JP2014034589A - Conductive ink composition, method for producing conductive pattern and conductive circuit - Google Patents

Abstract

Provided is a conductive ink composition that has a low viscosity, excellent printability, can be cured in a short time from a lower temperature, and has a high conductivity and a high-definition pattern.
A conductive ink composition containing a conductive filler, a thermosetting resin composition, and an organic solvent as an essential component, and at least selected from the group consisting of a phosphate group, a phosphate group, and a phosphate ester group. An electroconductive ink composition comprising an organic compound containing one functional group.
[Selection figure] None

Description

  The present invention relates to a conductive ink composition for forming a conductive film, a method for producing a conductive pattern, and a conductive circuit.

  Printing methods or etching methods are known as methods for forming conductive patterns such as conductive circuits and electrodes used in touch panels, electronic paper, and various electronic components.

  When forming a conductive pattern by an etching method, after forming a resist film patterned by photolithography on a substrate on which various metal films are vapor-deposited, an unnecessary vapor-deposited metal film is dissolved and removed chemically or electrochemically, Finally, it is necessary to remove the resist film, and the process is very complicated and poor in mass productivity.

  On the other hand, in the printing method, a desired pattern can be mass-produced at low cost, and conductivity can be easily imparted by drying or curing the printed coating film.

  As these printing methods, flexographic printing, screen printing, gravure printing, gravure offset printing, ink jet printing, and the like have been proposed in accordance with the line width, thickness, and production speed of the pattern to be formed.

  As a printed pattern, formation of a high-definition conductive pattern having a line width of 50 μm or less is required from the viewpoint of miniaturization of an electronic device and improvement in design.

  In addition, in order to respond to the increasing demand for thinner, lighter, more flexible electronic devices, and high-productivity roll-to-roll printing, high conductivity is achieved by printing on plastic films and firing at low temperature and short time. There is a need for conductive inks that can provide good properties, substrate adhesion, film hardness, and the like. Furthermore, among plastic films, when printed on a non-heat resistant substrate such as an inexpensive and highly transparent PET (polyethylene terephthalate) film or a transparent conductive film in which an ITO film is formed on the PET film, There is a need for conductive inks that can provide the desired physical properties.

Under such circumstances, a thermosetting conductive paste composition containing silver powder, a thermosetting (thermosetting resin composition) component, and a solvent, the thermosetting (thermosetting) (Resin composition) component is composed of a blocked polyisocyanate compound and a thermoplastic resin, and the thermoplastic resin is at least one selected from the group consisting of an epoxy resin, a linear polyester resin, and a vinyl chloride vinyl acetate copolymer. Various conductive ink compositions that are thermoplastic resins are known (Patent Documents 1 to 6).
However, none of these conductive ink compositions has a relatively high viscosity and excellent printability. In order to improve only the printability, it is possible to add a surfactant or the like to the conductive ink composition. However, even if the printability can be improved, the conductivity is often impaired.

JP2002-161123 JP 2006-302825 A JP 2009-26558 A JP 2009-24066 A JP2012-38614 JP2012-38615

  The problem to be solved by the present invention is to provide a conductive ink composition having a low viscosity, excellent printability and capable of obtaining a pattern having high conductivity.

  As a result of earnest research, the present inventors impair the high conductivity of the conductive pattern obtained after thermosetting by incorporating a phosphoric acid group-containing compound into an existing conductive ink composition. The inventors have found that a conductive ink composition capable of forming a conductive pattern having a low viscosity and excellent printability can be obtained, and the present invention has been completed.

  That is, the present invention is a conductive ink composition containing a conductive filler, a thermosetting resin composition, and an organic solvent as essential components, and is further selected from the group consisting of a phosphate group, a phosphate group, and a phosphate ester group. A conductive ink composition comprising an organic compound containing at least one functional group is provided.

  Moreover, this invention provides the manufacturing method of the electroconductive pattern which apply | coats said electroconductive ink composition on a non-heat-resistant base material, and heats it.

  Furthermore, this invention provides the electroconductive circuit containing the electroconductive pattern in which the cured film of said electroconductive ink composition was formed on the non-heat-resistant base material.

  Since the conductive ink composition of the present invention contains an organic compound containing at least one functional group selected from the group consisting of a phosphate group, a phosphate group, and a phosphate ester group, it has low viscosity and is printable. It has a particularly remarkable effect of being excellent. As a result, even when a non-heat resistant substrate such as a PET film is used, a highly conductive pattern can be produced.

(Conductive filler)
A well-known thing can be used as a conductive filler used by this invention. For example, nickel, copper, gold, silver, aluminum, zinc, nickel, tin, lead, chromium, platinum, palladium, tungsten, molybdenum, etc., and an alloy or mixture of these two or more, or a compound of these metals is good. Examples include those having conductivity. In particular, silver powder is preferable because it can easily realize stable conductivity and has good heat conduction characteristics.

(Silver powder)
When using silver powder as an electroconductive filler of this invention, it is preferable to use the spherical silver powder whose median particle diameter (D50) is 0.1-10 micrometers as an average particle diameter, and it is more preferable that it is 0.1-3 micrometers. This range is more effective in improving the fluidity of the conductive ink composition in combination with an organic compound containing at least one functional group selected from the group consisting of a phosphate group, a phosphate group, and a phosphate ester group. Large, better fluidity, and troubles occur even when printing continuously on these printing presses in certain printing methods such as flexographic printing, screen printing, gravure printing, or gravure offset printing. It is difficult to stably obtain a good conductive pattern.

  Examples of such silver powder include AG2-1C (manufactured by DOWA Electronics Co., Ltd., average particle diameter D50: 0.8 μm), SPQ03S (manufactured by Mitsui Metal Mining Co., Ltd., average particle diameter D50: 0.5 μm), EHD (Mitsui Metal Mining Co., Ltd., average particle size D50: 0.5 μm), Sylbest C-34 (Tokuriku Chemical Laboratory Co., Ltd., average particle size D50: 0.35 μm), AG2-1 (DOWA Electronics) Examples thereof include an average particle size D50: 1.3 μm manufactured by Co., Ltd., and Sylbest AgS-050 (average particle size D50: 1.4 μm manufactured by Tokuru Chemical Laboratory Co., Ltd.).

  The conductive filler may be a conductive filler whose surface is coated with an organic compound containing at least one functional group selected from the group consisting of a phosphate group, a phosphate group, and a phosphate ester group, which will be described later. .

  In the conductive ink composition of the present invention, the ratio between the conductive filler and the thermosetting resin composition described later is not particularly limited, but the thermosetting resin composition per 100 parts of the conductive filler in terms of mass. It is preferable to adjust to 3 to 15 parts from the viewpoint of the conductivity of the obtained conductive pattern.

(Thermosetting resin composition)
In the present invention, a thermosetting resin composition is used. The thermosetting resin composition is a combination of a main agent that cannot be cured by itself and a curing agent. Even if both a main ingredient and a hardening | curing agent are mixed, each is selected so that it may harden for the first time by heating, without reacting at normal temperature. As the main agent, a thermoplastic resin itself having a film-forming property is frequently used because a high-definition conductive pattern can be easily obtained. As such a thermosetting resin composition, for example, a combination of an epoxy compound as a main agent and an epoxy resin hardener such as an acid anhydride, an amine or a phenol resin, a vinyl chloride-acetic acid containing a hydroxyl group as a main agent A combination of a film-forming thermoplastic resin containing a hydroxyl group such as a vinyl resin, a polyester resin containing a hydroxyl group, an acrylic resin containing a hydroxyl group, and an isocyanate curing agent such as block polyisocyanate can be given. In preparing the thermosetting resin composition, the main agent and curing agent exemplified above may be used alone or in combination of two or more.

  As a commercial product of a film-forming thermoplastic resin containing a hydroxyl group, for example, as a vinyl chloride-vinyl acetate resin containing a hydroxyl group, a solvine series manufactured by Nisshin Chemical Industry, a polyester resin containing a hydroxyl group, Toyobo's Byron series.

  In particular, the combination of a block polyisocyanate and a film-forming thermoplastic resin containing a hydroxyl group is excellent in the dispersibility of the conductive filler, and can contain more of it in the composition. This is preferable because it can be further enhanced, and is excellent in adhesion to the substrate during curing. This adhesion can increase the flexibility of electrical and electronic parts provided with a conductive circuit when the object on which the conductive pattern is formed is a flexible non-heat-resistant substrate, and can be highly integrated. This is extremely advantageous.

(Block polyisocyanate)

  The block polyisocyanate used in the present invention in which a blocking agent is thermally dissociated to generate a free isocyanate group is composed of a polyisocyanate compound and a blocking agent.

  Although it does not specifically limit as a kind of polyisocyanate compound, A dimer or a trimer by modification | denaturation of an aromatic, aliphatic, alicyclic diisocyanate, a diisocyanate, a terminal isocyanate group containing compound, etc. are mentioned. It may be used alone or in combination. Examples of the aromatic diisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, dianisidine diisocyanate, and the like. Examples of the aliphatic diisocyanate include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (hereinafter referred to as HMDI), 2,2,4-trimethyl-1,6-hexamethylene. And diisocyanate. Examples of the alicyclic diisocyanate include lysine diisocyanate, isophorone diisocyanate (hereinafter referred to as IPDI), 1,3-bis (isocyanatomethyl) -cyclohexane, 4,4′-dicyclohexylmethane diisocyanate, and modification of these diisocyanates. And dimers or trimers. Examples of the modification method include biuretization and isocyanurate conversion. Alternatively, a terminal isocyanate group-containing compound obtained by reacting the above di- or polyisocyanate compound with an active hydrogen compound such as ethylene glycol, propylene glycol, trimethylolpropane, ethanolamine, polyester polyol, polyether polyol, polyamide, etc. It is done.

  Examples of the blocking agent include known and commonly used blocking agents such as phenol, methyl ethyl ketoxime, and sodium bisulfite. When providing the conductive pattern from the conductive ink composition of the present invention on a heat-resistant substrate such as glass, metal, silica or ceramics, any of these blocking agents can be used, When it is provided on a non-heat-resistant substrate such as PET film, PP film, transparent ITO electrode film, it is preferable to use a block polyisocyanate in which the blocking agent dissociates at a lower temperature and the isocyanate group is liberated. In particular, when a PET film is used as a plastic film as a plastic film, a block polyisocyanate compound using a blocking agent such that the temperature when an isocyanate group is generated is 70 to 125 ° C. is used as the conductive ink composition. If it is made to contain, a conductive pattern can be formed on it, without generating a curvature etc. in a PET film.

  Examples of such blocking agents that can be dissociated at a lower temperature include active methylene compounds and pyrazole compounds. Examples of active methylene compounds include Meldrum's acid, dialkyl malonate, alkyl acetoacetate, 2-acetoacetoxyethyl methacrylate, acetylacetone, ethyl cyanoacetate, and the like. Examples of pyrazole compounds include pyrazole, 3,5-dimethylpyrazole, 3- Examples include methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, and 3-methyl-5-phenylpyrazole. Of these, diethyl malonate, 3,5-dimethylpyrazole and the like are preferable.

  Such blocked polyisocyanate compounds that generate free isocyanate groups by thermal dissociation of the blocking agent are inherent absorptions based on isocyanate groups while monitoring the infrared absorption spectrum of polyisocyanate compounds having free isocyanate groups. It can be easily obtained by reacting the blocking agent until the spectrum disappears.

  Commercially available block polyisocyanates include duranate MF-K60B (manufactured by Asahi Kasei Chemicals) and desmodur BL-3475 (manufactured by Sumika Bayer Urethane Co., Ltd.) when the block agent is an active methylene compound. TRIXENE BI-7982 (manufactured by Baxenden) is a compound in which is a pyrazole compound, and TRIXENE BI-7992 (manufactured by Baxenden) is a mixed type of active methylene and a pyrazole compound.

  The main agent and the curing agent constituting the thermosetting resin composition may be selected in respective amounts so that their respective functional groups are consumed after curing. It can be 30-800 parts per 100 parts of the main agent in terms of mass.

  In a thermosetting resin composition having a combination of a film-forming thermoplastic resin containing a hydroxyl group and an isocyanate curing agent such as block polyisocyanate as essential components, the nonvolatile content of the isocyanate curing agent is 100 in terms of mass. It is more preferable that the nonvolatile content of the film-forming thermoplastic resin containing a hydroxyl group is 5 to 50 parts per part in terms of excellent printability.

(Epoxy compound)
When a combination of a block polyisocyanate and a film-forming thermoplastic resin containing a hydroxyl group is employed as the thermosetting resin composition in the present invention, the viscosity can be reduced by using an epoxy compound in combination with this. In addition, the crosslink density can be increased, and the adhesiveness and solvent resistance of the conductive pattern after curing can be further increased. Although it does not specifically limit as an epoxy compound to be used, It is preferable to use an aliphatic epoxy compound. Specifically, it is preferable to use epoxidized products such as glycidyl etherified products such as polyethylene glycol, polypropylene glycol, hexanediol, trimethylolpropane, glycerin, pentaerythritol, sorbitol, and alicyclic epoxy compounds. Of these, glycidyl etherified products such as polyethylene glycol, polypropylene glycol, and trimethylolpropane are more preferable.

  Since the aliphatic epoxy compound is liquid or semi-solid at room temperature, the main component constituting the thermosetting resin composition having a relatively high viscosity or solid can be reduced without impairing conductivity. Therefore, the fluidity of the conductive ink composition can be improved, and in a specific printing method such as flexographic printing, screen printing, gravure printing, or gravure offset printing, when continuously printed on these printing machines However, troubles do not easily occur and it becomes easy to obtain a stable conductive pattern. Some aromatic epoxy compounds are liquid or semi-solid, but are not preferred for safety reasons.

  In preparing the conductive ink composition of the present invention, when using an epoxy compound as a constituent of the thermosetting resin composition, the total thermosetting resin composition contained in the ink composition in terms of mass is used. It is preferable to use 5 to 50 parts per 100 parts of the nonvolatile content from the viewpoint of improving the performance of the conductive pattern such as conductivity, toughness, and solvent resistance finally obtained.

(Reaction catalyst for block polyisocyanate)
A reaction catalyst can be used in combination with the block polyisocyanate used in the present invention if necessary. The reaction catalyst is not particularly limited, but the blocked isocyanate reaction catalyst is preferably an organic ammonium salt or an organic amidine salt. Specifically, tetraalkylammonium halides, tetraalkylammonium hydroxides, tetraalkylammonium organic acid salts, etc. are used for organic ammonium salts, and 1,8-diazabicyclo [5.4.0] undecene-7 is used for organic amidine salts. (Hereinafter referred to as DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (hereinafter referred to as DBN) phenol salt, octylate, oleate, p-toluenesulfonate, formate. it can. Among them, it is preferable to use DBU-octylate, DBN-octylate and the like. Commercially available products include TOYOCAT-TR20 (manufactured by Tosoh Corporation) for organic ammonium salts, U-CAT SA1, U-CAT SA102, U-CAT SA106, U-CAT SA506, U-CAT SA603, U-CAT for organic amidine salts. SA1102 (manufactured by San-Apro) can be mentioned.

  Since the reaction catalyst of the block polyisocyanate is 3 to 30 parts per 100 parts of the block polyisocyanate in terms of mass, the performance of the conductive pattern such as conductivity and solvent resistance finally obtained can be improved. preferable.

(Organic solvent)
Since most of the various raw materials used in the present invention are themselves solid at 25 ° C., the fine line pattern of the conductive ink composition is usually applied on the substrate after being dissolved in a liquid medium. Or printing. Therefore, it is preferable to consider the solubility in a liquid medium when selecting the main agent and the curing agent constituting the thermosetting resin composition.

  From such a viewpoint, in the conductive ink composition of the present invention, a liquid organic compound is used at 25 ° C., which dissolves the thermosetting resin composition and has no reactivity therewith. Such an organic compound is a so-called organic solvent, and the type thereof is not limited, and examples thereof include ester, ketone, chlorine, alcohol, ether, hydrocarbon, and ether ester. Specifically, for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, n-butanol, iso-butanol, isophorone, γ-butyrolactone, DBE (manufactured by Invista Japan), N-methyl-2-pyrrolidone, ethyl carbitol acetate, butyl cellosolve Examples thereof include acetate and propylene glycol monoalkyl ether acetate. These may be used individually by 1 type, or may use 2 or more types together. Among these, in order to easily obtain a conductive pattern regardless of the type of printing method described later, it is preferable to use a solvent having a boiling point of 100 to 250 ° C. from the viewpoint of drying speed.

  As will be described later, when the gravure printing method or the gravure offset printing method is adopted, the organic solvent preferably has a silicone blanket swelling ratio of 5 to 20%, and particularly preferably diethylene glycol monobutyl ether acetate. And ether ester organic solvents such as diethylene glycol monoethyl ether acetate.

  The content of the organic solvent in the conductive ink composition is preferably 5 to 30% by mass, and more preferably 7 to 15% by mass. In this range, the paste viscosity becomes more appropriate, and in gravure printing or gravure offset printing, a higher-definition conductive pattern can be formed without causing pinhole defects at the corners of the image lines or at the intersections of the matrix. Can be formed.

The conductive ink composition of the present invention further contains at least one functional group selected from the group consisting of a phosphate group, a phosphate group, and a phosphate ester group in addition to the known and commonly used raw material components as described above. The greatest feature is that it contains an organic compound. The phosphate group is a group represented by —H ₂ PO ₄ (P atom is pentavalent), and the phosphate group is at least one hydrogen atom in —H ₂ PO ₄ is an alkali metal ion or alkaline earth. It is a group in the form of a salt substituted with a metal ion. The phosphate group is a group in which at least one hydrogen atom in —H ₂ PO ₄ is substituted with an alkyl group or a phenyl group.
Hereinafter, an organic compound containing a phosphate group, an organic compound containing a phosphate group, and an organic compound containing a phosphate ester group are collectively abbreviated as a phosphate group-containing organic compound.

  Examples of such organic compounds containing a phosphate group include polyalkylene glycol monophosphate, polyalkylene glycol monoalkyl ether monophosphate, perfluoroalkyl polyoxyalkylene phosphate, perfluoroalkylsulfonamide polyoxy Low molecular weight compounds such as alkylene phosphates, homopolymers of vinylphosphonic acid, acid phosphooxyethyl mono (meth) acrylate, acid phosphooxypropyl mono (meth) acrylate, and acid phosphoxypolyoxyalkylene glycol mono (meth) acrylate Alternatively, a polymer containing a phosphoric acid group such as a copolymer of the monomer and another comonomer may be mentioned as the polymer compound.

  In the above, only an organic compound containing a phosphate group is illustrated as a specific example. However, an organic compound containing a phosphate group is not limited to an alkali metal hydroxide or an organic compound containing a phosphate group. It can be easily obtained by reacting an alkaline earth metal hydroxide, and an organic compound containing a phosphate ester group can be obtained by dehydration condensation between an organic compound containing a phosphate group and an alcohol, or phosphoric acid. It can also be easily obtained by condensing an organic compound containing a chloride group and an alcohol by the action of a base.

  As a phosphoric acid group-containing organic compound, phosphoric acid can be used in comparison with an organic compound containing a phosphate ester group in that it can have a lower viscosity and a lower volume resistivity in comparison with the same amount of nonvolatile content used. An organic compound containing a group or an organic compound containing a phosphate group is preferred.

  As the above-mentioned low molecular compound, for example, EFKA series manufactured by Ciba Specialty Co., Ltd. can be selected and used as the polymer compound, for example, from DISPERBYK series manufactured by BYK Chemie.

  As the polymer compound, a phosphoric acid group-containing polymer having a number average molecular weight of 1,000 or more, in particular, a number average molecular weight of 1,000 to 10,000 is more conductive than the low molecular compound described above at the same use amount. This is preferable because the effect of improving the fluidity of the conductive ink composition is high without impairing the properties.

  It is preferable that the usage-amount of the phosphoric acid group containing organic compound used by this invention shall be 0.1-3 parts per 100 parts of mass conversion total of an electroconductive filler, a thermosetting resin composition, and an organic solvent.

  In addition to the above-described components, the conductive ink composition of the present invention may be appropriately mixed with various additives such as a dispersant, an antifoaming agent, a release agent, a leveling agent, and a plasticizer as necessary. it can.

  The conductive ink composition of the present invention can be applied or printed by any method, for example, on a substrate of any one of a plastic film, a ceramic film, a silicon wafer, glass, or a metal plate, thereby producing a conductive pattern equivalent. Can be formed. However, the true value of the conductive ink composition of the present invention can be fully demonstrated because a transparent conductive film such as a PET film, a PP film or an ITO film that cannot be exposed to a high temperature when obtaining a conductive pattern. It is.

  The conductive ink composition of the present invention is printed on an arbitrary substrate by, for example, a printing method such as flexographic printing, screen printing, gravure printing, or gravure offset printing, and the printed pattern is cured by heating to form a cured film. Thus, a conductive pattern can be formed.

Examples of the method for forming a conductive pattern from the conductive ink composition of the present invention include a method in which the conductive ink composition of the present invention is applied on a non-heat resistant substrate and heated. In the present invention, by adding the above-described phosphoric acid group-containing organic compound to the conductive ink composition, the viscosity at a shear rate of 10 s ⁻¹ at 25 ° C. can be easily set to ¹ to 50 Pa · s. . As a result, after filling the intaglio with the conductive ink composition, transferring the filled ink composition to a blanket roll, the ink composition is transferred from the blanket roll to a non-heat-resistant substrate, and then applied to the non-heat-resistant substrate. A conductive pattern can be formed by performing so-called gravure offset printing, in which a desired pattern is printed on the surface of the heat-resistant substrate, and then heating.

  The intaglio printing plate at this time is a normal gravure plate, an intaglio plate formed by exposing, developing and washing a photosensitive resin on a glass plate, a glass plate, a metal plate, an intaglio plate formed by chemical etching and laser etching. Can be used.

  The silicone blanket is a sheet having a layer structure such as a silicone rubber layer, a PET layer, or a sponge layer. Usually, it can be used in a state of being wound around a rigid cylinder called a blanket cylinder.

  In the method for forming a conductive pattern from the conductive ink composition of the present invention, when the gravure offset printing method is employed, the silicone blanket is required to have transferability from an intaglio and transferability to a substrate. In order to obtain sufficient transferability to the substrate, it is necessary to absorb the liquid component in the conductive ink composition at a certain ratio on the blanket surface. If the absorption is insufficient, the conductive ink composition layer is likely to delaminate at the time of transfer to the substrate. Conversely, if the absorption exceeds a certain ratio, the conductive ink composition dries on the surface of the blanket, and the substrate There has been a problem that it is liable to cause a transfer failure.

  When the conductive ink composition has a viscosity of 1 to 50 Pa · s at 25 ° C., and the conductive pattern is continuously printed using the gravure offset printing method, the corner portion of the image line In addition, pinhole defects are likely to occur at the intersections of the matrix, a good conductive fine line pattern can be formed, and problems of inking to the intaglio and transfer from the intaglio to the blanket are less likely to occur.

  For example, the conductive ink composition of the present invention can be applied to a substrate to form a printed pattern so that the line width is in the range of 10 to 150 μm, and then heat-cured to obtain a conductive pattern. .

  The printed pattern thus provided on the base material becomes, for example, a cured film when heated at 100 to 130 ° C. for 20 to 5 minutes, becomes a conductive pattern, and exhibits conductivity.

  The conductive pattern formed from the conductive ink composition of the present invention may be a solid line having a solid line width, but the characteristics when the conductive ink composition of the present invention is used are as described above. This is particularly remarkable when a line width image line thinner than the conventional one is provided on the substrate.

  As described above, since the conductive pattern from the conductive ink composition of the present invention can be formed at a lower temperature and in a shorter time than before, the characteristic of the conductive ink composition of the present invention is that of a ceramic film, glass or metal plate. This is particularly prominent when a conductive pattern is formed on a non-heat resistant substrate that has a lower heat resistance and is more likely to be thermally deformed than a substrate having such a high heat resistance. Therefore, the conductive pattern in which the cured film of the conductive ink composition of the present invention is formed on a non-heat resistant substrate can be suitably used as a conductive circuit formed on the non-heat resistant substrate.

  Thus, using the conductive ink composition of the present invention, a substrate provided with a conductive pattern by printing on various substrates by various printing methods and heating can be wired as necessary as a conductive circuit. By performing the above, various electric parts and electronic parts can be obtained. Specifically, the conductive ink composition of the present invention is also excellent in adhesion to a transparent conductive film such as a transparent ITO electrode.

  Examples of the final product include a touch panel extraction electrode, a display extraction electrode, electronic paper, a solar battery, and other wiring products.

  Hereinafter, the present invention will be specifically described with reference to examples. Here, “%” is “% by mass” unless otherwise specified.

  Using each raw material so as to have the parts by mass shown in Table 1, these raw materials are sufficiently mixed, and each conductive ink composition of the present invention which is an example and each conventional conductive ink which is a comparative example A composition was prepared.

  About each of these conductive ink compositions, the following measurement items evaluated the characteristics of the conductive ink composition itself and the characteristics of the conductive pattern obtained therefrom. The evaluation results are also shown in Table 1 and Table 2 below.

(viscosity)
Using a rotary rheometer, the viscosity of the conductive ink composition of the present invention at 25 ° C. and a shear rate of 10 s ⁻¹ was measured.

(Printability)
Using the conductive ink composition of the present invention, gravure offset printing was performed by the following method to prepare a conductive circuit.

  The conductive ink composition was inked on a glass intaglio plate with a doctor blade, and then pressed and brought into contact with a cylinder around which the blanket was wound, thereby transferring a desired pattern onto the blanket. Thereafter, the coating film on the blanket was pressed and transferred to a transparent conductive film as a base material to produce a conductive circuit having a line width of 30 μm to 100 μm. Among the conductive circuits described above, a line width of 30 μm was observed with a microscope, and fine line reproducibility was evaluated according to the following criteria.

◎: Excellent linearity of the wire, no disconnection ○ ○: Excellent linearity of the wire, no disconnection ×: Inferior linearity of the wire, disconnection

(Volume resistivity)
The applicator was used to apply the conductive ink composition onto the transparent conductive film (ITO film surface) so that the film thickness after drying was 4 μm, and dried at 125 ° C. for 10 minutes. Using the ink coating film, measurement was performed by a four-terminal method using a Loresta GP MCP-T610 (manufactured by Mitsubishi Chemical Corporation). Volume resistivity is a measure of conductivity.

・ Silver powder:
AG-2-1C (manufactured by DOWA Electronics Co., Ltd., average particle diameter D50: 0.8 μm)
Byron 200: Molecular weight 17,000, hydroxyl value 6, glass transition temperature (Tg) 67 ° C. thermoplastic polyester resin (manufactured by Toyobo Co., Ltd.)
・ Solvine AL: Vinyl chloride-vinyl acetate copolymer having a number average molecular weight of 22,000, a glass transition temperature (Tg) of 76 ° C., and a vinyl chloride / vinyl acetate / vinyl alcohol copolymer mass ratio of 93/2/5. (Manufactured by Nissin Chemical Industry Co., Ltd.)
Denacol EX-321: Trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX Corporation)
・ TRIXENE BI 7982: Block isocyanate whose blocking agent is 3,5-dimethylpyrazole (manufactured by Baxenden)
DISPER BYK-111: Phosphate group-containing polymer (polymer compound) in the range of number average molecular weight of 1,000 to 10,000 (manufactured by Big Chemie)
EFKA-8512: Phosphoric acid ester (low molecular compound) containing a polyoxyalkylene group (manufactured by Ciba Specialty)
U-CAT SA 102: DBU-octylate (manufactured by San Apro)
U-CAT SA 603: DBU-formate (manufactured by San Apro)
Cureazole 2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals)
・ BDGAc: Diethylene glycol monobutyl ether acetate

  As can be seen from the evaluation results in Table 1, the conductive ink composition of Example 4 containing an organic compound containing a phosphate ester group was compared with the conductive ink composition of Comparative Example 1 not containing it. It can be seen that both the viscosity and the printability are excellent. In comparison with Examples 3 and 4, the viscosity and conductivity of the polymer compound as the organic compound containing a phosphate group is higher than that when a low-molecular compound containing a phosphate ester group is used. You can see that it is clearly superior.

  In the conductive ink compositions of Examples 3 to 4, the relationship between the nonvolatile components of the film-forming thermoplastic resin containing a hydroxyl group and the isocyanate curing agent is rich in the latter curing agent, and the former thermoplasticity. It is clear that the printability is superior to the resin-rich conductive ink compositions of Examples 1-2.

  In addition, since the conductive ink composition of each example is a low-temperature dissociable active methylene compound and / or pyrazole compound, the blocked isocyanate blocking agent is a non-heat-resistant group such as a transparent conductive film or PET film. Even on the material, a conductive pattern made of a cured film could be formed at low temperature in a short time without warping, and the obtained conductive pattern was sufficiently satisfactory in terms of conductivity and substrate adhesion.

  The conductive ink composition of the present invention can be used as a conductive silver paste for forming conductive patterns of various electric parts and electronic parts.

Claims (9)

In the conductive ink composition containing an electroconductive filler, a thermosetting resin composition, and an organic solvent as an essential component, at least one functional group selected from the group consisting of a phosphate group, a phosphate group, and a phosphate group A conductive ink composition comprising an organic compound containing 2. The conductivity according to claim 1, wherein the organic compound is a polymer having a number average molecular weight of 1,000 or more and containing at least one functional group selected from the group consisting of a phosphate group, a phosphate group, and a phosphate ester group. Ink composition. The conductive ink composition according to claim 1, wherein the conductive filler is a spherical silver powder having an average particle size of 0.1 to 3 μm. The conductive ink composition according to claim 1, wherein the thermosetting resin composition is a thermosetting resin composition containing a film-forming thermoplastic resin containing a hydroxyl group and a block polyisocyanate. Furthermore, the conductive ink composition of Claim 4 which uses an epoxy compound together. The conductive ink composition according to any one of claims 1 to 5, wherein the viscosity at a shear rate of 10 s ^-1 at 25 ° C is ¹ to 50 Pa · s. The manufacturing method of the electroconductive pattern which apply | coats and heats the electroconductive ink composition as described in any one of Claims 1-5 on a non-heat-resistant base material. The conductive ink composition according to any one of claims 1 to 5 is filled in an intaglio, and after the transferred ink composition is transferred to a blanket roll, the ink composition is transferred from the blanket roll to a non-conductive support. The method for producing a conductive pattern according to claim 7, wherein a desired pattern is printed on the surface of the non-heat resistant substrate by transferring and transferring an object, and then heated. The electroconductive circuit containing the electroconductive pattern in which the cured film of the electroconductive ink composition as described in any one of Claims 1-5 was formed on the non-heat-resistant base material.