TW202216920A - Conductive composition, conductive film, and non-contact medium - Google Patents

Abstract

The present invention provides: an electrically conductive composition having particularly exceptional electrical conductivity, adhesion, and durability; an electrically conductive film in which said electrically conductive composition is used; and a non-contact medium that offers exceptional communication performance inexpensively. The problem noted above is solved by an electrically conductive composition that contains a binder resin (A), a carbon material (B), and a curing agent (C), the carbon material (B) containing graphite (B-1) and a carbon material (B-2) other than graphite, the carbon material (B) content being 65-85 mass% in 100 mass% of solid content of the electrically conductive composition, and the graphite (B-1) content being 70.0-99.0 mass% in 100 mass% of the carbon material (B).

Description

Conductive composition, conductive film and non-contact media

The present invention relates to a conductive composition, a conductive film and a non-contact medium using the same.

In recent years, the development of electronics has been remarkable, and the conductive materials used in various electronic parts and electronic equipment are increasingly required to reduce the cost of products and to increase their lifespan in various usage environments. For example, when manufacturing conductive circuits of electronic components represented by non-contact media, basic wiring of electronic equipment, wiring connecting electronic equipment, etc., a conductive composition having good conductivity is required. Here, a conductive composition using a metal filler such as silver or copper as a conductive substance imparting conductivity is generally used, but these metal fillers have a big problem in terms of cost.

On the other hand, various studies have been conducted on conductive compositions using conductive carbon that does not use metal as a conductive substance, but the conductivity is sometimes insufficient, and the use is limited to semiconductive applications such as antistatic applications.

Therefore, in Patent Documents 1 to 3, conductive compositions using carbon materials such as graphite and carbon nanotubes having a low volume resistivity of less than 10 ⁻² Ω·cm are proposed as conductive substances. However, although these carbon materials exhibit high electrical conductivity, there are many carbon materials having a large specific surface area, and it may be difficult to uniformly mix and disperse them in a resin or a solvent. Therefore, when a coating film or a molded product is produced using a conductive composition containing such a carbon material, a resin, a solvent, etc., due to poor contact between the carbon materials in the coating film or the molded product, electrical conductivity may not be sufficiently exhibited. sex.

In addition, as a method for improving dispersibility, a method using a dispersant is considered, but electrical conductivity may be lowered by using a dispersant.

Furthermore, in order to disperse|distribute a filler, bond between fillers, and adhere|attach a conductive composition and a base material, the resin component which is an organic material is usually added to a conductive composition. However, such an organic material tends to be deteriorated in a temperature and humidity environment in an outdoor environment, and the properties as a conductive composition may deteriorate over time, and there is a problem in durability. In this way, in addition to conductivity, the conductive composition is also required to have both adhesion and durability. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 3-7740 [Patent Document 2] Japanese Patent Laid-Open No. 2001-60413 [Patent Document 3] Japanese Patent Laid-Open No. 2002-20515

[The problem to be solved by the invention] An object of the present invention is to provide a conductive composition having particularly excellent conductivity, adhesion, and durability, and a conductive film using the conductive composition. Another object of the present invention is to provide a non-contact medium having a conductive circuit using the conductive composition, low cost, and excellent communication performance. [Means of Solving Problems]

The present invention is a conductive composition comprising a binder resin (A), a carbon material (B), and a curing agent (C), and the conductive composition is characterized by: Carbon material (B) contains graphite (B-1) and carbon material (B-2) other than graphite, The content of the carbon material (B) is 65% by mass to 85% by mass in 100% by mass of the solid content of the conductive composition, The content of graphite (B-1) is 70.0 mass % to 99.0 mass % in 100 mass % of carbon material (B).

In the conductive composition of the present invention, the content of the curing agent (C) is preferably 0.5 mass % to 20 mass % with respect to 100 mass % of the binder resin (A).

In the conductive composition of the present invention, the content of graphite (B-1) is preferably 80.0% by mass to 99.0% by mass in 100% by mass of the carbon material (B).

In the conductive composition of the present invention, the content of graphite (B-1) is more preferably 90.0% by mass to 97.5% by mass in 100% by mass of the carbon material (B).

In the conductive composition of the present invention, the content of the carbon material (B) is preferably 70% by mass to 80% by mass in 100% by mass of the solid content of the conductive composition.

In the conductive composition of the present invention, the curing agent (C) preferably contains an aziridine compound or an epoxy group-containing compound.

In the conductive composition of the present invention, the hardener (C) preferably contains a metal chelate compound.

In the conductive composition of the present invention, the metal chelate compound preferably contains an aluminum chelate compound.

In addition, the present invention is a conductive film formed by forming the conductive composition into a film.

In addition, the present invention is a non-contact medium on which a conductive circuit formed using the conductive composition and an integrated circuit (IC) chip are stacked. [Effect of invention]

ADVANTAGE OF THE INVENTION According to this invention, the electroconductive composition which is especially excellent in all of electroconductivity, adhesiveness, and durability, and the electroconductive film using the same can be provided. Further, according to the present invention, it is possible to provide a non-contact medium having a conductive circuit using the conductive composition, low cost, and excellent communication performance.

＜＜Conductive composition＞＞ The conductive composition of the present invention (hereinafter sometimes referred to as the present conductive composition) contains a binder resin (A), a carbon material (B), a curing agent (C), and a solvent (D) as needed.

In this electroconductive composition, the blending ratio of graphite which is a carbon material which is an electroconductive substance, and carbon other than graphite is made into a specific range. Therefore, the durability of the binder resin and the contact or adhesion between the carbon materials in the conductive film containing the conductive composition are good, and an excellent conductive network can be formed, thereby providing conductivity, durability, and adhesion. Conductive film with excellent properties.

According to the coating method of the conductive composition, the appropriate viscosity of the conductive composition is preferably 10 mPa·s or more and 30,000 mPa·s or less.

＜Binder resin (A)＞ First, the binder resin (A) will be described.

The binder resin (A) may contain a resin selected from the group consisting of polyurethane-based, polyamide-based, acrylonitrile-based, acrylic-based, butadiene-based, polyvinyl butyral-based, polyolefin-based, polyester-based, poly One or more of the group consisting of styrene-based, EVA-based, epoxy-based, polyvinylidene fluoride-based, and silicone-based resins. However, it is not limited to these resins. The binder resin (A) may be used alone or in combination of two or more.

In addition, the binder resin (A) may be a curable resin which undergoes a curing (crosslinking) reaction after the binder resin is applied to the base material. That is, the binder resin (A) may be selected from a self-curing resin, or may be combined with a curing agent to be described later, and the conductive composition may be printed or applied on a substrate and then reacted, that is, cured (crosslinked).

Moreover, as a binder resin (A), it is preferable to soften and flow suitably at the time of (hot) pressing. After printing or coating a conductive composition containing such a binder resin (A) on a substrate, when (hot) pressing is performed, the resin component is softened, and the flat pattern of the conductive film at the time of printing and coating is substantially maintained. shape while flowing in the thickness direction. As a result, the voids in the conductive film can be reduced, and the contact between the carbon materials (B), which are conductive substances, can be increased, so that reduction in the volume resistivity of the obtained conductive film can be expected.

From the above, it is preferable to use polyurethane resin, polyamide resin, and polyester resin as the binder resin (A) from the viewpoint of volume resistivity, adhesion to the base material, and durability. at least one of them.

(polyurethane resin) As the polyurethane resin, a conventionally known resin can be used, and the synthesis method thereof is not particularly limited. For example, as the polyurethane resin, a polyurethane resin obtained by the following synthesis method can be used. 1) A method of reacting a polyol compound (a) with a diisocyanate (b). 2) A method of obtaining a urethane prepolymer (d) having an isocyanate group by reacting a polyol compound (a), a diisocyanate (b), and a diol compound (c) having a carboxyl group. 3) A method of further reacting the urethane prepolymer (d) with the polyamine compound (e). In addition, as a polyurethane resin, the polyurethane resin obtained by making a reaction stopper react in the said three methods can also be used as needed.

· Polyol compound (a) Among the polyol compound (a), a conventionally known one can be appropriately used as the polyol component constituting the polyurethane resin. As the polyol compound (a), for example, polyether polyols (a-1), polyester polyols (a-2), polycarbonate polyols (a-3), polybutadiene diols can be used Alcohols (a-4), a mixture of these, and the like.

As polyether polyols (a-1), polymers, copolymers, etc., such as ethylene oxide, propylene oxide, and tetrahydrofuran, are mentioned.

As polyester polyols (a-2), ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, new Pentanediol, Pentanediol, 3-Methyl-1,5-Pentanediol, Hexanediol, Octanediol, 1,4-Butanediol, Diethylene glycol, Triethylene glycol, Dipropylene glycol, Saturated and unsaturated low-molecular-weight glycols such as dimer diols; and alkyl glycidyl ethers such as n-butyl glycidyl ether and 2-ethylhexyl glycidyl ether; monocarboxylic acids such as glycidyl neodecanoate Acid glycidyl esters; adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, Dicarboxylic acids such as suberic acid, azelaic acid, and sebacic acid; or polyester polyols obtained by dehydration condensation of these acid anhydrides; or polyester polyols obtained by ring-opening polymerization of cyclic ester compounds .

As the polycarbonate polyols (a-3), 1) a reaction product of diol or bisphenol and carbonate, and 2) a reaction product of diol or bisphenol and phosgene in the presence of a base can be used.

Examples of carbonates include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylidene carbonate, propylene carbonate, and the like. Moreover, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butanediol, 3-methyl-1,5-pentanediol, 2-methyl- 1,8-octanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3- Hexanediol, cyclohexanediol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl), 2,2,8,10-tetraoxospiro[5.5]undecane, etc. . Moreover, as a bisphenol, bisphenol A, bisphenol F, and bisphenols etc. which added alkylene oxides, such as ethylene oxide and propylene oxide, to bisphenols are mentioned.

The number average molecular weight (Mn) of the polyol compound (a) may take into consideration the solubility of the polyurethane resin when producing the conductive composition, the durability of the conductive film to be formed, or the resistance to the substrate. Then the intensity and the like are appropriately determined. Mn of the polyol compound (a) is preferably in the range of 580 to 8000, more preferably in the range of 1000 to 5000.

The polyol compound (a) may be used alone or in combination of two or more. Furthermore, within the range where the performance of the polyurethane resin is not lost, a part of the polyol compound (a) may be replaced with low molecular weight diols, such as those used in the production of the polyol compound. of various low molecular weight diols.

· Diisocyanate compound (b) As the diisocyanate compound (b), conventionally known ones can be suitably used, for example, aromatic diisocyanate (b-1), aliphatic diisocyanate (b-2), alicyclic diisocyanate (b-3), or mixture of these.

Examples of the aromatic diisocyanate (b-1) include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and 4,4'-diphenyldimethylmethane diisocyanate , 4,4'-benzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, Toluene diisocyanate, xylylene diisocyanate, etc.

Examples of the aliphatic diisocyanate (b-2) include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine Diisocyanate, etc.

Examples of alicyclic diisocyanate (b-3) include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, norbornane diisocyanate methyl ester, bis(4-isocyanate cyclohexyl group) ) methane, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexanediisocyanate, and the like.

Among these, it is preferable to use isophorone diisocyanate as the diisocyanate compound (b).

·Diol compound (c) having a carboxyl group Examples of the diol compound (c) having a carboxyl group include dimethylolalkanoic acids such as dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, and dimethylolvaleric acid, Hydroxysuccinic acid, dihydroxybenzoic acid. Among these, from the viewpoint of reactivity and solubility, as the diol compound (c), at least one of dimethylol propionic acid and dimethylol butyric acid is preferred.

·Polyamine compound (e) The polyamine-based compound (e) is used as a chain extender, and for example, the following ones can be used. Namely, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, norbornane Amines such as diamine, 2-(2-aminoethylamino)ethanol, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropanediamine, di-2-hydroxy Amines having a hydroxyl group such as ethylethylenediamine and di-2-hydroxypropylethylenediamine. Among these, as the polyamine-based compound (e), isophoronediamine is preferably used.

The conditions for obtaining a urethane prepolymer (d) having an isocyanate group by reacting a polyol compound (a), a diisocyanate (b), and a diol compound (c) having a carboxyl group are not excessive in the reaction system Except for the presence of an isocyanate group, it is not particularly limited. However, the equivalence ratio of the isocyanate group/hydroxyl group in the reaction system is preferably in the range of 1.05/1 to 3/1, more preferably in the range of 1.2/1 to 2/1. The reaction is usually carried out at a temperature in the range of room temperature (eg, 25°C) to 150°C. In addition, it is preferable to carry out this reaction at the temperature of the range of 60 degreeC - 120 degreeC from the viewpoint of control of production time and side reaction.

When a urethane prepolymer (d) having an isocyanate group is reacted with a polyamine compound (e) to synthesize a polyurethane resin, a reaction stopper can be used to adjust the obtained polyamine group Molecular weight of formate resin. As the reaction terminator, for example, dialkylamines such as di-n-butylamine; dialkanolamines such as diethanolamine; and alcohols such as ethanol and isopropanol can be used.

The conditions at the time of reacting the urethane prepolymer (d) having an isocyanate group, the polyamine group compound (e), and an optional reaction terminator are not particularly limited. However, when the free isocyanate groups present at both ends of the urethane prepolymer are set to 1 equivalent, the total equivalent of the amine groups in the polyamine compound (e) and the reaction terminator is preferably 1 equivalent. within the range of 0.5 to 1.3. It is more preferable that the total equivalent weight of the said amine group exists in the range of 0.8-0.995.

The weight average molecular weight (Mw) of the polyurethane resin is preferably in the range of 5,000 to 200,000 from the viewpoint of coatability and handleability.

When synthesizing a polyurethane resin, one kind of solvent can be used alone, or two or more kinds of solvents can be used in combination. Examples of the solvent include ester-based solvents, ketone-based solvents, glycol ether-based solvents, aliphatic-based solvents, aromatic-based solvents, alcohol-based solvents, carbonate-based solvents, and water.

As an ester solvent, ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, ethyl lactate, etc. are mentioned.

Examples of the ketone-based solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, diacetone alcohol, isophorone, cyclohexanone, and the like.

Examples of glycol ether-based solvents include ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, and acetates of these monoethers; diethylene glycol diethylene glycol Methyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and ethyl ethers of these monoethers acid esters, etc.

As aliphatic solvent, n-heptane, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc. are mentioned.

As an aromatic solvent, toluene, xylene, etc. are mentioned.

Examples of the alcohol-based solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and cyclohexanol.

As a carbonate type solvent, dimethyl carbonate, ethyl methyl carbonate, di-n-butyl carbonate, etc. are mentioned.

(polyamide resin) The polyamide resin in this specification refers to, for example, a polymer having an amide bond obtained by various reactions such as polycondensation of dibasic acid and diamine, polycondensation of aminocarboxylic acid, or ring-opening polymerization of lactamide. general name. However, the term "polyamide resin" includes various modified polyamide resins, including those produced from partially hydrogenated reactants, those produced by partial copolymerization of other monomers, or mixed with various additives, etc. A broad concept of substances such as polyamide resins.

The polyamide resin is not particularly limited as long as it satisfies the above conditions, but is preferably a dimer acid-modified polyamide resin obtained by polycondensing a dibasic acid containing a dimer acid as a main component and polyamines. In addition, the main component means the component whose compounding ratio (for example, molar % content rate) is the highest among all the components contained in an object (here, a dibasic acid).

The dimer acid may be a dimer acid obtained by polymerizing natural monounsaturated fatty acids contained in tall oil fatty acid, soybean oil fatty acid, etc., or may be saturated aliphatic or unsaturated aliphatic acid. , alicyclic, or aromatic various dicarboxylic acids, etc.

Commercially available products of the dimer acid include HARIDIMER 200, HARIDIMER 300 (all trade names, manufactured by Harima Chemical Co., Ltd.), BARIDIMER Varsadime 228, Varsadime 216, Empol 1018, Empol 1019, Empol 1061, Empol 1062 (all trade names, Corning ( Cognis), etc.

Furthermore, a hydrogenated dimer acid can also be used, and as a commercial item of the hydrogenated dimer acid, Pripol 1009 (trade name, manufactured by Croda Japan Co., Ltd.), Empol 1008 (trade name, manufactured by Cognis Corporation) and the like.

In addition to the above-mentioned dimer acid, various dicarboxylic acids can be used as the dibasic acid in order to obtain a polyamide resin having appropriate flexibility. As the dicarboxylic acid, specifically, oxalic acid, malonic acid, succinic acid (anhydride), maleic acid (anhydride), glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, 1,3- or 1,4-cyclohexanedicarboxylic acid, 1,18-octadecanedicarboxylic acid , 1,16-hexadecanedicarboxylic acid, etc.

It is also possible to use those having a phenolic hydroxyl group as the dibasic acid. By using a dibasic acid having a phenolic hydroxyl group, a phenolic hydroxyl group can be introduced into the side chain of the polyamide resin, which can be used for the reaction with a curing agent.

Examples of the dibasic acid having a phenolic hydroxyl group include hydroxyisophthalic acid such as 2-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, and 5-hydroxyisophthalic acid, and 2,5-dihydroxyl Dihydroxyisophthalic acid such as isophthalic acid, 2,4-dihydroxyisophthalic acid, 4,6-dihydroxyisophthalic acid; 2-hydroxyterephthalic acid, 2,3-dihydroxyp-phenylene Dihydroxyterephthalic acid such as dicarboxylic acid and 2,6-dihydroxyterephthalic acid; hydroxyphthalic acid such as 4-hydroxyphthalic acid and 3-hydroxyphthalic acid; 3,4-dihydroxyphthalic acid Dihydroxyphthalic acid such as phthalic acid, 3,5-dihydroxyphthalic acid, 4,5-dihydroxyphthalic acid, and 3,6-dihydroxyphthalic acid, etc. Furthermore, acid anhydrides of these compounds, ester derivatives such as polybasic acid methyl esters, etc. are also mentioned. Among these, the dibasic acid is preferably 5-hydroxyisophthalic acid from the viewpoints of copolymerizability and availability.

Furthermore, in order to make a polyamide resin which has suitable fluidity|liquidity at the time of heating, various monocarboxylic acid can also be used as needed. As the monocarboxylic acid, propionic acid, acetic acid, caprylic acid, stearic acid, oleic acid, etc. are specifically used.

As polyamines of the reactant at the time of manufacture of the said dimer acid-modified polyamide resin, various diamines, triamines, polyamines, etc., such as aliphatic, alicyclic, aromatic, etc. are mentioned, for example.

Specific examples of the diamine include ethylenediamine, propylenediamine, butanediamine, triethylenediamine, tetraethylenediamine, hexamethylenediamine, p-xylene diamine, or m-xylene Diamine, 4,4'-methylenebis(cyclohexylamine), 2,2-bis-(4-cyclohexylamine), polyethylene glycol diamine, isophorone diamine, 1,2- Cyclohexanediamine, 1,3-cyclohexanediamine, or 1,4-cyclohexanediamine, 1,4-bis-(2'-aminoethyl)benzene, N-ethylamino Piperazine, piperazine, etc. In addition, a dimer diamine obtained by converting a dimerized aliphatic nitrile group and reducing it with hydrogen can also be used.

Alkanolamines may be used in combination with diamines. Examples of alkanolamines include ethanolamine, propanolamine, diethanolamine, butanolamine, 2-amino-2-methyl-1-propanol, 2-(2-aminoethoxy)ethanol, and the like . Moreover, as a diamine, the polyether diamine which has oxygen in a skeleton can be used. The polyether diamine can be represented by the general formula: H ₂ NR ₁ -(RO) _n -R ₂ -NH ₂ (in the formula, n is an integer from 2 to 100, R ₁ and R ₂ are 1 to 14 carbon atoms) The alkylene group or the bivalent alicyclic hydrocarbon group, R is an alkylene group or a bivalent alicyclic hydrocarbon group with 1 to 10 carbon atoms. The alkylene group can be linear or branched. )express. As this polyether diamine, polyoxypropylene diamine etc. are mentioned, and as a commercial item, there are Jeffamines (made by Sun Techno Chemical). Moreover, bis-(3-aminopropyl)-polytetrahydrofuran is also mentioned as a polyether diamine.

Moreover, as a specific example of a triamine, diethylenetriamine etc. are mentioned. Specific examples of the polyamine include triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like. Moreover, as a polyamine, the compound which converted the carboxyl group of the polybasic acid compound which has a cyclic or acyclic hydrocarbon group of carbonic acid 20-48 into an amine group can be used. Examples of commercially available polyamines include: "Priamine 1071", "Priamine 1073", "Priamine 1073", "Priamine 1073", trade names manufactured by Croda Japan Co., Ltd. Min (Priamine) 1074", "Priamine (Priamine) 1075" or the trade name of Cognis Japan Co., Ltd.: "Versamine (Versamine) 551" etc.

The polyamines and dimer acids or various dicarboxylic acids are heated and condensed by conventional methods, and various polyamide resins including dimer acid-modified polyamide resins are produced by an amination step with dehydration. Amine resin. Usually, the reaction temperature is about 100°C to 300°C, and the reaction time is about 1 to 8 hours.

(polyester resin) The polyester resin is a polymer containing a polycarboxylic acid and a polyhydric alcohol as monomers. A known polyester resin can be used and is not particularly limited. However, the weight average molecular weight (Mw) of the polyester resin is preferably 1,000 to 100,000 from the viewpoint of securing the cohesive force of the resin. Moreover, from the viewpoint of adhesiveness, the glass transition temperature (Tg) of the polyester resin is preferably -10°C to 200°C.

As a polyhydric carboxylic acid component which comprises polyester resin, an aromatic dicarboxylic acid, aliphatic dicarboxylic acid, unsaturated dicarboxylic acid, a trivalent or more carboxylic acid, etc. are mentioned, for example. On the other hand, as a polyol component which comprises a polyester resin, aliphatic diols, ether diols, a polyhydric alcohol of trivalent or more, etc. are mentioned. Any of the polyvalent carboxylic acid and the polyhydric alcohol may be used alone or in combination of two or more.

Commercially available polyester resins include Vylon (manufactured by Toyobo Co., Ltd., "Vylon" is a registered trademark), POLYESTER (Nippon Synthetic Chemical Industry Co., Ltd. Company), "POLYESTER" is a registered trademark), Teslac (manufactured by Hitachi Chemical Polymer Co., Ltd., "Teslac" is a registered trademark), etc.

<Carbon material (B)> Next, the carbon material (B) will be described.

In this conductive composition, the carbon material (B) used as the conductive substance contains graphite (B-1) and carbon materials (B-2) other than graphite. Moreover, the content rate of the carbon material (B) is 65 mass % - 85 mass % in 100 mass % of solid content of an electroconductive composition, Preferably it is 70 mass % - 80 mass %.

When the content rate of the carbon material (B) exceeds 85 mass %, the resin component is insufficient, the adhesiveness of the conductive film is lowered, and the adhesion is poor. On the other hand, when the content rate of the carbon material (B) is less than 65 mass %, the contact between the carbon materials in the conductive film is reduced, and the conductivity is poor.

When the content rate of the carbon material (B) is 70% by mass to 80% by mass, in a state in which the conductive network in the conductive film containing the conductive composition is well formed, high conductivity and high conductivity can be easily expressed. Adhesion.

(Graphite (B-1)) As graphite (B-1), artificial graphite, natural graphite, etc. can be used, for example. Artificial graphite is artificially oriented graphite of irregularly arranged micrographite crystals by heat treatment of amorphous carbon, and is usually produced by using petroleum coke or coal-based pitch coke as the main raw material. As the natural graphite, flake graphite, block graphite, earthy graphite, etc. can be used. In addition, expanded graphite obtained by chemically treating flake graphite (also referred to as expanded graphite), or expanded graphite obtained by heat-treating and expanding expanded graphite, and then micronizing or pressing may also be used. Wait. Among these graphites, flaky graphites such as flaky graphite, expanded graphite, and exfoliated graphite are preferred from the viewpoint of electrical conductivity in the case of a conductive film used for a wiring sheet.

In order to increase the affinity with the binder resin (A), surface treatments such as epoxy treatment, urethane treatment, and silane coupling treatment may be applied to the surfaces of these graphites as long as the properties of the conductive composition are not impaired. and oxidation treatment.

In addition, the average particle diameter of the graphite (B-1) to be used is preferably 2 μm to 100 μm, and more preferably 20 μm to 50 μm.

When the average particle size of the graphite (B-1) is 2 μm or more, the aspect ratio of the graphite particles can be set in an appropriate range, and the contact between the graphite particles can be prevented from becoming point contact, so that a sufficient conductive network can be easily formed . In addition, when the average particle diameter of the graphite (B-1) is 100 μm or less, the voids between the graphite particles can be made to have an appropriate size, and the conductive paths formed between the carbon materials other than graphite in the conductive network can be The ratio of the conductive path via graphite is in an appropriate range, and excellent conductivity can be imparted.

The average particle size in the present specification refers to a particle size (D50) at which the volume ratio of the particles with a fine particle size is accumulated from the particles having a fine particle size in a volume particle size distribution of 50%. The average particle diameter can be measured by a general particle size distribution analyzer, for example, a particle size distribution analyzer of a dynamic light scattering method (manufactured by Nikkiso Co., Ltd., trade name: "MICROTRAC UPA").

As a commercially available graphite (B-1), the following graphite is mentioned, for example. Examples of flake graphite include trade names manufactured by Nippon Graphite Industries: CMX, CPB, UP-5, UP-10, UP-20, UP-35N, CSSP, CSPE, CSP, CP, CB-150, CB -100, ACP, ACP-1000, ACB-50, ACB-100, ACB-150, SP-10, SP-20, J-SP, SP-270, HOP, GR-15, LEP, F#1, F #2, F#3; trade names manufactured by Sino-Vietnamese Graphite Company: CX-3000, FBF, BF, CBR, SSC-3000, SSC-600, SSC-3, SSC, CX-600, CPF-8, CPF-3 , CPB-6S, CPB, 96E, 96L, 96L-3, 90L-3, CPC, S-87, K-3, CF-80, CF-48, CF-32, CP-150, CP-100, CP , HF-80, HF-48, HF-32, SC-120, SC-80, SC-60, SC-32; trade names manufactured by Ito Graphite Industries: EC1500, EC1000, EC500, EC300, EC100, EC50; Trade names manufactured by Nishimura Graphite Co., Ltd.: 10099M, PB-99, etc. Examples of spherical natural graphite include trade names: CGC-20, CGC-50, CGB-20, and CGB-50 manufactured by Nippon Graphite Industries. Examples of earthy graphites include trade names: Blue P, AP, AOP, and P#1 manufactured by Nippon Graphite Industrial Co., Ltd.; trade names: APR, S-3, AP-6, and 300F manufactured by Chuetsu Graphite Co., Ltd. Examples of artificial graphites include trade names: PAG-60, PAG-80, PAG-120, PAG-5, HAG-10W, HAG-150 manufactured by Nippon Graphite Industries; trade names: RA- 3000, RA-15, RA-44, GX-600, G-6S, G-3, G-150, G-100, G-48, G-30, G-50; trade names manufactured by SEC Carbon: SGP-100, SGP-50, SGP-25, SGP-15, SGP-5, SGP-1, SGO-100, SGO-50, SGO-25, SGO-15, SGO-5, SGO-1, SGX- 100, SGX-50, SGX-25, SGX-15, SGX-5, SGX-1. In addition, the graphite (B-1) is not limited to these. In addition, one type of graphite (B-1) may be used alone, or two or more types may be used in combination.

The content of graphite (B-1) in 100% by mass of the carbon material (B) in the conductive composition is 70.0% by mass to 99.0% by mass, preferably 75.0% by mass to 99.0% by mass, more preferably 80.0% by mass % by mass to 99.0% by mass, preferably 90.0% by mass to 97.5% by mass.

When the content rate of graphite (B-1) in the carbon material (B) is less than 70.0% by mass, the carbon material (B-2) other than the graphite is excessively present, resulting in a decrease in the orientation of the graphite particles, Furthermore, carbon materials other than graphite occupy most of the conductive network, so that particularly excellent high conductivity cannot be exhibited. On the other hand, when the content rate of graphite (B-1) in the carbon material (B) exceeds 99.0 mass %, the electrical conductivity based on the plane direction of the graphite particles becomes dominant, and the electrical conductivity of the conductive film reaches the limit .

When the content rate of the graphite (B-1) in the carbon material (B) is 75.0 mass % or more, the orientation of the graphite particles is not lowered, and high electrical conductivity can be easily expressed.

When the content rate of graphite (B-1) in the carbon material (B) is 80.0 mass % or more, the pinholes of the conductive film can be further reduced, and a good coating film can be easily formed.

When the content rate of the graphite (B-1) in the carbon material (B) is 90.0% by mass to 97.5% by mass, the carbon material (B-2) other than the graphite is an appropriate compounding amount and does not hinder the graphite particles The high conductivity in the plane direction can strengthen the conductive network in the vertical direction. As a result, very high electrical conductivity can be expressed. In addition, when the content rate of graphite (B-1) in the carbon material (B) is less than 90.0 mass %, a coating film with less unevenness of the conductive film can be easily obtained.

(Carbon materials other than graphite (B-2)) It does not specifically limit as a carbon material (B-2) other than graphite, A conventionally well-known thing can be used. Examples of the carbon material (B-2) include carbon black, conductive carbon fibers (carbon nanotubes, carbon nanofibers, and carbon fibers), fullerenes, and the like. Among these, carbon black is preferably used as the carbon material (B-2) from the viewpoint of particle diameter and specific surface area. The carbon material (B-2) other than graphite may be used alone or in combination of two or more.

Examples of carbon black include: furnace black produced by continuously thermally decomposing a gas or liquid raw material in a reaction furnace, especially Ketjen Black produced from ethylene heavy oil; combustion raw material gas The hot carbon black obtained by making the flame contact the bottom surface of the channel steel and quenching and precipitation; using the gas as a raw material, and periodically repeatedly burning and thermally decomposing the hot carbon black; especially the acetylene black as the raw material, etc. . Moreover, as carbon black, the carbon (black), hollow carbon, etc. which performed the normal oxidation process can also be used.

The oxidation treatment of carbon is generally performed to improve the dispersibility of carbon. Specifically, oxygen-containing polar functional groups such as phenol groups, benzoquinone groups, carboxyl groups, carbonyl groups, etc. are converted into Treatment for direct introduction (covalent bonding) to the carbon surface. However, as the introduction amount of the functional group increases, the conductivity of carbon tends to decrease. Therefore, it is preferable to use carbon that has not been subjected to an oxidation treatment.

The larger the specific surface area value of carbon black, the more contact points between carbon black particles, which is beneficial to reduce the volume resistivity. Specifically, it is desirable to use a specific surface area (BET) calculated from the nitrogen adsorption amount, preferably 20 m ² /g or more and 1500 m ² /g or less, more preferably 50 m ² /g or more, 1500 m ² /g or less, particularly preferably 100 m ² /g or more and 1500 m ² /g or less. When the specific surface area of carbon black is 20 m ² /g or more, sufficient electrical conductivity can be easily obtained, and when the specific surface area is 1500 m ² /g or less, it can be easily obtained as a commercially available material.

In addition, the particle diameter of carbon black is preferably 0.005 μm to 1 μm in terms of primary particle diameter, and more preferably 0.01 μm to 0.2 μm. Here, the primary particle diameter referred to here refers to an average value of particle diameters measured by an electron microscope or the like.

Commercially available carbon blacks include, for example, Toka Black #4300, Toka black #4400, Toka black #4500, Toka black #4500, manufactured by Tokay Carbon Co., Ltd. Toka black #5500; trade names from Degussa: PRINTEX L; Raven 7000, Raven 5750, Raven 5750 from Columbia Raven 5250, Raven 5000ULTRAIII, Raven 5000ULTRA, Conductex SCULTRA, Conductex 975ULTRA, PUERBLACK100, PUERBLACK 115, PUERBLACK205; trade names manufactured by Mitsubishi Chemical Corporation : #2350, #2400B, #2600B, #3050B, #3030B, #3230B, #3350B, #3400B, #5400B; Brand names manufactured by Cabot: MONARCH 1400, MONARCH MONARCH 1300, MONARCH 900, Vulcan XC-72R, BlackPearls 2000; trade name manufactured by TIMCAL: Ensaco 250G , Ensaco 260G, Ensaco 350G, Super P-Li and other furnace blacks; Trade names manufactured by Lion: EC-300J, EC-600JD and other Ketjen black; Trade names manufactured by Denka Industrial Co., Ltd.: Acetylene black such as DENKA BLACK, DENKA BLACK HS-100, and FX-35. However, it is not limited to these carbon blacks. One type of carbon black may be used alone, or two or more types may be used in combination.

As the conductive carbon fiber, a conductive carbon fiber obtained by sintering from a raw material derived from petroleum is suitable, and a conductive carbon fiber obtained by sintering from a raw material derived from a plant may also be used. In addition, carbon nanotubes include single-layered carbon nanotubes in which a graphite sheet is a single layer and a tube having a diameter of a nanometer region, and a multi-layered carbon nanotube in which the graphite sheet is a plurality of layers. Therefore, the diameter of the multilayered carbon nanotubes shows a value as large as 30 nm, relative to the typical single-walled carbon nanotubes of 0.7 nm to 2.0 nm.

Commercially available conductive carbon fibers or carbon nanotubes include: trade names from Showa Denko Co., Ltd.: vapor-phase carbon fibers such as VGCF, trade names from Meijo Nanocarbon Co., Ltd.: EC1.0, EC1.5, EC2 .0, EC1.5-P and other single-layer carbon nanotubes, trade names manufactured by CNano Company: FloTube 9000, FloTube 9100, FloTube ( FloTube 9110, FloTube 9200, trade name manufactured by Nanocyl Corporation: NC 7000, trade name manufactured by Knano Corporation: 100T, etc.

(hardener (C)) Next, the curing agent (C) will be described.

The hardener (C) is not particularly limited as long as it reacts with the reactive functional group contained in the binder resin (A). By curing the binder resin (A), the physical strength or chemical resistance of the resin is improved, and the durability of the conductive film is optimized. Furthermore, electrical conductivity is optimized by the effect of volume shrinkage of the conductive film during curing.

Examples of reactive functional groups include, but are not particularly limited to, hydroxyl groups, phenolic hydroxyl groups, carboxyl groups, amino groups, acid anhydride groups such as maleic anhydride, and thiol groups.

Examples of the curing agent (C) include epoxy group-containing compounds (C1), isocyanate group-containing compounds (C2), blocked isocyanate group-containing compounds (C3), aziridine compounds (C4), compounds containing Carbodiimide group compound (C5), benzoxazine compound (C6), phenol resin (C7), maleimide compound (C8), compound containing β-hydroxyalkyl imide group (C9) ), and metal chelates (C10). A hardener (C) may be used individually by 1 type, and may be used in combination of 2 or more types.

From the viewpoint of the durability of the conductive film, the curing agent (C) is preferably an epoxy group-containing compound (C1), an aziridine compound (C4), and a metal chelate compound (C10). From the viewpoint of this, the aziridine compound (C4) and the metal chelate compound (C10) are more preferred, and the aziridine compound (C4) is particularly preferred.

The aziridine compound (C4) has very good reactivity with a binder resin containing a carboxyl group, a phenolic hydroxyl group, an acid anhydride, and the like. Therefore, when the conductive film starts to harden immediately after drying, the hardening shrinkage occurs remarkably, so that the contact between the fillers becomes dense, and the electrical conductivity is greatly improved compared with the case of using other hardeners.

Metal chelate (C10) is a general term for compounds in which a compound having a multidentate ligand in the molecule forms a complex by sandwiching a metal ion. Metal chelate (C10) reacts with particles with functional groups on the surface such as carbon black, and functions as a dispersant. It can form a uniform conductive path by suppressing the irregular aggregation of conductive fillers during film formation. Therefore, Excellent electrical conductivity can be imparted.

· Compounds containing epoxy groups (C1) The epoxy group-containing compound (C1) is not particularly limited as long as it is a compound having an epoxy group in the molecule. However, as the epoxy group-containing compound (C1), a compound having an average of two or more epoxy groups in one molecule can be preferably used. As the epoxy group-containing compound (C1), for example, a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, or a cycloaliphatic (alicyclic type) epoxy resin can be used. Epoxy resin such as resin.

Examples of glycidyl ether type epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD type epoxy resins, and cresol novolac type epoxy resins. Epoxy resin, phenol novolac epoxy resin, α-naphthol novolak epoxy resin, bisphenol A novolak epoxy resin, dicyclopentadiene epoxy resin, tetrabromobisphenol A type Epoxy resin, brominated phenol novolak type epoxy resin, tris(glycidoxyphenyl)methane, or tetrakis(glycidoxyphenyl)ethane, and the like.

Examples of glycidylamine-type epoxy resins include tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, or tetraglycidyl-m-phenylene Dimethylamine, etc.

As a glycidyl ester type epoxy resin, diglycidyl phthalate, diglycidyl hexahydrophthalate, or diglycidyl tetrahydrophthalate, etc. are mentioned, for example.

As a cycloaliphatic (alicyclic type) epoxy resin, epoxycyclohexanecarboxylic acid-epoxycyclohexyl methyl ester, or bis(epoxycyclohexyl) adipate etc. are mentioned, for example.

As the epoxy group-containing compound (C1), these compounds may be used alone or in combination of two or more. As the epoxy group-containing compound (C1), from the viewpoint of durability, bisphenol A type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, tris(condensed) epoxy resin are preferably used glyceryloxyphenyl)methane, or tetrakis(glycidoxyphenyl)ethane.

· Compounds containing isocyanate groups (C2) The isocyanate group-containing compound (C2) is not particularly limited as long as it is a compound having an isocyanate group in the molecule.

For example, as the isocyanate group-containing compound (C2) having one isocyanate group in one molecule, n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate can be mentioned. base ester, (meth)acryloyloxyethyl isocyanate, 1,1-bis[(meth)acryloyloxymethyl]ethyl isocyanate, vinyl isocyanate, allyl isocyanate, ( Meth)acryloyl isocyanate, isopropenyl-α,α-dimethylbenzyl isocyanate, etc.

In addition, as the isocyanate group-containing compound (C2), a compound obtained by reacting a diisocyanate compound with a vinyl monomer containing a hydroxyl group, a carboxyl group, and an amide group at an equimolar ratio can also be used, and the diisocyanate compound is : 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, benzene diisocyanate Methyl (xylylene) diisocyanate, 2,4-diisocyanate tolylene (tolylene), toluene diisocyanate, 2,4-toluene diisocyanate, hexamethylene diisocyanate , 4-methyl-m-phenylene diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, tetramethylxylylene diisocyanate, cyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclic Hexyl diisocyanate, tolidine diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, m-tetramethylbenzene Dimethyl diisocyanate, p-tetramethylxylylene diisocyanate, dimer acid diisocyanate and the like.

As the isocyanate group-containing compound (C2) having two isocyanate groups in one molecule, for example, 1,3-phenylene diisocyanate, 4,4'-diphenyldiisocyanate, 1,4- Phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6- Aromatic aromatics such as triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenylether diisocyanate, 4,4',4''-triphenylmethane triisocyanate Diisocyanates; trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylidene diisocyanate, 2,3-butylene diisocyanate, Aliphatic diisocyanates such as 1,3-butylene diisocyanate, dodecylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate; ω,ω'-diisocyanate-1,3 -Dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene Aromatic aliphatic diisocyanates such as diisocyanate and 1,3-tetramethyl xylylene diisocyanate; 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate [alias: isophorone diisocyanate] , 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6 -Cyclohexanediisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, etc. Cycloaliphatic diisocyanates.

In addition, examples of the isocyanate group-containing compound having three isocyanate groups in one molecule include aromatic polyisocyanates, aliphatic polyisocyanates such as lysine triisocyanate, arylaliphatic polyisocyanates, and alicyclic polyisocyanates. Wait. In addition to these, trimethylolpropane adducts (adducts) of diisocyanates described above, biurets reacted with water, and trimers having isocyanurate rings can also be mentioned as examples. .

· Compounds containing blocked isocyanate groups (C3) The blocked isocyanate group-containing compound (C3) is not particularly limited as long as the isocyanate group in the isocyanate group-containing compound (C2) is protected (blocked) by a blocking agent. As a blocking agent, ε-caprolactam, methyl ethyl ketone (MEK) oxime, cyclohexanone oxime, pyrazole, phenol, etc. are mentioned, for example. In particular, when the hexamethylene diisocyanate trimer which has an isocyanurate ring and is blocked by MEK oxime or pyrazole is used in the conductive composition, the storage stability is naturally excellent. Excellent adhesion strength to polyimide or copper and excellent solder heat resistance.

·Aziridine compound (C4) The aziridine compound (C4) is not particularly limited as long as it is a compound having an aziridine group in the molecule.

As the aziridine compound (C4), for example, N,N'-diphenylmethane-4,4'-bis(1-aziridine carbonyl), N,N'-toluene-2,4- Bis(1-aziridine carbonyl), bisisophthaloyl-1-(2-methylaziridine), tris-1-aziridine phosphine oxide, N,N'-hexamethylene yl-1,6-bis(1-aziridine carbonyl), trimethylolpropane-tri-beta-aziridine propionate, tetramethylolmethane-tri-beta-aziridine propionate acid ester, tris-2,4,6-(1-aziridinyl)-1,3,5-triazine, trimethylolpropane tri[3-(1-aziridinyl)propionate] , trimethylolpropane tri[3-(1-aziridinyl)butyrate], trimethylolpropane tris[3-(1-(2-methyl)aziridinyl)propionate] , trimethylolpropane tri[3-(1-aziridinyl)-2-methylpropionate], 2,2'-bishydroxymethylbutanol tris[3-(1-aziridineyl) ) propionate], pentaerythritol tetrakis[3-(1-aziridinyl)propionate], diphenylmethane-4,4-bis-N,N'-ethylidene urea, 1,6-hexamethylene Methylenebis-N,N'-ethylideneurea, 2,4,6-(triphenylethylimino)-s-triazine, bis[1-(2-ethyl)aziridine] Benzene-1,3-carboxyamide, etc.

Of these, especially 2,2'-bishydroxymethylbutanol tris[3-(1-aziridinyl)propionate] is preferably used in this Conductive composition.

· Compounds containing carbodiimide groups (C5) As the carbodiimide group-containing compound (C5), for example, Carbodilite series from Nissin Textile Co., Ltd. can be used. Among them, the trade name: Carbodilite V-01, 03, 05, 07, 09 has excellent compatibility with organic solvents and is preferable.

· Benzoxazine compound (C6) As the benzoxazine compound (C6), for example, "P-a", "P-alp", "P-ala", "B-ala" described in Macromolecules, 36, 6010 (2003) can be used, "P-appe" and "Bappe" described in Macromolecules, 34, 7257 (2001), "B-a-type benzoxazine" and "F-a-type benzoxazine" manufactured by Shikoku Chemical Co., Ltd. , "B-m-type benzoxazine" and so on.

·Phenolic resin (C7) As the phenol resin (C7), for example, an addition compound of compounds such as phenol, cresols, and bisphenols and formaldehyde, or a partial condensate thereof can be used. More specifically, as the phenol resin (C-7), a phenol resin, a cresol resin, a t-butylphenol resin, a dicyclopentadiene cresol resin, a dicyclopentadiene phenol resin, and a xylene glycol can be mentioned. Base-modified phenol resin, tetraphenol resin, bisphenol A resin, resol type resin or novolak type resin of poly-p-vinylphenol resin. In addition, a naphthol-based compound, a triphenol-based compound, a phenol aralkyl resin, or the like can also be used as the phenol resin (C7). Among these, a resol type resin of a phenol resin is very excellent in heat resistance and curability, and can be suitably used for this conductive composition.

·Maleimide compound (C8) The maleimide compound (C8) is not particularly limited as long as it is a compound having at least one maleimide group in the molecule. As the maleimide compound (C8), for example, phenylmaleimide, 1-methyl-2,4-bismaleimidebenzene, N,N'-m-phenylenebis Maleimide, N,N'-p-phenylene bismaleimide, N,N'-4,4-biphenylene bismaleimide, N,N'-4,4 -(3,3-Dimethylbiphenylene)bismaleimide, N,N'-4,4-(3,3-dimethyldiphenylmethane)bismaleimide, N,N'-4,4-(3,3-Diethyldiphenylmethane)bismaleimide, N,N'-4,4-diphenylmethanebismaleimide, N ,N'-4,4-diphenylpropane bismaleimide, N,N'-4,4-diphenyl ether bismaleimide, N,N'-4,4-diphenyl Bismaleimide, 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane, 2,2-bis[3-dibutyl-3,4- (4-Maleimidophenoxy)phenyl]propane, 1,1-bis[4-(4-maleimidophenoxy)phenyl]decane, 4,4'-cycloidene Hexyl-bis[1-(4-maleimidophenoxy)phenoxy]-2-cyclohexylbenzene, 2,2-bis[4-(4-maleimidophenoxy)benzene base] hexafluoropropane, etc.

· Compounds containing β-hydroxyalkylamide groups (C9) As the β-hydroxyalkylamide group-containing compound (C9), for example, N,N,N',N'-tetrakis(hydroxyethyl)hexamethylenediamide (manufactured by EMS-Chemie, trade name: Primid XL-552) represented a variety of compounds.

Metal chelate (C10) As the metal chelate compound (C10), a chelate compound obtained by reacting a metal alkoxide with a chelating agent such as a β-diketone or a ketoester (ethyl acetate, etc.) can be mentioned. More specifically, as a metal chelate compound (C10), an aluminum chelate compound, a zirconium chelate compound, a titanium chelate compound, etc. are mentioned.

As the aluminum chelate compound, for example, bis(ethylacetate)aluminum monoacetylacetonate, aluminum diisopropoxide ethylacetate, aluminum tris(acetoacetonate), tris(acetoacetate) can be mentioned. ethyl ester) aluminum, aluminum isopropoxide, etc.

As a zirconium chelate compound, a zirconium tetraacetylacetonate, a zirconium tributoxymonoacetylacetonate, etc. are mentioned.

As a titanium chelate compound, titanium diisopropoxybis(acetylacetonate), titanium tetraacetylacetonate, titanium diisopropoxybis(ethylacetate), etc. are mentioned.

From the viewpoint of the conductivity of the conductive film, as the metal chelate compound (C10), an aluminum chelate compound is preferably used. The aluminum chelate compound has very good reactivity with binder resins containing carboxyl groups, phenolic hydroxyl groups, acid anhydrides, etc., and has a good effect on the dispersibility of carbon materials. Therefore, compared with the case of using other metal chelate compounds, the conductivity greatly improved. Among them, bis(ethylacetate)aluminum monoacetylacetonate is particularly preferred.

The usage-amount of a hardening|curing agent (C) should just be determined in consideration of the use etc. of this electroconductive composition, and will not be specifically limited. However, the content of the curing agent (C) is preferably 0.5 mass % to 20 mass % with respect to 100 mass % of the binder resin (A). When the content rate of the curing agent (C) is 0.5% or more, the crosslinking property becomes favorable, and both the conductivity and durability tend to become favorable, and when it is 20% or less, the pot life of the ink becomes more favorable. .

As the hardening agent (C), when the metal chelate compound (C10) and other hardening agents are used in combination, the mass ratio (metal chelate compound/other hardening agent) is preferably 1/99 to 60/40 The blending is more preferably 10/90 to 30/70.

<Solvent (D)> Next, the solvent (D) arbitrarily added to this conductive composition will be described. When uniformly mixing the binder resin (A), the carbon material (B), and the hardener (C) in the conductive composition, the solvent (D) can be appropriately used. As such a solvent (D), an organic solvent or water can be mentioned.

As the organic solvent, for example, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol methyl ether, and diethylene glycol methyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexyl Ketones such as ketones, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc., hydrocarbons such as hexane, heptane, octane, benzene, toluene, xylene, cumene Among aromatics such as ethyl acetate and butyl acetate, esters such as ethyl acetate and butyl acetate, etc., are appropriately selected and used according to the composition of the conductive composition. Moreover, a solvent (D) may be used individually by 1 type, and may be used in combination of 2 or more types.

Furthermore, in the case of using a printing coating method such as screen printing that requires a certain viscosity or higher for the conductive composition, the viscosity of the organic solvent at 25°C is preferably 30 mPa·s to 75,000 mPa·s. scope. When the viscosity of the organic solvent is 30 mPa·s or more, the resin content is suitable for expressing high conductivity, the viscosity suitable for coating and the good dispersibility of the conductive carbon material are easily obtained, and an excellent Coatability. When the viscosity of the organic solvent is 75000 mPa·s or less, the dispersibility of the carbon material is better. Examples of the organic solvent include terpineol, dihydroterpineol, 2,4-diethyl-1,5-pentanediol, 1,3-butanediol, and isobornylcyclohexanol. These high-viscosity solvents may be used alone or in combination of two or more. In addition, these high-viscosity solvents can also be used in combination with low-viscosity solvents with a viscosity of less than 30 mPa·s at 25°C, such as methyl ethyl ketone, toluene, and isopropanol.

＜Other ingredients＞ Next, other components will be described. To this conductive composition, as needed, an ultraviolet absorber, an ultraviolet stabilizer, a radical extender, a filler, a thixotropy imparting agent, an antiaging agent, an antioxidant, an anti- Static agent, flame retardant, thermal conductivity improver, plasticizer, anti-relaxation agent, antifouling agent, preservative, bactericide, defoamer, leveling agent, anti-blocking agent, tackifier, pigment dispersant , silane coupling agent and other additives.

<Disperser, mixer> As an apparatus used to obtain the present conductive composition from the above-mentioned components, a disperser, a mixer, or the like which are generally used in pigment dispersion and the like can be used.

Examples of the device include mixers such as a disperser, a homomixer, or a planetary mixer; "Clearmix" manufactured by M-technique; Homogenizers such as "Filmix" from PRIMIX; paint mixer (manufactured by Red Devil), ball mill, sand mill (SHINMARU ENTERPRISES) manufactured "Dyno-mill", etc.), attritor, pearl mill ("DCP mill" manufactured by Eirich, etc.), or Media type dispersing machines such as ball mills; wet jet mills (“Jenius PY” manufactured by Jenius Corporation, “Starburst (Starburst) manufactured by SUGINO MACHINE) )", "Nanomizer" manufactured by Nanomizer, etc.), "Clear SS-5" manufactured by M-technique, or "Clear SS-5" manufactured by Nara Machinery Co., Ltd. "MICROS" and other non-media dispersers; or other roller mills, etc., but not limited to these.

For example, when a media type disperser is used, it is preferable to use a method in which the stirrer and the container are made of ceramic or resin, or the method of applying tungsten carbide spraying or resin coating to the surface of the metal stirrer and the container is used. method of the disperser. Further, as the medium, glass beads, or ceramic beads such as zirconia beads or alumina beads are preferably used. For the dispersing device, only one kind of device may be used, or a plurality of kinds of devices may be used in combination.

＜Conductive film＞ The conductive film of the present invention (hereinafter sometimes referred to as the present conductive film) has a conductive film formed of the present conductive composition on a (sheet-like) substrate, in other words, has a conductive film formed by forming the present conductive composition into a film .

(sheet substrate) The shape of the sheet-like base material used for forming the conductive film is not particularly limited, but an insulating resin film is preferred, and a sheet-like base material suitable for various applications can be appropriately selected.

Examples of the material of the sheet-like base material include PET (polyethylene terephthalate), PEN (polyethylene naphthalate), polyimide, polyvinyl chloride, polyamide, and nylon. , OPP (stretched polypropylene), CPP (unstretched polypropylene), etc. However, it is not limited to these.

In addition, as the shape of the sheet-like base material, a film on a flat plate is usually used, but a surface-roughened one, a primer-treated one, a perforated one, and a mesh-like one can also be used.

There is no restriction|limiting in particular as a method of apply|coating an electroconductive composition to a sheet-like base material, A well-known method can be used suitably.

Specific examples of the coating method include die coating, dip coating, roll coating, blade coating, blade coating, spray coating, gravure coating, screen printing, and electrostatic coating. As a drying method after coating, for example, standing drying, a blow dryer, a warm air dryer, an infrared heater, a far infrared heater, etc. can be used, but it is not particularly limited to these.

In addition, after coating, a calendering process may be performed by a lithographic press, a calender roll, or the like, and the calendering process may be performed while heating in order to soften the conductive film and facilitate pressing. The thickness of the conductive film is usually 0.1 μm or more and 1 mm or less, preferably 1 μm or more and 200 μm or less.

(Volume Resistivity of Conductive Film) The volume resistivity of the conductive film is preferably less than 1.0×10 ⁻² Ω·cm. By making the volume resistivity less than 1.0×10 ^-2 Ω·cm, it can be suitably used as an electrode of a battery, a current collector, or a wiring of a battery or an electronic device.

＜Non-contact media＞ The non-contact type medium (non-contact type information recording medium) of the present invention (hereinafter sometimes referred to as the present non-contact type medium) is a non-contact type medium on which a conductive circuit and an IC chip are stacked, and the conductive circuit uses the above-mentioned conductive composition matter formation.

(conductive circuit) The conductive circuit used in this non-contact medium is a circuit (printed matter) obtained by printing the conductive composition on one side or both sides of a substrate such as paper, plastic, etc. by a normal printing method according to the application.

Examples of the printing method include screen printing, rotary screen printing, flexographic printing, gravure printing, gravure offset printing, offset printing, letterpress printing, and inkjet printing.

As the paper substrate, in addition to coated paper and uncoated paper, various processed papers such as synthetic paper, polyethylene-coated paper, impregnated paper, water-resistant processed paper, insulating processed paper, and telescopic processed paper can be used. Among these, from the viewpoint of obtaining a stable resistance value as a non-contact medium, as the paper base material, coated paper and processed paper are preferably used. In the case of coated paper, the higher the smoothness, the better.

In addition, as the plastic base material, polyester, polyethylene, polypropylene, cellophane, vinyl chloride, vinylidene chloride, polystyrene, vinyl alcohol, ethylene-vinyl alcohol, nylon, polyimide, polycarbonate can be used Ester and the like are generally used as a base material made of plastic for labels and cards.

By using this conductive composition (conductive ink), a conductive circuit can be formed by a normal printing method, so that a design that effectively utilizes existing equipment can be performed. That is, after performing normal printing for improving the designability of a non-contact medium such as a pattern, it is possible to directly print and form a conductive circuit. Therefore, the circuit formation using this conductive composition is very excellent in productivity, initial investment cost, and running cost compared with the conventional circuit formation method by etching method or transfer method.

In the process before printing and forming the conductive circuit, in order to improve the adhesion to the substrate, a tackifier or various varnishes can be applied to the substrate. In addition, after the conductive circuit is printed, an overprint varnish, various coating agents, etc. may be applied for the purpose of protecting the circuit. As the various varnishes and coating agents, any of the usual thermal drying type and active energy ray curing type can be used.

In addition, it is also possible to apply an adhesive on a conductive circuit, to directly bond a paper substrate or a plastic film with a pattern printed thereon, or to laminate by melt extrusion of plastic, etc., to obtain a non-contact medium. Of course, a substrate pre-coated with an adhesive or adhesive can also be used.

The conductive circuit manufactured by the above method is stacked on the base material together with the IC module to obtain a non-contact medium. The base material holds the conductive circuit and the IC chip, and the same paper, film, etc. as the base material of the conductive circuit can be used. In addition, the IC chip performs storage, accumulation, and calculation of data. Contactless media is used as RFID (RadioFrequencyIdentification (Radio Frequency Identification)), contactless IC card, contactless IC tag, data carrier (recording medium), wireless card, and the reader or reader, using radio waves. The identification of an individual or the medium through which information is sent and received. As the usage, there are ID management and history management of a toll collection system and the like, and position management of a road usage status management system, a cargo and baggage tracking-management system, and the like.

(Volume Resistivity of Conductive Circuit) The volume resistivity of the conductive circuit of the present non-contact medium is preferably less than 5.0×10 ⁻² Ω·cm. By making the volume resistivity less than 5.0×10 ^-2 Ω·cm, it can be suitably used as a non-contact type medium. Furthermore, as the volume resistivity is lower, even a thin film exhibits high electrical conductivity, so in consideration of material cost, productivity, and performance as a non-contact medium, the lower the volume resistivity is, the better. [Example]

Hereinafter, the present invention will be further specifically described with reference to the examples, but the following examples do not limit the scope of the rights of the present invention in any way. In addition, in Examples and Comparative Examples, unless otherwise specified, "part" means "mass part", "Mw" means "weight average molecular weight", and "Tg" means "glass transition temperature".

<Synthesis of Binder Resin A-1> The following materials were charged into a reaction vessel including a stirrer, a thermometer, a reflux cooler, a dropping device, and a nitrogen gas introduction tube, and the reaction was carried out at 90° C. for 3 hours under a nitrogen atmosphere. ・Polyester polyol obtained from terephthalic acid, adipic acid and 3-methyl-1,5-pentanediol ((stock) Kuraray), trade name: "Kuraray Polyester Alcohol P-2011", Mn=2011) 455.5 copies 16.5 parts of dimethylolbutyric acid; 105.2 parts of isophorone diisocyanate; 140 parts of toluene. Next, 360 parts of toluene were added to this reaction liquid to obtain a urethane prepolymer solution having an isocyanate group.

Next, 19.9 parts of isophoronediamine, 0.63 parts of di-n-butylamine, 294.5 parts of 2-propanol, and 335.5 parts of toluene were separately mixed. To the obtained mixture, 969.5 parts of the urethane prepolymer solution prepared above was added, and after reacting at 50°C for 3 hours, it was further reacted at 70°C for 2 hours. Next, the obtained reaction liquid was diluted with 126 parts of toluene and 54 parts of 2-propanols, and the solution of binder resin A-1 (urethane resin) was obtained. Furthermore, the Mw of the obtained binder resin A-1 was 61,000, the acid value was 10 mgKOH/g, and the polyamine compound and the free isocyanate groups at both ends of the urethane prepolymer were The total equivalent weight of the amine groups in the reaction terminator was 0.98.

<Synthesis of Binder Resin A-2> The following materials were put into a four-necked flask including a stirrer, reflux cooling tube, nitrogen introduction tube, introduction tube, and thermometer, and stirred until the temperature at which heat was generated became constant. 156.2 g of Pripol 1009 as a polyacid compound; 5.5 g of 5-hydroxyisophthalic acid; 146.4 g of Priamine 1074 as a polyamine compound; 100 g of ion-exchanged water. Next, after the temperature of the reaction liquid was stabilized, the temperature was raised to 110°C, and after confirming that water flowed out, the temperature was raised to 120°C after 30 minutes, and thereafter the dehydration reaction was continued while raising the temperature by 10°C every 30 minutes. Then, after the temperature of the reaction liquid reached 230° C., the reaction was continued at this temperature for 3 hours, and the temperature was lowered by maintaining the temperature under a vacuum of about 2 kPa for 1 hour. Finally, antioxidant was added to obtain binder resin A-2 (polyamide resin). Furthermore, the weight average molecular weight of the obtained binder resin A-2 was 24000, the acid value was 13.2 mgKOH/g, the hydroxyl value was 5.5 mgKOH/g, and the glass transition temperature was -32°C.

In addition, the evaluation of resin was performed as follows.

<Measurement method of weight average molecular weight (Mw)> For the measurement of Mw, Gel Permeation Chromatography (GPC) manufactured by Tosoh Co., Ltd., trade name: "HPC-8020" was used. GPC is a liquid chromatograph that separates and quantifies substances dissolved in a solvent (THF: tetrahydrofuran) based on the difference in molecular size. For the measurement, two "LF-604" (manufactured by Showa Denko Co., Ltd.: GPC column for rapid analysis: 6 mmID x 150 mm size) were connected in series and used at a flow rate of 0.6 ml/min and a column temperature of 40°C. The weight average molecular weight (Mw) was determined in terms of polystyrene.

<Measurement method of acid value> (Determination of acid value) About 1 g of the sample (resin) was precisely weighed in a conical flask with a ground stopper, and 100 ml of a toluene/ethanol (volume ratio: toluene/ethanol=2/1) mixed solution was added and dissolved. Phenolphthalein test solution was added as an indicator and kept for 30 seconds. Then, it titrated with a 0.1 N alcoholic potassium hydroxide solution until the solution turned pale red.

(Calculation of acid value) The acid value was determined by the following formula (1) (unit: mgKOH/g). Formula 1) Acid value (mgKOH/g)=(5.611×a×F)/S where, set to: S: Sample collection amount (g) a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml) F: Titer of 0.1N alcoholic potassium hydroxide solution.

<Measurement method of hydroxyl value> The hydroxyl value represents the amount of hydroxyl groups contained in 1 g of the hydroxyl group-containing resin by the amount (mg) of potassium hydroxide required to neutralize the acetic acid that is bonded to the hydroxyl group when hydroxyacetation is performed. The hydroxyl value can be measured according to Japanese industrial standard (JIS) K0070. When calculating the hydroxyl value, the calculation is performed in consideration of the acid value as shown in the following formula (2).

(Determination of hydroxyl value) About 1 g of the sample (resin) was precisely weighed in a conical flask with a ground stopper, and 100 ml of a toluene/ethanol (volume ratio: toluene/ethanol=2/1) mixed solution was added and dissolved. Furthermore, 5 ml of an acetylating agent (25 g of acetic anhydride was dissolved in pyridine to obtain a solution with a volume of 100 ml) was accurately added, and the mixture was stirred for about 1 hour. Phenolphthalein test solution was added as an indicator for 30 seconds. Then, it titrated with a 0.1 N alcoholic potassium hydroxide solution until the solution turned pale red.

(Calculation of hydroxyl value) The hydroxyl value can be obtained by the following formula (2) (unit: mgKOH/g). Formula (2) Hydroxyl value (mgKOH/g)=[{(b-a)×F×28.05}/S]+D where, set to: S: Sample collection amount (g) a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml) b: Consumption of 0.1N alcoholic potassium hydroxide solution in blank experiment (ml) F: titer of 0.1N alcoholic potassium hydroxide solution D: acid value (mgKOH/g)

<Measuring method of glass transition temperature> The binder resin from which the solvent was dried and removed was measured by using "DSC-1" manufactured by Mettler Toledo Co., Ltd. to raise the temperature to -80°C to 150°C at 2°C/min.

＜Adjustment of Binder Resin＞ The binder resins used in Examples and Comparative Examples to be described later were adjusted to have a solid content ratio of 20% using the solvent shown below. In addition, the composition ratio of a mixed solvent is described by mass ratio. ·Solution of Binder Resin A-1-1: The solution of Binder Resin A-1 was diluted with toluene/methyl ethyl ketone/2-propanol (1/1/1) to obtain a solution of Binder Resin A-1-1. ·Solution of Binder Resin A-2-1: Binder Resin A-2 was diluted with toluene/2-propanol (2/1) to obtain a solution of Binder Resin A-2-1. ·Solution of Binder Resin A-3-1: Binder resin A-3: Vylon UR3500 (trade name: manufactured by Toyobo Co., Ltd., polyurethane resin) was diluted with toluene/methyl ethyl ketone (1/1) to obtain a binder resin A-3-1 solution. ·Solution of Binder Resin A-4-1: Binder Resin A-4: Vylon GK130 (trade name: manufactured by Toyobo Co., Ltd., polyester resin) was diluted with toluene/methyl ethyl ketone (1/1) to obtain Binder Resin A-4- 1 solution.

<Adjustment of hardener> The curing agent used in the examples and comparative examples described later was adjusted to a solution having a solid content of 50% using the solvent shown below. In addition, the composition ratio of a mixed solvent is described by mass ratio. About the hardening|curing agent C-3 mentioned later, the commercial item whose solid content density|concentration is 50 mass % was used as it is. ·Solution of hardener C-1-1: Hardener C-1 (aziridine compound Chemitite PZ-33 (trade name, manufactured by Nippon Shokubai Co., Ltd.)) was diluted with toluene to obtain a solution of hardener C-1-1. ·Solution of hardener C-2-1: Hardener C-2 (epoxy compound TETRAD-X (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.)) was diluted with toluene to obtain a solution of hardener C-2-1. Solution of Hardener C-4-1: Hardener C-4 (Isocyanate Compound Takenate D-110N: manufactured by Mitsui Chemicals Co., Ltd.) was diluted with ethyl acetate to obtain Hardener C-4- 1 solution. ·Solution of Hardener C-5-1: Dilute hardener C-5 with toluene {aluminum chelate monoacetylacetonate bis(ethyl acetate) aluminum = Alumichelate D (trade name), Kawaken Fine Chemicals Co., Ltd. product} to obtain a solution of hardener C-5-1. ·Solution of hardener C-6-1: Hardener C-6 (titanium chelate tetraacetylacetonate titanium = ORGATIX TC-401 (trade name), manufactured by Matsumoto Fine Chemical Co., Ltd.) was diluted with toluene to obtain hardening A solution of agent C-6-1. ·Solution of Hardener C-7-1: Dilute hardener C-7 with toluene {titanium chelate diisopropoxybis(acetylpyruvic acid) titanium = ORGATIX TC-100 (trade name), Matsumoto Fine Chemical Co., Ltd. Co., Ltd.} to obtain a solution of hardener C-7-1. ·Solution of hardener C-8-1: Hardener C-8 (zirconium chelate tetraacetypyruvate zirconium = ORGATIX ZC-150 (trade name), manufactured by Matsumoto Fine Chemical Co., Ltd.) was diluted with toluene to obtain hardening A solution of agent C-8-1.

<Conductive composition, conductive film, and conductive circuit> [Example 1] (Preparation of Conductive Composition) The following materials were mixed in a mixer and further put into a sand mill for dispersion. ·Binder resin: 120 parts of A-1-1 solution (24 parts of resin solid content); Conductive carbon materials: B-1-1: 70 parts of flake graphite CPB (manufactured by Japan Graphite Company); Carbon materials other than graphite: B-2-1: 6 copies of Ketjen Black EC-300J (trade name, manufactured by LION SPECIALTY CHEMICALS); ·Solvent: 204 parts of toluene/methyl ethyl ketone/2-propanol (1/1/1). Then, 0.4 part (0.2 part of hardener solid content) was added as the solution of C-1-1 of a hardener, and the electroconductive composition (1) was obtained.

(Fabrication of conductive film) The obtained conductive composition (1) was coated on a PEN film having a thickness of 125 μm to be a sheet-like base material using a doctor blade, then heated and dried, and the thickness of the conductive film was adjusted to 60 μm. Finally, the coating film was hardened in an environment of 150°C. Furthermore, the conductive carbon material contained in the conductive film was 76% by mass. The obtained conductive film was evaluated by the following method. The evaluation results are shown in Table 6.

(Volume Resistivity of Conductive Film) The volume resistivity of the conductive film was measured by the four-terminal method (JIS-K7194) using Loresta GP (manufactured by Mitsubishi Chemical Analytical Technologies), and was based on the following evaluation criteria. determination. Furthermore, the lower the volume resistivity of the conductive film, the higher the conductivity of the conductive film, and the better the result. The evaluation results are shown in Table 6. Evaluation Criteria 8: [Volume resistivity is less than 3.0×10 ^-3 Ω·cm] 7: [Volume resistivity is 3.0×10 ^-3 Ω·cm or more and less than 3.5×10 ^-3 Ω·cm] 6: [Volume resistivity The resistivity is 3.5×10 ^-3 Ω·cm or more and less than 4.0×10 ^-3 Ω·cm] 5: [The volume resistivity is 4.0×10 ^-3 Ω·cm or more and less than 5.0×10 ^-3 Ω·cm] 4: [Volume resistivity is 5.0×10 ⁻³ Ω·cm or more and less than 1.0×10 ⁻² Ω·cm] 3: [Volume resistivity is 1.0×10 ⁻² Ω·cm or more and less than 5.0×10 ⁻² Ω·cm] 2: [The volume resistivity is 5.0×10 ⁻² Ω·cm or more and less than 1.0×10 ⁻¹ Ω·cm] 1: [The volume resistivity is 1.0×10 ⁻¹ Ω·cm or more]

(Adhesion of Conductive Film) A knife was used to form 6 incisions with a depth of 2 mm vertically and horizontally from the surface of the conductive film to the substrate on the conductive film prepared above, thereby forming a checkered incision. The pressure-sensitive adhesive tape was attached to the incision and immediately peeled off, and the degree of detachment of the conductive film was determined by visual inspection and based on the following evaluation criteria. The evaluation results are shown in Table 6. ·evaluation standard 4: [No Peeling] 3: [Slight peeling] 2: [Peel about halfway] 1: [mostly stripped]

(making of conductive circuits) The conductive composition (1) was coated on a PEN (polyethylene naphthalate) film with a thickness of 125 μm using a doctor blade, followed by heating and drying. Adjust the dry film thickness to 5 μm. Finally, the coating film was hardened at a temperature of 150° C. to obtain a conductive circuit (10 cm×10 cm coating film).

(Volume Resistivity of Conductive Circuit) The volume resistivity of the conductive circuit was measured by the four-terminal method (JIS-K7194) using Loresta GP (manufactured by Mitsubishi Chemical Analytical Technologies), and was based on the following evaluation criteria determination. Again, the lower the volume resistivity of the conductive circuit, the higher the conductivity of the conductive circuit, and the better the results. The evaluation results are shown in Table 6. Evaluation Criteria 8: [Volume resistivity is less than 3.0×10 ^-3 Ω·cm] 7: [Volume resistivity is 3.0×10 ^-3 Ω·cm or more and less than 3.5×10 ^-3 Ω·cm] 6: [Volume resistivity The resistivity is 3.5×10 ^-3 Ω·cm or more and less than 4.0×10 ^-3 Ω·cm] 5: [The volume resistivity is 4.0×10 ^-3 Ω·cm or more and less than 5.0×10 ^-3 Ω·cm] 4: [Volume resistivity is 5.0×10 ⁻³ Ω·cm or more and less than 1.0×10 ⁻² Ω·cm] 3: [Volume resistivity is 1.0×10 ⁻² Ω·cm or more and less than 5.0×10 ⁻² Ω·cm] 2: [The volume resistivity is 5.0×10 ⁻² Ω·cm or more and less than 1.0×10 ⁻¹ Ω·cm] 1: [The volume resistivity is 1.0×10 ⁻¹ Ω·cm or more]

(Conductive circuit adhesion) A knife was used to form 6 incisions with a depth of 2 mm from the surface of the conductive circuit to the base material, respectively, on the conductive circuit fabricated above, so as to form chessboard incisions. The pressure-sensitive adhesive tape was immediately peeled off on the cut, and the degree of detachment of the conductive circuit was determined by visual inspection and based on the following evaluation criteria. The evaluation results are shown in Table 6. ·Evaluation criteria 4: [No Peeling] 3: [Slight peeling] 2: [Peel about halfway] 1: [mostly stripped]

<Applicability evaluation> Using the conductive film and conductive circuit produced above, the applicability of the conductive composition (1) was evaluated as follows. That is, the produced conductive film and conductive circuit were visually observed, respectively, for coating unevenness (unevenness: evaluated by the shade of the coated surface) and pinholes (evaluated by the presence or absence of defects in the uncoated conductive film/conductive circuit), Judgment was made based on the following criteria. The evaluation results are shown in Table 6.

(uneven) 3: The shading of the conductive film/conductive circuit was not confirmed. 2: There are 1-3 shades of conductive film/conductive circuit, which are extremely small areas. 1: The shading of the conductive film/conductive circuit can be confirmed at 4 or more places, or the length of one or more shading stripes is 5 mm or more.

(pinhole) ○: Not a single pinhole was recognized. △: There are 1 to 3 pinholes, but they are extremely small. ×: Four or more pinholes were confirmed, or one or more pinholes with a diameter of 1 mm or more were confirmed.

<Durability Evaluation> The durability of the conductive film and the conductive circuit produced using the conductive composition (1) was evaluated based on the following criteria based on the rate of increase of the volume resistivity after the moist heat resistance test. The evaluation results are shown in Table 6. The method is shown below. First, the produced coating film (conductive film/conductive circuit) was put into a small environmental tester (Espec Co., Ltd.: model SH-661), and left at a temperature of 60°C and a relative humidity of 90% for 5000 hours Then, after returning to the room temperature environment, the measurement of the volume resistivity was performed using the above-mentioned method. ·evaluation standard 3: The increase rate of volume resistivity is less than 10% 2: The increase rate of volume resistivity is 10% or more and less than 20% 1: The increase rate of the volume resistivity is 20% or more.

(Non-contact media properties of conductive circuits) A flexo plate with a conductor pattern (DSF version: DuPont) was installed in the second unit of a CI type 6-color flexo printing machine SOLOFLEX (manufactured by Windmoeller & Hoelscher KG). manufacture). Then, the conductive composition (1) was sequentially printed on the PEN film (125 μm) at a speed of 70 m/min. Furthermore, the film thickness of the printed matter was measured with a digital micro-film thickness meter (manufactured by Nikon Corporation, trade name: MH15M), the printing conditions were appropriately adjusted so that the average film thickness was 5 μm to 10 μm, and after heating and drying, the obtained film was obtained. Conductive circuit for evaluation of non-contact media properties. An IC chip manufactured by Impinj was mounted on the obtained conductive circuit, and a non-contact medium was produced. Next, use Impinj's "fixed UHF band RFID reader/writer Speedway Revolution R420 (trade name)" to check whether communication is possible. The evaluation results are shown in Table 6. Y: able to read N: cannot read

[Example 2 to Example 81, Comparative Example 1 to Comparative Example 20] According to the composition ratios shown in Tables 1 to 5, by the same method as the conductive composition (1), the conductive compositions (2) to (81) and the conductive composition (a) were obtained - Conductive composition (t). The obtained conductive composition (2) to conductive composition (81) and conductive composition (a) to conductive composition (t) were used for evaluation in the same manner as in Example 1. The evaluation results are shown in Tables 6 to 10. Since the type of the binder resin of Example 14 is different from that of Example 1, the dilution solvent at the time of preparing the conductive composition was set to toluene/2-propanol (2/1). The types of binder resins in Examples 15 to 17 were different from those in Example 1, and therefore, the dilution solvent at the time of preparing the conductive composition was set to toluene/methyl ethyl ketone (1/1). Example 36, Example 37, Example 38, Example 40, Example 76, Example 77, Example 78, and Example 80 used two hardeners in combination, and added them at the same timing. In addition, C-1/C-2 (=0.85/16.15) in Example 36 means C-1 which is 0.85% by solid content and 16.15% of C with respect to 100 parts by mass of resin solid content. -2 The same applies to Example 37, Example 38, Example 40, Example 76, Example 77, Example 78, and Example 80.

[Table 1] Table 1 conductive composition Binder Resin (A) Graphite (B-1) Carbon materials other than graphite (B-2) Ratio (%) of carbon material (B) in solid content of conductive composition Hardener (C) type Amount of resin solid content added (parts by mass) type Amount added (parts by mass) Ratio in carbon material (%) type Amount added (parts by mass) Ratio in carbon material (%) type Amount of hardener solid content added (parts by mass) Additive solid content ratio (%) relative to 100 parts by mass of resin solid content Example 1 (1) A-1 twenty four B-1-1 70.00 92.1 B-2-1 6.00 7.89 75.82 C-1 0.24 1.0 Example 2 (2) A-1 twenty four B-1-1 65.00 85.5 B-2-1 11.00 14.47 75.82 C-1 0.24 1.0 Example 3 (3) A-1 twenty four B-1-1 75.00 98.7 B-2-1 1.00 1.32 75.82 C-1 0.24 1.0 Example 4 (4) A-1 33 B-1-1 64.00 95.5 B-2-1 3.00 4.48 66.78 C-1 0.33 1.0 Example 5 (5) A-1 18 B-1-1 79.00 96.3 B-2-1 3.00 3.66 81.85 C-1 0.18 1.0 Example 6 (6) A-1 33 B-1-1 57.00 85.1 B-2-1 10.00 14.93 66.78 C-1 0.33 1.0 Example 7 (7) A-1 33 B-1-1 66.00 98.5 B-2-1 1.00 1.49 66.78 C-1 0.33 1.0 Example 8 (8) A-1 18 B-1-1 71.00 86.6 B-2-1 11.00 13.41 81.85 C-1 0.18 1.0 Example 9 (9) A-1 18 B-1-1 81.00 98.8 B-2-1 1.00 1.22 81.85 C-1 0.18 1.0 Example 10 (10) A-1 29 B-1-1 56.00 80.0 B-2-1 14.00 20.00 70.50 C-1 0.29 1.0 Example 11 (11) A-1 29 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.50 C-1 0.29 1.0 Example 12 (12) A-1 29 B-1-1 59.50 85.0 B-2-1 10.50 15.00 70.50 C-1 0.29 1.0 Example 13 (13) A-1 29 B-1-1 61.25 87.5 B-2-1 8.75 12.50 70.50 C-1 0.29 1.0 Example 14 (14) A-2 29 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.50 C-1 0.29 1.0 Example 15 (15) A-3 29 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.50 C-1 0.29 1.0 Example 16 (16) A-3 29 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.50 C-4 0.29 1.0 Example 17 (17) A-4 29 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.50 C-4 0.29 1.0 Example 18 (18) A-1 29 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.60 C-1 0.15 0.5 Example 19 (19) A-1 29 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.30 C-1 0.58 2.0 Example 20 (20) A-1 28 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.42 C-1 1.40 5.0 Example 21 (twenty one) A-1 27 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.21 C-1 2.70 10.0 Example 22 (twenty two) A-1 twenty four B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.85 C-1 4.80 20.0 Example 23 (twenty three) A-1 27 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.21 C-2 2.70 10.0 Example 24 (twenty four) A-1 27 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.21 C-3 2.70 10.0 Example 25 (25) A-1 27 B-1-2 57.75 82.5 B-2-1 12.25 17.50 70.21 C-3 2.70 10.0

[Table 2] Table 2 conductive composition Binder Resin (A) Graphite (B-1) Carbon materials other than graphite (B-2) Ratio (%) of carbon material (B) in solid content of conductive composition Hardener (C) type Amount of resin solid content added (parts by mass) type Addition amount (parts by mass) Ratio in carbon material (%) type Addition amount (parts by mass) Ratio in carbon material (%) type Addition of hardener solid content (parts by mass) Additive solid content ratio (%) relative to 100 parts by mass of resin solid content Example 26 (26) A-1 27 B-1-3 57.75 82.5 B-2-1 12.25 17.50 70.21 C-3 2.70 10.0 Example 27 (27) A-1 27 B-1-4 57.75 82.5 B-2-1 12.25 17.50 70.21 C-3 2.70 10.0 Example 28 (28) A-1 27 B-1-5 57.75 82.5 B-2-1 12.25 17.50 70.21 C-3 2.70 10.0 Example 29 (29) A-1 32 B-1-1 64.00 95.5 B-2-1 3.00 4.48 65.56 C-3 3.20 10.0 Example 30 (30) A-1 32 B-1-1 64.00 95.5 B-2-2 3.00 4.48 65.56 C-3 3.20 10.0 Example 31 (31) A-1 32 B-1-1 64.00 95.5 B-2-3 3.00 4.48 65.56 C-3 3.20 10.0 Example 32 (32) A-1 32 B-1-1 64.00 95.5 B-2-4 3.00 4.48 65.56 C-3 3.20 10.0 Example 33 (33) A-1 32 B-1-1 64.00 95.5 B-2-5 3.00 4.48 65.56 C-3 3.20 10.0 Example 34 (34) A-1 29 B-1-1 53.20 76.0 B-2-1 16.80 24.00 70.50 C-1 0.29 1.0 Example 35 (35) A-1 29 B-1-1 49.70 71.0 B-2-1 20.30 29.00 70.50 C-1 0.29 1.0 Example 36 (36) A-1 twenty four B-1-1 70.00 92.1 B-2-1 6.00 7.89 73.02 C-1/C-2(=0.85/16.15) 4.08 17.0 Example 37 (37) A-1 twenty four B-1-1 70.00 92.1 B-2-1 6.00 7.89 73.02 C-1/C-2(=2/15) 4.08 17.0 Example 38 (38) A-1 twenty four B-1-1 70.00 92.1 B-2-1 6.00 7.89 73.02 C-1/C-2(=8.5/8.5) 4.08 17.0 Example 39 (39) A-1 twenty four B-1-1 70.00 92.1 B-2-1 6.00 7.89 73.02 C-1 4.08 17.0 Example 40 (40) A-1 25 B-1-1 56.00 80.0 B-2-1 14.00 20.00 70.53 C-1/C-2(=2/15) 4.25 17.0 Example 41 (41) A-1 25 B-1-1 56.00 80.0 B-2-1 14.00 20.00 70.53 C-1 4.25 17.0 Example 42 (42) A-1 twenty four B-1-1 70.00 92.1 B-2-1 6.00 7.89 75.82 C-5 0.24 1.0 Example 43 (43) A-1 twenty four B-1-1 65.00 85.5 B-2-1 11.00 14.47 75.82 C-5 0.24 1.0 Example 44 (44) A-1 twenty four B-1-1 75.00 98.7 B-2-1 1.00 1.32 75.82 C-5 0.24 1.0 Example 45 (45) A-1 33 B-1-1 64.00 95.5 B-2-1 3.00 4.48 66.78 C-5 0.33 1.0 Example 46 (46) A-1 18 B-1-1 79.00 96.3 B-2-1 3.00 3.66 81.85 C-5 0.18 1.0 Example 47 (47) A-1 33 B-1-1 57.00 85.1 B-2-1 10.00 14.93 66.78 C-5 0.33 1.0 Example 48 (48) A-1 33 B-1-1 66.00 98.5 B-2-1 1.00 1.49 66.78 C-5 0.33 1.0 Example 49 (49) A-1 18 B-1-1 71.00 86.6 B-2-1 11.00 13.41 81.85 C-5 0.18 1.0 Example 50 (50) A-1 18 B-1-1 81.00 98.8 B-2-1 1.00 1.22 81.85 C-5 0.18 1.0

[table 3] table 3 conductive composition Binder Resin (A) Graphite (B-1) Carbon materials other than graphite (B-2) Ratio (%) of carbon material (B) in solid content of conductive composition Hardener (C) type Amount of resin solid content added (parts by mass) type Amount added (parts by mass) Ratio in carbon material (%) type Amount added (parts by mass) Ratio in carbon material (%) type Amount of hardener solid content added (parts by mass) Additive solid content ratio (%) relative to 100 parts by mass of resin solid content Example 51 (51) A-1 29 B-1-1 56.00 80.0 B-2-1 14.00 20.00 70.50 C-5 0.29 1.0 Example 52 (52) A-1 29 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.50 C-5 0.3 1.0 Example 53 (53) A-1 29 B-1-1 59.50 85.0 B-2-1 10.50 15.00 70.50 C-5 0.3 1.0 Example 54 (54) A-1 29 B-1-1 61.25 87.5 B-2-1 8.75 12.50 70.50 C-5 0.3 1.0 Example 55 (55) A-2 29 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.50 C-5 0.3 1.0 Example 56 (56) A-3 29 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.50 C-5 0.3 1.0 Example 57 (57) A-3 29 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.50 C-8 0.3 1.0 Example 58 (58) A-4 29 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.50 C-8 0.3 1.0 Example 59 (59) A-1 29 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.60 C-5 0.1 0.5 Example 60 (60) A-1 29 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.30 C-5 0.6 2.0 Example 61 (61) A-1 28 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.42 C-5 1.4 5.0 Example 62 (62) A-1 27 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.21 C-5 2.7 10.0 Example 63 (63) A-1 twenty four B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.85 C-5 4.8 20.0 Example 64 (64) A-1 27 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.21 C-6 2.7 10.0 Example 65 (65) A-1 27 B-1-1 57.75 82.5 B-2-1 12.25 17.50 70.21 C-7 2.7 10.0 Example 66 (66) A-1 27 B-1-2 57.75 82.5 B-2-1 12.25 17.50 70.21 C-7 2.7 10.0 Example 67 (67) A-1 27 B-1-3 57.75 82.5 B-2-1 12.25 17.50 70.21 C-7 2.7 10.0 Example 68 (68) A-1 27 B-1-4 57.75 82.5 B-2-1 12.25 17.50 70.21 C-7 2.7 10.0 Example 69 (69) A-1 27 B-1-5 57.75 82.5 B-2-1 12.25 17.50 70.21 C-7 2.7 10.0 Example 70 (70) A-1 32 B-1-1 64.00 95.5 B-2-1 3.00 4.48 65.56 C-7 3.2 10.0 Example 71 (71) A-1 32 B-1-1 64.00 95.5 B-2-2 3.00 4.48 65.56 C-7 3.2 10.0 Example 72 (72) A-1 32 B-1-1 64.00 95.5 B-2-3 3.00 4.48 65.56 C-7 3.2 10.0 Example 73 (73) A-1 32 B-1-1 64.00 95.5 B-2-4 3.00 4.48 65.56 C-7 3.2 10.0 Example 74 (74) A-1 32 B-1-1 64.00 95.5 B-2-5 3.00 4.48 65.56 C-7 3.2 10.0 Example 75 (75) A-1 29 B-1-1 53.20 76.0 B-2-1 16.80 24.00 70.50 C-5 0.3 1.0

[Table 4] Table 4 conductive composition Binder Resin (A) Graphite (B-1) Carbon materials other than graphite (B-2) Ratio (%) of carbon material (B) in solid content of conductive composition Hardener (C) type Amount of resin solid content added (parts by mass) type Amount added (parts by mass) Ratio in carbon material (%) type Amount added (parts by mass) Ratio in carbon material (%) type Amount of hardener solid content added (parts by mass) Additive solid content ratio (%) relative to 100 parts by mass of resin solid content Example 76 (76) A-1 twenty four B-1-1 70.00 92.1 B-2-1 6 7.89 73.02 C-5/C-2(=0.85/16.15) 4.1 17.0 Example 77 (77) A-1 twenty four B-1-1 70.00 92.1 B-2-1 6 7.89 73.02 C-5/C-2(=2/15) 4.1 17.0 Example 78 (78) A-1 twenty four B-1-1 70.00 92.1 B-2-1 6 7.89 73.02 C-5/C-2(=8.5/8.5) 4.1 17.0 Example 79 (79) A-1 twenty four B-1-1 70.00 92.1 B-2-1 6 7.89 73.02 C-5 4.1 17.0 Example 80 (80) A-1 25 B-1-1 56.00 80.0 B-2-1 14 20.00 70.53 C-5/C-2(=2/15) 4.3 17.0 Example 81 (81) A-1 25 B-1-1 56.00 80.0 B-2-1 14 20.00 70.53 C-5 4.3 17.0

[table 5] table 5 conductive composition Binder Resin (A) Graphite (B-1) Carbon materials other than graphite (B-2) Ratio (%) of carbon material (B) in solid content of conductive composition Hardener (C) type Amount of resin solid content added (parts by mass) type Amount added (parts by mass) Ratio in carbon material (%) type Amount added (parts by mass) Ratio in carbon material (%) type Amount of hardener solid content added (parts by mass) Additive solid content ratio (%) relative to 100 parts by mass of resin solid content Comparative Example 1 (a) A-1 12 B-1-1 75.00 85.2 B-2-1 13.00 14.77 88.00 - 0.00 0.0 Comparative Example 2 (b) A-1 12 B-1-1 86.00 97.7 B-2-1 2.00 2.27 88.00 - 0.00 0.0 Comparative Example 3 (c) A-1 42 B-1-1 50.00 86.2 B-2-1 8.00 13.79 58.00 - 0.00 0.0 Comparative Example 4 (d) A-1 42 B-1-1 57.00 98.3 B-2-1 1.00 1.72 58.00 - 0.00 0.0 Comparative Example 5 (e) A-1 33 B-1-1 66.50 99.3 B-2-1 0.50 0.75 67.00 - 0.00 0.0 Comparative Example 6 (f) A-1 33 B-1-1 49.60 74.0 B-2-1 17.40 25.97 67.00 - 0.00 0.0 Comparative Example 7 (g) A-1 18 B-1-1 81.50 99.4 B-2-1 0.50 0.61 82.00 - 0.00 0.0 Comparative Example 8 (h) A-1 18 B-1-1 59.00 72.0 B-2-1 23.00 28.05 82.00 - 0.00 0.0 Comparative Example 9 (i) A-1 12 B-1-1 65.00 73.9 B-2-1 23.00 26.14 88.00 - 0.00 0.0 Comparative Example 10 (j) A-1 12 B-1-1 87.50 99.4 B-2-1 0.50 0.57 88.00 - 0.00 0.0 Comparative Example 11 (k) A-1 42 B-1-1 42.00 72.4 B-2-1 16.00 27.59 58.00 - 0.00 0.0 Comparative Example 12 (l) A-1 42 B-1-1 57.70 99.5 B-2-1 0.30 0.52 58.00 - 0.00 0.0 Comparative Example 13 (m) A-1 33 B-1-1 66.00 98.5 B-2-1 1.00 1.49 67.00 - 0.00 0.0 Comparative Example 14 (n) A-1 33 B-1-1 66.50 99.3 B-2-1 0.50 0.75 66.78 C-3 0.33 1.0 Comparative Example 15 (o) A-1 33 B-1-1 45.60 68.0 B-2-1 21.50 32.04 67.03 - 0.00 0.0 Comparative Example 16 (p) A-1 18 B-1-1 55.80 68.0 B-2-1 26.20 31.95 82.00 - 0.00 0.0 Comparative Example 17 (q) A-1 12 B-1-1 59.00 67.0 B-2-1 29.00 32.95 88.00 - 0.00 0.0 Comparative Example 18 (r) A-1 12 B-1-1 38.90 67.0 B-2-1 19.20 33.05 82.88 - 0.00 0.0 Comparative Example 19 (s) A-1 12 B-1-1 66.50 99.3 B-2-1 0.50 0.75 84.46 C-3 0.33 1.0 Comparative Example 20 (t) A-1 33 B-1-1 66.50 99.3 B-2-1 0.50 0.75 66.78 C-7 0.33 1.0

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

The materials used in the examples are shown below.

＜Binder resin (A)＞ ·A-1: Polyurethane resin (acid value: 10 mgKOH/g) ·A-2: Polyamide resin (acid value 13.2 mgKOH/g, hydroxyl value 5.5 mgKOH/g) A-3: Polyurethane resin Vylon UR3500 (trade name, acid value: 35 mgKOH/g, hydroxyl value: 10 mgKOH/g, manufactured by Toyobo Co., Ltd.) A-4: Polyester resin Vylon GK130 (trade name, hydroxyl value: 19 mgKOH/g, manufactured by Toyobo Co., Ltd.)

<Carbon material (B)> (Graphite (B-1)) · B-1-1: Flake graphite CPB (trade name, manufactured by Nippon Graphite Co., Ltd.) with an average particle size of 20 μm (catalog) B-1-2: Exfoliated graphite UP-20 (trade name, manufactured by Nippon Graphite Co., Ltd.) with an average particle size of 20 μm (catalog) · B-1-3: Expanded graphite GR15 (trade name, manufactured by Nippon Graphite Co., Ltd.) with an average particle size of 15 μm (catalog) B-1-4: Spherical graphite CGB-50 (trade name, manufactured by Nippon Graphite Co., Ltd.) with an average particle size of 50 μm (catalog) B-1-5: Artificial graphite PAG-5 (trade name, manufactured by Nippon Graphite Co., Ltd.) with an average particle size of 30 μm (catalog)

(Carbon materials other than graphite (B-2)) ·B-2-1: Ketjen Black EC-300J (trade name, manufactured by LION SPECIALTY CHEMICALS) ·B-2-2: Ketjen Black EC-600JD (trade name, manufactured by LION SPECIALTY CHEMICALS) ·B-2-3: Furnace black #3050B (trade name, manufactured by Mitsubishi Chemical Corporation) · B-2-4: DENKA BLACK HS-100 (trade name, manufactured by Electrochemical Industry Co., Ltd.) · B-2-5: Carbon nanotube VGCF-H (trade name, manufactured by Showa Denko Co., Ltd.)

＜Hardener (C)＞ ·C-1: Aziridine compound Chemitite PZ-33 (trade name, solid content 100% by mass, manufactured by Nippon Shokubai Co., Ltd.) C-2: Epoxy compound TETRAD-X (trade name, solid content 100% by mass, manufactured by Mitsubishi Kagas Chemical Co., Ltd.) ·C-3: Carbodiimide compound Carbodilite V-03 (trade name, solid content 50% by mass, manufactured by Nisshinbo Chemical Co., Ltd.) ·C-4: Isocyanate compound Takenate D-110N (trade name, solid content 75% by mass, manufactured by Mitsui Chemicals Co., Ltd.) ·C-5: Aluminum chelate compound Aluminchelate D (trade name, solid content 100% by mass, manufactured by Kawaken Seika Co., Ltd.) C-6: Titanium chelate compound ORGATIX TC-401 (trade name, solid content 65% by mass, manufactured by Matsumoto Fine Chemical Co., Ltd.) C-7: Titanium chelate Orgatix TC-100 (trade name, solid content 75% by mass, manufactured by Matsumoto Fine Chemical Co., Ltd.) ·C-8: Zirconium chelate compound ORGATIX ZC-150 (trade name, solid content 100% by mass, manufactured by Matsumoto Fine Chemical Co., Ltd.)

As shown in Tables 6 to 9, in the conductive films and conductive circuits using the conductive composition, by using the curing agent (C), the adhesiveness, conductivity, and durability can be improved compared with the conventional ones. sex. Furthermore, in Comparative Example 6, Comparative Example 8, and Comparative Example 13, the amount of binder resin or the ratio of graphite or carbon material other than graphite was within an appropriate range, but no curing agent was added and the binder resin was not cured, as a result. Insufficient durability. In Example 36, Example 37, Example 38, Example 76, Example 77, and Example 78, two kinds of hardeners were used in combination, and the reaction was carried out in a wider temperature range than using a monomer, so it was compared with only containing Compared with Example 39 and Example 79 of a hardener, very high conductivity was stably exhibited. In addition, as the characteristics of the non-contact type medium, since the resistance value of the conductive circuit is low in Examples 1 to 81, communication can be confirmed. On the other hand, since the resistance values of Comparative Example 3 to Comparative Example 6, Comparative Example 8, Comparative Example 9, Comparative Example 11, Comparative Example 12, Comparative Example 14 to Comparative Example 18, and Comparative Example 20 were high, communication could not be confirmed. In addition, in Comparative Example 1, Comparative Example 2, Comparative Example 7, Comparative Example 10, and Comparative Example 19, since the conductive particles were filled with a large amount and had a low resistance value, transmission and reception were possible. Since the adhesiveness is extremely poor, the practicability as a non-contact medium is poor. Furthermore, in Comparative Example 13, transmission and reception were also possible, but the durability of the conductive circuit was low, and the practicality as a non-contact medium was poor.

As described above, in a conductive composition containing a binder resin, a carbon material, and a hardener, by selectively controlling the blending ratio of the carbon material in the conductive composition and the ratio of graphite to carbon materials other than graphite The mixing ratio can form an excellent conductive network between the carbon materials, so that excellent conductivity, adhesion and durability can be exhibited. [Industrial Availability]

Since the conductive composition of the present invention has very excellent conductivity as a carbon material, it can be applied to a wide range of application fields including RFID antennas, wiring materials, planar heating elements, and electrode materials.

This application claims priority based on Japanese Patent Application No. 2020-182741 for which it applied on October 30, 2020, and the entire disclosure thereof is incorporated herein.

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Claims (10)

A conductive composition comprising a binder resin (A), a carbon material (B) and a hardener (C), wherein, Carbon material (B) includes graphite (B-1) and carbon material (B-2) other than graphite, The content rate of the carbon material (B) in 100% by mass of the solid content of the conductive composition is 65% by mass to 85% by mass, In 100 mass % of carbon materials (B), the content rate of graphite (B-1) is 70.0 mass % - 99.0 mass %. The conductive composition according to claim 1, wherein the content of the curing agent (C) is 0.5% by mass to 20% by mass relative to 100% by mass of the binder resin (A). The conductive composition according to claim 1 or claim 2, wherein the content of graphite (B-1) is 80.0% by mass to 99.0% by mass in 100% by mass of the carbon material (B). The conductive composition according to claim 1 or claim 2, wherein the content of graphite (B-1) is 90.0% by mass to 97.5% by mass in 100% by mass of the carbon material (B). The conductive composition according to claim 1 or claim 2, wherein the content of the carbon material (B) is 70% by mass to 80% by mass in 100% by mass of the solid content of the conductive composition. The conductive composition according to claim 1 or claim 2, wherein the curing agent (C) contains an aziridine compound or an epoxy group-containing compound. The conductive composition according to claim 1 or claim 2, wherein the hardener (C) contains a metal chelate compound. The conductive composition according to claim 7, wherein the metal chelate compound comprises an aluminum chelate compound. A conductive film formed by forming a film of the conductive composition according to any one of Claims 1 to 8. A non-contact medium on which a conductive circuit and an integrated circuit chip are stored using the conductive composition according to any one of Claims 1 to 8.