KR101451479B1 - Conductive resin composition and conductive circuit - Google Patents

Abstract

The present invention relates to a conductive resin composition comprising a carboxyl group-containing resin, an electrically conductive powder, at least any one of 2 to 4 functional group acrylate monomers and a photopolymerization initiator, applicable to a substrate which is weak to heat, Provided is a conductive circuit formed using a conductive resin composition.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a conductive resin composition,

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

Japanese Patent Laid-Open Publication No. 2003-280181 and Patent Document 2: Japanese Patent No. 4411113 disclose a conductive paste for forming a conductive pattern 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 DEG C or higher to remove the organic components in the paste to secure the conductivity of the conductive circuit layer.

However, since such a photosensitive conductive paste is baked at a temperature of 500 캜 or more, there is a problem that it is difficult to apply it to a substrate which is weak against heat.

An object of the present invention is to provide a conductive resin composition which can be applied to a substrate which is weak against heat and which can secure excellent conductivity, and a conductive circuit formed by using the conductive resin composition.

In order to solve the above problems, the present invention provides a conductive resin composition comprising a carboxyl group-containing resin, an electrically conductive powder, at least any one of 2-4 functional group acrylate monomers, and a photopolymerization initiator, Provided is a conductive circuit formed by using a conductive resin composition.

According to the present invention, it is possible to provide a conductive resin composition which can be applied to a substrate which is weak to heat and can secure excellent conductivity, and a conductive circuit formed using the conductive resin composition.

The conductive resin composition of the present invention has the largest feature in that the number of functional groups of the acrylate monomer is 2 to 4.

The number of functional groups of the acrylate monomer is specified to be 2 to 4 for the following reasons. When the number of the functional groups of the acrylate monomer is 2 or more, the photoreactivity is improved and the resolution is excellent. In addition, since the number of functional groups is 4 or less, the reaction proceeds more rapidly between functional groups of other acrylate monomers than in the case of reacting functional groups in the molecule of the acrylate monomer during photo-curing. As a result, intermolecular bonds are formed between the plurality of acrylate monomers, so that the conductive resin composition is cured and shrunk. Further, the intermolecular reaction is further promoted by heat treatment at a low temperature, so that the conductive resin composition is sufficiently cured and shrunk. As a result, it is considered that the conductive powder becomes denser and the resistivity value of the conductive pattern film becomes lower.

On the other hand, when the number of functional groups of the acrylate monomer is one, resolution is insufficient and resolution is not obtained. On the other hand, when the number of functional groups of the acrylate monomer is 5 or more, since the functional groups are preferentially reacted in the molecule of the acrylate monomer, intermolecular bonding is hardly formed. As a result, since the conductive resin composition is not sufficiently cured and shrunk, it is considered that the conductive powder is not densified and the resistivity value of the conductive pattern film is difficult to lower.

Therefore, the conductive resin composition of the present invention exhibits excellent conductivity even when it is treated at a temperature lower than 500 ° C at a temperature at which the carboxyl group-containing resin is thermally decomposed. Therefore, the conductive resin composition of the present invention can be applied to a substrate which is weak to heat. In addition, the conductive resin composition of the present invention can also ensure excellent resolution.

(A component to be blended in the conductive resin composition)

(Carboxyl group-containing resin)

As the carboxyl group-containing resin, a known 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 containing no double bond is preferable. Since the carboxyl group-containing resin containing no double bond does not react with the acrylate monomer, no intermolecular bond is formed. Therefore, the carboxyl group-containing resin is easily removed at the time of development because the molecular weight is not increased. As a result, the conductive powder becomes dense and the resistivity value of the conductive pattern film can be lowered.

In addition, even if the carboxyl group-containing resin has a very small proportion of double bonds, the carboxyl group-containing resin containing such a double bond may contain a double bond in the scope of the present invention Containing carboxyl group-containing resin ". As the carboxyl group-containing resin containing no double bond, for example, there can be mentioned those having a double bond equivalent of 10,000 or more.

The carboxyl group-containing resin is preferably a carboxyl group-containing resin containing no double bond and aromatic ring among the carboxyl group-containing resins not containing a double bond. By making the structure not contain an aromatic ring, the light absorption of the carboxyl group-containing resin itself can be suppressed and the photoreactivity of the acrylate monomer can be relatively improved.

Specific examples of the carboxyl group-containing resin containing no double bond and aromatic ring are listed below.

(1) a carboxyl group-containing resin obtained by copolymerizing at least one unsaturated carboxylic acid such as (meth) acrylic acid with at least one compound 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 copolymer of an acid anhydride having an unsaturated double bond and a compound having another unsaturated double bond with a compound having a hydroxyl group,

(4) a carboxyl group-containing resin obtained by reacting a saturated carboxylic acid with a copolymer of a compound having an epoxy group and an unsaturated double bond and a compound having an unsaturated double bond, and reacting the produced secondary hydroxyl group with a polybasic acid anhydride,

(5) a carboxyl group-containing resin obtained by reacting a hydroxyl group-containing polymer with a polybasic acid anhydride

However, the present invention is not limited to this.

In the present specification, (meth) acrylic acid is a generic term for 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 a large number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkali solution becomes possible.

The acid value of the carboxyl group-containing resin is preferably in the range of 40 to 200 mgKOH / g, and 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 portion by the developer proceeds, It is not preferable because it dissolves and peels off as a developing solution without distinction between the light portion and the unexposed portion and it becomes difficult to draw a normal conductive pattern.

The mass 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 deteriorate, the moisture resistance of the conductive pattern film after exposure may deteriorate, the film may decrease during development, and the resolution may deteriorate greatly . On the other hand, if the mass average molecular weight exceeds 150,000, the developability may be markedly deteriorated, and the storage stability may be deteriorated.

The amount of such a carboxyl group-containing resin is preferably 3 to 50 mass%, more preferably 5 to 30 mass%, in the total conductive resin composition. If it 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 is increased or the coating property is lowered.

(Conductive powder)

First, any material may be used as the material of the conductive powder as long as it imparts conductivity to the conductive resin composition. Examples of the conductive powder include Ag, Au, Pt, Pd, Ni, Cu, Al, Sn, Pb, Zn, Fe, Ir, Os, Rh, W, Mo and Ru. These conductive powders may be used in the form of the above-described component alone, but may also be used in the form of alloys or oxides. In addition, tin oxide (SnO ₂ ), indium oxide (In ₂ O ₃ ), indium tin oxide (ITO), or the like may be used. The conductive powder may be a carbon powder such as carbon black, graphite, carbon nanotube, or the like. Note, however, that light transmittance is deteriorated.

The shape of the conductive powder is not particularly limited, but it is preferable that the shape of the conductive powder is other than a flake shape, especially a needle shape or a spherical shape. As a result, the light transmittance is improved and a conductive pattern film having excellent resolution can be formed.

It is preferable that such a conductive powder has a maximum particle diameter of 30 mu m or less in order to form a fine line. By setting the maximum particle diameter to 30 mu m or less, the resolution of the conductive pattern film is improved.

The conductive powder is preferably an average particle diameter of 10 random conductive powders observed at 10,000 times using an electron microscope (SEM), and its range is preferably 0.1 to 10 mu m or less. If the average particle diameter is smaller than this range, the resistance value is increased due to the increase of the contact resistance, which is not preferable. On the other hand, when the average particle diameter is larger than the above range, when a conductor pattern is printed using a mesh screen plate, workability is deteriorated by clogging of the screen, and formation of fine lines becomes difficult Which is undesirable. The average particle size measured by a micro track is preferably 0.5 to 3.5 mu m.

The blending ratio of such conductive powder is preferably 800 to 900 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. If the mixing ratio of the conductive powder is too small, the resistance value of the conductive resin composition becomes high, and there is a fear that sufficient conductivity can not be obtained. On the other hand, when the conductive powder is contained in a large amount, the light transmittance is deteriorated and the formation of the conductive pattern film due to exposure deteriorates, which is not preferable.

(Acrylate monomers having 2 to 4 functional groups)

As the acrylate monomer, at least one of 2 to 4 functional group acrylate monomers is used.

Specific examples of the acrylate monomers having 2 to 4 functional groups are shown below.

(Acrylate monomer of bifunctional group)

Examples of the bifunctional (meth) acrylate monomers include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, (Meth) acrylate, bisphenol A (poly) ethoxydi (meth) acrylate, bisphenol A (poly) propoxydi (meth) acrylate, bisphenol F Di (meth) acrylate of ε-caprolactone adduct of neopentyl glycol diacrylate, glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate hydroxypivalic acid (for example, KAYARAD HX-220, HX-620, etc.), and the like.

(Acrylate monomer of trifunctional group)

Examples of the acrylate monomer of the trifunctional group include triacrylate or trimethacrylate of trihydric or higher polyhydric alcohols such as trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate and pentaerythritol trimethacrylate, And acrylates.

(4-functional acrylate monomers)

As the acrylate monomer of the 4-functional group, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate and the like can be given.

As the acrylate monomer of the tetrafunctional group, urethane acrylate monomers or ester acrylates having four functional groups represented by the following formulas (I) and (II) are preferable.

In the 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. Provided that 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 a bonding site with Z;

Z represents a divalent linking group.

As the acrylate monomers, L ¹ and L ² in the formula (I)

Is preferably a urethane acrylate represented by the following formula In the formula (III), * represents a bonding site with Z.

As the monomer represented by the formula (I), urethane acrylate represented by the following formula (IV) is preferable.

In the 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 represent a hydrogen atom or a methyl group. Provided that at least one of R ³ and R ⁴ represents a methyl group.

As the acrylate monomer having four functional groups, urethane acrylate or ester acrylate having one to one acrylic and methacrylic groups is particularly preferable.

As the urethane acrylate or ester acrylate of such a four-functional group, for example, it is preferable to add acrylic acid to glycidyl methacrylate and to react the resulting hydroxyl group with diisocyanate or dicarboxylic acid.

As a commercially available product of urethane acrylate having four functional groups, for example, NK Oligo U-4 HA (trade name, manufactured by Shin Nakamura Chemical Industries, Ltd.) and the like can be given.

Among these acrylate monomers having 2 to 4 functional groups, acrylate monomers having 4 functional groups represented by the formula (I) are preferable. Since the tetrafunctional acrylate monomer has a large number of functional groups, it is excellent in light reactivity and excellent in resolution.

Since X ¹ and X ² of the acrylate monomers of the four functional groups are different from each other, the reaction of X ¹ and X ² in the molecule during the photo-curing is slow. However, X ¹ or X ² of the acrylate monomer in the molecules with X ¹ or X ² of other acrylate monomer reacts faster than the reaction molecules. As a result, an intermolecular bond is formed between a plurality of acrylate monomers, so that the conductive resin composition is further cured and shrunk. Further, the intermolecular reaction is further promoted by heat treatment at a low temperature, so that the conductive resin composition is sufficiently cured and shrunk. As a result, it is considered that the conductive powder is dense and the resistivity value of the conductive pattern film is further lowered.

The blending amount of the acrylate monomer having 2 to 4 functional groups is not particularly limited, but is preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the blending amount is less than 10 parts by mass, photo-curability is deteriorated and it is not preferable because formation of a line of a conductive pattern becomes difficult due to alkali development after irradiation with active energy rays. On the other hand, if it exceeds 100 parts by mass, the solubility in an alkali aqueous solution decreases, and the conductive pattern film becomes weak, which is not preferable.

(Photopolymerization initiator)

The photopolymerization initiator is not particularly limited and may be a benzoin group or a phosphine oxide group. However, an acetophenone photopolymerization initiator having an oxime ester group having a group represented by the following formula (V) or a group represented by the following formula (VI) .

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

Of these oxime ester-based photopolymerization initiators, CGI-325, IRGACURE OXE01, Irgacure OXE02, N-1919 manufactured by ADEKA, NCI- 831, TOE-004 manufactured by Nippon Kagaku Kogyo Co., Ltd. and the like are preferable. As the photopolymerization initiator, Irgacure 389 may also be used. These photopolymerization initiators may be used alone or in combination of two or more.

Examples of the acetophenone photopolymerization initiator having a group represented by the above formula (VI) include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopro- Amino-1- (4-morpholinophenyl) -butan-1-one and 2- (dimethylamino) -2 - [ ] -1-butanone, N, N-dimethylaminoacetophenone, and the like. Commercial 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 preferably in the range of 0.01 to 30 parts by mass, and more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the blending amount of the photopolymerization initiator is less than 0.01 part by mass, the photocurability is insufficient, the conductive pattern film is peeled off, and the properties of the conductive pattern film such as chemical resistance are lowered. On the other hand, if it exceeds 30 parts by mass, the light absorption at the surface of the conductive pattern film of the photopolymerization initiator becomes serious, and the deep portion curing property tends to be lowered.

The conductive resin composition of the present invention may contain the above-mentioned carboxyl group-containing resin, conductive powder, 2 to 4 functional groups, and the like, in order to further improve the effect of the present invention or to exert other effects within a range not inhibiting the effect of the present invention , And other components exemplified below together with the photopolymerization initiator.

(Organic acid)

As the organic acid, an organic acid having no aromatic ring is preferable. By incorporating an organic acid having no aromatic ring, the light absorptivity of the organic acid itself is suppressed, the photoreactivity of the acrylate monomer having 2 to 4 functional groups is relatively improved, and excellent resolution can be obtained.

Specific examples of the organic acid include organic acids such as 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, malic acid, salicylic acid, Carboxylic acids such as phenylacetic acid, acrylic acid, maleic acid, fumaric acid and crotonic acid; Of phosphorous acid such as dibutyl phthalate, dibutyl phthalate, dibutyl phthalate, dibutyl phthalate, dibutyl phthalate, dibutyl phosphite, butyl phosphite, dimethyl phosphite, methyl phosphite, dipyridene anesinate, propyl phosphite, diphenyl phosphite, phenyl phosphite, diisopropyl phosphite, Mono or diesters; Such as dibutyl phosphate, dibutyl phosphate, butyl phosphate, dimethyl phosphate, methyl phosphate, dipropyl phosphate, propyl phosphate, diphenyl phosphate, phenyl phosphate, diisopropyl phosphate, isopropyl phosphate, and n-butyl- Mono or diesters, and the like. 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 amount of the organic acid is less than 0.1 part by mass based on 100 parts by mass of the conductive powder, the conductive powder reacts with the carboxyl group-containing resin to lower long-term storage stability. When the amount of the organic acid is more than 5 parts by mass, Moisture and the like in the air can be easily absorbed.

(Dispersant)

By blending a dispersant, dispersibility and sedimentation of the conductive resin composition can be improved.

Examples of the dispersing agent include antistatic agents such as ANTI-TERRA-U, ANTI-TERA-U100, ANTI-TERA-204, ANTI- -103, Dispersive-106, Dispersive-108, Dispersive-109, Dispersive-110, Dispersive-111, Dispersive-112, Dispersive-116, Dispersive- -142, Disperby-145, Disperby-161, Disperby-162, Disperby-163, Disperobic-164, Disperobic-166, Disperobic-167, Disperobic- -171, Dispersive-174, Dispersive-180, Dispersive-182, Dispersive-183, Dispersive-185, Dispersive-184, Dispersive-191, Dispersive-192, Dispersive- BYK-P104S, BYK-P104S, BYK-P104S, BYK-P104S, BYK-P104S, BYK-P104S, BYK-P104S, DISK- , BYK-P105, BYK-9076, BYK-9077, BYK-220S (manufactured by Big Chemie Japan K.K.) Dispalon PW-36, Dispalon DA-400, Dispalon KS-860, Dispalon KS-873N, Dispalon 7004, Dispalon 1830, Dispalon 1860, Dispalon 1850, 703-50 (ex Sumoto Chemical Industries, Ltd.), Floren G-450, Floren G-600, Floren G-820, Floren G-700, Floren DOPA-44, Floren DOPA-17 Manufactured by Kyoeisha Chemical Co., Ltd.).

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

(Photopolymerization inhibitor)

By adding a photopolymerization inhibitor, a certain amount of radical polymerization depending on the kind of the polymerization inhibitor and the addition amount thereof can be suppressed during the radical polymerization occurring in the conductive resin composition by exposure. Thus, it is possible to suppress the photoreaction to weak light such as scattered light. Therefore, a line of a finer conductive pattern film can be formed in a sharp manner, and thus can be preferably used. The photopolymerization inhibitor is not particularly limited as long as it can be used as a photopolymerization inhibitor. Examples of the photopolymerization inhibitor include p-benzoquinone, naphthoquinone, di-t-butyl paracresol, hydroquinone monomethyl ether,? -Naphthol, acetamidine Acetate, hydrazine hydrochloride, trimethylbenzylammonium chloride, dinitrobenzene, picric acid, quinone dioxime, pyrogallol, tannic acid, resorcin, couperone, 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 based on 100 parts by mass of the carboxyl group-containing resin. If it is less than this range, the effect of the polymerization inhibition is not exerted, and even at a low exposure dose due to light scattering, it is hardened and the line shape is likely to be thickened. Further, when the amount is larger than the above range, the sensitivity is lowered, and a large amount of exposure is required.

(filling)

In the conductive resin composition of the present invention, a filler may be added as needed to increase the physical strength of the coating film. As such a filler, an inorganic or organic filler for publicly known generations can be used. In particular, barium sulfate, silica, hydrotalcite and talc are preferably used.

(Thermosetting component)

A thermosetting component can be added to the conductive resin composition of the present invention to impart heat resistance. Examples of the thermosetting component used in the present invention include amine resins such as melamine resin and benzoguanamine resin, block isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins and melamine derivatives A known thermosetting resin may be used. Particularly preferred are thermosetting components having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in the molecule.

The thermosetting component having at least two cyclic (thio) ether groups in the molecule is a compound having at least two, three or four or five membered cyclic ether groups or cyclic thioether groups in the molecule, For example, 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 oxetane compound, a compound having two or more thioether groups in the molecule , An episulfide resin, and the like.

Examples of the polyfunctional epoxy compound include JER828, JER834, JER1001, JER1004 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon 840 manufactured by Dainippon Ink and Chemicals, Inc., Epiclon 850, Epiclon 1050, Epiclon 2055, YD-013, YD-127, YD-128 manufactured by Kasei Corporation, DER317, DER331, DER661, DER664 manufactured by Dow Chemical Company, Araldite 6071 of BASF Japan, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Co., Ltd., AER330, AER331 manufactured by Asahi Kasei Corporation, Bisphenol A type epoxy resins such as AER661 and AER664 (all trade names); JERYL903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon 152 manufactured by Dainippon Ink and Chemicals, Inc., Epiclon 165, Epototo YDB-400, YDB-500 manufactured by Dotogasei Co., DER542 manufactured by Dow Chemical Co., Brominated epoxy resin such as Aralidite 8011 manufactured by Japan Industrial Co., Ltd., SUMI EPOXY ESB-400, ESB-700 manufactured by Sumitomo Chemical Industry Co., Ltd., AER711 and AER714 manufactured by Asahi Kasei Corporation; JER152, JER154 manufactured by Japan Epoxy Resin Co., DEN431, DEN438 manufactured by Dow Chemical Company, Epiclon N-730 manufactured by Dainippon Ink and Chemicals, Inc., Epiclon N-770, Epiclon N-865, Araldite ECN1273, Araldite ECN1299, Araldite XPY307, EPPN-201 manufactured by Nippon Kayaku Co., Ltd., EOCN-701, YDCN- (All trade names) manufactured by Asahi Chemical Industry Co., Ltd., AERECN-235 and ECN-299 manufactured by Asahi Kasei Kogyo Co., Of novolak type epoxy resin; Epiclon 830 manufactured by Dainippon Ink and Chemicals, Inc., JER 807 manufactured by Japan Epoxy Resin Co., Ltd., Epototo YDF-170, YDF-175, YDF-2004 manufactured by Tokuga Seisaku Co., Ltd., Araldite XPY306 manufactured by BASF Japan (All trade names) of bisphenol F type epoxy resin; Hydrogenated bisphenol A type epoxy resins such as Epototo ST-2004, ST-2007 and ST-3000 (trade name) manufactured by Tokuga Seisakusho; JER604 manufactured by Japan Epoxy Resin Co., Ltd., Ephoto YH-434 manufactured by Toko Kasei Co., Araldite MY720 manufactured by BASF Japan, Sumi EPO ELM-120 manufactured by Sumitomo Chemical Co., Ltd. A diallylamine type epoxy resin; Heidantoin-type epoxy resin such as Araldite CY-350 (trade name) manufactured by BASF Japan; Alicyclic epoxy resins such as Celloxide 2021 manufactured by Daicel Chemical Industries, Ltd., Araldite CY175 and CY179 manufactured by BASF Japan Co. (all trade names); YL-933 manufactured by Japan Epoxy Resin Co., Ltd., T.E.N. produced by Dow Chemical Co., EPPN-501, EPPN-502 (all trade names), trihydroxyphenylmethane type epoxy resin; A biscylenol type or biphenol type epoxy resin such as YL-6056, YX-4000 and YL-6121 (all trade names) manufactured by Japan Epoxy Resins, or a mixture thereof; Bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., and EXA-1514 (trade name) manufactured by Dainippon Ink and Chemicals, Inc.; Bisphenol A novolak type epoxy resins such as JER157S (trade name) manufactured by Japan Epoxy Resin Co., Ltd.; JERYL-931 manufactured by Japan Epoxy Resin Co., Ltd., Araldite 163 manufactured by BASF Japan Co., Ltd. (all trade names), and the like; Araldite PT810 manufactured by BASF Japan Ltd., TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names), and the like; Diglycidyl phthalate resins such as Blumer DGT manufactured by Nippon Oil Polymer Co., Ltd.; Tetraglycidylcylenoyl ethane resins such as ZX-1063 manufactured by Toko Chemical Co., Ltd.; Epoxy resin containing naphthalene group such as ESN-190, ESN-360 manufactured by Shinnitetsu Chemical Co., Ltd., HP-4032, EXA-4750 and EXA-4700 manufactured by Dainippon Ink and Chemicals, Incorporated; An epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink and Chemicals, Incorporated; Glycidyl methacrylate copolymer-based epoxy resins such as CP-50S and CP-50M manufactured by Nippon Yushi Co., Ltd.; A copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives (e.g., PB-3600 manufactured by Daicel Chemical Industries, Ltd.) and CTBN-modified epoxy resins (e.g., YR-102 and YR-450 manufactured by Tokuga Seisakusho Co., Ltd.) , But is not limited thereto. These epoxy resins may be used alone or in combination of two or more. Of these, novolak type epoxy resins, heterocyclic epoxy resins, bisphenol A type epoxy resins, and mixtures thereof are particularly preferable.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [ Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (P-hydroxystyrene), cardo-type bisphenols, calixarene, calix resorcinarene or silsesquioxane, as well as polyfunctional hydrocarbons such as norbornene, And etherified with a resin having a hydroxyl group such as quinoxane. Other than these, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate may be mentioned.

Examples of the compound having two or more cyclic thioether groups in the molecule include a bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resin Co., An episulfide resin in which the oxygen atom of the epoxy group of the novolac epoxy resin is substituted with a sulfur atom can also be used by using the same synthetic method.

Further, in the conductive resin composition of the present invention, a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule may be added in order to improve the curability of the conductive resin composition and the toughness of the resulting cured film. Such a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound or a compound having two or more blocked isocyanate groups in one molecule, that is, a block isocyanate compound And the like.

As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m - xylylene diisocyanate and 2,4-tolylene diisocyanate dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. Examples of the above-mentioned isocyanate compounds include adduct, burette and isocyanurate.

The blocked isocyanate group contained in the block isocyanate compound is a group in which the isocyanate group is protected by a reaction with the blocking agent and is temporarily inactivated. When heated to a predetermined temperature, the block agent dissociates to produce an isocyanate group.

As the block isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate block agent is used. Examples of the isocyanate compound capable of reacting with the block agent include isocyanurate type, buret type, and adduct type. As the isocyanate compound, for example, the same aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate as described above is used.

Examples of the isocyanate block agent include phenolic block agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam-based blocking agents such as? -caprolactam,? -valerolactam,? -butyrolactam and? -propiolactam; Active methylene blockers such as ethyl acetoacetate and acetylacetone; But are not limited to, 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, Alcohol-based blocking agents such as butyl acetate, diacetone alcohol, methyl lactate and ethyl lactate; Oxime-based blocking agents such as formaldehyde scavengers, acetal aldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime; Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thiophenol and ethyl thiophenol; Acid amide type block agents such as acetic acid amide, benzamide and the like; Imide block agents such as succinic acid imide and maleic acid imide; Amine-based blocking agents such as xylidine, aniline, butylamine, and dibutylamine; Imidazole-based blocking agents such as imidazole and 2-ethylimidazole; Imine blockers such as methylene imine and propylene imine, and the like.

The block isocyanate compound may be a commercially available one, for example, 7950, 7951, 7960, 7961, 7982, 7990, 7991, 7992 (trade names, manufactured by Baxenden), Sumidor BL- , BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmotam 2170, Desmotrim 2265 (trade name, manufactured by Sumitomo Bayer Urethane Co., , Coronate 2513, Coronate 2520 (manufactured by Nippon Polyurethane Industry Co., Ltd.), B-830, B-815, B-846, B-870, B-874 and B-882 (manufactured by Mitsui Takeda Chemical Co., MF (trade name, manufactured by Showa Denko K.K., trade name, manufactured by Showa Denko K.K.), TPA-B80E, 17B-60PX, E402-B80T, MF- ) And the like. Further, SMILDIR BL-3175 and BL-4265 are obtained by using methyl ethyl oxime as a block agent.

The above-mentioned compounds having two or more isocyanate groups or blocked isocyanate groups in one molecule may be used alone or in combination of two or more.

The compounding amount of the compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is preferably 1 to 100 parts by mass, more preferably 2 to 70 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the blending amount is less than 1 part by mass, sufficient toughness of the coating film can not be obtained, which is not preferable. On the other hand, if it exceeds 100 parts by mass, the storage stability is lowered, which is not preferable.

(Thermosetting catalyst)

When a thermosetting component having two or more cyclic (thio) ether groups in the molecule is used in the conductive resin composition of the present invention, it is preferable that the composition contains a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- Compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine. 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd., U-CAT DBU, U-CATSA102, U-CAT5002 (all of bicyclic amidine compounds and salts thereof), and the like. But is not limited thereto and may be a catalyst for thermal curing of an epoxy resin or an oxetane compound or a catalyst for accelerating a reaction between an epoxy group and / or an oxetanyl group and a carboxyl group, or a mixture of two or more thereof may be used . Further, it is also possible to use one or more compounds selected from the group consisting of guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, isocyanuric acid Triazine derivatives such as adducts can be used, and a compound that also functions as such an adhesion-imparting agent is preferably used in combination with the above-mentioned thermosetting catalyst.

The amount of these thermosetting catalysts is usually sufficient in a usual quantitative ratio, and is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the thermosetting component having two or more cyclic (thio) ether groups in the carboxyl- More preferably 0.5 to 15 parts by mass.

(Thermal polymerization inhibitor)

The thermal polymerization inhibitor may be used to prevent thermal polymerization or aging polymerization of the conductive resin composition of the present invention. Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy- Benzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine,? -Naphthol, 2,6-di-t-butyl-4-cresol, 2,2'- butylphenol), reactants such as pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agents, methyl salicylate and phenothiazine, nitroso compounds, nitroso compounds and chelates of Al And the like.

(Chain transfer agent)

In the conductive resin composition of the present invention, N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole and the like known as chain transfer agents may be used for improving the sensitivity. Specific examples of the chain transfer agent include chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; Chain transfer agents having a hydroxyl group such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropane diol, mercaptobutanediol, hydroxybenzene thiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (ethylene dioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecylmercaptan , Propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclopentanethiol, cyclohexanethiol, thioglycerol, 4,4-thiobisbenzenethiol, and the like.

Further, a multifunctional mercaptan-based compound can be used, and there is no particular limitation, and examples thereof include hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethyl alcohol Aliphatic thiols such as xylylene dimethacrylate and feed, aromatic thiols such as xylylene dimercaptan, 4,4'-dimercaptodiphenylsulfide and 1,4-benzenedithiol; (Mercaptoacetate), ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylol ethane tris Poly (mercaptoacetates) of polyhydric alcohols such as mercaptoacetate), pentaerythritol tetrakis (mercaptoacetate), dipentaerythritol hexakis (mercaptoacetate); (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate), propylene glycol bis (3-mercaptopropionate), glycerin tris (3-mercaptopropionate) , Trimethylol ethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis - mercapto propionate); poly (3-mercaptopropionates) of polyhydric alcohols; 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine- 3H, 5H) -triene, and pentaerythritol tetrakis (3-mercaptobutyrate).

Examples of commercially available products thereof include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP and TEMPIC (manufactured by Sakai Chemical Industry Co., BD1 and car lens -NR1 (manufactured by Showa Denko K.K.).

Examples of the heterocyclic compound having a mercapto group functioning as a chain transfer agent include mercapto-4-butyrolactone (alias: 2-mercapto-4-butanololide), 2-mercapto- 4-butyrolactone, 2-mercapto-4-butyrolactone, 2-mercapto-4-butyrolactam, N-methoxy- 2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butyrolactam, N- 2-mercapto-4-butyrolactam, N- (2-ethoxy) ethyl-2-mercapto- Mercapto-5-valerolactone, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam Mercapto-5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, 2-mercaptobenzothiazole Mercapto-5-methylthiothiadiazole, 2-mercapto-6-hexanolactam, 2,4,6-trimercapto-s-triazine (Sankyo Kasei 2-dibutylamino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Kabushiki Kaisha: product name: Zysnet DB) and 2-anilino-4,6 -Dimercapto-s-triazine (manufactured by Sankyo Kasei Kabushiki Kaisha: product name: Zisset AF).

Particularly, as a heterocyclic compound having a mercapto group which is a chain transfer agent which does not impair the developability of the conductive resin composition, there can be exemplified 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2- Mercapto-4-methyl-4H-1,2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol , 1-phenyl-5-mercapto-1H-tetrazole are preferable. These chain transfer agents may be used alone or in combination of two or more.

(Other ingredients added)

Needless to say, the conductive resin composition of the present invention can be blended with known components, for example, a thickener, a defoaming agent, a leveling agent, a coupling agent, an antioxidant,

(Formation of a conductive circuit)

Next, an example of a method of 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 triaxial roll or a blender is used for kneading and dispersing the above essential components and optional components.

The conductive resin composition thus dispersed is applied on a substrate by a suitable application method such as a screen printing method, a bar coater, or a blade coater. Subsequently, the organic solvent is evaporated by drying at a temperature at which the carboxyl group-containing resin is not thermally decomposed at a temperature of, for example, about 60 to 120 DEG C for about 5 to about 40 minutes in a hot air circulation type drying furnace or a far- Is obtained.

In addition, the conductive resin composition may be formed in advance in the form of a film, and in this case, the film may be laminated on the substrate.

Subsequently, contact exposure or noncontact 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, and the like are used. As the exposure dose, the accumulated light quantity can be set to a low light quantity of 200 mJ / cm ² or less. It is also possible to form a pattern on a coating film by a laser direct imaging apparatus without using a mask.

Subsequently, the coating film is patterned by a phenomenon such as spraying or dipping. Examples of the developer include aqueous solutions of metal alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium silicate; aqueous amine solutions such as monoethanolamine, diethanolamine and triethanolamine; especially aqueous alkali solutions having a concentration of about 1.5% But it is preferable that the carboxyl group of the carboxyl group-containing resin in the conductive resin composition is saponified to remove the uncured portion (unexposed portion), and the developer is not limited to the above-mentioned developer. Further, in order to remove unnecessary developing solution after development, it is preferable to conduct the acid treatment or acid neutralization.

Further, 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 占 폚 or lower, more preferably 140 占 폚 or lower, and even more preferably 130 占 폚 or lower.

In these processes, since the substrate is not fired at a high temperature of 500 DEG C, a substrate made of resin having no heat resistance can be used. Specific examples of the resin base material include polyimide, polyester resin, polyethersulfone (PES), polystyrene (PS), polymethylmethacrylate (PMMA), polycarbonate (PC) (PA), polypropylene (PP), and polyphenylene oxide (PPO). A polyester resin can be preferably used. It may also be a glass substrate or the like.

(Example)

Hereinafter, the present invention will be described in detail based on examples. However, the present invention is not limited to these embodiments.

(Blending component)

[Resin containing a carboxyl group]

Synthesis Example 1

Methyl methacrylate and methacrylic acid were added in a molar ratio of 0.87: 0.13 to a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, and dipropylene glycol monomethyl ether as a solvent and azobisisobutyronitrile as a catalyst And the mixture was stirred at 80 DEG C for 6 hours in a nitrogen atmosphere to obtain a carboxyl group-containing resin solution. The carboxyl group-containing resin had a mass average molecular weight of about 10,000 and an acid value of 74 mgKOH / g. The mass average molecular weight of the obtained carboxyl group-containing resin was measured by the same method as that described in Example 1 except that 3 parts by weight of POD (registered trademark) KF-804, KF-803 and KF-802 manufactured by Shimadzu Seisakusho Pump LC- ≪ / RTI > by high performance liquid chromatography. Hereinafter, this carboxyl group-containing resin solution is referred to as A-1 varnish. Further, 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 diameter 30 mu m or less, average particle diameter 2 mu m (SEM)))

Needle-shaped conductive powder: Ag powder (maximum particle diameter 30 mu m or less, average particle diameter 2 mu m (SEM)))

[Acrylate Monomer]

Monofunctional acrylate monomer: trade name; Phenol EO-modified acrylate

Acrylate monomers of 2 functional groups: trade name; KAYARAD HX-220 (manufactured by Nippon Kayaku Co., Ltd.)

Acrylate monomers of 3 functional groups: trade name; Aronix M-350 (manufactured by Toagosei Co., Ltd.)

Acrylate monomers of 4 functional groups: trade name; NK Oligo U-4HA (Shin-Nakamura)

6-functional acrylate monomer: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Kabushiki Kaisha)

[Photopolymerization initiator]

(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Butanone

[Organic acid]

2,2'-thiodiacetic acid

[Dispersant]

Disperipig-111 (manufactured by Big Chemie Japan K.K.)

[Description of Examples and Comparative Examples]

As shown in Table 1 below, Examples 1 to 11 and 18 are blended with 4-functional group acrylate monomers, Examples 12, 14 and 16 are blended with 2-functional acrylate monomers, and Examples 13 and 15 , And 17 is a trifunctional acrylate monomer. Of these examples, Examples 1 to 3, 8 to 10, 12, and 13 are modified by adding the spherical conductive powder (Ag). Examples 4 to 6, 11, 14, and 15 were obtained by changing the amount of the conductive powder (Ag) in the form of needle. In Examples 7 and 16 to 18, spherical and needle-shaped conductive powders were mixed and blended.

Examples 8 to 11 are obtained by increasing the amount of the photopolymerization initiator added to the amount of the photopolymerization initiator of Examples 1 to 4.

On the other hand, as shown in the following Table 2, in Comparative Examples 1, 4, 6, and 8, monofunctional acrylate monomers as acrylate monomers were used in varying amounts. In Comparative Examples 2, 3, 5, and 7, the amount of the hexafunctional acrylate monomer as the acrylate monomer was varied and used.

(Assessment Methods)

Resistivity and specific resistance values of each of the conductive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 8 thus obtained were evaluated. The evaluation method is as follows.

Test Specimen Preparation:

Each conductive resin composition for evaluation was coated on the entire surface of the base material made of polyester resin using a 300 mesh polyester screen and then dried in a hot air circulation type drying furnace at 90 DEG C for 30 minutes to obtain a coating film having good touch- . Thereafter, pattern light exposure was performed using a high-pressure mercury lamp as a light source so that the amount of accumulated light on the conductive resin composition on the conductive resin composition became 200 mJ / cm ² through a negative mask, and then a 0.4 wt% Na ₂ CO ₃ aqueous solution having a liquid temperature of 30 캜 And developed. Finally, the resultant was dried at 130 占 폚 for 30 minutes to prepare a test piece having a conductive pattern film.

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

Resistivity value: A 4 mm x 10 cm pattern was formed by the above method, and a resistivity value and a film thickness were measured to calculate a specific resistance value. In the minimum line, those having no defects were evaluated as " good ".

The blending components, blending amount, resolution and specific resistance values of Examples 1 to 18 and Comparative Examples 1 to 5 are collectively shown in Tables 1 and 2. In Tables 1 and 2, " solids content of A-1 varnish " is the mass obtained by removing the solvent from A-1 varnish.

[Table 1-1]

[Table 1-2]

[Table 1-3]

[Table 2]

It was found that the conductive resin compositions according to Examples 1 to 18 can form highly precise conductive pattern films with L / S = 30/30 占 퐉 or less even by exposure at a low exposure dose of 200 mJ / cm ² or less . It was also found that a conductive pattern film having a resistivity value (Ω · cm) of 5.00 ^-4 or less can be formed without thermally decomposing the carboxyl group-containing resin. Accordingly, it was found that the conductive resin composition of the present invention can be applied to a substrate which is weak against heat, and excellent conductivity and resolution can be secured.

Claims (9)

A conductive resin, a carboxyl group-containing resin, an electrically conductive powder, an acrylate monomer having 2 to 4 functional groups, and a photopolymerization initiator. The conductive resin composition for non-foaming according to claim 1, wherein the acrylate monomer is an acrylate monomer having four functional groups represented by the following formula (I).

(In the 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, provided that at least one of X ³ and X ⁴ represents a group containing a methacryloyloxy group ,
L ¹ and L ² are each independently

Lt; / RTI >
* Represents a bonding site with Z,
Z represents a divalent linking group) The nonconductive conductive resin composition according to claim 2, wherein L ¹ and L ² in the formula (I) are represented by the following formula (III).

(In the formula (III), * represents a bonding site with Z) The nonconductive conductive resin composition according to claim 3, wherein the acrylate monomer having four functional groups represented by the formula (I) is represented by the following formula (IV).

(In the 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 represent a hydrogen atom or a methyl group, provided that at least one of R ³ and R ⁴ represents a methyl group) The nonconductive conductive resin composition according to any one of claims 1 to 4, wherein the carboxyl group-containing resin does not contain a double bond. 6. The conductive resin composition for non-foaming according to claim 5, wherein the carboxyl group-containing resin further contains no aromatic ring. The nonconductive conductive resin composition according to any one of claims 1 to 4, wherein the photopolymerization initiator is oxime ester or acetophenone. The nonconductive conductive resin composition according to any one of claims 1 to 4, further comprising an organic acid having no aromatic ring. A conductive circuit formed by using the conductive resin composition for non-foaming according to any one of claims 1 to 4 on a substrate.