JP2015195190A - Photosetting type conductive paste - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosetting type conductive paste providing high conductivity even under post heating conditions at low temperature for short time and excellent in adhesion property and coating suitability.SOLUTION: There is provided a photosetting type conductive paste containing a radical polymerizable compound (A), a conductive filler (B), a radical initiator (C) and an acid generator (D) and/or a base generator (E) with the content of (C) of 10 to 30 pts.wt. based on 100 pts.wt. of (A) and the total content of (D) and (E) of 5 to 50 pts.wt. based on 100 pts.wt. of (C).

Description

  The present invention relates to a photocurable conductive paste suitable for wiring formation in flat panel displays, touch panels, electronic component manufacturing, and the like.

  In recent years, a method using a conductive paste has become mainstream in wiring formation for flat panel displays, touch panels, electronic component manufacturing, and the like. As the conductive paste, in addition to the thermosetting type, a photocuring type that enables a reduction in heat treatment temperature and a reduction in process time is used.

  In a photocurable conductive paste, in order to improve conductivity, organic substances are decomposed and removed by heat treatment after photocuring. Since this heat treatment usually requires a treatment time of at least 1 hour at a high temperature of 150 ° C. or higher, there has been a problem that plastics such as PET having low heat resistance and paper cannot be applied to the substrate. In order to solve this problem, it has been proposed to use a certain amount or more of a specific shape of conductive filler (see, for example, Patent Document 1).

  On the other hand, as an important basic performance for use as a conductive paste, adhesion to a substrate can be mentioned. In general, good substrate adhesion can be obtained by increasing the proportion of the organic substance that becomes the binder, but then the content of the conductive filler is reduced, and the problem is that the conductivity is lowered. there were. For this reason, development of the electrically conductive paste which balances favorable base-material adhesiveness and electroconductivity was desired.

JP 2000-219829 A

  The present invention has been made in view of the above-mentioned problems, and the object of the present invention is to achieve high conductivity even under low-temperature and short-time post-heating conditions, and to achieve photocuring excellent in adhesion and coating suitability. It is to provide a mold conductive paste.

  As a result of intensive studies to achieve the above object, the present inventors have reached the present invention. That is, the present invention contains a radical polymerizable compound (A), a conductive filler (B), a radical initiator (C), and an acid generator (D) and / or a base generator (E). ) Content is 10-30 parts by weight with respect to 100 parts by weight (A), and the total content of (D) and (E) is 5-50 parts by weight with respect to 100 parts by weight (C). This is a photo-curing type conductive paste.

  The photo-curable conductive paste of the present invention has high conductivity even under low temperature and short time post-heating conditions, and is excellent in adhesion and coating suitability. For this reason, it can use suitably for wiring formation, such as a flat panel display, a touch panel, and electronic component manufacture.

The photocurable conductive paste of the present invention contains the following (1) to (4).
(1) Radical polymerizable compound (A)
(2) Conductive filler (B)
(3) Radical initiator (C)
(4) Acid generator (D) and / or base generator (E)

  Below, (A)-(E) which is an essential structural component of the photocurable conductive paste of this invention is demonstrated in order.

  As the radically polymerizable compound (A) in the present invention, a known compound containing an ethylenically unsaturated bond can be used. Examples of the ethylenically unsaturated bond include a vinyl group, a propenyl group, and a (meth) acryloyl group. Among these, it is preferable to contain (meth) acrylate (A1) which has a (meth) acryloyl group from a viewpoint of active energy ray curability. In the above and the following, when referring to both and / or “acryloyl” and “methacryloyl”, when referring to “(meth) acryloyl” and “acrylate” and / or “methacrylate”, “(meth) acrylate” ”And“ acryl ”and / or“ methacryl ”are described as“ (meth) acryl ”, respectively.

  Moreover, you may use polymerization inhibitors, such as hydroquinones, as needed with a radically polymerizable compound (A).

  (Meth) acrylate (A1) [excluding urethane (meth) acrylate (A5) and polyester (meth) acrylate (A6) described later. ] Having 4 to 50 carbon atoms is preferable. For example, monofunctional (meth) acrylate (A11), bifunctional (meth) acrylate (A12), trifunctional (meth) acrylate (A13), tetrafunctional (meta) ) Acrylate (A14), (meth) acrylate (A15) having 5 or more functional groups. These may be used alone or in combination of two or more.

As monofunctional (meth) acrylate (A11), ethyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) Acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate , Benzyl (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (Meth) acrylate, cyanoethyl (meth) acrylate, benzyl (meth) acrylate, butoxymethyl (meth) acrylate, methoxypropylene mono (meth) acrylate, 3-methoxybutyl (meth) acrylate, alkoxymethyl (meth) acrylate, 2-ethyl Hexyl carbitol (meth) acrylate, alkoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, 2,2,2- Tetrafluoroethyl (meth) acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4-butylphenyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (Meth) acrylate, 4-chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, Glycidyloxypropyl (meth) acrylate, diethylene glycol monovinyl ether mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyalkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate , 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dimethyl Aminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethylsilylpropyl ( (Meth) acrylate, polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, oligoethylene oxide monoalkyl ether (meth) acrylate, polyethylene Oxide monoalkyl ether (meth) acrylate, dipropylene glycol Cole (meth) acrylate, polypropylene oxide monoalkyl ether (meth) acrylate, oligopropylene oxide monoalkyl ether (meth) acrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, 2-methacryloyl Roxyethyl-2-hydroxypropyl phthalate, butoxydiethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, ethylene oxide (below) , Abbreviated as EO) (1 to 40 mol, the same shall apply hereinafter) addition phenol (meth) acrylate, EO addition cresol (meth) acrylate, EO addition nonylpheno (Meth) acrylate, propylene oxide (hereinafter, PO hereinafter) (1 to 40 mol, hereinafter the same) added nonylphenol (meth) acrylate and EO adduct of 2-ethylhexyl alcohol (meth) acrylate.
Among these, phenoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate are preferable from the viewpoint of conductivity.

  As bifunctional (meth) acrylate (A12), 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,4-dimethyl -1,5-pentanediol di (meth) acrylate, butylethylpropanediol di (meth) acrylate, ethoxylated cyclohexanemethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, Ethylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, EO-added bisphenol A di (meth) acrylate Bisphenol F polyethoxydi (meth) acrylate, polypropylene glycol di (meth) acrylate, oligopropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 2-ethyl-2-butyl-propanediol di (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, tricyclodecane di (meth) acrylate, and the like.

  As trifunctional (meth) acrylate (A13), trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, alkylene oxide of trimethylolpropane (EO, PO, etc., the following alkylene oxides are also the same) (1 to 40 mol, the same applies hereinafter) Adduct tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, Isocyanuric acid alkylene oxide adduct tri (meth) acrylate, dipentaerythritol propionate tri (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate, hydroxypivalar Hydrin-modified dimethylol propane tri (meth) acrylate, sorbitol tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate and ethoxylated glycerin tri (meth) acrylate. Among these, the alkylene oxide adduct tri (meth) acrylate of trimethylolpropane and the isocyanuric acid alkylene oxide adduct tri (meth) acrylate are preferable from the viewpoint of conductivity.

  As tetrafunctional (meth) acrylate (A14), pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate and pentaerythritol And EO adduct tetra (meth) acrylate. Among these, from the viewpoint of conductivity, pentaerythritol EO adduct tetra (meth) acrylate is preferable.

  As pentafunctional or higher functional (meth) acrylate (A15), sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide Examples include adduct hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

  Of these, monofunctional (meth) acrylate (A11), trifunctional (meth) acrylate (A13) and / or tetrafunctional (meta) are particularly preferable from the viewpoints of conductivity, adhesion to a substrate and coating properties. ) Acrylate (A14) [particularly (A13)], and the proportion of (A11) in the whole radical polymerizable compound (A) is more preferably 10 to 40% by weight.

  As the radical polymerizable compound (A), in addition to the (meth) acrylate (A1), an acrylamide compound (A2), an aromatic vinyl compound (A3), a vinyl ether compound (A4), a bifunctional or higher urethane (meth) acrylate. (A5) Bifunctional or higher functional polyester (meth) acrylate (A6) and other radical polymerizable compounds (A7) can be used.

  Examples of the (meth) acrylamide compound (A2) include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and Nn-butyl (meth). Acrylamide, Nt-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide and (meth) acryloylmorpholine.

  As the aromatic vinyl compound (A3), vinyl thiophene, vinyl furan, vinyl pyridine, styrene, methyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, Bromostyrene, vinyl benzoic acid methyl ester, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3 -Hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allylstyrene, isopropenyl styrene Emissions, butenylstyrene, octenyl styrene, 4-t-butoxycarbonyl styrene, 4-methoxystyrene and 4-t-butoxystyrene, and the like.

Examples of the vinyl ether compound (A4) include the following monofunctional or polyfunctional vinyl ethers.
Examples of the monofunctional vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methyl Cyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether , Tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxy Examples include ethyl vinyl ether, phenyl ethyl vinyl ether, and phenoxy polyethylene glycol vinyl ether.

  Examples of the polyfunctional vinyl ether include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether. Divinyl ethers such as: trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl Ether, EO-added trimethylolpropane trivinyl ether, PO-added trimethylolpropane trivinyl ether, EO-added ditrimethylolpropane tetravinyl ether, PO-added ditrimethylolpropane tetravinyl ether, EO-added pentaerythritol tetravinyl ether, PO-added pentaerythritol tetravinyl ether, EO addition Examples thereof include dipentaerythritol hexavinyl ether and PO-added dipentaerythritol hexavinyl ether.

  The bifunctional or higher (preferably 2 to 8 functional) urethane (meth) acrylate (A5) is not particularly limited as long as it is a compound obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with isocyanate. For example, it can be obtained by reacting 1 equivalent of a compound having two isocyanate groups with 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group in the presence of a tin compound.

  It does not specifically limit as isocyanate used as the raw material of urethane (meth) acrylate (A5) more than bifunctional, For example, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethyl Hexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, Lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, tetramethylxylene diisocyanate, 1,6,1 - Un de Country isocyanate, and the like.

  Examples of the isocyanate include, for example, a reaction between a polyol such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate. The resulting chain-extended isocyanate compound can also be used.

  It does not specifically limit as a (meth) acrylic acid derivative which has a hydroxyl group used as the raw material of bifunctional or more urethane (meth) acrylate (A5), For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Commercial products such as acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol , Mono (meth) acrylates of dihydric alcohols such as polyethylene glycol, mono (meth) acrylates or di (meth) acrylates of trivalent alcohols such as trimethylolethane, trimethylolpropane, glycerin, bisphenol A modified epoxy (meta Acu Epoxy (meth) acrylate of rate, and the like.

  As a commercial item of bifunctional or higher urethane (meth) acrylate (A5), for example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), Evekril 230, Evekril 270, Evecryl 4858, Evecril 8402, Evecril 8804, Evecril 8803, Evecril 8807, Evecril 9260, Evecril 5129, Evecril 4842, Evecril 210, Evecril 4827, Evecril 6700, Evecril 220, Evecryl 2220 Art Resin UN-9000H, Art Resin UN-9000A, Art Resin UN-7100, Art Resin UN-1255, Art Resin UN-330, Art Resin UN-33 0HB, Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Negami Kogyo Co., Ltd.), U-122P, U-108A, U-340P, U-4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA- 7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H, UA-4000, AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I, U-200PA, U-6LPA (all manufactured by Shin-Nakamura Chemical Co., Ltd.) It is below.

  The bifunctional or higher (preferably 2 to 8 functional) polyester (meth) acrylate (A6) is a (meth) acrylic group having a hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol. It can be obtained by esterification with an acid or by esterification of hydroxyl groups at both ends of an oligomer obtained by adding alkylene oxide to a polyvalent carboxylic acid with (meth) acrylic acid.

  Examples of the divalent alcohol which is a structural unit of the bifunctional or higher functional polyester (meth) acrylate (A6) include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, and 1,4-butanediol. , Neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol and other alkylene glycols; diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene Alkylene ether glycols such as glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; bisphenols such as bisphenol A, bisphenol F, and bisphenol S S; alkylene oxide bisphenol [EO, PO, butylene oxide, etc.] 2-8 mole adducts.

  Examples of the divalent carboxylic acid that is a structural unit of the bifunctional or higher polyester (meth) acrylate (A6) include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, and terephthalic acid. , Succinic acid, adipic acid, sevantinic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, isooctenyl succinic acid, n- Examples thereof include octyl succinic acid, isooctyl succinic acid and the like, and anhydrides or lower alkyl esters of these acids.

  Examples of commercially available bifunctional or higher-functional polyester (meth) acrylate (A6) include CN2203, CN2254, CN2270, CN2271, CN2273, CN2274 (all manufactured by Sartomer), Aronix M6500, Aronix M6100, Aronix M6200, Aronix M6250 ( All of them are manufactured by Toagosei Co., Ltd.).

  Other radical polymerizable compounds (A7) include acrylonitrile, vinyl ester compounds (such as vinyl acetate, vinyl propionate and vinyl versatate), allyl ester compounds (such as allyl acetate), and halogen-containing monomers (vinylidene chloride and chloride). Vinyl) and olefin compounds (ethylene and propylene, etc.).

  Further, from the viewpoint of coexistence of conductivity and substrate adhesion, the content of the radically polymerizable compound (A) in the photocurable conductive paste is 1 to 50% by weight, preferably 2 to 30% by weight, particularly Preferably it is 3 to 20% by weight.

  As the conductive filler (B) in the present invention, for example, metal powder and carbon material can be used. The average particle diameter of the conductive filler (B) is preferably 0.1 μm to 20 μm.

  Examples of the metal powder include silver powder, copper powder, gold powder, palladium powder, platinum powder, nickel powder, aluminum powder and indium tin oxide powder, and glass spheres whose surfaces are coated with metal.

  Among these, silver powder is preferable from the viewpoint of conductivity, and various shapes such as a spherical shape, a scale shape, a foil shape, and a flake shape can be used. Moreover, you may use these metal powders, after mixing with binder resin, an additive, etc.

  Examples of the carbon material include carbon black, carbon fiber, graphite, and carbon nanotube.

  Among these, carbon black is preferable from the viewpoint of coatability, and those produced by a known method such as acetylene black, furnace black, and channel black can be used.

  In addition, from the viewpoint of conductivity, substrate adhesion, and coating properties, the content of the conductive filler (B) in the photocurable conductive paste is 35 to 98% by weight, preferably 40 to 97% by weight. is there.

In the present invention, the radical initiator (C) means a compound that generates radicals by at least one of actinic rays, acids, and bases, radical initiator (C1) that generates radicals by actinic rays, and acids. In addition, a known compound such as a radical initiator (C2) that generates radicals with a base can be used.
For example, acylphosphine oxide derivative polymerization initiator (C121), α-aminoacetophenone derivative polymerization initiator (C122), benzyl ketal derivative polymerization initiator (C123), α-hydroxyacetophenone derivative polymerization initiator (C124). The benzoin derivative polymerization initiator (C125), the oxime ester derivative polymerization initiator (C126), the titanocene derivative polymerization initiator (C127), etc. can generate radicals by any of actinic rays, acids and bases. It can be applied as either (C1) or (C2).
The organic peroxide polymerization initiator (C21), the azo compound polymerization initiator (C22), the other radical initiator (C23), and the like can generate radicals with an acid and / or a base. .
(C) may be used alone or in combination of two or more.
In addition, (C121) shows that it is the 1st example of the compound (C12) applicable as both (C1) and (C2).

  As the acylphosphine oxide derivative polymerization initiator (C121), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [manufactured by BASF Japan (LUCIRIN TPO)] and bis (2,4,6-trimethylbenzoyl)- Phenylphosphine oxide [manufactured by BASF Japan Ltd. (IRGACURE 819)] and the like.

  As the α-aminoacetophenone derivative-based polymerization initiator (C122), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [manufactured by BASF Japan (IRGACURE 907)], 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone [manufactured by BASF Japan (IRGACURE 369)] and 1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 -[4- (4-morpholinyl) phenyl] -1-butanone [manufactured by BASF Japan Ltd. (IRGACURE 379)] and the like.

  Examples of the benzyl ketal derivative polymerization initiator (C123) include 2,2-dimethoxy-1,2-diphenylethane-1-one [manufactured by BASF Japan (IRGACURE 651)].

  As the α-hydroxyacetophenone derivative-based polymerization initiator (C124), 1-hydroxy-cyclohexyl-phenyl-ketone [manufactured by BASF Japan Ltd. (IRGACURE 184)], 2-hydroxy-2-methyl-1-phenyl-propane-1 -ON [BASF Japan (DAROCUR 1173)], 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one [BASF Japan (IRGACURE) 2959)] and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one [manufactured by BASF Japan Ltd. (IRGACURE 127 )] And the like.

  Examples of the benzoin derivative-based polymerization initiator (C125) include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

  As the oxime ester derivative polymerization initiator (C126), 1,2-octanedione-1- (4- [phenylthio) -2- (O-benzoyloxime)] [manufactured by BASF Japan Ltd. (IRGACURE OXE 01)] and Etanone-1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) [manufactured by BASF Japan Ltd. (IRGACURE OXE 02)] and the like. .

  As titanocene derivative polymerization initiator (C127), bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) Examples thereof include titanium [manufactured by BASF Japan (IRGACURE 784)].

  Examples of the organic peroxide polymerization initiator (C21) include benzoyl peroxide (BPO), t-butyl peroxyacetate, 2,2-di- (t-butylperoxy) butane, t-butyl peroxybenzoate, n-butyl 4,4-di- (t-butylperoxy) valerate, di- (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5,- Dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3 , 3, -Tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl Hydroperoxide and t- butyl trimethylsilyl peroxide.

  As the azo compound-based polymerization initiator (C22), 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2 Examples include '-azobis (N-cyclohexyl-2-methylpropionamide) and 2,2'-azobis (2,4,4-trimethylpentane).

  Examples of other polymerization initiator (C23) include 2,3-dimethyl-2,3-diphenylbutane.

  As the radical initiator (C2) that generates a radical by an acid and / or a base, an organic peroxide polymerization initiator (C21) and / or an azo compound polymerization initiator (C22) are preferable.

  Among these radical initiators (C), from the viewpoint of storage stability of the photocurable conductive paste, an organic peroxide polymerization initiator (C21) that generates radicals even by heat or an azo compound polymerization start. Those other than the agent (C22), that is, radical initiators (C1) [including (C12)] that generate radicals by actinic rays are preferable. In particular, when a base generator (E1) that generates a base by actinic rays is included in the photocurable conductive paste, (C12) is used because radical generation by the base generated from (E1) is further promoted. Is preferred.

The content of the radical initiator (C) in the photocurable conductive paste of the present invention is 0.1 to 15% by weight, preferably 0.3 to 6% by weight.
Furthermore, the content of the radical initiator (C) is 10 to 30 parts by weight, preferably 15 to 30 parts by weight, and more preferably from 100 parts by weight of the radical polymerizable compound (A) from the viewpoint of conductivity. Is 15 to 25 parts by weight.
By setting the content of the radical initiator (C) to 10 parts by weight or more with respect to 100 parts by weight of (A), good conductivity can be obtained and the photocurability is also good. Moreover, the coating property to a base material becomes favorable by setting it as 30 weight part or less.

In the present invention, the acid generator (D) means a compound that generates an acid by at least one of actinic rays, radicals, acids, and bases, and an acid generator (D1) that generates an acid by actinic rays, And known compounds such as an acid generator (D2) that generates an acid by at least one selected from the group consisting of radicals, acids and bases.
For example, the sulfonium salt derivative (D121) and the iodonium salt derivative (D122) can generate an acid by actinic rays or radicals, and can be applied as (D1) or (D2).
In addition, the sulfonic acid ester derivative (D21), the acetic acid ester derivative (D22), the phosphonic acid ester (D23) and the like can generate an acid with an acid and / or a base, and can be applied as (D2).
(D) may be used alone or in combination of two or more.
In addition, (D121) shows that it is the 1st example of the compound (D12) applicable as both (D1) and (D2).
Among these (D), an acid generator (D1) [including (D12)] that generates an acid by actinic rays is preferable.

  Examples of the sulfonium salt derivative (D121) in the present invention include compounds represented by the following general formula (1) or the following general formula (2).

  In General Formula (1) or (2), A1 is a divalent or trivalent group represented by any of the following General Formulas (3) to (10), and Ar1 to Ar7 are each independently a benzene ring skeleton. A halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and 1 to 1 carbon atoms. Substituted with at least one atom or substituent selected from the group consisting of 20 alkylsilyl groups, nitro groups, carboxyl groups, hydroxyl groups, mercapto groups, amino groups, cyano groups, phenyl groups, naphthyl groups, phenoxy groups, and phenylthio groups An aromatic hydrocarbon group or a heterocyclic group, Ar1 to Ar4, Ar6 and Ar7 are monovalent groups, Ar5 is a divalent group, and (X1)-and (X2)-are negative Represents ON, a is an integer of 0 to 2, b is an integer from 1 to 3, and a + b is an integer equal valence of 2 or 3 at A1.

  R1 to R7 in the general formulas (5) to (8) are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen atom, an acyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. Represents a phenyl group optionally substituted with at least one atom or substituent selected from the group consisting of an alkyl group, an amino group, a cyano group, a phenyl group, a naphthyl group, a phenoxy group and a phenylthio group, R1 and R2, R4 and R5, and R6 and R7 may be bonded to each other to form a ring structure.

  As A1 in the general formula (2), groups represented by the general formula (5) and the general formulas (7) to (10) are preferable from the viewpoint of acid generation efficiency. The general formulas (5) and (8) ) To (10) are more preferred.

Ar1 to Ar7 in the general formula (1) and the general formula (2) are groups that allow the compound represented by the general formula (1) or the general formula (2) to absorb in the ultraviolet to visible light region.
The number of benzene ring skeletons in Ar1 to Ar7 is preferably 1 to 5, more preferably 1 to 4.
As an example in the case of having one benzene ring skeleton, a residue obtained by removing one or two hydrogen atoms from benzene or a heterocyclic compound such as benzofuran, benzothiophene, indole, quinoline, coumarin, and the like can be given.
Examples of the case of having two benzene ring skeletons include one or two hydrogen atoms from heterocyclic compounds such as naphthalene, biphenyl, fluorene, or dibenzofuran, dibenzothiophene, xanthone, xanthene, thioxanthone, acridine, phenothiazine, and thianthrene. Residues excluded are listed.
As an example in the case of having three benzene ring skeletons, for example, one or two hydrogen atoms are removed from a heterocyclic compound such as anthracene, phenanthrene, terphenyl, p- (thioxanthyl mercapto) benzene, and naphthobenzothiophene. Residue.
As an example in the case of having four benzene ring skeletons, for example, a residue obtained by removing one or two hydrogen atoms from naphthacene, pyrene, benzoanthracene, triphenylene and the like can be mentioned.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and fluorine and chlorine are preferable.

  Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, and cyclohexylcarbonyl group.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n- or iso-propyl group, n-, sec- or tert-butyl group, n-, iso- or neo-pentyl group, hexyl group, A heptyl group, an octyl group, etc. are mentioned.

  Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n- or iso-propoxy group, n-, sec- or tert-butoxy group, n-, iso- or neo-pentyloxy group, A hexyloxy group, a heptyloxy group, an octyloxy group, etc. are mentioned.

  Examples of the alkylthio group having 1 to 20 carbon atoms include a methylthio group, an ethylthio group, an n- or iso-propylthio group, an n-, sec- or tert-butylthio group, an n-, iso- or neo-pentylthio group, and a hexylthio group. , Heptylthio group, octylthio group and the like.

  Examples of the alkylsilyl group having 1 to 20 carbon atoms include trialkylsilyl groups such as trimethylsilyl group and triisopropylsilyl group. Here, the alkyl may be a linear structure or a branched structure.

  As the atoms or substituents substituted by Ar1 to Ar7, from the viewpoint of acid generation efficiency, halogen atoms, cyano groups, phenyl groups, naphthyl groups, phenoxy groups, phenylthio groups, alkyl groups having 1 to 20 carbon atoms, carbon atoms are preferable. An alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms, more preferably a cyano group, a phenyl group, an alkyl group having 1 to 15 carbon atoms, and a carbon number. 1-15 alkoxy group, C1-C15 alkylthio group and C1-C15 acyl group, particularly preferably an alkyl group having 1-10 carbon atoms, an alkoxy group having 1-10 carbon atoms, carbon number An alkylthio group having 1 to 10 carbon atoms and an acyl group having 1 to 10 carbon atoms. The above alkyl moiety may be linear, branched or cyclic.

  Ar1-Ar4, Ar6 and Ar7 are preferably phenyl, p-methylphenyl, p-methoxyphenyl, p-tert-butylphenyl, 2,4,6-trimethylphenyl from the viewpoint of acid generation efficiency. Group, p- (thioxanthyl mercapto) phenyl group and m-chlorophenyl group.

  Ar5 is preferably a phenylene group, 2- or 3-methylphenylene group, 2- or 3-methoxyphenylene group, 2- or 3-butylphenylene group and 2- or 3-chlorophenylene from the viewpoint of acid generation efficiency. It is a group.

  Examples of the anion represented by (X1)-or (X2)-in the general formula (1) or (2) include a halide anion, a hydroxide anion, a thiocyanate anion, and a dialkyldithio having 1 to 4 carbon atoms. Carbamate anion, carbonate anion, bicarbonate anion, aliphatic or aromatic carboxy anion optionally substituted with halogen (benzoate anion, trifluoroacetate anion, perfluoroalkylacetate anion, phenylglyoxylate anion, etc.), halogen An aliphatic or aromatic sulfoxy anion (such as trifluoromethanesulfonate anion), a hexafluoroantimonate anion (SbF6-), a phosphorus anion [phosphorus hexafluoride anion (PF6-) and 3 fluorine Tris (perfluoroethyl) phosphorus anion PF3 (C2F5) 3-) etc.] and borate anions (tetraphenylborate, tetrakis (perfluorophenyl) borate, butyltriphenylborate anion, etc.) and the like. From the viewpoint of acid generation efficiency, phosphates containing fluorine atoms Anions or borate anions are preferred. More preferred are hexafluorophosphate anion, trifluoro [tris (perfluoroethyl)] phosphate anion and tetrakis (perfluorophenyl) borate anion, and particularly preferred is trifluoro [tris (perfluoroethyl)] phosphate anion and Tetrakis (perfluorophenyl) borate anion.

  As the sulfonium salt derivative (D121), compounds having a triphenylsulfonium cation, a tri-p-tolylsulfonium cation or a [p- (phenylmercapto) phenyl] diphenylsulfonium cation as a cation skeleton are preferable from the viewpoint of acid generation efficiency, and Compounds represented by the following general formulas (11) to (14) are preferable, and compounds represented by the following general formulas (11) to (14) are more preferable.

  (X3)-to (X6)-in the general formulas (11) to (14) represent anions, specifically exemplified as (X1)-or (X2)-in the general formula (1) or (2). The thing similar to what was done is mentioned, A preferable thing is also the same.

  Examples of the iodonium salt derivative (D122) in the present invention include compounds represented by the following general formula (15) or the following general formula (16).

  In the formula, A2 is a divalent or trivalent group represented by any one of the general formulas (3) to (10), and Ar8 to Ar12 each independently have at least one benzene ring skeleton, Atom, C1-C20 acyl group, C1-C20 alkyl group, C1-C20 alkoxy group, C1-C20 alkylthio group, C1-C20 alkylsilyl group, nitro group An aromatic hydrocarbon group that may be substituted with at least one substituent selected from the group consisting of a carboxyl group, a hydroxyl group, a mercapto group, an amino group, a cyano group, a phenyl group, a naphthyl group, a phenoxy group, and a phenylthio group Or Ar8 to Ar10 and Ar12 are monovalent groups, Ar11 is a divalent group, (X7)-and (X8)-represent an anion, and c is an integer of 0-2. , In an integer of 1 to 3, and c + d is an integer equal valence of A2 2 or 3.

  As a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms The thing similar to what was described by description of General formula (1) and General formula (2) is illustrated.

  As A2 in the general formula (16), the group represented by the general formula (5) and the general formulas (7) to (10) is preferable from the viewpoint of the efficiency of generating an acid, and the general formula (5) And groups represented by (8) to (10) are more preferred.

Ar8 to Ar12 in the general formula (15) or the general formula (16) are groups that allow the compound represented by the general formula (15) or the general formula (16) to absorb in the ultraviolet to visible light region.
The number of benzene ring skeletons in Ar8 to Ar12 is preferably 1 to 5, and more preferably 1 to 4. Specific examples of Ar8 to Ar12 include Ar1 to Ar7 in the general formula (1) or the general formula (2). The thing similar to what was illustrated as is mentioned, A preferable thing is also the same.

  Examples of (X7)-and (X8)-include the same as those exemplified as (X1)-or (X2)-in general formula (1) or (2), and preferred ones are also the same.

  As the iodonium salt derivative (D122), (4-methylphenyl) {4- (2-methylpropyl) phenyl} iodonium cation, [bis (4-t-butylphenyl)] iodonium is preferable from the viewpoint of acid generation efficiency. Cation, [bis (4-t-butylphenyl)] trifluoro [tris (perfluoroethyl)] iodonium cation and [bis (4-methoxyphenyl)] iodonium cation as cation skeleton, and the following other general compounds Compounds represented by the formulas (17) to (20) are preferable, and compounds represented by the following general formulas (17) to (20) (including exemplified compounds) are more preferable.

  In General Formulas (17) to (20), R8 to R13 are a hydrogen atom, a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a carbon number. An atom or substituent selected from the group consisting of an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, an amino group, a cyano group, a phenyl group, and a naphthyl group; Yes, (X9)-to (X12)-represent anions.

  As a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms The thing similar to what was described by description of General formula (1) and General formula (2) is illustrated.

  R8 to R13 are preferably a halogen atom, a cyano group, a phenyl group, a naphthyl group, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms, and more preferably a cyano group or a phenyl group. , An alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms and an acyl group having 1 to 15 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. And an acyl group having 1 to 10 carbon atoms. The above alkyl moiety may be linear, branched or cyclic.

  Examples of (X9)-to (X12)-in the general formulas (17) to (20) include the same as those exemplified as (X1)-or (X2)-in the general formula (1) or (2). The preferred ones are also the same.

  In general, a photopolymerization initiator that can be used for curing in the visible light region (360 nm to 830 nm; see JIS-Z8120) is colored by the initiator itself because it absorbs visible light, which adversely affects the hue of the cured film. However, by using the compound represented by the general formula (2) or the general formula (16), adverse effects on the hue of the cured film can be suppressed.

  Examples of the sulfonic acid ester derivative (D21) include methanesulfonic acid cyclohexyl ester, ethanesulfonic acid isopropyl ester, benzenesulfonic acid-t-butyl ester, p-toluenesulfonic acid cyclohexyl ester, and naphthalenesulfonic acid cyclohexyl ester.

  Examples of the acetate derivative (D22) include dichloroacetic acid cyclohexyl ester and trichloroacetic acid isopropyl ester.

  Examples of the phosphonic acid ester (D23) include triphenylphosphonic acid cyclohexyl ester.

In the present invention, the base generator (E) means a compound that generates a base with at least one of actinic rays, radicals, acids and bases, and a base generator (E1) that generates a base with actinic rays, In addition, a known compound such as a base generator (E2) that generates a base by at least one selected from the group consisting of radicals, acids and bases can be used.
For example, the oxime derivative (E121), the quaternary ammonium salt derivative (E122), the quaternary amidine salt derivative (E123) and the like can generate a base by actinic rays or radicals, and are applied as (E1) or (E2). it can.
Further, the carbamate derivative (E21) can generate a base with a base and can be applied as (E2).
(E) may be used alone or in combination of two or more.
In addition, (E121) shows that it is the 1st example of the compound (E12) applicable as both (E1) and (E2).
Among these (E), a base generator (E1) [including (E12)] that generates a base by actinic rays is preferable.

  Examples of the oxime derivative (E121) include O-acyloxime.

  Examples of the carbamate derivative (E21) include 1-Fmoc-4-piperidone and o-nitrobenzoyl carbamate.

  Examples of the quaternary ammonium salt derivative (E122) and the quaternary amidine salt derivative (E123) include compounds represented by any one of the following general formulas (21) to (23).

  R14 to R41 in the general formulas (21) to (23) are each a hydrogen atom, a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, carbon An alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, an amino group, a cyano group, a phenyl group, a naphthyl group, and the general formula (24). An atom or a substituent selected from the group consisting of a substituent and a substituent represented by General Formula (25), wherein any one of R14 to R23 is represented by General Formula (24) or General Formula (25) Any one of R24 to R31 is a substituent represented by the general formula (24) or the general formula (25), and any one of R32 to R41 is the general formula (24). Or general formula (25 In which a substituent represented.

  R42 to R45 in the general formulas (24) and (25) are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R46 to R48 are an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group. , (X13)-and (X14)-represent anions, and e is an integer of 2-4.

  In general formulas (21) to (23), a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and carbon Examples of the alkylsilyl group having 1 to 20 are the same as those described in the description of the general formula (1) and the general formula (2).

  The compound represented by the general formula (21) is an anthracene skeleton, the compound represented by the general formula (22) is a thioxanthone skeleton, and the compound represented by the general formula (23) is a compound having a benzophenone skeleton, i-line (365 nm). It is an example of a compound having a maximum absorption wavelength in the vicinity. R14 to R23 are modified in consideration of adjustment of absorption wavelength, adjustment of sensitivity, thermal stability, reactivity, decomposability, etc., hydrogen atom, halogen atom, C1-20 alkoxy group, nitro group A carboxyl group, a hydroxyl group, a mercapto group, an alkylsilyl group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, an amino group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a phenyl group, and a naphthyl group. The atom or substituent selected from the group is modified according to the purpose. However, any one of R14 to R23 is a substituent represented by General Formula (24) or General Formula (25).

  R14 to R23 are preferably a halogen atom, a cyano group, a phenyl group, a naphthyl group, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms, and more preferably a cyano group or a phenyl group. , An alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms and an acyl group having 1 to 15 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. And an acyl group having 1 to 10 carbon atoms. The above alkyl moiety may be linear, branched or cyclic.

  Specific examples of R14 to R23 include the compounds described in the description of R8 to R13 in the general formulas (17) to (19).

  The substituent represented by the general formula (24) is a substituent having a cationized amidine skeleton, and e is an integer of 2 to 4. Examples of the substituent include a substituent having a cationized structure of 1,8-diazabicyclo [5.4.0] -7-undecene in which e is 4, and 1,5-diazabicyclo [4. 3.0] -5-Nonene is preferably a substituent having a cationized structure. R42 and R43 represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. .

  The general formula (25) has a quaternary ammonium structure, and R44 and R45 represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R46 to R48 represent an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group, and may be linear, branched or cyclic. R46 to R48 are preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms.

  In formulas (24) and (25), (X13)-and (X14)-represent anions, specifically exemplified as (X1)-or (X2)-in formula (1) or (2). The same thing as what was done is mentioned. Of these, aliphatic or aromatic carboxy ions and borate anions are preferred from the viewpoint of photodegradability.

  The compound represented by the general formula (24) generates a basic compound having an amidine skeleton by cleaving the bond between carbon and nitrogen to which R42 and R43 are bonded by irradiation with actinic rays. When a compound represented by is irradiated with actinic rays, a bond between carbon and nitrogen to which R44 and R45 are bonded is cleaved to generate a tertiary amine.

  Examples of the carbamate derivative (E21) include 1-Z-4-piperidone.

  Even if any of the acid generator (D) and the base generator (E) is used in the photocurable conductive paste of the present invention, a cured product having excellent adhesion to various substrates can be obtained. From the viewpoints of properties and conductivity, it is preferable to use an acid generator (D).

In the present invention, (C1), (C2), (D1), (D2), (E1), or (E2) may be contained in any combination of the following (1) to (4) preferable.
(1) Contains (C1) and (D2) and / or (E2).
(2) Contains (D1) and (C2).
(3) Contains (E1) and (C2).
(4) A combination of two or more of (1) to (3) above.
(2) may further contain (E2), and (3) may further contain (D2).

In (1) above, radicals are generated as active species (H) upon irradiation with actinic rays, and acids and / or bases are generated as active species (I).
In (2) above, an acid is generated as the active species (H) by irradiation with actinic rays, and a radical and, if necessary, a base are generated as the active species (I).
In (3) above, a base is generated as an active species (H) by irradiation with actinic rays, and a radical and an acid are generated as necessary as an active species (I).

  Among these combinations, more preferred are those containing (C1) and (D2) of (1), (D1) and (C2) of (2) (C1), (C2) Containing the compound (C12) applicable as any of the above, and the compound (C12) applicable as any of (C1) and (C2) out of (E1) and (C2) in (3) Particularly preferred are those containing (C1) and (D2), and those containing (D1) and (C12).

The photocurable conductive paste of the present invention does not need to contain both the acid generator (D) and the base generator (E) at the same time.
Therefore, the content of (D) in the case of only (D), the content of (E) in the case of only (E), or (D) and (E) when (D) and (E) are used in combination. The total content of the photocurable conductive paste of the present invention is 0.005 to 7.5% by weight, preferably 0.05 to 3% by weight.
Furthermore, the content of (D) in the case of only (D), the content of (E) in the case of only (E), or (D) and (E) when (D) and (E) are used in combination From the viewpoint of conductivity, the total content of is preferably 5 to 50 parts by weight, more preferably 10 to 45 parts by weight with respect to 100 parts by weight of the radical initiator (C).
When the content of the acid generator (D) and / or the base generator (E) with respect to the radical initiator (C) is 5 parts by weight or more, the conductivity is excellent. This is because the sensitivity is increased and the macroscopic reaction rate distribution can be suppressed, so that curing shrinkage occurs effectively in the vicinity of the conductive filler (B), and the distance between the conductive fillers is reduced. It is considered that conductivity can be obtained.
On the other hand, when the amount exceeds 50 parts by weight, the amount of the acid or base generated is too large, and the strength of the cured coating film may be lowered during the heat treatment after curing.
Moreover, since base material adhesiveness improves compared with the case where neither (D) nor (E) is used, sufficient base material adhesiveness can be ensured even when the content of the radical polymerizable compound (A) is relatively small. . That is, since it is possible to increase the content of the conductive filler (B) in the photocurable conductive paste, it is possible to achieve both good conductivity and substrate adhesion, which has been difficult in the past.

The photocurable conductive paste of the present invention preferably does not contain (a polymerizable compound (F) other than the radically polymerizable compound (A)), a thermosetting compound (F1) or an ionic polymerization compound (F2).
The photocurable conductive paste of the present invention has little change between the viscosity immediately after compounding and the viscosity after storage at room temperature after compounding the conductive filler, and has good storage stability, so it is not necessary to store it in a cool and dark place. Has features. Moreover, the hardened | cured material obtained by hardening | curing the photocurable conductive paste of this invention has favorable adhesiveness to a base material.
However, when the photocurable conductive paste of the present invention further contains a polymerizable compound (F) other than the radical polymerizable compound (A), the viscosity after storage at room temperature is remarkably increased with respect to the viscosity immediately after blending. Or the adhesion to the substrate may be lowered, which is not preferable.
Here, examples of the polymerizable compound (F) other than the radically polymerizable compound (A), which is not preferable to be used in combination, include a thermosetting compound (F1) as a polymerizable compound that inhibits viscosity stability and an adhesive property. Examples of the polymerizable compound include an ionic polymer compound (F2).

The thermosetting compound (F1) that inhibits viscosity stability means a compound that can be a raw material for thermosetting to form a resin. Specifically, the epoxy compound, amine compound, polyhydric phenol, carboxylic acid Examples thereof include compounds such as anhydrides that do not have a radical polymerizable group in the molecule. These photocurable conductive pastes not containing a thermosetting compound have better storage stability at room temperature than photocurable conductive pastes containing a thermosetting compound, and therefore do not need to be stored in a cool and dark place.
On the other hand, for example, when a bisphenol A type epoxy resin (Epicoat 828EL, manufactured by Mitsubishi Chemical Corporation), which is a thermosetting compound (F1), is contained, the viscosity increases about 1.5 times when left at 25 ° C. for 2 weeks. May stick.

  Examples of the amine compound include compounds having one or more primary to tertiary amino groups in one molecule. Specifically, for example, aromatic amines such as metaphenylenediamine and diaminodiphenylmethane, imidazole compounds such as 2-methylimidazole, 1,2-dimethylimidazole and 1-cyanoethyl-2-methylimidazole, 2-methylimidazoline and the like Examples include imidazoline compounds, dihydrazide compounds such as sebacic acid dihydrazide and isophthalic acid dihydrazide, amine adducts such as Amicure PN-23, Amicure MY-24, and Amicure VDH (all manufactured by Ajinomoto Fine-Techno Co., Ltd.), and dicyandiamide.

  The polyhydric phenol is not particularly limited, and examples thereof include polyphenol compounds such as EpiCure 170 and EpiCure YL6065 (both manufactured by Mitsubishi Chemical Corporation), and novolak type phenol resins such as EpiCure MP402FPI (manufactured by Mitsubishi Chemical Corporation).

  It does not specifically limit as said carboxylic acid anhydride, For example, epicure YH-306, YH-307 (all are Mitsubishi Chemical Corporation make) etc. are mentioned, for example.

  Examples of the ion polymerizable compound (F2) include an epoxy compound having 3 to 20 carbon atoms and an oxetane compound having 4 to 20 carbon atoms. None of these compounds is contained in the photocurable conductive paste of the present invention. When an ion polymerizable compound is mixed, the adhesion of the cured product to the substrate may be reduced.

As said C3-C20 epoxy compound, the following monofunctional or polyfunctional epoxy compounds are mentioned, for example.
Examples of the monofunctional epoxy compound include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide. 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide and 3-vinylcyclohexene oxide. .

  Examples of the polyfunctional epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S diglycidyl ether. Epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexyl) Til) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6 '-Methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), Dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Serine triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2,7,8-di Examples include epoxy octane and 1,2,5,6-diepoxycyclooctane.

  Examples of the oxetane compound having 4 to 20 carbon atoms include compounds having 1 to 6 oxetane rings.

  Examples of the compound having one oxetane ring include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4 -Fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-ethyl-3 -Oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanyl) Methyl) ether, 2-ethylhexyl (3-ethyl-3-o Cetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, Dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxy Ethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) Ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether and bornyl (3-ethyl-3-oxetanylmethyl) ether.

  Examples of the compound having 2 to 6 oxetane rings include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- (2-methylenyl) propanediylbis ( Oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl ] Ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis (3-ethyl-3-oxetanyl) Methyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4 -Bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis ( 3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified di Pentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO Modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A Bis (3-ethyl-3-oxetanylmethyl) ether and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether are mentioned.

The photocurable conductive paste of the present invention can contain a solvent, a sensitizer, a leveling agent, and the like, if necessary.
However, it is better not to include those corresponding to the above-mentioned thermosetting compound (F1) and ionic polymerization compound (F2), and the amount should be kept to a minimum when blended.

Solvents include glycol ethers (ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol alkyl ether). Acetate and propylene glycol alkyl ether acetate, etc.), aromatic hydrocarbons (toluene, xylene, mesitylene, limonene, etc.), alcohols (methanol, ethanol, normal propanol, isopropanol, butanol, geraniol, linalool, citronellol, etc.) and ethers (Tetrahydrofuran and 1,8-cineole etc.). These may be used alone or in combination of two or more.
The content of the solvent is preferably 0 to 99% by weight, more preferably 3 to 95% by weight, and particularly preferably 5 to 90% by weight with respect to the photocurable conductive paste.

  Examples of the sensitizer include ketocoumarin, fluorene, thioxanthone, anthraquinone, naphthiazoline, biacetyl, benzyl and derivatives thereof, perylene, and substituted anthracene. The content of the sensitizer is preferably 0 to 10% by weight, more preferably 0 to 1% by weight with respect to the photocurable conductive paste.

  Examples of the leveling agent include fluorine-based leveling agents (perfluoroalkylethylene oxide adducts and the like) and silicone-based leveling agents (amino polyether-modified silicone, methoxy-modified silicone, polyether-modified silicone, and the like). Moreover, what has radical polymerizability and what does not have can be used. The content of the leveling agent is preferably 2% by weight or less, more preferably 0.5% by weight or less, from the viewpoint of the effect of addition and transparency with respect to the photocurable conductive paste.

  The photo-curable conductive paste of the present invention is further provided with an adhesion-imparting agent (such as a silane coupling agent), a dispersant, an antifoaming agent, a thixotropic agent, a slip agent, a flame retardant, a charge according to the purpose of use. An inhibitor, an antioxidant, an ultraviolet absorber and the like can be contained.

  The photocurable conductive paste of the present invention comprises a radical polymerizable compound (A), a conductive filler (B), a radical initiator (C), an acid generator (D) and / or a base generator (E), If necessary, it can be obtained by kneading other components and the like with a rotation and revolution type stirrer, a planetary mixer, a ball mill or a three-roll mill. The kneading temperature is preferably 10 ° C to 40 ° C, more preferably 20 ° C to 30 ° C.

  The viscosity at 25 ° C. of the photocurable conductive paste of the present invention is preferably 0.001 to 50 Pa · s, and preferably 0.01 to 30 Pa · s from the viewpoint of dispersibility and coating properties of the conductive filler. More preferably.

  As a method for applying the photocurable conductive paste of the present invention to a substrate, known coating methods such as spin coating, roll coating and spray coating, lithographic printing, carton printing, metal printing, offset printing, screen printing and gravure printing are used. A known printing method such as printing can be applied. In addition, ink-jet coating that continuously discharges fine droplets can also be applied.

  When the photocurable conductive paste of the present invention contains a solvent, it is preferably dried after coating. Examples of the drying method include hot air drying (circulation dryer, dryer, etc.). The drying temperature is usually 10 to 200 ° C., the upper limit is preferably 150 ° C. from the viewpoint of the smoothness and appearance of the coating film, and the lower limit is preferably 35 ° C. from the viewpoint of the drying speed.

Examples of the actinic rays used for curing the photocurable conductive paste of the present invention include visible rays and ultraviolet rays.
Since the photocurable conductive paste of the present invention can be photocured by irradiation with an actinic ray of 360 nm to 830 nm, in addition to a commonly used high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a high power metal halide lamp, and the like ( The latest trend of UV / EB curing technology, edited by Radtech Research Group, CM Publishing, page 138, 2006) can be used. Moreover, the irradiation apparatus using an LED light source can also be used conveniently. Furthermore, sunlight, a low-pressure mercury lamp, a semiconductor laser, etc. can be used. Heating may be performed for the purpose of diffusing the acid and / or base generated from the acid generator (D) and / or the base generator (E) during and / or after irradiation with actinic rays. The heating temperature is preferably 30 ° C to 200 ° C, more preferably 35 ° C to 150 ° C.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. Hereinafter, unless otherwise specified, “%” means “% by weight” and “part” means “part by weight”.

[Production of acid generator (D)]
Production Example 1
[Synthesis of sulfonium salt derivative (D121-1) {compound represented by chemical formula (26)} that generates an acid by actinic rays]

(1) Synthesis of 2- (phenylthio) thioxanthone [intermediate (D121-1-1)]:
11.0 parts of 2-chlorothioxanthone, 4.9 parts of thiophenol, 2.5 parts of potassium hydroxide and 162 parts of N, N-dimethylformamide were uniformly mixed and reacted at 130 ° C. for 9 hours. The product was cooled to room temperature (about 25 ° C.) and poured into 200 parts of distilled water to precipitate the product. This was filtered, and the residue was washed with water until the pH of the filtrate became neutral, and then the residue was dried under reduced pressure to obtain a yellow powdery product. Purification by column chromatography (eluent: toluene / hexane = 1/1: volume ratio) yielded 3.1 parts of intermediate (D121-1-1) (yellow solid).

(2) Synthesis of 2-[(phenyl) sulfinyl] thioxanthone [intermediate (D121-1-2)]:
While stirring 11.2 parts of the intermediate (D121-1-1), 215 parts of acetonitrile, and 0.02 part of sulfuric acid at 40 ° C., 4.0 parts of 30% aqueous hydrogen peroxide solution was gradually added dropwise thereto. After reacting at ˜45 ° C. for 14 hours, the reaction solution was cooled to room temperature (about 25 ° C.) and poured into 200 parts of distilled water to precipitate the product. This was filtered, and the residue was washed with water until the pH of the filtrate became neutral, and then the residue was dried under reduced pressure to obtain a yellow powdery product. The product was purified by column chromatography (eluent: ethyl acetate / toluene = 1/3: volume ratio) to obtain 13.2 parts of intermediate (D121-1-2) (yellow solid).

(3) Synthesis of sulfonium salt derivative (D121-1):
While stirring 4.3 parts of intermediate (D121-1-2), 4.1 parts of acetic anhydride and 110 parts of acetonitrile at 40 ° C., 2.4 parts of trifluoromethanesulfonic acid was gradually added dropwise to After reacting at 45 ° C. for 1 hour, the reaction solution is cooled to room temperature (about 25 ° C.), poured into 150 parts of distilled water, extracted with chloroform, and washed with water until the pH of the aqueous phase becomes neutral. did. After the chloroform phase was transferred to a rotary evaporator and the solvent was distilled off, 50 parts of toluene was added, dispersed in toluene with an ultrasonic cleaner, allowed to stand for about 15 minutes, and then the supernatant was removed three times to produce The washed solid was washed, and the residue was dried under reduced pressure. This residue was dissolved in 212 parts of dichloromethane, poured into 65 parts of 10% potassium {trifluoro [tris (perfluoroethyl)] phosphate} aqueous solution, and stirred at room temperature (about 25 ° C.) for 2 hours. After washing three times with water by a liquid separation operation, the organic solvent was distilled off under reduced pressure to obtain 5.5 parts of a sulfonium salt derivative (D121-1) (yellow solid).

Production Example 2
[Synthesis of Iodonium Salt Derivative (D122-1) {Compound Represented by Chemical Formula (27)} that Generates Acid by Active Light]

  6.5 parts of toluene [manufactured by Tokyo Chemical Industry Co., Ltd.], 8.1 parts of isopropylbenzene [manufactured by Tokyo Chemical Industry Co., Ltd.], 5.35 parts of potassium iodide [manufactured by Tokyo Chemical Industry Co., Ltd.] and acetic anhydride 20 parts were dissolved in 70 parts of acetic acid, cooled to 10 ° C., and a mixed solution of 12 parts of concentrated sulfuric acid and 15 parts of acetic acid was added dropwise over 1 hour while maintaining the temperature at 10 ± 2 ° C. It heated up to 25 degreeC and stirred for 24 hours. Thereafter, 50 parts of diethyl ether was added to the reaction solution, washed with water three times, and diethyl ether was distilled off under reduced pressure. An aqueous solution in which 118 parts of potassium {trifluoro [tris (perfluoroethyl)] phosphate} was dissolved in 100 parts of water was added to the residue, followed by stirring at 25 ° C. for 20 hours. Thereafter, 500 parts of ethyl acetate was added to the reaction solution, washed with water three times, and the organic solvent was distilled off under reduced pressure to obtain 14.0 parts of the target iodonium salt derivative (D122-1) (light yellow liquid). It was.

[Production of base generator (E)]
Production Example 3
[Synthesis of Base Generator (E122-1) {Compound Represented by Chemical Formula (28)}]

  Dissolve 2.0 parts of 9-chloromethylanthracene (manufactured by Aldrich) in chloroform and add 3.1 parts of trioctylamine [manufactured by Wako Pure Chemical Industries, Ltd.] little by little (slightly exothermic after addition) The mixture was stirred at room temperature (about 25 ° C.) for 1 hour to obtain a reaction solution. The reaction solution is dropped little by little into an aqueous solution consisting of 4.0 parts of sodium tetraphenylborate salt and 40 parts of water, and the mixture is further stirred for 1 hour at room temperature (about 25 ° C.). The layer was washed 3 times with water. The organic solvent was distilled off under reduced pressure to obtain 7.1 parts of a white solid. This white solid was recrystallized from acetonitrile to obtain 6.2 parts of a base generator (E122-1) (white solid).

Production Example 4
[Synthesis of Base Generator (E123-1) {Compound Represented by Chemical Formula (29)}]

  “Trioctylamine [manufactured by Wako Pure Chemical Industries, Ltd.] 3.1 parts” is replaced with “1,8-diazabicyclo [5.4.0] -7-undecene [San Apro Co., Ltd.“ DBU ”] 1.3. 4.7 parts of a base generator (E123-1) (white solid) was obtained in the same manner as in Production Example 3, except that it was changed to “parts”.

Examples 1-10
The number of radically polymerizable compounds (A), conductive filler (B), radical initiator (C), acid generator (D) or base generator (E), and other components shown in Table 1 are included. The number of parts listed in Table 1 were mixed and mixed for 10 minutes at 25 ° C. using a rotation and revolution type stirring device to produce the photocurable conductive pastes (Q-1) to (Q-10) of the present invention.

Comparative Examples 1-5
The number of radically polymerizable compounds (A), conductive filler (B), radical initiator (C), acid generator (D), and polymerizable compound (F) other than (A) shown in Table 1 And other components are blended in the number of parts shown in Table 1, and mixed for 10 minutes at 25 ° C. using a rotation and revolution type stirring device, and comparative photo-curing conductive pastes (Q′-1) to (Q '-5) was produced.

The contents indicated by the symbols in the table are as follows.
<Radically polymerizable compound (A)>
“Light acrylate PO-A”: Kyoeisha Chemical Co., Ltd. Phenoxyethyl acrylate “NK Ester A-200”: Shin-Nakamura Chemical Co., Ltd. Polyethylene glycol diacrylate “Aronix M-350”: Toagosei Co., Ltd. trimethylolpropane EO adduct Triacrylate “SR-494”: EO adduct tetraacrylate “Neomer DA-600” manufactured by Sartomer, Inc .: Dipentaerythritol pentaacrylate <conductive filler (B)> manufactured by Sanyo Chemical Industries
“CA-405NL”: Silver fine particle-containing paste manufactured by Daiken Chemical Co., Ltd. <Radical initiator (C)>
“LUCIRIN TPO”: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide manufactured by BASF Japan Ltd. “IRGACURE 819”: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide <additive> manufactured by BASF Japan Ltd.
“KF-615A”: Silicone leveling agent manufactured by Shin-Etsu Chemical Co., Ltd.

[Performance evaluation]
Viscosity at 25 ° C., rate of change in viscosity, coating of the photocurable conductive paste of the present invention prepared in Examples 1 to 11 and the photocurable conductive paste for comparison prepared in Comparative Examples 1 to 5 Property, curability, and substrate adhesion of a cured coating film, and conductivity (volume resistance value) were evaluated by the following methods.

[viscosity]
The viscosity (p) at 25 ° C. of the photocurable conductive pastes obtained in Examples 1 to 11 and Comparative Examples 1 to 5 was determined as an E type viscometer [manufactured by Toki Sangyo Co., Ltd., TVE-25 type viscometer]. It measured using.

[Coating properties]
A PET film (Lumirror # 100-U48, manufactured by Toray Industries, Inc.) having a thickness of about 10 μm obtained by subjecting about 1 g of the photocurable conductive paste obtained in Examples 1 to 11 and Comparative Examples 1 to 5 to a surface treatment. It applied to what was cut and was apply | coated so that it might become a film thickness of 10 micrometers using the applicator. The state of the coating film immediately after coating was visually observed and evaluated according to the following evaluation criteria.
○: Can be applied to the entire surface of the film, and there is almost no aggregation or film thickness fluctuation.
(Triangle | delta): Although it can apply to the whole film surface, an aggregate is seen. Or the film thickness fluctuation is slightly large.
X: The film was not sufficiently spread and spread and could not be applied to the entire film surface.

[Curing property]
The photocurable conductive paste obtained in Examples 1 to 11 and Comparative Examples 1 to 5 was applied to the PET film subjected to surface treatment so as to have a film thickness of 10 μm using an applicator. Next, it exposed using the belt conveyor type | mold UV irradiation apparatus (The product made by Fusion UV Systems Japan, "CV-1100-G"). The exposure amount was 3000 mJ / cm 2 at 365 nm.
The curability immediately after light irradiation of the coated film after curing was evaluated by the following evaluation criteria by scratching with a finger and nails.
A: There is no tack on the surface and it is not damaged by the nail.
○: There is no tack on the surface, but the nail is damaged.
Δ: There is tack on the surface and it is damaged by the nail.
X: Uncured.

[Adhesion]
The photo-curing conductive pastes obtained in Examples 1 to 11 and Comparative Examples 1 to 5 were subjected to surface treatment on the above-described PET film and surface-untreated PET film having a thickness of 100 μm (manufactured by Toray Industries, Inc., Lumirror) # 100-T60) was applied with an applicator so as to have a film thickness of 10 μm, and was exposed using the belt conveyor type UV irradiation apparatus. The exposure amount was 3000 mJ / cm 2 at 365 nm.
About each sample, the adhesiveness with respect to a base material was evaluated by the peeling test using cello tape CT-18 (trademark, Nichiban Co., Ltd. product). At this time, one minute after the cellophane tape was completely attached to the coating film, a peeling test was performed by holding the one end of the tape and pulling it off at a time while maintaining an angle of 90 ° with respect to the substrate. As evaluation criteria, the case where no peeling occurred was evaluated as ◯, the case where less than 1/5 was peeled off as Δ, and the case where 1/5 or more peeling occurred as x.

[Conductivity (Volume resistivity)]
The photo-curing conductive pastes obtained in Examples 1 to 11 and Comparative Examples 1 to 5 were subjected to surface treatment on the above-described PET film and surface-untreated PET film having a thickness of 100 μm (manufactured by Toray Industries, Inc., Lumirror) # 100-T60) was applied with an applicator so as to have a film thickness of 10 μm, and was exposed using the belt conveyor type UV irradiation apparatus. The exposure amount was 3000 mJ / cm 2 at 365 nm. Subsequently, it heated at 120 degreeC for 1 hour using the circulating air dryer.
About each sample, the volume resistivity of five places of a sample was measured using the resistivity meter (Mitsubishi Chemical Analytech Co., Ltd. product, "MCP-T600"), and the average value was made into conductivity (volume resistivity). It was.
These evaluation results are shown in Table 1.

The photocurable conductive pastes of Examples 1 to 11 of the present invention were good in any performance evaluation items.
On the other hand, in Comparative Example 1, the resin was not cured and the adhesion and volume resistivity could not be evaluated. In Comparative Example 2, the adhesiveness was insufficient and the volume resistivity was high. Comparative Example 3 was cured because of poor coatability, but did not form a uniform film and did not adhere to the substrate. In Comparative Example 4, the substrate adhesion after photocuring was good, but the conductivity was poor because the film strength was lowered and the adhesion deteriorated by the heat treatment during the conductivity test. In Comparative Example 5, adhesion to untreated PET was insufficient. Moreover, the volume resistivity was slightly high.

  The photocurable conductive paste of the present invention is excellent in coating suitability and storage stability at room temperature, and the substrate adhesion of the cured coating film is also good. In addition, since high conductivity is obtained even at a low temperature of 120 ° C. for 1 hour and a short time of post-heating conditions, it is extremely useful for forming a wiring for manufacturing a flat panel display, a touch panel, or an electronic component.

Claims (9)

  It contains a radical polymerizable compound (A), a conductive filler (B), a radical initiator (C), an acid generator (D) and / or a base generator (E), and the content of (C) is ( A) 10 to 30 parts by weight with respect to 100 parts by weight, and the total content of (D) and (E) is 5 to 50 parts by weight with respect to (C) 100 parts by weight A curable conductive paste.   The photocurable electrically conductive paste of Claim 1 in which a radically polymerizable compound (A) contains (meth) acrylate (A1).   The photocuring according to claim 2, wherein the (meth) acrylate (A1) contains a trifunctional (meth) acrylate (A13) and / or a tetrafunctional (meth) acrylate (A14) and a monofunctional (meth) acrylate (A11). Type conductive paste.   The photocurable conductive paste according to any one of claims 1 to 3, wherein the conductive filler (B) is a metal powder or a carbon material.   The photocurable conductive paste according to any one of claims 1 to 4, wherein the anion portion of the acid generator (D) is a phosphate anion or a borate anion containing a fluorine atom. The radical initiator (C) is a radical initiator (C1) that generates radicals by actinic rays or a radical initiator (C2) that generates radicals by acid and / or base, and the acid generator (D) is An acid generator (D1) that generates an acid by actinic rays, or an acid generator (D2) that generates an acid by at least one selected from the group consisting of radicals, acids and bases, and the base generator (E) A base generator (E1) that generates a base by actinic rays, or a base generator (E2) that generates a base by at least one selected from the group consisting of radicals, acids and bases, (C1), ( C2), (D1), (D2), (E1), or (E2) is contained in any combination of the following (1)-(4), The photocurable type in any one of Claims 1-5 Conductive paste.
(1) Contains (C1) and (D2) and / or (E2).
(2) Contains (D1) and (C2).
(3) Contains (E1) and (C2).
(4) A combination of two or more of (1) to (3) above. The photocurable electrically conductive paste in any one of Claims 1-6 which do not contain polymerizable compounds (F) other than a radically polymerizable compound (A).   The photocurable conductive paste according to any one of claims 1 to 7, wherein the polymerizable compound (F) is a thermosetting compound (F1) or an ionic polymerization compound (F2).   The photocurable conductive paste according to any one of claims 1 to 8, which is used for wiring formation in flat panel display, touch panel, or electronic component manufacturing.