JP6248561B2 - Radiation sensitive resin composition and laminate - Google Patents

Description

  The present invention relates to a radiation-sensitive resin composition and a laminate, and more specifically, a radiation-sensitive resin composition that provides a resin film having excellent exposure sensitivity and excellent reliability in a high-temperature and high-humidity environment, And a laminate having a resin film formed from the radiation-sensitive resin composition.

  Various display elements such as organic EL elements and liquid crystal display elements, integrated circuit elements, solid-state imaging elements, color filters, black matrices, and other electronic parts are provided with protective films, element surfaces and wiring to prevent their deterioration and damage. Various resin films are provided as a planarization film for planarization, an electrical insulation film for maintaining electrical insulation, and the like. In addition, the organic EL element is provided with a resin film as a pixel separation film in order to separate the light-emitting body portion. Further, in an element such as a display element for thin film transistor type liquid crystal or an integrated circuit element, a layered structure A resin film as an interlayer insulating film is provided to insulate between the arranged wirings.

  Conventionally, thermosetting resin materials such as epoxy resins have been widely used as resin materials for forming these resin films. In recent years, with the increase in the density of wiring and devices, the development of new radiation-sensitive resin materials that are capable of fine patterning on these resin materials and have excellent electrical properties such as low dielectric properties is required. ing.

  In order to meet these requirements, for example, Patent Document 1 has an acidic group in a radiation-sensitive resin composition containing an alicyclic olefin resin having an acidic group, an acid generator, a crosslinking agent, and a solvent. A technique using an alicyclic olefin resin having an acidic group content in a specific range is disclosed. However, the protective film obtained using the resin composition described in Patent Document 1 does not necessarily have sufficient reliability in a high-temperature and high-humidity environment. Therefore, improvement in reliability in a high-temperature and high-humidity environment is desired. It was.

International Publication No. 03/056391

  The present invention provides a radiation-sensitive resin composition that provides a resin film having excellent exposure sensitivity and reliability in a high-temperature and high-humidity environment, and a laminate having a resin film formed from the radiation-sensitive resin composition The purpose is to provide a body.

  As a result of diligent research to achieve the above object, the present inventors have found that the cyclic olefin polymer in which the content ratio of the monomer unit having a protic polar group is 40 mol% or more and less than 80 mol% is sensitized. It has been found that the above problems can be solved by a radiation-sensitive resin composition comprising a radiation compound, an ortho ester, and a crosslinking agent, and the present invention has been completed.

That is, according to the present invention, the cyclic olefin polymer (A), the radiation sensitive compound (B), and the orthoester in which the content ratio of the monomer unit having a protic polar group is 40 mol% or more and less than 80 mol%. A radiation-sensitive resin composition containing (C) and a crosslinking agent (D) is provided.
In the radiation sensitive resin composition of the present invention, the orthoester (C) content is preferably 3 to 70 parts by weight with respect to 100 parts by weight of the cyclic olefin polymer (A).

  Moreover, according to this invention, the laminated body which has a resin film formed using one of the said radiation sensitive resin compositions, and a board | substrate is provided.

  According to the present invention, a radiation-sensitive resin composition that provides a resin film having excellent exposure sensitivity and excellent reliability in a high-temperature and high-humidity environment, and a resin film formed from the radiation-sensitive resin composition are provided. The laminated body which has can be provided. In particular, since the laminate of the present invention has a resin film formed from the radiation-sensitive resin composition of the present invention, it has a resin film with excellent exposure sensitivity, and is reliable in a high temperature and high humidity environment. In particular, it has excellent reliability that it can effectively suppress an increase in off-leakage current value when kept in a high-temperature and high-humidity environment, and is useful as various electronic components, particularly semiconductor devices. is there.

  The radiation-sensitive resin composition of the present invention comprises a cyclic olefin polymer (A) and a radiation-sensitive compound (B) in which the content of monomer units having a protic polar group is 40 mol% or more and less than 80 mol%. , Orthoester (C), and a crosslinking agent (D).

(Cyclic olefin polymer (A) in which the content of monomer units having a protic polar group is 40 mol% or more and less than 80 mol%)
The cyclic olefin polymer (A) (hereinafter simply referred to as “cyclic olefin polymer (A)) having a content of monomer units having a protic polar group of 40 mol% or more and less than 80 mol% used in the present invention. Is a homopolymer or copolymer of a cyclic olefin monomer having a cyclic structure (alicyclic ring or aromatic ring) of a cyclic olefin monomer unit in the main chain, and As a monomer unit constituting the polymer, a monomer unit having a protic polar group is contained in a proportion of 40 mol% or more and less than 80 mol%.

  In the cyclic olefin polymer (A) used in the present invention, the content ratio of the monomer unit having a protic polar group is 40 mol% or more and less than 80 mol% in all monomer units, Preferably it is 45-75 mol%, More preferably, it is 50-70 mol%. In this invention, the exposure sensitivity of the resin film obtained can be improved by making the content rate of the monomer unit which has a protic polar group in a cyclic olefin polymer (A) into the said range. In addition, in the cyclic olefin polymer (A), when the content ratio of the monomer unit having a protic polar group is too small, the exposure sensitivity becomes insufficient, and the productivity is lowered. If it is too much, it will be dissolved in the developer during development, and it will not be possible to form a resin film having a predetermined pattern.

  As such a cyclic olefin polymer (A), a polymer of one or two or more cyclic olefin monomers, or one or two or more cyclic olefin monomers and a monomer copolymerizable therewith In the present invention, a cyclic olefin monomer (a1) having at least a protic polar group is used as a monomer for forming the cyclic olefin polymer (A). It is preferable to use it.

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

Specific examples of such protic polar groups include polar groups having oxygen atoms such as hydroxyl groups, carboxy groups (hydroxycarbonyl groups), sulfonic acid groups, phosphoric acid groups; primary amino groups, secondary amino groups A polar group having a nitrogen atom such as a primary amide group or a secondary amide group (imide group); a polar group having a sulfur atom such as a thiol group; Among these, those having an oxygen atom are preferable, an acidic group is more preferable, and a carboxy group is more preferable. For example, when the cyclic olefin polymer (A) having an acidic group is used as the protic polar group, the content ratio of the monomer unit having an acidic group is 40 mol% or more in the total monomer units. , Less than 80 mol%, preferably 45 to 75 mol%, more preferably 50 to 70 mol%, thereby adjusting the acid value of the cyclic olefin polymer (A) to a desired range. The exposure sensitivity can be increased more appropriately.
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 different types of protic polar groups may be included.

Specific examples of the cyclic olefin monomer (a) having a protic polar group (hereinafter, appropriately referred to as “monomer (a)”) include 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 ] dodec-4-ene, 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 . Carboxy group-containing cyclic olefin such as 0 ^2,7 ] dodec-4-ene; 5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5- (4-hydroxy Phenyl) bicyclo [2.2.1] hept-2-ene, 9- (4-hydroxyphenyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9- (4-hydroxyphenyl) tetracyclo [6.2.1.1 ^3,6 . Hydroxyl-containing cyclic olefins such as 0 ^2,7 ] dodec-4-ene. Among these, a carboxy group-containing cyclic olefin is preferable from the viewpoint that the obtained resin film has high adhesion, and 8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene is particularly preferred. These monomers (a) may be used alone or in combination of two or more.

  The content ratio of the monomer (a) unit in the cyclic olefin polymer (A) is such that the content ratio of the monomer unit having a protic polar group in the cyclic olefin polymer (A) is within the above range. However, it is usually 40 mol% or more and less than 80 mol%, preferably 45 to 75 mol%, more preferably 50 to 70 mol% with respect to all monomer units. . In addition, when not using the monomer which has a protic polar group as a copolymerizable monomer (b) mentioned later, by adjusting the usage-amount of a monomer (a), cyclic olefin type | system | group is used. The content ratio of the monomer unit having a protic polar group in the polymer (A) can be adjusted. When a monomer having a protic polar group other than the monomer (a) is further used as the copolymerizable monomer (b) to be described later, By adjusting the total amount of the monomer having a protic polar group other than the monomer (a), the monomer unit having a protic polar group in the cyclic olefin polymer (A) is adjusted. The content ratio can be adjusted.

  The cyclic olefin polymer (A) used in the present invention is obtained by copolymerizing a cyclic olefin monomer (a) having a protic polar group and a monomer (b) copolymerizable therewith. It may be a copolymer. Examples of such copolymerizable monomers include cyclic olefin monomers (b1) having polar groups other than protic polar groups, cyclic olefin monomers having no polar groups (b2), and cyclic olefins. Monomer (b3) (hereinafter referred to as “monomer (b1)”, “monomer (b2)”, “monomer (b3)” as appropriate).

  Examples of the cyclic olefin monomer (b1) having a polar group other than the protic polar group include cyclic olefins having an N-substituted imide group, an ester group, a cyano group, or a halogen atom.

（上記式（１）中、Ｒ^１は炭素数５〜１６の分岐状アルキル基またはフェニル基を表す。）

（上記式（２）中、Ｒ^２は炭素数１〜３の２価のアルキレン基、Ｒ^３は、炭素数１〜１０の１価のアルキル基、または、炭素数１〜１０の１価のハロゲン化アルキル基を表す。） Examples of the cyclic olefin having an N-substituted imide group include a monomer represented by the following formula (1) or a monomer represented by the following formula (2).

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

(In the above formula (2), R ² is a divalent alkylene group having 1 to ³ carbon atoms, R ³ is a monovalent alkyl group having 1 to 10 carbon atoms, or a monovalent alkyl group having 1 to 10 carbon atoms. Represents a halogenated alkyl group.)

In the above formula (1), R ¹ is a branched alkyl group having 5 to 16 carbon atoms or a phenyl group. Examples of the branched alkyl group having 5 to 16 carbon atoms include 1-methylbutyl group and 2-methylbutyl group. Group, 1-methylpentyl group, 1-ethylbutyl group, 2-methylhexyl group, 2-ethylhexyl group, 4-methylheptyl group, 1-methylnonyl group, 1-methyltridecyl group, 1-methyltetradecyl group, etc. Can be mentioned. Among these, a branched alkyl group having 6 to 14 carbon atoms is preferable, and a branched alkyl group having 7 to 10 carbon atoms is more preferable because of excellent heat resistance and solubility in a polar solvent. When the carbon number is 4 or less, the solubility in a polar solvent is poor, when the carbon number is 17 or more, the heat resistance is poor, and when the resin film is patterned, the pattern is lost by melting with heat. There is a problem.

  Specific examples of the monomer represented by the above formula (1) include N-phenyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methylbutyl). ) -Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-methylbutyl) -bicyclo [2.2.1] hept-5-ene-2,3- Dicarboximide, N- (1-methylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-methylpentyl) -bicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide, N- (1-ethylbutyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2 -Ethylbutyl) -bicyclo [2.2.1] hept-5-ene 2,3-dicarboximide, N- (1-methylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-methylhexyl) -bicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (3-methylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide N- (1-butylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-butylpentyl) -bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (1-methylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-methyl Heptyl) -bicyclo [2.2.1] hept-5 -2,3-dicarboximide, N- (3-methylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylheptyl)- Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imido, N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-ethylhexyl) -bicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide, N- (1-propylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-propylpentyl) ) -Bicyclo [2.2.1] he To-5-ene-2,3-dicarboximide, N- (1-methyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2- Methyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-methyloctyl) -bicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N- (4-methyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-ethylheptyl) -bicyclo [2 2.1] hept-5-ene-2,3-dicarboximide, N- (2-ethylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-ethylheptyl) -bicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (4-ethylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1 -Propylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-propylhexyl) -bicyclo [2.2.1] hept-5-ene- 2,3-dicarboximide, N- (3-propylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methylnonyl) -bicyclo [2 2.1] hept-5-ene-2,3-dicarboximide, N- (2-methylnonyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N -(3-Methylnonyl) -bicyclo [2. .1] Hept-5-ene-2,3-dicarboximide, N- (4-methylnonyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( 5-methylnonyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-ethyloctyl) -bicyclo [2.2.1] hept-5-ene- 2,3-dicarboximide, N- (2-ethyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-ethyloctyl) -bicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (4-ethyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide N- (1-methyldecyl) -bicyclo [2. .1] Hept-5-ene-2,3-dicarboximide, N- (1-methyldodecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-Methylundecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methyldodecyl) -bicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide, N- (1-methyltridecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methyltetra Decyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-methylpentadecyl) -bicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, and the like. These may be used alone or in combination of two or more.

On the other hand, in the above formula (2), R ² is a divalent alkylene group having 1 to 3 carbon atoms. Examples of the divalent alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, a propylene group, and an iso group. A propylene group is mentioned. Among these, a methylene group and an ethylene group are preferable because of good polymerization activity.

In the above formula (2), R ³ is a monovalent alkyl group having 1 to 10 carbon atoms or a monovalent halogenated alkyl group having 1 to 10 carbon atoms. Examples of the monovalent alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, hexyl group, and cyclohexyl group. . Examples of the monovalent halogenated alkyl group having 1 to 10 carbon atoms include a fluoromethyl group, a chloromethyl group, a bromomethyl group, a difluoromethyl group, a dichloromethyl group, a difluoromethyl group, a trifluoromethyl group, a trichloromethyl group, Examples include 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, and perfluoropentyl group. Among these, because of excellent solubility in polar solvents, as R ^3, methyl and ethyl are preferred.

  The monomers represented by the above formulas (1) and (2) can be obtained, for example, by an amidation reaction between a corresponding amine and 5-norbornene-2,3-dicarboxylic acid anhydride. The obtained monomer can be efficiently isolated by separating and purifying the reaction solution of the amidation reaction by a known method.

Examples of the cyclic olefin having an ester group include 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-acetoxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 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-methoxycarbonyltetracyclo [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 ] dodec-4-ene, 9-methyl-9-n-propoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-isopropoxycarbonyltetracyclo [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 ] dodec-4-ene and the like.

Examples of the cyclic olefin having a cyano group include 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.

Examples of the cyclic olefin having a halogen atom include 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 ] dodec-4-ene and the like.

  These monomers (b1) may be used alone or in combination of two or more.

Examples of the cyclic olefin monomer (b2) having no polar group include bicyclo [2.2.1] hept-2-ene (also referred to as “norbornene”), 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, tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene (conventional name: dicyclopentadiene), tetracyclo [10.2.1.0 ^2,11. 0 ^4,9 ] pentadeca-4,6,8,13-tetraene, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (also referred to as “tetracyclododecene”), 9-methyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyl-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-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-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] pentadeca-5,12-diene, cyclopentene, cyclopentadiene, 9-phenyl - tetracyclo [6.2.1.1 ^{3, 6.} 0 ^2,7] dodeca-4-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene, pentacyclo [9.2.1.1 ^3,9 . 0 ^2,10] pentadeca-12-ene, and the like.
These monomers (b2) may be used alone or in combination of two or more.

Specific examples of the monomer (b3) other than the cyclic olefin include 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, An α-olefin having 2 to 20 carbon atoms such as 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; Non-conjugated dienes such as hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, and derivatives thereof; cyclobutene, Ropenten, cyclohexene, cyclooctene, 3a, 5,6,7A- tetrahydro-4,7-methano -1H- indene cycloolefin, etc., such as. Among these, an α-olefin, particularly ethylene is preferable.
These monomers (b3) may be used alone or in combination of two or more.

  Among these monomers (b1) to (b3), the cyclic olefin monomer (b1) having a polar group other than the protic polar group is preferable from the viewpoint that the effect of the present invention becomes more remarkable. A cyclic olefin having an N-substituted imide group is particularly preferred.

  The content ratio of the copolymerizable monomer (b) unit in the cyclic olefin polymer (A) is the content of the monomer unit having a protic polar group in the cyclic olefin polymer (A). What is necessary is just to set it as a ratio that a ratio becomes the said range, and what is necessary is just to determine according to the content rate of the unit of the monomer (a) mentioned above.

In addition, in this invention, it is good also as a cyclic olefin polymer (A) by introduce | transducing a protic polar group into a cyclic olefin polymer which does not have a protic polar group using a well-known modifier. In this case, the content ratio of monomer units having a protic polar group (content ratio of monomer units having a protic polar group introduced by a modifier) is controlled to be in the above range. By doing so, a cyclic olefin polymer (A) can be obtained.
A polymer having no protic polar group is obtained by polymerizing at least one of the above-described monomers (b1) and (b2) and optionally combining the monomer (b3) as necessary. be able to.

As the modifier for introducing a protic polar group, a compound having a protic polar group and a reactive carbon-carbon unsaturated bond in one molecule is usually used.
Specific examples of such compounds include acrylic acid, methacrylic acid, angelic acid, tiglic acid, oleic acid, elaidic acid, erucic acid, brassic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, atropaic acid. Unsaturated carboxylic acids such as acids and cinnamic acids; allyl alcohol, methyl vinyl methanol, crotyl alcohol, methallyl alcohol, 1-phenylethen-1-ol, 2-propen-1-ol, 3-butene-1- All, 3-buten-2-ol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl- Saturation of 3-buten-1-ol, 4-penten-1-ol, 4-methyl-4-penten-1-ol, 2-hexen-1-ol, etc. Alcohol; and the like.
The modification reaction of the polymer using these modifiers may be performed according to a conventional method, and is usually performed in the presence of a radical generator.

  The cyclic olefin polymer (A1) used in the present invention may be a ring-opening polymer obtained by ring-opening polymerization of the above-described monomer, or an addition polymer obtained by addition polymerization of the above-described monomer. Although it may be a polymer, it is preferably a ring-opening polymer from the viewpoint that the effect of the present invention becomes more remarkable.

  The ring-opening polymer comprises a ring-opening metathesis polymerization of a cyclic olefin monomer having a protic polar group (a) and a copolymerizable monomer (b) used as necessary in the presence of a metathesis reaction catalyst. Can be manufactured. As a manufacturing method, the method etc. which are described in [0039]-[0079] of international publication 2010/110323 can be used, for example. On the other hand, the addition polymer comprises a cyclic olefin monomer having a protic polar group (a) and a copolymerizable monomer (b) used as required by a known addition polymerization catalyst such as titanium, It can be obtained by polymerization using a catalyst comprising a zirconium or vanadium compound and an organoaluminum compound.

  Further, when the cyclic olefin polymer (A) used in the present invention is a ring-opening polymer, a hydrogenation reaction is further performed, and hydrogenation in which a carbon-carbon double bond contained in the main chain is hydrogenated is performed. It is preferable to use a product. When the cyclic olefin polymer (A) is a hydrogenated product, the ratio of hydrogenated carbon-carbon double bonds (hydrogenation rate) is usually 50% or more, and 70% from the viewpoint of heat resistance. Preferably, it is 90% or more, more preferably 95% or more.

(Radiation sensitive compound (B))
The radiation-sensitive compound (B) used in the present invention is a compound that can cause a chemical reaction upon irradiation with radiation such as ultraviolet rays or electron beams. In the present invention, the radiation sensitive compound (B)) is preferably one capable of controlling the alkali solubility of the resin film formed from the radiation sensitive resin composition, and it is particularly preferable to use a photoacid generator.

  Examples of such a radiation-sensitive compound (B) include azide compounds such as acetophenone compounds, triarylsulfonium salts, and quinonediazide compounds, with azide compounds being preferred, and quinonediazide compounds being particularly preferred.

As the quinonediazide compound, for example, an ester compound of a quinonediazidesulfonic acid halide and a compound having a phenolic hydroxyl group can be used. Specific examples of the quinone diazide sulfonic acid halide include 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-benzoquinone diazide-5-sulfonic acid chloride, and the like. Can be mentioned. Typical examples of the compound having a phenolic hydroxyl group include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1. -[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and the like. Other compounds having a phenolic hydroxyl group include 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2-bis (4-hydroxyphenyl) propane, tris (4- Hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, novolac resin oligomer, phenolic hydroxyl group Examples thereof include oligomers obtained by copolymerizing one or more compounds and dicyclopentadiene.
Among these, a condensate of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and a compound having a phenolic hydroxyl group is preferable, and 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl)- A condensate of 3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) is more preferred.

In addition to quinonediazide compounds, radiation sensitive compounds (B) include onium salts, halogenated organic compounds, α, α′-bis (sulfonyl) diazomethane compounds, α-carbonyl-α′-sulfonyldiazomethane compounds, sulfones. Known compounds such as compounds, organic acid ester compounds, organic acid amide compounds, and organic acid imide compounds can be used.
These radiation sensitive compounds (B) can be used alone or in combination of two or more.

  Although content of the radiation sensitive compound (B) in the radiation sensitive resin composition of this invention is not specifically limited, Preferably it is 10-50 weight part with respect to 100 weight part of cyclic olefin type polymers (A), More preferably, it is 15-45 weight part, More preferably, it is the range of 25-40 weight part. If the content of the radiation sensitive compound (B) is within this range, when patterning a resin film made of the radiation sensitive resin composition, there is a difference in solubility in the developer between the radiation irradiated portion and the radiation unirradiated portion. It is preferable because it is large, radiation sensitivity is high, and patterning by development is easy.

（上記一般式（３）中、Ｒ^４は、水素原子、または炭素数１〜３のアルキル基、好ましくは、水素原子、または炭素数１〜２のアルキル基であり、Ｒ^５は、それぞれ独立して、炭素数１〜５のアルキル基、好ましくは、炭素数１〜３のアルキル基である。） (Orthoester (C))
The orthoester (C) used in the present invention is a compound having a structure in which three alkoxy groups are bonded to one carbon atom, and typically includes a compound represented by the following general formula (3). .

(In the general formula (3), R ⁴ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ⁵ is independently selected. And an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms.)

  In the radiation sensitive resin composition of this invention, it mix | blends orthoester (C), It acts as a water trap agent in the resin film obtained, for example, the radiation sensitive resin composition of this invention When a laminate of a resin film obtained using a product and a substrate is obtained and the laminate is held in a high-temperature and high-humidity environment, water enters the interface between the resin film and the substrate and performance degradation (for example, It is possible to effectively prevent the occurrence of deterioration in performance such as an increase in off-leakage current value. And thereby, the obtained laminated body can be made excellent in reliability.

  Specific examples of the orthoester (C) include orthoformates such as trimethyl orthoformate, triethyl orthoformate, trihexyl orthoformate; orthoacetic esters such as trimethyl orthoacetate, triethyl orthoacetate, trihexyl orthoacetate; orthopropionic acid Orthopropionates such as triethyl and triethyl orthopropionate; orthobutyric esters such as trimethyl orthobutyrate and triethyl orthobutyrate; orthooctanoates such as trimethyl orthooctanoate and triethyl orthooctanoate; trimethyl orthostearate; Orthostearic acid esters such as orthostearic acid triethyl; and the like. These orthoesters (C) can be used alone or in combination of two or more. Among these, orthoformate esters and orthoacetate esters are preferable, and trimethyl orthoformate, tributyl orthoformate, and trimethyl orthoacetate are preferable.

  The content of the ortho ester (C) in the radiation sensitive resin composition of the present invention is not particularly limited, but is preferably 3 to 70 parts by weight, more preferably 100 parts by weight with respect to 100 parts by weight of the cyclic olefin polymer (A). Preferably it is 5-60 weight part, More preferably, it is the range of 10-50 weight part. If the content of the orthoester (C) is within this range, the addition effect, that is, the reliability improvement effect under high-temperature and high-humidity conditions may be sufficient without impairing other characteristics such as electrical characteristics. This is preferable because it is possible.

(Crosslinking agent (D))
The crosslinking agent (D) used in the present invention forms a crosslinked structure between the crosslinking agent molecules by heating or forms a crosslinked structure between the resin molecules by reacting with the cyclic olefin polymer (A). Specific examples include compounds having two or more reactive groups. Examples of such a reactive group include an amino group, a carboxy group, a hydroxyl group, an epoxy group, and an isocyanate group, more preferably an amino group, an epoxy group, and an isocyanate group, and further preferably an amino group and an epoxy group. An epoxy compound having an epoxy group is particularly preferable. The epoxy group is preferably a terminal epoxy group or an alicyclic epoxy group, and more preferably an alicyclic epoxy group.

  Although the molecular weight of a crosslinking agent (D) is not specifically limited, Usually, it is 100-100,000, Preferably it is 300-50,000, More preferably, it is 500-10,000. A crosslinking agent can be used individually or in combination of 2 types or more, respectively.

  Specific examples of the crosslinking agent (D) include aliphatic polyamines such as hexamethylenediamine; aromatic polyamines such as 4,4′-diaminodiphenyl ether and diaminodiphenylsulfone; 2,6-bis (4′-azidobenzal) Azides such as cyclohexanone and 4,4′-diazidodiphenylsulfone; polyamides such as nylon, polyhexamethylenediamineterephthalamide and polyhexamethyleneisophthalamide; N, N, N ′, N ″, N ″ , N ″-(hexaalkoxyalkyl) melamine and other melamines which may have a methylol group or imino group (trade names “Cymel 303, Cymel 325, Cymel 370, Cymel 232, Cymel 235, Cymel 272, Cymel 212, My Coat 506 "{End Cymel series such as INDUSTRIES}, My Coat series); N, N ′, N ″, N ′ ″-(tetraalkoxyalkyl) glycoluril and other methylol groups and imino groups Good glycolurils (trade name “Cymel 1170” {Cytech series manufactured by Cytec Industries, Inc.}); acrylate compounds such as ethylene glycol di (meth) acrylate; hexamethylene diisocyanate polyisocyanate, isophorone diisocyanate polyisocyanate , Isocyanate compounds such as tolylene diisocyanate polyisocyanate and hydrogenated diphenylmethane diisocyanate; 1,4-di- (hydroxymethyl) cyclohexane, 1,4-di- (hydroxymethyl) norbornane; 1 3,4-trihydroxycyclohexane; bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, polyphenol type epoxy resin, cyclic aliphatic epoxy resin, aliphatic glycidyl ether, epoxy acrylate And epoxy compounds such as polymers.

  Specific examples of the epoxy compound include a trifunctional epoxy compound having a dicyclopentadiene skeleton (trade name “XD-1000”, manufactured by Nippon Kayaku Co., Ltd.), 2,2-bis (hydroxymethyl) 1-butanol. 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct (15-functional alicyclic epoxy resin having a cyclohexane skeleton and a terminal epoxy group, trade name “EHPE3150”, manufactured by Daicel Chemical Industries, Ltd.), epoxidation 3-cyclohexene-1,2-dicarboxylate bis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic trifunctional epoxy resin, trade name “Epolide GT301”, manufactured by Daicel Chemical Industries), epoxidized butane Tetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone (fat An epoxy compound having an alicyclic structure such as an aliphatic cyclic tetrafunctional epoxy resin, trade name “Epolide GT401” manufactured by Daicel Chemical Industries, Ltd .;

Bisphenol A type polyfunctional epoxy compound (trade names: Composeran “E103” “E103A” “E102” “E102B” “E201” “E202C” “SQ506” “SQ502-8”, manufactured by Arakawa Chemical Industries, Ltd.); Product name Oncoat "EX-1010" "EX-1011" "EX-1012" "EX-1020" "EX-1030" "EX-1040" "EX-1050" "EX-1051" "EX-1060" (Manufactured by Nagase ChemteX Corporation), (trade names “Ogsol PG100”, “Ogsol EG-200”, manufactured by Osaka Gas Chemical Co., Ltd.), heterocyclic-containing epoxy compounds (trade name “TEPIC”, manufactured by Nissan Chemical Industries, Ltd.), aromatic amine Type polyfunctional epoxy compound (trade name “H-434”, manufactured by Tohto Kasei Kogyo Co., Ltd.) Borac type polyfunctional epoxy compound (trade name “EOCN-1020”, manufactured by Nippon Kayaku Co., Ltd.), phenol novolac type polyfunctional epoxy compound (Epicoat 152, 154, manufactured by Japan Epoxy Resin Co., Ltd.), polyfunctional epoxy compound having a naphthalene skeleton (Trade name EXA-4700, manufactured by Dainippon Ink Chemical Co., Ltd.), chain alkyl polyfunctional epoxy compound (trade name “SR-MK3”, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), polyfunctional epoxy polybutadiene (trade name “Epolide PB3600”) , Daicel Chemical Industries, Ltd.), Glycerin glycidyl polyether compound (trade name “SR-GLG”, Sakamoto Pharmaceutical Co., Ltd.), diglycerin polyglycidyl ether compound (trade name “SR-DGE”, Sakamoto Pharmaceutical Co., Ltd.) Company-made polyglycerin polyglycidyl ether compound Trade name "SR-4GL", an epoxy compound having no alicyclic structure of Sakamoto made Yakuhin Kogyo Co., Ltd.) and the like; can be mentioned.

  Among epoxy compounds, a polyfunctional epoxy compound having two or more epoxy groups is preferable, and a resin film obtained using a radiation-sensitive resin composition can be excellent in heat-resistant shape retention. And a polyfunctional epoxy compound having 3 or more epoxy groups is particularly preferable.

  The content of the crosslinking agent (D) in the radiation-sensitive resin composition of the present invention is not particularly limited, and the heat resistance required when a pattern is provided on a resin film obtained using the resin composition of the present invention. Although it may be arbitrarily set in consideration of the degree, it is preferably 20 to 120 parts by weight, preferably 25 to 100 parts by weight, more preferably 30 to 80 parts by weight based on 100 parts by weight of the cyclic olefin polymer (A). Parts by weight. If the crosslinking agent (D) is too much or too little, the heat resistance tends to decrease.

(Solvent (E))
Moreover, the radiation sensitive resin composition of this invention may further contain the solvent (E). The solvent (E) is not particularly limited, and is known as a resin composition solvent, for example, acetone, methyl ethyl ketone, cyclopentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone. Linear ketones such as 2-octanone, 3-octanone and 4-octanone; alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and cyclohexanol; ethylene glycol dimethyl ether, ethylene glycol diethyl ether and dioxane Ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and other alcohol ethers; propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, propionic acid Esters such as chill, methyl butyrate, ethyl butyrate, methyl lactate, and ethyl lactate; cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; propylene glycol, propylene glycol monomethyl ether, propylene Propylene glycols such as glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, etc. Ethylene glycols; saturated γ-lactones such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-caprolactone; halogenated hydrocarbons such as trichloroethylene; aromatic hydrocarbons such as toluene and xylene; Examples include polar solvents such as dimethylacetamide, dimethylformamide, and N-methylacetamide. These solvents (E) may be used alone or in combination of two or more. The content of the solvent (E) is preferably 10 to 10000 parts by weight, more preferably 50 to 5000 parts by weight, and still more preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the cyclic olefin polymer (A). It is a range. In addition, when making a resin composition contain a solvent, a solvent will be normally removed after resin film formation.

(Other ingredients)
In addition, the radiation-sensitive resin composition of the present invention may be a surfactant, an acidic compound, a coupling agent or a derivative thereof, a sensitizer, a potential acid generator, if desired, as long as the effects of the present invention are not inhibited. May contain other compounding agents such as additives, antioxidants, light stabilizers, antifoaming agents, pigments, dyes, fillers, and the like.

  The surfactant is used for the purpose of preventing striation (after application stripes) and improving developability. Specific examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. Polyoxyethylene aryl ethers; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Fluorine surfactants; Silicone surfactants; Methacrylic acid copolymer System surfactants; acrylic acid copolymer system surfactants; and the like.

  The coupling agent or derivative thereof has an effect of further improving the adhesion between the resin film made of the radiation-sensitive resin composition and each layer including the semiconductor layer constituting the semiconductor element substrate. As the coupling agent or derivative thereof, a compound having one atom selected from a silicon atom, a titanium atom, an aluminum atom, and a zirconium atom and having a hydrocarbyloxy group or a hydroxy group bonded to the atom can be used.

As a coupling agent or a derivative thereof, for example,
Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane,
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, n-decyltrimethoxysilane, p-styryl Trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyl Nyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyl Limethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyl Triethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-ethyl (trimethoxysilylpropoxymethyl) oxetane, 3-ethyl (triethoxysilylpropoxymethyl) Kisetan, 3-triethoxysilyl-N-(1,3-dimethyl - butylidene) propylamine, trialkoxysilanes such as bis (triethoxysilylpropyl) tetrasulfide,
Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxy Silane, di-n-butyldimethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyl Dimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, Diphenyldie Xysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldiethoxysilane In addition to dialkoxysilanes such as N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane,
Silicon atom-containing compounds such as methyltriacetyloxysilane and dimethyldiacetyloxysilane;

Tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate, di-i-propoxybis (acetylacetonato) titanium, propanedioxy Titanium bis (ethyl acetoacetate), tri-n-butoxytitanium monostearate, di-i-propoxytitanium distearate, titanium stearate, di-i-propoxytitanium diisostearate, (2-n-butoxycarbonylbenzoyl) In addition to oxy) tributoxy titanium and di-n-butoxy bis (triethanolaminato) titanium, titanium atom-containing compounds such as the Plenact series (manufactured by Ajinomoto Fine Techno Co., Ltd.);
Aluminum atom-containing compounds such as acetoalkoxyaluminum diisopropylate;
Tetranormal propoxyzirconium, tetranormalbutoxyzirconium, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium butoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate), zirconium tetraacetylacetate And zirconium atom-containing compounds such as zirconium tributoxy systemate.

  Specific examples of the sensitizer include 2H-pyrido- (3,2-b) -1,4-oxazin-3 (4H) -ones, 10H-pyrido- (3,2-b) -1,4. -Benzothiazines, urazoles, hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, maleimides and the like.

  As the antioxidant, there can be used phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, lactone antioxidants and the like used in ordinary polymers. For example, as phenols, 2,6-di-t-butyl-4-methylphenol, p-methoxyphenol, styrenated phenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4 '-Hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-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 tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], alkylated bisphenols, etc. Can. Examples of the phosphorus-based antioxidant include triphenyl phosphite and tris (nonylphenyl) phosphite. Examples of the sulfur-based antioxidant include dilauryl thiodipropionate.

  Examples of light stabilizers include ultraviolet absorbers such as benzophenone-based, salicylic acid ester-based, benzotriazole-based, cyanoacrylate-based, and metal complex-based salts, hindered amine-based (HALS), and the like that capture radicals generated by light. Either is acceptable. Among these, HALS is a compound having a piperidine structure, and is preferable because it is less colored and has good stability with respect to the radiation-sensitive resin composition. Specific compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl 1,2,3,4 -Butanetetracarboxylate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.

The preparation method of the radiation sensitive resin composition of this invention is not specifically limited, What is necessary is just to mix each component which comprises a radiation sensitive resin composition by a well-known method.
The mixing method is not particularly limited, but it is preferable to mix a solution or dispersion obtained by dissolving or dispersing each component constituting the radiation-sensitive resin composition in the solvent (E). Thereby, a radiation sensitive resin composition is obtained with the form of a solution or a dispersion liquid.

  The method for dissolving or dispersing each component constituting the radiation-sensitive resin composition may be in accordance with a conventional method. Specifically, stirring using a stirrer and a magnetic stirrer, a high-speed homogenizer, a disper, a planetary stirrer, a twin-screw stirrer, a ball mill, a three-roll, etc. can be used. Further, after each component is dissolved or dispersed in a solvent, it may be filtered using, for example, a filter having a pore size of about 0.5 μm.

  The solid content concentration of the radiation-sensitive resin composition of the present invention is usually 1 to 70% by weight, preferably 5 to 60% by weight, and more preferably 10 to 50% by weight. If the solid content concentration is within this range, dissolution stability, coating properties, film thickness uniformity of the formed resin film, flatness, and the like can be highly balanced.

(Laminate)
The laminate of the present invention has a resin film formed from the above-described radiation-sensitive resin composition of the present invention and a substrate. For example, on the substrate using the radiation-sensitive resin composition of the present invention described above. After the resin film is formed, the resin film can be cross-linked as necessary.

  In the present invention, for example, a printed wiring board, a silicon wafer substrate, a glass substrate, a plastic substrate, or the like can be used as the substrate. The substrate surface may be physically and / or chemically surface treated, and may have a multiple layer structure in which other thin films are formed on the substrate surface. Further, a glass substrate, a plastic substrate, or the like used in the display field, in which various elements such as a thin transistor type liquid crystal display element, a thin film transistor, and an organic EL, a color filter, a black matrix, and the like are suitably used.

  The method for forming the resin film on the substrate is not particularly limited, and for example, a method such as a coating method or a film lamination method can be used.

  The application method is, for example, a method in which a radiation-sensitive resin composition is applied and then dried by heating to remove the solvent. Examples of the method for applying the radiation sensitive resin composition include various methods such as a spray method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a spin coating method, a bar coating method, and a screen printing method. Can be adopted. The heating and drying conditions vary depending on the type and blending ratio of each component, but are usually 30 to 150 ° C., preferably 60 to 120 ° C., usually 0.5 to 90 minutes, preferably 1 to 60 minutes, and more. Preferably it may be performed in 1 to 30 minutes.

  In the film lamination method, the radiation-sensitive resin composition is applied onto a B-stage film-forming substrate such as a resin film or a metal film, and then the solvent is removed by heat drying to obtain a B-stage film. In this method, a stage film is laminated on a substrate. The heating and drying conditions can be appropriately selected according to the type and mixing 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. . Film lamination can be performed using a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator or the like.

  The thickness of the resin film formed on the substrate is not particularly limited and may be set as appropriate according to the application. The thickness of the resin film is preferably 0.1 to 100 μm, more preferably 0. It is 5-50 micrometers, More preferably, it is 0.5-30 micrometers.

  Moreover, since the radiation sensitive resin composition of this invention contains a crosslinking agent (D), it can perform a crosslinking reaction about the resin film formed by the above-mentioned coating method or film lamination method. Such crosslinking may be appropriately selected according to the type of the crosslinking agent (D), but is usually performed by heating. The heating method can be performed using, for example, a hot plate or an oven. The heating temperature is usually 180 to 250 ° C., and the heating time is appropriately selected according to the area and thickness of the resin film, the equipment used, and the like. For example, when using a hot plate, the oven is usually used for 5 to 60 minutes. When used, it is usually in the range of 30 to 90 minutes. Heating may be performed in an inert gas atmosphere as necessary. Any inert gas may be used as long as it does not contain oxygen and does not oxidize the resin film. Examples thereof include nitrogen, argon, helium, neon, xenon, and krypton. Among these, nitrogen and argon are preferable, and nitrogen is particularly preferable. In particular, an inert gas having an oxygen content of 0.1% by volume or less, preferably 0.01% by volume or less, particularly nitrogen is suitable. These inert gases can be used alone or in combination of two or more.

Moreover, the resin film formed using the radiation sensitive resin composition of this invention may be patterned.
As a method of patterning the resin film, for example, the latent image pattern is formed by irradiating the resin film before patterning with active radiation, and then the developer is brought into contact with the resin film having the latent image pattern. The method of making it manifest is mentioned.

As the actinic radiation, the radiation-sensitive compound (B) contained in the radiation-sensitive resin composition can be activated to change the alkali solubility of the radiation-sensitive resin composition containing the radiation-sensitive compound (B). If it is, it will not specifically limit. Specifically, ultraviolet rays, ultraviolet rays having a single wavelength such as g-line or i-line, light rays such as KrF excimer laser light and ArF excimer laser light; particle beams such as electron beams; As a method for selectively irradiating these actinic radiations in a pattern to form a latent image pattern, a conventional method may be used. For example, ultraviolet, g-line, i-line, KrF excimer is used by a reduction projection exposure apparatus or the like. A method of irradiating a light beam such as a laser beam or an ArF excimer laser beam through a desired mask pattern, a method of drawing with a particle beam such as an electron beam, or the like can be used. When light is used as the active radiation, it may be single wavelength light or mixed wavelength light. Irradiation conditions may be appropriately selected depending on the active radiation to be used, for example, when using a light beam of wavelength 200 to 450 nm, the amount of irradiation is usually 10~1,000mJ / cm ^2, preferably 50 to 500 mJ / It is a range of cm ² and is determined according to irradiation time and illuminance. After irradiation with actinic radiation in this way, the protective film is heat-treated at a temperature of about 60 to 130 ° C. for about 1 to 2 minutes as necessary.

  Next, the latent image pattern formed on the resin film before patterning is developed and made visible. As the developer, an aqueous solution of an alkaline compound is usually used. As the alkaline compound, for example, an alkali metal salt, an amine, or an ammonium salt can be used. The alkaline compound may be an inorganic compound or an organic compound. Specific examples of these compounds include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate and sodium metasilicate; ammonia water; primary amines such as ethylamine and n-propylamine; diethylamine Secondary amines such as di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and choline Alcohol alcohols such as dimethylethanolamine and triethanolamine; pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5 -En, N-Me Cyclic amines such as Rupiroridon; and the like. These alkaline compounds can be used alone or in combination of two or more.

As an aqueous medium of the alkaline aqueous solution, water; water-soluble organic solvents such as methanol and ethanol can be used. The alkaline aqueous solution may have a surfactant added in an appropriate amount.
As a method of bringing the developer into contact with the resin film having the latent image pattern, for example, a paddle method, a spray method, a dipping method, or the like is used. The development is usually appropriately selected in the range of 0 to 100 ° C, preferably 5 to 55 ° C, more preferably 10 to 30 ° C, and usually 30 to 180 seconds.

The resin film on which the target pattern is formed in this manner can be rinsed with a rinsing liquid in order to remove the development residue, if necessary. After the rinse treatment, the remaining rinse liquid is removed with compressed air or compressed nitrogen.
Furthermore, in order to deactivate the radiation sensitive compound (B), the entire surface of the substrate can be irradiated with actinic radiation as necessary. For irradiation with actinic radiation, the method exemplified in the formation of the latent image pattern can be used. The resin film may be heated simultaneously with irradiation or after irradiation. Examples of the heating method include a method of heating the substrate in a hot 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, the resin film can be subjected to a crosslinking reaction after being patterned. Crosslinking may be performed according to the method described above.

  According to the present invention, since the resin film constituting the laminate is formed using the above-described radiation-sensitive resin composition of the present invention, the laminate of the present invention is provided with a resin film excellent in exposure sensitivity, In addition, the reliability in a high-temperature and high-humidity environment, particularly the excellent reliability that an increase in off-leakage current value when held in a high-temperature and high-humidity environment can be effectively suppressed can be achieved. . Therefore, the laminate of the present invention is useful as various electronic components, particularly as a semiconductor device, and in particular, it is possible to effectively suppress an increase in off-leakage current value when held in a high temperature and high humidity environment. And a thin film transistor constituting an active matrix substrate (specifically, a thin film transistor obtained by using a resin film obtained by using the radiation sensitive resin composition of the present invention as a gate insulating film or a protective film). be able to.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. “Part” and “%” in each example are based on weight unless otherwise specified.
In addition, the definition and evaluation method of each characteristic are as follows.

<Exposure sensitivity>
A radiation sensitive resin composition was applied onto a soda glass substrate by spin coating, and prebaked at 110 ° C. for 2 minutes using a hot plate to form a resin film having a thickness of 2.5 μm. Next, after developing for 40 seconds at 23 ° C. using an aqueous 2.38 wt% tetramethylammonium hydroxide solution, the substrate was rinsed with ultrapure water for 30 seconds. Then, to pattern the resin film, the contact hole pattern of 5μm using a formable mask, by varying the exposure amount from 200 mJ / cm ² to 350 mJ / cm ² per 50 mJ / cm ^2, air Then, by performing post-baking by heating at 230 ° C. for 30 minutes in a nitrogen atmosphere using an oven, a resin film having contact hole patterns with different exposure amounts and a soda glass substrate are used. The resulting laminate was obtained.

And the contact hole formation part of the obtained laminated body was observed using the optical microscope, and the length of the longest part of the contact hole pattern of the resin film of the part exposed by each exposure amount was measured, respectively. Then, an approximate curve is created from the relationship between each exposure amount and the length of the longest part of the contact hole pattern of the resin film formed at the corresponding exposure amount, and the exposure amount when the contact hole pattern becomes 5 μm is calculated. The exposure amount was calculated as exposure sensitivity. The lower the exposure when the contact hole pattern is 5 μm, the more preferable it is because the contact hole can be formed with low energy or in a short time.
○: exposure amount when the contact hole pattern is 5μm is less than 250mJ / cm ² △: exposure amount when the contact hole pattern is 5μm is 250 mJ / cm ² or more, 300 mJ / cm ² less ×: contact hole The exposure when the pattern is 5 μm is 300 mJ / cm ² or more

<Off-leakage current value after holding in high temperature and high humidity environment>
The active matrix substrate was held in a high temperature and high humidity environment of 60 ° C. and 90% RH for 200 hours, and the off-leak current value was measured for the active matrix substrate after being held in a high temperature and high humidity environment. Specifically, a voltage of 20 V is applied between the source electrode and the drain electrode of the active matrix substrate after being maintained in a high temperature and high humidity environment, and the voltage applied to the gate electrode is changed to -20 to +30 V, The current flowing between the source electrode and the drain electrode was measured using a manual prober and a semiconductor parameter analyzer (manufactured by Agilent, 4156C), thereby measuring the off-leakage current value.

<< Synthesis Example 1 >>
<Preparation of Cyclic Olefin Polymer (A-1)>
40 mol% N-phenyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NBPI), and 4-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-9-ene (TCDC) 60 parts by mole monomer mixture 100 parts, 1,5-hexadiene 2.0 parts, (1,3-dimesitylimidazoline-2-ylidene) ( Tricyclohexylphosphine) benzylideneruthenium dichloride (synthesized by the method described in Org. Lett., Volume 1, page 953, 1999) and 200 parts of diethylene glycol ethyl methyl ether made of nitrogen-substituted glass The polymerization reaction liquid was obtained by charging into a pressure-resistant reactor and making it react at 80 degreeC for 4 hours, stirring.

And the obtained polymerization reaction liquid was put into an autoclave, and it stirred at 150 degreeC and the hydrogen pressure of 4 MPa for 5 hours, and performed the hydrogenation reaction, and obtained the polymer solution containing a cyclic olefin polymer (A-1). . The polymerization conversion rate of the obtained cyclic olefin polymer (A-1) was 99.7%, polystyrene-equivalent weight average molecular weight was 7,150, number average molecular weight was 4,690, molecular weight distribution was 1.52, and hydrogenation rate. Was 99.7%, and the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A-1) was 34.4% by weight. Further, N-phenyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NBPI) unit in the cyclic olefin polymer (A-1) and 4-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . The content ratio with the 0 ^2,7 ] dodec-9-ene (TCDC) unit was the same as the charging ratio (the same applies to Synthesis Examples 2 to 5 described later).

<< Synthesis Example 2 >>
<Preparation of cyclic olefin polymer (A-2)>
As a monomer mixture, N-phenyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NBPI) 30 mol%, and 4-hydroxycarbonyltetracyclo [6.2. 1.1 ^{3, 6} . [0 ^2,7 ] Dodeca-9-ene (TCDC) A polymer solution containing a cyclic olefin polymer (A-2) was obtained in the same manner as in Synthesis Example 1 except that one comprising 70 mol% was used. . The polymerization conversion rate of the obtained cyclic olefin polymer (A-2) was 99.7%, the weight average molecular weight in terms of polystyrene was 7,100, the number average molecular weight was 4,750, the molecular weight distribution was 1.52, and the hydrogenation rate. Was 99.8%. Moreover, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A-2) was 34.4% by weight.

<< Synthesis Example 3 >>
<Preparation of Cyclic Olefin Polymer (A-3)>
As a monomer mixture, N-phenyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NBPI) 50 mol%, and 4-hydroxycarbonyltetracyclo [6.2. 1.1 ^{3, 6} . [0 ^2,7 ] Dodeca-9-ene (TCDC) A polymer solution containing a cyclic olefin polymer (A-3) was obtained in the same manner as in Synthesis Example 1 except that the composition was 50 mol%. . The resulting cyclic olefin polymer (A-3) had a polymerization conversion of 99.5%, a polystyrene-equivalent weight average molecular weight of 7,180, a number average molecular weight of 4,680, a molecular weight distribution of 1.52, and a hydrogenation rate. Was 99.6%. Moreover, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A-3) was 34.4% by weight.

<< Synthesis Example 4 >>
<Preparation of cyclic olefin polymer (A'-4)>
As a monomer mixture, N-phenyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NBPI) 70 mol%, and 4-hydroxycarbonyltetracyclo [6.2. 1.1 ^{3, 6} . [0 ^2,7 ] Dodeca-9-ene (TCDC) A polymer solution containing a cyclic olefin polymer (A′-4) was obtained in the same manner as in Synthesis Example 1 except that one comprising 30 mol% was used. It was. The resulting cyclic olefin polymer (A′-4) had a polymerization conversion of 99.7%, a polystyrene-equivalent weight average molecular weight of 7,120, a number average molecular weight of 4,710, a molecular weight distribution of 1.53, and hydrogenation. The rate was 99.7%. Moreover, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A′-4) was 34.4% by weight.

<< Synthesis Example 5 >>
<Preparation of cyclic olefin polymer (A'-5)>
As the monomer mixture, N-phenyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (NBPI) 20 mol%, and 4-hydroxycarbonyltetracyclo [6.2. 1.1 ^{3, 6} . ^0,7 ] Dodeca-9-ene (TCDC) A polymer solution containing a cyclic olefin polymer (A′-5) was obtained in the same manner as in Synthesis Example 1 except that one comprising 80 mol% was used. It was. The resulting cyclic olefin polymer (A′-5) had a polymerization conversion of 99.6%, a polystyrene-equivalent weight average molecular weight of 7,090, a number average molecular weight of 4,630, a molecular weight distribution of 1.49, and hydrogenation. The rate was 99.8%. Moreover, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A′-5) was 34.4% by weight.

<< Synthesis Example 6 >>
(Preparation of acrylic resin)
20 parts of styrene, 25 parts of butyl methacrylate, 25 parts of 2-ethylhexyl acrylate, 30 parts of methacrylic acid, 0.5 part of 2,2-azobisisobutyronitrile and 300 parts of propylene glycol monomethyl ether acetate are stirred in a nitrogen stream. The mixture was heated at 80 ° C. for 5 hours. The obtained resin solution was concentrated by a rotary evaporator to obtain an acrylic resin solution having a solid content concentration of 35%.

<< Synthesis Example 7 >>
(Preparation of polyimide)
In a four-necked flask under a dry air stream, 9.61 parts of 4,4′-diaminodiphenyl ether, 17.3 parts of bis [4- (4-aminophenoxy) phenyl] sulfone, bis (3-aminopropyl) tetramethyl 1.24 parts of disiloxane and 102.5 parts of cyclopentanone were charged and dissolved at 40 ° C. Then, pyromellitic anhydride 6.54 parts, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride 9.67 parts, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride 12.41 parts and 30 parts of cyclopentanone were added and reacted at 50 ° C. for 3 hours. This solution was concentrated by a rotary evaporator to obtain a polyimide solution having a solid concentration of 35%.

Example 1
<Preparation of radiation-sensitive resin composition>
As the cyclic olefin polymer (A), 100 parts of the cyclic olefin polymer (A-1) obtained in Synthesis Example 1, and as the radiation-sensitive compound (B), 1,1,3-tris (2,5-dimethyl- 30 parts of a condensate of 4-hydroxyphenyl) -3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2 mol), and 30 parts of trimethyl orthoformate as the orthoester (C) As a crosslinking agent (D), (3 ′, 4′-epoxycyclohexane) methyl 3,4-epoxycyclohexanecarboxylate (trade name “Celoxide 2021P”, manufactured by Daicel Chemical Industries, Ltd., molecular weight 250, SP measured by ASPEN PLUS Value (SP ₁ ) 19699.55 (J / CUM) ^1/2 ) 20 parts, also as a crosslinking agent (D), fluorene Type epoxy resin (trade name “ONCOAT EX-1040”, manufactured by Nagase ChemteX Corp.) 20 and 100 parts of diethylene glycol ethyl methyl ether (EDM) as a solvent (E) were dissolved and dissolved. A radiation sensitive resin composition was prepared by filtration through a 45 μm polytetrafluoroethylene filter.

<Production of active matrix substrate>
On a glass substrate (trade name “Corning 1737”, manufactured by Corning), a sputtering apparatus is used to form chromium with a film thickness of 200 nm, re-patterning is performed by photolithography, and a gate electrode, a gate signal line, and a gate A terminal part was formed. Next, the gate electrode and the gate electrode are covered with a CVD apparatus, the silicon nitride film serving as the gate insulating film is 450 nm thick, the a-Si layer (amorphous silicon layer) serving as the semiconductor layer is 250 nm thick, ohmic An n + Si layer to be a contact layer was continuously formed with a thickness of 50 nm, and the n + Si layer and the a-Si layer were patterned in an island shape. Further, chromium is formed to a thickness of 200 nm on the gate insulating film and the n + Si layer by a sputtering apparatus, and a source electrode, a source signal line, a drain electrode, and a data terminal portion are formed by photolithography, and the source electrode and the drain are formed. An unnecessary n + Si layer between the electrodes was removed to form a back channel, thereby obtaining an array substrate in which a plurality of thin film transistors were formed on a glass substrate.

The obtained array substrate was spin-coated with the radiation-sensitive resin composition obtained above, and then pre-baked at 90 ° C. for 2 minutes using a hot plate to obtain a resin film having a thickness of 1.2 μm. Formed. Next, the resin film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5 mW / cm ² in the air for 40 seconds through a 10 μm × 10 μm hole pattern mask. Next, after developing for 90 seconds at 25 ° C. using a 0.4 wt% tetramethylammonium hydroxide aqueous solution, rinsing with ultrapure water for 30 seconds to form a contact hole pattern, 230 ° C. The array substrate on which the protective film (resin film) was formed was obtained by performing post-baking by heating for 15 minutes.

  Then, the array substrate on which the protective film (resin film) is formed as described above is transferred to a vacuum chamber, and a mixed gas of argon and oxygen (volume ratio 100: 4) is used as the sputtering gas, pressure 0.3 Pa, DC output 400 W. Then, by performing DC sputtering through a mask, an In—Sn—O-based amorphous transparent conductive layer (pixel electrode) having a thickness of 200 nm was formed so as to be in contact with the drain electrode, thereby obtaining an active matrix substrate.

  And using the radiation sensitive resin composition obtained above, measurement of exposure sensitivity, and using the active matrix substrate obtained above, off-leakage current value after holding in a high temperature and high humidity environment Each of the measurements was performed. The results are shown in Table 1.

Example 2
A radiation-sensitive resin composition and an active matrix substrate were obtained in the same manner as in Example 1 except that the blending amount of trimethyl orthoformate as the orthoester (C) was changed from 30 parts to 10 parts, and evaluated in the same manner. Went. The results are shown in Table 1.

Example 3
A radiation-sensitive resin composition and an active matrix substrate were obtained in the same manner as in Example 1 except that the blending amount of trimethyl orthoformate as the orthoester (C) was changed from 30 parts to 50 parts, and evaluated in the same manner. Went. The results are shown in Table 1.

Example 4
As the orthoester (C), a radiation sensitive resin composition and an active matrix substrate were obtained in the same manner as in Example 1 except that 30 parts of tributyl orthoformate was used instead of 30 parts of trimethyl orthoformate. Was evaluated. The results are shown in Table 1.

Example 5
A radiation-sensitive resin composition and an active matrix substrate were obtained in the same manner as in Example 1 except that 30 parts of trimethyl orthoacetate was used as the orthoester (C) instead of 30 parts of trimethyl orthoformate. Was evaluated. The results are shown in Table 1.

Example 6
Example except that 100 parts of the cyclic olefin polymer (A-2) obtained in Synthesis Example 2 was used instead of 100 parts of the cyclic olefin polymer (A-1) as the cyclic olefin polymer (A). In the same manner as in No. 1, a radiation-sensitive resin composition and an active matrix substrate were obtained and evaluated in the same manner. The results are shown in Table 1.

Example 7
Example except that 100 parts of the cyclic olefin polymer (A-3) obtained in Synthesis Example 3 was used as the cyclic olefin polymer (A) instead of 100 parts of the cyclic olefin polymer (A-1). In the same manner as in No. 1, a radiation-sensitive resin composition and an active matrix substrate were obtained and evaluated in the same manner. The results are shown in Table 1.

<< Comparative Example 1 >>
Implementation was performed except that 100 parts of the cyclic olefin polymer (A′-4) obtained in Synthesis Example 4 was used instead of 100 parts of the cyclic olefin polymer (A-1) as the cyclic olefin polymer (A). In the same manner as in Example 1, a radiation-sensitive resin composition and an active matrix substrate were obtained and evaluated in the same manner. The results are shown in Table 1.

<< Comparative Example 2 >>
Implementation was performed except that 100 parts of the cyclic olefin polymer (A′-5) obtained in Synthesis Example 5 was used instead of 100 parts of the cyclic olefin polymer (A-1) as the cyclic olefin polymer (A). In the same manner as in Example 1, a radiation-sensitive resin composition and an active matrix substrate were obtained and evaluated in the same manner. The results are shown in Table 1.

<< Comparative Example 3 >>
A radiation-sensitive resin composition and an active matrix substrate were obtained and evaluated in the same manner as in Example 1 except that trimethyl orthoformate as the orthoester (C) was not blended. The results are shown in Table 1.

<< Comparative Example 4 >>
In the same manner as in Example 1, except that 100 parts of the acrylic resin obtained in Synthesis Example 6 was used instead of 100 parts of the cyclic olefin polymer (A-1) as the cyclic olefin polymer (A), A radiation resin composition and an active matrix substrate were obtained and evaluated in the same manner. The results are shown in Table 1.

<< Comparative Example 5 >>
In the same manner as in Example 1, except that 100 parts of the polyimide obtained in Synthesis Example 7 was used instead of 100 parts of the cyclic olefin polymer (A-1) as the cyclic olefin polymer (A), radiation sensitivity was obtained. The functional resin composition and the active matrix substrate were obtained and evaluated in the same manner. The results are shown in Table 1.

  As shown in Table 1, the cyclic olefin polymer (A), the radiation-sensitive compound (B), the orthoester (the content ratio of the monomer unit having a protic polar group is 40 mol% or more and less than 80 mol% C) and a resin film obtained using the radiation-sensitive resin composition containing the crosslinking agent (D) are excellent in exposure sensitivity, and a laminate (active matrix substrate) obtained using the resin film is The increase in off-leakage current value after holding in a high temperature and high humidity environment was suppressed, and the reliability was excellent (Examples 1 to 7).

On the other hand, when the cyclic olefin polymer (A) having a protic polar group content of less than 40 mol% was used, the resulting resin film was inferior in exposure sensitivity (Comparative Example). 1).
Further, when the cyclic olefin polymer (A) having a protic polar group content of 80 mol% or more was used, it was dissolved during development, and the resin film could not be patterned. (Comparative example 2).
Furthermore, when the orthoester (C) is not blended, an acrylic resin is used instead of the cyclic olefin polymer (A) in which the content ratio of the monomer unit having a protic polar group is 40 mol% or more and less than 80 mol%. When using polyimide or polyimide, the resulting laminate (active matrix substrate) has a high rise in off-leakage current value after being held in a high-temperature and high-humidity environment, resulting in poor reliability (comparison) Examples 3-5).

Claims (3)

Cyclic olefin polymer (A), photoacid generator (B), orthoester (C), and crosslinking agent having a content of monomer units having a protic polar group of 40 mol% or more and less than 80 mol% A radiation-sensitive resin composition containing (D).   2. The radiation-sensitive resin composition according to claim 1, wherein a content ratio of the orthoester (C) is 3 to 70 parts by weight with respect to 100 parts by weight of the cyclic olefin polymer (A).   The laminated body which has a resin film formed using the radiation sensitive resin composition of Claim 1 or 2, and a board | substrate.