development time shortening rate here is based on the developability of the comparative example not containing the basic compound (B), and the same composition and amount (solid content) except that the basic compound (B) is not included. ), The developability of the examples containing the component (A) and the ethylenically unsaturated compound (E) is a value determined according to the following formula.
Development time shortening rate (%) = 100 × [(developability of comparative example) − (developability of example)] / (developability of comparative example)

[Conductivity (Volume resistance)]
A conductive ink described in Examples 1 to 139 and Comparative Examples 1 to 36 was screen-printed on a 75 μm thick polyethylene terephthalate (hereinafter referred to as PET) film with a 3 mm × 90 mm pattern, and was printed in a box oven at 150 ° C. 10 After drying for a minute, the resistivity of the obtained printed material was measured with a Sanwa Digital Multimeter manufactured by Sanwa Electric Meter Co., Ltd.
The film thickness was measured using a MH-15M type measuring instrument manufactured by Sendai Nikon.

[Calculation of volume resistivity]
The volume resistance value was calculated from the resistivity measured by the above method and the film thickness.
The evaluation criteria are as follows.
<Evaluation>
◎: less than ^{1.0 × 10 -5 Ω · cm ○} : 1.0 × 10 -5 Ω · cm or more 5.0 × 10 below ^{-5 Ω · cm △: 5.0 ×} 10 -5 Ω · cm or more Less than 1.0 × 10 ⁻⁴ Ω · cm ×: 1.0 × 10 ⁻⁴ Ω · cm or more

  As is clear from the results shown in Tables 2 to 5, it was confirmed that the photosensitive conductive ink of the present invention can easily improve the developability. Furthermore, when a quaternary ammonium salt is used as the compound (B) having a functional group that can be neutralized, the conductivity is also improved.

  The photosensitive conductive ink of the present invention can be widely used for conductive ink applications. In particular, it can be suitably used as a fine conductive circuit formed in the frame portion of the touch screen panel. Furthermore, since the photosensitive conductive ink of the present invention is excellent in conductivity and can form a high-definition pattern, it is possible to form a fine pattern that looks transparent, and it can also be applied as a transparent electrode used in the display part of a touch screen panel. It is.

1: Lower substrate 2: Upper substrate 3: Conductive ink pattern layer 4: Insulating layer 5: Adhesive material (bonding)
6: Transparent electrode on the lower substrate 7: Transparent electrode on the upper substrate 8: Dot spacer 9, 10: Upper drive electrode 11, 12: Upper connection electrode 13, 14: Lower drive electrode 15, 16: Lower connection electrode 17: Handling circuit

Claims (18)

  Component (A) having an acidic functional group, an acid value of 5 to 200 (mg KOH / g), and a number average molecular weight of 2,000 or more, at least a part of the acidic functional group in the component (A) Monomer having a compound (B) having a functional group capable of neutralization, conductive particles (C), a photopolymerization initiator (D) and an active energy ray-reactive functional group and having a number average molecular weight of less than 2,000 A photosensitive conductive ink containing (E).   The photosensitive conductive ink of Claim 1 whose compound (B) is an organic base with a boiling point of 200 degrees C or less.   The photosensitive conductive ink of Claim 1 or 2 whose compound (B) is a quaternary ammonium salt.   The photosensitive electroconductivity of any one of Claims 1-3 whose content of a compound (B) is an quantity which can neutralize 5-95% of the acidic functional groups which a component (A) has. ink.   The photosensitive conductive ink of any one of Claims 1-4 whose number average molecular weights of a component (A) are 2,000 or more and 1,000,000 or less.   The photosensitive conductive ink of any one of Claims 1-5 whose component (A) is a component (A1) which has an active energy ray reactive functional group.   Component (A) is selected from the group consisting of phenoxy resins, acrylic resins, urethane resins, polyester resins, polyolefin resins, urea resins, urethane urea resins, epoxy resins, polyamide resins, and polyimide resins. The photosensitive conductive ink according to claim 1, wherein the photosensitive conductive ink is at least one.   The photosensitivity according to any one of claims 1 to 7, wherein the acidic functional group of the component (A) is at least one selected from the group consisting of a carboxyl group, a sulfo group, a phosphate group, and a phenolic hydroxyl group. Conductive ink.   The photosensitive conductive ink of any one of Claims 1-8 whose content of electroconductive particle (C) is 60-95 mass% in solid content of 100 mass% of photosensitive conductive ink.   The photosensitive conductive ink of any one of Claims 4-9 whose active energy ray reactive functional group equivalent which a component (A1) has is 300-5000 (g / mol). Component (A) having an acidic functional group and an acid value of 5 to 200 (mgKOH / g) and a number average molecular weight of 2,000 or more is at least a part of the acidic functional group in component (A). A neutralized product (AB) obtained by neutralizing with a compound (B) having a functional group capable of neutralizing
A photosensitive conductive ink comprising a conductive particle (C), a photopolymerization initiator (D), and a monomer (E) having an active energy ray-reactive functional group and a number average molecular weight of less than 2,000. The component (A) having an acidic functional group and an acid value of 5 to 200 (mgKOH / g) and a number average molecular weight of 2,000 or more includes at least a part of the acidic functional group in the component (A). Compound (B) having a functional group capable of neutralizing the above, to obtain a neutralized product (AB) of the component (A),
Next, the neutralized product (AB), conductive particles (C), photopolymerization initiator (D), and monomer (B) having an active energy ray-reactive functional group and a number average molecular weight of less than 2,000 A method for producing a photosensitive conductive ink to be mixed.   Hardened | cured material formed by hardening | curing the photosensitive conductive ink in any one of Claims 1-11. A laminate with a conductive pattern comprising a substrate and a conductive pattern formed on the substrate,
The laminated body with a conductive pattern in which the said conductive pattern is formed with the photosensitive conductive ink of any one of Claims 1-11.   The laminated body with a conductive pattern of Claim 14 which further comprises the insulating layer laminated | stacked so that the said conductive pattern might be coat | covered.   The laminate with a conductive pattern according to claim 14 or 15, wherein another conductive pattern electrically connected to the conductive pattern and having a predetermined pattern is further provided between the base material and the conductive pattern. .   The laminated body with a conductive pattern according to any one of claims 14 to 16, wherein the other conductive pattern is a transparent conductive pattern mainly composed of indium oxide doped with tin.   The laminated body with a conductive pattern of any one of Claims 14-17 used for a touch screen panel use.