KR102426654B1 - Conductive paste - Google Patents

Abstract

The present invention provides a low-resistance conductive paste having good sensitivity, resolution and adhesion, specifically, a polymerization initiator (A) comprising at least one oxime ester compound represented by the general formula (I), a binder resin It is to provide the electrically conductive paste containing (B), an ethylenically unsaturated compound (C), electroconductive particle (D), and a solvent (E). In the electrically conductive paste of this invention, Preferably, as binder resin (B), the epoxy addition compound which has the structure which added unsaturated monobasic acid to the epoxy compound represented by General formula (II), or the said epoxy addition compound and a polybasic acid An esterified anhydride is used. Formulas (I) and (II) are as described herein.

Description

Conductive paste {CONDUCTIVE PASTE}

This invention relates to the electrically conductive paste containing a specific polymerization initiator.

Photolithography is known as a method of forming a conductive pattern on a substrate such as glass, ceramic, or silicon wafer, and in recent years, miniaturization and high precision are required in mobile electronic devices such as smartphones and touch panels.

Although various electrically conductive pastes were disclosed by patent documents 1-4, the resolution which can satisfy was not acquired.

Japanese Patent Laid-Open No. 2001-154345 Japanese Patent Laid-Open No. 2013-101861 Japanese Patent Laid-Open No. 2013-210498 Japanese Patent Publication No. 3620861

The problem to be solved is that there has been no conductive paste having good sensitivity, resolution and adhesion, and having a low resistance so far.

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

The present invention relates to a polymerization initiator (A), a binder resin (B), an ethylenically unsaturated compound (C), conductive particles (D), and a solvent (E) comprising at least one oxime ester compound represented by the following general formula (I) ) to achieve the above object by providing a conductive paste containing.

(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 an arylalkyl group having 2 to carbon atoms 20 represents a heterocycle-containing group,

The hydrogen atom of the group represented by R ¹¹ , R ¹² and R ¹³ is 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 ,

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 an arylalkyl group having 2 to carbon atoms 20 represents a heterocycle-containing group,

A 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 group in the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is -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 atom is not adjacent,

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 heterocycle-containing group having 2 to 20 carbon atoms,

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 chain or may be a cyclic alkyl;

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 heterocycle-containing group having 2 to 20 carbon atoms, R ³ When the group represented by has an alkyl moiety, the alkyl moiety may have a branched chain or may be cyclic alkyl,

The hydrogen atom of the group represented by R ³ is 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 , a hydroxyl group, a nitro group, CN, a 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,

In addition, 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 each form a ring together,

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 indicate,

n represents 0 or 1.)

Moreover, this invention provides the electrically conductive pattern which consists of the said electrically conductive paste.

In addition, the present invention relates to a method for forming a conductive pattern including 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 firing at 100 to 300°C is to provide

Another object of the present invention is to provide a touch panel including the conductive pattern.

Hereinafter, the electrically conductive paste of this invention is demonstrated in detail based on preferable embodiment.

The electrically conductive paste of this invention contains a polymerization initiator (A) containing 1 or more types of the oxime ester compound represented by the said General formula (I), binder resin (B), an ethylenically unsaturated compound (C), and electroconductive particle (D) and solvent (E). Hereinafter, each component is demonstrated in order.

<Polymerization Initiator (A)>

The polymerization initiator (A) used by this invention contains 1 or more types of the oxime ester compound represented by the said General formula (I).

Although the geometric isomer by the double bond of an oxime exists in the oxime ester compound represented by the said General formula (I), these are not distinguished.

That is, in the present specification, the oxime ester compound represented by the general formula (I) and the exemplary compound thereof represent a mixture of both or either one when a geometric isomer exists in the compound, and one geometric isomer specified in the present specification. is not limited to

As an alkyl group having 1 to 20 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 in the general formula (I), , 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, etc. are mentioned.

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, triyl, , xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl, biphenylyl, naphthyl, and 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.

As the heterocyclic-containing 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), for example, Pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, iso The group which combined 5-7 membered heterocyclic ring, such as thiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, morpholinyl, and a methylene chain, is mentioned.

As the ring which 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 each can form together in the general formula (I), for example, 5-7 membered rings, such as a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, and a lactam ring, are mentioned preferably.

In addition, R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in formula (I), and R ³ , R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and Examples of the halogen atom which may be substituted for R ²³ include fluorine, chlorine, bromine and iodine.

The methylene group in the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ in the general formula (I) is -O-, -S-, -COO-, -OCO-, -NR ²² Even if oxygen atoms are substituted 1 to 5 times by -, -NR ²² CO-, -NR ²² COO-, -OCONR ²² -, -SCO-, -COS-, -OCS- or -CSO- In this case, the bonding group to be substituted may be contributed by one or two or more, and in the case of a group that can be continuously substituted, two or more may be continuously substituted.

Further, 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, the alkyl (alkylene) moiety is It may have a branched chain and may be cyclic alkyl. Examples of the cyclic alkyl include cyclic alkyl having 4 to 8 carbon atoms, such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. For example, as the group 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 cyclic alkyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, Cyclobutylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl, cycloheptylmethyl, cycloheptylethyl, cycloheptylpropyl, cycloheptyl C5-C12 cycloalkyl groups, such as butyl, etc. are mentioned.

Therefore, as a preferable specific example of the compound represented by the said General formula (I), the following compounds No.1-No.30 are mentioned. However, the present invention is not limited by the following compounds.

As a compound represented by the said general formula (I),

It is preferable that R ¹ is a linear alkyl group having 1 to 12 carbon atoms or a cycloalkylalkyl group having 5 to 12 carbon atoms,

It is preferable that R ² is a linear alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms (especially, 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 (especially a phenyl group)], a hydroxyl group, a nitro group, CN , a halogen atom or an amino group substituted or unsubstituted phenyl group, preferably an arylalkyl group having 7 to 10 carbon atoms (especially a benzyl group),

R ⁴ , R ⁵ , R ⁶ or R ⁷ is a hydrogen atom, a cyano group, OR ¹¹ [R ¹¹ is an unsubstituted alkyl group having 1 to 6 carbon atoms substituted with a hydroxyl group or a carboxyl group], in particular R ⁵ is preferably a cyano group, OR ¹¹ [R ¹¹ is an unsubstituted alkyl group having 1 to 6 carbon atoms substituted with a hydroxyl group or a carboxyl group],

It is preferable that R< ⁸ > is a hydrogen atom and a C1-C6 linear alkyl group.

The total amount of content of the oxime ester compound represented by the said General formula (I) in the said polymerization initiator (A) becomes like this. Preferably it is 30-100 mass %, More preferably, it is 50-100 mass %.

As said polymerization initiator (A), you can also use together with well-known polymerization initiators other than the oxime ester compound represented by the said General formula (I).

Preferred examples of the known polymerization initiator include acetphenone-based compounds, benzyl-based compounds, benzophenone-based compounds, thioxanthone-based compounds, bisimidazole-based compounds, acridine-based compounds, and acylphosphine-based compounds.

Examples of the acetphenone-based compound include diethoxyacetphenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 4'-isopropyl-2-hydroxy-2-methylpropiophenone. , 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, p-dimethylaminoacetphenone, p-tert-butyldichloroacetphenone, p -tert-butyltrichloroacetphenone, p-azidebenzalacetphenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone- 1,2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, benzoin, 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-propan-1-one, etc. are mentioned.

Benzyl etc. are mentioned as said benzyl type compound.

Examples of the benzophenone-based compound include benzophenone, o-benzoyl methyl benzoate, mihiraketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 4-benzoyl-4' -Methyldiphenyl sulfide, etc. are mentioned.

Examples of the thioxanthone-based compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and the like. can be heard

As the bisimidazole-based compound, hexaarylbisimidazole (HABI, a dimer of triaryl-imidazole) can be used, and 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'-biimi Dazole, 2,2'-bis(2,4,6-trichlorophenyl)-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'-hexaphenylbisimidazole, 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-dichloro Phenyl)-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-Tryl-4,5,4',5'-tetraphenylbisimidazole, 2,2'-bis(2-ethoxyphenyl)-4,5,4',5'-tetraphenylbisimi Dazole and 2,2'-bis(2,6-difluorophenyl)-4,5,4',5'-tetraphenylbisimidazole, 5'-tet Ra(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'-bi imidazole, 5,5'-tetra(p-chloronaphthyl)biimidazole, etc. or 1,2'-, 1,4'-, 2,4' disclosed in Japanese Patent Publication No. 45-37377 tautomers covalently bonded with -, compounds described in WO00/52529, and the like.

Examples of the acridine-based compound include acridine, 9-phenylacridine, 9-(p-methylphenyl)acridine, 9-(p-ethylphenyl)acridine, and 9-(p-iso-propylphenyl). ) acridine, 9- (p-n-butylphenyl) acridine, 9- (p-tert-butylphenyl) acridine, 9- (p-methoxyphenyl) acridine, 9- (p- Toxyphenyl) acridine, 9-(p-acetylphenyl) acridine, 9-(p-dimethylaminophenyl) acridine, 9-(p-cyanophenylphenyl) acridine, 9-(p -Chlorophenyl) acridine, 9- (p-bromophenyl) acridine, 9- (m-methylphenyl) acridine, 9- (m-n-propylphenyl) acridine, 9- (m-iso -Propylphenyl) acridine, 9-(m-n-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-methyl acridine, 9-ethyl acridine, 9 -n-propyl acridine, 9-iso-propyl acridine, 9-cyanoethyl acridine, 9-hydroxyethyl acridine, 9-chloroethyl acridine, 9-bromoacridine, 9-hydroxyacridine, 9-nitroacridine, 9-aminoacridine, 9-methoxyacridine, 9-ethoxyacridine, 9-n-propoxyacridine, 9-iso- Propoxyacridine, 9-chloroethoxyacridine, 4,6-bis(dimethylamino)acridine, 10-acridine, 10-methylacetate acridine, 3,6-dimethylacridine Dean, 7,13-dimethylacridine, 7,13-bis(dimethylamino)acridine, 3,6-dimethyl-10-acridine, 3,5-dimethyl-10-methylacetate acridine , 7,13-dimethyl-10-acridine acetate, 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-phenyl Acridine, 2,7-bis(α-acetoxybenzyl)-9-phenyl Acridine, 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-chlorobenzoyl) -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-phenylaminocarbonyl) Oxy-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-phenyla Creidine, 4-phenylacridine, 1-benzylacridine, 4-benzylacridine, 1-chloroacridine, 2,3-dichloroacridine, 10-butyl-2-chloroacridine -9(10H)-one, 10-propyl-2-chloroacridin-9(10H)-one, 10-butyl-2-chloroacridin-9(10H)-one, 1,2-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-bis(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-octadecyl-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, 1,6-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, 1,12-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]acrylic acid Dean, 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-acridinesulfonate, 3,6-bis-(dimethylamino )-acridinesulfonate, 3,6-diamino-10-methyl-acridinium chloride, and 9-acridinecarboxylic acid.

Examples of the acylphosphine-based compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO; manufactured by BASF), isobutyryl-methylphosphinate methyl ester, isobutyryl-phenylphosphinate methyl ester, and p Valoyl-phenylphosphinic acid methyl ester, 2-ethylhexanoyl-phenylphosphinic acid methyl ester, pivaloyl-phenylphosphinic acid isopropyl ester, p-toluyl-phenylphosphinic acid methyl ester, o-toluyl-phenylphos Methyl phinate, 2,4-dimethylbenzoyl-phenylphosphinate methyl ester, p-tert-butylbenzoyl-phenylphosphinic acid isopropyl ester, acryloyl-phenylphosphinate methyl ester, isobutyryl-diphenylphosphine Oxide, 2-ethylhexanoyl-diphenylphosphine oxide, o-toluyl-diphenylphosphine oxide, p-tert-butylbenzoyl-diphenylphosphine oxide, 3-pyridylcarbonyl-diphenylphosphine oxide , acryloyl-diphenylphosphine oxide, benzoyl-diphenylphosphine oxide, pivaloyl-phenylphosphine vinyl ester, azifoyl-bis-diphenylphosphine oxide, pivaloyl-diphenylphosphine oxide, p-toluyl-diphenylphosphine oxide, 4-(tertiary butyl)-benzoyl-diphenylphosphine oxide, 2-methylbenzoyl-diphenylphosphine oxide, 2-methyl-2-ethylhexanoyl-diphenyl Phosphine oxide, 1-methyl-cyclohexanoyl-diphenylphosphine oxide, pivaloyl-phenylphosphinic acid methyl ester and pivaloyl-phenylphosphinic acid isopropyl ester, 4-octylphenylphosphine oxide, terephthalo 1-bis-diphenylphosphine oxide, 1-methyl-cyclohexyl carbonyldiphenylphosphine oxide, versatoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-di Isobutoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Irgacure819; 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-ethoxyphenyl Phosphine oxide, bis( 2-methyl-1-naphthoyl)-2-naphthylphosphine oxide, bis(2-methyl-1-naphthoyl)-4-propylphenylphosphine oxide, bis(2-methyl-1-naphthoyl)- 2,5-dimethylphenylphosphine oxide, bis(2-methoxy-1-naphthoyl)-4-ethoxyphenylphosphine oxide, bis(2-chloro-1-naphthoyl)-2,5-dimethylphenyl Phosphine 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-naphthylphos Pinoxide, bis(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide (CGI403), 6- trimethylbenzoyl-ethyl-phenyl-phosphinate (SPEEDCURE TPO-L; Lambson's product) etc. are mentioned.

It is preferable that it is 0.1-10 mass parts with respect to 100 mass parts of solid content of the electrically conductive paste of this invention, and, as for content of the said polymerization initiator (A), it is preferable that it is 0.5-5 mass parts. In addition, solid content means the component except a solvent among certain components. It is the same in the following description.

<Binder resin (B)>

As binder resin, For example, polyolefin polymers, such as polyethylene, a polypropylene, and polyisobutylene; diene-based polymers such as polybutadiene and polyisoprene; polymers having a conjugated polyene structure such as polyacetylene-based polymers and polyphenylene-based polymers; vinyl polymers such as polyvinyl chloride, polystyrene, vinyl acetate, polyvinyl alcohol, polyacrylic acid, polyacrylic acid ester, polyacrylamide, polyacrylonitrile, and polyvinylphenol; polyethers such as polyphenylene ether, polyoxirane, polyoxetane, polytetrahydrofuran, polyether ketone, polyether ether ketone, and polyacetal; phenol resins such as novolac resins and resol resins; polyesters such as polyethylene terephthalate, polyphenolphthalein terephthalate, polycarbonate, alkyd resin, and unsaturated polyester resin; polyamides such as nylon-6, nylon 66, water-soluble nylon, and polyphenylenamide; polypeptides such as gelatin and casein; epoxy resins such as novolac epoxy resins, bisphenol epoxy resins, novolac epoxy acrylates and resins modified with acid anhydrides and modified products thereof; Polyurethane, polyimide, melamine resin, urea resin, polyimidazole, polyoxazole, polypyrrole, polyaniline, polysulfide, polysulfone, cellulose, etc. are mentioned.

The weight average molecular weight (Mw) of the binder resin (B) is in terms of polystyrene by gel permeation chromatography (GPC), preferably 1,000 to 500,000, more preferably 2,000 to 200,000, most preferably 3,000 to 100,000. When the Mw of the binder resin is less than 1,000, the heat resistance of the film tends to decrease, and when it exceeds 500,000, the developability and applicability of the film tend to decrease. In addition, the acid value of the binder resin (B) is preferably 30 to 300 mgKOH/g. When the value of an acid value is less than 30 mgKOH/g, there exists a possibility that developability may worsen, and when the value of an acid value is more than 300 mgKOH/g, there exists a possibility that deterioration of resin may progress.

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 an ester product of the epoxy addition compound and a polybasic acid anhydride, has sensitivity and resolution is high, so it is preferable.

(Wherein, 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), 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 represents a number from 0 to 10.)

(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 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or carbon represents an aryl group having 6 to 20 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 the methylene group in the alkyl group and the arylalkyl group is an unsaturated bond, -O Oxygen atoms may be substituted by - or -S- on condition that they 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 may form a ring with each other. * means bonding with an adjacent group at the * part.)

Examples of the alkylene group having 1 to 4 carbon atoms in the general formula (II) include those represented by -(CH ₂ ) _1-4 - as the straight-chain 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-ethylethane-1,2-diyl, 1-methylpropane-1,3-diyl, etc. are mentioned.

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, and noradamane. tyl, 2-methyladamantyl, 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, tetracyclodo decanyl, cedrol, cyclododecanyl, and the like.

R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ in the general formula (II) represent an alkyl group having 1 to 10 carbon atoms, and M represented by 6 to 12 carbon atoms. of an aryl group, R ¹⁰⁹ , R ¹¹⁰ , R ¹¹¹ , R ¹¹² , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R in Formula (II-1), (II-2) or (II-3) Carbon atoms represented by 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 . Examples of the alkyl group having 1 to 10 carbon atoms, the aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms and the heterocycle-containing group having 2 to 20 carbon atoms are the carbon atoms of the general formula (I). A predetermined number of carbon atoms among the groups exemplified in the description of 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 heterocycle-containing group having 2 to 20 carbon atoms. There are groups that satisfy

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 in the general formula (II), the general formula (II-1) 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 in (II-2) or (II-3) Examples of the alkoxy group having 1 to 10 carbon atoms represented by ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ¹³¹ and R ¹³² include methyloxy; Ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tertiary amyloxy, hexyloxy, cyclohexyloxy, heptyloxy , isoheptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, and the like.

R ¹⁰⁹ , R ¹¹⁰ , R ¹¹¹ , R ¹¹² , R ¹¹⁷ , R ¹¹⁸ , R ¹¹⁹ , R ¹²⁰ , R ¹²⁵ , R ¹²⁶ in Formula (II-1), (II-2) or (II-3) , 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 may form a ring between R ³ and R ⁷ , R ³ and R ⁸ , R ⁴ and R in the general formula (I). ⁵ , R ⁵ and R ⁶ , or R ⁶ and R ⁷ may each form the same ring together.

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

As said unsaturated monobasic acid made to act on the epoxy compound represented by the said general formula (II), acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate maleate, hydroxyethyl acrylic acid lactate maleate, hydroxypropyl methacrylate maleate, hydroxypropyl acrylate maleate, dicyclopentadiene maleate, etc. are mentioned, Especially, acrylic acid and methacrylic acid are preferable.

Further, as the polybasic acid anhydride to be acted upon after the unsaturated monobasic acid has been reacted, biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, trimellitic anhydride, and pyromelli Tonic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydrotrimellitate, glycerol trisanhydrotrimellitate, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Na Dixic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxyl acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methylhimic anhydride, etc. are mentioned, and nonphthalic anhydride, tetrahydrophthalic anhydride, and succinic anhydride are especially preferable.

It is preferable that the reaction molar ratio of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride is carried out as follows.

That is, the epoxy addition compound is preferably added such that the carboxyl groups of the unsaturated monobasic acid are 0.1 to 1.0, particularly 0.4 to 1.0, with respect to one epoxy group of the epoxy compound, and the ethylenically unsaturated The compound preferably has a ratio of 0.1 to 1.0, particularly 0.4 to 1.0, of the acid anhydride structure of the polybasic acid anhydride with respect to one hydroxyl group of the epoxy adduct.

Reaction of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride can be performed according to a conventional method.

It is preferable that it is 1-50 mass parts in conversion of solid content with respect to 100 mass parts of electrically conductive pastes of this invention, and, as for the said binder resin (B), it is more preferable that it is 10-30 mass parts. In addition, conversion of solid content means removing a solvent and converting. It is the same in the following description.

<Ethylenic unsaturated compound (C)>

The ethylenically unsaturated compound (C) means a compound having an ethylenically unsaturated bond in its structure, and examples of such compounds include ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, and vinyl fluoride. unsaturated aliphatic hydrocarbons such as leadene and tetrafluoroethylene; (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono[2- Acryloyloxyethyl], phthalic acid mono[2-acryloyloxyethyl], ω-carboxypolycaprolactone monoacrylate, etc. Polymer monoacrylate having a carboxyl group and a hydroxyl group at both terminals, succinic acid mono[2-meth acryloyloxyethyl], phthalic acid mono[2-methacryloyloxyethyl], omega-carboxypolycaprolactone monomethacrylate, etc. polymer monoacrylates or methacrylates having a carboxyl group and a hydroxyl group at both terminals; Hydroxyethyl acrylate maleate, hydroxypropyl acrylate maleate, dicyclopentadiene maleate or polyfunctional acrylate having one carboxyl group and two or more acryloyl groups, hydroxyethyl methacrylate unsaturated polybasic acids such as maleate, hydroxypropyl methacrylate maleate, dicyclopentadiene maleate or polyfunctional methacrylate having one carboxyl group and two or more methacryloyl groups; Acrylic acid-2-hydroxyethyl, acrylic acid-2-hydroxypropyl, glycidyl acrylate, methacrylic acid-2-hydroxyethyl, methacrylic acid-2-hydroxypropyl, glycidyl methacrylate, the following compounds No.A1 to No.A4, methyl acrylate, butyl acrylate, isobutyl acrylate, acrylate-t-butyl, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, lauryl acrylate, Methoxyethyl acrylate, dimethylaminomethyl acrylate, dimethylaminoethyl acrylate, aminopropyl acrylate, dimethylaminopropyl acrylate, ethoxyethyl acrylate, poly(ethoxy)ethyl acrylate, butoxyethoxyethyl acrylate, ethylhexyl acrylate, phenoxy acrylate Cyethyl, tetrahydrofuryl acrylate, vinyl acrylate, allyl acrylate, benzyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, 1 ,4-butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, pentaeryth Ritol tetraacrylate, pentaerythritol triacrylate, tricyclodecanedimethylol diacrylate, tri[acryloylethyl]isocyanurate, polyester acrylate oligomer, methyl methacrylate, butyl methacrylate, methacrylic Isobutyl acid, t-butyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, isononyl methacrylate, stearyl methacrylate, lauryl methacrylate, methacrylic acid Methoxyethyl acid, dimethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, aminopropyl methacrylate, dimethylaminopropyl methacrylate, ethoxyethyl methacrylate, poly(ethoxy)ethyl methacrylate, methacrylic acid Butoxyethoxyethyl acid, ethylhexyl methacrylate, phenoxyethyl methacrylate, tetrahydrofuryl methacrylate, vinyl methacrylate, allyl methacrylate, benzyl methacrylate, ethylene glycol dimethacrylate, diethylene Glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol di Methacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, dipenta Erythritol hexamethacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, tricyclodecanedimethylol dimethacrylate, tri[methacryloylethyl]iso esters of unsaturated monobasic acids and polyhydric alcohols or polyphenols such as cyanurate and polyester methacrylate oligomers; metal salts of unsaturated polybasic acids such as zinc acrylate, magnesium acrylate, zinc methacrylate, and magnesium methacrylate; Maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3 -Acid anhydrides of unsaturated polybasic acids, such as cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride- maleic anhydride adduct, dodecenyl succinic anhydride, and methyl hymic anhydride; Acrylamide, methylenebis-acrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, methacrylamide, methylenebis-methacrylamide , amides of unsaturated monobasic acids and polyvalent amines such as diethylenetriaminetrismethacrylamide, xylylenebismethacrylamide, α-chloroacrylamide and N-2-hydroxyethylmethacrylamide; unsaturated aldehydes such as acrolein; unsaturated nitriles such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, and allyl cyanide; Styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid , unsaturated aromatic compounds such as vinyl benzyl methyl ether and vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone and vinylpiperidine; vinyl alcohol such as allyl alcohol and clothyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and allyl glycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; indene, such as indene and 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Macromonomers having a monoacryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl acrylate, poly-n-butyl acrylate, polysiloxane, polymethyl methacrylate, poly-n-butyl methacrylate, polysiloxane macromonomers having a monomethacryloyl group at the terminal of the polymer molecular chain, such as; Vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinylimidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl The vinyl urethane compound of a pyridine, a hydroxyl-containing vinyl monomer, and a polyisocyanate compound, the vinyl epoxy compound of a hydroxyl-containing vinyl monomer, and a polyepoxy compound are mentioned. The said ethylenically unsaturated compound (C) can be used individually or in mixture of 2 or more types.

Among these, a polymer monoacrylate or methacrylate having a carboxyl group and a hydroxyl group at both terminals, a polyfunctional acrylate or polyfunctional methacrylate having one carboxyl group and two or more acryloyl or methacryloyl groups, unsaturated Ester of a monobasic acid and polyhydric alcohol or polyhydric phenol is preferable from a viewpoint of sclerosis|hardenability and chromaticity characteristic.

The electrically conductive paste of this invention WHEREIN: It is preferable that it is 1-50 mass parts with respect to 100 mass parts of solid content of the electrically conductive paste of this invention, and, as for content of the said ethylenically unsaturated compound (C), it is more preferable that it is 1-10 mass parts.

<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, palladium, metal particles such as zinc and aluminum; alloy particles such as silver-palladium and silver-copper; a multilayer body using the metal particles or alloy particles as a core or a coating layer; metal oxides such as tin oxide, indium oxide, ITO, aluminum oxide, boron oxide, silica, titanium oxide, zirconia, magnesium oxide, calcium oxide, strontium oxide, and barium oxide; Calcium carbonate etc. are mentioned. Especially, since silver has good electroconductivity, it is preferable.

As a shape of the said electroconductive particle (D), although spherical shape, plate shape, lump shape, conical shape, needle shape, rod shape, flake shape, and a dentrite shape can be used, a spherical thing is preferable because dispersibility is good. do.

The average particle diameter of the said electroconductive particle (D) is 0.05-10 micrometers, Preferably it is 0.1-5 micrometers.

In addition, an average particle diameter is calculated|required by calculating the average which measured 10 random electroconductive particle (D) observed using SEM (scanning electron microscope).

The electrically conductive paste of this invention WHEREIN: With respect to 100 mass parts of solid content of the electrically conductive paste of this invention, content of the said electroconductive particle (D) becomes like this. Preferably it is 30-90 mass parts, More preferably, it is 50-85 mass parts.

<Solvent (E)>

As a solvent (E), normally, as needed, each component (a polymerization initiator (A) containing 1 or more types of the oxime ester compound represented by the said General formula (I), binder resin (B), an ethylenically unsaturated compound (C), a solvent capable of dissolving or dispersing the conductive particles (D)), for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexane ketones such as one and 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; 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 ether ester solvents such as; BTX solvents, such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; Paraffinic solvents, such as mineral spirit, Swasol #310 (Cosmo Matsuyama Seki Co., Ltd.), and Solveso #100 (Exxon Chemicals); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol-based solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N,N-dimethylformamide; N,N-dimethylacetamide; N-methylpyrrolidone; dimethyl sulfoxide; water etc. are mentioned, These solvent can be used as 1 type or 2 or more types of mixed solvent.

Among these, ketones, ether ester solvents, etc., especially propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc. are preferable since they have good compatibility with said each component.

In the electrically conductive paste of this invention, content of the said solvent (E) becomes like this with respect to 100 mass parts of solid content of the electrically conductive paste of this invention. Preferably it is 50-1000 mass parts, More preferably, it is 80-150 mass parts.

The electrically conductive paste of this invention can be made to contain inorganic compounds other than electroconductive particle (D) further. 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, Milori Blue, calcium carbonate, magnesium carbonate, cobalt, manganese, glass powder (especially glass frit, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfide, selenide, aluminum silicate , calcium silicate, aluminum hydroxide, platinum, gold, silver, copper, etc. One or two or more of these inorganic compounds may be used.

Among these, glass frit, titanium oxide, silica, a layered clay mineral, silver, and the like are preferable.

In the electrically conductive paste of this invention, content of the said inorganic compound becomes like this with respect to 100 mass parts of solid content of the electrically conductive paste of this invention, Preferably it is 5-1000 mass parts, Preferably it is 50-100 mass parts.

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.

A dispersing agent for dispersing the conductive particles (D) and/or the inorganic compound can be added to the conductive paste of the present invention. 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, the BYK series manufactured by Bikchemi, etc. can be used. In particular, a polymer dispersing agent made of polyester, polyether, or polyurethane having a basic functional group, having a nitrogen atom as the basic functional group, the functional group having a nitrogen atom is an amine and/or a quaternary salt thereof, and the amine value is 1 to 100 mg KOH/g is suitably used.

Moreover, in the electrically conductive paste of this invention, thermal polymerization inhibitors, such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, and phenothiazine, as needed; transferability-imparting agents; thermal polymerization initiator; coloring agent; plasticizer; adhesion promoter; fillers; antifoaming agent (消泡劑); leveling agent; surface conditioning agent; antioxidants; UV absorbers; stabilizator; dispersing aid; anti-aggregation agent; catalyst; effect enhancers; crosslinking agent; thickener; Conventional additives, such as a release agent, can be added.

The electrically conductive paste of this invention WHEREIN: The polymerization initiator (A) containing 1 or more types of the oxime ester compound represented by the said general formula (I), binder resin (B), an ethylenically unsaturated compound (C), electroconductive particle (D) ), the amount of the optional component (however, the inorganic compound (filler) is excluded) is appropriately selected depending on the intended use and is not particularly limited, but preferably 100 parts by mass of solid content of the conductive paste of the present invention. to 50 parts by mass or less in total.

Moreover, the characteristic of hardened|cured material can also be improved for the electrically conductive paste of this invention by using another organic polymer with the said binder resin (B). 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, polyamide-imide resin, polyamic acid resin, epoxy resin, etc. are mentioned, Among these, polystyrene, acrylic acid -Methylmethacrylate copolymer, methacrylic acid-methylmethacrylate copolymer, and an epoxy resin are preferable.

A chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine, etc. can be used together with the electrically conductive paste of this invention further.

As the chain transfer agent or sensitizer, a compound containing a sulfur atom 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-mercaptoethane Sulfonic 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-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzoimidazole, 2-mercapto-3-pyridinol, Mercapto compounds, such as 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), and pentaerythritol tetrakis (3-mercaptopropionate), the said mercapto compound Disulfide compounds obtained by oxidizing iodine acetic acid, iodopropionic acid, 2-iodethanol, 2-iodethanesulfonic acid, 3-iodopropanesulfonic acid, alkyl iodide compounds such as trimethylolpropane tris(3-mercaptoisobutylate) , Butanediolbis(3-mercaptoisobutylate), hexanedithiol, decanedithiol, 1,4-dimethyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate , Trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakistioglycol aliphatic such as lactate, trishydroxyethyl tristhiopropionate, diethylthioxanthone, diisopropylthioxanthone, compound No.C1 below, trimercaptopropionate tris(2-hydroxyethyl)isocyanurate, etc. A polyfunctional thiol compound, the Showa Denko Co., Ltd. product Karenz MT BD1, PE1, NR1, etc. are mentioned.

As said surfactant, Fluorosurfactant, such as perfluoroalkyl phosphate ester and a perfluoroalkyl carboxylate; anionic surfactants such as alkali salts of higher fatty acids, alkyl sulfonates, and alkyl sulfates; cationic surfactants such as higher amine halides and quaternary ammonium salts; nonionic surfactants such as polyethylene glycol alkyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, and fatty acid monoglyceride; amphoteric surfactants; Surfactants, such as a silicone type surfactant, 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 can be used, and among them, a silane coupling agent having an isocyanate group, such as KBE-9007, KBM-502, and KBE-403, a methacryloyl group, or an epoxy group I am used appropriately.

Examples of the melamine compound include active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylolmeramine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea) and compounds in which all or part (at least two) have been alkyl etherified.

Here, as an alkyl group which comprises an alkyl ether, a methyl group, an ethyl group, or a butyl group is mentioned, It may mutually be same or different. In addition, the methylol group which is not alkyl-etherified may self-condensate within 1 molecule, it may condense between 2 molecules, and as a result, the oligomer component may be formed.

Specifically, hexamethoxymethyl meramine, hexabutoxymethyl meramine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, or the like can be used.

Among these, alkyl-etherified melamines, such as hexamethoxymethylmeramine and hexabutoxymethylmeramine, are preferable.

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

The process of said (1) is a process of apply|coating the electrically conductive paste of this invention prepared to the target board|substrate, and forming a coating film on a board|substrate. Examples of the target substrate include soda glass, quartz glass, semiconductor substrate, metal, paper, plastic, and the like. Moreover, you may use what surface-treated the board|substrate. The coating method is not particularly limited, and known means such as a spin coater, a roll coater, a bar coater, a die coater, a blade coater, a curtain coater, various types of printing and immersion can be employed.

In addition, in the formation of the coating film of the conductive paste of the present invention on a substrate, the coating film of the conductive paste of the present invention is once formed on a substrate such as a film, and then transferred onto another substrate. There is no limitation on the formation method.

The process of said (2) is a process for drying (prebaking) the coating film formed on the board|substrate, and removing the solvent (E) from the coating film. The prebaked coating film is poorly soluble in an alkaline solution, and the part irradiated with an energy ray by irradiating an energy ray in the next exposure step (hereinafter, sometimes referred to as an exposure part) is alkali-soluble. becomes this

Although the temperature of prebaking also varies depending on the kind of solvent (E) used, when the temperature is too low, the residual amount of the solvent (E) increases, which may cause a decrease in exposure sensitivity and resolution, and if the temperature is too low, When it is too high, hardening of the whole coating film advances by prebaking, the solubility with respect to the alkaline developing solution of the part irradiated with energy rays falls, and exposure sensitivity and resolution may fall as a result, so 80-150 degreeC is preferable, and 90-120 degreeC is more preferable. Although the time of a prebaking changes with the kind of solvent (E) used, and the temperature of a prebaking, 30 second - 10 minutes are preferable, and 1-5 minutes are more preferable.

The step (3) is a step of irradiating the dried coating film with radiation (energy rays) through a mask having a predetermined pattern shape, and curing the coating film of the conductive paste of the present invention. As a light source of an energy ray used when curing the coating film of the conductive paste of the present invention, an ultra-high 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, a carbon arc lamp, Electromagnetic energy with a wavelength of 2000 angstroms to 7000 angstroms obtained from metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, CRT light sources, etc., or high energy rays such as electron beams, X-rays, and radiation However, preferably, an ultra-high pressure mercury lamp that emits light having a wavelength of 300 to 450 nm, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, and the like are used.

As a light source of energy rays used when curing the coating film of the conductive paste of the present invention, there is also a laser direct drawing method in which an image is formed directly from digital information such as a computer without using a mask by using a laser light as an exposure light source, It is useful because not only productivity but also resolution and positional accuracy can be improved, and as the laser beam, light having a wavelength of 340 to 430 nm is suitably used, but excimer laser, nitrogen laser, argon ion laser, helium Those emitting light in the visible to infrared range, such as a cadmium laser, a helium neon laser, a krypton ion laser, various semiconductor lasers, and a YAG laser, are also used. In the case of using these lasers, a sensitizing dye that absorbs the region from visible to infrared is added.

As the mask, both a negative type mask and a positive type mask can be used in accordance with the components to be used, and as the mask, a multi-gradation mask such as a halftone mask or a gray scale mask can also be used.

The process of said (4) is a process of forming a predetermined pattern by removing the part whose alkali solubility improved by irradiation light among the said coating film after exposure using a developing solution.

As a developing method, any method of a spreading method, an immersion method, a shower method, a spray method, etc. can also be used, for example.

Although development time changes with the kind, molecular weight of each component, the temperature of a developing solution, etc., it is 30 to 180 second normally.

The developing solution used in the developing step is not particularly limited as long as the exposed portion can be dissolved or dispersed in the solution and removed. For example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, and ammonia Ryu; 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, and triethanolamine; pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0] cyclic tertiary amines such as -5-nonene; aromatic tertiary amines such as pyridine, collidine, lutidine and quinoline; Aqueous solutions of alkalis, such as aqueous solutions of quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, can be used, The density|concentration may just be the alkali concentration of the developing solution normally used. The aqueous solution of these alkalis may further contain an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and/or a surfactant.

After removing an exposed part with a developing solution, it is preferable to rinse with water with flowing water or a shower, and you may dehydrate and dry in the range of 50-120 degreeC as needed.

The process of said (5) is a process of baking (post-baking) the said coating film after image development.

In this process, curing shrinkage of binder resin occurs by baking the said coating film, electroconductive particle contacts, sufficient electroconductivity is acquired, and chemical-resistance also improves.

Post-baking, Preferably, it is 100-300 degreeC in inert gas atmosphere, such as nitrogen, helium, and argon, It is preferable to perform within the time of 10 to 60 minutes.

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

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

Example

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 addition, in the following description, "%" represents mass % unless otherwise indicated.

[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, 0.26 g of 2,6-di-tert-butyl-p-cresol, 0.11 tetra-n-butylammonium bromide g and 105 g of PGMEA were put, and the mixture was stirred at 120°C for 16 hours. The reaction liquid was cooled to room temperature, 160 g of PGMEA, 59 g of nonphthalic anhydride, and 0.24 g of tetra-n-butylammonium bromide were added, and it stirred at 120 degreeC for 4 hours. In addition, after adding 20 g of tetrahydrophthalic anhydride, stirring at 120 ° C. for 4 hours, 100 ° C. for 3 hours, 80 ° C. for 4 hours, 60 ° C. for 6 hours, and at 40 ° C. for 11 hours, 128 g of PGMEA was added, It was set as a PGMEA solution, and 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 89.9g, acrylic acid 23.5g, 2,6-di-tert-butyl-p-cresol 0.457g, benzyl 0.534 g of triethylammonium chloride and 75.6 g of PGMEA were put, and it stirred at 120 degreeC for 16 hours. It cooled to room temperature, 12.0 g of 2, 4- pentanedione and 1.0 g of triethylamine were put, and it stirred at 92 degreeC 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, followed by stirring at 100°C for 5 hours. It cooled to room temperature, 46.7 g of PGMEA was added, and it was set as the PGMEA solution, and binder resin B-2 was obtained (Mw=3500, solid content 44.0%, acid value 90 mgKOH/g).

[Examples 1 to 3 and Comparative Examples 1 to 3] Preparation of conductive pastes No. 1 to 3 and comparative conductive pastes No. 1 to 3

According to the compounding|blending of Table 1, each component was mixed, and electrically conductive paste No. 1-3 and comparative electrically conductive paste No. 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 corresponding to the 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 What was obtained in Preparation Example 1

B-2 What was obtained in Preparation Example 2

B-3 SPC-1000 (Mw=32000, solid content 29.0%, acid value 110 mgKOH/g, acrylate; Showa Denko Co., Ltd. product)

C-1 Kayarrad DPHA (polyfunctional acrylate; manufactured by Nippon Kayaku)

D-1 FA-333 (binder resin + conductive particles; manufactured by Fujikura Kasei Corporation)

E-1 Propylene glycol-1-monomethyl ether-2-acetate

F-1 F-554 (leveling agent; manufactured by DIC)

[Assessment Methods]

It dried after apply|coating electrically conductive paste No. 1-3 and comparative electrically conductive paste No. 1-3, respectively on the wafer with a spin coater. Exposure was performed using a photomask. Then, development and rinsing were performed using a 0.4% sodium carbonate developer to obtain a pattern. After that, it was cured with a curing furnace, and the following sensitivity, resolution, and overhang amount were evaluated.

(Sensitivity)

It was set as the sensitivity with the exposure amount resolved so that the line|wire width of 30 micrometers might not peel off.

(resolution)

When the line width was 30 µm, it was measured how many µm the line spacing was resolved.

(Overhang amount)

When the cut surface of the pattern was viewed with an SEM (scanning electron microscope), the difference in the pattern width between the surface side of the pattern and the substrate side was measured.

(Adhesiveness)

It dried after apply|coating electrically conductive paste No. 1-3 and comparative electrically conductive paste No. 1-3, respectively on the wafer with a spin coater. Next, 300 mJ/cm<2> of energy was irradiated with an ultra-high pressure mercury lamp, and the sample was produced. The adhesive tape peeling of the produced sample was performed, and the peeling of a pattern was evaluated. The evaluation criteria are as follows.

○: No pattern peeling

(triangle|delta): peeling exists in a part of pattern

×: With pattern peeling

(Specific resistance value)

It dried after apply|coating electrically conductive paste No. 1-3 and comparative electrically conductive paste No. 1-3, respectively on the wafer with a spin coater. Next, 300 mJ/cm<2> of energy was irradiated with an ultra-high pressure mercury lamp, and the sample was produced. The specific resistance value was measured for the produced sample by the 4-step needle method by Loresta HP [DIA Instruments product: brand name].

Therefore, the electrically conductive paste of this invention is excellent in a sensitivity, a resolution, and adhesiveness, and since a specific resistance value is low, it is useful as an electrically conductive pattern.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in a sensitivity, resolution, and adhesiveness, and can provide the electrically conductive paste which is low resistance.

Claims (5)

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), conductive particles (D) and a solvent (E) are contained As a conductive paste to
Content of the said polymerization initiator (A) is 0.5-5 mass parts with respect to 100 mass parts of solid content of an electrically conductive paste,
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 an ester product of the epoxy addition compound and a polybasic acid anhydride, and the binder resin Content of (B) is 10-30 mass parts in conversion of solid content with respect to 100 mass parts of electrically conductive pastes,
The said ethylenically unsaturated compound (C) is a polyfunctional acrylate which has one carboxyl group and two or more acryloyl groups or methacryloyl groups, and content of the said ethylenically unsaturated compound (C) is 100 mass of solid content of an electrically conductive paste 1 to 10 parts by mass per part,
The said electroconductive particle (D) is a silver particle, and content of the said electroconductive particle is 30-90 mass parts with respect to 100 mass parts of solid content of an electrically conductive paste,
The said solvent (E) is an ether ester solvent, and content of the said solvent (E) is 80-150 mass parts with respect to 100 mass parts of solid content of an electrically conductive paste, The electrically conductive paste characterized by the above-mentioned.

(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 an arylalkyl group having 2 to carbon atoms 20 represents a heterocycle-containing group,
The hydrogen atom of the group represented by R ¹¹ , R ¹² and R ¹³ is 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 ,
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 an arylalkyl group having 2 to carbon atoms 20 represents a heterocycle-containing group,
A 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 group in the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is -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 atom is not adjacent,
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 heterocycle-containing group having 2 to 20 carbon atoms,
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 chain or may be a cyclic alkyl;
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 heterocycle-containing group having 2 to 20 carbon atoms, R ³ When the group represented by has an alkyl moiety, the alkyl moiety may have a branched chain or may be cyclic alkyl,
The hydrogen atom of the group represented by R ³ is 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 , a hydroxyl group, a nitro group, CN, a 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,
In addition, 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 each form a ring together,
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 indicate,
n represents 0 or 1.)

(wherein, 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), R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ each independently represent 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 represents a number from 0 to 10.)

(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 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or carbon represents an aryl group having 6 to 20 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 the methylene group in the alkyl group and the arylalkyl group is an unsaturated bond, -O Oxygen atoms may be substituted by - or -S- on condition that they 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 may form a ring with each other. * means bonding with an adjacent group at the * part.) According to claim 1,
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 conductive pattern which consists of the electrically conductive paste of Claim 1 or 2. Conduction including the process of applying the electrically conductive paste of Claim 1 or 2 on a board|substrate, the process of drying, the process of exposing using a mask, the process of developing, and the process of baking at 100-300 degreeC How to form a pattern. A touch panel provided with the conductive pattern of Claim 3.