JP2015193705A - Conductive composition, conductive circuit and production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive composition which can be applied to a base material weak against heat and has low resistance and high resolution, a conductive circuit formed using the conductive composition, and a production method of the conductive circuit.SOLUTION: A conductive composition comprises a carboxyl group-containing resin free from double bonds, a compound represented by general formula (I), a conductive particulate, and a photoinitiator.

Description

  The present invention relates to a conductive composition, a conductive circuit formed using the conductive composition, and a method for manufacturing the conductive circuit.

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

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

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

  In addition, the baking type conductive paste as described above generally contains glass frit together with conductive particles, 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.

JP 2003-280181 A Japanese Patent No. 4411113

  The present invention has been made to solve the above-described problems, and can be applied to a heat-sensitive substrate, and has a low resistance and a high resolution, and uses this conductive composition. It is an object of the present invention to provide a conductive circuit and a method for manufacturing the conductive circuit.

In order to solve the above problems, the conductive composition of the present invention includes a carboxyl group-containing resin not containing a double bond, a compound represented by the following general formula (I), conductive particles, and initiation of photopolymerization. And an agent.

In general formula (I):
n is an integer from 0 to 4,
R is a hydrogen atom or a methyl group;
L ₁ is an —O— group, —O (CH ₂ CH ₂ ) _a O— group (where a is an integer of 1 to 8) or —O (CH ₂ CH ₂ CH ₂ ) _b O— group (where b is an integer of 1 to 8),
L ₂ represents a methylene group, an alkylene group having 2 to 8 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, an unsubstituted or substituted phenylene group, and an unsubstituted or substituted cyclohexylene group or unsaturated cyclohexyl group. It is a group selected from the group consisting of silylene groups.

  In the present invention, by using the compound represented by the general formula (I) together with a carboxyl group-containing resin not containing a double bond, a conductive circuit having low resistance and high resolution can be formed without firing at high temperature. It is.

<Conductive composition>
First, components blended in the conductive composition according to the present invention will be described.

(Carboxyl group-containing resin not containing double bond)
The electrically conductive composition of this invention contains carboxyl group-containing resin which does not contain a double bond. As the carboxyl group-containing resin that does not contain a double bond that is suitably blended, a known and commonly used resin compound that does not contain a double bond in the molecule and contains a carboxyl group can be used.
Specific examples of carboxyl group-containing resins that do not contain a double bond that can be suitably used (any of oligomers and polymers) are listed below.

  (1) Dialcohol compounds, polycarbonate-based polyols containing diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and carboxyl groups such as dimethylolpropionic acid and dimethylolbutanoic acid, A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyether polyol, polyester polyol, polyolefin polyol, bisphenol A alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (2) A carboxyl group-containing urethane resin by a polyaddition reaction of diisocyanate and a carboxyl group-containing dialcohol compound.

  (3) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.

  (4) A dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid is reacted with a bifunctional epoxy resin or a bifunctional oxetane resin, and the resulting hydroxyl groups such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. A carboxyl group-containing polyester resin to which a dibasic acid anhydride is added.

  (5) A carboxyl group-containing resin obtained by ring-opening an epoxy resin or an oxetane resin and reacting the generated hydroxyl group with a polybasic acid anhydride.

  (6) A polybasic acid anhydride is added to a reaction product such as a polyalcohol resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule, that is, a polyphenol compound with an alkylene oxide such as ethylene oxide or propylene oxide. A carboxyl group-containing resin obtained by reacting.

(7) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid and a compound having an unsaturated double bond such as methyl (meth) acrylate.

  (8) An epoxy group of a copolymer of an unsaturated double bond such as methyl (meth) acrylate and a glycidyl (meth) acrylate has one carboxyl group in one molecule, and an ethylenically unsaturated bond A carboxyl group-containing resin obtained by reacting an organic acid not having a hydrogen atom and reacting the resulting secondary hydroxyl group with a polybasic acid anhydride.

  (9) A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride with a hydroxyl group-containing polymer such as polyvinyl alcohol.

Although the above is mentioned, it is not limited to these.
In addition, in this specification, (meth) acrylic acid is a term which generically refers to acrylic acid, methacrylic acid and mixtures thereof, and the same applies to other similar expressions.

  Since the carboxyl group-containing resin not containing a double bond 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 not containing a double bond 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 it exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds, so the line becomes thinner than necessary. In some cases, it is difficult to draw a normal conductive pattern, which is not preferable.

  Moreover, although the mass average molecular weight of the carboxyl group-containing resin not containing the double bond varies depending on the resin skeleton, it is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. Is preferred. If the mass average molecular weight is less than 2,000, the tack-free performance may be inferior, the moisture resistance of the conductive pattern film after exposure may be poor, the film may be reduced during development, and the resolution may be greatly inferior. On the other hand, when the mass average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.

(Compound represented by formula (I))
The conductive composition of the present invention contains a compound represented by the following general formula (I). This compound can be used as a photopolymerizable monomer.

In general formula (I), n is an integer of 0-4. R is a hydrogen atom or a methyl group. L ₁ represents a —O— group, a —O (CH ₂ CH ₂ ) _a O— group (where a is an integer of 1 to 8) or a —O (CH ₂ CH ₂ CH ₂ ) _b O— group. (Where b is an integer of 1 to 8).

In the general formula (I), L ₂ has a methylene group, an alkylene group having 2 to 8 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, an unsubstituted or substituted phenylene group, and an unsubstituted or substituted group. A group selected from the group consisting of a cyclohexylene group and a group in which a part of the cyclohexylene group is an unsaturated bond (hereinafter also referred to as “unsaturated cyclohexylene group”).

The alkylene group having 2 to 8 carbon atoms representing the group L ₂ may be either a straight chain or a branched chain. For example, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene Among them, an alkylene group having 2 to 4 carbon atoms is preferable.

The alkenylene group having 2 to 8 carbon atoms representing the group L ₂ may be either a straight chain or a branched chain. For example, a vinyl group, 1-methylidene-ethylene group (—C (═CH ₂ ) CH ₂ -).

Examples of the unsaturated cyclohexylene group representing the group L ₂ include a cyclohexenylene group.

  Examples of the group that can be substituted with a phenylene group, a cyclohexylene group, or an unsaturated cyclohexylene group include, for example, an alkyl group having 1 to 4 carbon atoms such as a methyl group and an ethyl group, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms. Etc.

The group L ₂ is preferably a methylene group or an alkylene group having 2 to 4 carbon atoms, and is preferably a methylene group.

Preferable examples of the compound represented by the general formula (I) include compounds in which n is 1, R is a hydrogen atom, L ₁ is an —O— group, and L ₂ is an ethylene group.

  The compound represented by the general formula (I) has a carboxylic acid. When such a compound is contained in the composition together with a photopolymerization initiator described later, when the composition is polymerized by exposure, the solubility in the developer is reduced, and the alkali-insoluble or poorly-soluble alkali is reduced. It becomes. Therefore, the contrast between the exposed portion and the unexposed portion with respect to the alkaline developer can be easily provided, the pattern can be made high definition, and the pattern shape can be easily controlled.

  As the photopolymerizable monomer, the compound represented by the general formula (I) may be used alone, or the compound represented by the general formula (I) may be used in combination with one or more other compounds. .

  The compounding quantity of the compound represented by general formula (I) in an electroconductive composition is 10-100 mass parts with respect to 100 mass parts of carboxyl group-containing resin which does not contain the said double bond in conversion of solid content. It is preferable that it is in the range of 30 to 80 parts by mass. When the blending amount exceeds this range, the tackiness of the coating film may be deteriorated, dust is likely to adhere, and patterning defects may occur at the dust adhering portion. On the other hand, if it is less than 30 parts by mass, the monomer component is small and pattern formation may be difficult.

(Conductive particles)
The conductive composition of the present invention includes conductive particles. Any material can be used as the conductive particle material as long as it imparts conductivity to the resin composition. Examples of such conductive particles include Ag, Au, Pt, Pd, Ni, Cu, Al, Sn, Pb, Zn, Fe, Co, Cr, Mn, Ir, Os, Rh, W, Mo, Ru, and the like. Can be mentioned.

  These conductive particles 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 (SnO2), indium oxide (In2O3), ITO (Indium Tin Oxide), etc. can also be used.

  In order to reduce the resistance, the conductive particles are preferably formed from a material selected from Ag, Cu, Au, Sn, and alloys thereof.

  The conductive particles may be carbon powder such as carbon black, graphite, or carbon nanotube. However, care should be taken because the light transmittance is lowered.

  The shape of the conductive particles is not particularly limited, but is 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.

  The conductive particles preferably have 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 pattern film is improved.

  The conductive particles have an average particle diameter of 10 random particles observed at 10,000 times using an electron microscope (SEM), and the range is preferably 0.1 μm or more and 10 μm or less. If the average particle size is smaller than this range, the resistance value may increase due to an increase in contact resistance, which is not preferable. On the other hand, if the average particle size is larger than the above range, the paste coating film surface becomes rough, and a pinhole or disconnection occurs in a thin film having a thickness of 4 μm, resulting in a decrease in circuit pattern formation yield. In addition, it is preferable to use a thing with the magnitude | size of 0.1-10 micrometers in the average particle diameter measured with the micro track | truck.

The conductive particles preferably have a specific surface area in the range of 0.5 to ³ m ² / g. When fine circuit formation is performed by photolithography, because the specific surface area is 0.5 or less, line thickening is likely to occur, the reproducibility of the line width is reduced, and it is difficult to form a fine circuit. UV transmittance is reduced, curing is insufficient in the deep part of the coating film, and circuit defects are likely to occur during development when forming a fine circuit. The specific surface area is a value measured by the BET method.

  The blending amount of the conductive particles in the conductive composition is preferably in the range of 200 to 1400 parts by mass, in terms of solid content, with respect to 100 parts by mass of the carboxyl group-containing resin not including the double bond. More preferably, it is in the range of ˜900 parts by mass. Moreover, it is preferable that the content rate in solid content of electroconductive particle is 55-90 wt%, and it is more preferable that it is 65-85 wt%. If the blending ratio of the conductive particles is too small, the resistance value of the conductive composition becomes high and sufficient conductivity may not be obtained. On the other hand, a large amount of conductive particles is not preferable because the light transmittance is deteriorated and the formation of the pattern film by exposure may be deteriorated.

(Photopolymerization initiator)
The conductive composition of the present invention contains a photopolymerization initiator. It does not specifically limit as a photoinitiator, The well-known photoinitiator used for the photosensitive resin composition can be used. Specific examples include benzoin-based and phosphine oxide-based photopolymerization initiators, which are represented by the oxime ester-based group having the group represented by the following general formula (II) or the following general formula (III). It is preferable to use an acetophenone photopolymerization initiator having a group.

  In formula (II), 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 (III), 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 (III) 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, Irgacure 379 / 379EG manufactured by BASF Japan.

  Although the compounding quantity of the photoinitiator in an electroconductive composition is not specifically limited, 0.01-30 mass parts with respect to 100 mass parts of carboxyl group-containing resin which does not contain the said double bond in conversion of solid content. 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 may be insufficient, and the conductive pattern film may be peeled off or the characteristics of the conductive pattern film such as chemical resistance may be deteriorated. This is not preferable. On the other hand, if the amount exceeds 30 parts by mass, light absorption on the surface of the conductive pattern film of the photopolymerization initiator becomes violent and the deep curability may be lowered, which is not preferable.

(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.

  As a compounding quantity of the said organic acid, it is preferable that it is the range of 0.1-10 mass parts with respect to 100 mass parts of carboxyl group-containing resin which does not contain a double bond. When the blending amount is less than 0.1 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin not containing a double bond, the reaction between the inorganic particles and the carboxyl group-containing resin occurs, thereby reducing long-term storage stability. On the other hand, when the blending amount exceeds 10 parts by mass, it is not preferable because moisture in the air may be easily absorbed.

(Dispersant)
By mix | blending a dispersing agent, the dispersibility and sedimentation property of an electrically conductive 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 Co., Ltd.), Disparon 2150, Disparon 1210, Disparon KS-860, Disparon KS-873N, Spalon 7004, Disparon 1830, Disparon 1860, Disparon 1850, Disparon DA-400N, Disparon PW-36, Disparon DA-703-50 (manufactured by Enomoto Kasei Co., Ltd.), Floren G-450, Floren G-600, Floren G-820 , Floren G-700, Floren DOPA-44, Floren DOPA-17 (manufactured by Kyoeisha Chemical Co., Ltd.).

  The content of the dispersant is 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin not containing a double bond in order to effectively achieve the above object. Is preferred.

(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 polymerization, among radical polymerizations occurring in the conductive 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 within a range of 0.001 to 3 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin not containing a double bond. is there. If the amount is less than this range, the effect of inhibiting polymerization is not exhibited, and even a low exposure amount due to light scattering may cure and the line shape may easily become thick. In addition, if it exceeds this range, sensitivity is lowered, and a large amount of exposure may be required, so care must be taken.

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

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

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

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

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

  The compounding quantity of these thermosetting components is sufficient in a normal quantitative ratio, and is 20 to 70 parts by mass, preferably 40 to 60 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin not containing a double bond. The range of is appropriate.

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

  Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.

  The blending amount of these thermosetting catalysts is sufficient in a normal quantitative ratio, for example, preferably 0.1 to 20 parts by weight, more preferably 100 parts by weight of carboxyl group-containing resin not containing a double bond. 0.5 to 15 parts by mass.

(Thermal polymerization inhibitor)
The thermal polymerization inhibitor can be used for preventing thermal polymerization or temporal polymerization of the conductive 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 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).

  Particularly, as a heterocyclic compound having a mercapto group which is a chain transfer agent that does not impair the developability of the resin composition, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Kawaguchi Chemical) Axel 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.

(Silane coupling agent)
In the conductive composition of the present invention, a silane coupling agent can be used in order to improve adhesion to the base and stability over time.

Specific examples of silane coupling agents include vinylmethoxysilane, vinylethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3 -Glycidoxypropyltriethoxysilane,
3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyl Methyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and the like can be used.

  As commercial products, KBM-502, KBM-503, KBE-502, KBE-503 manufactured by Shin-Etsu Polymer Co., Ltd., A-143, A-150, A-151, A-171 manufactured by Nihon Unicar Co., Ltd. A-172, A-174, A-186, A-187, A-189, A-1100, A-1120 and A-1160, TSL-8310, TSL-8311, TSL- manufactured by Toshiba Silicone Co., Ltd. 8320, TSL-8395, TSL-8325, TSL-8331, TSL-8340, TSL-8345, TSL-8380, TSL-8350, TSL-8355, TSL-8370, and TSL-8375.

  Although the compounding quantity of such a silane coupling agent is not specifically limited, The range of 0.5-9 mass parts with respect to the said carboxyl-containing resin is preferable, Preferably the range of 1-7 mass parts is suitable. If the blending amount of the silane coupling agent is less than 0.5 parts by mass, the effect of the coupling agent may not be obtained and adhesion may be deteriorated. On the other hand, when the amount exceeds 9 parts by mass, the optical characteristics may be deteriorated and the pattern formation may be affected.

(Other additive components)
It goes without saying that the conductive composition of the present invention can be appropriately mixed with known and commonly used components such as thickeners, defoaming / leveling agents, antioxidants, rust inhibitors and the like as necessary. .

  As described above, the conductive composition according to the present invention includes a combination of a carboxyl group-containing resin not containing a double bond and a compound of formula (I) having a structure containing a carboxylic acid. With such a configuration, the conductive composition according to the present invention can be patterned without firing, and can form a conductive circuit with low resistance and high resolution.

  In addition, since the conductive composition according to the present invention can be patterned without firing, it is not necessary to include glass as an essential component such as an adhesive.

(Method for preparing conductive composition)
Next, a method for preparing the conductive composition according to the present invention will be described.
The conductive composition according to the present invention includes a carboxyl group-containing resin that does not contain the above double bond, a compound represented by the general formula (I), conductive particles, a photopolymerization initiator, and others that are used as necessary. These components can be prepared by kneading together with a solvent using a kneader such as a roll kneader, a mixer, a homomixer, a ball mill, or a bead mill.

  The solvent is used for imparting appropriate fluidity or plasticity and good film-forming property to the conductive composition. As the solvent to be used, it is preferable that the above-described components have good solubility, can impart an appropriate viscosity to the obtained conductive composition, and can be easily removed by evaporation.

  As the solvent, ketones, alcohols, esters, aliphatic / aromatic hydrocarbons, petroleum solvents and the like having a normal boiling point (boiling point at 1 atm) of 100 to 300 ° C. can be used.

  Examples of preferred solvents include ketones such as diethyl ketone, methyl butyl ketone, dipropyl ketone, cyclohexanone; n-pentanol, 4-methyl-2-pentanol, cyclohexanol, diacetone alcohol, dihydroxyterpineol, 2, Alcohols such as 2,4-trimethyl-1,3-pentanediol monoisobutyrate; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether Alcohols; saturated aliphatic monocarboxylic acid alkyl esters such as acetic acid-n-butyl and amyl acetate; lactic acid esters such as ethyl lactate and lactic acid-n-butyl; Ether-based esters such as cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, and aliphatic hydrocarbons such as octane and decane; aromatic carbonization such as toluene, xylene, and tetramethylbenzene Examples of hydrogen: Petroleum solvents such as petroleum ether, petroleum naphtha, water-based petroleum naphtha, solvent naphtha, etc. Among them, methyl butyl ketone, cyclohexanone, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether , Ethyl lactate, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, dihydroxyterpineol, 2,2,4-trimethyl-1 Etc. 3- pentanediol mono-isobutyrate. These solvents can be used alone or in combination of two or more.

  Examples of other preferred solvents include ethyl cellosolve, methyl cellosolve, terpineol, butyl carbitol acetate, butyl carbitol, isopropyl alcohol, benzyl alcohol and the like.

  The content ratio of the solvent in the conductive composition can be appropriately selected within a range in which good film forming properties (fluidity or plasticity) can be obtained.

<Conductive circuit and manufacturing method thereof>
Next, an example of a method for producing a conductive circuit using the conductive composition according to the present invention will be described.

  The conductive composition 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 a touch-drying property, a temperature at which the carboxyl group-containing resin containing no double bond is not thermally decomposed in a hot-air circulating drying furnace, a far-infrared drying furnace, etc., for example, about 60 to 120 ° C. for about 5 to 40 minutes The organic solvent is evaporated by drying to obtain a tack-free coating film.

  In addition, the resin composition can be formed into a film in advance. 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 2 is preferably used, as long as the carboxyl group of the resin containing no double bond in the resin composition is saponified and the uncured part (unexposed part) is removed. The developer is not limited to the above. Moreover, it is preferable to perform washing with water and acid neutralization in order to remove an unnecessary developer after development. The obtained patterned coating film is cured at a temperature at which the carboxyl group-containing resin containing no double bond is not thermally decomposed. Thereby, a conductive circuit can be formed. The curing temperature is preferably in the range of 80 ° C to 300 ° C, more preferably 100 to 250 ° C. Since the photosensitive resin composition of the present invention can obtain a conductive circuit by curing at a relatively low temperature of 300 ° C. or lower, it can be used on a substrate having low heat resistance or in combination with a material having low heat resistance.

  Examples of the substrate used in the present invention include a resin substrate and a glass substrate such as a glass substrate. Examples of the resin substrate include acrylic resin, polyethylene terephthalate (PET), epoxy, polyetherimide resin, polyether ketone resin, polysulfone resin, polyimide, polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN). Such polyester resins, polyethersulfone (PES), polystyrene (PS), polymethyl methacrylate (PMMA), polycarbonate (PC), polyamide (PA), polypropylene (PP), polyphenylene oxide (PPO), etc. However, it is not limited to these.

  According to the method for producing a conductive circuit according to the present invention, since the conductive composition of the present invention is used as a constituent material of the constituent element, a heat-sensitive substrate can be used, and the resistance is low and the solution is low. A conductive circuit with high image quality can be provided.

The present invention will be specifically described below based on examples. However, the present invention is not limited to these examples.
(Example 1)
[Resin R-1]
A carboxyl group-containing resin R-1 containing no double bond was synthesized.

Synthesis example 1
A flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser is charged with methyl methacrylate and methacrylic acid in a molar ratio of 0.87: 0.13, dipropylene glycol monomethyl ether as a solvent, and azobis as a catalyst. Isobutyronitrile was added and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere to obtain a carboxyl group-containing resin solution. This carboxyl group-containing resin had a mass average molecular weight of about 30,000 and an acid value of 100 mgKOH / g. In addition, the mass average molecular weight of the obtained carboxyl group-containing resin was obtained by connecting three pumps LC-6AD manufactured by Shimadzu Corporation and columns Shodex (registered trademark) KF-804, KF-803, and KF-802 manufactured by Showa Denko. It was measured by high performance liquid chromatography. Hereinafter, this carboxyl group-containing resin solution is referred to as R-1 varnish. This carboxyl group-containing resin does not contain a double bond.

[Photopolymerizable monomer]
As monomer A, M-510 manufactured by Toa Gosei Co., Ltd. having a carboxylic acid group was used. The acid value of this monomer A was 100 mgKOH / g.

[Conductive particles]
Spherical Ag powder was used. The average particle diameter of the Ag powder was 0.4 μm. In addition, an average particle diameter is an average particle diameter of 10 random particles observed at 10,000 times using an electron microscope (SEM).

[Photopolymerization initiator]
Product Name: OXE02
[Silane coupling agent]
Product name: KBM-503 (3-methacryloxypropyltrimethoxysilane)
[Additive]
Product name: Disperbyk-111
[Preparation of resin composition]
Resin R-1 100 parts by mass, conductive particles 820 parts by mass, monomer A 60 parts by mass, photopolymerization initiator 10 parts by mass, silane coupling agent 5 parts by mass, additive 5 parts by mass. Using carbitol acetate as a solvent, the mixture was kneaded and dispersed by a three roll or blender. Thereby, the conductive composition of Example 1 was obtained. The silver content rate (in solid) in this electroconductive composition was 82 wt%.

(Example 2)
A resin composition was prepared in the same manner as in Example 1 except that the monomer B was used as the photopolymerizable monomer. As monomer B, M-520 manufactured by Toa Gosei Co., Ltd. having a carboxylic acid group was used. The acid value of this monomer B was 30 mgKOH / g.

(Example 3)
A resin composition was prepared in the same manner as in Example 1 except that the monomer C was used as the photopolymerizable monomer. As monomer C, PE3A-MS manufactured by Kyoeisha Co., Ltd. having a carboxylic acid group was used. The acid value of this monomer C was 85 mgKOH / g. Monomer C has a structure represented by the following formula (IV).

Example 4
A resin composition was prepared in the same manner as in Example 1 except that the monomer D was used as the photopolymerizable monomer. As monomer D, DPE6A-MP manufactured by Kyoeisha Co., Ltd. having a carboxylic acid group was used. The acid value of this monomer D was 36 mgKOH / g. The monomer D has a structure represented by the following formula (V).

(Example 5)
A resin composition was prepared in the same manner as in Example 1 except that 40 parts by mass of the monomer A having a carboxylic acid group and 20 parts by mass of the monomer E having no carboxylic acid group were used as the photopolymerizable monomer. As monomer E, M-350 manufactured by Toa Gosei Co., Ltd. was used. The acid value of this monomer D was 1 mgKOH / g or less. Monomer E has a structure represented by the following formula (VI).

  In formula (VI), n≈1.

(Comparative Example 1)
A resin composition was prepared in the same manner as in Example 1 except that 60 parts by mass of monomer E was used as the photopolymerizable monomer.

(Comparative Example 2)
A resin composition was prepared in the same manner as in Example 1 except that the monomer F was used as the photopolymerizable monomer. As monomer F, A-9550 manufactured by Shin-Nakamura Chemical Co., Ltd. which does not have a carboxylic acid group was used. The acid value of this monomer F was 1 mgKOH / g or less. The monomer F has a structure represented by the following formula (VII).

In formula (VII), R represents a hydrogen atom or a group represented by the following formula (VIII).

(Comparative Example 3)
[Resin R-2]
A carboxyl group-containing resin R-2 containing a double bond was synthesized.

Synthesis example 2
In a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introducing tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate (Nippon Yushi) as a polymerization initiator 21.4 g of Perbutyl O) was added and heated to 90 ° C. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (Dacel Chemical Industry Plaxel FM1) were added to the bis (4- A carboxyl group-containing copolymer resin was obtained by adding dropwise over 2 hours together with 21.4 g of t-butylcyclohexyl) peroxydicarbonate (Nippon Yushi Co., Ltd. Parroyl TCP), and further aging for 6 hours. The reaction was performed under a nitrogen atmosphere.

  Next, to the obtained carboxyl group-containing copolymer resin, 363.9 g of 3,4-epoxycyclohexylmethyl acrylate (Cyclomer A200 manufactured by Daicel Chemical Industries), 3.6 g of dimethylbenzylamine as a ring-opening catalyst, and as a polymerization inhibitor 1.80 g of hydroquinone monomethyl ether was added, heated to 100 ° C., and stirred to carry out an epoxy ring-opening addition reaction. After 16 hours, a solution containing 53.8% by weight (nonvolatile content) of a carboxyl group-containing resin having no aromatic ring and having an acid value of solids of 108.9 mgKOH / g and a weight average molecular weight of 25,000 was obtained. . Hereinafter, this carboxyl group-containing resin solution is referred to as R-2 varnish. In addition, this carboxyl group-containing resin contains a double bond.

  The carboxyl group-containing resin R-2 containing a double bond had a mass average molecular weight of about 11000 and an acid value of 55 mgKOH / g.

  A resin composition was prepared in the same manner as in Example 1 except that the resin R-2 was used instead of the resin R-1.

(Resolution evaluation)
The conductive compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were each applied onto a glass substrate so that the dry thickness was 5 μm, and dried at 90 ° C. for 30 minutes to form a coating film. A high-pressure mercury lamp was used as a light source, and exposure was performed through a photomask having a line and space (L / S) of 15 μm / 15 μm so that the integrated light amount on the dried coating film was 150 mJ / cm ² . Then developed with 0.4 wt% _Na 2 CO ₃ aqueous solution at a liquid temperature 30 ° C., washed with water, by heat treatment at 230 ° C. 20 minutes to obtain a conductive pattern.

  The pattern was observed using an optical microscope, and a pattern having no residue between the patterns and having no pattern peeling was evaluated as good.

(Measurement of specific resistance)
The specific resistance values of the conductive compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated. The evaluation method is as follows.
Test piece preparation: Each conductive composition for evaluation was applied on the entire surface of a polyester resin base material using a 300-mesh polyester screen, and then dried in a hot-air circulating drying oven at 90 ° C. for 30 minutes. As a result, a coating film with good dryness to the touch was formed. Thereafter, using a high-pressure mercury lamp as a light source and pattern exposure so that the integrated light quantity on the conductive composition is 200 mJ / cm ² through a negative mask, 0.4 mass% Na ₂ CO _{3 at} a liquid temperature of 30 ° C. Development was performed using an aqueous solution and washed with water. Finally, it was dried at 130 ° C. for 30 minutes to prepare a test piece on which a conductive pattern was formed.

  Specific Resistance Value: A 4 mm × 10 cm pattern was formed by the above method, and the specific resistance value was calculated by measuring the resistance value and film thickness.

(result)
Table 1 summarizes the test conditions and test results.

  All the patterns produced using the conductive compositions according to Examples 1 to 5 had good resolution and low specific resistance. On the other hand, Comparative Examples 1 to 3 all had high specific resistance. In particular, Comparative Examples 1 and 2 were shown to be inferior in resolution.

  From the above examples, it was shown that according to the present invention, a conductive composition that can provide a conductive pattern with low resistance and high resolution can be obtained.

Claims (4)

A conductive composition comprising a carboxyl group-containing resin not containing a double bond, a compound represented by the following general formula (I), conductive particles and a photopolymerization initiator.

In general formula (I):
n is an integer from 0 to 4,
R is a hydrogen atom or a methyl group;
L ₁ is an —O— group, —O (CH ₂ CH ₂ ) _a O— group (where a is an integer of 1 to 8) or —O (CH ₂ CH ₂ CH ₂ ) _b O— group (where b is an integer of 1 to 8),
L ₂ represents a methylene group, an alkylene group having 2 to 8 carbon atoms, an alkenylene group having 2 to 8 carbon atoms, an unsubstituted or substituted phenylene group, and an unsubstituted or substituted cyclohexylene group or unsaturated cyclohexyl group. It is a group selected from the group consisting of silylene groups.   The conductive composition according to claim 1, wherein the conductive particles are formed of at least one material selected from the group consisting of Ag, Cu, Au, Sn, and alloys thereof.   A method for producing a conductive circuit, comprising: applying a conductive composition according to claim 1 or 2 onto a substrate, drying, exposing, developing, and then heat-treating at a temperature of 80 ° C. or higher and 300 ° C. or lower. .   A conductive circuit produced by applying the conductive composition according to claim 1 or 2 onto a substrate, drying, exposing, and developing, and then heat-treating at a temperature of 80 ° C. or higher and 300 ° C. or lower.