WO2017170493A1

WO2017170493A1 - Conductive paste

Info

Publication number: WO2017170493A1
Application number: PCT/JP2017/012548
Authority: WO
Inventors: 大樹三原; 惇哉三宅; 直美佐藤
Original assignee: 株式会社Adeka
Priority date: 2016-03-31
Filing date: 2017-03-28
Publication date: 2017-10-05
Also published as: TW201807093A; CN108369831A; KR102426654B1; KR20220038174A; JPWO2017170493A1; KR20180132598A

Abstract

The present invention provides a conductive paste which has good sensitivity, resolution and adhesion properties, while having low resistance. The present invention specifically provides a conductive paste which contains (A) a polymerization initiator containing one or more oxime ester compounds represented by general formula (I), (B) a binder resin, (C) an ethylenically unsaturated compound, (D) conductive particles and (E) a solvent. The conductive paste according to the present invention preferably uses, as the binder resin (B), an epoxy addition compound having a structure wherein an unsaturated monobasic acid is added to an epoxy compound represented by general formula (II) or an esterified product of the epoxy addition compound and a polybasic acid anhydride. In this connection, general formula (I) and general formula (II) are as defined in the description.

Description

Conductive paste

The present invention relates to a conductive paste containing a specific polymerization initiator.

Photolithography is known as a method for forming a conductive pattern on a substrate such as glass, ceramic, or silicon wafer. In recent years, mobile electronic devices such as smartphones and touch panels are required to be smaller and have higher definition. .

Patent Documents 1 to 4 disclose various conductive pastes, but satisfactory resolution has not been obtained.

JP 2001-154345 A JP 2013-101861 A JP 2013-210498 A Japanese Patent No. 3620861

The problem to be solved is that there has never been a conductive paste having good sensitivity, resolution and adhesion and low resistance.

Therefore, an object of the present invention is to provide a conductive paste having good sensitivity, resolution and adhesion and low resistance.

The present invention includes a polymerization initiator (A) containing at least one oxime ester compound represented by the following general formula (I), a binder resin (B), an ethylenically unsaturated compound (C), and conductive particles (D). And the said objective is achieved by providing the electrically conductive paste containing a solvent (E).

(Wherein R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN;
R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon atom. Represents a heterocyclic-containing group of formula 2 to 20,
The hydrogen atoms of the groups represented by R ¹¹ , R ¹² and R ¹³ are further R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , —NR ²² —OR ²³ , —NCOR ²² -OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , hydroxyl group, nitro group, CN, amino group, halogen atom or COOR ²¹ may be substituted ,
R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon atom. Represents a heterocyclic-containing group of formula 2 to 20,
The hydrogen atom of the group represented by R ²¹ , R ²² and R ²³ may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, a hydroxyl group or a carboxyl group,
The methylene groups in the groups represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ are —O—, —S—, —COO—, —OCO—, —NR ²⁴ —, — NR ²⁴ COO—, —OCONR ²⁴ —, —SCO—, —COS—, —OCS— or —CSO— may be substituted 1 to 5 times under the condition that the oxygen atoms are not adjacent to each other,
R ²⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. Represent,
When the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ has an alkyl moiety, the alkyl moiety may have a branched side chain and is a cyclic alkyl. In some cases,
R ³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. And when the group represented by R ³ has an alkyl moiety, the alkyl moiety may have a branched side chain or a cyclic alkyl,
The hydrogen atom of the group represented by R ³ is further represented by R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , —NR ²² —OR ²³ , —NCOR ²² —OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , hydroxyl group, nitro group, CN, halogen atom or COOR ²¹ may be substituted,
R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹⁴ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ¹¹ , a hydroxyl group, CN or a halogen atom,
R ³ and R ⁷ , R ³ and R ⁸ , R ⁴ and R ⁵ , R ⁵ and R ⁶ or R ⁶ and R ⁷ may be combined to form a ring,
R ¹⁴ , R ¹⁵ and R ¹⁶ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
R ⁸ is R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹¹ , CSOR ¹¹ , hydroxyl group, CN or halogen atom Represents
n represents 0 or 1. )

The present invention also provides a conductive pattern made of the above conductive paste.

In addition, the present invention provides a method for forming a conductive pattern comprising a step of applying the conductive paste on a substrate, a step of drying, a step of exposing using a mask, a step of developing, and a step of baking at 100 to 300 ° C. Is to provide.

The present invention also provides a touch panel provided with the above conductive pattern.

Hereinafter, the conductive paste of the present invention will be described in detail based on preferred embodiments.

The conductive paste of the present invention includes a polymerization initiator (A) containing at least one oxime ester compound represented by the general formula (I), a binder resin (B), an ethylenically unsaturated compound (C), and conductive particles. (D) and a solvent (E) are contained. Hereinafter, each component will be described in order.

<Polymerization initiator (A)>
The polymerization initiator (A) used in the present invention contains one or more oxime ester compounds represented by the above general formula (I).
The oxime ester compound represented by the general formula (I) has geometric isomers due to oxime double bonds, but these are not distinguished.
That is, in this specification, the oxime ester compound represented by the above general formula (I) and the exemplified compound thereof represent a mixture of both or one of them when a geometric isomer is present in the compound. It is not limited to one geometric isomer specified in the specification.

In the general formula (I), the number of carbon atoms represented by R ³ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ and R ²⁴ is 1 to Examples of the alkyl group of 20 include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t -Octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl and the like.

Examples of the aryl group having 6 to 30 carbon atoms represented by R ³ , R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ in the general formula (I) include: Phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl, biphenylyl, naphthyl, anthryl substituted with one or more of the above alkyl groups.

Examples of the arylalkyl group having 7 to 30 carbon atoms represented by R ³ , R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ in the general formula (I) include , Benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and the like.

Examples of the heterocyclic group having 2 to 20 carbon atoms represented by R ³ , R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ , and R ²⁴ in the general formula (I) include For example, pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, morpholinyl, etc. And a group in which a 5- to 7-membered heterocyclic ring and a methylene chain are combined.

In the general formula (I), R ³ and R ⁷ , R ³ and R ⁸ , R ⁴ and R ⁵ , R ⁵ and R ^6, or R ⁶ and R ⁷ can be combined to form a ring. Preferred examples include 5- to 7-membered rings such as cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring and lactam ring.

Further, R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 in} the general formula (I), and R ³ , R ¹¹ , R ¹² , R ¹³ , R ^{21 in the} general formula (I). , R ²² and R ²³ may be substituted with fluorine, chlorine, bromine and iodine.

In the general formula (I), the methylene groups in the groups represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ are —O—, —S—, —COO—, — 1 under the condition that oxygen atoms are not adjacent to each other by OCO—, —NR ²² —, —NR ²² CO—, —NR ²² COO—, —OCONR ²² —, —SCO—, —COS—, —OCS— or —CSO—. The bonding group to be replaced at this time may be one kind or two or more kinds. In the case of a group which can be continuously replaced, two or more groups may be continuously replaced.
In addition, when the group represented by R ³ , R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ in the general formula (I) has an alkyl (alkylene) moiety, ) Moiety may have a branched side chain or may be a cyclic alkyl. Examples of the cyclic alkyl include cyclic alkyl having 4 to 8 carbon atoms such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. For example, groups in which the alkyl moiety of the group represented by R ³ , R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is a cyclic alkyl include cyclobutylmethyl, cyclobutylethyl, cyclobutyl Carbon atoms such as propyl, cyclobutylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl, cycloheptylmethyl, cycloheptylethyl, cycloheptylpropyl, cycloheptylbutyl, etc. Examples thereof include 5 to 12 cycloalkyl groups.

Accordingly, preferred specific examples of the compound represented by the above general formula (I) include the following compound Nos. 1-No. 30. However, the present invention is not limited by the following compounds.

As the compound represented by the general formula (I),
R ¹ is preferably a linear alkyl group having 1 to 12 carbon atoms and a cycloalkylalkyl group having 5 to 12 carbon atoms,
R ² is preferably a linear alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms (particularly a phenyl group),
R ³ is a linear alkyl group having 1 to 6 carbon atoms, COR ²¹ [R ²¹ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms (particularly a phenyl group)], A hydroxyl group, a nitro group, CN, a halogen atom or an amino group, or an unsubstituted phenyl group or an arylalkyl group having 7 to 10 carbon atoms (particularly a benzyl group) is preferable.
R ⁴ , R ⁵ , R ⁶ or R ⁷ is a hydrogen atom, a cyano group, OR ¹¹ [R ¹¹ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms substituted with a hydroxyl group or a carboxyl group] And particularly preferably R ⁵ is a cyano group, OR ¹¹ [R ¹¹ is a hydroxyl group or carboxyl group-substituted or unsubstituted alkyl group having 1 to 6 carbon atoms]
R ⁸ is preferably a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms.

The total content of the oxime ester compound represented by the general formula (I) in the polymerization initiator (A) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.

The polymerization initiator (A) can be used in combination with a known polymerization initiator other than the oxime ester compound represented by the general formula (I).

Preferred examples of the known polymerization initiator include acetophenone compounds, benzyl compounds, benzophenone compounds, thioxanthone compounds, bisimidazole compounds, acridine compounds, acylphosphine compounds, and the like.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl- 2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tertiarybutyldichloroacetophenone, p-tertiarybutyltrichloroacetophenone, p-azidoben Salacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone-1, Be Zoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane -1-one and the like.

Examples of the benzylic compound include benzyl.

Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, and the like. It is done.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

As the bisimidazole compound, hexaarylbisimidazole (HABI, dimer of triaryl-imidazole) can be used. Specifically, for example, 2,2′-bis (2-chlorophenyl) -4 , 4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-Ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2 , 2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophene) ) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,4,5,2', 4 ', 5'-hexaphenyl Bisimidazole, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenylbisimidazole, 2,2'-bis (2-bromophenyl) -4,5,4', 5'-tetraphenylbisimidazole, 2,2'-bis (2,4-dichloroph Nyl) -4,5,4 ′, 5′-tetraphenylbisimidazole, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetrakis (3-methoxyphenyl) bisimidazole, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetrakis (3,4,5-trimethoxyphenyl) -bisimidazole, 2,5,2', 5'-tetrakis ( 2-chlorophenyl) -4,4'-bis (3,4-dimethoxyphenyl) bisimidazole, 2,2'-bis (2,6-dichlorophenyl) -4,5,4 ', 5'-tetraphenylbisimidazole 2,2'-bis (2-nitrophenyl) -4,5,4 ', 5'-tetraphenylbisimidazole, 2,2'-di-o-tolyl-4,5,4', 5'- Tetraphenylbisimida Sol, 2,2'-bis (2-ethoxyphenyl) -4,5,4 ', 5'-tetraphenylbisimidazole and 2,2'-bis (2,6-difluorophenyl) -4,5,4 ', 5'-tetraphenylbisimidazole, 5'-tetra (p-iodophenyl) biimidazole, 2,2'-bis (o-chlorophenyl-4,4', 5,5'-tetra (m-methoxyphenyl) ) Biimidazole), 2,2'-bis (p-methylthiophenyl) -4,5,4 ', 5'-diphenyl-1,1'-biimidazole, bis (2,4,5-triphenyl)- 1,1'-biimidazole, 5,5'-tetra (p-chloronaphthyl) biimidazole, etc., and 1,2'-, 1,4'-, 2, disclosed in JP-B-45-37777 4'- covalently linked to each other Isomers include compounds described in JP WO00 / 52529.

Examples of the acridine compounds include acridine, 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (p-ethylphenyl) acridine, 9- (p-iso-propylphenyl) acridine, 9- (p -N-butylphenyl) acridine, 9- (p-tert-butylphenyl) acridine, 9- (p-methoxyphenyl) acridine, 9- (p-ethoxyphenyl) acridine, 9- (p-acetylphenyl) acridine 9- (p-dimethylaminophenyl) acridine, 9- (p-cyanophenylphenyl) acridine, 9- (p-chlorophenyl) acridine, 9- (p-bromophenyl) acridine, 9- (m-methyl) Phenyl) acridine, 9- (mn-propylphenyl) acridine, 9- (mi o-propylphenyl) acridine, 9- (mn-butylphenyl) acridine, 9- (m-tert-butylphenyl) acridine, 9- (m-methoxyphenyl) acridine, 9- (m-ethoxyphenyl) Acridine, 9- (m-acetylphenyl) acridine, 9- (m-dimethylaminophenyl) acridine, 9- (m-diethylaminophenyl) acridine, 9- (cyanophenyl) acridine, 9- (m-chlorophenyl) acridine 9- (m-bromophenyl) acridine, 9-methylacridine, 9-ethylacridine, 9-n-propylacridine, 9-iso-propylacridine, 9-cyanoethylacridine, 9-hydroxyethylacridine, 9-chloroethyl Acridine, 9-bromoacridine, 9- Droxyacridine, 9-nitroacridine, 9-aminoacridine, 9-methoxyacridine, 9-ethoxyacridine, 9-n-propoxyacridine, 9-iso-propoxyacridine, 9-chloroethoxyacridine, 4,6-bis ( Dimethylamino) acridine, 10-acetic acid acridine, 10-methylacetacridine, 3,6-dimethylacridine, 7,13-dimethylacridine, 7,13-bis (dimethylamino) acridine, 3,6-dimethyl-10-acetic acid Acridine, 3,5-dimethyl-10-methyl acetate acridine, 7,13-dimethyl-10-acetate acridine, 7,13-dimethyl-10-methyl acetate acridine, 1,7-bis (9-acridinyl) heptane, 1 , 5-Bis (9-acridinyl ) Pentane, 1,3-bis (9-acridinyl) propane, 2,7-dibenzoyl-9-phenylacridine, 2,7-bis (α-hydroxybenzyl) -9-phenylacridine, 2,7-bis (α -Acetoxybenzyl) -9-phenylacridine, 2,7-dimethyl-9- (4-methylphenyl) acridine, 2,7-dimethyl-9-phenylacridine, 2,7-bis (3,4-dimethyl-benzoyl) ) -9- (3,4-dimethylphenyl) acridine, 2,7-bis (α-acetoxy-4-tert-butylbenzyl) -9- (4-tert-butylphenyl) acridine, 2,7-dimethyl- 9- (3,4-dichlorophenyl) acridine, 2,7-dimethyl-9- (4-benzoylphenyl) acridine, 2,7-bis (2-c Lobenzoyl) -9- (2-chlorophenyl) acridine, 2- (α-hydroxy-3-bromobenzyl) -6-methyl-9- (3-bromophenyl) acridine, 2,5-bis (4-tert- Butylbenzoyl) -9- (4-tert-butylphenyl) acridine, 1,4-bis (2,7-dimethyl-9-acridinyl) benzene,
2,7-bis (α-phenylaminocarbonyloxy-3,4-dimethylbenzyl) -9- (3,4-dimethylphenyl) acridine and 2,7-bis (3,5-dimethyl-4-hydroxy-4) '-Fluorodiphenylmethyl) -9- (4-fluorophenyl) acridine, 9,10-dihydroacridine, 1-methylacridine, 4-methylacridine, 2,3-dimethylacridine, 1-phenylacridine, 4-phenylacridine 1-benzylacridine, 4-benzylacridine, 1-chloroacridine, 2,3-dichloroacridine, 10-butyl-2-chloroacridine-9 (10H) -one, 10-propyl-2-chloroacridine-9 ( 10H) -one, 10-butyl-2-chloroacridine-9 (10H) -one 1, -Bis (9-acridinyl) ethane, 1,3-bis (9-acridinyl) propane, 1,4-bis (9-acridinyl) butane, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane, 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9 -Acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane, 1,14-bis (9-acridinyl) tetradecane, 1,16-bis (9-acridinyl) hexadecane, 1,18-bis (9-acridinyl) ) Octadecane, 1,20-bis (9-acridinyl) eicosane, 1,3-bis (9-acridinyl) -2-thiapropane, 1,5-bi (9-acridinyl) -3-thiapentane,
7-methyl-benzo [c] acridine, 7-ethyl-benzo [c] acridine, 7-propyl-benzo [c] acridine, 7-butyl-benzo [c] acridine, 7-pentyl-benzo [c] acridine, 7-hexyl-benzo [c] acridine, 7-heptyl-benzo [c] acridine, 7-octyl-benzo [c] acridine, 7-nonyl-benzo [c] acridine, 7-decyl-benzo [c] acridine, 7-undecyl-benzo [c] acridine, 7-dodecyl-benzo [c] acridine, 7-tridecyl-benzo [c] acridine, 7-tetradecyl-benzo [c] acridine, 7-pentadecyl-benzo [c] acridine, 7-hexadecyl-benzo [c] acridine, 7-heptadecyl-benzo [c] acridine, 7-octa Sil-benzo [c] acridine, 7-nonadecyl-benzo [c] acridine, 1,1-bis (7-benzo [c] acridinyl) methane, 1,2-bis (7-benzo [c] acridinyl) ethane, 1,3-bis (7-benzo [c] acridinyl) propane, 1,4-bis (7-benzo [c] acridinyl) butane, 1,5-bis (7-benzo [c] acridinyl) pentane, 6-bis (7-benzo [c] acridinyl) hexane, 1,7-bis (7-benzo [c] acridinyl) heptane, 1,8-bis (7-benzo [c] acridinyl) octane, 1,9- Bis (7-benzo [c] acridinyl) nonane, 1,10-bis (7-benzo [c] acridinyl) decane, 1,11-bis (7-benzo [c] acridinyl) undecane, 2-bis (7-benzo [c] acridinyl) dodecane, 1,13-bis (7-benzo [c] acridinyl) tridecane, 1,14-bis (7-benzo [c] acridinyl) tetradecane, 1,15- Bis (7-benzo [c] acridinyl) pentadecane, 1,16-bis (7-benzo [c] acridinyl) hexadecane, 1,17-bis (7-benzo [c] acridinyl) heptadecane, 1,18-bis ( 7-benzo [c] acridinyl) octadecane, 1,19-bis (7-benzo [c] acridinyl) nonadecane, 1,20-bis (7-benzo [c] acridinyl) eicosane, 7-phenyl-benzo [c] Acridine, 7- (2-chlorophenyl) -benzo [c] acridine, 7- (4-methylphenyl) -benzo [c] acridine, 7- (4-Nitrophenyl) -benzo [c] acridine, 1,3-bis (7-benzo [c] acridinyl) benzene, 1,4-bis (7-benzo [c] acridinyl) benzene, 7- [ 1-propen-3-yl (benzo [c] acridine)], 7- [1-ethylpentyl- (benzo [c] acridine)], 7- [8-heptadecenyl- (benzo [c] acridine)], 7 , 8-Diphenyl-1,14-bis (7-benzo [c] acridinyl) tetradecane, 1,2-bis (7-benzo [c] acridinyl) ethylene, 1-methyl-1,2-bis (7-benzo [C] acridinyl) ethylene, 7-styryl-benzo [c] acridine, 7- (1-propenyl) -benzo [c] acridine, 7- (1-pentenyl) -benzo [c] acridine, 9 (2-pyridyl) acridine, 9- (3-pyridyl) acridine, 9- (4-pyridyl) acridine, 9- (4-pyrimidinyl) acridine, 9- (2-pyrazinyl) acridine, 9 (5-methyl-2 -Pyrazinyl) acridine, 9- (2-quinolinyl) acridine, 9- (2-pyridyl) -2-methyl-acridine, 9- (2-pyridyl) -2-ethylacridine, 9- (3-pyridyl) -2 -Methyl-acridine, 9- (3-pyridyl) -2,4-diethyl-acridine, 3,6-diamino-acridine sulfonate, 3,6-bis- (dimethylamino) -acridine sulfonate, 3, Examples include 6-diamino-10-methyl-acridinium chloride and 9-acridine carboxylic acid.

Examples of the acylphosphine compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO; manufactured by BASF), isobutyryl-methylphosphinic acid methyl ester, isobutyryl-phenylphosphinic acid methyl ester, and pivaloyl-phenylphosphinic acid methyl. Ester, 2-ethylhexanoyl-phenylphosphinic acid methyl ester, pivaloyl-phenylphosphinic acid isopropyl ester, p-toluyl-phenylphosphinic acid methyl ester, o-toluyl-phenylphosphinic acid methyl ester, 2,4-dimethylbenzoyl-phenyl Phosphinic acid methyl ester, p-tert-butylbenzoyl-phenylphosphinic acid isopropyl ester, acryloyl-phenylphosphite Acid methyl ester, isobutyryl-diphenylphosphine oxide, 2-ethylhexanoyl-diphenylphosphine oxide, o-toluyl-diphenylphosphine oxide, p-tertiarybutylbenzoyl-diphenylphosphine oxide, 3-pyridylcarbonyl-diphenylphosphine oxide, acryloyl- Diphenylphosphine oxide, benzoyl-diphenylphosphine oxide, pivaloyl-phenylphosphinic acid vinyl ester, adipoyl-bis-diphenylphosphine oxide, pivaloyl-diphenylphosphine oxide, p-toluyl-diphenylphosphine oxide, 4- (tertiarybutyl) -benzoyl- Diphenylphosphine oxide, 2-methylbenzoyl-diphenylphosphine Oxide, 2-methyl-2-ethylhexanoyl-diphenylphosphine oxide, 1-methyl-cyclohexanoyl-diphenylphosphine oxide, pivaloyl-phenylphosphinic acid methyl ester and pivaloyl-phenylphosphinic acid isopropyl ester, 4-octylphenylphosphine oxide Terephthaloyl-bis-diphenylphosphine oxide, 1-methyl-cyclohexylcarbonyldiphenylphosphine oxide, versatoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-diisobutoxyphenylphosphine oxide, bis (2 , 4,6-trimethylbenzoyl) phenylphosphine oxide (Irgacure 819; manufactured by BASF), bis (2,4,6-trimethylbenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis ( 2,6-dichloro-3,4,5-trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methyl- 1-naphthoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2-naphthylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-propylphenylphosphine oxide, bis (2 -Methyl-1-naphthoyl) -2,5-dimethylphenylphospho Fin oxide, bis (2-methoxy-1-naphthoyl) -4-ethoxyphenylphosphine oxide, bis (2-chloro-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-dioctyloxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4- Diisopropoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-dihexyloxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2-propoxy-4-methylphenylphosphine Oxide, bis (2 4,6-trimethylbenzoyl) -2,4-diisopentyloxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine Oxide, bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-biphenylylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide Bis (2,6-dichlorobenzoyl) -2-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl -Pencil And phosphine oxide (CGI403), 6-trimethylbenzoyl-ethyl-phenyl-phosphinate (SPEEDCURE TPO-L; manufactured by Lambson), and the like.

The content of the polymerization initiator (A) is preferably 0.1 to 10 parts by mass and preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the solid content of the conductive paste of the present invention. Is preferred. In addition, solid content means the component except a solvent among a certain component. The same applies to the following description.

<Binder resin (B)>
Examples of the binder resin include polyolefin polymers such as polyethylene, polypropylene and polyisobutylene; diene polymers such as polybutadiene and polyisoprene; polymers having a conjugated polyene structure such as polyacetylene polymers and polyphenylene polymers; polyvinyl chloride and polystyrene. , Vinyl acetate, polyvinyl alcohol, polyacrylic acid, polyacrylic acid ester, polyacrylamide, polyacrylonitrile, polyvinylphenol, and other vinyl polymers; polyphenylene ether, polyoxirane, polyoxetane, polytetrahydrofuran, polyetherketone, polyetheretherketone, Polyethers such as polyacetals; phenolic resins such as novolak resins and resol resins; polyethylene terephthalates Polyesters such as polyphenolphthalein terephthalate, polycarbonate, alkyd resin, unsaturated polyester resin; polyamides such as nylon-6, nylon 66, water-soluble nylon, polyphenyleneamide; polypeptides such as gelatin and casein; novolac epoxy resin, bisphenol epoxy Resins, epoxy resins such as modified resins with novolac epoxy acrylate and acid anhydrides and modified products thereof; polyurethane, polyimide, melamine resin, urea resin, polyimidazole, polyoxazole, polypyrrole, polyaniline, polysulfide, polysulfone, celluloses, etc. It is done.
The weight average molecular weight (Mw) of the binder resin (B) is that converted into polystyrene by gel permeation chromatography (GPC), preferably 1,000 to 500,000, more preferably 2,000 to 200,000. Most preferably, it is 3,000 to 100,000. If the Mw of the binder resin is less than 1,000, the heat resistance of the film tends to decrease, whereas if it exceeds 500,000, the developability and coating property of the film tend to decrease. The acid value of the binder resin (B) is preferably 30 to 300 mgKOH / g. If the acid value is less than 30 mgKOH / g, the developability may be deteriorated, and if the acid value is more than 300 mgKOH / g, the resin may be deteriorated.

As the binder resin (B), an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the following general formula (II), or the epoxy addition compound and a polybasic acid anhydride An esterified product with a product is preferable because of its high sensitivity and resolution.

(In the formula, M is a direct bond, an alkylene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, an aryl group having 6 to 12 carbon atoms, O, S, SO ₂ , SS, SO, CO, OCO or a group represented by the following general formula (II-1), (II-2) or (II-3) is represented, and R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a halogen atom, and s is a number from 0 to 10 Represents.)

( ^R109 , ^R110 , ^R111 , ^R112 , ^R113 , ^R114 , ^R115 , ^R116 , ^R117 , ^R118 , ^R119 , ^R120 , ^R121 , ^R122 , ^R123 , ^R124 , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ¹³¹ and R ¹³² are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. Represents an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or a halogen atom, and methylene in the above alkyl group and arylalkyl group groups, unsaturated bonds, by -O- or -S- sometimes oxygen atoms are replaced by conditions that are not ^adjacent, R ^{109, R 110} ^{^{^{^{R 111, R 112, R 117}}}} , R 118, R 119, R 120, R 125, R 126, R 127, R 128, R 129, R 130, R 131 and ^{R 132} are adjacent ^R ^{109, R 110} , R ¹¹¹ , R ¹¹² , R ¹¹⁷ , R ¹¹⁸ , R ¹¹⁹ , R ¹²⁰ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ^131, or R ¹³² form a ring. In some cases, * means that it is bonded to an adjacent group at the * part.)

In the general formula (II), examples of the alkylene group having 1 to 4 carbon atoms include those represented by — (CH ₂ ) _1-4 — as the linear alkylene,
Examples of branched alkylene include 1-methylmethane-1,1-diyl, 1-ethylmethane-1,1-diyl, 1-propylmethane-1,1-diyl, 1-methylethane-1,2-diyl, 1- Examples include ethylethane-1,2-diyl, 1-methylpropane-1,3-diyl and the like.
Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms in the general formula (II) include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecanyl, 1-adamantyl, 2-adamantyl, noradamantyl, and 2-methyl. Adamantyl, norbornyl, isonorbornyl, perhydronaphthyl, perhydroanthracenyl, bicyclo [1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [3. 1.0] hexyl, bicyclo [2.1.1] hexyl, bicyclo [2.2.0] hexyl, bicyclo [4.1.0] heptyl, bicyclo [3.2.0] heptyl, bicyclo [3. 1.1] heptyl, bicyclo [2.2.1] heptyl, bicyclo [5.1.0] octyl, bicyclo [4 2.0] octyl, bicyclo [4.1.1] octyl, bicyclo [3.3.0] octyl, bicyclo [3.2.1] octyl, bicyclo [2.2.2] octyl, spiro [4 4] Nonanyl, spiro [4,5] decanyl, decalin, tricyclodecanyl, tetracyclododecanyl, cedrol, cyclododecanyl and the like.
An alkyl group having 1 to 10 carbon atoms represented by R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ in the general formula (II), represented by M; An aryl group having 6 to 12 carbon atoms, R ¹⁰⁹ , R ¹¹⁰ , R ¹¹¹ , R ¹¹² , R ¹¹³ , R in the above general formula (II-1), (II-2) or (II-3) ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ , R ¹¹⁸ , R ¹¹⁹ , R ¹²⁰ , R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , alkyl group having 1 to 10 carbon atoms represented by R ¹³¹ and ^{R 132,} an aryl group having 6 to 20 carbon atoms, the double of the arylalkyl group and the carbon atom number of 2 to 20 carbon atoms 7-20 Examples of the ring-containing group include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, and 2 to 2 carbon atoms. Of the groups exemplified in the description of the 20 heterocycle-containing groups, groups satisfying a predetermined number of carbon atoms can be mentioned.
In the general formula (II), an alkoxy group having 1 to 10 carbon atoms represented by R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ , II-1), (II-2) or (II-3), R ¹⁰⁹ , R ¹¹⁰ , R ¹¹¹ , R ¹¹² , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ , R ¹¹⁸ , R ¹¹⁹ , R ¹²⁰ , R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ^131, and R ¹³² and 1 to 10 carbon atoms Examples of the alkoxy group include methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy. , Amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tert-heptyloxy, n-octyloxy, isooctyloxy, tert-octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy Etc.
R ¹⁰⁹ , R ¹¹⁰ , R ¹¹¹ , R ¹¹² , R ¹¹⁷ , R ¹¹⁸ , R ¹¹⁹ , R ¹²⁰ , R ¹²⁵ in the general formula (II-1), (II-2) or (II-3) R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ¹³¹ and R ¹³² are adjacent to R ¹⁰⁹ , R ¹¹⁰ , R ¹¹¹ , R ¹¹² , R ¹¹⁷ , R ¹¹⁸ , R ¹¹⁹ , R ¹²⁰ , R ^125. , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ^131, or R ¹³² , R ³ and R ⁷ , R ³ and R ^{8 in the} above general formula (I) can be used. , R ⁴ and R ⁵ , R ⁵ and R ^6, or a ring similar to the ring that R ⁶ and R ⁷ can form together.

As an epoxy compound represented by the general formula (II),
A compound in which M is a group represented by the general formulas (II-1) to (II-3);
A compound in which R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ or R ¹⁰⁸ is a hydrogen atom is preferred.

The unsaturated monobasic acid that acts on the epoxy compound represented by the general formula (II) includes acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / malate, hydroxyethyl acrylate / malate. , Hydroxypropyl methacrylate / malate, hydroxypropyl acrylate / malate, dicyclopentadiene / malate and the like, and acrylic acid and methacrylic acid are particularly preferable.

In addition, the polybasic acid anhydride to be acted after the unsaturated monobasic acid is allowed to act is biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, Trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, hexahydrophthalic anhydride , Methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene -1,2-dicarboxylic anhydride, trialkylte Rahidoro phthalic anhydride - maleic acid adduct, dodecenyl succinic anhydride, include anhydride methylhymic Mick acid, especially biphthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride preferred.

The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows.
That is, the epoxy addition compound has a ratio of 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid to one epoxy group of the epoxy compound, particularly 0.4 to 1.0. The ethylenically unsaturated compound is preferably added such that the acid anhydride structure of the polybasic acid anhydride is 0.1 to 1.0 with respect to one hydroxyl group of the epoxy adduct. It is preferable that the ratio is one, particularly 0.4 to 1.0.
Reaction of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride can be performed in accordance with a conventional method.

The binder resin (B) is preferably 1 to 50 parts by mass, more preferably 10 to 30 parts by mass in terms of solid content with respect to 100 parts by mass of the conductive paste of the present invention. In addition, solid content conversion means converting except a solvent. The same applies to the following description.

<Ethylenic unsaturated compound (C)>
The ethylenically unsaturated compound (C) means a compound having an ethylenically unsaturated bond in the structure. Examples of such a compound include ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, fluorine. Unsaturated aliphatic hydrocarbons such as vinylidene fluoride and tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinylacetic acid Allyl acetate, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2-acryloyloxyethyl], phthalic acid mono [2-acryloyloxyethyl], ω-carboxypolycaprolactone monoacrylate, etc. Monoacrylate and succinic acid monoacrylate of polymer having hydroxyl group and hydroxyl group Monoacrylate or methacrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, such as [2-methacryloyloxyethyl], mono [2-methacryloyloxyethyl] phthalate, and ω-carboxypolycaprolactone monomethacrylate; Acrylate malate, hydroxypropyl acrylate malate, dicyclopentadiene malate or polyfunctional acrylate having one carboxyl group and two or more acryloyl groups, hydroxyethyl methacrylate malate, hydroxypropyl methacrylate malate, dicyclopentadiene .Unsaturated polybasic acids such as malate or polyfunctional methacrylate having one carboxyl group and two or more methacryloyl groups; acrylic acid-2-hydroxyethyl , Acrylic acid 2-hydroxypropyl, glycidyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl, glycidyl methacrylate, the following compound No. A1-No. A4, methyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, lauryl acrylate, methoxy acrylate Ethyl, dimethylaminomethyl acrylate, dimethylaminoethyl acrylate, aminopropyl acrylate, dimethylaminopropyl acrylate, ethoxyethyl acrylate, poly (ethoxy) ethyl acrylate, butoxyethoxyethyl acrylate, ethylhexyl acrylate, acrylic acid Phenoxyethyl, tetrahydrofuryl acrylate, vinyl acrylate, allyl acrylate, benzyl acrylate, ethylene glycol diacrylate, diethylene glycol di Acrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, dipenta Erythritol hexaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, tricyclodecane dimethylol diacrylate, tri [acryloylethyl] isocyanurate, polyester acrylate oligomer, methyl methacrylate, butyl methacrylate, methacrylic acid Isobutyl, methacrylate-t-butyl, methacrylate Cyclohexyl acid, n-octyl methacrylate, isooctyl methacrylate, isononyl methacrylate, stearyl methacrylate, lauryl methacrylate, methoxyethyl methacrylate, dimethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, aminopropyl methacrylate, dimethyl methacrylate Aminopropyl, ethoxyethyl methacrylate, poly (ethoxy) ethyl methacrylate, butoxyethoxyethyl methacrylate, ethyl hexyl methacrylate, phenoxyethyl methacrylate, tetrahydrofuryl methacrylate, vinyl methacrylate, allyl methacrylate, benzyl methacrylate, ethylene glycol Dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol penta Unsaturated monobasic acids such as methacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, tricyclodecane dimethylol dimethacrylate, tri [methacryloylethyl] isocyanurate, polyester methacrylate oligomers, and esters of polyhydric alcohols or polyphenols; acrylics Zinc oxide, magnesium acrylate, zinc methacrylate, Metal salts of unsaturated polybasic acids such as magnesium crylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- ( 2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methyl hymic anhydride Unsaturated polybasic acid anhydrides such as acrylamide, methylene bis-acrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, methacrylamide, methylene bis-methacryl Amides of unsaturated monobasic acids and polyvalent amines such as amide, diethylenetriamine trismethacrylamide, xylylene bismethacrylamide, α-chloroacrylamide, N-2-hydroxyethylmethacrylamide; unsaturated aldehydes such as acrolein; acrylonitrile, methacrylate Unsaturated nitriles such as nitrile, α-chloroacrylonitrile, vinylidene cyanide, allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene Unsaturated aromatic compounds such as vinyl toluene, vinyl benzoic acid, vinyl phenol, vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; Unsaturated ketones such as ru vinyl ketone; Unsaturated amine compounds such as vinyl amine, allyl amine, N-vinyl pyrrolidone and vinyl piperidine; Vinyl alcohols such as allyl alcohol and crotyl alcohol; Vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl Vinyl ethers such as vinyl ether and allyl glycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; indenes such as indene and 1-methylindene; fats such as 1,3-butadiene, isoprene and chloroprene Group conjugated dienes; macromonomers having a monoacryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl acrylate, poly-n-butyl acrylate, polysiloxane, etc. Macromonomers having a monomethacryloyl group at the end of the polymer molecular chain such as limethyl methacrylate, poly-n-butyl methacrylate and polysiloxane; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate , Triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl urethane compound of hydroxyl group-containing vinyl monomer and polyisocyanate compound, vinyl epoxy compound of hydroxyl group-containing vinyl monomer and polyepoxy compound Is mentioned. The said ethylenically unsaturated compound (C) can be used individually or in mixture of 2 or more types.
Among these, a monoacrylate or methacrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, a polyfunctional acrylate or polyfunctional methacrylate having one carboxyl group and two or more acryloyl groups or methacryloyl groups, unsaturated one Basic acids and esters of polyhydric alcohols or polyhydric phenols are preferred from the viewpoints of curability and chromaticity characteristics.

In the conductive paste of the present invention, the content of the ethylenically unsaturated compound (C) is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the solid content of the conductive paste of the present invention. More preferred is part by mass.

<Conductive particles (D)>
As the conductive particles (D), powders of various metals and alloys, or oxides thereof can be used. For example, gold, silver, platinum, iridium, rhodium, tungsten, molybdenum, ruthenium, aluminum, copper, nickel, Metal particles such as palladium, zinc, aluminum, etc .; alloy particles such as silver-palladium, silver-copper, etc .; multilayer bodies having the metal particles or alloy particles as a core or coating layer; tin oxide, acid value indium, ITO, aluminum oxide, Examples thereof include metal oxides such as boron oxide, silica, titanium oxide, zirconia oxide, magnesium oxide, calcium oxide, strontium oxide, and barium oxide; calcium carbonate and the like. Of these, silver is preferable because of its good conductivity.

As the shape of the conductive particles (D), a spherical shape, a plate shape, a lump shape, a conical shape, a needle shape, a rod shape, a flake shape, and a dentlite shape can be used. Is preferable.

The conductive particles (D) have an average particle size of 0.05 to 10 μm, preferably 0.1 to 5 μm.
In addition, an average particle diameter is calculated | required by calculating the average which measured 10 random electroconductive particles (D) observed using SEM (scanning electron microscope).

In the conductive paste of the present invention, the content of the conductive particles (D) is preferably 30 to 90 parts by mass, more preferably 50 to 85 parts by mass with respect to 100 parts by mass of the solid content of the conductive paste of the present invention. It is.

<Solvent (E)>
As the solvent (E), usually, each of the above components (a polymerization initiator (A) containing one or more oxime ester compounds represented by the above general formula (I), a binder resin (B), ethylene as required) A solvent capable of dissolving or dispersing the unsaturated compound (C), conductive particles (D), etc., such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone Ketones such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether, etc .; methyl acetate, ethyl acetate, acetic acid-n-propyl, acetic acid Isopropyl, n-butyl acetate, cyclohexyl acetate, ethyl lactate Ester solvents such as dimethyl succinate and texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol, etc. Alcohol solvents: ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, ethoxyethyl ether propionate, etc. Ether ester solvents; BTX solvents such as benzene, toluene, xylene; hexane, heptane, octane, cyclohexa Aliphatic hydrocarbon solvents such as terpene oils, terpene hydrocarbon oils such as terpine oil, D-limonene, pinene, etc .; paraffins such as mineral spirits, Swazol # 310 (Cosmo Matsuyama Petroleum), Solvesso # 100 (Exxon Chemical) Solvent: Halogenated aliphatic hydrocarbon solvent such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane; Halogenated aromatic hydrocarbon solvent such as chlorobenzene; Carbitol solvent; Aniline; Triethylamine; Pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, and the like. These solvents may be used alone or as a mixture of two or more. It can be used as a solvent.
Among these, ketones, ether ester solvents, etc., particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, and the like are preferable because of their good compatibility with the above components.
In the conductive paste of the present invention, the content of the solvent (E) is preferably 50 to 1000 parts by mass, more preferably 80 to 150 parts by mass with respect to 100 parts by mass of the solid content of the conductive paste of the present invention. .

The conductive paste of the present invention can further contain an inorganic compound other than the conductive particles (D). Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; graphite, layered clay mineral, miloli blue, carbonic acid Calcium, magnesium carbonate, cobalt, manganese, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, Examples include platinum, gold, silver, and copper. These inorganic compounds can use 1 type (s) or 2 or more types.
Among these, glass frit, titanium oxide, silica, layered clay mineral, silver and the like are preferable.
In the conductive paste of the present invention, the content of the inorganic compound is preferably 5 to 1000 parts by mass, preferably 50 to 100 parts by mass with respect to 100 parts by mass of the solid content of the conductive paste of the present invention.

These inorganic compounds are used, for example, as fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, and the like.

In the conductive paste of the present invention, a dispersant for dispersing the conductive particles (D) and / or inorganic compounds can be added. The dispersing agent is not limited as long as it can disperse and stabilize the conductive particles (D) or the inorganic compound, and a commercially available dispersing agent, for example, BYK series manufactured by BYK Chemie Corporation can be used. In particular, a polymer dispersant comprising a polyester, polyether, or polyurethane having a basic functional group, a nitrogen atom as the basic functional group, and the functional group having a nitrogen atom is an amine and / or a quaternary salt thereof. And those having an amine value of 1 to 100 mgKOH / g are preferably used.

Further, in the conductive paste of the present invention, if necessary, thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; transferability imparting agent; thermal polymerization initiator; colorant; Plasticizer; Adhesion promoter; Filler; Defoamer; Leveling agent; Surface conditioner; Antioxidant; Ultraviolet absorber; Stabilizer; Dispersion aid; Anti-agglomeration agent; Catalyst; Effect promoter; A conventional additive such as a sticking agent; a release agent can be added.

In the conductive paste of the present invention, a polymerization initiator (A) containing at least one oxime ester compound represented by the above general formula (I), a binder resin (B), an ethylenically unsaturated compound (C), conductive particles The amount of optional components other than (D) (excluding the above-mentioned inorganic compounds (fillers)) is appropriately selected according to the purpose of use and is not particularly limited, but is preferably solid of the conductive paste of the present invention. The total amount is 50 parts by mass or less per 100 parts by mass.

Also, the properties of the cured product can be improved by using another organic polymer together with the binder resin (B) in the conductive paste of the present invention. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, polyacrylic acid, polymethacrylic acid, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, acrylic acid. -Methyl methacrylate copolymer, methacrylic acid-methyl methacrylic acid copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane Resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin, etc., among these, polystyrene Acrylate - methyl methacrylate copolymer, methacrylic acid - methyl methacrylate copolymers, and epoxy resins.

Further, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, melamine and the like can be used in combination with the conductive paste of the present invention.

As the chain transfer agent or sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3- Mercapto compounds such as mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compound, iodoacetates such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Alkyl compounds, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, diethylthioxanthone, diisopropylthioxanthone, the following compound No. C1, aliphatic polyfunctional thiol compounds such as trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, Karenz MT BD1, PE1, NR1, etc. manufactured by Showa Denko K.K.

Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates; higher amines Cationic surfactants such as halogenates and quaternary ammonium salts; Nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides; amphoteric surfactants; silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, an isocyanate group, a methacryloyl group or an epoxy group such as KBE-9007, KBM-502, KBE-403, etc. A silane coupling agent is preferably used.

Examples of the melamine compound include all or part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Examples include compounds in which (at least two) are alkyl etherified.
Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other. Moreover, the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed.
Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used.
Among these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.

The conductive pattern of the present invention comprises (1) a step of applying the conductive paste of the present invention onto a substrate and forming a coating film on the substrate, (2) a step of drying the coating film, and (3) the dried A step of irradiating and curing radiation (energy rays) through a mask having a predetermined pattern shape, (4) a step of developing the cured coating layer, and (5) baking the coating layer after development. It is preferably formed by the process of performing. Hereinafter, each process is demonstrated in order.

The step (1) is a step of applying the prepared conductive paste of the present invention to a target substrate and forming a coating film on the substrate. Examples of the target substrate include soda glass, quartz glass, semiconductor substrate, metal, paper, and plastic. Moreover, you may use the substrate which surface-treated. The coating method is not particularly limited, and known means such as a spin coater, roll coater, bar coater, die coater, blade coater, curtain coater, various printing and dipping can be employed.
Moreover, the formation of the coating film of the conductive paste of the present invention on a substrate can be transferred to another substrate after the coating film of the conductive paste of the present invention is once formed on a substrate such as a film. There is no restriction | limiting in the formation method.

The step (2) is a step for drying (pre-baking) the coating film formed on the substrate and removing the solvent (E) from the coating film. The pre-baked coating film is hardly soluble in an alkaline solution, and a portion irradiated with energy rays (hereinafter sometimes referred to as an exposed portion) is irradiated with energy rays in the next exposure step to be alkali-soluble. .

The pre-baking temperature varies depending on the type of the solvent (E) used, but if the temperature is too low, the residual amount of the solvent (E) increases, which may cause a reduction in exposure sensitivity and resolution. If the temperature is too high, the entire coating is cured by pre-baking, and the solubility in the alkaline developer of the part irradiated with the energy rays is reduced, and as a result, the exposure sensitivity and resolution may be reduced. 80 to 150 ° C is preferable, and 90 to 120 ° C is more preferable. The prebaking time varies depending on the kind of the solvent (E) used and the prebaking temperature, but is preferably 30 seconds to 10 minutes, and more preferably 1 to 5 minutes.

The step (3) is a step of curing the coating film of the conductive paste of the present invention by irradiating the dried coating film with radiation (energy rays) through a mask having a predetermined pattern shape. . The energy ray light source used for curing the coating film of the conductive paste of the present invention includes an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury vapor arc lamp, a xenon arc lamp, carbon High energy such as electromagnetic wave energy, electron beam, X-ray, radiation, etc. having a wavelength of 2000 angstrom to 7000 angstrom obtained from arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, excimer lamp, germicidal lamp, light emitting diode, CRT light source, etc. An ultra high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, and the like that emit light having a wavelength of 300 to 450 nm are preferable.

As an energy ray light source used for curing the coating film of the conductive paste of the present invention, an image is directly formed from digital information such as a computer without using a mask by using a laser beam as an exposure light source. The laser direct writing method is useful because it can improve not only productivity but also resolution and positional accuracy. As the laser light, light having a wavelength of 340 to 430 nm is preferably used. Lasers that emit light in the visible to infrared region such as excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers, and YAG laser are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.
As the mask, either a negative type mask or a positive type mask can be used in accordance with the components to be used. As the mask, a multi-tone mask such as a halftone mask or a gray scale mask is used. It can also be used.

The step (4) is a step of forming a predetermined pattern by removing a portion of the coating film after the exposure whose alkali solubility has been improved by irradiation light using a developer.

As the developing method, for example, any method such as a liquid filling method, a dipping method, a shower method, or a spray method can be used.

Develop time varies depending on the type and molecular weight of each component, developer temperature, etc., but is usually 30 to 180 seconds.

The developer used in the development step is not particularly limited as long as the exposed portion can be removed by dissolving or dispersing in the solution. For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate Inorganic alkalis such as ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine Tertiary alkanolamines such as dimethylethanolamine, methyldiethanolamine, triethanolamine; pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene 1,5-diazabicik [4.3.0] Cyclic tertiary amines such as 5-nonene; Aromatic tertiary amines such as pyridine, collidine, lutidine and quinoline; Quaternary ammonium such as tetramethylammonium hydroxide and tetraethylammonium hydroxide An alkaline aqueous solution such as an aqueous salt solution can be used, and the concentration thereof may be the alkali concentration of a commonly used developer. These alkaline aqueous solutions may further contain an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant.

After removing the exposed portion with a developer, it is preferably rinsed with running water or water with a shower, and may be dehydrated and dried at 50 to 120 ° C. if necessary.

The step (5) is a step of baking (post-baking) the coated film after development.
By baking the coating film in this step, curing shrinkage of the binder resin occurs and the conductive particles come into contact with each other to obtain sufficient conductivity, and chemical resistance is also improved.
The post-bake is preferably performed in an atmosphere of an inert gas such as nitrogen, helium or argon at 100 to 300 ° C. for 10 to 60 minutes.

The conductive pattern formed by the steps (1) to (5) preferably has a thickness of 3 to 5 μm and a conductor width of 5 to 20 μm because a good pattern can be obtained with low resistance.

The conductive pattern of the present invention can be used for applications such as touch panels, touch sensors, and three-dimensional mounting.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and the like. In the following description, “%” represents mass% unless otherwise specified.

[Production Example 1] Preparation of binder resin B-1 184 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane, 58 g of acrylic acid, 2,6-di-tert-butyl-p -Cresol 0.26 g, tetra-n-butylammonium bromide 0.11 g and PGMEA 105 g were charged and stirred at 120 ° C for 16 hours. The reaction solution was cooled to room temperature, 160 g of PGMEA, 59 g of biphthalic anhydride and 0.24 g of tetra-n-butylammonium bromide were added, and the mixture was stirred at 120 ° C. for 4 hours. Further, 20 g of tetrahydrophthalic anhydride was added, and after stirring at 120 ° C. for 4 hours, at 100 ° C. for 3 hours, at 80 ° C. for 4 hours, at 60 ° C. for 6 hours, and at 40 ° C. for 11 hours, 128 g of PGMEA was added, As a result, binder resin B-1 was obtained (Mw = 5000, solid content 44.0%, acid value = 100 mgKOH / g).

[Production Example 2] Preparation of binder resin B-2 Bis [4- (2,3-epoxypropoxy) phenyl] -4-biphenylyl (cyclohexyl) methane 89.9 g, acrylic acid 23.5 g, 2,6-di- 0.457 g of tert-butyl-p-cresol, 0.534 g of benzyltriethylammonium chloride and 75.6 g of PGMEA were charged and stirred at 120 ° C. for 16 hours. The mixture was cooled to room temperature, charged with 12.0 g of 2,4-pentanedione and 1.0 g of triethylamine, and stirred at 92 ° C. for 17 hours. After cooling to room temperature, 25.6 g of succinic anhydride, 1.39 g of tetra-n-butylammonium bromide and 40.42 g of PGMEA were added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 46.7 g of PGMEA was added to obtain a binder resin B-2 as a PGMEA solution (Mw = 3500, solid content 44.0%, acid value 90 mgKOH / g).

[Examples 1 to 3 and Comparative Examples 1 to 3] Conductive paste No. 1 1 to 3 and comparative conductive paste No. 1 Preparation of 1 to 3 Each component was mixed according to the formulation of [Table 1]. 1 to 3 and comparative conductive paste No. 1 1-3 were obtained. In addition, a number represents a mass part.

Among the following components, components other than B-1, B-2 and B-3 and E-1 which is a solvent do not contain a solvent and have a solid content of 100%.
A-1 Compound No. 6
A'-1 IRGACURE-907 (polymerization initiator; manufactured by BASF)
A'-2 OXE-02 (polymerization initiator; manufactured by BASF)
B-1 Obtained in Production Example 1 B-2 Obtained in Production Example 2 B-3 SPC-1000 (Mw = 32000, solid content 29.0%, acid value 110 mgKOH / g, acrylate; Showa Denko)
C-1 Kayalad DPHA (multifunctional acrylate; manufactured by Nippon Kayaku Co., Ltd.)
D-1 FA-333 (binder resin + conductive particles; manufactured by Fujikura Kasei Co., Ltd.)
E-1 Propylene glycol-1-monomethyl ether-2-acetate F-1 F-554 (leveling agent; manufactured by DIC)

[Evaluation methods]
Conductive paste No. on the wafer with a spin coater. 1 to 3 and comparative conductive paste No. 1 Each of 1 to 3 was applied and then dried. It exposed using the photomask. Next, development and rinsing were performed using a 0.4% sodium carbonate developer to obtain a pattern. Thereafter, curing was performed in a curing furnace, and the following sensitivity, resolution, and overhang amount were evaluated.
(sensitivity)
Sensitivity was defined as the exposure amount at which a line width of 30 μm was resolved without peeling.
(resolution)
When the line width was 30 μm, it was measured how many μm the space between the lines was resolved.
(Overhang amount)
When the cross section of the pattern was viewed with an SEM (scanning electron microscope), the difference in pattern width between the surface side of the pattern and the substrate side was measured.
(Adhesion)
Conductive paste No. on the wafer with a spin coater. 1 to 3 and comparative conductive paste No. 1 Each of 1 to 3 was applied and then dried. Subsequently, an energy of 300 mJ / cm ² was irradiated with an ultrahigh pressure mercury lamp to prepare a sample. The produced sample was peeled off with an adhesive tape and evaluated by checking whether there was any peeling of the pattern. The evaluation criteria are as follows.
○: No pattern peeling △: Peeling part of the pattern ×: Pattern peeling (specific resistance value)
Conductive paste No. on the wafer with a spin coater. 1 to 3 and comparative conductive paste No. 1 Each of 1 to 3 was applied and then dried. Subsequently, an energy of 300 mJ / cm ² was irradiated with an ultrahigh pressure mercury lamp to prepare a sample. The specific resistance value of the prepared sample was measured by a four-end needle method using Loresta HP (manufactured by Dia Instruments: trade name).

Therefore, the conductive paste of the present invention is useful as a conductive pattern because it is excellent in sensitivity, resolution and adhesion and has a low specific resistance value.

According to the present invention, it is possible to provide a conductive paste which is excellent in sensitivity, resolution and adhesion and has low resistance.

Claims

Polymerization initiator (A) containing at least one oxime ester compound represented by the following general formula (I), binder resin (B), ethylenically unsaturated compound (C), conductive particles (D) and solvent (E ) Containing conductive paste.

(Wherein R 1 and R 2 each independently represent R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN;
R 11 , R 12 and R 13 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon atom. Represents a heterocyclic-containing group of formula 2 to 20,
The hydrogen atoms of the groups represented by R 11 , R 12 and R 13 are further R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , —NR 22 —OR 23 , —NCOR 22 -OCOR 23 , NR 22 COR 21 , OCOR 21 , COOR 21 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , hydroxyl group, nitro group, CN, amino group, halogen atom or COOR 21 may be substituted ,
R 21 , R 22 and R 23 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon atom. Represents a heterocyclic-containing group of formula 2 to 20,
The hydrogen atom of the group represented by R 21 , R 22 and R 23 may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, a hydroxyl group or a carboxyl group,
The methylene groups in the groups represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 are —O—, —S—, —COO—, —OCO—, —NR 24 —, — NR 24 COO—, —OCONR 24 —, —SCO—, —COS—, —OCS— or —CSO— may be substituted 1 to 5 times under the condition that the oxygen atoms are not adjacent to each other,
R 24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. Represent,
When the group represented by R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 has an alkyl moiety, the alkyl moiety may have a branched side chain and is a cyclic alkyl. In some cases,
R 3 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. And when the group represented by R 3 has an alkyl moiety, the alkyl moiety may have a branched side chain or a cyclic alkyl,
The hydrogen atom of the group represented by R 3 is further represented by R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , —NR 22 —OR 23 , —NCOR 22 —OCOR 23 , NR 22 COR 21 , OCOR 21 , COOR 21 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , hydroxyl group, nitro group, CN, halogen atom or COOR 21 may be substituted,
R 4 , R 5 , R 6 and R 7 are each independently R 11 , OR 11 , SR 11 , COR 14 , CONR 15 R 16 , NR 12 COR 11 , OCOR 11 , COOR 14 , SCOR 11 , OCSR 11 , COSR 14 , CSOR 11 , a hydroxyl group, CN or a halogen atom,
R 3 and R 7 , R 3 and R 8 , R 4 and R 5 , R 5 and R 6 or R 6 and R 7 may be combined to form a ring,
R 14 , R 15 and R 16 represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
R 8 is R 11 , OR 11 , SR 11 , COR 11 , CONR 12 R 13 , NR 12 COR 11 , OCOR 11 , COOR 11 , SCOR 11 , OCSR 11 , COSR 11 , CSOR 11 , hydroxyl group, CN or halogen atom Represents
n represents 0 or 1. )
The conductive paste according to claim 1, wherein the binder resin (B) has an acid value of 30 to 300 mgKOH / g and a weight average molecular weight (Mw) of 1,000 to 500,000.
The binder resin (B) is an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the following general formula (II), or the epoxy addition compound and a polybasic acid anhydride The conductive paste according to claim 1, wherein the conductive paste is an esterified product.

(In the formula, M is a direct bond, an alkylene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, an aryl group having 6 to 12 carbon atoms, O, S, SO 2 , SS, SO, CO, OCO or a group represented by the following general formula (II-1), (II-2) or (II-3) is represented, and R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 and R 108 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a halogen atom, and s is a number from 0 to 10 Represents.)

( R109 , R110 , R111 , R112 , R113 , R114 , R115 , R116 , R117 , R118 , R119 , R120 , R121 , R122 , R123 , R124 , R 125 , R 126 , R 127 , R 128 , R 129 , R 130 , R 131 and R 132 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. Represents an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or a halogen atom, and methylene in the above alkyl group and arylalkyl group groups, unsaturated bonds, by -O- or -S- sometimes oxygen atoms are replaced by conditions that are not adjacent, R 109, R 110 R 111, R 112, R 117 , R 118, R 119, R 120, R 125, R 126, R 127, R 128, R 129, R 130, R 131 and R 132 are adjacent R 109, R 110 , R 111 , R 112 , R 117 , R 118 , R 119 , R 120 , R 125 , R 126 , R 127 , R 128 , R 129 , R 130 , R 131, or R 132 form a ring. In some cases, * means that it is bonded to an adjacent group at the * part.)
A conductive pattern comprising the conductive paste according to any one of claims 1 to 3.
A step of applying the conductive paste according to any one of claims 1 to 3 on a substrate, a step of drying, a step of exposing using a mask, a step of developing, and a step of baking at 100 to 300 ° C. A method for forming a conductive pattern.
A touch panel provided with the conductive pattern according to claim 4.