JP6168510B2 - Conductive composition, method for producing wiring board using the same, and wiring board - Google Patents

Description

  The present invention relates to a conductive composition, a method for manufacturing a wiring board using the same, and a wiring board. Specifically, a wiring pattern excellent in adhesion to a base substrate and low resistance can be formed satisfactorily. The present invention relates to a conductive composition, a method for manufacturing a wiring board using the same, and a wiring board.

  Conventionally, as a technique for forming a fine wiring pattern, a technique of patterning a metal thin film formed by a heating vapor deposition method or a sputtering method by a photolithography method is known. However, a vacuum environment is indispensable for the heating vapor deposition method and the sputtering method, and the production cost is a problem. In addition, since the photolithography method uses a large amount of a solvent, the burden on the environment is also cited as a problem.

  On the other hand, a wiring pattern forming technique by a printing method is already practically used because a large amount of products can be efficiently manufactured at a low cost. However, in the method of forming a wiring pattern having higher conductivity by the printing method, it is necessary to remove the binder component and the like contained in the formed conductive pattern by baking at a high temperature. For this reason, the conductive pattern is mostly formed on a heat-resistant hard substrate such as glass.

  On the other hand, rapid spread of flexible sheet displays, flexible RF-ID (radio frequency recognition) systems, and the like is expected as recent electronic devices. In order to realize these flexible devices, a wiring pattern must be formed on a flexible plastic film. However, since many flexible plastic films are softened and melted at a high temperature, it is difficult to form a wiring pattern on the plastic film.

  For example, in Patent Document 1, a low resistivity (about 10 μΩ) is obtained by applying metal particles having a nano-order particle diameter on a base substrate and heating at low temperature (200 to 300 ° C.). A conductive nanoparticle paste capable of producing a (cm) wiring pattern has been proposed. However, since metal particles having a nano-order particle size are generally expensive, it is difficult to manufacture a wiring board at a low cost.

  On the other hand, Patent Document 2 does not use nano-order metal particles, does not require high-temperature heating, and inexpensively produces a wiring pattern on a resinous substrate, and a method for producing the wiring substrate Has been proposed. Specifically, a conductive paste is applied to the surface of the base substrate in a desired wiring pattern, and the obtained wiring pattern is pressed with a pressure roller and then heated at a temperature of 150 ° C. or lower. Thus, a wiring board in which the base substrate and the wiring pattern are firmly adhered is manufactured.

JP 2004-273205 A JP 2010-21470 A

  Certainly, according to the method for manufacturing a wiring board described in Patent Document 2, it can be applied when silver is used as the metal particles. However, when the present invention is applied to metal particles other than silver such as aluminum and copper, the present inventors have found a new problem that the formed wiring pattern cannot obtain sufficient adhesion with the base substrate.

  Accordingly, an object of the present invention is to provide a conductive composition that can efficiently produce a wiring board at low cost and that can satisfactorily form a wiring pattern excellent in adhesion to the base substrate and low resistance. The present invention provides a method for manufacturing a wiring board using the above and a wiring board.

  As a result of intensive studies to solve the above problems, the present inventors have found that a binder in a conductive composition used in a method for manufacturing a wiring board that reduces resistance by pressurizing a wiring pattern formed on a base substrate. By using a thermoplastic resin and a thermosetting resin in combination as the resin, even if metal particles other than silver such as aluminum or copper are used as the conductive particles, the adhesion between the wiring pattern and the substrate substrate As a result, the present invention has been completed.

That is, the conductive composition of the present invention is a conductive composition used in a method for manufacturing a wiring board that is subjected to a resistance reduction treatment by pressurizing a wiring pattern formed on a base substrate.
A thermoplastic resin and a thermosetting resin as a binder resin, a curing agent, and metal particles are contained.

  In the conductive composition of the present invention, the thermoplastic resin is preferably at least one selected from polyester resins and phenoxy resins. The thermosetting resin is preferably an epoxy resin.

Further, the method for manufacturing a wiring board according to the present invention includes a coating step of coating a conductive composition on a base substrate and forming a wiring pattern made of the conductive composition on the base substrate, and the coating step. In a method for manufacturing a wiring board, comprising: a thermosetting step for thermosetting the wiring pattern formed by the step; and a pressing step for pressing the base substrate having the wiring pattern thermoset by the thermosetting step.
As the conductive composition, the conductive composition of the present invention is used.

  Furthermore, the wiring board of the present invention is manufactured by the above-described method for manufacturing a wiring board of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the electrically conductive composition which can manufacture a wiring board inexpensively and efficiently, and can form the wiring pattern excellent in adhesiveness with a base substrate and low resistance favorably is used. It is possible to provide a method for manufacturing a wiring board and a wiring board.

It is a flowchart which shows the manufacturing method of a wiring board. It is a schematic diagram which shows the application | coating process which apply | coats an electroconductive composition to a base material board | substrate. It is a schematic diagram which shows the pressurization process which pressurizes with respect to the apply | coated electrically conductive composition.

Hereinafter, embodiments of the present invention will be described in detail.
The conductive composition of the present invention is a conductive composition that can be suitably used in a method for manufacturing a wiring board that is subjected to resistance reduction treatment by pressurizing a wiring pattern formed on a base substrate, and as a binder resin A thermoplastic resin and a thermosetting resin, a curing agent, and metal particles. Thus, the conductive composition of the present invention has the greatest feature in that a thermoplastic resin and a thermosetting resin are used in combination as a binder resin. As a result, according to the present invention, even when aluminum other than silver, copper, or the like is used as the metal particles, the formed wiring pattern has excellent adhesion to the base substrate, and has a resistance value. The effect that it can reduce can also be acquired. Hereinafter, each component of the electrically conductive composition of this invention is demonstrated in detail.

<Thermoplastic resin>
In the present invention, as the thermoplastic resin constituting the conductive composition, polyester resin, phenoxy resin, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, Polybutadiene resin, polycarbonate resin, thermoplastic polyimide resin, polyamide resin such as 6-nylon or 6,6 nylon, acrylic resin, polyamideimide resin, or fluorine resin can be used. In the present invention, these thermoplastic resins may be used alone or in combination of two or more. In particular, in the present invention, it is preferable to use at least one thermoplastic resin selected from polyester resins and phenoxy resins.

  The polyester resin is obtained by polycondensing at least one selected from unsaturated fatty acids and saturated fatty acids and one or more selected from glycols under normal pressure or reduced pressure by a known method. Can be used. Examples of unsaturated fatty acids include maleic anhydride, fumaric acid, citraconic acid, itaconic acid and the like. Examples of saturated fatty acids include het acid, phthalic anhydride, isophthalic acid, terephthalic acid, endomethylenetetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic acid, adipic acid, azelaic acid, sebacic acid, and the like. . Examples of glycols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,5-pentanediol, , 6-hexanediol, neopentyl glycol, 2,2,4-trimethylpentane-1,3-diol, hydrogenated bisphenol A, pentaerythritol diallyl ether, trimethylene glycol, 2-ethyl 1,3-hexanediol, etc. Can be mentioned.

  Examples of the phenoxy resin include a phenoxy resin having a bisphenol A skeleton, a phenoxy resin having a bisphenol F skeleton, a phenoxy resin having a bisphenol S skeleton, and a bisphenol M skeleton (4,4 ′-(1,3-phenylenedioxide). Phenoxy resin having isopropylidene) bisphenol skeleton), phenoxy resin having bisphenol P (4,4 ′-(1,4) -phenylenediisopridiene) bisphenol skeleton), bisphenol Z (4,4′-cyclohexene) Phenoxy resin having a bisphenol skeleton, such as a phenoxy resin having a sidiene bisphenol skeleton), a phenoxy resin having a novolac skeleton, a phenoxy resin having an anthracene skeleton, a phenoxy resin having a fluorene skeleton, dicyclo Phenoxy resins having Ntajien skeleton, phenoxy resins having a norbornene skeleton, phenoxy resins having a naphthalene skeleton, phenoxy resins having a biphenyl skeleton include phenoxy resins having an adamantane skeleton.

  Such a thermoplastic resin preferably has a number average molecular weight (Mn) of 2,000 to 200,000, more preferably 5,000 to 100,000. If the number average molecular weight is less than 2000, a transfer failure during printing tends to occur, and it may be difficult to form a good wiring pattern. On the other hand, if the number average molecular weight exceeds 200000, whisker defects or line waviness due to stringing of the conductive composition is likely to occur during printing, and printability may be impaired. The number average molecular weight is a standard polystyrene equivalent value measured by gel permeation chromatography (GPC).

<Thermosetting resin>
In the present invention, an epoxy resin, a phenol resin, an amino resin, an unsaturated polyester resin, a polyurethane resin, a silicone resin, a thermosetting polyimide resin, or the like is used as the thermosetting resin constituting the conductive composition. it can. Among these, it is preferable to use an epoxy resin. In the present invention, these thermosetting resins may be used alone or in combination of two or more.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, and cresol novolac. Type epoxy resin, bisphenol A novolak type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin, alicyclic epoxy resin, aliphatic chain Epoxy resin, phosphorus-containing epoxy resin, anthracene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, aminophenol type epoxy resin Resin, amino cresol type epoxy resins, phenol type epoxy resin.

  Such a thermosetting resin preferably has a number average molecular weight (Mn) of 100 to 50,000, and more preferably 150 to 10,000. If the number average molecular weight deviates from such a range, the adhesion with the base substrate may be impaired.

  The thermoplastic resin and thermosetting resin as the binder resin as described above are preferably blended in a mass ratio of 95: 5 to 30:70, more preferably 90:10 to 50:50. Mix in proportions. By setting the blending ratio of the thermoplastic resin and the thermosetting resin within the above range, it is possible to form a wiring pattern with excellent adhesion to the base substrate, and to reduce the resistance value of the wiring pattern. Can be made. In addition, it is preferable that it is 1-25 mass% in solid content conversion in a conductive composition, and, as for the compounding quantity as binder resin, it is more preferable that it is the range of 3-20 mass%. The more the binder resin is, the more excellent adhesion with the base substrate can be secured, but sufficient conductivity may not be obtained. On the other hand, if the binder resin is reduced, the adhesion with the base substrate may be impaired.

<Curing agent>
In the present invention, the curing agent constituting the conductive composition is not particularly limited as long as it can cure a thermosetting resin such as an epoxy resin, and a known one can be appropriately used. For example, phenol resins, imidazole compounds, acid anhydrides, aliphatic amines, alicyclic polyamines, aromatic polyamines, tertiary amines, dicyandiamide, guanidines, or epoxy adducts and microencapsulated products thereof, triphenyl By treating the surface of an organic phosphine compound such as phosphine, tetraphenylphosphonium, tetraphenylborate, and the epoxy adduct described in JP-A-06-73156 with a boric acid ester compound, etc. The resulting one-component epoxy compound, for example, an epoxy-phenol-borate compound, etc. can be used. These curing agents may be used alone or in combination of two or more.

  As for the compounding quantity of such a hardening | curing agent, 1-20 mass parts is preferable with respect to 100 mass parts of thermosetting resins. By setting the blending amount of the curing agent in such a range, the thermosetting resin of the wiring pattern can be cured well, the metal particles in the wiring pattern can be retained, and excellent adhesion to the base substrate can be ensured. It becomes possible. In addition, it is preferable that it is 0.01-5 mass% in conversion of solid content in the electrically conductive composition, and, as for the addition amount of a hardening | curing agent, it is more preferable that it is the range of 0.05-3 mass%.

<Metal particles>
In the present invention, examples of the metal particles constituting the conductive composition include aluminum, copper, silver, and gold particles. From the viewpoint of cost, low resistance treatment, and migration, aluminum and copper particles. Is preferred. These metal particles have an average particle diameter of 10 random metal particles observed at 10000 times using an electron microscope (SEM), preferably 0.1 to 15 μm, and in the range of 0.5 to 5 μm. More preferably. These metal particles can improve the contact state between the metal particles as the average particle size is small, and it is possible to improve the conductivity of the formed wiring pattern. If the value is on the nano order, the effect of reducing the resistance may not be sufficiently obtained. On the other hand, when the average particle size of the metal particles is increased, the adhesion to the base substrate may be impaired.

  In the conductive composition of the present invention, the shape of the metal particles to be used is not particularly limited, but a spherical shape is suitable for the resistance reduction treatment. The compounding amount of such metal particles is preferably 50 to 90% by volume in terms of solid content in the conductive composition, and more preferably 60 to 85% by volume. If the blending amount of the metal particles is less than 50% by volume, the contact points between the metal particles in the wiring pattern may be reduced, and sufficient conductivity may not be obtained. On the other hand, when the blending amount of the metal particles exceeds 90% by volume, the amount of the binder resin is relatively decreased, and thus the adhesion between the wiring pattern and the base substrate may be lowered. In addition, it is preferable that it is 65-99 mass% in conversion of solid content in a conductive composition, and, as for mass ratio, it is more preferable that it is the range of 75-97 mass%.

  The conductive composition of the present invention includes, for example, a metal dispersant, a thixotropy imparting agent, an antifoaming agent, a leveling agent, a diluent, a plasticizer, an antioxidant, and a metal as long as printability is not impaired. You may mix | blend additives, such as a deactivator, a coupling agent, and a filler.

  When a wiring pattern is printed on a base substrate using the conductive composition of the present invention, the conductive composition of the present invention is usually used by diluting with a solvent. It is preferable to use a material having good dispersibility and volatility. For example, methanol, ethanol, isopropyl alcohol (IPA), methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), ethyl acetate, cyclohexanone, toluene, xylene, diethylene glycol monoethyl ether acetate, dipropylene glycol monoethyl methyl ether, dipropylene glycol Examples thereof include monomethyl ether, 1- (2-methoxy-2-methylethoxy) -2-propanol, propylene glycol monomethyl ether acetate, and water. Each of these solvents may be used alone, or two or more of them may be mixed and used in an arbitrary ratio.

Next, the manufacturing method of the wiring board of this invention and the wiring board of this invention are demonstrated.
The method for manufacturing a wiring board according to the present invention includes a coating step of coating a conductive composition on a base substrate and forming a wiring pattern made of the conductive composition on the base substrate, and the coating step. A thermosetting process for thermosetting the wiring pattern formed, and a pressurizing process for pressing the base substrate having the wiring pattern thermoset by the thermosetting process. In the method for producing a wiring board of the present invention, it is important to use the conductive composition of the present invention as the conductive composition. This is because, as described above, the conductive composition of the present invention can efficiently produce a wiring board at low cost and can form a wiring pattern with excellent adhesion to a base substrate. Hereafter, the manufacturing method of the wiring board of this invention is demonstrated in detail.

  First, a method for manufacturing a wiring board will be described with reference to FIG. FIG. 1 is a flowchart showing a method for manufacturing a wiring board according to the present invention. As shown in the drawing, a wiring board is formed by applying a conductive composition onto a base substrate and forming a wiring pattern made of the conductive composition as a base. An application step (S1) formed on the substrate, a thermosetting step (S2) for thermosetting the wiring pattern formed by the application step, and the base substrate having the wiring pattern thermoset by the thermosetting step. And a pressurizing step (S3) for applying pressure. In the application step (S1), the conductive composition of the present invention is applied to the base substrate surface in a predetermined wiring pattern. There is no restriction | limiting in particular as an application | coating method, A well-known method is applicable as a method of apply | coating an electroconductive composition. Examples of the coating method include various printing methods (screen printing method, intaglio printing method, relief printing method, lithographic printing method), dispensing method, ink jet method and the like.

  Next, in the substrate substrate on which the conductive composition of the present invention has been applied in the application step (S1), the wiring pattern is heat-cured in the thermosetting step (S2). In this step, the applied wiring pattern can be dried at the same time, but if necessary, a coating film drying step may be performed in advance to dry the wiring pattern. The binder resin of the conductive composition of the present invention is composed of a thermoplastic resin and a thermosetting resin. As described above, since the thermosetting resin exists in the binder resin, the binder resin is subjected to this thermosetting step. Good adhesion to the substrate can be obtained. Here, the thermosetting conditions are preferably 80 to 200 ° C. for 1 to 120 minutes, more preferably 100 to 170 ° C. for 10 to 60 minutes.

  Next, the wiring board on which the wiring pattern is heat-cured in the thermosetting step (S2) is pressurized in the pressurizing step (S3). Here, in the pressing step (S3), the pressing body is driven so that a horizontal pressure is applied between the printed conductive composition and the pressing body, and shear stress is applied to the surface of the conductive composition. Is generated. Thereby, the metal particles are plastically deformed and pressed between adjacent metal particles to form a conductive metal bond. As a result, a resistance reduction process is realized.

  Furthermore, if necessary, the base substrate having the wiring pattern that has been subjected to the resistance reduction treatment in the pressurizing step (S3) is heated in the heating step. In this heating step, the contact probability between the metal particles is further increased by curing and shrinking the wiring pattern. In addition, you may implement this heating process simultaneously during a pressurization in a pressurization process (S3).

  Here, the application | coating process (equivalent to S1 in FIG. 1) of an electroconductive composition is demonstrated using FIG. In FIG. 2, the case where the screen printing method is employ | adopted as a method of apply | coating the electroconductive composition 4 which has the binder 2 and the metal particle 3 to a predetermined pattern on the base-material board | substrate 1 is shown. As shown in FIG. 2, in the coating process, a screen plate 5 capable of printing a predetermined wiring pattern is disposed on the base substrate 1. Then, the conductive composition is disposed on the screen plate 5.

  Next, the conductive composition 4 placed on the screen plate 5 is stretched while being pressed against the base substrate 1 using the squeegee 6. Thereby, it will be in the state by which the conductive composition 4 was apply | coated on the base-material board | substrate 1 in the predetermined wiring pattern shape.

  Next, a thermosetting process (corresponding to S2 in FIG. 1) will be described. In the thermosetting step, the conductive composition pressed in the pressing step is heated and thermoset. Through the above steps, a wiring board in which a wiring pattern is formed is manufactured. In the present invention, the conductive composition is preferably thermoset at a heating temperature of preferably 80 to 200 ° C, more preferably 100 to 170 ° C. Thereby, even when a resinous material that is relatively weak against heat is used as the material of the base substrate, it is possible to form a wiring pattern without affecting the physical properties of the base substrate.

  Next, the pressurizing step (corresponding to S3 in FIG. 1) will be described with reference to FIG. As shown in the figure, in the pressurizing step, a pressurizing body 7 is placed on the conductive composition 4 constituting the wiring pattern thermoset by the thermosetting step (see FIG. 1), and horizontal pressure is applied. Thus, the pressurizing body 7 is driven to pressurize the conductive composition 4. Thereby, the metal particles 3 are plastically deformed and pressed between the adjacent metal particles 3 to form conductive metal bonds 3a, thereby improving the conductivity of the wiring pattern. In the illustrated example, a pressure roller is used as the pressure body 7, but in the present invention, the pressure body is not limited to this.

  As described above, the conductive composition of the present invention is applied on a base substrate to form a wiring pattern. Thereby, since the thermosetting resin and the base substrate are firmly adhered, it is possible to produce a wiring substrate having a wiring pattern excellent in adhesion and realizing low resistance.

  In addition, there is no restriction | limiting in particular about the base substrate used for the manufacturing method of the wiring board of this invention, The resin material conventionally used as a material of a base substrate can be used. In particular, when a resin base material is used as the base material substrate, for example, polyimide, polyester resin, polyethersulfone (PES), polystyrene (PS), polymethyl methacrylate (PMMA), polycarbonate (PC), polyamide ( PA), polypropylene (PP), polyphenylene oxide (PPO) and the like can be mentioned, and a polyester-based resin can be preferably used.

  Examples of the polyester resin include polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polybutylene naphthalate (PBN). Moreover, in these resin materials, in order to improve the adhesiveness of the conductive composition, a primer may be applied or a treatment such as a corona treatment may be performed, but such a treatment may be performed. .

Hereinafter, the present invention will be described in more detail with reference to implementation.
<Example 1>
83 parts by mass of thermoplastic resin (amorphous polyester resin: Byron 290 manufactured by Toyobo Co., Ltd.), 17 parts by mass of thermosetting resin (bisphenol A type epoxy resin: EPICLON 840 manufactured by DIC Corporation), 241 masses of organic solvent Parts (diethylene glycol monoethyl ether acetate), curing agent (1) 1.7 parts by mass (epoxy-phenol-borate ester compound: L-07N manufactured by Shikoku Kasei Kogyo Co., Ltd.), curing agent (2) 3. 2 parts by mass (epoxyimidazole adduct: P0505 manufactured by Shikoku Kasei Kogyo Co., Ltd.), 5 parts by mass of leveling / foaming agent (Polyflow No. 90 manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by mass of surface modifier (silane) Coupling agent: Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and 433 parts by mass of aluminum particles (spherical powder, average particle size 2 m) was stirred 500 rpm, 20 min at dissolver. Then, it knead | mixed 3 times with 3 rolls made from 7 inch size ceramics, and produced the electrically conductive composition. In addition, aluminum content was 60 volume% in conversion of solid content in an electroconductive composition.

<Example 2>
83 parts by mass of thermoplastic resin (amorphous polyester resin: Byron 290 manufactured by Toyobo Co., Ltd.), 17 parts by mass of thermosetting resin (bisphenol A epoxy resin: EPICLON 840 manufactured by DIC Corporation), 289 masses of organic solvent Parts (diethylene glycol monoethyl ether acetate), curing agent (1) 1.7 parts by mass (epoxy-phenol-borate ester compound: L-07N manufactured by Shikoku Kasei Kogyo Co., Ltd.), curing agent (2) 3. 2 parts by mass (epoxyimidazole adduct: P0505 manufactured by Shikoku Kasei Kogyo Co., Ltd.), 5 parts by mass of leveling / foaming agent (Polyflow No. 90 manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by mass of surface modifier (silane) Coupling agent: Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and 675 parts by mass of aluminum particles (spherical powder, average particle size 2) m) was stirred 500 rpm, 20 min at dissolver. Then, it knead | mixed 3 times with 3 rolls made from 7 inch size ceramics, and produced the electrically conductive composition. In addition, aluminum content was 70 volume% in conversion of solid content in an electroconductive composition.

<Example 3>
83 parts by mass of thermoplastic resin (amorphous polyester resin: Byron 290 manufactured by Toyobo Co., Ltd.), 17 parts by mass of thermosetting resin (bisphenol A type epoxy resin: EPICLON 840 manufactured by DIC Corporation), 414 masses of organic solvent Parts (diethylene glycol monoethyl ether acetate), curing agent (1) 1.7 parts by mass (epoxy-phenol-borate ester compound: L-07N manufactured by Shikoku Kasei Kogyo Co., Ltd.), curing agent (2) 3. 2 parts by mass (epoxyimidazole adduct: P0505 manufactured by Shikoku Kasei Kogyo Co., Ltd.), 5 parts by mass of leveling / foaming agent (Polyflow No. 90 manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by mass of surface modifier (silane) Coupling agent: Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and 1152 parts by mass of aluminum particles (spherical powder, average particle size) μm) and the mixture was stirred 500rpm, 20 minutes in the dissolver. Then, it knead | mixed 3 times with 3 rolls made from 7 inch size ceramics, and produced the electrically conductive composition. In addition, aluminum content was 80 volume% in conversion of solid content in an electroconductive composition.

<Example 4>
83 parts by mass of thermoplastic resin (phenoxy resin: YP-50 manufactured by Nippon Steel Chemical Co., Ltd.), 17 parts by mass of thermosetting resin (bisphenol A type epoxy resin: EPICLON 840 manufactured by DIC Corporation), organic solvent 289 Parts by mass (diethylene glycol monoethyl ether acetate), curing agent (1) 1.7 parts by mass (epoxy-phenol-borate ester compound: L-07N manufactured by Shikoku Kasei Kogyo Co., Ltd.), curing agent (2) 3 .2 parts by mass (epoxyimidazole adduct: P0505 manufactured by Shikoku Kasei Kogyo Co., Ltd.), 5 parts by mass of leveling / foaming agent (Polyflow No. 90 manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by mass of surface modifier ( Silane coupling agent: Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and 675 parts by mass of aluminum particles (spherical powder, average particle size 2 μm) And the mixture was stirred 500rpm, 20 minutes at Izoruba. Then, it knead | mixed 3 times with 3 rolls made from 7 inch size ceramics, and produced the electrically conductive composition. In addition, aluminum content was 70 volume% in conversion of solid content in an electroconductive composition.

<Example 5>
83 parts by mass of thermoplastic resin (amorphous polyester resin: Byron 290 manufactured by Toyobo Co., Ltd.), 17 parts by mass of thermosetting resin (bisphenol A epoxy resin: EPICLON 840 manufactured by DIC Corporation), 289 masses of organic solvent Parts (diethylene glycol monoethyl ether acetate), curing agent (1) 1.7 parts by mass (epoxy-phenol-borate ester compound: L-07N manufactured by Shikoku Kasei Kogyo Co., Ltd.), curing agent (2) 3. 2 parts by mass (epoxyimidazole adduct: P0505 manufactured by Shikoku Kasei Kogyo Co., Ltd.), 5 parts by mass of leveling / foaming agent (Polyflow No. 90 manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by mass of surface modifier (silane) Coupling agent: Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and 675 parts by mass of aluminum particles (long fine powder, flat in the long axis direction) Particle size 4 [mu] m, a minor axis average particle diameter 2 [mu] m) was stirred 500 rpm, 20 min at dissolver. Then, it knead | mixed 3 times with 3 rolls made from 7 inch size ceramics, and produced the electrically conductive composition. In addition, aluminum content was 70 volume% in conversion of solid content in an electroconductive composition.

<Example 6>
83 parts by mass of thermoplastic resin (amorphous polyester resin: Byron 290 manufactured by Toyobo Co., Ltd.), 17 parts by mass of thermosetting resin (bisphenol A epoxy resin: EPICLON 840 manufactured by DIC Corporation), 289 masses of organic solvent Parts (diethylene glycol monoethyl ether acetate), curing agent (1) 1.7 parts by mass (epoxy-phenol-borate ester compound: L-07N manufactured by Shikoku Kasei Kogyo Co., Ltd.), curing agent (2) 3. 2 parts by mass (epoxyimidazole adduct: P0505 manufactured by Shikoku Kasei Kogyo Co., Ltd.), 5 parts by mass of leveling / foaming agent (Polyflow No. 90 manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by mass of surface modifier (silane) Coupling agent: Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and 2220 parts by mass of copper particles (spherical powder, average particle size 3 μm) And the mixture was stirred 500rpm, 20 minutes at Izoruba. Then, it knead | mixed 3 times with 3 rolls made from 7 inch size ceramics, and produced the electrically conductive composition. In addition, copper content was 70 volume% in conversion of solid content in an electroconductive composition.

<Comparative Example 1>
100 parts by weight of thermoplastic resin (amorphous polyester resin: Byron 290 manufactured by Toyobo Co., Ltd.), 277 parts by weight of organic solvent (diethylene glycol monoethyl ether acetate), 5 parts by weight of leveling / foaming agent (Kyoeisha Chemical Co., Ltd.) Polyflow No. 90), surface modifier 5 parts by mass (silane coupling agent: Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and aluminum particles 416 parts by mass (spherical powder, average particle size 2 μm) The mixture was stirred with a dissolver at 500 rpm for 20 minutes. Then, it knead | mixed 3 times with 3 rolls made from 7 inch size ceramics, and produced the electrically conductive composition. In addition, aluminum content was 60 volume% in conversion of solid content in an electroconductive composition.

<Comparative example 2>
100 parts by weight of thermoplastic resin (amorphous polyester resin: Byron 290 manufactured by Toyobo Co., Ltd.), 338 parts by weight of organic solvent (diethylene glycol monoethyl ether acetate), 5 parts by weight of leveling / foaming agent (Kyoeisha Chemical Co., Ltd.) Polyflow No. 90), surface modifier 5 parts by mass (silane coupling agent: Z-6040 manufactured by Toray Dow Corning Co., Ltd.) and aluminum particles 648 parts by mass (spherical powder, average particle size 2 μm) The mixture was stirred with a dissolver at 500 rpm for 20 minutes. Then, it knead | mixed 3 times with 3 rolls made from 7 inch size ceramics, and produced the electrically conductive composition. In addition, aluminum content was 70 volume% in conversion of solid content in an electroconductive composition.

<Production of substrate>
A wiring board was produced using the obtained conductive compositions of Examples 1 to 6 and Comparative Examples 1 and 2. A polyimide film of 50 μm was used as the base substrate. Screen printing (pattern printing) was performed on the base substrate using the obtained conductive composition. For screen printing, a 300 mesh polyester screen plate was used. The wiring pattern of the substrate for specific resistance measurement was 0.1 cm × 40 cm, and the wiring pattern of the substrate for adhesion evaluation was 2 cm × 5 cm. Next, the wiring pattern formed on the base substrate was dried and heat-cured at 150 ° C. for 30 minutes, and then a resistance reduction process described later was performed to produce a wiring board.

<Low resistance treatment>
A wiring pattern formed with a screen-printed conductive composition is placed on a pressure machine stage with a vacuum chuck or adhesive tape, and shear stress is generated between the pressure body and the surface of the wiring pattern of the conductive composition. Thus, the speed of the pressurizer stage and the pressurizing body was adjusted. The shear stress generated at this time was measured with a prescale (manufactured by Fuji Film Co., Ltd.) and was 55 MPa or more.

<Specific resistance value>
With respect to the resistance value measurement wiring pattern (0.1 cm × 40 cm) subjected to the resistance reduction treatment, the line resistance value of the wiring pattern was measured using a HIOKI 3540 mΩ high tester manufactured by HIOKI. From the obtained line resistance value, a specific resistance value was calculated using the following formula.
Specific resistance (Ω · cm) = Line resistance (Ω) × film thickness (cm) × line width (cm) / line length (cm)
The obtained results are shown in Tables 1 and 2 below.

<Adhesion>
With respect to the wiring pattern (2 cm × 5 cm) of the substrate for adhesion evaluation subjected to the low resistance treatment, 25 wiring patterns were cut into a 1 mm-interval grid pattern according to the cross-cut method (JIS K-5600). . Adhesion was evaluated according to the state when a tape was applied and peeled off. The case where there was no peeling was marked with ◯, and the case where there was peeling was marked with ×. The obtained results are shown in Tables 1 and 2 below.

※１ 熱可塑性樹脂Ａ：非晶性ポリエステル樹脂：東洋紡（株）社製 バイロン２９０
※２ 熱可塑性樹脂Ｂ：フェノキシ樹脂：新日鐵化学（株）社製 ＹＰ−５０
※３ 熱硬化性樹脂：ビスフェノールＡ型エポキシ樹脂：ＤＩＣ（株）社製 ＥＰＩＣＬＯＮ８４０
※４ 硬化剤１：エポキシ−フェノール−ホウ酸エステル配合物：四国化成工業（株）社製 Ｌ−０７Ｎ
※５ 硬化剤２：エポキシイミダゾールアダクト：四国化成工業（株）社製 Ｐ０５０５
※６ 金属粒子Ａ：アルミニウム粒子、球状粉、平均粒径２μｍ
※７ 金属粒子Ｂ：アルミニウム粒子、長細粉、長軸方向平均粒径４μｍ、短軸方向平均粒径２μｍ
※８ 金属粒子Ｃ：銅粒子、球状粉、平均粒径３μｍ
※９ レベリング・消泡剤：アルリル系レベリング・消泡剤：共栄社化学（株）社製 ポリフローＮｏ．９０
※１０ 表面改質剤：シランカップリング剤：東レ・ダウコーニング（株）社製 Ｚ−６０４０
※１１ 有機溶剤：ジエチレングリコールモノエチルエーテルアセテート
※１２ ＨＩＯＫＩｍΩハイテスタの測定レンジを超えて測定不能（非導電性）

* 1 Thermoplastic resin A: Amorphous polyester resin: Byron 290 manufactured by Toyobo Co., Ltd.
* 2 Thermoplastic resin B: Phenoxy resin: YP-50 manufactured by Nippon Steel Chemical Co., Ltd.
* 3 Thermosetting resin: Bisphenol A type epoxy resin: EPICLON840 manufactured by DIC Corporation
* 4 Curing agent 1: Epoxy-phenol-borate ester compound: L-07N manufactured by Shikoku Kasei Kogyo Co., Ltd.
* 5 Curing agent 2: Epoxy imidazole adduct: P0505 manufactured by Shikoku Kasei Kogyo Co., Ltd.
* 6 Metal particles A: Aluminum particles, spherical powder, average particle size 2μm
* 7 Metal particle B: Aluminum particles, long fine powder, long axis direction average particle size 4 μm, short axis direction average particle size 2 μm
* 8 Metal particle C: Copper particle, spherical powder, average particle size 3μm
* 9 Leveling and antifoaming agent: Allyl leveling and antifoaming agent: Polyflow No. manufactured by Kyoeisha Chemical Co., Ltd. 90
* 10 Surface modifier: Silane coupling agent: Z-6040 manufactured by Toray Dow Corning Co., Ltd.
* 11 Organic solvent: Diethylene glycol monoethyl ether acetate * 12 Cannot be measured beyond the measurement range of HIOKIMmΩ HiTester (non-conductive)

  From Tables 1 and 2, the wiring pattern formed on the base substrate using the conductive composition of the present invention has strong adhesion to the base substrate and has a sufficiently low specific resistance value. It can be seen that it is. As mentioned above, the electroconductive composition of this invention can be used suitably for manufacture of electronic devices, such as RF-ID.

DESCRIPTION OF SYMBOLS 1 Base substrate 2 Binder resin 3 Metal particle 3a Metal bond 4 Conductive composition 5 Screen plate 6 Squeegee 7 Pressurized body

Claims (4)

In the conductive composition used in the method of manufacturing a wiring board for reducing resistance by pressurizing the wiring pattern formed on the base substrate,
Containing a thermoplastic resin and a thermosetting resin as a binder resin, a curing agent, and metal particles ,
The conductive composition, wherein a mass ratio of the thermoplastic resin to the thermosetting resin is in a ratio of 95: 5 to 50:50 .   The electrically conductive composition according to claim 1, wherein the thermoplastic resin is at least one selected from polyester resins and phenoxy resins.   The conductive composition according to claim 1, wherein the thermosetting resin is an epoxy resin. Applying a conductive composition on a substrate substrate, forming a wiring pattern made of the conductive composition on the substrate substrate, and thermosetting curing the wiring pattern formed by the coating step In a method for manufacturing a wiring board, comprising: a step and a pressurizing step of pressurizing the base substrate having the wiring pattern thermoset by the thermosetting step,
The manufacturing method of the wiring board characterized by using the conductive composition as described in any one of Claims 1-3 as the said conductive composition.

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