JP5409954B1 - Conductive resin composition and cured product thereof - Google Patents

Abstract

Disclosed is a conductive resin composition capable of improving coating strength and adhesion.
The conductive resin composition of the present invention comprises a hydroxyl group- and carboxyl group-containing resin having no aromatic ring, a conductive powder, a polyfunctional acrylate monomer, a photopolymerization initiator, and a blocked isocyanate, The total of hydroxyl equivalents of the hydroxyl group and carboxyl group-containing resin having no ring is 300 or more and 3000 or less.
[Selection figure] None

Description

  The present invention relates to a conductive resin composition and a cured product formed using this 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 organic components in the paste, thereby ensuring the conductivity of the cured product 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

  This invention is made | formed in order to eliminate the said problem, and provides the hardened | cured material formed using the conductive resin composition applicable to the base material weak to a heat | fever, and this conductive resin composition. There is.

  Furthermore, this invention is providing the conductive resin composition which can improve both coating-film intensity | strength and adhesiveness with a base material, and the hardened | cured material formed using this conductive resin composition. .

  In order to solve the above problems, the present invention includes a hydroxyl group- and carboxyl group-containing resin having no aromatic ring, a conductive powder, a polyfunctional acrylate monomer, a photopolymerization initiator, and a blocked isocyanate, The total of the hydroxyl group equivalents of the hydroxyl group-containing resin and carboxyl group-containing resin is 300 or more and 3000 or less.

  Alternatively, the present invention includes a hydroxyl group-containing resin having no aromatic ring, a carboxyl group-containing resin conductive powder having no aromatic ring, a polyfunctional acrylate monomer, a photopolymerization initiator, and a blocked isocyanate, Provided is a conductive resin composition in which the total of hydroxyl equivalents of hydroxyl group-containing resin and carboxyl group-containing resin is 300 or more and 3000 or less.

  The conductive resin composition of the present invention is preferably used for forming a conductive circuit.

  And this invention provides the hardened | cured material formed by using this conductive resin composition on a base material.

  According to the present invention, a conductive resin composition that can be applied to a heat-sensitive substrate and that is excellent in both coating film strength and adhesion to a base substrate, and formed using this conductive resin composition Cured product can be provided.

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

(Hydroxyl group and carboxyl group-containing resin having no aromatic ring, the hydroxyl group equivalent of 300 to 3000)
By making this carboxyl group-containing resin have a structure having no aromatic ring, it is possible to suppress the light absorption of the carboxyl group-containing resin itself and to relatively improve the photoreactivity of the (meth) acrylate monomer.

  Further, by having a hydroxyl group and specifying the total of the hydroxyl group equivalents in the range of 300 or more and 3000 or less, the coating film strength and the adhesion to the base substrate can be made particularly excellent. The reason why the total of hydroxyl equivalents is specified to be 300 or more and 3000 or less is that when it is within this range, the coating film strength is improved and the contact resistance value with ITO is lowered.

  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.

  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.

  As the hydroxyl group- and carboxyl group-containing resin having no aromatic ring, a known and commonly used resin compound can be used. Specific examples of this resin are listed below.

(1) copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid, one or more compounds having an unsaturated double bond, and a compound having a hydroxyl group and a (meth) acrylic group. A hydroxyl group- and carboxyl group-containing resin obtained by
(2) a hydroxyl group- and 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;
(3) 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. Hydroxyl group and carboxyl group-containing resin obtained by
(4) A hydroxyl group- and carboxyl group-containing resin obtained by reacting a hydroxyl group-containing polymer with a polybasic acid anhydride 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 hydroxyl group- and carboxyl group-containing resin having no aromatic ring as described above has a large number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes 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.

  Moreover, although the mass average molecular weight of the said carboxyl group containing resin changes with resin frame | skeleton, what is generally in the range of 20,000-150,000, Furthermore, 40,000-100,000 is preferable. If the mass average molecular weight is less than 20,000, tack-free performance may be inferior, the moisture resistance of the conductive pattern film after exposure may be poor, and film loss may occur during development, and 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 a cured film such as a 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.

  As mentioned above, although the case where the hydroxyl group and carboxyl group-containing resin which does not have an aromatic ring are mix | blended is demonstrated, it replaces with said carboxyl group-containing resin, and this invention is the hydroxyl group-containing resin and aromatic which do not have an aromatic ring. A carboxyl group-containing resin having no ring can also be used in combination. Alternatively, at least one of a hydroxyl group-containing resin having no aromatic ring and a carboxyl group-containing resin not having an aromatic ring can be used in combination with the carboxyl group-containing resin. Also in this case, as in the case of “hydroxyl and carboxyl group-containing resin having no aromatic ring”, the total of hydroxyl equivalents of these resins is set to 300 or more and 3000 or less. Further, when the resin is mixed as described above, suitable acid value, mass average molecular weight, blending amount, and the like are the same as those of the above-mentioned “hydroxyl and carboxyl group-containing resin having no aromatic ring”.

  As the hydroxyl group-containing resin having no aromatic ring, a known and commonly used resin composition can be used. Specific examples of this resin are listed below.

(1) ... Functional group having no aromatic ring obtained by copolymerizing a compound having a hydroxyl group and a (meth) acryl group and an unsaturated group-containing compound such as a lower alkyl (meth) acrylate or isobutylene Although a hydroxyl-containing resin is mentioned, it is not limited to this.

  Examples of the hydroxyl group-containing resin having no aromatic ring include Toa Gosei ARUFON UH-2000 series (UH-2000, UH-2032, UH-2041, UHE-2012, etc.).

  Moreover, the well-known and usual resin composition can also be used for carboxyl group-containing resin which does not have an aromatic ring. Specific examples of this resin are listed below.

(1) ... Carboxyl group having no aromatic ring obtained by copolymerizing with unsaturated carboxylic acid such as (meth) acrylic acid and one or more other compounds having an unsaturated double bond Containing resin,
(2)... Carboxyl having no aromatic ring obtained by copolymerizing an acid anhydride having an unsaturated double bond such as maleic anhydride and other compounds having an unsaturated double bond. Although group-containing resin is mentioned, it is not limited to these.

  Examples of the carboxyl group-containing resin having no aromatic ring include Toa Gosei ARUFON UC-3000 series.

(Conductive powder)
As the conductive powder, any conductive powder may be used 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, use of these powders requires attention because the light transmittance is lowered.

  The shape of these powders is not particularly limited, but is preferably other than flakes, particularly preferably acicular or spherical. As a result, a light-transmitting property can be improved and a pattern film having excellent resolution can be formed.

  Such a 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 cured product is improved.

  The powder is an average particle diameter of 10 random powders observed at 10,000 times using an electron microscope (SEM), and the range is preferably 0.1 to 10 μm or less. 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 the conductive powder is preferably 800 to 900 parts by mass with respect to 100 parts by mass of the hydroxyl group- and carboxyl group-containing resin having no aromatic ring. When there are too few compounding ratios, there exists a possibility that resistance value of a conductive resin composition may become high, and sufficient electroconductivity may not be obtained. On the other hand, when a large amount of powder is contained, the light transmittance is deteriorated and the formation of the pattern film by exposure is deteriorated, which is not preferable. In addition, when blending “a hydroxyl group-containing resin not having an aromatic ring and a carboxyl group-containing resin not having an aromatic ring”, further “an aromatic ring having a hydroxyl group and a carboxyl group-containing resin not having an aromatic ring” Also in the case of blending at least one of “hydroxyl group-containing resin not having” and “carboxyl group-containing resin not having an aromatic ring”, the conductive powder of the total amount of these resins is 100 parts by mass. The mixing ratio is preferably 800 to 900 parts by mass.

  Hereinafter, regarding the blending amounts of these resins, “hydroxyl group- and carboxyl group-containing resins having no aromatic ring” will be described as representatives. However, the blending amounts shown therein are “hydroxyl group-containing resins and aromatic rings having no aromatic ring”. In the case of blending “carboxyl group-containing resin not having an aromatic ring”, “hydroxyl group-containing resin not having an aromatic ring” and “having no aromatic ring” together with “hydroxyl group and carboxyl group-containing resin not having an aromatic ring” It is also applied to the case of at least one of “carboxyl group-containing resin”.

(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; Polyhydric acrylates such as lenoxide adducts, propylene oxide adducts, or ε-caprolactone adducts; polyvalent acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide or propylene oxide adducts of these phenols Acrylates; glyceryl diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyglycerides of glycidyl ether such as triglycidyl isocyanurate; 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.

  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, L1 and L2 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 R3 and R4 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.

  The blending amount of such a polyfunctional (meth) acrylate monomer is not particularly limited, but is preferably 10 to 100 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the “hydroxyl group and carboxyl group-containing resin having no aromatic ring”. The ratio of 20 to 80 parts by mass is appropriate. When the blending amount is less than 10 parts by mass, the photocurability is lowered, and formation of a conductive pattern line may be 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 may become 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 photopolymerization initiators, BASF Japan CGI-325, IRGACURE OXE01, IRGACURE OXE02, ADEKA N-1919, NCI-831, Nippon Kagaku Kogyo TOE-004, etc. are preferable. . 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 the “hydroxyl and carboxyl group-containing resin not having an aromatic ring” or the “hydroxyl and carboxyl group-containing resin not having an aromatic ring, an aromatic ring” 0.01 to 30 parts by mass with respect to 100 parts by mass of two or more kinds of resins selected from the group of a hydroxyl group not having a hydroxyl group and a carboxyl group-containing resin having no aromatic ring (hereinafter referred to as a resin) The range of 0.5 to 15 parts by mass is preferable. When the blending amount of the photopolymerization initiator is less than 0.01 parts by mass, the photocurability is insufficient, the conductive pattern film is peeled off, and the characteristics of the conductive pattern film such as chemical resistance and the coating strength are reduced. It is not preferable because there is a case. 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, which is not preferable because deep part curability and coating film strength may be reduced.

(Block isocyanate compound)
In order to improve the toughness of the cured film obtained from the conductive resin composition and the adhesion to the underlying substrate, a compound having a blocked isocyanate group in one molecule, that is, a blocked isocyanate compound is blended. Moreover, heat resistance etc. can be provided by mix | blending a block isocyanate compound.

  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 blocked isocyanate compound may be commercially available, for example, 7950, 79
51, 7960, 7961, 7982, 7990, 7991, 7992 (above, manufactured by Baxenden, trade name) Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Death Module TPLS-2957, TPLS-2062 TPLS-2078, TPLS-2117, Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, Nippon Polyurethane Industry Co., Ltd., trade name), B- 830, B-815, B-846, B-870, B-874, B-882 (trade name, manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T, MF-B60B, MF- K60B, SBN-70 D (Asahi Kasei Chemicals, product name), Karenz MOI-BM (Showa Denko, product name) and the like. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

  The compounds having a blocked isocyanate group can be used alone or in combination of two or more.

  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 resin. When the amount is less than 1 part by mass, sufficient toughness of the coating film may not be obtained, which is not preferable. On the other hand, when it exceeds 100 mass parts, storage stability may fall and it is not preferable.

  Although the dissociation temperature of the blocking agent of the blocked isocyanate is not particularly limited, 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.

  The conductive resin composition of the present invention is a hydroxyl group that does not have the aromatic ring described above in order to further improve the effects of the present invention or to exhibit further effects within a range that does not inhibit the effects of the present invention. Other components exemplified below can be included together with the containing resin, the conductive powder, the polyfunctional (meth) acrylate monomer, the photopolymerization initiator, and the blocked isocyanate compound.

(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 dispersant include 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, DISPERBYK-162, DISPERBYK-163, DISPERBYK -164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, DISPERBYK-185, DISPERBYK-184, DISPERBYK-191 , DISPERBYK-192, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2009, DISPERBYK-2020, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2095, DISPERBYK-2096, DISPERBYK-2150, BYK-P104, BYK -P104S, BYK-P105, BYK-9076, BYK-9077, BYK-220S (by Big Chemie 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), Floren G-450, Floren G-600, Floren G-820, Examples include Floren G-700, Floren DOPA-44, and Floren DOPA-17 (manufactured by Kyoeisha Chemical Co., Ltd.).

  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 hydroxyl group- and carboxyl group-containing resin having no aromatic ring. Within range. 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 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 amount of these thermosetting catalysts is sufficient in the usual quantitative ratio, for example, preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the hydroxyl group and carboxyl group-containing resin having no aromatic ring, More preferably, it is 0.5-15 mass parts.

(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 (above, Showa Denko)

  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 (Sankyo Kasei Co., Ltd .: trade name Gisnet F), 2-dibutylamino-4,6-dimercapto-s-triazine (Sankyo Kasei Co., Ltd .: trade name Gisnet DB) , And 2-anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name: DYSNET 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), 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 cured product)
Next, an example of a method for forming a cured product 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, 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 cured product is cured at a temperature at which the carboxyl group-containing resin is not thermally decomposed. The curing temperature is preferably in the range of 130 ° C to 400 ° C, more preferably 150 to 400 ° C. Since the conductive resin composition of the present invention can obtain a cured product (for example, a conductive pattern film) by curing at a relatively low temperature of 400 ° C. or lower, it can be used on a substrate having low heat resistance or a material having low heat resistance. Can be used.

(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)
Synthesis Example 1 [Hydroxyl and carboxyl group-containing resin having no aromatic ring]
In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, methyl methacrylate, methacrylic acid, and 2-hydroxyethyl acrylate are charged in a molar ratio of 47:15:38, and dipropylene glycol monomethyl ether as a solvent. Azobisisobutyronitrile was added as a catalyst, and the mixture was stirred at 80 ° C. for 6 hours in a nitrogen atmosphere to obtain a “hydroxyl and carboxyl group-containing resin having no aromatic ring” varnish. This carboxyl group-containing resin had a hydroxyl group equivalent of 300.

  Hereinafter, this “hydroxyl group and carboxyl group-containing resin” varnish is referred to as binder A-1 (A-1).

  Moreover, changing the compounding quantity of each component of a synthesis example, the hydroxyl group equivalent "hydroxyl group and carboxyl group containing resin" varnish different from A-1 was created. These are designated as binders A-2 to A-5.

Table 1 shows the hydroxyl group equivalent (preparation ratio and calculated value) of binders A-1 to A-5, methyl methacrylate, methacrylic acid, 2-hydroxyethyl acrylate, and acid value, respectively.

The binder A-6 used in the comparative example is a “resin containing a hydroxyl group and a carboxyl group” varnish having an aromatic ring, a cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., 2200 g of epoxy equivalent 220), 134 g of dimethylolpropionic acid, 648.5 g of acrylic acid, 4.6 g of methylhydroquinone, 1131 g of carbitol acetate and 484.9 g of solvent naphtha were heated and stirred at 90 ° C. to dissolve the reaction mixture. . Next, the reaction solution was cooled to 60 ° C., charged with 13.8 g of triphenylphosphine, heated to 100 ° C., and reacted for about 32 hours to obtain a reaction product having an acid value of 0.5 mgKOH / g. Next, 364.7 g of tetrahydrophthalic anhydride, 137.5 g of carbitol acetate and 58.8 g of solvent naphtha were charged into this, heated to 95 ° C., reacted for about 6 hours, cooled, and the solid acid value of 40 mgKOH / g. A “carboxyl group-containing photosensitive resin” varnish having a nonvolatile content of 65% was obtained.

Synthesis Example 7 [Hydroxyl-containing resin having no aromatic ring, but no carboxyl group]
A flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser is charged with methyl methacrylate, t-butyl methacrylate, and 2-hydroxyethyl acrylate in a molar ratio of 62:15:23, and dipropylene glycol monomethyl ether as a solvent. Azobisisobutyronitrile was added as a catalyst, and the mixture was stirred at 80 ° C. for 6 hours under a nitrogen atmosphere to obtain a “hydroxyl-containing resin having no aromatic ring” varnish. This hydroxyl group-containing resin had a hydroxyl group equivalent of 500.

  Hereinafter, this “hydroxyl group-containing resin” varnish is referred to as binder B-1 (B-1).

Moreover, the "hydroxyl group-containing resin solution" of the hydroxyl equivalent equivalent different from B-1 was created changing the compounding quantity of each component of a synthesis example. These are designated as Binder B-2 (B-2).

Table 2 shows the hydroxyl equivalent (charge ratio and calculated value) of binders B-1 to B-2, methyl methacrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, and acid value to be blended.

Synthesis example [carboxyl group-containing resin having no aromatic ring, but no hydroxyl group]
A flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser is charged with methyl methacrylate, methacrylic acid, and t-butyl methacrylate in a molar ratio of 74:15:11. Dipropylene glycol monomethyl ether as a solvent, catalyst As an azobisisobutyronitrile, the mixture was stirred at 80 ° C. for 6 hours under a nitrogen atmosphere to obtain a “carboxyl group-containing resin having no aromatic ring” varnish. This carboxyl group-containing resin does not contain a hydroxyl group.

  Hereinafter, this “carboxyl group-containing resin” varnish is referred to as binder C-1 (C-1).

Table 3 shows the hydroxyl group equivalent (preparation ratio and calculated value) of binder C-1, methyl methacrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, and acid value, respectively.

[Conductive powder]
Spherical conductive powder: Ag powder (maximum particle size 30 μm or less, average particle size 2 μm (SEM)))
[Acrylate monomer]
Tetrafunctional (meth) acrylate monomer: Trade name; NK Oligo U-4HA (manufactured by Shin-Nakamura Chemical 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 BI7982 (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 was applied on the entire surface of a polyester resin substrate using a 300-mesh polyester screen, and then dried in a hot-air circulating 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. Development was performed using ₃ aqueous solutions 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.

Coating film strength: L / S = 30/30 μm pattern formation was performed under the above-mentioned test piece preparation conditions, and a load of 750 g was applied using a pencil hardness tester which is an apparatus described in JIS K5600-5-4. The case where the line was not broken when scratched perpendicularly to the side of the line was evaluated as “good”. Those with defects were evaluated as “bad”. The pencil used was Mitsubishi High Uni (Mitsubishi Pencil Co., Ltd., hardness: 3H).

Contact resistance value: On a ITO film with a sheet resistance value of 150Ω, I-type lines with a length of 50mm and a width of 100um were formed at 5mm intervals under the conditions for creating the test piece, and a tester was placed on the center of the pattern for measurement. .

Adhesion: L / S = 30/30 μm pattern was formed, cellotape (registered trademark) peel was performed, and no defect was evaluated as “good”. Those with defects were evaluated as “bad”.

Resolution: A line pattern was formed under the conditions for preparing the test piece, and the minimum line width was evaluated.

Specific resistance value: Pattern formation of 4 mm × 10 cm was performed under the above-mentioned test piece preparation conditions, 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”.

About Examples 1-7 included in the scope of the present invention and Comparative Examples 1-7 outside the scope of the present invention, the blending amount of the conductive resin composition, the hydroxyl equivalent, and the evaluation results are shown in Tables 4 and 5 below, respectively. Summarized in

* 1 -OH group calculation method In Examples 1, 2, 3, 4, and 6: Total hydroxyl group equivalent of each binder x Blending ratio (%) In Examples 5 and 7: Hydroxyl equivalent of each binder x 100 / Total amount
* 2 Does not contain hydroxyl groups

* 1 Calculation method of hydroxyl equivalent In Comparative Examples 1, 2, 3, 4, 5, 7: Total hydroxyl equivalent of each binder x Total proportion of blending ratio (%) In Comparative Examples 3 and 6: Hydroxyl equivalent of each binder x 100 / total amount
* 2 Meaning that no hydroxyl group is contained From Examples 1 to 7, the conductive resin composition according to the present invention can be applied to a heat-sensitive substrate, and can ensure excellent conductivity and resolution. Furthermore, it was confirmed that even under severe conditions, it is possible to obtain a conductive resin composition excellent in both coating film strength and adhesion to the base substrate.

Claims (6)

  Hydroxyl group and carboxyl group-containing resin having no aromatic ring, conductive powder, polyfunctional acrylate monomer, photopolymerization initiator, and hydroxyl group equivalent of hydroxyl group and carboxyl group-containing resin having no aromatic ring A total of 300 or more and 3000 or less is a conductive resin composition.   Two or more kinds of resins selected from the group consisting of a hydroxyl group- and carboxyl group-containing resin having no aromatic ring, a hydroxyl group-containing resin having no aromatic ring, and a carboxyl group-containing resin having no aromatic ring, conductive powder, A conductive resin composition comprising a polyfunctional acrylate monomer, a photopolymerization initiator, and a blocked isocyanate, wherein the total of hydroxyl equivalents of the two or more resins is from 300 to 3,000.   The conductive resin composition according to claim 1, wherein the hydroxyl group- and carboxyl group-containing resin having no aromatic ring does not contain a double bond.   Two or more kinds of resins selected from the group consisting of the hydroxyl group- and carboxyl group-containing resin having no aromatic ring, the hydroxyl group-containing resin not having an aromatic ring, and the carboxyl group-containing resin not having an aromatic ring, 3. The conductive resin composition according to claim 2, which does not contain a double bond.   The conductive resin composition according to claim 1, wherein the conductive resin composition is for forming a conductive circuit.   Hardened | cured material formed by apply | coating and drying the resin composition in any one of Claims 1-5 on a base material.