JP5358732B1 - Conductive resin composition for forming conductive circuit and conductive circuit - Google Patents

Abstract

A conductive resin composition that can be applied to a heat-sensitive substrate, can ensure excellent conductivity and resolution, and is excellent in both coating film strength and adhesion to an underlying substrate, and this Provided is a conductive circuit formed using a conductive resin composition.
A carboxyl group-containing resin, conductive powder, polyfunctional (meth) acrylate monomers, photoinitiator, and, by using a conductive resin composition and the conductive resin composition comprising a block iso shea Aneto compound A conductive circuit is provided.
[Selection figure] None

Description

The present invention relates to a conductive resin composition for forming a conductive circuit and a conductive circuit formed using the conductive resin composition.

  Patent Documents 1 and 2 are known documents that disclose a conductive paste for forming a conductive pattern film on a substrate.

    Patent Documents 1 and 2 disclose a conductive paste containing a conductive powder, an organic binder, a photopolymerizable monomer, and a photopolymerization initiator.

    These conductive pastes are fired at a temperature of 500 ° C. or higher to remove the organic components in the paste, thereby ensuring the conductivity of the conductive circuit layer.

  In addition, the baking type conductive paste as described above generally contains glass frit together with the conductive powder, and by baking, the organic components in the paste are removed and the glass frit is melted to conduct the conductive pattern. And adhesion between the substrate and the substrate are ensured.

    However, since such a photosensitive conductive paste is baked at a temperature of 500 ° C. or higher, there is a problem that it is difficult to apply it on a heat-sensitive substrate.

Japanese Patent Laid-Open No. 2003-280181 Japanese Patent No. 4411113

The present invention has been made to solve the above problems, and is applicable to a heat-sensitive substrate and can be applied to a heat-sensitive substrate, and can provide excellent conductivity, and a conductive resin composition for forming a conductive circuit and the conductive resin. It is providing the electrically conductive circuit formed using a composition.

Furthermore, the present invention provides a conductive resin composition for forming a conductive circuit capable of improving both coating film strength and adhesion to a base material, and a conductive circuit formed using this conductive resin composition. There is to do.

In order to solve the above problems, the present invention is a carboxyl group-containing resin, conductive powder, polyfunctional (meth) acrylate monomer, a photopolymerization initiator, and comprises a block iso Aia sulfonate compound, the carboxyl group-containing resin Provides a conductive resin composition for forming a conductive circuit , characterized in that it does not contain a double bond, and a conductive circuit formed on a substrate using this conductive resin composition.

  According to the present invention, a conductive resin composition that can be applied to a heat-sensitive substrate, can ensure excellent conductivity, and has excellent coating film strength and adhesion to an underlying substrate, and its conductivity. The conductive circuit formed using the conductive resin composition can be provided.

  First, the component mix | blended in the composition based on this invention is demonstrated.

(Components blended in the conductive resin composition)
(Carboxyl group-containing resin)
As the carboxyl group-containing resin, a known and commonly used resin compound containing a carboxyl group in the molecule can be used.
The carboxyl group-containing resin may be a carboxyl group-containing photosensitive resin containing a double bond, but a carboxyl group-containing resin not containing a double bond is preferred. Since the carboxyl group-containing resin not containing a double bond does not react with the (meth) acrylate monomer, no intermolecular bond is formed. For this reason, the carboxyl group-containing resin does not increase in molecular weight and is easily removed during development. As a result, the conductive powder becomes dense, and the specific resistance value of the conductive pattern film can be lowered.

  In addition, even if the carboxyl group-containing resin has a double bond at an extremely small ratio, the carboxyl group-containing resin containing such a double bond is within the range where the ratio has the same effect as the present invention. And “carboxyl group-containing resin not containing a double bond” of the present invention. Examples of the carboxyl group-containing resin not containing a double bond include those having a double bond equivalent of 10,000 or more.

  Among the carboxyl group-containing resins not containing a double bond, the carboxyl group-containing resin is particularly preferably a carboxyl group-containing resin containing neither a double bond nor an aromatic ring. By adopting a structure that does not contain an aromatic ring, the light absorption of the carboxyl group-containing resin itself can be suppressed, and the photoreactivity of the (meth) acrylate monomer can be relatively improved.

  Specific examples of the carboxyl group-containing resin not containing a double bond and an aromatic ring are listed below.

(1) a carboxyl group-containing resin obtained by copolymerizing with an unsaturated carboxylic acid such as (meth) acrylic acid and one or more other compounds having an unsaturated double bond;
(2) a carboxyl group-containing resin obtained by copolymerizing an acid anhydride having an unsaturated double bond such as maleic anhydride and a compound having another unsaturated double bond;
(3) a carboxyl group-containing resin obtained by reacting a compound having a hydroxyl group with a copolymer of an acid anhydride having an unsaturated double bond and another compound having an unsaturated double bond;
(4) A saturated carboxylic acid is reacted with a copolymer of an epoxy group, a compound having an unsaturated double bond, and a compound having an unsaturated double bond, and a polybasic acid anhydride is reacted with the resulting secondary hydroxyl group. Carboxyl group-containing resin obtained by
(5) A carboxyl group-containing resin obtained by reacting a hydroxyl group-containing polymer with a polybasic acid anhydride may be mentioned, but is not limited thereto.
In addition, in this specification, (meth) acrylic acid is a term which generically refers to acrylic acid, methacrylic acid and mixtures thereof, and the same applies to other similar expressions.

Since the carboxyl group-containing resin as described above has many free carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution is possible.
The acid value of the carboxyl group-containing resin is preferably in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary. Depending on the case, the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal conductive pattern.

  The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. If the mass average molecular weight is less than 2,000, the tack-free performance may be inferior, the moisture resistance of the conductive pattern film after exposure may be poor, the film may be reduced during development, and the resolution may be greatly inferior. On the other hand, when the mass average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.

  The blending amount of such a carboxyl group-containing resin is preferably 3 to 50% by mass and more preferably 5 to 30% by mass in the total conductive resin composition. When the amount is less than the above range, the strength of the conductive pattern film is lowered, which is not preferable. On the other hand, when the amount is larger than the above range, the viscosity becomes high or the coating property and the like are lowered, which is not preferable.

(Conductive powder)
First, any material can be used for the conductive powder as long as it imparts conductivity in the conductive resin composition. Examples of such conductive powder include Ag, Au, Pt, Pd, Ni, Cu, Al, Sn, Pb, Zn, Fe, Ir, Os, Rh, W, Mo, Ru, and the like. Among these, Ag is preferable. These conductive powders may be used in the form of a single component, but may be used in the form of an alloy or oxide. Furthermore, tin oxide (SnO ₂ ), indium oxide (In ₂ O ₃ ), ITO (Indium Tin Oxide), or the like can also be used. The conductive powder may be carbon powder such as carbon black, graphite, or carbon nanotube. However, care should be taken because the light transmittance is lowered.

  The shape of the conductive powder is not particularly limited, but is preferably other than flakes, particularly preferably acicular or spherical. As a result, the light transmittance is improved, and a conductive pattern film having excellent resolution can be formed.

  Such a conductive powder preferably has a maximum particle size of 30 μm or less in order to form fine lines. By setting the maximum particle size to 30 μm or less, the resolution of the conductive pattern film is improved.

  In addition, the conductive powder is an average particle diameter of 10 random conductive powders observed at 10,000 times using an electron microscope (SEM), and the range is 0.1 to 10 μm or less. preferable. If the average particle size is smaller than this range, the resistance value increases due to an increase in contact resistance, which is not preferable. On the other hand, when the average particle size is larger than the above range, when a conductor pattern is printed using a mesh screen plate, workability is deteriorated due to clogging of the screen, and formation of fine lines becomes difficult, which is not preferable. In addition, it is preferable to use the thing of the magnitude | size of 0.5-3.5 micrometers in the average particle diameter measured with the micro track | truck.

  The blending ratio of such conductive powder is preferably 800 to 900 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When there are too few compounding ratios of electroconductive powder, there exists a possibility that resistance value of an electroconductive resin composition may become high and sufficient electroconductivity may not be obtained. On the other hand, if a large amount of conductive powder is contained, the light transmission property is deteriorated and the formation of the conductive pattern film by exposure is deteriorated.

(Multifunctional (meth) acrylate monomer)
As the (meth) acrylate monomer, a polyfunctional (meth) acrylate monomer (bifunctional or higher (meth) acrylate monomer) is used. The reason for using the polyfunctional (meth) acrylate monomer is that the photoreactivity is improved and the resolution is excellent as compared with the case where the number of functional groups is one.

Examples of the (meth) acrylate monomer include conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, and epoxy (meth) acrylate. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethylacrylamide Acrylamides such as N-methylol acrylamide and N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like; Les emission oxide adducts, propylene oxide adducts or polyhydric acrylates such as ε- caprolactone adduct; phenoxy acrylate, bisphenol A diacrylate, and multi such as ethylene oxide adducts or propylene oxide adducts of these phenols Polyvalent acrylates of glycidyl ether such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate; not limited to the above, polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene Directly acrylated polyol such as polyester polyol, or urethane acrylate via diisocyanate Acrylates and melamine acrylates, and at least one of each methacrylate corresponding to the acrylate.

  Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, or a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. An epoxy urethane acrylate compound obtained by reacting a half urethane compound may be used as a photoreactive monomer. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

  Among these, a tetrafunctional (meth) acrylate monomer is preferable. Examples of tetrafunctional (meth) acrylate monomers include pentaerythritol tetraacrylate and pentaerythritol tetramethacrylate.

The tetrafunctional (meth) acrylate monomer is preferably a tetrafunctional urethane acrylate monomer or ester acrylate described in the chemical formulas (I) and (II).

In formula (I),
X ¹ represents a group containing an acryloyloxy group.

X ² represents a group containing a methacryloyloxy group.

X ³ and X ⁴ each independently represent a group containing an acryloyloxy group or a group containing a methacryloyloxy group. However, at least one of X ³ and X ⁴ represents a group containing a methacryloyloxy group.

L ¹ and L ² are each independently

Represents.

* Represents a binding site with Z.

Z represents a divalent linking group.

As the acrylate monomer, L ¹ and L ² in the general formula (I) are

It is preferable that it is urethane acrylate represented by these. In formula (III), * represents a binding site with Z.

Furthermore, as a monomer represented by general formula (I), urethane acrylate represented by the following formula (IV) is preferable.

In formula (IV),
Z ¹ represents an alkylene group.

R ¹ represents a hydrogen atom.

R ² represents a methyl group.

R ³ and R ⁴ each independently represents a hydrogen atom or a methyl group. However, at least one of R ³ and R ⁴ represents a methyl group.

  Furthermore, urethane acrylate or ester acrylate in which acrylic and methacryl are in a one-to-one relationship is particularly preferable as the tetrafunctional acrylate monomer.

  As such a 4-functional urethane acrylate or ester acrylate, for example, a product obtained by adding acrylic acid to glycidyl methacrylate and reacting the generated hydroxyl group with diisocyanate or dicarboxylic acid is preferable.

  Examples of commercially available products of tetrafunctional urethane acrylate include NK Oligo U-4HA (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.).

  Of these polyfunctional (meth) acrylate monomers, tetrafunctional acrylate monomers represented by the formula (I) are preferred. Since this tetrafunctional acrylate monomer has a large number of functional groups, it has excellent photoreactivity and excellent resolution.

In addition, since X ¹ and X ² of the tetrafunctional acrylate monomer are different from each other, the reaction between X ¹ and X ² in the molecule is slow during photocuring. However, the acrylate monomer X ¹ or X ² reacts faster than the intramolecular reaction between the other acrylate monomers X ¹ or X ² . Thereby, since an intermolecular bond is formed between a plurality of acrylate monomers, the conductive resin composition is further cured and contracted. And only by heat-processing at low temperature, intermolecular reaction is further accelerated | stimulated and the conductive resin composition fully cures and shrinks. As a result, it is considered that the conductive powder becomes dense and the specific resistance value of the conductive pattern film is further lowered.

  Although the compounding quantity of such a polyfunctional (meth) acrylate monomer is not specifically limited, 10-100 mass parts with respect to 100 mass parts of said carboxyl group-containing resin, More preferably, the ratio of 20-80 mass parts is. Is appropriate. When the blending amount is less than 10 parts by mass, photocurability is lowered, and formation of a conductive pattern line is difficult due to alkali development after irradiation with active energy rays. On the other hand, when the amount exceeds 100 parts by mass, the solubility in an alkaline aqueous solution is lowered and the conductive pattern film becomes brittle.

(Photopolymerization initiator)
The photopolymerization initiator is not particularly limited, and may be a benzoin type or a phosphine oxide type, but is represented by the oxime ester type having a group represented by the following general formula (V) or the following general formula (VI). It is preferable to use an acetophenone-based photopolymerization initiator having the above group.

  In formula (V), R6 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

  In formula (VI), R8 and R9 each independently represent an alkyl group having 1 to 12 carbon atoms or an arylalkyl group, and R10 and R11 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Or R10 and R11 may combine to form a cyclic alkyl ether group.

  Among the oxime ester-based photopolymerization initiators, CGI-325, IRGACURE OXE01, IRGACURE OXE02 manufactured by BASF Japan, N-1919 manufactured by ADEKA, NCI-831, manufactured by Nippon Chemical Industry Co., Ltd. TOE-004 is preferred. Further, IRGACURE 389 may be used as a photopolymerization initiator. In addition, these photoinitiators can be used individually or in combination of 2 or more types.

  Examples of the acetophenone photopolymerization initiator having a group represented by the general formula (VI) include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2. -Dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] Examples include -1-butanone and N, N-dimethylaminoacetophenone. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by BASF Japan.

The blending amount of such a photopolymerization initiator is not particularly limited, but is suitably 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. It is. When the blending amount of the photopolymerization initiator is less than 0.01 parts by mass, the photocurability is insufficient, and the conductive pattern film may be peeled off or the characteristics of the conductive pattern film such as chemical resistance may be deteriorated. Absent. On the other hand, if it exceeds 30 parts by mass, light absorption on the surface of the conductive pattern film of the photopolymerization initiator becomes violent, and the deep curability tends to decrease, such being undesirable.
(Block isocyanate compound)
In order to improve the toughness of the cured film obtained from the conductive resin composition and the adhesion to the base substrate, a compound having a blocked isocyanate group in one molecule, that is, a blocked isocyanate compound, and the like can be mentioned.

  The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.

  As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As this isocyanate compound, for example, the same aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate as described above is used.

  Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid And alcohol-based blocking agents such as ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block agents such as succinimide and maleic imide; Amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine It is.

The block isocyanate compound may be commercially available, for example, 7950, 7951, 7960, 7961, 7982, 7990, 7991, 7992 (above, trade name, manufactured by Baxenden) Sumijour BL-3175, BL-4165, BL-1100, BL-1265, Death Module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmotherm 2170, Desmotherm 2265 (supplied by Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (supplied by Nippon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B-846, B-870, B-874, B-882 (Mitsui Takeda Chemical Co., trade name), TPA -B80E, 17 Examples include B-60PX, E402-B80T, MF-B60B, MF-K60B, SBN-70D (trade name, manufactured by Asahi Kasei Chemicals), Karenz MOI-BM (trade name, manufactured by Showa Denko KK), and the like. In addition, Sumidur BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent. The above-mentioned compounds having a blocked isocyanate group are used singly or in combination of two or more. be able to.

  The compounding amount of such a compound having a blocked isocyanate group is suitably 1 to 100 parts by mass, more preferably 2 to 70 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 mass parts, storage stability falls and it is not preferable.

  The dissociation temperature of the blocking agent of the blocked isocyanate is not particularly limited, but it is desirable that the blocking agent does not react at the temporary drying temperature (for example, 80 to 90 ° C.) but reacts at the final heat treatment. A temperature higher than the temporary drying temperature, for example, 100 ° C. or higher is preferable. In addition, when a polyester-based resin is used as the base material, for example, the dissociation temperature of the blocking agent of the blocked isocyanate can be prevented from being discolored, for example, 140, because the base material is easily discolored if the heat treatment temperature is too high. It is preferable that heat treatment can be performed at a temperature at which the base material is not discolored at a temperature not higher than ° C.

In order to further improve the effects of the present invention, or to exhibit further effects within a range that does not impair the effects of the present invention, the conductive resin composition of the present invention is the above-described carboxyl group-containing resin, conductive property. powder, polyfunctional (meth) acrylate monomers, photoinitiator, and, together with the block iso shea Aneto compounds, can contain other components illustrated below.

(Organic acid)
As the organic acid, an organic acid having no aromatic ring is preferable. By blending an organic acid that does not have an aromatic ring, the light absorption of the organic acid itself is suppressed, the photoreactivity of the tetrafunctional (meth) acrylate monomer is relatively improved, and excellent resolution is achieved. Can be obtained.

  Specific examples of organic acids include 2,2′-thiodiacetic acid, adipic acid, isobutyric acid, formic acid, citric acid, glutaric acid, acetic acid, oxalic acid, tartaric acid, lactic acid, pyruvic acid, malonic acid, butyric acid, Carboxylic acids such as malic acid, salicylic acid, benzoic acid, phenylacetic acid, acrylic acid, maleic acid, fumaric acid, crotonic acid; dibutyl phosphite, butyl phosphite, dimethyl phosphite, methyl phosphite, phosphorous acid Mono- or diesters of phosphorous acid such as dipropyl, propyl phosphite, diphenyl phosphite, phenyl phosphite, diisopropyl phosphite, isopropyl phosphite, phosphorous acid-n-methyl-2-ethylhexyl; phosphorus Dibutyl phosphate, butyl phosphate, dimethyl phosphate, methyl phosphate, dipropyl phosphate, propyl phosphate, diphenyl phosphate, phenyl phosphate, Examples thereof include mono- or diesters of phosphoric acid such as diisopropyl phosphate, isopropyl phosphate, and phosphoric acid-n-butyl-2-ethylhexyl. As the organic acid, 2,2'-thiodiacetic acid is preferable.

  The blending amount of the organic acid is preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the conductive powder. When the blending amount of the organic acid is less than 0.1 parts by mass with respect to 100 parts by mass of the conductive powder, the reaction between the conductive powder and the carboxyl group-containing resin occurs, and the long-term storage stability is reduced When the amount exceeds 5 parts by mass, it is not preferable because moisture in the air is easily absorbed.

(Dispersant)
By mix | blending a dispersing agent, the dispersibility and sedimentation property of a conductive resin composition can be improved.

  Examples of the dispersing agent include, for example, ANTI-TERRA-U, ANTI-TERRA-U100, ANTI-TERRA-204, ANTI-TERRA-205, DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-108. DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-161, DISPERBY63-62 -164, DISPERBYK- 66, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, DISPERBYK-185, DISPERBYK-184, DISPERBY92 DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2009, DISPERBYK-2020, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2095, DISPERBYK-2096, DISPERBYK-150P, DISPERBYK-2150 -P104S, BYK-P105, BYK-9076, BYK-9077, BYK-220S (manufactured by BYK Japan), Disparon 2150, Disparon 1210, Disparon KS-860, Disparon KS-873N, Disparon 7004, Disparon 1830, Disparon 1860, Disparon 1850, Disparon DA-400N, Disparon PW-36, Disparon DA-703-50 (manufactured by Enomoto Kasei Co., Ltd.), Floren G-450, Floren G-600, Floren G-820, Floren G-700, Floren DOPA-44 and Florene DOPA-17 (manufactured by Kyoeisha Chemical Co., Ltd.) can be mentioned.

  The content of the dispersant is preferably 0.1 to 10 parts by mass, and preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the conductive powder in order to effectively achieve the above object.

(Photopolymerization inhibitor)
By adding the photopolymerization inhibitor, it is possible to suppress a certain amount of radical polymerization in accordance with the type of polymerization inhibitor and the amount of the addition among the radical polymerization that occurs inside the conductive resin composition by exposure. Thereby, the photoreaction with respect to weak light like scattered light can be suppressed. Therefore, since a finer line of the conductive pattern film can be formed sharply, it can be preferably used. The photopolymerization inhibitor is not particularly limited as long as it can be used as a photopolymerization inhibitor. For example, p-benzoquinone, naphthoquinone, di-t-butyl paracresol, hydroquinone monomethyl ether, α-naphthol, acetamidine acetate Hydrazine hydrochloride, trimethylbenzylammonium chloride, dinitrobenzene, picric acid, quinonedioxime, pyrogallol, tannic acid, resorzine, cuperone, phenothiazine, and the like.

  The addition amount of the photopolymerization inhibitor is preferably 0.001 to 3 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. If it is less than this range, the effect of inhibiting polymerization is not exhibited, and even a low exposure amount due to light scattering is cured, and the line shape tends to be thickened. Also, if it exceeds this range, the sensitivity is lowered and a large amount of exposure is required, so care must be taken.

(Filler)
In the conductive resin composition of the present invention, a filler can be blended as necessary in order to increase the physical strength of the coating film. As such a filler, publicly known and commonly used inorganic or organic fillers can be used, and barium sulfate, silica, hydrotalcite and talc are particularly preferably used.

(Thermosetting component)
A thermosetting component can be added to the conductive resin composition of the present invention in order to impart heat resistance. Examples of thermosetting components used in the present invention include amine resins such as melamine resins and benzoguanamine resins, block isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives, and the like. A thermosetting resin can be used. Particularly preferred is a thermosetting component having in the molecule at least one of two or more cyclic ether groups and cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups).

  Such a thermosetting component having two or more cyclic (thio) ether groups in the molecule is either one of the three-, four- or five-membered cyclic ether groups in the molecule, or the cyclic thioether group, or two of them. A compound having at least two epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having at least two oxetanyl groups in the molecule, that is, a polyfunctional compound. Examples include oxetane compounds, compounds having two or more thioether groups in the molecule, that is, episulfide resins.

  Examples of the polyfunctional epoxy compound include JER828, JER834, JER1001, JER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840 manufactured by DIC, Epicron 850, Epicron 1050, Epicron 2055, Epototo YD-011, YD manufactured by Tohto Kasei Co., Ltd. -013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Sumitomo Epoxy ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); JERYL903 manufactured by Mitsubishi Chemical Corporation, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., manufactured by Dow Chemical Of D. E. R. 542, Sumitomo Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); JER152 and JER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd., EPPN-201, EOCN-1025, EOCN manufactured by Nippon Kayaku Co., Ltd. -1020, EOCN-104S, RE-306, Sumitomo Epoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Co., Ltd. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, JER807 manufactured by Mitsubishi Chemical Co., Ltd. Epototo YDF-170, YDF-175, YDF-2004 manufactured by Tohto Kasei Co., Ltd. (All trade names) bisphenol F-type epoxy resin; hydrogenated bisphenol A-type epoxy resins such as Epototo ST-2004, ST-2007, ST-3000 (trade name) manufactured by Toto Kasei Co., Ltd .; Gercidylamine type epoxy resin such as JER604, Etototo YH-434 manufactured by Tohto Kasei Co., Ltd., Sumitomo Epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (both trade names); Hydantoin type epoxy resin; Celoxide manufactured by Daicel Chemical Industries 2021 grade (trade name) alicyclic epoxy resin; YL-9 manufactured by Mitsubishi Chemical Corporation 3, manufactured by Dow Chemical Company of T. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all trade names) Type or biphenol type epoxy resin or a mixture thereof; bisphenol S type epoxy resin such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by DIC Co., Ltd .; Bisphenol A novolac type epoxy resin such as JER157S (trade name) manufactured by KK; tetraphenylolethane type epoxy resin such as JERRY-931 manufactured by Mitsubishi Chemical Co., Ltd .; TEPIC manufactured by Nissan Chemical Industries, Ltd. (trade name) ) Heterocyclic epoxy resin; diglycidyl phthalate such as Bremer DGT manufactured by NOF Corporation Resin; Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Tohto Kasei; Naphthalene groups such as ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by DIC Containing epoxy resin; epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by NOF Corporation; and cyclohexylmaleimide And glycidyl methacrylate copolymer epoxy resin; epoxy-modified polybutadiene rubber derivatives (for example, PB-3600 manufactured by Daicel Chemical Industries), CTBN-modified epoxy resins (for example, YR-102, YR-450 manufactured by Toto Kasei Co., Ltd.), etc. These are mentioned The present invention is not limited. These epoxy resins can be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.

  Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene), cardo-type bisphenol Le ethers, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the compound having two or more cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

(Thermosetting catalyst)
When using the thermosetting component which has a 2 or more cyclic (thio) ether group in the said molecule | numerator in the conductive resin composition of this invention, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, the present invention is not limited to these, and any epoxy resin or oxetane compound thermosetting catalyst, or any one that promotes the reaction of a carboxyl group with at least one of an epoxy group and an oxetanyl group, alone or 2 A mixture of seeds or more may be used. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.

  The blending amount of these thermosetting catalysts is sufficient in the usual quantitative ratio, for example, with respect to 100 parts by mass of the carboxyl group-containing resin or thermosetting component having two or more cyclic (thio) ether groups in the molecule. The amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass.

(Thermal polymerization inhibitor)
The thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization of the conductive resin composition of the present invention. Examples of thermal polymerization inhibitors include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil. , Naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4 -Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

(Chain transfer agent)
In the conductive resin composition of the present invention, known N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole and the like can be used as chain transfer agents in order to improve sensitivity. Specific examples of chain transfer agents include, for example, chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol Chain transfer agents having a hydroxyl group such as 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2, 2 -(Ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclo Ntanchioru, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzenethiol like.

  A polyfunctional mercaptan-based compound can be used and is not particularly limited. For example, hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide. Aliphatic thiols such as xylylene dimercaptan, 4,4′-dimercaptodiphenyl sulfide, and aromatic thiols such as 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), Propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythritol Poly (mercaptoacetate) polyhydric alcohols such as rutetrakis (mercaptoacetate) and dipentaerythritol hexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate) ), Propylene glycol bis (3-mercaptopropionate), glycerin tris (3-mercaptopropionate), trimethylolethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), penta Poly (3-mercaptopropionate) of polyhydric alcohol such as erythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 ( Poly (mercaptobutyrate) s such as 1H, 3H, 5H) -trione and pentaerythritol tetrakis (3-mertabutbutyrate) can be used.

  Examples of these commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP, and TEMPIC (above, manufactured by Sakai Chemical Industry Co., Ltd.), Karenz MT-PE1, Karenz MT-BD1, And Karenz-NR1 (manufactured by Showa Denko KK).

  Further, examples of the heterocyclic compound having a mercapto group acting as a chain transfer agent include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, and 2-mercapto. -4-ethyl-4-butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4- Butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) Ethyl-2-mercapto-4-butyrolactam, 2-mercapto-5-va Lolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto- 5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, 2-mercaptobenzothiazole, 2-mercapto-5-methylthio-thiadiazole, 2-mercapto-6-hexanolactam, 2 , 4,6-Trimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name Disnet F), 2-dibutylamino-4,6-dimercapto-s-triazine (manufactured by Sankyo Chemical Co., Ltd .: trade name Disnet) DB), and 2-anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name: Gisnet AF).

  In particular, as a heterocyclic compound having a mercapto group that is a chain transfer agent that does not impair the developability of the conductive resin composition, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade names: Accelerator M) manufactured by Kawaguchi Chemical Industry Co., Ltd., 3-mercapto-4-methyl-4H-1,2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5 Mercapto-1H-tetrazole is preferred. These chain transfer agents can be used alone or in combination of two or more.

(Other additive components)
In the conductive resin composition of the present invention, known and commonly used components such as thickeners, defoaming / leveling agents, coupling agents, antioxidants, rust inhibitors and the like can be appropriately blended as necessary. Of course you can.

(Formation of conductive circuit)
Next, an example of a method for forming a conductive circuit using the conductive resin composition according to the present invention will be described.
With respect to the conductive resin composition of the present invention, a machine such as a three-roll roll or a blender is used for kneading and dispersing the above-described essential components and optional components.
The conductive resin composition thus dispersed is applied onto the substrate by an appropriate application method such as a screen printing method, a bar coater, or a blade coater. Next, in order to obtain dryness to the touch, the organic solvent is removed by drying at a temperature at which the carboxyl group-containing resin is not thermally decomposed, for example, about 60 to 120 ° C. for about 5 to 40 minutes in a hot air circulation drying oven, a far infrared drying oven or the like. Evaporate to obtain a tack-free coating.

  Note that the conductive resin composition can be formed into a film in advance, and in this case, the film may be laminated on the substrate.

Next, contact exposure or non-contact exposure is performed using a negative mask having a predetermined exposure pattern. As the exposure light source, a halogen lamp, a high-pressure mercury lamp, a laser beam, a metal halide lamp, a black lamp, an electrodeless lamp, or the like is used. As the exposure amount, the integrated light amount can be a low light amount of 200 mJ / cm ² or less. In addition, you may form a pattern in a coating film with a laser direct imaging apparatus, without using a mask.

  Next, the coating film is formed into a pattern by development such as spraying or dipping. Developers include aqueous alkali metal solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium silicate, and aqueous amine solutions such as monoethanolamine, diethanolamine and triethanolamine, especially about 1.5% by mass or less. A dilute alkaline aqueous solution having a concentration of 1 is preferably used, as long as the carboxyl group of the carboxyl group-containing resin in the conductive resin composition is saponified and the uncured portion (unexposed portion) is removed, as described above The developer is not limited to such a developer. Moreover, it is preferable to perform washing with water and acid neutralization in order to remove an unnecessary developer after development.

  Then, the obtained conductive pattern film is dried at a temperature at which the carboxyl group-containing resin is not thermally decomposed. Thus, a conductive circuit having a low resistance and a fine conductive pattern film can be formed. The drying temperature is preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and even more preferably 130 ° C. or lower.

(Base material)
In these steps, since baking is not performed at a high temperature of 500 ° C., a resin base material having no heat resistance can be used as the base material. Specifically, as a resin base material, for example, a polyester resin such as polyimide, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), or polyethersulfone (PES). , Polystyrene (PS), polymethyl methacrylate (PMMA), polycarbonate (PC), polyamide (PA), polypropylene (PP), polyphenylene oxide (PPO), etc., preferably using a polyester resin Can do. A glass substrate or the like may be used.

The present invention will be specifically described below based on examples. However, the present invention is not limited to these examples.
(Compounding ingredients)
[Carboxyl group-containing resin containing no double bond]
Synthesis example 1
A flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser is charged with methyl methacrylate and methacrylic acid in a molar ratio of 0.87: 0.13, dipropylene glycol monomethyl ether as a solvent, and azobis as a catalyst. Isobutyronitrile was added and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere to obtain a carboxyl group-containing resin solution. This carboxyl group-containing resin had a mass average molecular weight of about 10,000 and an acid value of 74 mgKOH / g. In addition, the mass average molecular weight of the obtained carboxyl group-containing resin was obtained by using Shimadzu Corporation pump LC-6AD and Showa Denko Co., Ltd. column Shodex (registered trademark) KF-804, KF-803, and KF-802. The measurement was performed by high performance liquid chromatography connected to a triplet. Hereinafter, this carboxyl group-containing resin solution is referred to as A-1 varnish. This carboxyl group-containing resin does not contain a double bond and does not contain an aromatic ring.

[Conductive powder]
Spherical conductive powder: Ag powder (maximum particle size 30 μm or less, average particle size 2 μm (SEM)))
[Acrylate monomer]
Bifunctional (meth) acrylate monomer: Trade name; KAYARAD HX-220 (manufactured by Nippon Kayaku Co., Ltd.)
Trifunctional (meth) acrylate monomer: Trade name; Aronix M-350 (manufactured by Toa Gosei Co., Ltd.)
Tetrafunctional (meth) acrylate monomer: Trade name; NK Oligo U-4HA (manufactured by Shin-Nakamura Chemical Co., Ltd.)
Hexafunctional (meth) acrylate monomer: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
[Photoinitiator]
Product Name: IRGACURE 379EG (BASF Japan), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone
[Block isocyanate]
Product name 7982 (manufactured by Baxenden) Isocyanate HDI trimer Blocking agent Dimethylpyrazole
[Organic acid]
2,2'-thiodiacetic acid
[Dispersant]
Product name DISPERBYK-111 (by Big Chemie Japan)
(Evaluation method)
Specimen creation:
Each conductive resin composition for evaluation is applied on the entire surface of a polyester resin substrate using a 300 mesh polyester screen, and then dried in a hot air circulation drying oven at 80 ° C. for 30 minutes to touch. A coating film having good drying property was formed. Thereafter, using a high-pressure mercury lamp as a light source, pattern exposure was performed through a negative mask so that the integrated light amount on the conductive resin composition was 200 mJ / cm ^2, and then 0.4 mass% Na ₂ CO at a liquid temperature of 30 ° C. then developed using a ₃ solution, and washed with water. Finally, it was dried at 140 ° C. for 30 minutes to prepare a test piece on which a conductive pattern film was formed.

Resolution: The minimum line width of the test piece prepared by the above method was evaluated.

Specific Resistance Value: A 4 mm × 10 cm pattern was formed by the above method, and the specific resistance value was calculated by measuring the resistance value and film thickness. In the minimum line, a sample having no defect was evaluated as “good”.

Adhesiveness: Pattern formation of L / S = 30/30 um was performed, cellotape (registered trademark) peel was performed, and no defect was evaluated as “good”. Those with defects were evaluated as “bad”.

Tables 1 and 2 below summarize the experimental conditions and evaluation results of Examples 1 to 4 included in the scope of the present invention and Comparative Examples 1 to 4 that do not fall within the scope of the present invention (no blended isocyanate). It was.

Coating film strength: L / S = 30 / 30um pattern was formed, and a load of 750g was applied using a pencil hardness tester, which is an apparatus described in JIS K5600-5-4, perpendicular to the side of the line. A sample that was not broken when scratched was evaluated as “good”. Those with defects were evaluated as “bad”. The pencil used was Mitsubishi High Uni (Mitsubishi Pencil Co., Ltd., hardness: 3H).

  From Examples 1 to 4, the conductive resin composition according to the present invention can be applied to a heat-sensitive substrate, can ensure excellent conductivity and resolution, and further has a coating strength, a base substrate and It was confirmed that a conductive resin composition excellent in any of the adhesive properties can be obtained.

Claims (8)

A conductive resin for forming a conductive circuit , comprising a carboxyl group-containing resin, a conductive powder, a polyfunctional acrylate monomer, a photopolymerization initiator, and a blocked isocyanate, wherein the carboxyl group-containing resin does not contain a double bond. Composition. The conductive resin composition for forming a conductive circuit according to claim 1, wherein the polyfunctional acrylate monomer is a tetrafunctional acrylate monomer. The conductive resin composition for forming a conductive circuit according to claim 2, wherein the tetrafunctional acrylate monomer is an acrylate monomer represented by the following chemical formula (I).

In formula (I),
X ¹ represents a group containing an acryloyloxy group.
X ² represents a group containing a methacryloyloxy group.
X ³ and X ⁴ each independently represent a group containing an acryloyloxy group or a group containing a methacryloyloxy group. However, at least one of X ³ and X ⁴ represents a group containing a methacryloyloxy group.
L ¹ and L ² are each independently

Represents.
* Represents a binding site with Z.
Z represents a divalent linking group. L ₁ and L ₂ in the general formula (I) are

(In formula (III), * represents a binding site with Z.)
The conductive resin composition for conductive circuit formation of Claim 3 represented by these. The conductive resin composition for conductive circuit formation according to claim 3, wherein the acrylate monomer having a tetrafunctional group represented by the general formula (I) is represented by the following formula (IV).

In formula (IV),
Z ¹ represents an alkylene group.
R ¹ represents a hydrogen atom.
R ² represents a methyl group.
R ³ and R ⁴ each independently represents a hydrogen atom or a methyl group. However, at least one of R ³ and R ⁴ represents a methyl group. The conductive resin composition for forming a conductive circuit according to claim 1, wherein the photopolymerization initiator is an oxime ester type. The conductive resin composition for forming a conductive circuit according to claim 1, wherein the carboxyl group-containing resin not containing a double bond does not further contain an aromatic ring. On a substrate, a conductive circuit formed conductive resin composition according to any one of claims 1 to 7 coated conductive circuit formed is formed by dry.