TWI579349B - Conductive ink composition, method for producing conductive pattern and conductive circuit - Google Patents

Description

Conductive ink composition, method for producing conductive pattern, and conductive circuit

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.

As a method of forming a conductive pattern such as a conductive circuit or an electrode used in a touch panel, electronic paper, and various electronic components, a printing method or an etching method is known.

In the case where a conductive pattern is formed by an etching method, after forming a patterned resist film by photolithography on a substrate on which various metal films are vapor-deposited, it is necessary to dissolve an unnecessary vapor-deposited metal film by chemical or electrochemical means. Removal, and finally the resist film is removed, this step is very complicated and cannot be mass-produced.

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

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

As a printed pattern, it is required to form a high-definition conductive pattern having a line width of 50 μm or less from the viewpoints of downsizing of an electronic device and improvement in design properties.

In addition, in order to cope with the demand for thinning, weight reduction, and softening of electronic equipment, or for high-volume roll-to-roll printing, it is required to print on a plastic film and burn it at a low temperature for a short period of time, thereby obtaining high conductivity. A conductive ink such as substrate adhesion or film hardness. Further, it is required to be in a plastic film such as a PET (polyethylene terephthalate) film which is inexpensive and highly transparent, or a transparent conductive film in which an indium tin oxide (ITO) film is formed on a PET film. When printing on a non-heat-resistant substrate, the above-mentioned physical conductive ink can be obtained.

In such a case, various conductive ink compositions are known to be a heat-curable conductive paste composition containing a silver powder, a heat curable (thermosetting resin composition) component, and a solvent, and the above-described heat curable (thermosetting resin composition) The component comprises a blocked polyisocyanate compound and a thermoplastic resin, the thermoplastic resin being at least one thermoplastic resin selected from the group consisting of epoxy resins, linear polyester resins, and vinyl chloride vinyl acetate copolymers ( Patent Document 1 to Patent Document 6).

However, these conductive ink compositions have high viscosity and are not excellent in printability. Further, in order to improve the printing adaptability, a surfactant or the like may be added to the conductive ink composition, but in most cases, although the printing suitability can be improved, the conductivity is adversely affected.

Patent Document 1: Japanese Patent Laid-Open 2002-161123

Patent Document 2: Japanese Patent Laid-Open No. 2006-302825

Patent Document 3: Japanese Patent Special Opening 2009-26558

Patent Document 4: Japanese Patent Special Open 2009-24066

Patent Document 5: Japanese Patent Special Opening 2012-38614

Patent Document 6: Japanese Patent Special Opening 2012-38615

An object of the present invention is to provide a conductive ink composition which is low in viscosity and excellent in printability and which can obtain a pattern having high conductivity.

In order to solve the above problems, the inventors of the present invention have intensively studied and found that by including a compound having a phosphoric acid group in a conventional conductive ink composition, high conductivity of the obtained conductive pattern is not damaged even after heat curing. In order to obtain a conductive ink composition capable of forming a conductive pattern having low viscosity and excellent printability, the present invention has been completed.

In other words, the conductive ink composition is a conductive ink composition containing a conductive filler, a thermosetting resin composition, and an organic solvent as essential components, and further contains a phosphoric acid composition. An organic compound of at least one functional group selected from the group consisting of a group, a phosphate group, and a phosphate group.

Further, the present invention provides a method for producing a conductive pattern, wherein the conductive ink composition is applied onto a non-heat resistant substrate and heated.

Further, the present invention provides a conductive circuit comprising a conductive pattern of a cured film in which the conductive ink composition is formed on a non-heat resistant substrate.

Since the conductive ink composition of the present invention contains an organic compound having at least one functional group selected from the group consisting of a phosphate group, a phosphate group, and a phosphate group, low viscosity and excellent printability can be achieved. This is particularly remarkable. Thereby, even when a non-heat resistant base material such as a PET film is used, a highly conductive conductive pattern can be produced.

(conductive filler)

As the conductive filler used in the present invention, a known one can be used. Examples thereof include nickel, copper, gold, silver, aluminum, zinc, tin, lead, chromium, platinum, palladium, tungsten, molybdenum, and the like, and these two or more alloys, mixtures or compounds of these metals and have good electrical conductivity. Substance and so on. In particular, silver powder is preferable since it can easily achieve stable conductivity and also has good heat conduction characteristics.

(silver powder)

When silver powder is used as the conductive filler of the present invention, as the average particle diameter, spherical silver powder having a median diameter (D50) of 0.1 μm to 10 μm is preferably used, and more preferably 0.1 μm to 3 μm. In this range, 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 group, the fluidity of the conductive ink composition can be improved. Larger, more fluid, in flexographic, screen, gravure or gravure offset In a specific printing method such as a brush, even when printing is continuously performed on these printing machines, it is easy to obtain a conductive pattern which is difficult to be broken and which is stable and stable.

Examples of such a silver powder include AG2-1C (manufactured by DOWA Electronics Co., Ltd., average particle diameter D50: 0.8 μm), SPQ03S (manufactured by Mitsui Mining Co., Ltd., average particle diameter D50: 0.5 μm), and EHD (EHD). Mitsui Metals Co., Ltd., average particle size D50: 0.5μm), SYLVESTER C-34 (made by Deli Chemical Research Institute, average particle size D50: 0.35μm), AG2-1 (DOWA Electronics) Manufactured, average particle diameter D50: 1.3 μm), SYLVESTER AgS-050 (manufactured by Deli Chemical Laboratory, average particle diameter D50: 1.4 μm), and the like.

The conductive filler may be a conductive filler which is formed by surface coating of an organic compound containing at least one functional group selected from the group consisting of a phosphate group, a phosphate group, and a phosphate group described later.

In the conductive ink composition of the present invention, the ratio of the conductive filler to the thermosetting resin composition to be described later is not particularly limited, but from the viewpoint of conductivity of the obtained conductive pattern, it is preferably 100 parts by mass. In the conductive filler, the thermosetting resin composition is prepared in an amount of from 3 parts to 15 parts.

(thermosetting resin composition)

A thermosetting resin composition is used in the present invention. The thermosetting resin composition is only a composition composed of a combination of a main agent which cannot be cured and a curing agent. The main agent and the curing agent are each selected so as not to react at room temperature even when the two are mixed, and the curing is started by heating. As the main agent, a thermoplastic resin having a film forming property itself is often used because it is easy to obtain high-precision conductivity. pattern. Examples of such a thermosetting resin composition include a combination of an epoxy compound as a main component and an epoxy resin curing agent such as an acid anhydride, an amine or a phenol resin, and a hydroxyl group-containing vinyl chloride-vinyl acetate resin as a main component. A combination of a film-forming thermoplastic resin containing a hydroxyl group such as a hydroxyl group-containing polyester resin or a hydroxyl group-containing acrylic resin, and an isocyanate curing agent such as a blocked polyisocyanate. When the thermosetting resin composition is prepared, the above-exemplified main component or curing agent may be used singly or in combination of two or more kinds.

As a commercially available product of a hydroxy group-containing film-forming thermoplastic resin, for example, a chloroethylene-vinyl acetate resin containing a hydroxyl group, a SOLBIN series manufactured by Nissin Chemical Industry Co., Ltd., and a polyester resin containing a hydroxyl group may be mentioned. BYRON series, etc.

In particular, it is preferable to combine a polyisocyanate and a film-forming thermoplastic resin having a hydroxyl group, because the dispersibility of the conductive filler can be excellent, and the composition is more contained in the composition, and as a result, the conductivity can be further improved. It is excellent in the adhesiveness with respect to the base material at the time of hardening. In the case where the article forming the conductive pattern is a soft non-heat-resistant substrate, the adhesion is extremely advantageous in terms of improving the flexibility of the electric and electronic component provided with the conductive circuit.

(closed polyisocyanate)

The blocked polyisocyanate used in the present invention and which thermally dissociates the blocking agent to produce a free isocyanate group consists of a polyisocyanate compound and a blocking agent.

The type of the polyisocyanate compound is not particularly limited, and may be an aromatic, aliphatic, alicyclic diisocyanate or a modified product obtained from a diisocyanate. A polymer or a trimer, a compound containing a terminal isocyanate group, or the like. Can be used alone or in combination. Examples of the aromatic diisocyanate include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, and 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 HMDI), 2, 2, 4-trimethyl-1,6-hexamethylene diisocyanate or the like. Examples of the alicyclic diisocyanate include a perisic acid diisocyanate, isophorone diisocyanate (hereinafter IPDI), 1,3-bis(isocyanatomethyl)-cyclohexane, 4,4'- Examples of the dicyclohexylmethane diisocyanate and the like include a dimer or a trimer obtained by upgrading these diisocyanates. Examples of the method of upgrading include biuretization, isomeric cyanation, and the like. Alternatively, the above-mentioned diisocyanate compound or polyisocyanate compound may be reacted with an active hydrogen compound such as ethylene glycol, propylene glycol, trimethylolpropane, ethanolamine, polyester polyol, polyether polyol or polyamine. a terminal isocyanate group compound or the like.

The blocking agent may, for example, be a conventionally known blocking agent such as phenol, methyl ethyl ketone oxime or sodium hydrogen sulfite. When the conductive pattern formed of the conductive ink composition of the present invention is provided on a heat-resistant substrate such as glass, metal, ceria or ceramic, any substance may be used as the blocking agent, but In the case of being provided on a non-heat-resistant substrate such as a PET film, a PP film or a transparent ITO electrode film, it is preferred to use a blocked polyisocyanate which is cleaved at a lower temperature to release an isocyanate group. Especially in the case of using PET film as a plastic film on the substrate. In the case where the conductive ink composition contains a blocked polyisocyanate compound using a blocking agent such that the temperature at which the isocyanate group is generated is 70° C. to 125° C., warpage does not occur on the PET film. A conductive pattern can be formed thereon.

As such a blocking agent which can dissociate at a lower temperature, an active methylene compound or a pyrazole compound is mentioned. Examples of the active methylene compound include meldrum's acid, dialkyl malonate, alkyl acetoacetate, 2-ethyl acetoxyethyl methacrylate, and acetamidine. And ethyl cyanoacetate, etc., as pyrazole compounds, pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4 -Nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, 3-methyl-5-phenylpyrazole, and the like. Among them, diethyl malonate, 3,5-dimethylpyrazole and the like are preferable.

The blocked polyisocyanate compound which thermally dissociates the blocking agent to generate a free isocyanate group can react with the blocking agent while monitoring the infrared absorption spectrum for the polyisocyanate compound having a free isocyanate group until The intrinsic absorption spectrum of the isocyanate group disappears and is easily obtained.

As a commercially available product of a preferred blocked polyisocyanate, DURANATE MF-K60B (manufactured by Asahi Kasei Chemicals Co., Ltd.) and DESMODUR BL-3475 (manufactured by Sumitomo Bayer Polyurethane Co., Ltd.) in which the blocking agent is an active methylene compound, The blocking agent was a TRIXENE BI-7982 (manufactured by Baxenden Co., Ltd.) of a pyrazole compound, and a mixed type of TRIXENE BI-7992 (manufactured by Baxenden Co., Ltd.) of an active methylene group and a pyrazole compound.

The main agent and curing agent constituting the thermosetting resin composition, as long as it is cured In the case where each of the functional groups is consumed, the respective amounts of use may be selected. In short, for example, the amount of the non-volatile component may be from 30 parts to 800 parts per 100 parts of the main agent.

In the thermosetting resin composition containing a combination of a film-forming thermoplastic resin containing a hydroxyl group and an isocyanate curing agent such as a blocked polyisocyanate as an essential component, the isocyanate curing agent is not in terms of mass in terms of mass compatibility. The nonvolatile content of the film-forming thermoplastic resin containing a hydroxyl group per 100 parts of the volatile component is more preferably 5 parts to 50 parts.

(epoxy compound)

In the case of using a combination of a blocked polyisocyanate and a film-forming thermoplastic resin containing a hydroxyl group in the thermosetting resin composition of the present invention, crosslinking can be improved while reducing the viscosity by using an epoxy compound in combination. The density and the adhesion to the substrate of the conductive pattern after curing are further improved or solvent resistance. The epoxy compound to be used is not particularly limited, but an aliphatic epoxy compound is preferably used. Specifically, an epoxide or an alicyclic epoxy compound such as glycidyl etherate such as polyethylene glycol, polypropylene glycol, hexanediol, trimethylolpropane, glycerin, pentaerythritol or sorbitol is preferably used. Among them, glycidyl ether compounds 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 of the thermosetting resin composition which is relatively high in viscosity or solid can be reduced without impairing conductivity, so that conductivity can be made. The fluidity of the ink composition becomes good, in flexographic, screen printing, gravure or gravure offset printing In a specific printing method such as a brush, even when printing is continuously performed on these printing machines, it is possible to easily obtain a conductive pattern which is stable and difficult to cause an obstacle. The partially aromatic epoxy compound is a liquid or semi-solid, but it is not preferred for safety reasons.

When the conductive ink composition of the present invention is prepared, when an epoxy compound is used as a constituent component of the thermosetting resin composition, the performance of the conductive pattern such as conductivity, toughness, and solvent resistance finally obtained is improved. In view of mass, the non-volatile content of the total thermosetting resin composition contained in the ink composition is preferably 5 parts to 50 parts per 100 parts.

(Reaction catalyst for blocking polyisocyanate)

In the blocked polyisocyanate used in the present invention, a reaction catalyst may be used in combination if necessary. The reaction catalyst is not particularly limited, but the reaction catalyst for blocking the polyisocyanate is preferably an organic ammonium salt or an organic phosphonium salt. Specifically, a tetraalkylammonium halide, a tetraalkylammonium hydroxide, a tetraalkylorganic acid ammonium salt or the like as an organic ammonium salt can be used as the 1,8-diazabicyclo ring of the organic phosphonium salt [5.4.0 a phenate, an octanoate, an oleate, a p-toluenesulfonate of undecene-7 (hereinafter DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (hereinafter DBN), Formate. Among them, DBU-octanoate, DBN-octanoate or the like is preferably used. As a commercial product, the organic ammonium salt is exemplified by TOYOCAT-TR20 (manufactured by Tosoh Corporation), and the organic phosphonium salt is exemplified by U-CAT SA1, U-CAT SA102, U-CAT SA106, U-CAT SA506, U-CAT SA603, U-CAT SA1102 (manufactured by San-APRO Co., Ltd.).

Improve the conductivity of conductive patterns such as conductivity and solvent resistance finally obtained In terms of energy, in terms of mass conversion, it is preferably 3 parts to 30 parts per 100 parts of the blocked polyisocyanate as a reaction catalyst for blocking the polyisocyanate.

(Organic solvents)

Since most of the raw materials used in the present invention are solid at 25 ° C in themselves, it is usually necessary to apply or print a fine line pattern of a conductive ink composition on a substrate after dissolving in a liquid medium or the like. Therefore, when the main agent and the curing agent constituting the thermosetting resin composition are selected, it is preferable to consider the solubility to the liquid medium.

From such a viewpoint, in the conductive ink composition of the present invention, an organic compound which is soluble in a thermosetting resin composition and which is not reactive therewith and which is liquid at 25 ° C is used. Such an organic compound is an organic solvent, and the type thereof is not limited, and examples thereof include an ester system, a ketone system, a chlorine system, an alcohol system, an ether system, a hydrocarbon system, and an ether ester system. Specific examples thereof include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, n-butanol, isobutanol, isophorone, γ-butyrolactone, and DBE (manufactured by INVISTA Japan). , N-methyl-2-pyrrolidone, ethyl carbitol acetate, butyl cellosolve acetate, propylene glycol monoalkyl ether acetate, and the like. These may be used alone or in combination of two or more. In the organic solvent, it is preferable to use a solvent having a boiling point of 100° C. to 250° C. from the viewpoint of drying speed, regardless of the type of the printing method to be described later.

As described later, in the case of the gravure printing method or the gravure offset printing method, it is preferred that the swelling ratio of the ketone ketone cloth of the organic solvent is 5% to 20%, and particularly preferably diethylene glycol monobutyl ether acetate. An ether ester such as an ester or diethylene glycol monoethyl ether acetate is an organic solvent.

The content of the organic solvent in the conductive ink composition is preferably 5% by mass to 30% by mass, and more preferably 7% by mass to 15% by mass. If it is in this range, the paste viscosity becomes more appropriate, especially in gravure printing or gravure offset printing, pinhole defects are not generated at the intersection of the corners of the line or the matrix, and a higher precision can be formed. Conductive pattern.

The conductive ink composition of the present invention is characterized, in addition to the well-known conventional raw material components as described above, to further contain at least a group selected from the group consisting of a phosphate group, a phosphate group, and a phosphate group. A functional group of organic compounds. The phosphoric acid group means a group represented by -H ₂ PO ₄ (P atom is 5-valent), and the phosphate group means that at least one of hydrogen atoms in -H ₂ PO ₄ is alkali metal ion or alkaline earth metal The ion is substituted to form a group in the form of a salt. Further, the phosphate group means a group in which at least one of hydrogen atoms in -H ₂ PO ₄ is substituted with an alkyl group or a phenyl group.

Hereinafter, an organic compound containing a phosphoric acid group, an organic compound containing a phosphate group, and an organic compound containing a phosphate group are collectively abbreviated as an organic compound containing a phosphoric acid group.

Examples of such an organic compound containing a phosphoric acid group include a polyalkylene glycol monophosphate, a polyalkylene glycol monoalkyl ether monophosphate, a perfluoroalkyl polyoxyalkylene phosphate, and a perfluoroalkyl group. Low molecular compound such as sulfonamide polyoxyalkylene phosphate, vinylphosphonic acid, acid phosphonium ethyl mono(meth)acrylate, acid phosphoniumpropyl mono(meth)acrylate, acid A homopolymer of a phosphonium polyoxyalkylene glycol mono(meth)acrylate or a polymer containing a phosphate group such as a copolymer of the above monomer and another comonomer is used as a polymer compound.

Further, in the above, as a specific example, only an organic compound containing a phosphoric acid group is exemplified, but an organic compound containing a phosphate group may be obtained by using an alkali metal hydroxide or an alkaline earth metal hydroxide with a phosphate group. The organic compound is easily obtained by a reaction, and the organic compound containing a phosphate group can be condensed with an alcohol by dehydration condensation of an organic compound containing a phosphate group with an alcohol or by a base action. The land is easy to obtain.

As an organic compound containing a phosphoric acid group, in comparison with the amount of the nonvolatile component used, it is comparable to an organic compound containing a phosphate group in terms of being able to have both a lower viscosity and a lower volume resistivity. One of an organic compound containing a phosphate group or an organic compound containing a phosphate group is preferred.

As the low molecular compound, for example, the EFKA series manufactured by Ciba Specialty Chemicals Co., Ltd. can be used, and the polymer compound can be selected and used, for example, from the DISPERBYK series manufactured by BYK Corporation.

The polymer compound preferably has a number average molecular weight of 1,000 or more, and a phosphate group-containing polymer having a number average molecular weight of 1,000 to 10,000, because it does not impair conductivity in the same amount of use as the above-mentioned low molecular compound. In the case where the fluidity of the conductive ink composition is improved, the effect is improved.

The amount of the phosphoric acid group-containing organic compound used in the present invention is preferably 0.1 part by weight to 3 parts per 100 parts by mass of the conductive filler, the thermosetting resin composition, and the organic solvent.

In the conductive ink composition of the present invention, in addition to the above components, a dispersing agent, an antifoaming agent, a releasing agent, a leveling agent, and the like may be appropriately formulated as needed. Various additives such as plasticizers.

The conductive ink composition of the present invention can be formed into a corresponding conductive pattern by any method such as coating or printing on any of a plastic film, a ceramic film, a ruthenium wafer, a glass or a metal plate. However, in order to realize the true value of the conductive ink composition of the present invention, a transparent conductive film such as a PET film, a PP film or an ITO film which cannot be exposed to high temperatures is used in obtaining a conductive pattern.

The conductive ink composition of the present invention can be printed on any substrate by 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, thereby forming Conductive pattern.

The method for forming the conductive pattern composed of the conductive ink composition of the present invention includes a method in which the conductive ink composition of the present invention is applied onto a non-heat-resistant substrate and heated. The conductive ink composition of the present invention can more easily make the viscosity at a shear rate of 10 s ^-1 at 25 ° C of 1 Pa by containing the above-mentioned organic compound having a phosphoric acid group. s~50Pa. s. As a result, the conductive ink composition is filled in the intaglio plate, and the filled ink composition is transferred to the blanket roll, and then the ink composition is transferred from the blanket roll to the non-heat resistant substrate, thereby A desired pattern is printed on the surface of the non-heat resistant substrate, so-called gravure offset printing is performed, and then a conductive pattern is formed by heating.

As the gravure printing plate at this time, a gravure plate formed by exposing, developing, and washing the photosensitive resin on the glass plate can be used. An intaglio plate formed by chemical etching and laser etching of a plate, a metal plate, and a metal roll.

Further, the fluorene ketone tape is a sheet having a layer structure such as an fluorenone rubber layer, a PET layer or a sponge layer, and can be usually used in a state of being wound around a rigid cylinder called a blanket cylinder.

In the method of forming a conductive pattern composed of the conductive ink composition of the present invention, in the case of using the above-described gravure offset printing method, transferability from a gravure and transfer property to a substrate are required for an anthrone tape. . 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 surface of the tape. If the absorption is insufficient, the conductive ink composition layer is liable to cause interlayer peeling when the substrate is transferred. Conversely, if the absorption exceeds a certain ratio, the conductive ink composition is dried on the surface of the adhesive tape, and there is a possibility that the substrate is easily transferred. Bad printing and other issues.

By making the conductive ink composition at 25 ° C, the viscosity is 1 Pa. s~50Pa. s, when the conductive pattern is continuously printed by the gravure offset printing method, pinhole defects are likely to occur at the intersection of the corners of the line or the matrix, and a good conductive thin line pattern can be formed, and also It is difficult to produce a problem of the ink transfer property to the intaglio and the transfer property from the intaglio to the tape.

The conductive ink composition of the present invention is applied onto a substrate to form a printed pattern so as to have a line width of, for example, a range of 10 μm to 150 μm, and by heating and solidifying it, a conductive pattern can be formed.

Then, the printed pattern provided on the substrate is heated, for example, at 100 ° C to 130 ° C for 20 to 5 minutes to form a cured film, and a conductive pattern is formed to exhibit electrical conductivity. Sex.

The conductive pattern formed of the conductive ink composition of the present invention may be a line having a line width as thick as β, but the characteristics in the case of using the conductive ink composition of the present invention are as described above. A finer line width is particularly noticeable when the line is placed on the substrate.

As described above, since the conductive pattern composed of the conductive ink composition of the present invention can be formed at a lower temperature and in a shorter time than before, the conductive ink composition of the present invention is characterized by a ceramic film, a glass or a metal plate. The conductive material having a high heat resistance is particularly remarkable when a conductive pattern is formed on a non-heat-resistant substrate which is less heat-resistant and is easily thermally deformed. Therefore, the conductive pattern of the cured film in which the conductive ink composition of the present invention is formed on the non-heat resistant substrate can be preferably used as a conductive circuit formed on the non-heat resistant substrate.

In the conductive ink composition of the present invention, the substrate on which the conductive pattern is formed by printing and heating by using various printing methods on various substrates can be formed into a conductive circuit by performing wiring or the like as needed. Electrical components, electronic components. 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 an extraction electrode of a touch panel, an extraction electrode of a display, an electronic paper, a solar battery, and other wiring products.

Example

The invention will be specifically described below by way of examples. Here, "%" is "% by mass" unless otherwise specified.

Each raw material was used in accordance with the mass parts described in Table 1, and these raw materials were sufficiently mixed to prepare each of the conductive ink compositions of the present invention as examples and the conventional conductive ink compositions of the comparative examples.

With respect to each of these conductive ink compositions, the characteristics of the conductive ink composition itself and the characteristics of the conductive pattern obtained therefrom were evaluated by the following measurement items. The evaluation results are also collectively shown in Tables 1 and 2 below.

(viscosity)

The viscosity of the conductive ink composition of the present invention at a shear rate of 10 s ^-1 at 25 ° C was measured using a rotary rheometer.

(printing adaptability)

Using the conductive ink composition of the present invention, gravure offset printing was carried out by the following method to produce a conductive circuit.

After the conductive ink composition was inked on a glass gravure using a doctor blade, it was pressed and contacted on a cylinder wound with a tape to transfer a desired pattern onto the tape. Thereafter, the coating film on the tape was pressed and transferred onto a transparent conductive film as a substrate to prepare a conductive circuit having a line width of 30 μm to 100 μm. In the above-described conductive circuit, the line width of the microscopic observation line was 30 μm, and the fine line reproducibility was evaluated based on the following criteria.

◎: The linearity of the line is particularly excellent, and there is no disconnection place.

○: The linearity of the line is excellent, and there is no disconnection place.

×: The linearity of the line is poor, and there is a broken place.

(volume resistivity)

The conductive ink composition was applied onto a transparent conductive film (ITO film surface) so that the film thickness after drying was 4 μm using an applicator, and dried at 125 ° C for 10 minutes. The ink coating film was measured by a four-terminal method using LORESTA GP MCP-T610 (manufactured by Mitsubishi Chemical Corporation). The volume resistivity is a standard of conductivity.

Silver powder: AG-2-1C (DOWA Electronics (stock) system, average particle size D50: 0.8μm)

BYRON 200: molecular weight 17,000, hydroxyl value 6, glass transition point temperature (Tg) 67 ° C, thermoplastic polyester resin (manufactured by Toyobo Co., Ltd.)

SOLBIN AL: a vinyl chloride-vinyl acetate copolymer having a number average molecular weight of 22,000, a glass transition point temperature (Tg) of 76 ° C, and a copolymerization mass ratio of vinyl chloride/vinyl acetate/vinyl alcohol of 93/2/5 (Japanese letter) Chemical Industry Corporation)

DENACOL EX-321: Trimethylolpropane polyglycidyl ether (Nagasechemtex)

TRIXENE BI 7982: Blocking agent is blocked isocyanate of 3,5-dimethylpyrazole (Baxenden)

DISPER BYK-111: a number average molecular weight in the range of 1,000 to 10,000 Polymer containing a phosphate group (polymer compound) (manufactured by BYK)

EFKA-8512: Phosphate (low molecular compound) containing a polyoxyalkylene group (manufactured by Ciba Specialty Chemicals Co., Ltd.)

U-CAT SA 102: DBU-octanoate (manufactured by San-APRO Co., Ltd.)

U-CAT SA 603: DBU-formate (manufactured by San-APRO Co., Ltd.)

CUREZOL 2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd.)

EDGAc: diethylene glycol monoethyl ether acetate

From the evaluation results of Table 1, it is understood that the conductive ink composition of Example 4 containing an organic compound having a phosphate group has viscosity and printability as compared with the conductive ink composition of Comparative Example 1 not containing the conductive ink composition. Both are excellent. As is clear from the comparison between Example 3 and Example 4, when a polymer compound is used as the organic compound containing a phosphate group, the viscosity and conductivity are remarkably superior as compared with the case of using a low molecular compound containing a phosphate group. .

It is understood that the conductive ink composition of Examples 3 to 4 has a relationship between the ratio of each non-volatile component of the film-forming thermoplastic resin containing a hydroxyl group and the isocyanate curing agent, and the latter has more curing agent and thermoplasticity of the former. The resin was more excellent in printing suitability than the conductive ink compositions of Examples 1 to 2.

In addition, since the conductive ink composition of the examples is a blocking agent for blocking isocyanate, which is a low-temperature dissociable active methylene compound and/or a pyrazole compound, it is not heat-resistant even in a transparent conductive film or a PET film. On the substrate, a conductive pattern composed of a cured film can be formed at a low temperature for a short period of time without warpage, and the obtained conductive pattern is sufficiently satisfactory in terms of conductivity and substrate adhesion.

[Industrial availability]

The conductive ink composition of the present invention can be used as a conductive silver paste for forming a conductive pattern of various electrical components and electronic components.

Claims (9)

A conductive ink composition comprising a conductive filler, a thermosetting resin composition, an organic solvent as an essential component, and further comprising a phosphoric acid group, a phosphate group, and a phosphate group. An organic compound of at least one functional group selected from the group consisting of a group, and the thermosetting resin composition contains a blocked polyisocyanate of an active methylene compound or a pyrazole compound. The conductive ink composition according to claim 1, wherein the organic compound is at least one functional group selected from the group consisting of a phosphate group, a phosphate group, and a phosphate group, and A polymer having a number average molecular weight of 1,000 or more. The conductive ink composition according to claim 1, wherein the conductive filler is a spherical silver powder having an average particle diameter of 0.1 μm 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 having a hydroxyl group. The conductive ink composition according to claim 4, wherein an epoxy compound is further used in combination. 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 Pa. s~50Pa. s. A method for manufacturing a conductive pattern, as in the first item of the patent application scope The conductive ink composition according to any one of the items 5, wherein the conductive ink composition is applied to a non-heat-resistant substrate and heated. The method for producing a conductive pattern according to claim 7, wherein the conductive ink composition according to any one of claims 1 to 5 is filled in a gravure, and the filled portion is filled. After the conductive ink composition is transferred to the blanket roll, the desired pattern is printed on the surface of the non-heat resistant substrate by transferring the conductive ink composition from the blanket roll to the non-conductive support. Then proceed with heating. A conductive circuit comprising a conductive pattern of a cured film of the conductive ink composition according to any one of claims 1 to 5, which is formed on a non-heat-resistant substrate.