Thermosetting conductive resin composition and manufacturing method of electronic component

Abstract

The thermosetting conductive resin composition of the present invention comprises: a conductive powder containing a base metal, a thermosetting polysiloxane resin with hydroxyl groups, and at least one of an amine additive and an acid additive. According to the present invention, even when containing a thermosetting polysiloxane resin with hydroxyl groups and a conductive powder containing a base metal such as Cu, a thermosetting conductive resin composition for electrode formation of electronic components exhibits high viscosity stability, suppressed conductivity reduction (good conductivity), and the ability to form a conductive resin layer with excellent moisture resistance.

Description

Technical Field

[0001] This invention relates to a thermosetting conductive resin composition for forming electrodes in electrode substrates for electronic components, such as multilayers for multilayer electronic components and cathode substrates for solid-state electrolytic capacitors, thereby manufacturing electronic components. Furthermore, this invention relates to a method for manufacturing electronic components by forming electrodes in electrode substrates for electronic components, such as multilayers for multilayer electronic components and cathode substrates for solid-state electrolytic capacitors, thereby manufacturing electronic components. Prior Technology

[0002] In recent years, as electronic machines have been used in more demanding environments than previously known, even the electronic components on these machines are required to remain functional even when used in more demanding environments.

[0003] Specifically, for example, it is required that when mobile devices such as smartphones are dropped, or when electronic devices in automobiles are impacted by vibrations during driving, the connection between the substrate and the electronic components will not crack or peel off, causing the electronic components to detach from the substrate, or the electronic components themselves will not crack, thus exhibiting high impact resistance.

[0004] Furthermore, since mobile devices and automobiles are also exposed to high humidity environments, electronic components in mobile devices and automobiles are required to have high moisture resistance so that moisture cannot penetrate into them.

[0005] Here, Patent Document 1 discloses that a composition consisting of gel-like polysiloxane (polydimethylsiloxane) and conductive powder, which does not contain epoxy resin, is described as forming a conductive resin layer on the outer surface of the external electrode of a multilayer ceramic capacitor by using the composition. This results in moisture resistance that effectively blocks the penetration of plating solution, and superior bending strength of the external electrode compared to the case of using a composition containing epoxy resin. [Previous Technical Documents] [Patent Literature]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2014-135463 Summary of the Invention

[0007] (The problem the invention aims to solve)

[0008] As mentioned above, although Patent Document 1 records that a certain degree of moisture resistance can be obtained when using polysiloxane rubber, because polysiloxane rubber and polysiloxane resin have very high insulation properties, they are mostly used for insulation purposes. If used for conductive purposes, it is usually not easy to obtain conductivity.

[0009] Therefore, through in-depth research, the inventors discovered that by using a thermosetting conductive resin composition containing a thermosetting polysiloxane resin with hydroxyl groups to form a conductive resin layer, both moisture resistance and conductivity can be achieved. However, the inventors found that if the conductive powder of the composition is a conductive powder containing a base metal such as Cu, new problems arise over time, such as an increase in the viscosity of the conductive resin composition or a decrease in conductivity (inability to obtain good conductivity).

[0010] Therefore, the present invention aims to provide a conductive resin composition for forming electrodes of electronic components that, even when containing thermosetting polysiloxane resin with hydroxyl groups and conductive powder containing base metals such as Cu, still exhibits high viscosity stability, suppressed conductivity reduction (good conductivity), and can form an excellent moisture-resistant conductive resin layer. (Technical means to solve the problem)

[0011] Through in-depth research, the inventors discovered that by including at least one additive among amine and acid additives in addition to conductive powder containing a base metal such as Cu and thermosetting polysiloxane resin with hydroxyl groups, a thermosetting conductive resin composition with high viscosity stability, suppressed conductivity reduction (good conductivity) and capable of forming an excellent moisture-resistant conductive resin layer can be obtained, thus completing the present invention.

[0012] That is, the thermosetting conductive resin composition provided by the present invention (1) contains: Conductive powder containing basal metals; Thermosetting polysiloxanes with hydroxyl groups; and At least one of the amine-based additives and the acid-based additives.

[0013] Furthermore, the present invention (2) is a thermosetting conductive resin composition as in (1), wherein the molecular weight of the above-mentioned amine additive or the above-mentioned acid additive is in the range of 30 or more and 2000 or less.

[0014] Furthermore, the present invention (3) is a thermosetting conductive resin composition as in (1) or (2), wherein the boiling point Tb of the above-mentioned amine additive or the above-mentioned acid additive at 1 atmosphere, or the 90% mass reduction temperature Td90, is above 80°C and below 400°C.

[0015] Furthermore, the present invention (4) is a thermosetting conductive resin composition as described in any one of (1) to (3), wherein the above-mentioned amine additive contains at least one of secondary amines and tertiary amines.

[0016] Furthermore, the present invention (5) is a thermosetting conductive resin composition as described in any one of (1) to (4), wherein the above-mentioned acid additive contains dicarboxylic acid.

[0017] Furthermore, the present invention (6) is a thermosetting conductive resin composition as in (1), wherein the content of the amine additive is 0.6 parts by mass or more and 10.0 parts by mass or less relative to 100 parts by mass of the thermosetting polysiloxane resin with hydroxyl groups, and / or the content of the acid additive is 0.1 parts by mass or more and 1.6 parts by mass or less relative to 100 parts by mass of the conductive powder containing cadmium metal.

[0018] Furthermore, the manufacturing method of the electronic component provided by the present invention (7) includes: The preparation steps involve preparing electrode substrates for electronic components; and The electrode forming step involves forming an electrode on the outer surface of the electrode substrate for the electronic component. The electrode forming step involves coating any one of (1) to (6) of a thermosetting conductive resin composition onto an electrode substrate for electronic components, and then forming a conductive resin layer on the electrode substrate for electronic components by curing the thermosetting conductive resin composition. (Compared to the effectiveness of previous technologies)

[0019] According to the present invention, a thermosetting conductive resin composition for electrode forming of electronic parts can be provided, even when containing: thermosetting polysiloxane resin with hydroxyl groups and conductive powder containing low metals such as Cu, but with high viscosity stability, suppressed conductivity reduction (good conductivity), and the ability to form a conductive resin layer with excellent moisture resistance. Implementation

[0020] The thermosetting conductive resin composition of the present invention comprises: a conductive powder containing a base metal, a thermosetting polysiloxane resin with hydroxyl groups, and at least one of an amine additive and an acid additive. This allows the formation of a conductive resin layer with excellent moisture resistance and conductivity, as well as excellent viscosity stability. The reason for achieving these effects is not yet determined, but the inventors speculate as follows: When the composition contains a thermosetting polysiloxane resin with hydroxyl groups and a conductive powder containing a base metal such as Cu, the viscosity of the composition increases over time due to the reaction between the base metal such as Cu and the hydroxyl groups, and heat curing is inhibited. By including an amine additive in the composition, the amine additive coordinates with the hydroxyl groups of the resin, protecting the hydroxyl groups from the influence of the base metal such as Cu, thus inhibiting the increase in viscosity of the composition over time and preventing hindered curing. Therefore, the conductivity of the obtained conductive resin layer can be prevented from decreasing (good conductivity can be obtained). Furthermore, by including acidic additives in the composition, these additives bind to the surface of the conductive powder, preventing low-grade metals such as Cu from contacting the hydroxyl groups of the thermosetting polysiloxane resin. This inhibits the increase in viscosity of the composition over time and prevents hindered curing, thus suppressing the decrease in conductivity of the obtained conductive resin layer (resulting in good conductivity).

[0021] The thermosetting conductive resin composition of the present invention is a thermosetting conductive resin composition that hardens upon heating to form a hardened film (conductive resin layer). There are no particular limitations on the heating temperature, for example, within the range of 150°C to 300°C or 180°C to 250°C.

[0022] The thermosetting conductive resin composition of the present invention contains conductive powder. The conductive powder in the thermosetting conductive resin composition of the present invention is a conductive powder containing at least a base metal. Examples of base metal-containing conductive powders include: base metal powder, base metal alloy powder composed of two or more base metals, noble metal-coated base metal powder with a noble metal coating on its surface, and alloy powders of base metal and noble metal. Examples of base metal-containing conductive powders include: copper powder, silver-coated copper powder, copper alloy powder, silver-lead alloy powder, tin powder, nickel powder, silver-coated nickel powder, copper-nickel alloy powder, iron powder, zinc powder, and aluminum powder. Because silver powder readily induces ion migration, from the viewpoint of minimizing ion migration, it is preferable to use a powder that does not contain silver, i.e., a base metal powder, and more preferably copper powder. Furthermore, from the viewpoint of low cost, conductive powders containing base metals are preferably silver-coated copper powder, copper powder, or copper alloy powder that does not contain high-priced metal components such as precious and rare metals, and more preferably copper powder. From the viewpoint of excellent conductivity, conductive powders containing base metals are preferably silver-coated copper powder. Silver-coated copper powder only requires that silver coats at least a portion of the surface of the copper powder. From the above-mentioned viewpoints, the conductive powder in the thermosetting conductive resin composition of the present invention preferably contains Cu. On the other hand, in compositions containing thermosetting polysiloxane resins with hydroxyl groups, while the use of conductive powders containing base metals can easily lead to problems of increased viscosity and decreased conductivity, these problems are particularly likely to occur when using conductive powders containing Cu. In the thermosetting conductive resin composition of the present invention, by using amine-based or acid-based additives, the aforementioned problems that occur when thermosetting polysiloxane resins with hydroxyl groups are combined with conductive powders containing base metals can be solved. In particular, by using Cu as the base metal, the problems encountered when combining thermosetting polysiloxane resins with hydroxyl groups and conductive powders containing Cu can be solved while maximizing the advantages of the aforementioned Cu-containing conductive powders. That is, in the present invention, the effects of the present invention are particularly evident by combining Cu-containing conductive powders, thermosetting polysiloxane resins with hydroxyl groups, and at least one of amine-based and acid-based additives. In addition, in this specification, "base metals" refers to copper, iron, nickel, aluminum, lead, zinc, tin, etc., and metals with a greater tendency to ionize than copper; "precious metals" refers to gold, silver, platinum, etc., and metals with a less tendency to ionize than copper.

[0023] In the thermosetting conductive resin composition of the present invention, the shape of the conductive powder is not particularly limited, and can be, for example, spherical or flake-shaped. However, from the viewpoint of excellent conductivity and adhesion, flake-shaped is preferred.

[0024] In addition to the aforementioned conductive powder containing a base metal, the thermosetting conductive resin composition of the present invention may further contain other conductive powders. That is, the conductive powder in the thermosetting conductive resin composition of the present invention may contain only conductive powder containing a base metal, or it may contain conductive powder containing a base metal and conductive powder containing a noble metal. The shape of the aforementioned other conductive powders is not particularly limited; they may be, for example, spherical or sheet-like. From the viewpoint of superior conductivity and adhesion, sheet-like shapes are preferred.

[0025] In the thermosetting conductive resin composition of the present invention, the content ratio of the flake-shaped conductive powder to the total conductive powder is preferably 20.0% by mass or more, more preferably 40.0% by mass or more, and particularly preferably 60.0% by mass or more. By setting the content ratio of the flake-shaped conductive powder to the total conductive powder within the above range, the conductivity and adhesion of the obtained conductive resin layer can be improved.

[0026] The aspect ratio of the sheet-like conductive powder is preferably 1.5 to 50.0, more preferably 2.0 to 30.0, and particularly preferably 5.0 to 20.0. By setting the aspect ratio of the sheet-like conductive powder within the above range, the conductivity and adhesion of the obtained conductive resin layer can be improved. Furthermore, this invention measures the aspect ratio of 50 randomly selected conductive powders from scanning electron microscopy (SEM) images, and sets the average aspect ratio of the aspect ratio to the thickness (aspect ratio / thickness) as the aspect ratio of the sheet-like conductive powder.

[0027] When measured using a scanning electron microscope (SEM), the number-average particle size of the flake-shaped conductive powder is preferably 0.1~20.0 μm, more preferably 0.3~15.0 μm, particularly preferably 0.5~10.0 μm, and even more preferably 1.0~5.0 μm. By setting the number-average particle size of the flake-shaped conductive powder within the above range, the conductivity and adhesion of the obtained conductive resin layer can be improved. Furthermore, this invention measures the major axis of 50 randomly selected conductive powder particles from SEM images and sets the average value as the number-average particle size of the flake-shaped conductive powder.

[0028] The specific surface area of ​​the flake-shaped conductive powder is preferably 0.5~5.0 m² / g, more preferably 0.6~4.0 m² / g. By setting the specific surface area of ​​the flake-shaped conductive powder within the above range, the conductivity and adhesion of the obtained conductive resin layer can be improved.

[0029] The volumetric cumulative 50% particle size (D 50) of the spherical conductive powder is preferably 0.01~7.0 μm, more preferably 0.03~5.0 μm. By setting the D 50 of the spherical conductive powder within the above range, the conductivity and adhesion of the obtained conductive resin layer can be improved. In addition, in this invention, the relevant D 50 is obtained by using a laser diffraction particle size distribution measuring device to determine the 50% value of the volumetric integral fraction (D 50).

[0030] The specific surface area of ​​the spherical conductive powder is preferably 0.2~3.0 m² / g, more preferably 0.3~2.5 m² / g. By setting the specific surface area of ​​the spherical conductive powder within the above range, the conductivity and adhesion of the obtained conductive resin layer can be improved.

[0031] The thermosetting conductive resin composition of the present invention contains a resin binder. Furthermore, in the thermosetting conductive resin composition of the present invention, the resin binder contains at least a thermosetting polysiloxane resin having hydroxyl groups. Preferably, the thermosetting polysiloxane resin having hydroxyl groups is a condensation-type thermosetting polysiloxane resin that undergoes a condensation reaction and cures upon heating; more preferably, it is a dehydration-condensation-type polysiloxane resin having hydroxyl groups and curing upon heating through a dehydration-condensation reaction; and most preferably, it is a dehydration-condensation-type thermosetting polysiloxane resin having hydroxyl groups (silyl groups) bonded to silicon atoms and undergoing a dehydration-condensation reaction upon heating.

[0032] In the thermosetting conductive resin composition of the present invention, the proportion of hydroxyl-containing thermosetting polysiloxane resin relative to the total resin binder is preferably 25.0% by mass or more, more preferably 30.0% by mass or more, particularly preferably 40.0% by mass or more, even more preferably 50.0% by mass or more, even more preferably 60.0% by mass or more, most preferably 70.0% by mass or more, even more preferably 80.0% by mass or more, even more preferably 90.0% by mass or more, and especially preferably 95.0% by mass or more. By including hydroxyl-containing thermosetting polysiloxane resin in the thermosetting conductive resin composition within the above-mentioned range, the moisture resistance of the conductive resin layer can be improved, and the reduction in resistivity caused by the use of amine-based or acid-based additives and the inhibition of tackification effect can be increased.

[0033] Thermosetting polysiloxane resins with hydroxyl groups are those that harden upon heating without the use of hardeners or catalysts. A preferred form of heat curing is the condensation-curing type, which undergoes a condensation reaction upon heating. Even better is the dehydration-condensation type, which undergoes a dehydration-condensation reaction upon heating.

[0034] The position and number of hydroxyl groups in thermosetting polysiloxane resins with hydroxyl groups are not particularly limited; for example, they can be located at one end of the polymer, at two ends of the polymer, or on the side chains of the polymer. From the viewpoint of excellent conductivity, it is more preferable that at least the side chains have multiple hydroxyl groups. Hydroxyl groups can also be bonded to silicon atoms or to other atoms (e.g., carbon atoms). In addition, in this specification, the OH group bonded to Si in the silanol group is also referred to as a "hydroxyl group".

[0035] The backbone (main chain) of thermosetting polysiloxane resins with hydroxyl groups only needs to contain siloxane units, such as polymers composed solely of siloxane units (polysiloxane) and copolymers containing siloxane units. Examples of copolymer systems containing siloxane units include: copolymers of at least one monomer, oligomer, and polymer containing siloxane units with at least one monomer, oligomer, and polymer not containing siloxane units. These polymers and copolymer systems can be linear or branched.

[0036] Thermosetting polysiloxane resins containing hydroxyl groups may also have other functional groups besides hydroxyl groups on the side chains or ends of the polymer, such as: alkenyl, hydrosilyl, (meth)acrylyl, epoxy, amino, methanol, mercapto, carboxyl, phenolic, aryl, methyl, and other alkyl groups; phenyl and other aromatic groups, etc. From the viewpoint of moisture resistance, alkyl groups such as methyl are preferred for thermosetting polysiloxane resins; from the viewpoint of conductivity, hydroxyl groups are preferred for aromatic groups such as phenyl, and from the viewpoint of adhesion, epoxy groups are preferred.

[0037] Thermosetting polysiloxane resins with hydroxyl groups can be modified resins in which various oligomers or polymers are introduced (grafted) into the side chains or ends of the polymer, or cross-linked resins formed by inter-resin cross-linking.

[0038] There are no particular limitations on the molecular weight (weight average molecular weight Mw) of thermosetting polysiloxanes with hydroxyl groups, but it is preferably 1,000 to 300,000, and more preferably 2,000 to 200,000.

[0039] The thermosetting conductive resin composition of the present invention may further contain a curing agent or catalyst, such as platinum-based, titanium-based, aluminum-based, zinc-based, iron-based, or phosphoric acid-based curing agents or catalysts.

[0040] The thermosetting conductive resin composition of the present invention may also contain a resin binder other than a thermosetting polysiloxane resin with hydroxyl groups, without impairing the effects of the present invention. The resin binder other than a thermosetting polysiloxane resin with hydroxyl groups may be a thermosetting resin or a thermoplastic resin. Examples of resin binders other than thermosetting polysiloxane resins with hydroxyl groups include: cellulose resins such as ethyl cellulose; acetal resins such as polyvinyl acetal resin; polyimide resins, polyamide resins, polyamide-imide resins, epoxy resins, acrylic resins, polybutadiene and other butadiene resins; (meth)acrylic resins, styrene resins, phenolic resins, alkyd resins, polyurethane resins, and polysiloxane resins different from the aforementioned thermosetting polysiloxane resins with hydroxyl groups.

[0041] The resin binder content in the thermosetting conductive resin composition of this invention, relative to 100.0 parts by weight of conductive powder, is preferably 3.0 to 30.0 parts by weight, more preferably 3.0 to 28.0 parts by weight, particularly preferably 3.0 to 25.0 parts by weight, even more preferably 5.0 to 25.0 parts by weight, even more preferably 7.0 to 23.0 parts by weight, and most preferably 11.0 to 20.0 parts by weight. By setting the resin binder content within the above range, a conductive resin layer with excellent conductivity and adhesion can be easily obtained. Furthermore, it facilitates excellent printability when coating the thermosetting conductive resin composition onto the electrode substrate.

[0042] The thermosetting conductive resin composition of the present invention contains at least one additive selected from amine additives and acid additives. By containing amine additives and / or acid additives, even when containing thermosetting polysiloxane resins with hydroxyl groups and conductive powders containing base metals, the viscosity stability can be improved, and the reduction in conductivity can be suppressed (good conductivity can be obtained). In particular, the effects of the present invention can be easily obtained by using amine additives, which is preferred. Furthermore, the effects of the present invention can be easily obtained by using both amine additives and acid additives, which is also preferred.

[0043] There are no particular limitations on the amine additives used; examples include primary amines, secondary amines, and tertiary amines. The effects of this invention are particularly well achieved when the amine additive is a secondary or tertiary amine, and therefore preferred; secondary amines are especially preferred.

[0044] The molecular weight of the amine additive is preferably in the range of 10 or more and 5000 or less, more preferably in the range of 20 or more and 3000 or less, particularly preferably in the range of 30 or more and 2000 or less, even more preferably in the range of 40 or more and 1000 or less, even more preferably in the range of 50 or more and 500 or less, most preferably in the range of 80 or more and 350 or less, and even more preferably in the range of 100 or more and 300 or less. By setting the molecular weight of the amine additive within the above ranges, the effects of the present invention can be obtained more effectively.

[0045] The amine additive preferably has 6 or more and 20 or less carbon atoms, and more preferably 7 or more and 18 or less. This allows for a better attainment of the effects of the present invention.

[0046] The pKa of the amine additive, measured in water at 25°C, is preferably 7.5 or higher and 12.0 or lower. This allows for better attainment of the effects of the present invention.

[0047] When the curing temperature of the conductive resin composition is set as the reference temperature, the boiling point Tb of the amine additive at 1 atmosphere or the 90% mass loss temperature Td90 is preferably between -100°C and +30°C, more preferably between -75°C and +20°C, and particularly preferably between -50°C and +10°C. Furthermore, the boiling point Tb of the amine additive at 1 atmosphere or the 90% mass loss temperature Td90 is preferably between 80°C and 400°C, more preferably between 80°C and 350°C, particularly preferably between 80°C and 300°C, further preferably between 100°C and 250°C, and particularly preferably between 120°C and 230°C. By setting the boiling point Tb of the amine additive at 1 atmosphere or the 90% mass reduction temperature Td90 within the aforementioned range, it will act in the conductive resin composition until just before curing, thus making it easier to obtain the effects of the present invention. Furthermore, by setting the boiling point Tb of the amine additive at 1 atmosphere or the 90% mass reduction temperature Td90 within the aforementioned range, it is easy for it to vaporize or decompose before curing is complete, thus not hindering curing and easily obtaining the effects of the present invention. Also, because it is not easy to remain in the cured film, the obtained conductive resin layer easily becomes one with excellent conductivity and moisture resistance. In addition, the "90% mass reduction temperature Td90" referred to in this specification refers to the temperature at which 90% mass reduction occurs when heating at a rate of 10°C / min under atmospheric conditions at 1 atmosphere.

[0048] Amine additives can be, for example, monoamines, diamines, and triamines. However, the effects of the present invention can be significantly obtained by using diamines and triamines, which is preferable. Furthermore, the effects of the present invention can be more significantly obtained by using diamines, which is even better. More systematic examples of amine additives include: monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, diisopropylamine, tripropylamine, monobutylamine, dibutylamine, tributylamine, monopentylamine, dipentylamine, tripentylamine, monohexylamine, dihexylamine, trihexylamine, monoheptylamine, diheptylamine, triheptylamine, monooctylamine, dioctylamine, dimethyloctylamine, trioctylamine, dimethylethylamine, diethanolamine, polyoxyethylene laurylamine, N-lauryl diethanolamine, 3-(2-ethylhexyloxy)propylamine, N-2-(aminoethyl)-3-aminopropylamine. N-methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, poly(tetramethylene / 3-methyltetramethylene ether)diol bis(4-aminobenzoate), poly(di-p-aminobenzoic acid tetramethylene oxide), triethanolamine. When the amine additive contains at least one of dibutylamine, triethanolamine, diisopropylamine, dihexylamine, dimethyl octylamine and polyoxyethylene laurylamine, the effects of the present invention can be obtained better, and therefore it is preferred. In particular, when the amine additive contains at least one of dibutylamine, triethanolamine and polyoxyethylene laurylamine, the effects of the present invention can be obtained better, and therefore it is preferred.

[0049] The acid additive is defined as an organic acid, with no particular restrictions on other types, such as monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids. Especially when the acid additive is a dicarboxylic acid, the effects of this invention are more effectively achieved, and therefore preferred. Examples of dicarboxylic acids include: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, p-phthalic acid, octenylsuccinic acid, and octadecyl succinic acid. Especially when the acid additive is octadecyl succinic acid, the effects of this invention are more effectively achieved, and therefore preferred.

[0050] The molecular weight of the acid-based additive is preferably in the range of 10 or more and 5000 or less, more preferably in the range of 20 or more and 3000 or less, particularly preferably in the range of 30 or more and 2000 or less, even more preferably in the range of 100 or more and 1000 or less, and even more preferably in the range of 250 or more and 750 or less. By setting the molecular weight of the acid-based additive within the above range, the effects of the present invention can be obtained more effectively.

[0051] The acid-based additive preferably has 10 or more and 35 or less carbon atoms, and more preferably 15 or more and 25 or less. This allows for a better attainment of the effects of the present invention.

[0052] The pKa of the acid-based additive, measured in water at 25°C, is preferably 2.0 or higher and 6.5 or lower. This allows for better attainment of the effects of the present invention.

[0053] When the boiling point of the acid additive at 1 atmosphere or the 90% mass reduction temperature Td90 is used as the reference temperature for the curing temperature of the conductive resin composition, it is preferably between -100°C and +30°C, more preferably between -75°C and +20°C, and particularly preferably between -50°C and +10°C. Furthermore, the boiling point Tb of the acid additive at 1 atmosphere or the 90% mass reduction temperature Td90 is preferably between 80°C and 350°C, more preferably between 80°C and 300°C, particularly preferably between 100°C and 250°C, and even more preferably between 120°C and 230°C. By setting the boiling point Tb of the acid additive at 1 atmosphere or the 90% mass reduction temperature Td90 within the above range, it will act in the conductive resin composition until just before curing, thus making it easier to obtain the effects of the present invention. Furthermore, by setting the boiling point Tb of the acid-based additive at 1 atmosphere or the 90% mass reduction temperature Td90 within the above-mentioned range, it is easy to vaporize or decompose before the curing is completed, thus not hindering the curing process and easily obtaining the effects of the present invention. Also, because it is not easy to remain in the cured film, the obtained conductive resin layer easily becomes one with excellent conductivity and moisture resistance.

[0054] The thermosetting conductive resin composition of the present invention contains only amine additives among the amine additives and acid additives. The content of the amine additives in the thermosetting conductive resin composition of the present invention, relative to 100 parts by weight of the thermosetting polysiloxane resin with hydroxyl groups, is preferably 0.3 parts by weight or more and 20.0 parts by weight or less, more preferably 0.6 parts by weight or more and 10.0 parts by weight or less, and particularly preferably 1.8 parts by weight or more and 6.0 parts by weight or less. By setting the content of the amine additives within the above range, the effects of the present invention can be more effectively obtained.

[0055] The thermosetting conductive resin composition of the present invention contains only amine additives among the amine additives and acid additives. The content of the amine additives in the thermosetting conductive resin composition of the present invention, relative to 100 parts by weight of the conductive powder containing base metal, is preferably 0.05 parts by weight or more and 3.2 parts by weight or less, more preferably 0.1 parts by weight or more and 1.6 parts by weight or less, and particularly preferably 0.3 parts by weight or more and 1.4 parts by weight or less. By setting the content of the amine additives within the above range, the effects of the present invention can be obtained more effectively.

[0056] The thermosetting conductive resin composition of the present invention contains only the acid additive among the amine additive and the acid additive. The content of the acid additive in the thermosetting conductive resin composition of the present invention, relative to 100 parts by weight of the thermosetting polysiloxane resin with hydroxyl groups, is preferably 0.3 parts by weight or more and 20.0 parts by weight or less, more preferably 0.6 parts by weight or more and 10.0 parts by weight or less, and particularly preferably 1.8 parts by weight or more and 6.0 parts by weight or less. By setting the content of the acid additive within the above range, the effects of the present invention can be obtained more effectively.

[0057] The thermosetting conductive resin composition of the present invention contains only the acid additive among the amine additive and acid additive. The content of the acid additive in the thermosetting conductive resin composition of the present invention, relative to 100 parts by weight of the conductive powder containing base metal, is preferably 0.05 parts by weight or more and 3.2 parts by weight or less, more preferably 0.1 parts by weight or more and 1.6 parts by weight or less, and particularly preferably 0.3 parts by weight or more and 1.4 parts by weight or less. By setting the acid additive content within the above range, the effects of the present invention can be obtained more effectively.

[0058] The thermosetting conductive resin composition of the present invention contains both amine and acid additives. The total content of the amine and acid additives in the thermosetting conductive resin composition of the present invention, relative to 100 parts by weight of the thermosetting polysiloxane resin with hydroxyl groups, is preferably 0.3 parts by weight or more and 20.0 parts by weight or less, more preferably 0.6 parts by weight or more and 10.0 parts by weight or less, and particularly preferably 1.8 parts by weight or more and 6.0 parts by weight or less. By setting the total content of the amine and acid additives within the above range, the effects of the present invention can be more effectively obtained.

[0059] The thermosetting conductive resin composition of the present invention contains both amine and acid additives. The total content of the amine and acid additives in the thermosetting conductive resin composition of the present invention, relative to 100 parts by weight of the conductive powder containing base metal, is preferably 0.05 parts by weight or more and 3.2 parts by weight or less, more preferably 0.1 parts by weight or more and 1.6 parts by weight or less, and particularly preferably 0.3 parts by weight or more and 1.4 parts by weight or less. By setting the total content of the amine and acid additives within the above range, the effects of the present invention can be more effectively obtained.

[0060] The thermosetting conductive resin composition of the present invention contains both amine additives and acid additives. The content of the amine additives in the thermosetting conductive resin composition of the present invention, relative to 100 parts by weight of the thermosetting polysiloxane resin with hydroxyl groups, is preferably 0.3 parts by weight or more and 20.0 parts by weight or less, more preferably 0.6 parts by weight or more and 10.0 parts by weight or less, and particularly preferably 1.8 parts by weight or more and 6.0 parts by weight or less. The content of the acid additives in the thermosetting conductive resin composition of the present invention, relative to 100 parts by weight of the conductive powder containing base metal, is preferably 0.05 parts by weight or more and 3.2 parts by weight or less, more preferably 0.1 parts by weight or more and 1.6 parts by weight or less, and particularly preferably 0.3 parts by weight or more and 1.4 parts by weight or less.

[0061] The thermosetting conductive resin composition of the present invention may further contain organic solvents. There are no particular limitations on the organic solvents contained therein, and examples include: terpineol, dihydroterpineol, dihydroterpineol acetate, dibutanol, butylcarbitol, butylcarbitol acetate, benzyl alcohol, etc. From the viewpoint of adhesive strength, acetate-based solvents are preferred, and butylcarbitol acetate is more preferred.

[0062] In addition to the above-mentioned components, the thermosetting conductive resin composition of the present invention may also contain additives such as defoamers, plasticizers, dispersants, and rheology modifiers, as needed. Examples of plasticizers include: dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di(2-ethylhexyl) phthalate, di-n-octyl phthalate, butyl benzyl phthalate, dioctyl adipate, diisononyl adipate, dibutyl sebacate, diethyl sebacate, dioctyl sebacate, tricresyl phosphate, chlorinated paraffin hydrocarbons, and diisononyl cyclohexane-1,2-dicarboxylic acid (DINCH). Examples of rheology modifiers include: silicon dioxide powder.

[0063] The thermosetting conductive resin composition of the present invention is well-suited for forming external electrodes of multilayer electronic components and for forming cathodes of solid electrolytic capacitors.

[0064] The moisture permeability of the thermosetting conductive resin composition of the present invention is preferably 80.0 mg or less, more preferably 40.0 mg or less, particularly preferably 20.0 mg or less, and even more preferably 10.0 mg or less. By setting the moisture permeability within the above range, when a conductive resin layer is formed using the conductive resin composition of the present invention, electronic components with excellent moisture resistance can be obtained. Furthermore, the method for measuring the moisture permeability of the conductive resin composition of the present invention is not particularly limited; for example, it can be measured using the following moisture permeability measurement test. <Moisture Permeability Measurement Test> The conductive resin composition was cast onto a PET film with a thickness of 250 μm and cured at 200 °C for 60 minutes. The resulting cured film was then cut into a circle with a diameter of 7.5 mm. The circle was then fixed with an adhesive in the same way that a 5 ml glass bottle containing 2 g of silica gel was sealed. The cured film was then placed into a 750 ml container containing 100 ml of pure water, ensuring that it would not come into contact with the pure water, thus forming a sealed state. The container was then placed in a desiccant set at 65 °C and left to stand for 15 hours. The moisture permeability was then calculated according to the following formula (1). Moisture permeability (weight increase) = Weight of glass bottle after being placed in the dryer - Weight of glass bottle before being placed in the dryer (1)

[0065] The resistivity of the conductive resin layer obtained using the thermosetting conductive resin composition of the present invention is preferably 1.0 × 10⁵ μΩ·cm or less, more preferably 5.0 × 10⁴ μΩ·cm or less, particularly preferably 1.0 × 10⁴ μΩ·cm or less, even more preferably 5.0 × 10³ μΩ·cm or less, and even more preferably 1.0 × 10³ μΩ·cm or less. Furthermore, the method for measuring the resistivity of the conductive resin composition of the present invention is not particularly limited; for example, it can be measured using the following resistivity measurement test. <Resistivity Measurement Test> A conductive resin composition was cast onto a glass slide substrate to form a film 1 cm wide, 5 cm long, and 50 μm thick. After curing at 200 °C for 60 minutes to obtain a hardened film, the surface resistance of the hardened film was measured using a digital multimeter (e.g., Keithley Instruments KEITHLEY2002) with a four-terminal method. The specific resistance was calculated from the obtained value and the thickness of the sample.

[0066] The resistivity reduction rate of the thermosetting conductive resin composition of the present invention is preferably 15% or more, more preferably 30% or more, particularly preferably 50% or more, even more preferably 70% or more, even more preferably 80% or more, most preferably 90% or more, and even more preferably 95% or more. By setting the resistivity reduction rate within the above range, when a conductive resin layer is formed using the thermosetting conductive resin composition of the present invention, electronic components with excellent conductivity can be obtained. Furthermore, the method for calculating the resistivity reduction rate of the thermosetting conductive resin composition of the present invention is not particularly limited; for example, it can be calculated using the resistivity reduction rate calculation method described below. <Method for Calculating Resistivity Reduction Rate> The thermosetting conductive resin composition of the present invention containing at least one of the additives of the present invention (amine additives and acid additives) is designated as composition (X). The thermosetting conductive resin composition that is identical to composition (X) except that it does not contain the additives of the present invention (amine additives and acid additives) is designated as composition (Y). Using the above composition (X) and the above composition (Y), the specific resistance of each is measured by the aforementioned specific resistance measurement test. The specific resistances obtained are designated as (A) and (B), respectively. Then, the specific resistance reduction rate is calculated by the following formula (2). Resistivity reduction rate [%] = (1 - ((A) / (B))) × 100 (2)

[0067] The viscosity determination method of the thermosetting conductive resin composition of the present invention is not particularly limited. For example, a rotary viscometer (manufactured by BROOKFIELD, model: HADV-II+Pro or HBDV-II+) can be used to determine the viscosity at 25°C and a shear rate of 4 (1 / s).

[0068] The viscosity increase rate of the thermosetting conductive resin composition of the present invention is preferably 10.0 times or less, more preferably 8.0 times or less, particularly preferably 6.0 times or less, even more preferably 4.0 times or less, even more preferably 2.0 times or less, and most preferably 1.5 times or less. By setting the viscosity increase rate within the above range, a thermosetting conductive resin composition with excellent viscosity stability can be obtained. When the viscosity stability is low, the viscosity increases over time. If the viscosity increases, the printable shape will deteriorate. Therefore, when the thermosetting conductive resin composition of the present invention is printed to form external electrodes or cathodes on electrode substrates for electronic components, such as multilayer electronic components or cathode substrates for solid electrolytic capacitors, the printable shape will deteriorate. If the printable shape is poor, for example, the thickness of the external electrode of the multilayer electronic component or the corner of the cathode of the solid electrolytic capacitor will become thinner, thus failing to obtain the moisture resistance required when forming electronic components. The thermosetting conductive resin composition of the present invention exhibits excellent viscosity stability, thus enabling the easy and stable production of electronic components with high moisture resistance when used to form such components. Furthermore, the method for calculating the viscosity increase rate of the thermosetting conductive resin composition of the present invention is not particularly limited; for example, it can be calculated using the viscosity increase rate calculation method described below. <Method for Calculating Viscosity Increase Rate> The viscosity of the thermosetting conductive resin composition of the present invention after 1 day of preparation and after 1 week of preparation were measured using the aforementioned viscosity measurement method, and then the viscosity increase rate was calculated using the following formula (3). Viscosity increase rate [times] = Viscosity after 1 week of preparation / Viscosity after 1 day of preparation (3)

[0069] (Viscosity inhibition rate) The viscosity inhibition rate of the thermosetting conductive resin composition of the present invention is preferably 10% or more, more preferably 20% or more, particularly preferably 30% or more, even more preferably 40% or more, even more preferably 50% or more, best 60% or more, even better 70% or more, even more preferably 80% or more, and most preferably 90% or more. By setting the viscosity inhibition rate within the above range, a thermosetting conductive resin composition with excellent viscosity stability can be obtained. Due to the excellent viscosity stability, for the same reasons as described above, highly moisture-resistant electronic components can be easily and stably obtained. Furthermore, the method for calculating the viscosity inhibition rate of the thermosetting conductive resin composition of the present invention is not particularly limited; for example, it can be calculated using the following viscosity inhibition rate calculation method. <Method for Calculating Viscosity Inhibition Rate> The thermosetting conductive resin composition of the present invention containing at least one of the additives of the present invention (amine additives and acid additives) is designated as composition (X). The thermosetting conductive resin composition that is identical to composition (X) except that it does not contain the additives of the present invention (amine additives and acid additives) is designated as composition (Y). Using the above composition (X) and the above composition (Y), the viscosity increase rate of each is measured by the aforementioned viscosity increase rate measurement test. The obtained viscosity increase rates are designated as (C) and (D), respectively. Then, the viscosity inhibition rate is calculated by the following formula (4). Viscosity inhibition rate [%] = (1 - ((C) / (D))) × 100 (4)

[0070] The adhesive strength of the conductive resin layer obtained using the thermosetting conductive resin composition of the present invention is preferably 3.0 kg or more, more preferably 4.0 kg or more, particularly preferably 5.0 kg or more, and even more preferably 6.0 kg or more. Furthermore, the adhesive strength of the conductive resin layer obtained using the thermosetting conductive resin composition of the present invention is not particularly limited, for example, it can be set to 20.0 kg or less. By forming a conductive resin layer with an adhesive strength within the above-mentioned range between the metal layer and the plating layer of the external electrode of a multilayer electronic component, cracking and interface peeling are less likely to occur at the connection between the substrate and the electronic component, and the electronic component itself is less likely to crack, thus improving the impact resistance of the electronic component. Therefore, by using the conductive resin composition of the present invention to form between the metal layer and the plating layer of the external electrode of a multilayer electronic component, the impact resistance of the electronic component can be improved. Furthermore, due to the excellent adhesive strength, the conductive resin layer is less likely to peel off from the electrode substrate of the electronic component, thus moisture resistance can be easily maintained during the formation of the electronic component. Furthermore, there are no particular limitations on the method for measuring adhesive strength; for example, the following adhesive strength test can be used. <Adhesion Strength Test> A conductive resin composition with a thickness of 50 μm was cast onto a glass slide substrate, and then an alumina sheet with a length of 1.5 mm, a width of 3.0 mm, and a height of 1.0 mm was placed on it. The substrate was then cured at 200°C for 60 minutes. A welding tester (manufactured by Xijin Trading Co., Ltd., model: SS-30WD) was used to apply force in the horizontal direction at a speed of 0.3 mm / s. The value of the alumina sheet peeling off was measured.

[0071] The curing film density of the thermosetting conductive resin composition of the present invention is preferably 2.0 g / cm³ or higher, more preferably 2.5 g / cm³ or higher, particularly preferably 3.0 g / cm³ or higher, even more preferably 3.5 g / cm³ or higher, and even more preferably 4.0 g / cm³ or higher. By setting the curing film density within the above range, when forming a conductive resin layer using the conductive resin composition of the present invention, electronic components with excellent conductivity and moisture resistance can be obtained. Furthermore, the method for measuring the curing film density of the conductive resin composition of the present invention is not particularly limited. For example, the conductive resin composition is cast onto a PET film with a thickness of 250 μm to form a coating film. This coating film is then cured in an atmospheric environment at 200°C for 60 minutes to form a curing film. The obtained curing film is cut into a circle, and the weight and volume of the cut curing film are measured. The ratio of weight (g) to volume (cm³) is calculated and set as the curing film density (g / cm³).

[0072] The thermosetting conductive resin composition of the present invention is particularly suitable for use in the manufacture of electronic components, as a thermosetting conductive resin composition for forming electrodes on electrode substrates (hereinafter also referred to as "electrode substrates for electronic components"). Furthermore, the thermosetting conductive resin composition of the present invention is particularly suitable for forming external electrodes of multilayer electronic component laminates and for forming cathodes of cathode substrates for solid electrolytic capacitors.

[0073] In one example of use, in a method for manufacturing an electronic component that includes a preparation step of preparing an electrode substrate for an electronic component and an electrode forming step of forming an electrode on the outer surface of the electrode substrate for the electronic component, the thermosetting conductive resin composition of the present invention can be used, and the thermosetting conductive resin composition of the present invention can be used in the electrode forming step to form a conductive resin layer on the electrode substrate for the electronic component, thereby forming an electrode.

[0074] The preparation step refers to the step of preparing the electrode substrate for electronic components. The electrode substrate for electronic components refers to the object on which electrodes are formed during the manufacturing process of electronic components. Examples of electrode substrate systems for electronic components include: multilayer electronic components consisting of multiple ceramic layers and multiple internal electrode layers; cathode substrates for solid electrolytic capacitors consisting of an anode and a dielectric layer formed on the surface of the anode; and electrode substrates for wafer resistors having end-face electrodes.

[0075] A multilayer system for multilayer electronic components consists of a plurality of ceramic layers and a plurality of internal electrode layers. A multilayer body for multilayer electronic components connects adjacent ceramic layers via internal electrode layers disposed between them. Examples of multilayer systems for multilayer electronic components include: multilayer bodies for multilayer ceramic capacitors, multilayer bodies for multilayer ceramic inductors, and multilayer bodies for piezoelectric actuators.

[0076] Examples of ceramic layer forming materials that constitute multilayer electronic components include barium titanate, strontium titanate, calcium titanate, barium zirconate, strontium zirconate, calcium zirconate, and calcium strontium zirconate.

[0077] The material forming the internal electrode layer of the multilayer used in multilayer electronic components may be, for example, any one of nickel, palladium, silver, copper and gold, or an alloy containing one or more of these (e.g., an alloy of silver and palladium).

[0078] A cathode system for a solid electrolytic capacitor consists of an anode and a dielectric layer formed on the surface of the anode. Examples of material combinations for the anode and dielectric layer include tantalum and tantalum pentoxide, aluminum and aluminum oxide, and niobium and niobium pentoxide.

[0079] The electrode forming step is the step of forming an electrode on the outer surface of the electrode substrate for an electronic component. Furthermore, in this invention, the formation of a conductive resin layer on the electrode substrate for an electronic component includes both: directly forming a conductive resin layer on the surface of the electrode substrate for an electronic component, and first forming other layers or films (e.g., metal layers, conductive layers) on the electrode substrate for an electronic component, and then forming a conductive resin layer on its surface. Therefore, the electronic component obtained using the manufacturing method of this invention includes both: directly forming a conductive resin layer on the surface of the electrode substrate for an electronic component, and forming a conductive resin layer with other layers or films (e.g., metal layers, conductive layers) interposed between the electrode substrates for an electronic component.

[0080] In the electrode forming process, the location, method, thickness, number, type of metal constituting the electrode, and shape of the conductive powder used in electrode forming are selected appropriately according to the electronic component to be manufactured.

[0081] In the electrode forming step, a conductive resin layer is formed on the electrode substrate for electronic components using the thermosetting conductive resin composition of the present invention.

[0082] In the electrode formation step, the thermosetting conductive resin composition of the present invention is coated onto the electrode substrate for electronic components, thereby forming a layer of the thermosetting conductive resin composition of the present invention at a predetermined position on the electrode substrate for electronic components. Then, the thermosetting conductive resin composition of the present invention is cured to form a conductive resin layer. Furthermore, the aforementioned curing is performed using heat.

[0083] In the electrode forming step, by directly coating the thermosetting conductive resin composition of the present invention onto the surface of the electrode substrate for electronic components, a conductive resin layer can be directly formed on the surface of the electrode substrate for electronic components. Furthermore, in the electrode forming step, appropriate steps can be provided depending on the type of electronic component before forming the conductive resin layer on the electrode substrate for electronic components. For example, in the case of multilayer electronic components, in the electrode forming step, after forming a metal layer at a predetermined location on the electrode substrate for electronic components, the thermosetting conductive resin composition of the present invention is coated onto the surface of the metal layer to form a layer of the thermosetting conductive resin composition of the present invention at the predetermined location on the electrode substrate for electronic components. Then, by curing the thermosetting conductive resin composition of the present invention, a conductive resin layer is formed on the surface of the metal layer. Furthermore, in the case of a solid electrolytic capacitor, for example, in the electrode forming step, after forming a conductive layer composed of a carbon layer at a predetermined position on the cathode substrate of the solid electrolytic capacitor, a thermosetting conductive resin composition layer of the present invention is formed at the predetermined position on the electrode substrate of the electronic component by coating the surface of the conductive layer with the thermosetting conductive resin composition of the present invention, etc., and then a conductive resin layer is formed on the surface of the conductive layer by curing the thermosetting conductive resin composition of the present invention. Furthermore, in the electrode forming step, after forming a conductive resin layer on the electrode substrate of the electronic component, appropriate steps may be provided depending on the type of electronic component. For example, in the case of a multilayer electronic component, after forming a conductive resin layer at a predetermined position on the electrode substrate of the electronic component in the electrode forming step, a plating layer is formed on the surface of the conductive resin layer.

[0084] In the electrode forming step, an electrode can be formed by forming a conductive resin layer on the electrode substrate for electronic components. That is, in this form, an electrode can be constituted solely by a conductive resin layer.

[0085] In the electrode formation step, when forming a conductive resin layer on the electrode substrate of the electronic component using the thermosetting conductive resin composition of the present invention, the thermosetting conductive resin composition of the present invention is coated on the electrode substrate of the electronic component by means of an impregnation method, so that a layer of the thermosetting conductive resin composition of the present invention can be formed at a predetermined position on the electrode substrate of the electronic component.

[0086] The first form of the electrode forming step (hereinafter also referred to as "electrode forming step (1)") is an electrode forming step when the electrode being formed for an electronic component is a multilayer electronic component consisting of a ceramic layer and an internal electrode layer. The electrode forming step (1) includes at least a conductive resin layer forming step (1A) in which a conductive resin layer is formed on the outer surface of the multilayer electronic component using the thermosetting conductive resin composition of the present invention. If the electrode forming step (1) includes the conductive resin layer forming step (1A) in which a conductive resin layer is formed on the outer surface of the multilayer electronic component using the conductive resin composition of the present invention, there are no other particular limitations. For example, the electrode forming step (1) may consist of at least a metal layer forming step, a conductive resin layer forming step (1A), and a plating layer forming step.

[0087] The metal layer formation step involves forming a metal layer that is electrically coupled to the internal electrode layer on the outer surface of a multilayer body used in multilayer electronic components. Examples of metals used to form the metal layer include at least one of Cu, Ag, Pd, Ni, Sn, Al, Au, and Pt, or alloys containing one or more of these. There are no particular limitations on the method of forming the metal layer; methods include, for example, immersion coating, plating, roller coating, screen printing, and sputtering. The thickness, shape, location, and quantity of the metal layer can be appropriately selected.

[0088] The conductive resin layer forming step (1A) is a step of forming a conductive resin layer on the surface of a metal layer formed by performing the metal layer forming step using the thermosetting conductive resin composition of the present invention.

[0089] In the conductive resin layer formation step (1A), the thermosetting conductive resin composition of the present invention is coated onto the surface of the metal layer formed by the metal layer formation step, thereby forming a layer of the thermosetting conductive resin composition of the present invention on the surface of the metal layer. Then, the thermosetting conductive resin composition of the present invention is cured to form the conductive resin layer. The method for forming the conductive resin layer is not particularly limited, and methods such as impregnation, screen printing, and roller coating are used. Among these, impregnation is preferred. The thickness, shape, position, and quantity of the thermosetting conductive resin composition layer of the present invention can be appropriately selected.

[0090] The plating layer formation step is the step of forming a plating layer on the surface of a conductive resin layer. The metal used to form the plating layer can be, for example, at least one of Ni, Cu, Sn, Ag, and Au, or an alloy containing one or more of these. There are no particular limitations on the method of forming the plating layer; for example, electrolytic plating or electroless plating can be used. The thickness, shape, location, and quantity of the plating layer can be appropriately selected.

[0091] The second form of the electrode forming step (hereinafter also referred to as "electrode forming step (2)") is the electrode forming step when the electrode substrate for electronic components is a cathode substrate for a solid electrolytic capacitor. The electrode forming step (2) includes at least a conductive resin layer forming step (2A) in which a conductive resin layer is formed on the outer surface of the cathode substrate for a solid electrolytic capacitor using the thermosetting conductive resin composition of the present invention. The electrode forming step (2) is a conductive resin layer forming step (2A) in which a conductive resin layer is formed on the outer surface of the cathode substrate for a solid electrolytic capacitor using the thermosetting conductive resin composition of the present invention is formed. There are no other particular limitations. For example, the electrode forming step (2) can be composed of at least a solid electrolyte layer forming step, a carbon layer forming step, and a conductive resin layer forming step (2A).

[0092] The solid electrolyte layer formation step is a step of forming a solid electrolyte layer on the outer surface of the cathode substrate for a solid electrolytic capacitor. There are no particular limitations on the method of forming the solid electrolyte layer; it can be formed using a known solid electrolyte manufactured by chemical methods. The solid electrolyte can be, for example, a conductive polymer such as polypyrrole, polyaniline, polythiophene, or polyacetylene.

[0093] The carbon layer formation step is the step of forming a carbon layer on a solid electrolyte layer. There are no particular limitations on the method of forming the carbon layer; for example, a carbon paste containing resin, solvent, and carbon powder can be applied to the solid electrolyte layer by impregnation, followed by drying and / or hardening. There are no particular limitations on the carbon powder, but graphite powder is preferred.

[0094] Step (2A) of forming the conductive resin layer is a step of forming a conductive resin layer on the carbon layer using the thermosetting conductive resin composition of the present invention. There are no particular limitations on the method for forming the conductive resin layer; for example, the conductive resin composition of the present invention can be coated using methods such as impregnation, screen printing, or roller coating, followed by curing the thermosetting conductive resin composition.

[0095] Another form of the electrode forming step can be, for example, the electrode forming step (3) when the electrode forming system for electronic components is formed into a wafer resistor electrode having end face electrodes. The electrode forming step (3) described above includes at least the step of forming a conductive resin layer on the end face electrodes. There are no particular limitations on the method of forming the conductive resin layer. For example, the thermosetting conductive resin composition of the present invention can be coated by means of impregnation, screen printing, roller coating, etc., and then the thermosetting conductive resin composition of the present invention can be cured. The wafer resistor electrode having end face electrodes can, for example, include: an insulating substrate, a pair of top electrodes formed on the insulating substrate, a resistor formed between the pair of top electrodes, a protective layer formed in a manner that covers a portion of the pair of top electrodes and the resistor, and end face electrodes formed on the end face of the insulating substrate.

[0096] Another form of the electrode formation step is, for example, the electrode formation step (4) when the electrode substrate for an electronic component is used as a substrate. The electrode formation step (4) includes at least the step of forming a conductive resin layer on the substrate. There are no particular limitations on the method of forming the conductive resin layer. For example, the thermosetting conductive resin composition of the present invention can be applied by screen printing, inkjet printing, or dispensing printing, and then the conductive composition of the present invention can be cured. Examples of substrates include: alumina substrates, glass epoxy boards, paper phenolic substrates, and paper epoxy boards.

[0097] Another form of the electrode formation step can be, for example, the electrode formation step (5) when the electrode for electronic components is formed as a thin film. The electrode formation step (5) includes at least the step of forming a conductive resin layer on the thin film. There are no particular limitations on the method of forming the conductive resin layer; for example, it can be a method of applying the thermosetting conductive resin composition of the present invention using screen printing, inkjet printing, or dispensing printing, followed by curing the conductive composition of the present invention. Examples of thin films include, for example, polyimide films and PET films.

[0098] The present invention will now be described with reference to specific experimental examples, but the present invention is not limited thereto. [Example]

[0099] <Manufacturing of Spherical Silver-Coated Copper Powder> Spherical silver-coated copper powder (conductive powder 1) was prepared by coating 90 parts by mass of spherical copper powder (Mitsui Metals, model: MA-CO3K) with silver in a ratio of 10 parts by mass. The obtained spherical silver-coated copper powder was subjected to a laser diffraction particle size distribution measuring device, and the 50% value of the volume integral fraction (D 50) was obtained. Furthermore, the specific surface area was determined according to the BET method.

[0100] <Manufacturing of Thin-Layer Silver-Coated Copper Powder> Spherical silver-coated copper powder was prepared using the aforementioned method. The resulting spherical silver-coated copper powder was then pulverized using a ball mill with palmitic acid as a lubricant to produce flake-shaped silver-coated copper powder (conductive powder 2). The number-average particle size (D50) and aspect ratio of 50 randomly selected powders from SEM (scanning electron microscopy) images were measured, and the average value was calculated. Furthermore, the specific surface area was determined according to the BET method.

[0101] <Manufacturing of Spherical Silver Powder> First, spherical silver powder (conductive powder 5) was prepared according to the spray thermal decomposition method described in Japanese Patent Publication No. 63-31522. Specifically, an aqueous solution containing dissolved silver salts was spray-decomposed onto the spherical silver powder, and the collected silver powder was then graded to adjust the D50 value. Furthermore, the obtained silver powder was subjected to a laser diffraction particle size distribution measuring device to determine the 50% value of the volume integral fraction (D50). Finally, the specific surface area was measured according to the BET method.

[0102] <Manufacturing of Thin Flake Silver Powder> Spherical silver powder was prepared according to the aforementioned method. The obtained spherical silver powder was then pulverized using a ball mill with stearic acid as a lubricant to produce flake-shaped silver powder (conductive powder 3). The number average particle size (D50) and aspect ratio of 50 randomly selected silver powders from SEM image observations were measured, and the average value was calculated. Furthermore, the specific surface area was determined according to the BET method.

[0103] <Preparation of Conductive Resin Composition> Conductive resin compositions were prepared by blending conductive powder and polysiloxane resin according to the blending ratios shown in Tables 1 and 2. Furthermore, the units of the values ​​shown in Tables 1 and 2 are parts by mass. Also, "BCA" in the tables is an abbreviation for butyl carbitol acetate, and "BZA" is an abbreviation for benzyl alcohol. ·Conductive powder 1 Spherical silver-coated copper powder, D 50: 4.0 μm, specific surface area: 0.5 m² / g ·Conductive powder 2 Thin-film silver-coated copper powder, aspect ratio: 20, diameter (D50): 8.0 μm, specific surface area: 1.5 m² / g ·Conductive powder 3 Thin flake-shaped silver powder, aspect ratio: 30, diameter (D50): 6.0 μm, specific surface area: 1.0 m² / g ·Conductive powder 4 Spherical nickel powder, D50: 0.8μm, specific surface area: 1.2m² / g · Conductive powder 5 Spherical silver powder, D 50: 2.3μm, specific surface area: 0.5m² / g ·Polysiloxane 1 Thermosetting polysiloxane resin with hydroxyl groups, dehydration condensation type, manufactured by Shin-Etsu Chemical Industry Co., Ltd., model: ES-1001N; In addition, polysiloxane 1 series uses batch numbers A and B, respectively. ·Polysiloxane 2 Thermosetting polysiloxane resin without hydroxyl groups, addition-curing type, manufactured by Shin-Etsu Chemical Industry Co., Ltd., model: X-40-2756 (single-component type with curing catalyst), other functional groups: alkenyl, methyl, phenyl ·Amine additive 1: Dibutylamine Secondary amine, molecular weight: 129.2, carbon number: 8, boiling point: 159℃, pKa: 11.3 ·Amine additive 2: N-Lauryl diethanolamine Tertiary amine, molecular weight: 273.5, carbon number: 16, pKa: 14 ·Amine additive 3: Triethanolamine Tertiary amine, molecular weight: 149.2, carbon number: 6, boiling point: 335.4, pKa: 7.8 ·Amine additive 4: Diisopropylamine Secondary amine, molecular weight: 101.2, carbon number: 6, boiling point: 84℃, pKa: 11.1 ·Amine additive 5: Dihexylamine Secondary amine, molecular weight: 185.4, carbon number: 12, boiling point: 194℃ ·Amine additive 6: Dimethyloctylamine Tertiary amine, molecular weight: 157.3, carbon number: 10, boiling point: 195℃ • Acid additive 1: Octadecyl succinic acid Dicarboxylic acid, molecular weight: 369, carbon number: 22, Td90: 350℃ • Acid additive 2: Octenylsuccinic acid Dicarboxylic acid, molecular weight: 228.3, carbon number: 12 • Acid / base mixed additive 1 HIPLAAD ED401, manufactured by Kusumoto Chemical Co., Ltd. In addition, the resin amount in the table below refers to the amount of resin itself excluding solvent.

[0104] (Comparative Example 1) Polysiloxane 1, conductive powder 1, conductive powder 2, and butyl carbitol acetate were mixed in the proportions recorded in Table 1 and then kneaded using a three-roll mill (manufactured by Inoue Manufacturing Co., Ltd.) to obtain a paste-like composition.

[0105] (Example 1) Polysiloxane 1, conductive powder 1, conductive powder 2, amine additive 1, and butyl carbitol acetate were mixed in the proportions recorded in Table 1 and then kneaded using a three-roll mill (manufactured by Inoue Manufacturing Co., Ltd.) to obtain a paste-like composition.

[0106] (Example 2) Polysiloxane 1, conductive powder 1, conductive powder 2, amine additive 2, and butyl carbitol acetate were mixed in the proportions recorded in Table 1 and then kneaded using a three-roll mill (manufactured by Inoue Manufacturing Co., Ltd.) to obtain a paste-like composition.

[0107] (Examples 3-22, Comparative Examples 2-6) The ingredients listed in Table 1 or Table 2 are mixed according to the ratios listed in Table 1 or Table 2, and then kneaded using a three-roll mill (manufactured by Inoue Manufacturing Co., Ltd.) to obtain a paste-like composition.

[0108] The paste-like compositions obtained from Examples 1-19, Examples 21-22, Comparative Examples 1-3, and Comparative Examples 5-6 were diluted with butyl carbitol acetate, while the paste-like compositions obtained from Example 20 and Comparative Example 4 were diluted with benzyl alcohol. The viscosity was adjusted to 30 Pa·s at 25°C and a shear rate of 4 (1 / s), and then the following evaluation was performed. The results are shown in Tables 3 and 4.

[0109] <Performance Evaluation> (Moisture permeability) A conductive resin composition was cast onto a PET film to a thickness of 250 μm and cured at 200°C for 60 minutes to obtain a cured film. The cured film was cut into 7.5 mm diameter circles and fixed with an adhesive, similar to how 2 g of silica gel is sealed in a 5 ml glass bottle. Then, the cured film was placed in a 750 ml container filled with 100 ml of pure water, ensuring it did not come into contact with the water, thus creating a sealed environment. The container was then placed in a desiccant set at 65°C and left to stand for 15 hours. The weight of the glass bottle before and after placement in the desiccant was measured, and the increase in weight was defined as the moisture permeability. A moisture permeability exceeding 80.0 mg was rated as "unacceptable, low moisture resistance," while a value below 80.0 mg was rated as "acceptable, high moisture resistance."

[0110] (Specific resistance) A conductive resin composition was cast onto a glass slide substrate with a width of 1 cm, a length of 5 cm, and a thickness of 50 μm. The mixture was then cured at 200°C for 60 minutes to obtain a hardened film. The surface resistance of the hardened film was measured using a digital multimeter (Keithley Instruments, KEITHLEY2002) via a four-terminal method. The resistivity was calculated from the obtained value and the sample thickness.

[0111] (Resistivity reduction rate) The resistivity of the paste composition (X) containing additives (at least one of amine additives and acid additives) and with adjusted viscosity, calculated according to the aforementioned method, and the resistivity of the paste composition (Y) having the same composition as the above-mentioned paste composition (X) except that it does not contain additives (at least one of amine additives and acid additives) and with adjusted viscosity, are respectively designated as (A) and (B). The resistivity reduction rate is calculated by the following formula. Resistivity reduction rate [%] = (1 - ((A) / (B))) × 100

[0112] (Viscosity increase rate) The viscosity of the viscosity-adjusted paste composition after 1 day of preparation, and after 1 week or 4 weeks of preparation, was measured using a rotary viscometer (BROOKFIELD, model: HADV-II+Pro or HBDV-II+) at 25°C and a shear rate of 4 (1 / s). The ratio of the viscosity after 1 week or 4 weeks to the viscosity after 1 day of preparation was calculated and defined as the viscosity increase rate. The prepared viscosity-adjusted paste composition was stored in a sealed container at 25°C. Furthermore, the viscosity increase rate in Examples 21-22 and Comparative Examples 5-6 was calculated from the viscosity after 4 weeks of preparation, while the viscosity increase rate in the remaining examples and comparative examples was calculated from the viscosity after 1 week of preparation.

[0113] (Viscosity inhibition rate) The viscosity increase rate of the paste composition (X) containing additives (at least one of amine additives and acid additives) and having undergone viscosity adjustment, calculated according to the aforementioned method, and the viscosity increase rate of the paste composition (Y) having the same composition as the above-mentioned paste composition (X) except that it does not contain additives (at least one of amine additives and acid additives) and having undergone viscosity adjustment, are respectively designated as (C) and (D). The specific resistivity reduction rate is calculated from the following formula. Viscosity inhibition rate [%] = (1 - ((C) / (D))) × 100

[0114] (Adhesive strength) A conductive resin composition with a thickness of 50 μm was poured onto a glass slide substrate, and then a 3 mm diameter aluminum column was placed on it. The mixture was then cured at 200°C for 60 minutes. Finally, a welding tester (manufactured by Xijin Trading Co., Ltd., model: SS-30WD) was used to stretch the sample vertically at a speed of 0.5 mm / s, and the fracture value was measured.

[0115] (Density of hardened film) A conductive resin composition was cast onto a PET film to form a coating film with a thickness of 250 μm. The coating film was then cured in an atmospheric environment at 150 °C for 10 minutes to form a hardened film. The obtained hardened film was cut into circles, and the weight and volume of the cut hardened film were measured. The ratio of weight (g) to volume (cm 3) was calculated and set as the density of the hardened film (g / cm 3).

[0116] [Table 1] Conductive powder 1 Conductive powder 2 Conductive powder 3 Conductive powder 4 Polysiloxane 1 Resin batch number Butyraldehyde resin 1 Solvent types amine series Additive 1 amine series Additive 2 amine series Additive 3 amine series Additive 4 amine series Additive 5 amine series Additive 6 Acid-based additive 1 Acid / base mixed additive 1 Additive parts per 100 parts by weight of polysiloxane Comparative Example 1 40 60 - - 16.0 A - BCA - - - - - - - - - Example 1 40 60 - - 16.0 A - BCA 0.8 - - - - - - - 5.0 Example 2 40 60 - - 16.0 A - BCA - 0.8 - - - — - - 5.0 Comparative Example 2 40 60 - - 16.0 B - BCA - - - - - - - - - Example 3 40 60 - - 16.0 B - BCA 0.05 - - - - - - - 0.3 Example 4 40 60 - - 16.0 B - BCA 0.1 - - - - - - - 0.6 Example 5 40 60 - - 16.0 B - BCA 0.8 - - - - - - - 5.0 Example 6 40 60 - - 16.0 B - BCA 1.6 - - - - - - - 10.0 Example 7 40 60 - - 16.0 B - BCA 3.2 - - - - - - - 20.0 Example 8 40 60 - - 16.0 B - BCA - - 0.8 - - - - - 5.0 Example 9 40 60 - - 16.0 B - BCA - - - 0.8 — — - - 5.0 Example 10 40 60 - - 16.0 B - BCA - - - - 0.8 - - - 5.0 Example 11 40 60 - - 16.0 B - BCA - - - - - 0.8 - - 5.0 Example 12 40 60 - - 16.0 B - BCA - - - - - - 0.05 - 0.3 Example 13 40 60 - - 16.0 B - BCA - - - - - - 0.1 - 0.6 Example 14 40 60 - - 16.0 B - BCA - - - - - - 0.8 - 5.0 Example 15 40 60 - - 16.0 B - BCA - - - - - - 1.6 - 10.0 Example 16 40 60 - - 16.0 B - BCA - - - - - - 3.2 - 20.0 Example 17 40 60 - - 16.0 B - BCA 0.4 - - - - - 0.4 - 5.0 Example 18 40 60 - - 16.0 B - BCA - - - - - - - 0.8 5.0 Comparative Example 3 40 60 - - 8.0 B 8.0 BCA - - - - - - - - - Example 19 40 60 - - 8.0 B 8.0 BCA 0.4 - - - - - - - 5.0 Comparative Example 4 40 60 - - 16.0 B - BZA - - - - - - - - - Example 20 40 60 - - 16.0 B - BZA 0.8 - - - - - - - 5.0

[0117] [Table 2] Conductive powder 1 Conductive powder 2 Conductive powder 3 Conductive powder 4 Polysiloxane 1 Resin batch number Butyraldehyde resin 1 Solvent types amine series Additive 1 amine series Additive 2 amine series Additive 3 amine series Additive 4 amine series Additive 5 amine series Additive 6 Acid-based additive 1 Acid / base mixed additive 1 Additive parts per 100 parts by weight of polysiloxane Comparative Example 5 - - 60 40 16.0 B - BCA - - - - - - - - - Example 21 - - 60 40 16.0 B - BCA 0.8 - - - - - - - 5.0 Comparative Example 6 40 60 - - 4.8 B 11.2 BCA - - - - - - - - - Example 22 40 60 - - 4.8 B 11.2 BCA 0.24 - - - - - - - 5.0

[0118] [Table 3] Moisture permeability [mg] resistivity [μΩ·cm] Reduction in resistivity [%] viscosity increase rate [times] Viscosity inhibition rate [%] Adhesive strength [kg] Hardened film density [g / cm 3] Comparative Example 1 8.3 6.6×10⁵ - 15.8 - 7.2 4.3 Example 1 9.2 2.4×10⁴ 96 1.7 89.2 7.4 4.1 Example 2 9.7 1.5×10⁴ 98 1.5 90.5 7.3 4.1 Comparative Example 2 3.3 1.2×10³ - 14.0 - 6.7 4.7 Example 3 4.1 9.0×10 2 25 10.1 27.9 7.0 4.7 Example 4 4.9 5.4×10 2 55 3.7 73.6 7.8 4.6 Example 5 4.1 5.4×10 2 55 1.2 91.4 7.5 4.1 Example 6 3.8 4.5×10 2 63 1.4 90.0 7.2 4.1 Example 7 7.0 1.2×10 2 90 2.9 79.3 5.8 4.1 Example 8 28.3 2.3×10 2 81 1.5 89.3 4.7 3.6 Example 9 6.4 8.1×10 2 33 1.7 87.9 5.0 4.0 Example 10 6.5 9.4×10 2 twenty two 1.8 87.1 4.4 4.0 Example 11 15.8 9.8×10 2 18 2.0 85.7 3.9 3.8 Example 12 4.3 5.5×10 2 54 7.8 44.3 8.1 4.6 Example 13 3.9 4.3×10 2 64 7.7 45.0 7.2 4.4 Example 14 7.1 6.4×10 2 46 1.5 89.3 6.5 4.2 Example 15 6.5 7.8×10 2 35 1.3 90.7 4.7 4.0 Example 16 6.2 8.3×10 2 31 1.3 90.7 3.7 3.9 Example 17 3.8 2.9×10 2 76 1.3 90.7 8.3 4.4 Example 18 4.1 1.4×10 2 89 2.6 81.4 9.0 4.3 Comparative Example 3 21.4 6.2×10 2 - 4.2 - 5.9 - Example 19 25.5 4.2×10 2 32 1.4 66.7 5.7 - Comparative Example 4 4.0 1.4×10³ - 2.8 - 3.1 4.5 Example 20 3.8 6.0×10 2 57 1.4 50.0 3.2 4.5

[0119] [Table 4] Moisture permeability [mg] resistivity [μΩ·cm] Reduction in resistivity [%] viscosity increase rate [times] Viscosity inhibition rate [%] Adhesion strength [kg] Hardened film density [g / cm 3] Comparative Example 5 4.3 3.8×10 2 - 2.4 - 7.0 - Example 21 4.5 3.0×10 2 52 1.2 50.0 6.2 - Comparative Example 6 33.3 4.7×10 2 - 2.4 - 4.2 - Example 22 34.0 4.0×10 2 15 1.7 29.2 4.1 -

[0120] From the results in Tables 3 and 4, Examples 1 and 2 exhibit extremely low resistivity compared to Comparative Example 1, and also show higher viscosity stability. This indicates that electronic components with superior conductivity can be manufactured compared to the conductive resin composition of Comparative Example 1. Furthermore, because the viscosity stability is higher than that of Comparative Example 1, even when manufacturing electronic components using a conductive resin composition that has been in preparation for a certain period of time, a good coating shape can still be obtained. This shows that electronic components with higher moisture resistance can be manufactured compared to the conductive resin composition of Comparative Example 1. Similarly, Examples 3-22 also demonstrate the effects of reduced resistivity and suppressed thickening, as seen in Examples 1 and 2.

[0121] (Refer to Example 1) Except for the conductive powder being changed to use 5:40 parts by weight and 3:60 parts by weight of conductive powder, the other components were prepared according to the same method as in Comparative Example 1 to obtain a viscosity-adjusted paste composition. After performing the above evaluation, the viscosity increase rate was 1.1 times. That is, when silver powder was used as the conductive powder, there was no problem with the viscosity stability.

[0122] (See Example 2 for reference) Except for replacing polysiloxane 1 with polysiloxane 2, the paste-like composition was obtained by following the same method as in Comparative Example 1. The obtained paste-like composition was diluted with butyl carbitol acetate and adjusted to a viscosity of 30 Pa·s at 25°C and a shear rate of 4 (1 / s). The above evaluation was then performed, and the viscosity increase rate was 0.9 times. That is, when an addition-curing polysiloxane was used, the viscosity stability was not problematic.

[0123] (Example 23) Except for the conductive powders, which are 100 parts by weight each of spherical tin powder, spherical zinc powder, and spherical aluminum powder, the other metal pastes were prepared and evaluated in the same manner as in Comparative Example 1 and Example 1. The results confirmed the reduction in resistivity and the inhibition of thickening caused by the amine additives, and also confirmed the high moisture resistance. In particular, when spherical tin powder was used as the conductive powder, if neither the amine additive nor the acid additive of the present invention was present, the resistivity exceeded the upper limit of the test. In contrast, the amine additive 1 of the present invention, which contains 5.0 parts by weight relative to 100 parts by weight of polysiloxane resin, significantly improved conductivity, with a resistivity of 2.9 × 10³ μΩ·cm and a resistivity reduction rate of over 99%.

[0124] (Example 24) In addition to replacing polysiloxane 1, other thermosetting polysiloxanes with hydroxyl groups were used. The paste was prepared in the same manner as in Comparative Example 1 and Example 1. After evaluation, the results confirmed the reduction in resistivity and the inhibition of thickening effect caused by the amine additive, and also confirmed the high moisture resistance.

Claims

1. A thermosetting conductive resin composition comprising: a conductive powder containing a base metal; a thermosetting polysiloxane resin having hydroxyl groups and curing by heat without the use of a hardener or catalyst; and at least one of an amine additive and an acid additive.

2. The thermosetting conductive resin composition as claimed in claim 1, wherein, The molecular weight of the above-mentioned amine additives or acid additives is 30 or more and 2000 or less.

3. The thermosetting conductive resin composition as claimed in claim 1, wherein, The boiling point Tb or the 90% mass loss temperature Td90 of the above-mentioned amine additives or acid additives at 1 atmosphere pressure is above 80°C and below 400°C.

4. The thermosetting conductive resin composition as claimed in claim 1, wherein, The aforementioned amine additives contain at least one of the secondary and tertiary amines.

5. The thermosetting conductive resin composition as claimed in claim 1, wherein, The above-mentioned acid additives contain dicarboxylic acids.

6. The thermosetting conductive resin composition as claimed in claim 1, wherein, The content of the above-mentioned amine additives is 0.6 parts by mass or more and 10.0 parts by mass or less relative to 100 parts by mass of the above-mentioned thermosetting polysiloxane resin with hydroxyl groups, and / or the content of the above-mentioned acid additives is 0.1 parts by mass or more and 1.6 parts by mass or less relative to 100 parts by mass of the above-mentioned conductive powder containing cadmium metal.

7. The thermosetting conductive resin composition as claimed in claim 1, wherein, The aforementioned thermosetting polysiloxane resin, which has hydroxyl groups and is cured by heating without the use of a hardener or catalyst, is a dehydration condensation type thermosetting polysiloxane resin that has hydroxyl groups and is cured by heating through a dehydration condensation reaction without the use of a hardener or catalyst.

8. The thermosetting conductive resin composition of claim 1, which is used for forming external electrodes of multilayer electronic components or for forming cathodes of solid electrolytic capacitors.

9. The thermosetting conductive resin composition as claimed in claim 1, wherein, Therefore, it contains organic solvents.

10. The thermosetting conductive resin composition as claimed in claim 1, wherein, Furthermore, it contains resin adhesives other than the aforementioned thermosetting polysiloxane resins that have hydroxyl groups and are cured by heat without the use of a hardener or catalyst.

11. The thermosetting conductive resin composition as claimed in claim 1, wherein, The aforementioned base metal is Cu, and it contains the aforementioned amine additives.

12. The thermosetting conductive resin composition of claim 1 is a thermosetting conductive resin composition that is cured by heating at a temperature in the range of 150°C or higher and 300°C or lower.

13. A method for manufacturing an electronic component, comprising: a preparation step, which involves preparing an electrode substrate for the electronic component; and an electrode forming step, which involves forming an electrode on the outer surface of the electrode substrate for the electronic component; wherein... The electrode forming step involves coating the thermosetting conductive resin composition of claim 1 onto the electrode substrate for electronic components, and then forming a conductive resin layer on the electrode substrate for electronic components by curing the thermosetting conductive resin composition.

14. A method for manufacturing an electronic component as described in claim 13, wherein, The above-mentioned thermosetting conductive resin composition is cured by heating at a temperature in the range of 150°C or higher and 300°C or lower.