JP5413097B2 - Radiation sensitive resin composition and laminate - Google Patents

Description

  The present invention relates to a radiation-sensitive resin composition and a laminate, and more particularly, has excellent adhesion to various materials, and ITO electrode processability (in a state where the resin film is penetrated or on the surface of the resin film, an ITO electrode) The present invention relates to a radiation-sensitive resin composition that gives a resin film excellent in pattern processability and heat resistance, 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, the organic EL element is layered. 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, alkali-soluble cyclic polyolefin resins have been studied as radiation-sensitive resin materials. For example, Patent Document 1 discloses an addition polymer of a N-substituted cyclic imide structure-containing cyclic olefin, a ring-opening polymer, and a hydrogenated product thereof having a carboxylic acid ester in the substituent. It is disclosed that this polymer and its hydrogenated product are excellent in heat resistance, solubility in polar solvents, and adhesion to inorganic substrates.

  However, in Patent Document 1, an N-substituted cyclic imide structure-containing cyclic olefin addition polymer, a ring-opening polymer, and a hydrogenated product thereof disclosed in the document are used as radiation-sensitive resin materials, and the above-described various types. There is no disclosure about a specific formulation for forming a resin film for constituting an electronic component, and therefore characteristics required for such a resin film for an electronic component, for example, adhesion to a plurality of materials, In some cases, characteristics such as ITO electrode processability and pattern processability cannot be satisfied.

JP 2008-222935 A

  The present invention is excellent in adhesion to various materials, has high heat resistance, ITO electrode processability (processability when the ITO electrode is formed on the surface of the resin film) It aims at providing the radiation sensitive resin composition which gives the resin film excellent in workability, and the laminated body which has a resin film formed from this radiation sensitive resin composition.

  As a result of intensive studies to achieve the above object, the present inventors have found that a specific thiol compound, a resin composition containing a cyclic olefin polymer having a protic polar group, a crosslinking agent, and a radiation sensitive compound, And it discovered that the said subject could be solved by adding a carboxyl group-containing compound, and came to complete this invention.

（式（１）中、Ｘ^１〜Ｘ^３は、それぞれ独立して−ＳＨ、−ＳＲ、−ＮＲ’Ｒ’’又は−ＳＭ（Ｒ、Ｒ’及びＲ’’は、それぞれ独立して炭素数１〜５の直鎖又は分岐のアルキル基であり、Ｍはアルカリ金属である。）であり、これらのうち少なくとも１つは−ＳＨである。） That is, according to the present invention, a cyclic olefin polymer (A) having a protic polar group, a crosslinking agent (B), a radiation sensitive compound (C), and a thiol compound represented by the following general formula (1) ( D) and a radiation sensitive resin composition containing a carboxyl group-containing compound (E) are provided.

(In the formula (1), X ^{1 to} X ³ are each independently —SH, —SR, —NR′R ″ or —SM (R, R ′ and R ″ are each independently carbon number) 1-5 linear or branched alkyl groups, and M is an alkali metal.), At least one of which is —SH.

Preferably, at least two of X ^{1 to} X ^{3 in} the general formula (1) are —SH.
Preferably, the thiol compound (D) is 2,4,6-trimercapto-s-triazine.
Preferably, the carboxyl group-containing compound (E) has an acid dissociation constant pKa of 2.5 or more and 4.5 or less.
Preferably, the carboxyl group-containing compound (E) has at least two carboxyl groups.

  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, excellent adhesion to various materials, high heat resistance, and ITO electrode processability (processability when penetrating a resin film or when an ITO electrode is formed on the surface of a resin film) And the radiation sensitive resin composition which gives the resin film excellent in pattern workability, and a laminated body provided with the resin film formed from this radiation sensitive resin composition can be provided.

(Radiation sensitive resin composition)
The radiation sensitive resin composition of the present invention comprises a cyclic olefin polymer (A) having a protic polar group, a crosslinking agent (B), a radiation sensitive compound (C), a predetermined thiol compound (D), and a carboxyl group. It is a composition containing a containing compound (E).

(Cyclic olefin polymer having a protic polar group (A))
The cyclic olefin polymer (A) having a protic polar group used in the present invention (hereinafter simply referred to as “cyclic olefin polymer (A)”) has a cyclic olefin monomer unit in its main chain. A homopolymer or copolymer of a cyclic olefin monomer having a cyclic structure (alicyclic ring or aromatic ring) and having a protic polar group.

  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, and a carboxy group is more preferable.
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 (a1) having a protic polar group (hereinafter, appropriately referred to as “monomer (a1)”) 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 (a1) may be used alone or in combination of two or more.

  The cyclic olefin polymer (A) used in the present invention is obtained by copolymerizing a cyclic olefin monomer (a1) having a protic polar group and a monomer (a2) copolymerizable therewith. A copolymer may also be used. As such a copolymerizable monomer, a cyclic olefin monomer having a polar group other than a protic polar group (a2-1), a cyclic olefin monomer having no polar group (a2-2), And monomer other than cyclic olefin (a2-3) (hereinafter, “monomer (a2-1)”, “monomer (a2-2)”, “monomer (a2-3)” as appropriate) Said).

  Examples of the cyclic olefin monomer (a2-1) having a polar group other than the protic polar group include a cyclic olefin having an N-substituted imide group, an ester group, a cyano group, or a halogen atom.

（上記一般式（２）中、Ｒ^１は炭素数５〜１６の分岐状アルキル基又はフェニル基を表す。）

（上記一般式（３）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 general formula (2) or a monomer represented by the following general formula (3).

(In the general formula (2), R ¹ represents a branched alkyl group having 5 to 16 carbon atoms or a phenyl group.)

(In the general formula (3), 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 monovalent having 1 to 10 carbon atoms. Represents a halogenated alkyl group.)

In the general formula (2), R ¹ is a branched alkyl group having 5 to 16 carbon atoms or a phenyl group, and examples of the branched alkyl group having 5 to 16 carbon atoms include 1-methylbutyl group, 2- Methylbutyl 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. Is 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 general formula (2) 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- -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-di Carboximide, 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 -Methylheptyl) -bicyclo [2.2.1] hept- -Ene-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-di Carboximide, 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-propyl) Pentyl) -bicyclo [2.2.1 Hept-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-di Carboximide, 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- Methyltetradecyl) -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 general formula (3), 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 isopropylene group is mentioned. Among these, a methylene group and an ethylene group are preferable because of good polymerization activity.

In the general formula (3), 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 general formulas (2) and (3) 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 (a2-1) may be used alone or in combination of two or more.

Examples of the cyclic olefin monomer having no polar group (a2-2) include bicyclo [2.2.1] hept-2-ene (also referred to as “norbornene”) and 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 (common 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 (a2-2) may be used alone or in combination of two or more.

Specific examples of the monomer (a2-3) other than 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- An α-olefin having 2 to 20 carbon atoms such as hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; 1 , 4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, non-conjugated dienes such as 1,7-octadiene, and derivatives thereof; cyclobutene Cyclopentene, 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 (a2-3) may be used alone or in combination of two or more.

  Among these monomers (a2-1) to (a2-3), a cyclic olefin monomer having a polar group other than a protic polar group (a2) from the viewpoint that the effect of the present invention becomes more remarkable. -1) is preferred, and cyclic olefins having an N-substituted imide group are particularly preferred.

  In the cyclic olefin polymer (A) of the present invention, the ratio of the units of the cyclic olefin monomer (a1) having a protic polar group to the copolymerizable monomer (a2) is “single”. The weight ratio of unit of monomer (a1): unit of monomer (a2) ”is preferably 90:10 to 20:80, more preferably 80:20 to 30:70, and still more preferably 70. : 30 to 40:60. If the number of units of the cyclic olefin monomer (a1) having a protic polar group is too small, the solubility in the developing solution is lowered, so that patterning becomes impossible or the pattern is formed when the resin film after patterning is heated. On the other hand, if too much, the solubility ratio in the developer is too high, so the solubility ratio of the film remaining part and the film dissolving part at the time of patterning becomes small, and patterning becomes impossible. In some cases, the water absorption of the resin film increases, making it difficult to apply to applications that dislike the presence of moisture.

In the present invention, a protic polar group is introduced into the cyclic olefin polymer (A) by introducing a protic polar group into the cyclic olefin polymer having no protic polar group using a known modifier. Groups may be introduced.
The polymer having no protic polar group is an arbitrary combination of at least one of the monomers (a2-1) and (a2-2) described above and, if necessary, the monomer (a2-3). Can be obtained by polymerization.

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

  In addition, the cyclic olefin polymer (A) used in the present invention may be a ring-opening polymer obtained by ring-opening polymerization of the above-described monomer, or addition polymerization of the above-described monomer. Although it may be an addition 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 (a1) and a copolymerizable monomer (a2) used as necessary in the presence of a metathesis reaction catalyst. Can be manufactured.

  The metathesis reaction catalyst may be any catalyst as long as it is a group 3-11 transition metal compound of the periodic table and performs ring-opening metathesis polymerization of the cyclic olefin monomer (a1) having a protic polar group. For example, as a metathesis reaction catalyst, one described in Olefin Metathesis and Metathesis Polymerization (KJ Ivinand JC Mol, Academic Press, San Diego 1997) can be used.

  As a metathesis reaction catalyst, a periodic table group 3-11 transition metal carbene complex catalyst is mentioned, for example. Among these, use of a ruthenium carbene complex catalyst is preferable.

  Examples of the periodic table Group 3-11 transition metal-carbene complex catalyst include a tungsten alkylidene complex catalyst, a molybdenum alkylidene complex catalyst, a rhenium alkylidene complex catalyst, and a ruthenium carbene complex catalyst.

Specific examples of the tungsten alkylidene complex ^{_{catalysts, 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 and the like.

Specific examples of molybdenum alkylidene complex _{^{catalyst, 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) (CHCMe2Ph) (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 rhenium alkylidene complex ^{catalyst, 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 and the} like.

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

  Further, specific examples of the ruthenium carbene complex catalyst include compounds represented by the following general formula (4) or general formula (5).

In the general formulas (4) and (5), ═CR ⁴ R ⁵ and ═C═CR ⁴ R ⁵ are carbene compounds containing a carbene carbon as a reaction center. R ⁴ and R ⁵ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom or silicon atom, The carbene compound may or may not contain a heteroatom. L ¹ represents a heteroatom-containing carbene compound, and L ² represents a heteroatom-containing carbene compound or any neutral electron-donating compound.

Here, the hetero atom-containing carbene compound refers to a compound containing a carbene carbon and a hetero atom. Both L ¹ and L ² or L ¹ is a heteroatom-containing carbene compound, and a ruthenium metal atom is directly bonded to the carbene carbon contained therein, and a group containing a heteroatom is bonded.

L ³ and L ⁴ each independently represent an arbitrary anionic ligand. Also, two, three, four, five or six of R ⁴ , R ⁵ , L ¹ , L ² , L ³ and L ⁴ are bonded to each other to form a multidentate chelating ligand. May be. Specific examples of heteroatoms include 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 atom is particularly preferable.

In the general formulas (4) and (5), the anionic (anionic) ligands L ³ and L ⁴ are ligands having a negative charge when separated from the central metal, for example, Halogen atoms such as fluorine, chlorine, bromine and iodine; hydrocarbons containing oxygen such as diketonate, alkoxy, aryloxy and carboxyl groups; substituted with halogen atoms such as cyclopentadienyl chloride And alicyclic hydrocarbon groups. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

When L ² is a neutral electron donating compound, L ² may be any ligand as long as it has a neutral charge when separated from the central metal. Specific examples thereof include carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, thiocyanates, and the like. Among these, phosphines and pyridines are preferable, and trialkylphosphine is more preferable.

  Examples of the ruthenium complex catalyst represented by the general formula (4) include benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl). Imidazolidine-2-ylidene) (3-methyl-2-butene-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octahydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) Ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydrobenzimidazole-2 -B Den) (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) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesitylimidazolidine-2-ylidene) pyridine ruthenium dichloride, etc. Ruthenium carbene complex in which a hetero atom-containing carbene compound and a neutral electron donating compound are bonded; benzylidenebis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride, benzylidenebis (1,3 Ruthenium carbene complex-diisopropyl-4-imidazolin-2-ylidene) two hetero atom-containing carbene compounds such as ruthenium dichloride are bonded; and the like.

  Examples of the ruthenium carbene complex catalyst represented by the general formula (5) include (1,3-dimesitylimidazolidine-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butyl). Vinylidene) (1,3-diisopropyl-4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylidene ruthenium dichloride, and the like.

  The amount of the metathesis reaction catalyst used is the molar ratio of monomer to catalyst, 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 catalyst is too large, it may be difficult to remove the catalyst, and if it is too small, sufficient polymerization activity may not be obtained.

  Ring-opening polymerization using a metathesis reaction catalyst can be carried out in a solvent or without a solvent. When the hydrogenation reaction is carried out as it is without isolating the produced polymer after completion of the polymerization reaction, the polymerization is preferably carried out in a solvent.

  The solvent is not particularly limited as long as it dissolves the produced polymer and does not inhibit the polymerization reaction. Examples of the solvent used include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, and bicyclo Alicyclic hydrocarbons such as heptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; nitrogen-containing compounds such as nitromethane, nitrobenzene, acetonitrile, propionitrile and benzonitrile Hydrocarbons; ethers such as diethyl ether, tetrahydrofuran, dioxane, etc .; acetone, ethyl methyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc. Ketones; methyl acetate, ethyl acetate, ethyl propionate, methyl benzoate, chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, halogenated hydrocarbons such as chlorobenzene; and the like. Among these, the use of aromatic hydrocarbons, alicyclic hydrocarbons, ethers, ketones or esters is preferable.

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

  The metathesis reaction catalyst may be dissolved in a solvent and added to the reaction system, or may be added as it is without being dissolved. Examples of the solvent for preparing the catalyst solution include the same solvents as those used in the polymerization reaction described above.

  In the polymerization reaction, a molecular weight modifier can be added to the reaction system in order to adjust the molecular weight of the polymer. Examples of molecular weight modifiers include α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrenes such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; Halogen-containing vinyl compounds such as allyl chloride; oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol and glycidyl methacrylate; nitrogen-containing vinyl compounds such as acrylonitrile and acrylamide can be used. A polymer having a desired molecular weight is obtained by using 0.05 to 50 mol% of a molecular weight modifier with respect to the monomer mixture containing the cyclic olefin monomer (a1) having a protic polar group. Can do.

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

  On the other hand, the addition polymer is obtained by converting a cyclic olefin monomer (a1) having a protic polar group and a copolymerizable monomer (a2) used as necessary into 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. These polymerization catalysts can be used alone or in combination of two or more. The amount of the polymerization catalyst is a molar ratio of the metal compound to the monomer in the polymerization catalyst and is usually in the range of 1: 100 to 1: 2,000,000.

  Further, when the cyclic olefin polymer (A) used in the present invention is a ring-opening polymer, a hydrogenation reaction is further performed, and hydrogen in which carbon-carbon double bonds contained in the main chain are hydrogenated. An additive is preferred. 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 from the viewpoint of heat resistance, 70 % Or more is preferable, 90% or more is more preferable, and 95% or more is further preferable.

Hydrogenation ratio of the hydrogenated product may, for example, carbon in the ^{1 H-NMR} spectrum of the ring-opening polymer - a peak intensity derived from the carbon-carbon double bond, carbon in the ^{1 H-NMR} spectrum of the hydrogenated product - carbon double It can obtain | require by comparing with the peak intensity derived from a coupling | bonding.

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

  The hydrogenation catalyst to be used is not particularly limited, such as a homogeneous catalyst and a heterogeneous catalyst, and those generally used for hydrogenation of olefin compounds can be used as appropriate.

  Examples of homogeneous catalysts include transitions such as cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, a combination of titanocene dichloride and n-butyllithium, zirconocene dichloride and sec-butyllithium, tetrabutoxytitanate and dimethylmagnesium, etc. Ziegler catalyst comprising a combination of a metal compound and an alkali metal compound; ruthenium carbene complex catalyst, dichlorotris (triphenylphosphine) rhodium described in the above section of ring-opening metathesis reaction catalyst, JP-A-7-2929, JP-A-7 -149823, JP-A-11-109460, JP-A-11-158256, JP-A-11-193323, JP-A-11-109460, etc. Noble metal complex catalyst consisting ruthenium compound; and the like.

  Examples of the heterogeneous catalyst include a hydrogenation catalyst in which a metal such as nickel, palladium, platinum, rhodium, and ruthenium is supported on a carrier such as carbon, silica, diatomaceous earth, alumina, and titanium oxide. More specifically, for example, nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like can be used. These hydrogenation catalysts can be used alone or in combination of two or more.

  Among these, rhodium, ruthenium, and the like from the point that the carbon-carbon double bond in the polymer can be selectively hydrogenated without causing side reactions such as modification of the functional group contained in the ring-opening polymer. The use of a noble metal complex catalyst and a palladium supported catalyst such as palladium / carbon is preferred, and the use of a ruthenium carbene complex catalyst or a palladium supported catalyst is more preferred.

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

  When a ring-opening metathesis reaction and a hydrogenation reaction are continuously performed using a ruthenium carbene complex catalyst, a vinyl compound such as ethyl vinyl ether or a catalyst modifier such as an α-olefin is added to activate the catalyst. Then, a method of starting the hydrogenation reaction is preferably employed. Furthermore, it is also preferable to employ a method of improving the activity by adding a base such as triethylamine or N, N-dimethylacetamide.

  The hydrogenation reaction is usually performed in an organic solvent. As an organic solvent, it can select suitably by the solubility of the hydride to produce | generate, The organic solvent similar to the said polymerization solvent can be used. Therefore, after the polymerization reaction, the hydrogenation catalyst can be added to the reaction solution or the filtrate obtained by filtering the metathesis reaction catalyst from the reaction solution without replacing the solvent.

  The conditions for the hydrogenation reaction may be appropriately selected according to the type of hydrogenation catalyst 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 with respect to 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. Conversely, at a high temperature, a side reaction tends to occur. The pressure of hydrogen is usually 0.01 to 10.0 MPa, preferably 0.05 to 8.0 MPa, more preferably 0.1 to 6.0 MPa.

  The time for the hydrogenation reaction is 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, most preferably, of the carbon-carbon double bonds of the main chain in the polymer. 95% or more can be hydrogenated.

(Crosslinking agent (B))
The crosslinking agent (B) used in the present invention forms a crosslinked structure between crosslinking agent molecules by heating, or reacts with the cyclic olefin polymer (A) to form a crosslinked structure between resin molecules. 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. It is a group. Moreover, as an epoxy group, a terminal epoxy group and an alicyclic epoxy group are preferable, and an alicyclic epoxy group is more preferable.

  Although the molecular weight of a crosslinking agent (B) 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 (B) 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 ″, Melamines which may have a methylol group such as N ″-(hexaalkoxyalkyl) melamine or an imino group (trade names “Cymel 303, Cymel 325, Cymel 370, Cymel 232, Cymel 235, Cymel 272, Cymel 212, My Coat 506 "{End Cymel series, Mycoat series, etc. made by Ndustries Co., Ltd.]; even if it has a methylol group or imino group such as N, N ′, N ″, N ′ ″-(tetraalkoxyalkyl) glycoluril, etc. 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, hydrogenated diphenylmethane diisocyanate; 1,4-di- (hydroxymethyl) cyclohexane, 1,4-di- (hydroxymethyl) norbornane; , 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 heavy And epoxy compounds such as coalescence;

  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 .;

  Aromatic amine type polyfunctional epoxy compound (trade name “H-434”, manufactured by Tohto Kasei Kogyo Co., Ltd.), cresol novolac type polyfunctional epoxy compound (trade name “EOCN-1020”, manufactured by Nippon Kayaku Co., Ltd.), phenol novolac type Polyfunctional epoxy compounds (Epicoat 152, 154, manufactured by Japan Epoxy Resin Co., Ltd.), polyfunctional epoxy compounds having a naphthalene skeleton (trade name EXA-4700, manufactured by Dainippon Ink & Chemicals, Inc.), chain alkyl polyfunctional epoxy compounds (products) Name “SR-TMP”, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., multifunctional epoxy polybutadiene (trade name “Epolide PB3600”, manufactured by Daicel Chemical Industries, Ltd.), glycerin glycidyl polyether compound (trade name “SR-GLG”, Sakamoto Yakuhin) Kogyo Co., Ltd.), diglycerin polyglycidyl ether compound ( Product name “SR-DGE”, Sakamoto Yakuhin Kogyo Co., Ltd., polyglycerol polyglycidyl ether compound (trade name “SR-4GL”, Sakamoto Yakuhin Kogyo Co., Ltd.) and other epoxy compounds having no alicyclic structure; be able to.

  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 (B) 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 usually 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 (B) is too much or too little, the heat resistance tends to decrease.

(Radiation sensitive compound (C))
The radiation-sensitive compound (C) used in the present invention is a compound that can cause a chemical reaction upon irradiation with radiation such as ultraviolet rays and electron beams. In the present invention, the radiation sensitive compound (C) is preferably one that can control the alkali solubility of a 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 (C) include azide compounds such as acetophenone compounds, triarylsulfonium salts, quinonediazide compounds, and the like, preferably azide compounds, and particularly preferably quinonediazide compounds.

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

  The content of the radiation sensitive compound (C) in the radiation sensitive resin composition of the present invention is preferably 10 to 50 parts by weight, more preferably 15 to 100 parts by weight with respect to 100 parts by weight of the cyclic olefin polymer (A). It is 45 weight part, More preferably, it is the range of 20-40 weight part. If the content of the radiation sensitive compound (C) 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.

(Thiol compound (D))
The radiation-sensitive resin composition of the present invention includes the following general formula (1) in addition to the above-described cyclic olefin polymer (A) having a protic polar group, a crosslinking agent (B), and a radiation-sensitive compound (C). The thiol compound (D) represented by this is contained.

In the general formula (1), X ^{1 to} X ³ are each independently —SH, —SR, —NR′R ″ or —SM (R, R ′ and R ″ are each independently carbon. A linear or branched alkyl group of 1 to 5 and M is an alkali metal). In addition, at least one of X ^{1 to} X ³ is —SH, and in the present invention, at least two of X ^{1 to} X ³ are preferably —SH.

  By incorporating the thiol compound (D) together with the carboxyl group-containing compound (E) described later into the radiation-sensitive resin composition of the present invention, the resulting resin film has high adhesion to various materials, and the ITO electrode It can be excellent in processability, pattern processability and heat resistance.

Specific examples of such a thiol compound (D) include 2-dibutylamino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s-triazine, and 2-morpholyl-4,6. -Triazine dithiol compounds such as dimercapto-s-triazine, 2-monolauryl-4,6-dimercapto-s-triazine; 2,4,6-trimercapto-s-triazine, 2,4,6-trimercapto-s -Triazine trithiol compounds such as triazine-monosodium salt;
Among these, 2-dibutylamino-4,6-dimercapto-s-triazine and 2,4,6-trimercapto-s-triazine are preferable from the viewpoint of high adhesion improving effect, and 2,4 2,6-trimercapto-s-triazine is particularly preferred. The thiol compounds can be used alone or in combination of two or more.

  The content of the thiol compound (D) in the radiation-sensitive resin composition of the present invention is preferably 1 to 10 parts by weight, more preferably 1.5 parts per 100 parts by weight of the cyclic olefin polymer (A). It is -7.5 weight part, More preferably, it is the range of 2-5 weight part. When the content of the thiol compound (D) is too small, there is a problem in that the adhesiveness decreases, the ITO electrode processability decreases, and further, the pattern changes when the resin film after patterning is heated. On the other hand, if it is too much, the transparency of the resin film will decrease, and if the radiation sensitive resin composition is stored, the viscosity will change and the storage stability will increase so that the fine particles will increase. May get worse.

(Carboxyl group-containing compound (E))
Moreover, the radiation sensitive resin composition of this invention is the above-mentioned cyclic olefin polymer (A) which has a protic polar group, a crosslinking agent (B), a radiation sensitive compound (C), and a thiol compound (D). In addition, it contains a carboxyl group-containing compound (E).

The carboxyl group-containing compound (E) is not particularly limited as long as it is a compound containing a carboxyl group, but those having an acid dissociation constant pKa in the range of 2.5 to 4.5 are preferred. Moreover, when it is a compound which has two or more carboxyl groups, what has 1st dissociation constant pKa1 in the said range is preferable. The pKa is obtained according to pKa = −logKa by measuring the acid dissociation constant Ka = [H ₃ O ⁺ ] [B ⁻ ] / [BH] under dilute aqueous solution conditions. Here, BH represents an organic acid, and B ⁻ represents a conjugate base of the organic acid.
Moreover, the measuring method of pKa can calculate hydrogen ion concentration, for example using a pH meter, and can calculate from the density | concentration of a applicable substance, and hydrogen ion concentration.

Moreover, the carboxyl group-containing compound (E) may have a substituent other than the carboxyl group.
As such substituents, in addition to hydrocarbon groups such as alkyl groups and aryl groups, halogen atoms; alkoxy groups, aryloxy groups, acyloxy groups, heterocyclic oxy groups; substituted with alkyl groups, aryl groups, or heterocyclic groups Polar groups having no proton such as amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group; alkylthio group, arylthio group, heterocyclic thio group; Examples thereof include a hydrocarbon group substituted with a polar group having no proton.

  Specific examples of such a carboxyl group-containing compound (E) include methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid and decane. Acid, glycolic acid, glyceric acid, ethanedioic acid (also referred to as “oxalic acid”), propanedioic acid (also referred to as “malonic acid”), butanedioic acid (also referred to as “succinic acid”), pentanedioic acid Hexane diacid (also referred to as “adipic acid”), 1,2-cyclohexanedicarboxylic acid, 2-oxopropanoic acid, 2-hydroxybutanedioic acid, 2-hydroxypropanetricarboxylic acid, mercaptosuccinic acid, dimercaptosuccinic acid, etc. An aliphatic carboxylic acid compound of

  Benzoic acid, p-hydroxybenzenecarboxylic acid, o-hydroxybenzenecarboxylic acid, 2-naphthalenecarboxylic acid, methylbenzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, 3-phenylpropanoic acid, 2-hydroxybenzoic acid, dihydroxybenzoic acid , Dimethoxybenzoic acid, benzene-1,2-dicarboxylic acid (also referred to as “phthalic acid”), benzene-1,3-dicarboxylic acid (also referred to as “isophthalic acid”), benzene-1,4-dicarboxylic acid ( Also referred to as “terephthalic acid”), benzene-1,2,3-tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, benzenehexacarboxylic acid, biphenyl-2 , 2'-dicarboxylic acid, 2- (carboxymethyl) benzoic acid, 3- (carboxymethyl) 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- Aromatic carboxylic acid compounds such as mercapto-6-naphthalenecarboxylic acid and 2-mercapto-7-naphthalenecarboxylic acid;

  Nicotinic acid, isonicotinic acid, 2-furoic acid, pyrrole-2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid, imidazole Five-membered nitrogen atoms such as 2,4-dicarboxylic acid, imidazole-2,5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, pyrazole-3,5-dicarboxylic acid Carboxylic acid compound having a heterocyclic ring; 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-dicarboxylic acid, isothiazole-3,4-dicarbo Acid, isothiazole-3,5-dicarboxylic acid, 1,2,4-thiadiazole-2,5-dicarboxylic acid, 1,3,4-thiadiazole-2,5-dicarboxylic acid, 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-thiadiazole) -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) succinate 2- (5-mercapto-1,3,4-thiadiazol-2-ylthio) succinic acid, 4- (3-mercapto-1,2,4-thiadiazol-5-yl) thiobutanesulfonic acid, 4- ( Carboxylic acid compounds having a 5-membered heterocyclic ring containing a nitrogen atom and a sulfur atom, such as 2-mercapto-1,3,4-thiadiazol-5-yl) thiobutanesulfonic 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, pyridazine-3,4-dicarboxylic acid, pyridazine-3,5-dicarboxylic acid, pyridazine-3,6-dicarboxylic acid, pyridazine-4,5-dicarboxylic acid, pyrimidine-2,4-dicarboxylic acid, pyrimidine -2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, pyridine-2,6- And carboxylic acid compounds having a six-membered heterocyclic ring containing a nitrogen atom such as dicarboxylic acid and triazine-2,4-dicarboxylic acid.
Among these, the number of carboxyl groups is preferably 2 or more, and particularly preferably 2 from the viewpoint that the adhesion of the protective film obtained can be further improved.

  The content of the carboxyl group-containing compound (E) in the radiation sensitive resin composition of the present invention is preferably 1 to 15 parts by weight, more preferably 1 with respect to 100 parts by weight of the cyclic olefin polymer (A). .5 to 10 parts by weight, more preferably 2 to 5 parts by weight. If the content of the carboxyl group-containing compound (E) is too small, there is a disadvantage that the adhesiveness is lowered, the ITO electrode processability is lowered, and the pattern is changed when the resin film after patterning is heated. On the other hand, if the amount is too large, the solubility ratio in the developing solution is too high, so that the solubility ratio of the remaining film portion and the film dissolving portion at the time of patterning becomes small, and patterning becomes impossible or radiation sensitive. When the functional resin composition is stored, the storage stability may deteriorate such that the viscosity changes or the fine particles increase.

  Moreover, in addition to each said component, the solvent may contain in the radiation sensitive resin composition of this invention. The solvent is not particularly limited, and is known as a solvent for the radiation sensitive resin composition, 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, propio Esters such as ethyl acid, methyl butyrate, ethyl butyrate, methyl lactate, 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 glycols such as propylene 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 Diethylene 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 may be used alone or in combination of two or more. The content of the solvent is preferably 400 to 2,000 parts by weight, more preferably 450 to 1,600 parts by weight, and even more preferably 500 to 1,200 parts by weight with respect to 100 parts by weight of the polymer (A). It is a range.

  Furthermore, the radiation-sensitive resin composition of the present invention is a surfactant, a coupling agent or a derivative thereof, a sensitizer, a latent acid generator, an oxidation, if desired, as long as the effects of the present invention are not inhibited. It may contain other compounding agents such as an inhibitor, a light stabilizer, an antifoaming agent, a pigment, a dye, and a filler;

  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 of the resin film made of the radiation sensitive resin composition. 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 atoms such as methyltriacetyloxysilane, dimethyldiacetyloxysilane, trade names X-12-414, KBP-44 (manufactured by Shin-Etsu Chemical Co., Ltd.), 217FLAKE, 220FLAKE, 233FLAKE, z6018 (manufactured by Toray Dow Corning Co., Ltd.) Containing compounds;

(Tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate, di-i-propoxybis (acetylacetonato) titanium, propanedi Oxytitanium bis (ethylacetoacetate), tri-n-butoxytitanium monostearate, di-i-propoxytitanium distearate, titanium stearate, di-i-propoxytitanium diisostearate, (2-n-butoxycarbonyl Titanium atom-containing compounds such as benzoyloxy) tributoxytitanium, di-n-butoxy bis (triethanolaminato) titanium, as well as the preneact 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 tetraacetyl Zirconium atom-containing compounds such as acetonate and 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.

  The latent acid generator is used for the purpose of improving the heat resistance and chemical resistance of the radiation-sensitive resin composition of the present invention. Specific examples thereof include sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts, which are cationic polymerization catalysts that generate an acid upon heating. Of these, sulfonium salts and benzothiazolium salts are preferred.

  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 a solvent. 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 (B), a crosslinking reaction can be performed about the resin film formed by the above-mentioned coating method or film lamination method. Such crosslinking may be appropriately selected depending on the type of the crosslinking agent (B), 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 actinic radiation, what can activate the radiation sensitive compound (C) contained in a radiation sensitive resin composition, and can change the alkali solubility of the radiation sensitive resin composition containing a radiation sensitive compound (C). 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 followed. 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 (C), 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 has excellent adhesion to various materials and is high. It has heat resistance and is provided with a resin film excellent in ITO electrode processability (processability when the ITO electrode is formed on the surface of the resin film) it can. Therefore, the laminate of the present invention is useful as various electronic components, particularly as a semiconductor device. In particular, since the resin film constituting the laminate of the present invention is excellent in ITO electrode processability and pattern processability, the laminate of the present invention is in a state of penetrating the resin film or on the surface of the resin film. Suitable as an active matrix substrate (for example, an active matrix substrate in which a plurality of thin film transistors are mounted on a substrate) manufactured by forming an electrode (Indium Tin Oide) and patterning a resin film in a predetermined pattern It is.

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

<Adhesion>
After spin-coating the radiation sensitive resin composition on the substrate, it was prebaked at 90 ° 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 25 ° C. using a 2.38 wt% tetramethylammonium hydroxide aqueous solution, the substrate was rinsed with ultrapure water for 30 seconds. Next, post-baking was performed by heating at 230 ° C. for 60 minutes in a nitrogen atmosphere using an oven to obtain a laminate including a resin film and a substrate.
And about the obtained laminated body, the peeling strength was measured using the surface / interface physical-property analyzer (SAICAS D20) made from Daipura-Wintes. When measuring the peel strength, a 1 mm wide cut was made in the resin film formed in the laminate using a cutter, and then the interface between the resin film and the substrate in the cut portion was peeled off with a 1 mm cutting blade. . And the horizontal force applied to a cutting blade in that case was measured, and the value which converted the measured horizontal force per 1 m was observed as adhesiveness.
In this example, a laminate using a Cu substrate, a Mo substrate, a SiNx substrate, and an a-Si substrate (amorphous silicon substrate) as a substrate was prepared, and the adhesion between the resin film and each of these substrates was prepared. Evaluated.

<ITO electrode workability>
A radiation-sensitive resin composition is applied onto a glass substrate (Corning, product name Corning 1737) by spin coating, and is heated and dried (prebaked) at 90 ° C. for 2 minutes using a hot plate. A 5 μm resin film was formed. Next, a development process was performed, and light was irradiated to the entire surface of the resin film using a high-pressure mercury lamp to decompose the undecomposed photosensitive agent remaining in the film. And the laminated body which consists of a resin film and a glass substrate was obtained by heating for 30 minutes at 230 degreeC in nitrogen atmosphere. Next, an ITO film having a thickness of 120 nm was formed on the surface of the resin film of the obtained laminate by a sputtering method. Next, a positive photoresist (ZPP-1800U3 manufactured by Nippon Zeon Co., Ltd.) used as an etching mask to form a contact hole pattern on the ITO film is applied onto the ITO film by a spin coating method, and a hot plate is used. A 1.5 μm resist film was formed by removing the solvent. Next, an exposure process and a development process were performed, and the resist film was patterned. In the exposure process, a mask capable of forming contact hole patterns having different sizes every 0.5 μm from 0.5 μm to 5.0 μm and contact hole patterns of 10 μm, 25 μm, and 50 μm was used. Then, using a 4% oxalic acid dihydrate aqueous solution, the ITO film was patterned by wet etching to form a contact hole pattern in the ITO film. Next, the resist film is removed using a stripping solution of a mixed solution of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO) (MEA / DMSO = 7/3), so that the resin film and the size of the resist film on the substrate are removed. A laminate having ITO films having different contact hole patterns was obtained.
And the contact hole formation part of the obtained laminated body was observed using the optical microscope, and ITO electrode processability was evaluated by confirming the presence or absence of a crack. In this evaluation, the maximum length of one side of the contact holes where cracks were observed was observed as a crack during processing of the ITO electrode. In addition, when no crack was observed, the crack at the time of ITO electrode processing was set to “None”. When the crack at the time of ITO electrode processing is “None”, the ITO electrode can be processed with an accuracy of 0.5 μm or less, so that it is particularly excellent in ITO electrode processability. Even when a crack occurs, the smaller the crack during ITO electrode processing, the more fine the ITO electrode can be processed. Therefore, it can be judged that the ITO electrode processability is excellent and good.

<Pattern workability>
A radiation sensitive resin composition is applied by spin coating on a silicon nitride film substrate (a substrate in which a 200 nm thick silicon nitride film is formed on a silicon substrate by chemical vapor deposition (CVD)), and hot A plate was used to heat dry (pre-bake) at 90 ° C. for 2 minutes to form a resin film having a thickness of 2.5 μm. Next, in order to pattern the resin film, a mask capable of forming a line and space pattern having a width varying from 0.5 μm to 5.0 μm every 0.5 μm and a line and space pattern of 10 μm, 25 μm, and 50 μm is used. An exposure process was performed. Next, after developing for 40 seconds at 25 ° C. using a 2.38 wt% tetramethylammonium hydroxide aqueous solution, the substrate was rinsed with ultrapure water for 30 seconds. As a result, a laminate including a resin film on which a plurality of line and space patterns having different widths were formed and a silicon nitride film substrate was obtained.
Then, using an optical microscope, observe the line-and-space formation portion of the resin film of the obtained laminate, and among the line patterns in which line pattern defects were observed, determine the maximum width of the line pattern width. The pattern was missing. When no pattern defect was observed, the pattern defect was judged as “none”. When the pattern chipping is “None”, the pattern processing is possible with an accuracy of 0.5 μm or less, so that the pattern processing is particularly excellent. Even when the pattern chipping occurs, the pattern chipping is small. Since the resin film can be patterned with a finer pattern, it can be judged that the pattern processability is excellent and good.

<Heat resistance>
A radiation sensitive resin composition is applied by spin coating on a silicon nitride film substrate (a substrate in which a 200 nm thick silicon nitride film is formed on a silicon substrate by chemical vapor deposition (CVD)), and hot A plate was used to heat dry (pre-bake) at 90 ° C. for 2 minutes to form a resin film having a thickness of 2.5 μm. Next, in order to pattern the resin film, a mask capable of forming contact hole patterns having different sizes every 0.5 μm from 0.5 μm to 5.0 μm and la contact hole patterns of 10 μm, 25 μm, and 50 μm is formed. And an exposure step was performed. Next, after developing for 40 seconds at 25 ° C. using a 2.38 wt% tetramethylammonium hydroxide aqueous solution, rinsing with ultrapure water for 30 seconds forms contact hole patterns of different sizes. A laminate comprising the resin film and the silicon nitride film substrate was obtained.
And the length (L1) of the longest part of the 5 micrometer square contact hole pattern of the resin film of the obtained laminated body was measured using the optical microscope. The laminate was then heated using an oven at 230 ° C. for 30 minutes in a nitrogen atmosphere. And the laminated body after a heating is observed using an optical microscope, The length (L2) of the longest part of the contact hole pattern observed before a heating is measured, (L2 / L1) x100 (a unit is% ), The heat retention of the resin film was evaluated by calculating the pattern retention after heating. It can be determined that the closer the pattern retention after heating is to 100%, the smaller the change in the contact hole pattern after the heating step, and the better the heat resistance.

<< Synthesis Example 1 >>
8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene 65 parts, N-phenyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide 35 parts, and 1,5-hexadiene 2.8 Parts, (1,3-dimesitylimidazolin-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium chloride 0.05 parts, and ethylene glycol ethyl methyl ether 400 parts were charged into a nitrogen-substituted glass pressure-resistant reactor, The mixture was reacted at 80 ° C. for 2 hours with stirring to obtain a polymerization reaction solution.

  And the obtained polymerization reaction liquid was put into the 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 cyclic olefin type polymer (A1). The resulting cyclic olefin polymer (A1) had a polymerization conversion rate of 99.9%, a weight average molecular weight of 4,430, a number average molecular weight of 2,570, a molecular weight distribution of 1.72, and a hydrogenation rate of 99.99. It was 9%.

<< Synthesis Example 2 >>
8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . Instead of 65 parts ^{17, 10} ] dodec-3-ene and 35 parts N-phenyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide Cyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene 60 parts and N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide 40 parts. In the same manner as in Synthesis Example 1, a polymerization reaction and a hydrogenation reaction were performed to obtain a cyclic olefin polymer (A2). The resulting cyclic olefin polymer (A2) had a polymerization conversion of 99.6%, a weight average molecular weight of 7,180, a number average molecular weight of 4,650, a molecular weight distribution of 1.55, and a hydrogenation rate of 99.99. It was 8%.

<< Synthesis Example 3 >>
A glass reactor in which 100 parts of L-aspartic acid and 120 parts of ethanol were substituted with nitrogen was charged, and 107 parts of thionyl chloride was added dropwise while cooling with ice water and stirring, and then reacted at 80 ° C. The reaction solution was concentrated 3 times using a rotary evaporator, and the obtained concentrated solution, 53.5 parts of pyridine, and 111.2 parts of 5-norbornene-2,3-dicarboxylic acid anhydride were placed in a nitrogen-substituted glass reactor. The reaction was conducted at 170 ° C. for 2 hours with stirring. The reaction solution was concentrated with a rotary evaporator and cooled at −20 ° C. to obtain a precipitate. From the IR spectrum and ¹ H-NMR spectrum, it was confirmed that the precipitate was N- (endo-bicyclo [2.2.1] hept-5-ene-2,3-diyldicarbonyl) ethyl aspartate. The yield was 81%.

And 8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . Instead of 65 parts ^{17, 10} ] dodec-3-ene and 35 parts N-phenyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide Cyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] dodec-3-ene 65 parts, and ethyl N- (endo-bicyclo [2.2.1] hept-5-ene-2,3-diyldicarbonyl) aspartate obtained above Except having used 35 parts, it carried out similarly to the synthesis example 1, and performed the polymerization reaction and the hydrogenation reaction, and obtained the cyclic olefin type polymer (A3). The resulting cyclic olefin polymer (A3) had a polymerization conversion rate of 99.9%, a weight average molecular weight of 4,200, a number average molecular weight of 2,830, a molecular weight distribution of 1.66, and a hydrogenation rate of 99.99. It was 9%.

Example 1
100 parts of the cyclic olefin polymer (A1) obtained in Synthesis Example 1, epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone (trade name “Epolide GT401”) as a crosslinking agent (B) , Daicel Chemical Industries, Ltd., 30 parts of an aliphatic cyclic tetrafunctional epoxy resin), 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3- as the radiation-sensitive compound (C) 30 parts condensate of phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) (trade name “TS200”, manufactured by Toyo Gosei Co., Ltd.), thiol compound (D) 2,4,6-trimercapto-s-triazine as 5 parts, 3 parts of phthalic acid as carboxyl group-containing compound (E), and as solvent By mixing 500 parts of ethylene glycol ethyl methyl ether to obtain a radiation-sensitive resin composition.

  And according to the said method using the obtained radiation sensitive resin composition, each evaluation of the adhesiveness, ITO electrode workability, a pattern chip, and the pattern retention after a heating was performed. The results are shown in Table 1.

Example 2
The same procedure as in Example 1 was conducted except that 100 parts of the cyclic olefin polymer (A2) obtained in Synthesis Example 2 was used instead of 100 parts of the cyclic olefin polymer (A1) obtained in Synthesis Example 1. A radiation sensitive resin composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 3
The same procedure as in Example 1 was conducted except that 100 parts of the cyclic olefin polymer (A3) obtained in Synthesis Example 3 was used instead of 100 parts of the cyclic olefin polymer (A1) obtained in Synthesis Example 1. A radiation sensitive resin composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4
Example 1 except that 5 parts of 2-dibutylamino-4,6-dimercapto-s-triazine was used in place of 5 parts of 2,4,6-trimercapto-s-triazine as the thiol compound (D). In the same manner as above, a radiation sensitive resin composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 5
A radiation-sensitive resin composition was prepared and carried out in the same manner as in Example 1 except that 3 parts of 2-carboxymethylbenzoic acid was used as the carboxyl group-containing compound (E) instead of 3 parts of phthalic acid. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Example 6
As the carboxyl group-containing compound (E), a radiation sensitive resin composition was prepared in the same manner as in Example 1 except that 3 parts of benzoic acid was used instead of 3 parts of phthalic acid. And evaluated. The results are shown in Table 1.

<< Comparative Example 1 >>
A radiation-sensitive resin composition was prepared in the same manner as in Example 1 except that 3 parts of phthalic acid as the carboxyl group-containing compound (E) was not used, and evaluated in the same manner as in Example 1. . The results are shown in Table 1.

<< Comparative Example 2 >>
A radiation sensitive resin composition was prepared in the same manner as in Example 1 except that 5 parts of 2,4,6-trimercapto-s-triazine as the thiol compound (D) was not used. Evaluation was performed in the same manner. The results are shown in Table 1.

<< Comparative Example 2 >>
Except that 5 parts of 2,4,6-trimercapto-s-triazine as the thiol compound (D) and 3 parts of phthalic acid as the carboxyl group-containing compound (E) were not used, the same manner as in Example 1 was performed. A radiation sensitive resin composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

  As shown in Table 1, a radiation-sensitive resin containing a cyclic olefin polymer (A), a crosslinking agent (B), a radiation-sensitive compound (C), a thiol compound (D), and a carboxyl group-containing compound (E) The resin film obtained using the composition has excellent adhesion to various materials (Cu, Mo, SiNx and a-Si), ITO electrode processability, pattern processability (pattern chipping), and heat resistance (pattern after heating). (Retention rate) was excellent (Examples 1 to 6).

  On the other hand, as a radiation-sensitive resin composition, when any one of the nitrogen-containing heterocyclic compound (D) and the carboxyl group-containing compound (E) or a compound that does not contain both is used, In contrast, the adhesion was low, and furthermore, it was inferior to any of ITO electrode processability, pattern processability (pattern chipping), and heat resistance (pattern retention after heating) (Comparative Examples 1 to 3). .

Claims (6)

Cyclic olefin polymer (A) having a protic polar group, crosslinking agent (B), radiation sensitive compound (C), thiol compound (D) represented by the following general formula (1), and carboxyl group-containing compound A radiation-sensitive resin composition comprising (E).

(In the formula (1), X ^{1 to} X ³ are each independently —SH, —SR, —NR′R ″ or —SM (R, R ′ and R ″ are each independently carbon number) 1-5 linear or branched alkyl groups, and M is an alkali metal.), At least one of which is —SH. The radiation sensitive resin composition according to claim 1, wherein at least two of X ^{1 to} X ^{3 in} the general formula (1) are —SH.   The radiation-sensitive resin composition according to claim 1 or 2, wherein the thiol compound (D) is 2,4,6-trimercapto-s-triazine.   The radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the carboxyl group-containing compound (E) has an acid dissociation constant pKa of 2.5 or more and 4.5 or less.   The radiation sensitive resin composition according to any one of claims 1 to 4, wherein the carboxyl group-containing compound (E) has at least two carboxyl groups.   The laminated body which has a resin film formed using the radiation sensitive resin composition in any one of Claims 1-5, and a board | substrate.