TWI417658B - Semiconductor element substrate - Google Patents

Description

Semiconductor element substrate

The present invention relates to a semiconductor element substrate, and more particularly to a semiconductor element substrate having high reliability and excellent various electrical characteristics (for example, low dielectric constant characteristics, low leakage current characteristics, high dielectric breakdown voltage characteristics), and A resin film having high transparency and excellent pattern formability by development.

A protective film for preventing deterioration or damage of various electronic components such as various display elements such as an organic electroluminescence device or a liquid crystal display device, an integrated circuit device, a solid-state imaging device, a color filter, and a black matrix is provided for Various resin films such as a planarizing film for flattening the surface of the device or wiring, and an electrically insulating film for maintaining electrical insulation. Further, in the organic electroluminescence device, a resin film as a pixel separation film is provided in order to separate the illuminant portion, and a device such as a display element or an integrated circuit element for a thin film transistor type liquid crystal is used. The wiring between the wirings arranged in a layered manner is provided with a resin film as an interlayer insulating film.

Conventionally, a thermosetting resin material such as an epoxy resin has been widely used as a resin material for forming such a resin film. In recent years, with the increase in the density of wiring or devices, it has been demanded to develop a new radiation-sensitive resin material which can be finely patterned and has excellent dielectric properties such as low dielectric properties.

In order to meet such requirements, a radiation-sensitive resin composition containing a composition of an alkali-soluble cyclic olefin resin as a main component has been studied. For example, Patent Document 1 discloses a radiation sensitive resin composition comprising a ring-opening polymerization of a vinylidene-based monomer containing an ester group, hydrogenation, and partial hydrolysis of an ester group to obtain a carboxyl group. Alkali-soluble alicyclic olefin resin; acid generator; and crosslinking agent.

However, the protective film obtained by using the resin composition described in Patent Document 1 has a good electrical property, but has low pattern formation property during development. Therefore, there is a problem that fine patterning cannot be achieved, or processing precision is poor. problem.

Prior technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei 10-307388

An object of the present invention is to provide a semiconductor element substrate which has high reliability and various electrical characteristics, and has a resin film which is high in transparency and excellent in pattern formation property by development.

In order to achieve the above object, the inventors of the present invention have found that a composition for forming a resin film which is used in contact with a surface of a semiconductor element mounted on a semiconductor element substrate or a semiconductor layer included in a semiconductor element is used. Radiation-sensitive radiation of a polymer, a crosslinking agent, and a radiation-sensitive compound of a monomer having a structure in which a cyclic quinone imine skeleton having a specific structure of a nitrogen atom has a carbon-carbon bond structure The resin composition can be excellent in reliability and various electrical characteristics of the semiconductor element substrate, and the obtained resin film is high in transparency and excellent in pattern formation property by development, and the present invention has been completed.

That is, according to the present invention, there is provided a semiconductor element substrate having a polymer (A), a crosslinking agent (B), and a radiation-sensitive compound comprising a unit (a1) of a monomer represented by the following general formula (1). (C) a resin film comprising a radiation-sensitive resin composition, wherein the resin film is formed in contact with a surface of a semiconductor element mounted on the semiconductor element substrate or a semiconductor layer included in the semiconductor element. .

(In the above formula (1), R ₁ represents a branched alkyl group having 5 to 16 carbon atoms.)

In the polymer (A), the unit (a1) content of the monomer represented by the above formula (1) is preferably from 10 to 90 mol%.

Preferably, the polymer (A) further contains a unit (a2) of a monomer copolymerizable with the monomer represented by the above formula (1).

The unit (a2) of the copolymerizable monomer is preferably a unit of a cyclic olefin monomer having a protic polar group, and more preferably a unit of a cyclic olefin monomer having a carboxyl group.

Preferably, the polymer (A) is a polymer obtained by ring-opening copolymerization of a monomer represented by the above formula (1) and a cyclic olefin monomer having a protic polar group, or the polymerization. a hydride of matter.

Preferably, the crosslinking agent (B) is a combination of an amine group-containing compound and an epoxy group-containing compound. The epoxy group-containing compound is preferably an epoxy group-containing compound having an alicyclic structure.

Preferably, the semiconductor element substrate is an active matrix substrate or an organic electroluminescent element substrate.

According to the present invention, a composition including a resin film used in contact with a semiconductor layer mounted on a semiconductor element substrate or a semiconductor layer contained in a semiconductor element is used, and a unit containing a monomer represented by the above formula (1) is used. (a1) a radiation-sensitive resin composition composed of the polymer (A), the crosslinking agent (B), and the radiation-sensitive compound (C), so that the reliability of the semiconductor element substrate can be high and the dielectric is low. It is excellent in various electrical characteristics such as a rate characteristic, a low leakage current characteristic, and a high dielectric breakdown voltage characteristic, and the resin film contained in the semiconductor element substrate can have high transparency and excellent pattern formation property by development, and as a result, reliability can be provided. A semiconductor device substrate having high electrical and electrical characteristics and high performance.

(Formation of implementing the invention)

The semiconductor element substrate of the present invention is characterized in that it has a polymer (A), a crosslinking agent (B), and a radiation-sensitive compound (a) containing a unit (a1) of a monomer represented by the following general formula (1). C) A resin film comprising a radiation-sensitive resin composition formed by contacting a surface of a semiconductor element mounted on the semiconductor element substrate or a semiconductor layer included in the semiconductor element.

Hereinafter, the radiation sensitive resin composition used in the present invention will be described first.

(sensing radiation resin composition)

The radiation sensitive resin composition used in the present invention is for forming a resin film formed by contacting a surface of a semiconductor element mounted on the semiconductor element substrate or a semiconductor layer included in the semiconductor element, and comprising: (1) A polymer (A), a crosslinking agent (B), and a radiation-sensitive compound (C) which are obtained by the unit (a1) of the monomer.

(Polymer (A))

The polymer (A) used in the present invention is a unit (a1) containing a monomer represented by the following formula (1).

(In the above formula (1), R ₁ represents a branched alkyl group having 5 to 16 carbon atoms.)

In the above formula (1), R ₁ is a branched alkyl group having 5 to 16 carbon atoms, for example, 1-methylbutyl group, 2-methylbutyl group, 1-methylpentyl group, 1-ethylbutyl group. Base, 2-methylhexyl, 2-ethylhexyl, 4-methylheptyl, 1-methylindenyl, 1-methyltridecyl, 1-methyltetradecyl, and the like. Among these, from the viewpoints of further excellent heat resistance and solubility in a polar solvent, a branched alkyl group having 6 to 14 carbon atoms and a branched alkyl group having 7 to 10 carbon atoms are more preferable. When the carbon number is 4 or less, the solubility in a polar solvent is poor, and when the carbon number is 17 or more, the heat resistance is inferior, and the patterned resin film may be melted by heat to cause the pattern to disappear.

Specific examples of the monomer represented by the above formula (1) are, for example, N-(1-methylbutyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarlimine, N-(2-methylbutyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(1-methylpentyl)-bicyclo[2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine, N-(2-methylpentyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N- (1-ethylbutyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(2-ethylbutyl)-bicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine, N-(1-methylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2 -Methylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(3-methylhexyl)-bicyclo[2.2.1]hept-5-ene- 2,3-Dicarboxy quinone imine, N-(1-butylpentyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2-butyl Pentyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(1-methylheptyl)-bicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinone imine, N-(2-methylheptyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(3-methylglycol ))-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(4- Cycloheptyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(1-ethylhexyl)-bicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinone imine, N-(2-ethylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(3-ethylhexyl) -bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(1-propylpentyl)-bicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine, N-(2-propylpentyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(1-methyloctyl)- Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(2-methyloctyl)-bicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-(3-methyloctyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(4-methyloctyl)-bicyclic [2.2.1] H--5-ene-2,3-dicarboxy quinone imine, N-(1-ethylheptyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium imine, N-(2-ethylheptyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(3-ethylheptyl)-bicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(4-ethylheptyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindole Imine, N-(1-propylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N -(2-propylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(3-propylhexyl)-bicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine, N-(1-methylindolyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2 -Methylmercapto)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(3-methylindolyl)-bicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine, N-(4-methylindolyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(5- Methyl fluorenyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(1-ethyloctyl)-bicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine, N-(2-ethyloctyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(3-B Benzyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(4-ethyloctyl)-bicyclo[2.2.1]hept-5-ene- 2,3-Dicarboxy quinone imine, N-(1-methylindolyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(1-methyl Twelve-based)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(1-methylundenyl)-bicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine, N-(1-methyldodecyto)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium imine, N-(1-methyltridecyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-(1-methyltetradecyl)- Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(1-methylpentadecyl)-bicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine and the like. Further, these may be used alone or in combination of two or more.

The method for producing the monomer represented by the above formula (1) is not particularly limited, and for example, it can be obtained by a guanidation reaction of a corresponding amine with 5-northene-2,3-dicarboxylic anhydride. Further, the reaction liquid of the guanidine reaction can be separated and purified by a known method, and the obtained monomer can be efficiently isolated.

In the polymer (A), the content of the unit (a1) of the monomer represented by the above formula (1) is preferably from 10 to 90 mol% based on the total monomer unit, and the above formula (1) If the content ratio of the unit (a1) of the monomer is too small, the solubility of the polymer (A) to the polar solvent may be insufficient, and if too large, the radiation of the radiation-sensitive linear resin composition may be linearly lowered or developed. Dissolving residues may occur.

In addition, the preferable range of the content of the unit (a1) of the monomer represented by the above formula (1) differs depending on the type of the resin film composed of the radiation-sensitive resin composition used in the present invention. Specifically, when the resin film is a resin film patterned by photolithography such as a protective film of an active matrix substrate or a sealing film of an organic electroluminescence device substrate, the monomer represented by the above formula (1) The content of the unit (a1) is preferably from 30 to 60 mol%, particularly preferably from 40 to 50 mol%. On the other hand, when the resin film is a gate insulating film of an active matrix substrate or a pixel separation film of an organic electroluminescence device substrate, and the like, a resin film which is patterned by photolithography is represented by the above formula (1). The content of the monomer unit (a1) is preferably from 20 to 80 mol%, particularly preferably from 30 to 70 mol%.

The polymer (A) preferably further contains a unit (a2) of a monomer copolymerizable with the monomer represented by the above formula (1).

The monomer which can be copolymerized, for example, a cyclic olefin monomer having a protic polar group (a2-1), or a ring having a polar group other than a protonic polar group other than the monomer represented by the general formula (1) Olefin monomer (a2-2), cyclic olefin monomer (a2-3) having no polar group, and monomer (a2-4) other than cyclic olefin (these monomers are hereinafter referred to as monomers (a2) -1)~(a2-4)). Here, the monomer (a2-4) may have a protic polar group or a polar group other than the above, or may have no polar group at all.

Here, the protic polar group means a group containing an atom in which a hydrogen atom is directly bonded to a group 15 or a group 16 of the periodic table. An atom belonging to Group 15 or Group 16 of the periodic table, preferably an atom of the first or second period belonging to Group 15 or Group 16 of the periodic table, more preferably an oxygen atom, a nitrogen atom or a sulfur atom, particularly preferably It is an oxygen atom.

Specific examples of such a protic polar group include a polar group having an oxygen atom such as a hydroxyl group, a carboxyl group (hydroxycarbonyl group), a sulfonic acid group or a phosphoric acid group; a first-order amine group, a second-order amine group, and a first-order fluorene group; A polar group having a nitrogen atom such as an amine group or a second-order guanidino group (indenylene group); a polar group having a sulfur atom such as a thiol group; and the like. Among these, those having an oxygen atom are preferred, and more preferably a carboxyl group.

In the present invention, the number of protic polar groups bonded to the cyclic olefin resin having a protic polar group is not particularly limited, and may also contain different kinds of protic polar groups.

Specific examples of the cyclic olefin monomer (a2-1) having a protic polar group, for example, 5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo[2.2 .1]hept-2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-dihydroxycarbonylbicyclo[2.2.1]hept-2-ene, 8-Hydroxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 9-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]12-4- Alkene, 9-methyl-9-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9,10-dihydroxycarbonyltetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ] a cyclic olefin having a carboxyl group such as dodec-4-ene; 5-(4-hydroxyphenyl)bicyclo[2.2.1]hept-2-ene, 5-methyl-5-(4- Hydroxyphenyl)bicyclo[2.2.1]hept-2-ene, 9-(4-hydroxyphenyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-A a cyclic olefin having a hydroxyl group such as a group of 9-(4-hydroxyphenyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, etc., in order to make a semiconductor The adhesion of the other layer constituting the semiconductor element substrate is improved, and a cyclic olefin having a carboxyl group is preferable. These monomers (a2-1) may be used alone or in combination of two or more.

The cyclic olefin monomer (a2-2) having a polar group other than the protonic polar group other than the monomer represented by the above formula (1), for example, has an ester group, an N-substituted quinone group, and a cyano group. Or a cyclic olefin of a halogen atom.

a cyclic olefin having an ester group, for example, 5-acetoxybicyclo[2.2.1]hept-2-ene, 5-methoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-methyl -5-methoxycarbonylbicyclo[2.2.1]hept-2-ene, 9-ethoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-A butoxycarbonyl tetracyclo [6.2.1.1 ^3,6 .0 ^2,7] twelve-4-ene, 9-ethoxycarbonyl tetracyclo [6.2.1.1 ^3,6 .0 ^2,7] -4 twelve - alkene, 9-n-propoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-isopropoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-n-butoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-methyl-9-methoxy Carbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-methyl-9-ethoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] Di-4-ene, 9-methyl-9-n-propoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-methyl-9-isopropyloxy Alkylcarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-methyl-9-n-butoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] dodec-4-ene, 9-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-methyl -9-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[ 6.2.1.1 ^3,6 .0 ^2,7 ]12-4-ene and so on.

a cyclic olefin having an N-substituted quinone imine group, for example, N-phenylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(endo-phenylbicyclo[ 2.2.1] Hept-5-ene-2,3-diyldicarbonyl) methyl aspartic acid methyl ester or the like.

a cyclic olefin having a cyano group, for example, 9-cyanotetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-methyl-9-cyanotetracyclo[6.2. 1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 5-cyanobicyclo[2.2.1]hept-2-ene, and the like.

a cyclic olefin having a halogen atom, for example, 9-chlorotetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-methyl-9-chlorotetracyclo[6.2.1.1 ^{3 , 6} .0 ^2,7 ] ^12-4 -ene and the like.

These monomers (a2-2) may be used alone or in combination of two or more.

Specific examples of the cyclic olefin monomer (a2-3) having no polar group, for example, bicyclo [2.2.1] hept-2-ene (also referred to as "northene"), 5-ethyl-bicyclo[2.2 .1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1]hept-2-ene, 5-methylidene-bicyclo[ 2.2.1] Hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, septene [5.2.1.0 ^2,6 ]-indole-3,8-diene (common name: Dicyclopentadiene), tetracyclo[10.2.1.0 ^2,11 .0 ^4,9 ] fifteen-4,6,8,13-tetraene, tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 12-4-ene (also known as "tetracyclododecene"), 9-methyl-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]12-4-ene, 9-B Base-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-methylidene-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene , 9-ethylidene-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-vinyl-tetracyclic [6.2.1.1 ^3,6 .0 ^2,7 ]12 4-ene, 9-propenyl-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, pentacyclo[9.2.1.1 ^3,9 .0 ^2,10 ] fifteen- 5,12-diene, cyclopentene, cyclopentadiene, 9-phenyl-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, tetracyclo[9.2.1.0 ^{2 , 10} .0 ^3,8 ] fourteen -3,5,7,12-tetraene, five rings [9.2.1.1 ^3,9 .0 ^{2 , 10} ] fifteen-12-ene and the like.

These monomers (a2-3) may be used alone or in combination of two or more.

Specific examples of the monomer (a2-4) other than the cyclic olefin, for example, a monomer which can be used in the addition polymerization, for example, ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-Dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene , 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-icosene, etc., 2 to 20 carbon atoms; 1,4- Non-conjugated dienes such as hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, and the like . Among these, an α-olefin is preferred, and especially ethylene is preferred.

The monomers (a2-4) other than the above-mentioned cyclic olefins may be used alone or in combination of two or more.

Among the above-mentioned copolymerizable monomers, a cyclic olefin having a protic polar group is preferred from the viewpoint that the polymer (A) has a protic polar group and is excellent in heat resistance and adhesion. The monomer (a2-1), particularly a cyclic olefin having a carboxyl group, is preferred.

In the polymer (A), the content of the unit (a2) of the copolymerizable monomer is preferably from 10 to 90 mol% based on the total monomer unit. If the content ratio of the unit (a2) of the copolymerizable monomer is too small, the radiation sensitivity of the radiation sensitive resin composition may be lowered, or dissolution residue may occur during development, and if too much, the polymer (A) may be present. The solubility in polar solvents becomes insufficient.

Moreover, the preferable range of the content ratio of the unit (a2) of the monomer which can be copolymerized differs depending on the kind of the resin film which consists of the radiation sensitive resin composition used by this invention. Specifically, when the resin film is a protective film of an active matrix substrate or a sealing film of an organic electroluminescent element substrate, a unit of a monomer which can be copolymerized when a resin film patterned by photolithography is used (a2) The content ratio is preferably 40 to 70 mol%, and particularly preferably 50 to 60 mol%. On the other hand, when the resin film is a gate insulating film of an active matrix substrate or a pixel separation film of an organic electroluminescence device substrate, a unit of a monomer which can be copolymerized when a resin film which is patterned by photolithography is not used. The content ratio of (a2) is preferably from 20 to 80 mol%, particularly preferably from 30 to 70 mol%.

Further, in the present invention, a proton polar group may be introduced into the polymer (A) by introducing a protic polar group into a polymer having no protic polar group by a known modifier.

A polymer having no protic polar group can be obtained by arbitrarily combining and polymerizing the above monomers (a2-2) to (a2-4).

A modifier for introducing a protic polar group is generally used for a compound having a protic polar group and a reactive carbon-carbon unsaturated bond in one molecule.

Specific examples of such compounds are, for example, acrylic acid, methacrylic acid, angelic acid, tiglic acid, oleic acid, elaidic acid, erucic acid, ebutyric acid. (brassidic acid), maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, atropic acid, cinnamic acid and other unsaturated carboxylic acids; allyl alcohol, methyl vinyl methanol , crotyl alcohol, methyl allyl alcohol, 1-phenylvinyl-1-ol, 2-propen-1-ol, 3-buten-1-ol, 3-buten-2-ol, 3-methyl 3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butene-1- An unsaturated alcohol such as an alcohol, 4-penten-1-ol, 4-methyl-4-penten-1-ol or 2-hexen-1-ol;

The modification reaction of the polymer using these modifiers can be carried out according to a usual method, usually in the presence of a radical generator.

The weight average molecular weight of the polymer (A) used in the present invention can be arbitrarily selected depending on the purpose of production of the polymer, but is usually 1,000 to 1,000,000, preferably 1,500 to 500,000, more preferably 2,000 to 50,000. The weight average molecular weight (Mw) of the polymer (A) is a value obtained by gel permeation chromatography (GPC) in terms of polystyrene.

Further, the polymer (A) of the present invention may be a ring-opening polymerization in which at least one of the monomers represented by the above formula (1) and, if necessary, a copolymerizable monomer are subjected to ring-opening polymerization. The addition polymer may be an addition polymer obtained by addition polymerization of these monomers, but a ring-opening polymer is preferred from the viewpoint of further enhancing the effects of the present invention.

The ring-opening polymer can be subjected to ring-opening displacement in the presence of a shift-shifting reaction catalyst by using at least one of the monomers represented by the above formula (1) and, if necessary, a copolymerizable monomer. Manufactured by changing polymerization.

The shift-shifting reaction catalyst is a transition metal compound of Groups 3 to 11 of the periodic table, and any catalyst that changes the ring-opening shift of the monomer represented by the above formula (1) can be used. For example, a shift change reaction catalyst can be used as described in Olefin Metathesis and Metathesis Polymerization (K. J. Ivin and J. C. Mol, Academic Press, San Diego 1997).

Shift-change reaction catalysts, for example, transition metal-carbene complex catalysts of Groups 3 to 11 of the periodic table. Group 3~11 transition metal-carbene complex catalysts of the periodic table, for example: tungsane-based complex catalyst, molybdenum-based complex catalyst, decane-based complex Catalyst, ruthenium carbene complex catalyst, etc. Among these, a ruthenium carbene complex catalyst is preferably used.

Specific examples of the tungsane-based complex catalyst, for example, W(N-2,6-Pr ⁱ ₂ C ₆ H ₃ )(CHBu ^t )(OBu ^t ) ₂ , W(N-2,6-Pr ⁱ ₂ C ₆ H ₃ )(CHBu ^t )(OCMe ₂ CF ₃ ) ₂ , W(N-2,6-Pr ⁱ ₂ C ₆ H ₃ )(CHBu ^t )(OCMe(CF ₃ ) ₂ ) ₂ , W (N-2,6-Pr ⁱ ₂ C ₆ H ₃ )(CHCMe ₂ Ph)(OBu ^t ) ₂ , W(N-2,6-Pr ⁱ ₂ C ₆ H ₃ )(CHCMe ₂ Ph)(OCMe ₂ CF ₃ ) ₂ , W(N-2,6-Pr ⁱ ₂ C ₆ H ₃ )(CHCMe ₂ Ph)(OCMe(CF ₃ ) ₂ ) ₂ or the like.

Specific examples of the molybdenum alkyl complex catalyst, for example, Mo(N-2,6-Pr ⁱ ₂ C ₆ H ₃ )(CHBu ^t )(OBu ^t ) ₂ , Mo(N-2,6-Pr ⁱ ₂ C ₆ H ₃ )(CHBu ^t )(OCMe ₂ CF ₃ ) ₂ , Mo(N-2,6-Pr ⁱ ₂ C ₆ H ₃ )(CHBu ^t )(OCMe(CF ₃ ) ₂ ) ₂ , Mo (N-2,6-Pr ⁱ ₂ C ₆ H ₃ )(CHCMe ₂ Ph)(OBu ^t ) ₂ , Mo(N-2,6-Pr ⁱ ₂ C ₆ H ₃ )(CHCMe ₂ Ph)(OCMe ₂ CF ₃ ) ₂ , Mo(N-2,6-Pr ⁱ ₂ C ₆ H ₃ )(CHCMe ₂ Ph)(OCMe(CF ₃ ) ₂ ) ₂ , Mo(N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (CHCMe ₂ Ph) (BIPHEN), Mo (N-2, 6-Pr ⁱ ₂ C ₆ H ₃ ) (CHCME ₂ Ph) (BINO) (THF), and the like.

Specific examples of the decane-based complex catalyst, for example, Re(CBu ^t )(CHBu ^t )(O-2,6-Pr ⁱ ₂ C ₆ H ₃ ) ₂ , Re(CBu ^t )(CHBu ^t ) (O-2-Bu ^t C ₆ H ₄ ) ₂ , Re(CBu ^t )(CHBu ^t )(OCMe ₂ CF ₃ ) ₂ , Re(CBu ^t )(CHBu ^t )(OCMe(CF ₃ ) ₂ ) ₂ , Re(CBu ^t )(CHBu ^t )(O-2,6-Me ₂ C ₆ H ₃ ) ₂ or the like.

In the above formula, Pr ⁱ represents an isopropyl group, Bu ^t represents a third butyl group, Me represents a methyl group, Ph represents a phenyl group, and BIPHEN represents 5,5',6,6'-tetramethyl-3,3'- Di-tert-butyl-1,1'-biphenyl-2,2'-dioxy, BINO represents 1,1'-dinaphthyl-2,2'-dioxy, and THF represents tetrahydrofuran.

Further, specific examples of the ruthenium carbene complex catalyst are, for example, compounds represented by the following formula (2) or (3).

In the above formulae (2) and (3), =CR ₃ R ₄ and =C=CR ₃ R ₄ are carbene-carbon-containing carbene compounds at the reaction center. R ₃ and R ₄ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphate or a ruthenium atom, and these carbene compounds may contain or Contains no heteroatoms. L ₁ represents a carbene compound containing a hetero atom, and L ₂ represents a carbene compound containing a hetero atom or an arbitrary neutral electron donating compound.

Here, the carbene compound containing a hetero atom means a compound containing a carbene carbon and a hetero atom. Both L ₁ and L ₂ or L ₁ are carbene compounds containing a hetero atom, and the carbene carbons contained therein are directly bonded to a ruthenium metal atom and bonded to a hetero atom-containing group. Further, specific examples of the hetero atom include, for example, N, O, P, S, As, and Se atoms. Among these, from the viewpoint of obtaining a stable carbene compound, N, O, P, S atoms and the like are preferable, and N atoms are particularly preferable.

Specific examples of the carbene compound containing a hetero atom, for example, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3 -dicyclohexyl-4-imidazolin-2-ylidene, 1,3-bis(methylphenyl)-4-imidazolin-2-ylidene, 1,3-bis(methylnaphthyl)-4 -Imidazoline-2-subunit, 1,3-two Base-4-imidazolin-2-ylidene, 1,3-di Base-4,5-dichloro-4-imidazolin-2-ylidene, 1,3-di 4-,5-dibromo-4-imidazolin-2-ylidene, 1,3-diadamantyl-4-imidazolin-2-ylidene, 1,3-diphenyl-4-imidazoline- 2-subunit, 1,3,4,5-tetramethyl-4-imidazolin-2-ylidene, and 1,3,4,5-tetraphenyl-4-imidazolin-2-ylidene, etc. N,N-disubstituted imidazolin-2-ylidene, or 1,3-diisopropylimidazolidin-2-ylidene, 1,3-dicyclohexyl imidazolidin-2-ylidene, 1,3- Di(methylphenyl)imidazolidine-2-ylidene, 1,3-bis(methylnaphthyl)imidazolidin-2-ylidene, 1,3-di Imidazolidin-2-ylidene, 1,3-diadamanylimidazolidin-2-ylidene, 1,3-diphenylimidazolidin-2-ylidene, and 1,3,4,5-tetramethyl N,N-disubstituted imidazolidin-2-ylidene and the like, such as imidazolidine-2-ylidene.

When L ₂ is a neutral electron-providing compound, L ₂ may be a ligand having a neutral charge when it is away from the central metal. Specific examples thereof include carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, and thiocyanates. Among these, a phosphine or a pyridine is preferred, and a trialkylphosphine is more preferred.

L ₃ and L ₄ are each independently and represent an arbitrary anionic ligand. Further, two, three, four, five or six of R ₃ , R ₄ , L ₁ , L ₂ , L ₃ , and L ₄ may be bonded to each other to form a multi-seat chelated ligand. .

In the above formulas (2) and (3), the anionic ligands L ₃ and L ₄ are ligands having a negative charge when they are far from the central metal, for example, fluorine atoms, chlorine atoms, a halogen atom such as a bromine atom or an iodine atom; an oxygen-containing hydrocarbon group such as a ketonate group, an alkoxy group, an aryloxy group or a carboxyl group; an alicyclic hydrocarbon group substituted with a halogen atom such as a chlorocyclopentadienyl group; . Among these, a halogen atom is preferred, and a chlorine atom is more preferable.

The ruthenium complex catalyst represented by the above formula (2), for example, benzylidene (1,3-di) Imidazolidinium-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-di Imidazolidin-2-ylidene (3-methyl-2-butene-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-di) - octahydrobenzimidazole-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-bis(1-phenylethyl)-4-imidazolin-2-ene (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-di) Base-2,3-dihydrobenzimidazole-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2, 3,4,5-tetrahydro-1H-1,2,4-triazole-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (B Oxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-di) Imidazolidinium-2-ylidenepyridinium dichloride, (1,3-di) Base-4,5-dibromo-4-imidazolin-2-ylidene) (tricyclohexylphosphine) (4-acetoxyphenylmethylene) ruthenium dichloride or the like bonded with a hetero atom a carbene compound of a carbene compound and a neutral electron-providing compound; benzylidene bis(1,3-dicyclohexyl imidazolidin-2-ylidene) ruthenium dichloride, benzylidene bis (1) a 3-nonyl-4-imidazolin-2-ylidene) ruthenium dichloride or the like having a ruthenium carbene compound having a carbene compound containing two hetero atoms;

a ruthenium carbene complex catalyst represented by the above formula (3), for example: (1,3-di) Imidazolidin-2-ylidene (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butylvinylidene) (1,3-diisopropyl-4-imidazoline) -2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis(1,3-dichlorohexyl-4-imidazolin-2-ylidene)phenylvinylidene dichloride or the like.

The shifting reaction reaction catalyst is used in a molar ratio of monomer to catalyst, and the catalyst: monomer = 1:100 to 1:2,000,000, preferably 1:500 to 1:1,000,000, more preferably It is 1:1,000~1:500,000. If the amount of the catalyst is too large, the catalyst may be difficult to remove, and if it is too small, sufficient polymerization activity may not be obtained.

Ring-opening polymerization using a shift-shifting reaction catalyst can be carried out in a solvent or without a solvent. After the completion of the polymerization reaction, it is preferred to carry out the polymerization in a solvent without directly hydrolyzing the produced polymer.

The solvent to be used is not particularly limited as long as it is a solvent which dissolves the produced polymer and does not interfere with the polymerization reaction. The solvent to be used, for example, an aliphatic hydrocarbon such as n-pentane, n-hexane or n-heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, B Alicyclic hydrocarbons such as cyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydroanthracene, cyclooctane; benzene, toluene, xylene, mesitylene, etc. a hydrocarbon; a nitrogen-containing hydrocarbon such as nitromethane, nitrobenzene, acetonitrile, propionitrile or benzonitrile; diethyl ether, tetrahydrofuran, Ethers such as alkane; ketones such as acetone, ethyl methyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone; esters such as methyl acetate, ethyl acetate, ethyl propionate, methyl benzoate a halogenated hydrocarbon such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene or trichlorobenzene; Among these, aromatic hydrocarbons, alicyclic hydrocarbons, ethers, ketones or esters are preferred.

The monomer concentration in the solvent is preferably from 1 to 50% by weight, more preferably from 2 to 45% by weight, still more preferably from 5 to 40% by weight. When the concentration of the monomer is less than 1% by weight, the productivity of the polymer may be deteriorated. When the concentration exceeds 50% by weight, the viscosity after polymerization is too high, and subsequent hydrogenation may become difficult.

The shift change reaction catalyst may be added to the reaction system after being dissolved in a solvent, or may be added directly without being dissolved. The solvent for preparing the catalyst solution is, for example, the same solvent as the solvent used in the above polymerization reaction.

Further, in the polymerization reaction using the shift change reaction catalyst, a molecular weight modifier may be added to the reaction system in order to adjust the molecular weight of the polymer. A molecular weight modifier, for example, an α-olefin such as 1-butene, 1-pentene, 1-hexene or 1-octene; 1,4-pentadiene, 1,4-hexadiene, 1,5- Non-conjugated dienes such as hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl-1,5-hexadiene; 1,3 -butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, etc. Conjugated diene; styrene such as styrene or vinyl toluene; ethers such as ethyl vinyl ether, isobutyl vinyl ether, allyl epoxidized ether; halogen-containing ethylene such as allyl chloride Base compound; oxygen-containing vinyl compound such as allyl acetate, allyl alcohol, glycidyl methacrylate; nitrogen-containing vinyl compound such as acrylonitrile or acrylamide; A polymer having a desired molecular weight can be obtained by using a molecular weight modifier of 0.05 to 50 mol% with respect to the entire monomer.

The polymerization temperature is not particularly limited and is usually -100 ° C to +200 ° C, preferably -50 ° C to +180 ° C, more preferably -30 ° C to +160 ° C, and even more preferably 0 ° C to + 140 ° C. The polymerization time is usually from 1 minute to 100 hours, and the progress of the reaction can be appropriately adjusted.

On the other hand, the addition polymer may be a known addition polymerization catalyst using at least one of the monomers represented by the above formula (1) and, if necessary, a copolymerizable monomer, for example, It is obtained by polymerization of a catalyst composed of a titanium, zirconium or vanadium compound and an organoaluminum compound. These catalysts may be used alone or in combination of two or more. The amount of the polymerization catalyst is usually in the range of 1:100 to 1:2,000,000 in terms of the molar ratio of the metal compound:monomer in the polymerization catalyst.

Moreover, when the polymer (A) used in the present invention is a ring-opening polymer, it is preferred to further carry out a hydrogenation reaction to obtain a hydrogenated product of a carbon-carbon double bond contained in the main chain. When the polymer (A) is a hydride, the ratio (hydrogenation ratio) of the hydrogenated carbon-carbon double bond is usually 50% or more, and from the viewpoint of heat resistance, 70% or more is preferable, and 90% or more is more preferable. More than % is better.

The hydrogenation rate of the hydride, for example, can be obtained by comparing the peak intensity from the carbon-carbon double bond in the ¹ H-NMR band of the ring-opening polymer, and from the carbon in the ¹ H-NMR band of the hydride. The peak intensity of the carbon double bond is obtained.

The hydrogenation reaction can be carried out, for example, by changing the carbon-carbon double bond in the main chain of the ring-opening polymer to a saturated single bond using hydrogen gas in the presence of a hydrogenation catalyst.

The hydrogenation catalyst to be used is not particularly limited as a homogeneous catalyst or a heterogeneous catalyst, and a general user can be suitably used when hydrogenating an olefin compound.

Uniform system catalyst, for example: cobalt acetate and triethyl aluminum, acetonitrile acetone and triisobutyl aluminum, combination of ferrocene dichloride and n-butyl lithium, zirconocene dichloride and second a Ziegler-based catalyst composed of a combination of a transition metal compound such as butyllithium, tetrabutoxytitanate and dimethylmagnesium and an alkali metal compound; and a ruthenium carbene described in the item of the ring-opening shift change reaction catalyst The complex catalyst, the dichloro ginseng (triphenylphosphine) ruthenium, the Japanese Patent Laid-Open No. Hei 7-2929, the Japanese Patent Laid-Open No. Hei 7-149823, the Japanese Patent Laid-Open No. Hei 11-109460, and the Japanese Patent Laid-Open No. 11-158256 A noble metal complex catalyst composed of a ruthenium compound described in Japanese Laid-Open Patent Publication No. Hei 11-109460, and the like.

The heterogeneous catalyst is, for example, a hydrogenation catalyst obtained by supporting a metal such as nickel, palladium, platinum, rhodium or ruthenium on a support such as carbon, ceria, diatomaceous earth, alumina or titania. More specifically, for example, nickel/cerium oxide, nickel/diatomaceous earth, nickel/aluminum oxide, palladium/carbon, palladium/ceria, palladium/diatomaceous earth, palladium/alumina, and the like. These hydrogenation catalysts may be used singly or in combination of two or more.

Among these, a side reaction such as modification of a functional group contained in a ring-opening polymer does not cause a viewpoint of selectively hydrogenating a carbon-carbon double bond in the polymer, and a noble metal such as ruthenium or osmium is used. Preferably, the catalyst is a palladium-supporting catalyst such as palladium/carbon, and the ruthenium carbene complex catalyst or the palladium-supporting catalyst is more preferable.

The above ruthenium carbene complex catalyst can be used as a ring opening shift reaction catalyst and a hydrogenation catalyst. In this case, the ring-opening shift change reaction and the hydrogenation reaction can be continuously performed.

Further, when the ring-opening shift change reaction and the hydrogenation reaction are continuously carried out using a ruthenium carbene complex catalyst, a catalyst such as a vinyl compound such as ethyl vinyl ether or a catalyst modifier such as an α-olefin is added to make the contact After the activation of the medium, a method of starting the hydrogenation reaction is also preferred. Further, a method of increasing the activity by adding a base such as triethylamine or N,N-dimethylacetamide is also preferred.

The hydrogenation reaction is usually carried out in an organic solvent. The organic solvent can be appropriately selected depending on the solubility of the produced hydride, and the same organic solvent as the above-mentioned polymerization solvent can be used. Therefore, after the polymerization reaction, the solvent may be added without changing the solvent, and a hydrogenation catalyst may be added to the filtrate obtained by filtering the shift-shifting reaction catalyst from the reaction liquid to react.

The conditions of the hydrogenation reaction can be appropriately selected depending on the kind of the hydrogenation catalyst to be used. The amount of the hydrogenation catalyst used is usually 0.01 to 50 parts by weight, preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the ring-opening polymer. The reaction temperature is usually -10 ° C to +250 ° C, preferably -10 ° C to + 210 ° C, more preferably 0 ° C to + 200 ° C. At a temperature lower than this range, the reaction rate becomes slow, and conversely, at a high temperature, a side reaction easily occurs. The pressure of hydrogen is usually from 0.01 to 10.0 MPa, preferably from 0.05 to 8.0 MPa, more preferably from 0.1 to 6.0 MPa.

The time of the hydrogenation reaction can be appropriately selected in order to control the hydrogenation rate. The reaction time is usually in the range of 0.1 to 50 hours, and 50% or more, preferably 70% or more, more preferably 90% or more, and most preferably 95% of the carbon-carbon double bonds of the main chain in the polymer. More than % is hydrogenated.

(crosslinking agent (B))

The crosslinking agent (B) used in the present invention is a structure in which a crosslinking structure is formed between molecules of a crosslinking agent by heating, or a crosslinking structure is formed between resin molecules by reacting with the polymer (A), specifically, for example, A compound having two or more reactive groups. Such a reactive group is, for example, an amine group, a carboxyl group, a hydroxyl group, an epoxy group, an isocyanate group or the like, more preferably an amine group, an epoxy group and an isocyanate group, still more preferably an amine group and an epoxy group, and particularly, The amine group compound is preferably used in combination with the compound having an epoxy group.

The molecular weight of the crosslinking agent (B) is not particularly limited and is usually from 100 to 100,000, preferably from 300 to 50,000, more preferably from 500 to 10,000. The crosslinking agent may be used alone or in combination of two or more.

Specific examples of the crosslinking agent (B) include, for example, aliphatic polyamines such as hexamethylenediamine; aromatic polyamines such as 4,4'-diaminodiphenyl ether and diaminodiphenyl hydrazine; 2,6-bis(4'-azidobenzylidene)cyclohexanone, azide such as 4,4'-diazide diphenyl hydrazine; nylon, polyhexamethylenediamine p-xylene Polyamines such as decylamine and polyhexamethylene metabenzamide; N, N, N', N', N", N"-(hexaalkyloxyalkyl) melamine, etc. may have a hydroxyl group A melamine type or an imine group (commercial name "CYMEL303, CYMEL325, CYMEL370, CYMEL232, CYMEL235, CYMEL272, CYMEL212, mycoat 506 {above, Cytech Industries", etc. Cymel series, Mycoat series"; N, N', N", N'''-(tetraalkoxyalkyl)glycol glycoluril, etc., may also have a hydroxymethyl or imine group of glycolurireas (trade name "Cymel 1170" {above, for Cytech Industries Company system}Cymel series); acrylate compound such as (meth)acrylic acid glycol; hexamethylene diisocyanate polyisocyanate, isophorone diisocyanate polyisocyanate, tolylene diisocyanate Gather Isocyanate compound such as isocyanate or hydrogenated diphenylmethane diisocyanate; 1,4-di-(hydroxymethyl)cyclohexane, 1,4-bis-(hydroxymethyl)norbornane; 1,3,4- Trihydroxycyclohexane; bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac resin epoxy resin, cresol novolac resin epoxy resin, polyphenol epoxy resin, cyclic aliphatic An epoxy compound such as an epoxy resin, an aliphatic propylene glycol ether or an epoxy acrylate polymer;

Specific examples of the epoxy compound include a trifunctional epoxy compound having a structure of dicyclopentadiene (trade name "XD-1000", manufactured by Nippon Kayaku Co., Ltd.), and 2,2-bis(hydroxymethyl). 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 1-butanol (15-functional alicyclic epoxy having a cyclohexane skeleton and a terminal epoxy group) Resin, trade name "EHPE3150", manufactured by Daicel Chemical Industry Co., Ltd.), epoxidized 3-cyclohexene-1,2-dicarboxylic acid bis(3-cyclohexenylmethyl) modified ε-caprolactone (fat Acyclic trifunctional epoxy resin, trade name "EPOLEAD GT 301", manufactured by Daicel Chemical Industry Co., Ltd.), epoxidized butane tetracarboxylate (3-cyclohexenylmethyl) modified ε-caprolactone An epoxy compound having an alicyclic structure such as an aliphatic cyclic tetrafunctional epoxy resin (trade name "EPOLEAD GT 401", manufactured by Daicel Chemical Industry Co., Ltd.).

An aromatic amine type polyfunctional epoxy compound (trade name "H-434", manufactured by Tohto Kasei Co., Ltd.), a cresol novolac type polyfunctional epoxy compound (trade name "EOCN-1020", manufactured by Nippon Kayaku Co., Ltd.), A phenol novolac type polyfunctional epoxy compound ("Epicoat 152, Epicoat 154", manufactured by Japan Epoxy Resin Co., Ltd.), a polyfunctional epoxy compound having a naphthalene skeleton (trade name "EXA-4700", Dainippon Printing Chemical Co., Ltd.) , a chain-like alkyl polyfunctional epoxy compound (trade name "SR-TMP", manufactured by Sakamoto Pharmaceutical Co., Ltd.), and polyfunctional epoxy polybutadiene (trade name "EPOLEAD PB3600", manufactured by Daicel Chemical Industry Co., Ltd.) Epoxy propyl polyether compound (trade name "SR-GLG", manufactured by Sakamoto Pharmaceutical Co., Ltd.), diglycerin polyglycidyl ether compound (trade name "SR-DGE", Sakamoto Pharmaceutical Industry (" An epoxy compound having no alicyclic structure, such as a polyglycerol polyglycidyl ether compound (trade name "SR-4GL", manufactured by Sakamoto Pharmaceutical Co., Ltd.).

Among the epoxy compounds, a polyfunctional epoxy compound having two or more epoxy groups is preferred, and the resin film obtained by using the radiation sensitive resin composition is excellent in heat-resistant shape retention, and has an alicyclic structure. Further, an epoxy group is preferably three or more polyfunctional epoxy compounds.

In the radiation-sensitive resin composition used in the present invention, the content of the crosslinking agent (B) is not particularly limited, and may be arbitrarily set in consideration of the degree of heat resistance required for setting the pattern of the resin film obtained by using the resin composition of the present invention. However, it is usually 1 to 500 parts by weight, preferably 5 to 300 parts by weight, more preferably 10 to 150 parts by weight, per 100 parts by weight of the polymer (A). Too much or some of the crosslinking agent (B) tends to have reduced heat resistance.

(sensing radiation compound (C))

The radiation-sensitive compound (C) used in the present invention is a compound capable of initiating a chemical reaction by irradiation of radiation such as ultraviolet rays or electron beams. In the present invention, the radiation sensitive compound (C) is preferably one which can control the alkali solubility of the resin film formed of the resin composition, and in particular, a photoacid generator is preferably used.

Such a radiation sensitive compound (C) is, for example, an azide compound such as an acetophenone compound, a triarylsulfonium salt or a benzoquinonediazide compound, but is preferably an azide compound, particularly preferably a benzoquinonediazide compound. .

As the phenylhydrazine diazide compound, for example, an ester compound of a phenylhydrazine diazidosulfonic acid halide and a compound having a phenolic hydroxyl group can be used. Specific examples of the phenylhydrazine diazidosulfonic acid halide are, for example, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1 , 2-benzyl quinonediazide-5-sulfonic acid chloride or the like. Representative examples of compounds having a phenolic hydroxyl group, for example: 1,1,3-gin(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1-[ 4-[1-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol. Other compounds having a phenolic hydroxyl group other than these, such as 2,3,4-trihydroxydiphenyl ketone, 2,3,4,4'-tetrahydroxydiphenyl ketone, 2-bis(4-hydroxybenzene) Propane, ginseng (4-hydroxyphenyl)methane, 1,1,1-cis (4-hydroxy-3-methylphenyl)ethane, 1,1,2,2-indole (4-hydroxybenzene) An oligomer obtained by copolymerizing an oligomer of ethane or a phenol resin, a compound having one or more phenolic hydroxyl groups, and dicyclopentadiene.

Among these, a condensate of a 1,2-naphthoquinonediazide-5-sulfonic acid chloride and a compound having a phenolic hydroxyl group, 1,1,3-glycol (2,5-dimethyl group) is preferred. More preferably, the condensate of 4-hydroxyphenyl)-3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.9 mol).

Further, as the photoacid generator, in addition to phenylhydrazine diazide, a phosphonium salt, a halogenated organic compound, an α,α-bis(sulfonyl)diazomethane compound, or an α-carbonyl-α'-sulfonate may also be used. A known compound such as a mercaptodiazomethane compound, an anthraquinone compound, an organic acid ester compound, an organic acid decylamine compound, or an organic acid quinone imine compound.

These radiation sensitive compounds may be used alone or in combination of two or more.

In the radiation sensitive resin composition used in the present invention, the content of the radiation sensitive compound (C) is preferably 10 to 100 parts by weight, more preferably 15 to 70 parts by weight, based on 100 parts by weight of the polymer (A). More preferably, it is in the range of 20 to 50 parts by weight. When the content of the radiation-sensitive compound (C) is within this range, when the resin film composed of the radiation-sensitive resin composition is patterned, the difference in solubility between the radiation-irradiated portion and the radiation-irradiated portion in the developer increases, and the radiation sensitivity It is also high and is easily patterned by development, so it is preferable.

Further, the radiation sensitive resin composition used in the present invention may contain a solvent. The solvent is not particularly limited, and is known as a solvent for a radiation-sensitive resin composition, for example, acetone, methyl ethyl ketone, cyclopentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, and 4- Linear ketones such as heptanone, 2-octanone, 3-octanone and 4-octanone; alcohols such as n-propanol, isopropanol, n-butanol and cyclohexanol; ethylene glycol dimethyl ether, B Glycol diethyl ether, two Ethers such as alkyl ethers; alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyric acid Methyl ester, ethyl butyrate, methyl lactate, ethyl lactate and other esters; 赛路苏 acetate, methyl sarbuta acetate, ethyl serosu acetate, propyl 赛苏苏乙Ruthenium esters such as acid esters and butyl racelusacetate; propylene glycols such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether; Diethylene glycol such as diol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether; γ-butyrolactone, γ-pentyl Saturated γ-lactones such as lactone, γ-caprolactone and γ-decalactone; halogenated hydrocarbons such as trichloroethylene; aromatic hydrocarbons such as toluene and xylene; dimethylacetamide and dimethyl A polar solvent such as formamide or N-methylacetamide. These solvents may be used singly or in combination of two or more. The content of the solvent is preferably from 10 to 10,000 parts by weight, more preferably from 50 to 5,000 parts by weight, still more preferably from 100 to 1,000 parts by weight, per 100 parts by weight of the polymer (A). Further, when the radiation-sensitive resin composition contains a solvent, the solvent is usually removed after the resin film is formed.

Further, the radiation-sensitive resin composition used in the present invention may contain a surfactant, an acidic compound, a coupling agent or a derivative thereof, a sensitizer, a latent acid generator, or the like, without departing from the scope of the present invention. Other compounding agents such as antioxidants, photosensitizers, defoamers, pigments, dyes, fillers, etc.;

The surfactant is used for preventing streaks (coating streaks), improving developability, and the like. Specific examples of the surfactant, for example, polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl stearyl ether, polyoxyethyl ether ether, polyoxyethylene ethyl ether; polyoxyethylene ethyl octane Polyoxyethylene ethyl aryl ethers such as phenylene ether and polyoxyethylidene phenyl ether; polyoxyethylene ethyl laurate, polyoxyethylene ethyl distearate, etc. Nonionic surfactant such as dialkyl ester; fluorine surfactant; anthrone surfactant; methacrylic copolymer surfactant; acrylic copolymer surfactant;

The acidic compound is used to improve the adhesion between the resin film composed of the radiation sensitive resin composition and the respective layers including the semiconductor layer constituting the semiconductor element substrate.

As the acidic compound, an aliphatic compound having an acidic group, an aromatic compound, a heterocyclic compound or the like can be used. The acidic group may be an acidic functional group, and specific examples thereof include a strongly acidic group such as a sulfonic acid group or a phosphoric acid group; and a weakly acidic group such as a carboxyl group, a thiol group or a carboxymethylenethio group. Among these, a carboxyl group, a thiol group or a carboxymethylenethio group is preferred, and a carboxyl group is particularly preferred. Specific examples are, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, glycolic acid, glyceric acid, oxalic acid (also known as oxalic acid), Malonic acid (also known as malic acid), succinic acid (also known as succinic acid), glutaric acid, adipic acid (also known as adipic acid), 1,2-cyclohexanedicarboxylic acid, 2 -oxypropionic acid, 2-hydroxysuccinic acid, 2-hydroxypropane tricarboxylic acid, mercapto succinic acid, dimercaptosuccinic acid, 2,3-dimercapto-1-propanol, 1,2,3-three Mercaptopropane, 2,3,4-trimercapto-1-butanol, 2,4-dimercapto-1,3-butanediol, 1,3,4-trimercapto-2-butanol, 3,4- An aliphatic compound such as dimercapto-1,2-butanediol or 1,5-dimercapto-3-thiopentane; benzoic acid, p-hydroxybenzenecarboxylic acid, o-hydroxybenzenecarboxylic acid, 2-naphthalenecarboxylic acid, benzene Methyl formate, dimethyl benzoate, trimethyl benzoate, 3-phenylpropionic acid, 2-hydroxybenzoic acid, dihydroxybenzoic acid, dimethoxybenzoic acid, benzene-1,2-dicarboxylic acid (also known as phthalic acid), benzene-1,3-dicarboxylic acid (also known as isophthalic acid), benzene-1,4-dicarboxylic acid (also known as terephthalic acid), benzene- 1,2,3-tricarboxylic acid, benzene-1,2, 4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, benzene hexacarboxylic acid, biphenyl-2,2'-dicarboxylic acid, 2-(carboxymethyl)benzoic acid, 3-(carboxyl Benzoic acid, 4-(carboxymethyl)benzoic acid, 2-(carboxycarbonyl)benzoic acid, 3-(carboxycarbonyl)benzoic acid, 4-(carboxycarbonyl)benzoic acid, 2-mercaptobenzoic acid, 4- Mercaptobenzoic acid, 2-mercapto-6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-didecylbenzene, 1, 4-naphthalene dithiol, 1,5-naphthalene dithiol, 2,6-naphthalene dithiol, 2,7-naphthalene dithiol, 1,2,3-trimethylbenzene, 1,2,4- Trimethyl benzene, 1,3,5-trimercaptobenzene, 1,2,3-nonyl(decylmethyl)benzene, 1,2,4-nonyl(decylmethyl)benzene, 1,3,5-para Aromatic groups such as fluorenylmethyl)benzene, 1,2,3-cis (mercaptoethyl)benzene, 1,2,4-nonyl(decylethyl)benzene, 1,3,5-nonyl(decylethyl)benzene a compound; nicotinic acid, isonicotinic acid, 2-decanoic acid, pyrrole-2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3, 4-dicarboxylic acid, imidazole-2,4-dicarboxylic acid, imidazole-2,5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, pyrazole- Five-membered heterocyclic compound containing a nitrogen atom such as 3,5-dicarboxylic acid; -2,3-dicarboxylic acid, thiophene-2,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole -2,5-dicarboxylic acid, thiazole-4,5-dicarboxylic acid, isothiazole-3,4-dicarboxylic acid, isothiazole-3,5-dicarboxylic acid, 1,2,4-thiadiazole -2,5-dicarboxylic acid, 1,3,4-thiadiazole-2,5-dicarboxylic acid, 3-amino-5-mercapto-1,2,4-thiadiazole, 2-amino group -5-mercapto-1,3,4-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, 3 -(5-mercapto-1,2,4-thiadiazol-3-ylsulfanyl)succinic acid, 2-(5-mercapto-1,3,4-thiadiazol-2-ylsulfanyl) Succinic acid, (5-mercapto-1,2,4-thiadiazol-3-ylthio)acetic acid, (5-mercapto-1,3,4-thiadiazol-2-ylthio)acetic acid, 3-( 5-mercapto-1,2,4-thiadiazol-3-ylthio)propionic acid, 2-(5-mercapto-1,3,4-thiadiazol-2-ylthio)propionic acid, 3-( 5-mercapto-1,2,4-thiadiazol-3-ylthio)succinic acid, 2-(5-mercapto-1,3,4-thiabis8-2-ylthio)succinic acid, 4-( 3-mercapto-1,2,4-thiadiazol-5-ylthio)thiobutanesulfonic acid, 4-(2-mercapto-1,3,4-thiadiazol-5-ylthio)thiobutane a five-membered heterocyclic compound containing a nitrogen atom and a sulfur atom such as a sulfonic acid; pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid Pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5-dicarboxylic acid, despair -3,4-dicarboxylic acid, hydrazine -3,5-dicarboxylic acid, hydrazine -3,6-dicarboxylic acid, hydrazine -4,5-dicarboxylic acid, pyrimidine-2,4-dicarboxylic acid, pyrimidine-2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyridyl -2,3-dicarboxylic acid, pyridyl -2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, three -2,4-dicarboxylic acid, 2-diethylamino-4,6-dimercapto-s-three 2-dipropylamino-4,6-dimercapto-s-three 2-dibutylamino-4,6-dimercapto-s-three 2-anilino-4,6-dimercapto-s-three , 2,4,6-trimethyl-s-three A six-membered heterocyclic compound containing a nitrogen atom.

Among these, the number of acidic groups is preferably two or more from the viewpoint that the effect of improving the adhesion between the resin film composed of the radiation-sensitive resin composition and the semiconductor layer-containing layers constituting the semiconductor element substrate is high. 2 are especially good.

a compound having two acidic groups, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, 1,2-cyclohexanedicarboxylic acid, benzene-1,2-dicarboxylic acid (also known as phthalic acid), benzene-1,3-dicarboxylic acid (also known as isophthalic acid), benzene-1,4-dicarboxylic acid (also known as terephthalic acid), biphenyl -2,2'-dicarboxylic acid, 2-(carboxymethyl)benzoic acid, 3-(carboxymethyl)benzoic acid, 4-(carboxymethyl)benzoic acid, 2-mercaptobenzoic acid, 4-mercaptobenzene Formic acid, 2-mercapto-6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-didecylbenzene, 1,4- An aromatic compound having two acidic groups of naphthalene dithiol, 1,5-naphthalene dithiol, 2,6-naphthalene dithiol, 2,7-naphthalene dithiol; pyrrole-2,3-dicarboxylate Acid, pyrrole-2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid, imidazole-2,4-dicarboxylic acid, imidazole-2,5-dicarboxylate Acid, imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, pyrazole-3,5-dicarboxylic acid, thiophene-2,3-dicarboxylic acid, thiophene-2,4- Dicarboxylic acid, thiophene-2,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole-2,5-dicarboxylic acid, thiazole-4,5- Dicarboxylate , isothiazole-3,4-dicarboxylic acid, isothiazole-3,5-dicarboxylic acid, 1,2,4-thiadiazole-2,5-dicarboxylic acid, 1,3,4-thiadiazole -2,5-dicarboxylic acid, (5-mercapto-1,2,4-thiadiazol-3-ylthio)acetic acid, (5-mercapto-1,3,4-thiadiazol-2-ylsulfide Acetic acid, pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-di Carboxylic acid, pyridine-3,5-dicarboxylic acid, hydrazine -3,4-dicarboxylic acid, hydrazine -3,5-dicarboxylic acid, hydrazine -3,6-dicarboxylic acid, hydrazine -4,5-dicarboxylic acid, pyrimidine-2,4-dicarboxylic acid, pyrimidine-2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyridyl -2,3-dicarboxylic acid, pyridyl -2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, three A heterocyclic compound having 2 acidic groups of a 2,4-dicarboxylic acid is preferred.

The coupling agent or its derivative has an effect of improving the adhesion between the resin film composed of the radiation sensitive resin composition and the respective layers of the semiconductor layer including the semiconductor element substrate. As the coupling agent or a derivative thereof, a compound having one atom selected from the group consisting of a ruthenium atom, a titanium atom, an aluminum atom, and a zirconium atom and having a hydrocarbonoxy group or a hydroxyl group bonded to the atom can be used.

a coupling agent or a derivative thereof, for example, a tetraalkoxy decane such as tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane or tetra-n-butoxy decane; Methyl trimethoxy decane, methyl triethoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, n-propyl trimethoxy decane, n-propyl triethoxy decane, isopropyl Trimethoxydecane, isopropyltriethoxydecane, n-butyltrimethoxydecane, n-butyltriethoxydecane, n-pentyltrimethoxydecane, n-hexyltrimethoxydecane, n-heptyltrimethyl Oxydecane, n-octyltrimethoxydecane, n-decyltrimethoxydecane, p-styryltrimethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane,cyclohexyltrimethoxydecane , cyclohexyltrimethoxydecane, cyclohexyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, 3-chloropropyltrimethoxydecane, 3-chloropropyltriethoxy Decane, 3,3,3-trifluoropropyltrimethoxydecane, 3,3,3-trifluoropropyltriethoxydecane, 3-amine Propyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-phenyl-3-amine Propyltrimethoxydecane, 2-hydroxyethyltrimethoxydecane, 2-hydroxyethyltriethoxydecane, 2-hydroxypropyltrimethoxydecane, 2-hydroxypropyltriethoxydecane, 3 -hydroxypropyltrimethoxydecane, 3-hydroxypropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-isocyanatepropyltrimethoxy Decane, 3-isocyanatepropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 2-(3,4- Epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 3-(meth)acrylic acid oxypropyltrimethoxydecane, 3-( Methyl) oxypropyl triethoxy decane, 3-ureidopropyl trimethoxy decane, 3-ureidopropyl triethoxy decane, 3-ethyl (trimethoxy decyl propyloxy) Propylene oxide, 3-ethyl(triethoxydecylpropoxymethyl) propylene oxide 3-triethoxydecyl-N-(1,3-dimethyl-butylidene) propylamine, bis(triethoxymethylpropyl)tetrasulfide, etc., alkoxy decane, dimethyldi Methoxy decane, dimethyl diethoxy decane, diethyl dimethoxy decane, diethyl diethoxy decane, di-n-propyl dimethoxy decane, di-n-propyl diethoxy Decane, diisopropyldimethoxydecane, diisopropyldiethoxydecane, di-n-butyldimethoxydecane, di-n-pentyldimethoxydecane, di-n-pentyldiethoxy Decane, di-n-hexyldimethoxydecane, di-n-hexyldiethoxydecane, di-n-heptyldimethoxydecane, di-n-heptyldiethoxydecane, di-n-octyldimethoxydecane, Di-n-octyldiethoxydecane, di-n-cyclohexyldimethoxydecane, di-n-cyclohexyldiethoxydecane, diphenyldimethoxydecane, diphenyldiethoxydecane, 3- Glycidoxypropylmethyldiethoxydecane, 3-methacryloxypropylmethyldimethoxydecane, 3-acryloxypropylmethyldimethoxydecane, 3-methyl Acrylic oxypropylmethyldiethoxy a dialkoxy decane such as decane, 3-acryloxypropylmethyldiethoxydecane or N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane. , Methyltriethyl decyl oxane, dimethyldiethyl decyl oxane, trade name X-12-414, KBP-44 (manufactured by Shin-Etsu Chemical Co., Ltd.), 217 FLAKE, 220 FLAKE, 233 FLAKE , z6018 (made by Toray Dow Cornings Co., Ltd.) and other compounds containing a halogen atom; (tetra-isopropoxy peptide, titanium tetra-n-butoxide, titanium (2-ethylhexyloxy), isopropoxy Titanyl methoxide, titanium di-isopropoxy bis(acetic acetone), propane dioxy titanium bis(ethyl ethinyl acetate), tri-n-butoxy titanium monostearate, two Titanium isopropoxide, stearyl stearate, titanium stearate, titanium diisopropoxy diisostearate, titanium (2-n-butoxycarbonylbenzhydryloxy) tributoxide, di-n-butyl Titanium oxybis(triethanolamine), a compound containing a titanium atom such as a PLENACT series (manufactured by Ajinomoto Fine Techno Co., Ltd.), or an aluminum atom such as (ethyl acetyl alkoxydiisopropylate) Compound; (tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetraethyl fluorenyl) Zirconium ketone, zirconium tributoxyacetate, zirconium butoxide, bis(ethylacetamidoacetate), zirconium dibutoxy bis(ethyl acetamidine acetate), A compound containing a zirconium atom such as zirconium tetraethylacetate or zirconium tributoxystearate.

Specific examples of the sensitizer, for example, 2H-pyrido-(3,2-b)-1,4- -3(4H)-ketones, 10H-pyrido-(3,2-b)-1,4-benzo Classes, urazoles, carbendazim, barbituric acid, glycine anhydride, 1-hydroxybenzotriazole, alloxan, maleimide, and the like.

The latent acid generator is used to improve the heat resistance and chemical resistance of the radiation sensitive resin composition used in the present invention. Specific examples thereof include a cationic polymerization catalyst which generates an acid by heating, for example, a phosphonium salt, a benzothiazole salt, an ammonium salt, a phosphonium salt or the like. Among these, an onium salt and a benzothiazole salt are preferred.

As the antioxidant, a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a lactone-based antioxidant, or the like which is used in a usual polymer can be used. For example, phenols, for example: 2,6-di-tert-butyl-4-methylphenol, p-methoxyphenol, styrenated phenol, n-octadecyl-3-(3',5'-di Tert-butyl-4'-hydroxyphenyl)propionate, 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2-tert-butyl-6- (3'-Tertibutyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 4,4'-butylidene-bis-(3-methyl-6- Tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), pentaerythritol bismuth [3-(3,5-di-t-butyl-4-hydroxybenzene) Base) propionate], alkylated bisphenol, and the like. Phosphorus-based antioxidants such as triphenyl phosphite, decyl phenyl phosphite, and sulfur such as dilauryl thiodipropionate.

The light stabilizer may be, for example, a UV absorber such as a diphenyl ketone, a salicylate, a benzotriazole, a cyanoacrylate or a metal salt, or a hindered amine (HALS). The free radicals produced can be used. Among these, HALS is a compound having a piperidine structure, and it is preferable because it has less coloring and a good stability to a radiation sensitive resin composition. Specific compounds, for example: bis(2,2,6,6-tetramethyl 4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidinyl/ Tridecyl 1,2,3,4-butane tetracarboxylate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, and the like.

The method for preparing the radiation sensitive resin composition used in the present invention is not particularly limited, and each component constituting the radiation sensitive resin composition may be mixed by a known method.

The method of mixing is not particularly limited, and it is preferred to mix a solution or a dispersion obtained by dissolving or dispersing each component constituting the radiation sensitive resin composition in a solvent. Thereby, the radiation sensitive resin composition can be obtained in the form of a solution or a dispersion.

The method of dissolving or dispersing each component constituting the radiation sensitive resin composition in a solvent can be carried out in accordance with a usual method. Specifically, it can be carried out by stirring using a stirrer and a magnetic stirrer, a high-speed homogenizer, a disperser, a planetary mixer, a twin-shaft mixer, a ball mill, a three-roller, or the like. Further, after dissolving or dispersing each component in a solvent, it can be filtered, for example, using a filter having a pore diameter of about 0.5 μm.

The solid content concentration of the radiation sensitive resin composition used in the present invention is usually from 1 to 70% by weight, preferably from 5 to 60% by weight, more preferably from 10 to 50% by weight. When the solid content concentration is in this range, the solubility stability, the coatability, the film thickness uniformity of the formed resin film, the flatness, and the like can be obtained in a highly balanced manner.

(semiconductor element substrate)

Next, the semiconductor element substrate of the present invention will be described. The semiconductor element substrate of the present invention has a resin film composed of the radiation sensitive resin composition, and the resin film is formed in contact with a surface of a semiconductor element mounted on a semiconductor element substrate or a semiconductor layer included in the semiconductor element.

The semiconductor element substrate of the present invention has a configuration in which a semiconductor element is mounted on a substrate, and is not particularly limited. For example, an active matrix substrate, an organic electroluminescence device substrate, an integrated circuit device substrate, and a solid-state imaging device substrate are used. The active matrix substrate and the organic electroluminescence device substrate are preferred from the viewpoint that the effect of improving the characteristics of the resin film composed of the radiation sensitive resin composition is particularly remarkable.

The active matrix substrate which is an example of the semiconductor element substrate of the present invention is not particularly limited. For example, a switching element such as a thin film transistor (TFT) may be arranged in a matrix on the substrate, and a gate signal for driving the switching element may be supplied. The gate signal line, and the configuration in which the source signal lines for supplying the display signals to the switching elements are arranged to cross each other. Further, the thin film transistor as an example of the switching element has, for example, a structure including a gate electrode, a gate insulating layer, a semiconductor layer, a source electrode, and a germanium electrode on the substrate.

In addition, the organic electroluminescent element substrate which is an example of the semiconductor element substrate of the present invention has, for example, an anode, a hole injection transport layer, an organic light-emitting layer as a semiconductor layer, an electron injection layer, and a cathode. The illuminant portion and the configuration of the pixel separation film for separating the illuminant portion.

In addition, the resin film constituting the semiconductor element substrate of the present invention is formed of the above-described radiation sensitive resin composition and is in contact with the surface of the semiconductor element mounted on the semiconductor element substrate or the semiconductor layer included in the semiconductor element. The resin film is not particularly limited. However, when the semiconductor element substrate of the present invention is an active matrix substrate or an organic electroluminescence device substrate, the following configuration may be employed. That is, for example, when the semiconductor element substrate of the present invention is an active matrix substrate, the resin film composed of the radiation sensitive resin composition may be a protective film formed on the surface of the active matrix substrate or a thin film constituting the active matrix substrate. A gate insulating film formed by contacting a semiconductor layer of a crystal (for example, an amorphous germanium layer). Alternatively, when the semiconductor element substrate of the present invention is an organic electroluminescence element substrate, it may be a sealing film formed on the surface of the organic electroluminescent element substrate or used to illuminate the illuminant portion contained in the organic electroluminescent element (usually A pixel separation membrane is formed by an anode, a hole injection transport layer, an organic light-emitting layer as a semiconductor layer, an electron injection layer, and a cathode.

In the semiconductor element substrate of the present invention, the method of forming the resin film is not particularly limited, and for example, a coating method or a film lamination method can be used.

The coating method is, for example, a method in which a radiation sensitive resin composition is applied, followed by heating and drying, and removing the solvent. Examples of the method of coating the radiation sensitive resin composition include a spray coating method, a spin coating method, a roll coating method, a die coating method, a knife coating method, a spin coating method, a bar coating method, and a screen printing method. method. The heating and drying conditions vary depending on the type or blending ratio of each component, and are usually from 30 ° C to 150 ° C, preferably from 60 ° C to 120 ° C, usually from 0.5 to 90 minutes, preferably from 1 to 60 minutes, more preferably. It is 1~30 minutes.

In the film lamination method, the radiation-sensitive resin composition is applied onto a substrate for forming a B-stage film such as a resin film or a metal film, and then the solvent is removed by heating and drying to obtain a B-stage film. Next, the B-stage film is removed. The method of lamination. The heating and drying conditions can be appropriately selected depending on the type or blending ratio of each component, but the heating temperature is usually 30 to 150 ° C, and the heating time is usually 0.5 to 90 minutes. The film laminate can be carried out using a press machine such as a press laminator, a press, a vacuum laminator, a vacuum press, a roll laminator, or the like.

The thickness of the resin film is not particularly limited, and may be appropriately set as the protective film. When the resin film is a protective film for an active matrix substrate or a sealing film for an organic electroluminescent device substrate, the thickness of the resin film is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, and more preferably 0.5 to 30 μm.

Moreover, since the radiation sensitive resin composition used in the present invention contains the crosslinking agent (B), the crosslinking reaction can be carried out on the resin film formed by the above coating method or film lamination method. Such crosslinking is appropriately selected depending on the type of the crosslinking agent (B), and is usually carried out by heating. The heating method can be carried out, for example, using a hot plate, an oven, or the like. The heating temperature is usually 180 to 250 ° C, and the heating time is appropriately selected depending on the area or thickness of the resin film and the use equipment. For example, when using a hot plate, it is usually 5 to 60 minutes, and when using an oven, it is usually 30 to 90 minutes. range. Heating can be carried out in a passive gas atmosphere. The passive gas may be any one that does not contain oxygen and does not oxidize the resin film, for example, nitrogen, argon, helium, neon, xenon, xenon, and the like. Among these, nitrogen and argon are preferred, and nitrogen is preferred. In particular, a passive gas having an oxygen content of 0.1% by volume or less, preferably 0.01% by volume or less, particularly preferably nitrogen. These passive gases may be used alone or in combination of two or more.

In addition, when the resin film for the active matrix substrate, the protective film for the active matrix substrate, or the sealing film for the organic electroluminescent device substrate, which is formed of the above-described radiation-sensitive resin composition, is formed in a predetermined pattern, it may be patterned. A method of patterning a resin film, for example, a method in which a resin film before patterning is irradiated with active radiation to form a latent image pattern, and a resin film having a latent image pattern is brought into contact with a developer to thereby cause a pattern to appear.

The actinic radiation is not particularly limited as long as it activates the radiation sensitive compound (C) contained in the radiation sensitive resin composition and changes the alkali solubility of the radiation sensitive resin composition containing the radiation sensitive compound (C). Specifically, ultraviolet rays, a single-wavelength ultraviolet light such as a g-ray or an i-line, a KrF excimer laser light, an ArF excimer laser light or the like, a particle beam such as an electron beam, or the like can be used. The method of selectively irradiating these active radiation lines in a pattern and forming a latent image pattern can be performed according to a conventional method, for example, using a reduced projection exposure apparatus, ultraviolet light, g-line or i-line, KrF excimer laser light, ArF excimer. A method in which light such as laser light is irradiated through a desired mask pattern, or a method in which a particle beam such as an electron beam is used for drawing. When light is used as the active radiation, it may be a single wavelength light or a mixed wavelength light. The irradiation conditions can be appropriately selected depending on the active radiation to be used. For example, when light having a wavelength of 200 to 450 nm is used, the irradiation amount is usually in the range of 10 to 1,000 mJ/cm ² , preferably 50 to 500 mJ/cm ² , depending on the irradiation time and the illuminance. . After the active radiation is irradiated in this manner, the protective film is heat-treated at a temperature of about 60 to 130 ° C for about 1 to 2 minutes as needed.

Next, the latent image pattern formed on the resin film before patterning is developed to cause an image to appear. An aqueous solution of a basic compound can usually be used as the developer. As the basic compound, for example, an alkali metal salt, an amine or an ammonium salt can be used. The basic compound may be an inorganic compound or an organic compound. Specific examples of such compounds include, for example, alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, and sodium metasilicate; aqueous ammonia; first-grade amines such as ethylamine and n-propylamine; diethylamine; a second-order amine such as di-n-propylamine; a tertiary amine such as triethylamine or methyldiethylamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, choline a fourth-order ammonium salt; an alcohol amine such as dimethylethanolamine or triethanolamine; pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diaza a cyclic amine such as bicyclo[4.3.0]non-5-ene or N-methylpyrrolidone; These basic compounds may be used alone or in combination of two or more.

As the aqueous medium of the alkaline aqueous solution, water; a water-soluble organic solvent such as methanol or ethanol can be used. An alkaline aqueous solution may be added with a surfactant or the like in an appropriate amount.

A method of bringing a resin film having a latent image into contact with a developing solution, for example, a method such as puddle, spray coating, or immersion. The development is usually in the range of 0 to 100 ° C, preferably 5 to 55 ° C, more preferably 10 to 30 ° C, and is usually suitably selected in the range of 30 to 180 seconds.

The resin film of the pattern thus formed may be rinsed with a rinse liquid in order to remove the development residue as needed. After the rinsing treatment, the remaining rinsing liquid is removed by using compressed air or compressed nitrogen.

Further, in order to inactivate the radiation sensitive compound (C), the semiconductor element substrate may be entirely irradiated with active radiation as needed. The irradiation of the actinic radiation can be utilized in the method of forming the above-described latent image pattern. It is also possible to heat the resin film at the same time as or after the irradiation. The heating method is, for example, a method of heating a semiconductor element substrate in a heating plate or an oven. The temperature is usually in the range of 100 to 300 ° C, preferably 120 to 200 ° C.

In the present invention, after the resin film is patterned, a crosslinking reaction can be carried out. Crosslinking can be carried out in accordance with the above method.

The semiconductor element substrate according to the present invention is a composition for forming a resin film which is used in contact with a surface of a semiconductor element mounted on a semiconductor element substrate or a semiconductor layer included in a semiconductor element, and includes a composition containing the above formula (1). The radiation-sensitive resin composition of the polymer (A), the crosslinking agent (B), and the radiation-sensitive compound (C) which are the unit (a1) of the monomer, can make the semiconductor element substrate reliable. The semiconductor element substrate is excellent in various electrical characteristics, such as high and low dielectric constant characteristics, low leakage current characteristics, and high dielectric breakdown voltage characteristics, and the resin film contained in the semiconductor element substrate can be highly transparent and developed. Excellent in formability. Therefore, according to the present invention, the semiconductor element substrate can be made highly reliable and excellent in various electrical characteristics, and the resin film contained in the semiconductor element substrate can be patterned with high precision, thereby providing a high-performance semiconductor element substrate. .

In particular, when the semiconductor element substrate of the present invention is an active matrix substrate, it is possible to increase the voltage with respect to the gate electrode, and the current between the source electrode and the drain electrode rises linearly, and even in a high-temperature and high-humidity environment. Since the leakage current characteristics or the threshold voltage do not change for a long period of time, the active matrix substrate can be long-lived and low in power consumption, and is highly contrasted.

Example

The present invention will be more specifically described below by way of examples and comparative examples. Parts and % in each case, unless otherwise specified, indicate a weight basis.

Further, the definition and evaluation methods of the respective characteristics are as follows.

<Residue at the time of development, unevenness of the surface of the unexposed portion>

The radiation sensitive resin composition was spin-coated on a tantalum wafer, and then prebaked at 100 ° C for 2 minutes using a hot plate to form a 2.5 μm thick resin film. Next, this resin film was irradiated with ultraviolet rays having a light intensity of 5 mW/cm ² at 365 nm for 40 seconds in the air through a mask of a hole pattern of 5 μm × 5 μm. Then, using a 0.4% by weight aqueous solution of tetramethylammonium hydroxide, the development treatment was carried out at 23 ° C for 60 seconds, and then rinsed with ultrapure water for 30 minutes to form a pattern of contact holes.

Then, with respect to the resin film having the pattern of the contact holes obtained in this manner, a scanning electron microscope (SEM) was used to evaluate whether or not the residue in the contact hole was dissolved and whether the surface of the unexposed portion was not flat. When the dissolution residue is not observed and the surface of the unexposed portion is not observed to be uneven, it is preferable because the pattern formation property of development is excellent.

<Pore state at the time of calcination, film hardness at the time of calcination>

The resin film having the pattern of the contact holes obtained in the same manner as above was irradiated with ultraviolet rays having a light intensity of 5 mW/cm ² at 365 nm for 90 seconds in air, followed by post-baking at 230 ° C for 1 hour using an oven. Then, with respect to the obtained resin film after post-baking, the contact hole was observed with an optical microscope, and the state of the hole at the time of baking was evaluated according to the following criteria.

○: No burying of the contact hole and deformation of the shape of the contact hole were observed.

×: The contact hole is buried, or the shape of the contact hole is deformed.

Moreover, the pencil hardness at the time of baking was evaluated by measuring the pencil hardness with respect to the obtained resin film after post-baking, respectively. It is preferred that the film has a high hardness at the time of calcination.

<specific dielectric ratio>

After the radiation-sensitive resin composition was spin-coated on the tantalum wafer, it was prebaked at 100 ° C for 2 minutes using a hot plate to form a 0.12 μm thick resin film. Next, the resin film is entirely irradiated with light using a high-pressure mercury lamp to decompose the undecomposed radiation sensitive compound remaining in the resin film. Subsequently, the film was heated at 230 ° C for 1 hour in a nitrogen atmosphere to obtain a test sample composed of a tantalum wafer on which a resin film was formed.

Further, using the obtained test sample, the specific dielectric constant of the resin film was measured at 10 kHz (room temperature) in accordance with JIS C6481. It is better than the lower dielectric constant.

<Insulation breakdown voltage>

A test sample was prepared in the same manner as the above-described evaluation of the specific dielectric constant, and the obtained test sample was used to measure the dielectric breakdown voltage of the resin film. Further, in the present embodiment, a DC voltage of 50 V/min was applied to the resin film, and a voltage at which the leak current became 1 × 10 ^-6 mA/cm ³ or more was used as the dielectric breakdown voltage. It is preferable that the dielectric breakdown voltage is high.

<Transparency>

In the same manner as the above evaluation of the specific dielectric constant, a test sample was prepared, and a spectrophotometer (manufactured by JASCO Corporation, UV-Vis spectrophotometer V-560) was used for the obtained test sample. The transmittance of the resin film was evaluated by measuring the transmittance at a wavelength of 400 nm.

<leakage current, threshold current>

A voltage of 20 V was applied between the source electrode and the 汲 electrode of the active matrix substrate, and the voltage applied to the gate electrode was changed from -20 to +30 V, and was measured using a manual probe and a semiconductor parameter analyzer (manufactured by Agilent, 4156C). A current flowing between the source electrode and the ruthenium electrode, thereby measuring the leakage current and the threshold voltage. Further, the measurement system was carried out for the active matrix substrate in the initial state (before being kept in a high temperature and high humidity environment) and on the active matrix substrate after being kept at 50 ° C and 80 RH % in a high temperature and high humidity environment for 100 hours.

<<Synthesis example 1>>

Will be composed of N-(2-ethylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine (NEHI) 40 mol%, and 8-hydroxycarbonyltetracyclo [4.4. 0.1 ^2,5 .1 ^7,10 ] ^Dodec -3-ene (TCDC) 60 mole % of monomer mixture 100 parts, 1,5-hexadiene 2 parts, (1,3- two Imidazolin-2-yl)(tricyclohexylphosphine)benzylidenephosphonium chloride (synthesized by Org. Lett., Vol. 1, p. 953, 1999) 0.02 parts, and diethylene glycol 400 parts of methyl ethyl ether was placed in a pressure-resistant reactor made of glass substituted with nitrogen, and reacted at 80 ° C for 4 hours while stirring to obtain a polymerization reaction liquid.

Then, the obtained polymerization reaction liquid was placed in a autoclave, and hydrogenated at 150 ° C under a hydrogen pressure of 4 MPa for 5 hours to obtain a polymer (I). The obtained polymer (I) had a polymerization conversion ratio of 99.7%, a weight average molecular weight of 7,150, a number average molecular weight of 4,690, a molecular weight distribution of 1.52, and a hydrogenation ratio of 99.7%.

<<Composite example 2>>

The mixing ratio of N-(2-ethylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarlimine (NEHI) was changed to 50 mol%, 8-hydroxycarbonyltetra Polymer (II) was obtained in the same manner as in Synthesis Example 1 except that the mixing ratio of the ring [4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene (TCDC) was changed to 50 mol%. . The obtained polymer (II) had a polymerization conversion ratio of 99.5%, a weight average molecular weight of 5,670, a number average molecular weight of 3,520, a molecular weight distribution of 1.61, and a hydrogenation ratio of 99.9%.

<<Example 1>> <Preparation of a radiation sensitive resin composition>

100 parts of the polymer (I) obtained in Synthesis Example 1, 550 parts of diethylene glycol ethyl ether (EDM) as a solvent, and N, N, N', N', N as a crosslinking agent (B) , N"-(hexaalkyloxyalkyl) melamine-based crosslinking agent (trade name "Cymel 370", manufactured by Cytech Industries Co., Ltd.) 15 parts, also as a crosslinking agent (B) 2,2-bis (hydroxyl group) 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 1-butanol (trade name "EHPE 3150", manufactured by Daicel Chemical Industry Co., Ltd., having a cyclohexane skeleton 10 parts of a 15-functional alicyclic epoxy resin having a terminal epoxy group, 1, 1, ginseng (2,5-dimethyl-4-hydroxyphenyl) as a radiation sensitive compound (C) 30 parts of a condensate of -3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.9 mol), and (3-epoxy) as a coupling agent 40 parts of propoxypropyl)trimethoxydecane (trade name "SH6040", manufactured by Toray Dow Cornings Co., Ltd.) was mixed, and after dissolving, it was filtered through a membrane made of polytetrafluoroethylene having a pore size of 0.45 μm to prepare a radiation sensitive resin. Composition.

<Production of Active Matrix Substrate>

A chromium film was formed on a glass substrate (trade name "Corning 1737", manufactured by Corning Co., Ltd.) using a sputtering apparatus at a film thickness of 200 nm, and patterned by photolithography to form a gate electrode, a gate signal line, and a gate terminal portion. Then, the gate electrode and the gate electrode are covered with a CVD device, and the germanium nitride film serving as the gate insulating film has a thickness of 450 nm, and the a-Si layer (amorphous germanium layer) which becomes a semiconductor layer has a thickness of 250 nm and becomes ohmic. The n+Si layer of the contact layer is continuously formed with a thickness of 50 nm, and the n+Si layer and the a-Si layer are patterned in an island shape. Further, a chromium film is formed on the gate insulating film and the n+Si layer by a sputtering apparatus at a film thickness of 200 nm, and a source electrode, a source signal line, a germanium electrode, and a data terminal portion are formed by photolithography, and the source is An unnecessary n+Si layer between the electrode and the ruthenium electrode is removed to form a back channel, and an array substrate in which a plurality of thin film transistors are formed on the glass substrate is obtained.

Further, the obtained radiation sensitive resin composition was spin-coated on the obtained array substrate, and then baked at 90 ° C for 2 minutes using a hot plate to form a resin film having a film thickness of 1.2 μm. Next, this resin film was irradiated with ultraviolet rays having a light intensity of 5 mW/cm ² at 365 nm for 40 seconds in a mask through a mask of a hole pattern of 10 μm × 10 μm. Next, using a 0.4% by weight aqueous solution of tetramethylammonium hydroxide, the development treatment was carried out at 25 ° C for 90 seconds, and then rinsed with ultrapure water for 30 seconds to form a pattern of contact holes, and then heated at 230 ° C for 15 minutes on a hot plate. Thereafter, post-baking was performed to obtain an array substrate on which a protective film (resin film) was formed.

Further, the array substrate on which the protective film (resin film) was formed was transferred to a vacuum chamber, and a mixed gas of argon gas and oxygen gas (volume ratio: 100:4) was used as a sputtering gas, and the pressure was set to 0.3 Pa, and the DC output was set to 400 W, DC sputtering was performed by a mask, and an In-Sn-O-based amorphous transparent conductive layer (pixel electrode) having a film thickness of 200 nm was formed to be connected to a tantalum electrode to obtain an active matrix substrate.

Moreover, the evaluation of the residue, the unevenness of the surface of the unexposed part, the pore state at the time of firing, the film hardness at the time of firing, the specific dielectric constant, the dielectric breakdown voltage, and the transparency at the time of development using the radiation-sensitive resin composition obtained by the above-mentioned radiation-sensitive resin composition And using the active matrix substrate, each evaluation of leakage current and threshold current was performed. The results are shown in Table 1.

<<Example 2>>

100 parts of the polymer (I) obtained in Synthesis Example 1, 550 parts of diethylene glycol ethyl ether (EDM) as a solvent, and N, N, N', N', N' as a crosslinking agent (B) ', N''-(hexa-alkoxyalkyl) melamine-based crosslinking agent (trade name "Cymel 232", manufactured by Cytech Industries) 30 parts, also as the crosslinking agent (B) epoxidized butane tetracarboxylic acid Acid oxime (3-cyclohexenylmethyl) modified ε-caprolactone (trade name "EPOLEAD GT 401", manufactured by Daicel Chemical Industry Co., Ltd., aliphatic cyclic tetrafunctional epoxy resin) 10 parts, as radiation 1,1,3-glycol (2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane (1 mol) of compound (C) and 1,2-naphthoquinonediazide-5 - 30 parts of a condensate of sulfonate chloride (1.9 mol), and 2,4,6-tridecyl-s-three as an acidic compound (Product name "Zisnet-F", manufactured by Sankyo Chemical Co., Ltd.) 5 parts were mixed and dissolved, and then filtered through a polytetrafluoroethylene filter having a pore size of 0.45 μm to prepare a radiation sensitive resin composition. Moreover, the active matrix substrate was obtained in the same manner as in Example 1 except that the obtained radiation sensitive resin composition was used.

Moreover, each evaluation was performed in the same manner as in Example 1 using the radiation sensitive resin composition obtained above and the active matrix substrate. The results are shown in Table 1.

<<Example 3>>

100 parts of the polymer (II) obtained in Synthesis Example 2, 550 parts of diethylene glycol ethyl ether (EDM) as a solvent, and N, N, N', N', N as a crosslinking agent (B) 40 parts of N"-(hexaalkyloxyalkyl) melamine-based crosslinking agent (trade name "Cymel 370", manufactured by Cytech Industries), and ruthenium epoxide tetracarboxylate as cross-linking agent (B) (3-cyclohexenylmethyl) modified ε-caprolactone (trade name "EPOLEAD GT 401", manufactured by Daicel Chemical Industry Co., Ltd., aliphatic cyclic tetrafunctional epoxy resin) 10 parts, as a radiation sensitive compound ( C) 1,1,3-glycol (2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonate Acid chloride (1.9 mol) condensate 30 parts, and pyridyl as an acidic compound 1 part of 2,3-dicarboxylic acid, and 10 parts of (3-glycidoxypropyl)trimethoxydecane (trade name "SH6040", manufactured by Toray Dow Cornings Co., Ltd.) as a coupling agent After dissolving, it was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 μm to prepare a radiation sensitive resin composition. Moreover, the active matrix substrate was obtained in the same manner as in Example 1 except that the obtained radiation sensitive resin composition was used.

Moreover, each evaluation was performed in the same manner as in Example 1 using the radiation sensitive resin composition obtained above and the active matrix substrate. The results are shown in Table 1.

<<Comparative example 1>>

100 parts of the polymer (I) obtained in Synthesis Example 1 was changed to 100 parts using a cycloolefin polymer (trade name "ARTON (F5023)", manufactured by JSR), and 550 parts of ethylene glycol diethyl ether (EDM) was changed. A radiation sensitive resin composition was prepared in the same manner as in Example 1 except that 900 parts of mesitylene was used. Moreover, the active matrix substrate was obtained in the same manner as in Example 1 except that the obtained radiation sensitive resin composition was used.

Moreover, each evaluation was performed in the same manner as in Example 1 using the radiation sensitive resin composition obtained above and the active matrix substrate. The results are shown in Table 1.

<<Comparative Example 2>>

In Comparative Example 2, a radiation sensitive resin composition (trade name "OPTOMER (PC403)", manufactured by JSR Corporation) containing an acrylic resin was prepared as a radiation sensitive resin composition. Moreover, the active matrix substrate was obtained in the same manner as in Example 1 using the prepared radiation sensitive resin component.

Moreover, each evaluation was performed in the same manner as in Example 1 using the above-mentioned prepared radiation-sensitive resin composition containing an acrylic resin and the active matrix substrate obtained above. The results are shown in Table 1.

<<Comparative Example 3>>

In Comparative Example 3, a radiation sensitive resin composition (trade name "PHOTONEECE PW-2100", manufactured by Toray Co., Ltd.) containing a polyimide resin was prepared as a radiation sensitive resin composition. Moreover, the active matrix substrate was obtained in the same manner as in Example 1 using the prepared radiation sensitive resin composition.

Moreover, each of the evaluations was carried out in the same manner as in Example 1 using the polyimide-containing radiation sensitive resin composition prepared above and the active matrix substrate obtained above. The results are shown in Table 1.

As shown in Table 1, the resin film obtained by using the radiation sensitive resin composition of the present invention as a result of Examples 1 to 3, the residue at the time of development, the unevenness of the surface of the unexposed portion, the pore state at the time of firing, and the calcination When the film hardness was good, it was confirmed that it was excellent in pattern formability at the time of development, and it was possible to pattern with high precision. In addition, as a result of the results of the first to third embodiments, the resin film obtained by using the radiation sensitive resin composition of the present invention has a lower dielectric constant, a higher dielectric breakdown voltage, and is excellent in transparency. The semiconductor element substrate can be excellent in various characteristics. Further, the active matrix substrates of the first to third embodiments have a small leakage current and do not change in leakage current characteristics or threshold voltage even in a high-temperature and high-humidity environment, and have high reliability.

From these results, the resin film obtained by using the predetermined radiation sensitive resin composition of the present invention can be suitably used as a resin element substrate, in particular, a resin film of an active matrix substrate.

On the other hand, when the resin contained in the radiation sensitive resin composition is a cycloolefin polymer containing no unit of the unit (a1) of the monomer of the present invention as a result of the comparative example 1, residue occurs during development, and calcination occurs. The state of the hole is also poor, and the pattern formation property at the time of development is inferior.

Further, as a result of Comparative Examples 2 and 3, when an acrylic resin or a polyimide resin was used as the resin contained in the radiation sensitive resin composition, the dielectric breakdown voltage was low and the leakage current was also large. Further, in Comparative Examples 2 and 3, since the leak current was too large, the leakage current and the threshold voltage after the high-temperature and high-humidity conditions were maintained could not be measured.

<<Example 4>>

In Example 4, an organic electroluminescence device substrate having a sealing film composed of the radiation sensitive resin composition prepared in Example 1 was produced in the following manner.

That is, first, a reverse-push type having a film thickness of 3.5 μm is provided on a glass plate having a patterned chrome electrode layer 12 having a size of 25 mm × 75 mm × 1.1 mm on the surface thereof with a light-shielding film having a thickness of 1.0 μm. A substrate for an organic electroluminescence device having a structure of a resin barrier layer. Further, the substrate was fixed to a substrate holder of a commercially available vapor deposition device [manufactured by Nippon Vacuum Technology Co., Ltd.], and N,N'-bis(3-methylphenyl)-N was placed in a molybdenum electric resistance heating boat. , N'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (hereinafter abbreviated as TPD) 200mg, and then placed in another 4,4'-double by a molybdenum resistance heating boat 200 mg of (2,2'-diphenylvinyl)biphenyl (hereinafter abbreviated as DPVBi), and thereafter, the vacuum chamber was depressurized to 1 × 10 ^-4 Pa.

Next, the boat containing the TPD was heated to 215 to 220 ° C, and the TPD was vapor-deposited at an evaporation rate of 0.1 to 0.3 nm/sec to form a hole injection-transporting layer having a film thickness of 60 nm. The substrate temperature at this time was room temperature. These were not taken out from the vacuum tank, the boat in which the DPVBi was placed was heated to 240 ° C, and the DPVBi was vapor-deposited on the above-described hole injection transport layer at a deposition rate of 0.1 to 0.3 nm/sec to form a light-emitting layer having a film thickness of 40 nm. The substrate temperature at this time is also room temperature. The illuminating layer was taken out from the vacuum chamber, and a stainless steel mask was placed on the luminescent layer, and then fixed on the substrate holder, and then placed in a molybdenum boat into a ginseng (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq ₃ ) 200 mg. In another molybdenum boat, 1 g of magnesium tape was placed, and then 500 mg of silver wire was placed in a tungsten basket, and the boats were installed in a vacuum tank. Next, after depressurizing the vacuum chamber to 1 × 10 ^-4 Pa, the boat containing Alq ₃ is heated to 230 ° C, and Alq ₃ is vapor-deposited onto the above-mentioned light-emitting layer at a vapor deposition rate of 0.01 to 0.03 nm/sec. An electron injecting layer having a film thickness of 20 nm. Further, silver was vapor-deposited into the electron injecting layer at a deposition rate of 0.01 nm/sec, and magnesium was vapor-deposited at the deposition rate of 0.14 nm/sec into the electron injecting layer to form a mixed metal of magnesium and silver. Electrons having a film thickness of 10 nm were implanted into the metal layer. Finally, it was transferred to another vacuum chamber, and an In-Zn-O-based amorphous transparent conductive layer having a thickness of 200 nm was formed on the electron injecting metal layer by DC sputtering through the same mask. Further, in the DC sputtering condition, a mixed gas of argon gas and oxygen gas (volume ratio: 1000:5) was used as a sputtering gas, and the pressure was 0.3 Pa, and the DC output was 40 W. In this manner, a transparent electrode layer (cathode) composed of an electron injecting metal layer and an amorphous transparent conductive layer is formed, whereby the illuminant portion of the organic electroluminescent element is formed.

Further, the radiation-sensitive resin composition prepared in Example 1 was spin-coated on the surface of the substrate on which the illuminant portion was formed to have an illuminant portion, and the thickness was 3.5 μm, and then a hot plate was used to pre-treat at 90 ° C. Bake for 2 minutes to form a resin film. Next, the resin film was subjected to development treatment at 25 ° C for 90 seconds using a 0.4% by weight aqueous solution of tetramethylammonium hydroxide, and then rinsed with ultrapure water for 30 minutes, and heated at 230 ° C for 15 minutes on a hot plate. This was post-baked to prepare an organic electroluminescence device substrate on which a sealing film (resin film) was formed.

Next, the obtained organic electroluminescence device substrate was calcined at 220 ° C for 30 minutes using GC-MS ("GC6890N/MSD5973 (product name)" manufactured by Agilent Co., Ltd.), and the amount of degassing was measured. The decane-converted value was used as the amount of degassing. As a result, the weight of the sealing film (resin film) contained in the sample was measured to be 1 g, and the amount of degassing was 98 mg, which was a small amount, which was a good result.

Further, from the results of the above Examples 1 to 3, the resin film obtained by using the radiation sensitive resin composition of the present invention, the residue at the time of development, the unevenness of the surface of the unexposed portion, the state of the pores during firing, the hardness of the film during firing, The specific dielectric constant and the leakage current are both good, and as a result of Example 4, the amount of outgassing when the organic electroluminescent element substrate is formed is also small. Therefore, the radiation sensitive resin composition of the present invention is used. The obtained resin film is also suitably used as a resin film for an organic electroluminescence device.

Claims (10)

A semiconductor element substrate having a polymer (A), a crosslinking agent (B), and a radiation sensitive compound (C) containing a unit (a1) of a monomer represented by the following general formula (1) A resin film composed of a resin composition, wherein the resin film is formed in contact with a surface of a semiconductor element mounted on the semiconductor element substrate or a semiconductor layer included in the semiconductor element; In the above formula (1), R ₁ represents a branched alkyl group having a carbon number of 5 to 16. In the semiconductor element substrate of the first aspect of the invention, in the polymer (A), the content ratio of the unit (a1) of the monomer represented by the general formula (1) is 10 to 90 mol%. The semiconductor element substrate of claim 1 or 2, wherein the polymer (A) further comprises a unit (a2) of a monomer copolymerizable with the monomer represented by the formula (1). The semiconductor element substrate of claim 3, wherein the unit (a2) of the copolymerizable monomer is a unit of a cyclic olefin monomer having a protic polar group. The semiconductor element substrate according to claim 4, wherein the unit of the cyclic olefin monomer having a protic polar group is a unit of a cyclic olefin monomer having a carboxyl group. The semiconductor element substrate of claim 4, wherein the polymer (A) is subjected to ring-opening of the monomer represented by the formula (1) and the cyclic olefin monomer having a protic polar group. Polymerized polymer. The semiconductor device substrate according to claim 6, wherein the polymer (A) is subjected to ring-opening of the monomer represented by the formula (1) and the cyclic olefin monomer having a protic polar group. a hydride of a polymerized polymer. The semiconductor element substrate according to claim 1 or 2, wherein the crosslinking agent (B) is a combination of an amine group-containing compound and an epoxy group-containing compound. The semiconductor element substrate of claim 8, wherein the epoxy group-containing compound is an epoxy group-containing compound having an alicyclic structure. The semiconductor element substrate of claim 1 or 2 is an active matrix substrate or an organic electroluminescent element substrate.