TWI494345B - A polymer, a hydrogen additive, a resin composition, a resin film, and an electronic component - Google Patents

Description

Polymer, hydrogen additive, resin composition, resin film, and electronic component

The present invention relates to a polymer, a hydrogen additive of the polymer, a resin composition containing the polymer and/or the hydrogen additive, a resin film formed of the resin composition, and an electronic component having the resin film. In particular, the present invention relates to a polymer having high solubility to a polar solvent, low water absorbability, and high adhesion to a substrate; a hydrogen additive of the polymer; using the above polymer and/or the above hydrogen additive a resin composition; a resin film formed of the resin composition; and an electronic component having the resin film.

In recent years, a polymer of a cyclic olefin having a functional group and a hydrogen additive thereof have been attracting attention as polymers containing a functional group excellent in heat resistance, electrical properties, and low water absorbability. Further, the polymer is excellent in adhesion to an inorganic material such as metal or glass, and is compatible with organic materials such as an antioxidant, a plasticizer, an ultraviolet absorber, a colorant, a hardener, and a flame retardant. Excellent, and is expected to be widely used in composite applications.

For example, Patent Document 1 discloses a ring-opening polymer of a cycloolefin having a spiro ring of an N-substituted cyclic quinone imine structure and a hydrogen additive thereof. It is revealed that the polymer and the hydrogen additive are excellent in heat resistance and electrical properties.

Further, Patent Document 2 discloses an addition polymer, a ring-opening polymer, and a hydrogen additive thereof, which have a cyclic olefin having an N-substituted cyclic quinone imine structure having a carboxylic acid ester in a substituent. It is revealed that the polymer and its hydrogen additive are excellent in heat resistance, solubility in a polar solvent, and adhesion to an inorganic substrate.

Further, Patent Document 3 discloses a cycloolefin polymer having a structure of an N-alkyl group, an N-cycloalkyl group or an N-aryl group, and a hydrogen additive thereof. It is revealed that the polymer and hydrogen additive exhibit high thermal oxidation stability.

However, the polymer specifically disclosed in the above Patent Documents 1 to 3 or a hydrogen additive thereof is particularly widely used for a resin composition containing a bridging agent or a radiation-sensitive compound, and the like, and propylene glycol monomethyl ether acetate (PGMEA). Among the various solvents represented by methyl isobutyl ketone (MIBK), etc., there is a problem that it is insoluble in a highly volatile polar solvent such as MIBK used as a cleaning solvent for a resin composition, and is limited. Its use. Moreover, it is necessary to further improve water absorption or adhesion depending on the use.

Prior technical literature

[Patent Document 1] JP-A-2003-301032 (Patent Document 1) JP-A-2008-222935

[Patent Document 1] Japanese Patent Laid-Open No. 4-300917

The present invention is in such a case as to provide a cycloolefin polymer excellent in solubility to a polar solvent, solubility to a polar solvent, and adhesion to a substrate, and a hydrogen additive thereof; the polymer is provided and/or has the hydrogen A resin composition of an additive; a resin film formed of the resin composition and an electronic component having the resin film are provided for the purpose.

The present inventors have found a cyclic olefin having a structure in which a cyclic quinone imine skeleton having a specific structure of a substituent on a nitrogen atom and a cyclic olefin has one carbon-carbon bond in a polymerization unit for the purpose of achieving the above object. The polymer and its hydrogen additive are excellent in low water absorbability, solubility in a polar solvent, and adhesion to a substrate, and the present invention has been completed based on these findings.

Accordingly, the present invention provides a polymer comprising a polymerization unit of a monomer represented by the general formula (1):

[Chemical 1]

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

In the polymer of the present invention, in addition to the polymerization unit of the monomer represented by the above formula (1), a polymer having a polymerization unit copolymerizable therewith is preferred. Further, in the polymer of the present invention, the copolymerizable monomer is preferably a cycloolefin monomer having a protic polar group, and more preferably a carboxyl group-containing cycloolefin monomer.

In the polymer of the present invention, the polymer is preferably a ring-opening polymer.

Further, the present invention provides a hydrogen additive of the above-mentioned ring-opening polymer.

Moreover, the present invention provides a resin composition comprising a polymer comprising a polymerization unit of a monomer represented by the formula (1) and/or a hydrogen additive (A) thereof and a solvent (B).

Moreover, the present invention provides a resin composition comprising: a polymer comprising a polymerization unit of a monomer represented by the formula (1) and/or a hydrogen additive (A) thereof, a solvent (B), and Bridging agent (C).

Moreover, the present invention provides a resin composition comprising: a polymer comprising a polymerization unit of a monomer represented by the formula (1) and/or a hydrogen additive (A) thereof, a solvent (B), and Radiation sensitive compound (D).

Moreover, the present invention provides a resin composition comprising: a polymer comprising a polymerization unit of a monomer represented by the formula (1) and/or a hydrogen additive (A) thereof, a solvent (B), and a bridge The agent (C) and the radiation sensitive compound (D).

Moreover, the present invention provides a resin film formed using the above resin composition.

Moreover, the present invention provides an electronic component comprising the above resin film.

According to the present invention, a polymer excellent in solubility in a polar solvent, having low water absorbability and high adhesion; a hydrogen additive of the polymer; a resin composition having the polymer and/or the hydrogen additive; a resin film formed of the resin composition; and an electronic component having the resin film. Further, the polymer and the hydrogen additive of the present invention have high reliability with various characteristics as described above, and are excellent in various electrical characteristics (for example, low dielectric properties, low leakage characteristics, high insulation breakdown voltage characteristics), and high transparency. Since the pattern formation property by development is excellent, it can be suitably used for a resin such as a resist, an electrical insulating film for semiconductor manufacturing, and a transparent film of a display element.

The polymer of the present invention is a polymer comprising a polymerization unit of a monomer represented by the following formula (1).

[Chemical 2]

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

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

The monomer represented by the above formula (1) can be easily produced. That is, the monomer represented by the formula (1) can be obtained by amidation reaction of the corresponding amine with 5-norbornene-2,3-dicarboxylic anhydride. The monomer represented by the above formula (1) can be effectively isolated by separating the reaction solution of the above amidoximation reaction by a conventional method.

(polymer)

The polymer of the present invention contains a polymer of a polymerization unit of a monomer represented by the above formula (1). The polymer of the present invention may be a ring-opening polymer or an addition polymer, but has electrical characteristics represented by heat resistance, low dielectric constant characteristics, low leakage current characteristics, and high insulation breakdown voltage characteristics. As a result of excellent water absorption and the like, a ring-opening polymer is preferred.

Further, the polymer of the present invention may be a monomer represented by the above formula (1) and copolymerized with a monomer copolymerizable therewith. The above copolymerizable monomer can be appropriately selected depending on the use of the polymer.

In the total monomer used to obtain the above polymer, the ratio of the monomer represented by the formula (1) can be arbitrarily selected according to the purpose of production of the polymer, but considering heat resistance, low dielectric constant, and low leakage current. The balance of electrical characteristics, low water absorption, high adhesion, and compatibility with various materials represented by high insulation breakdown voltage is preferably 5 to 90 m, and more preferably 10 to 80 mol%.

The weight average molecular weight of the polymer of the present invention can be arbitrarily selected in accordance with the purpose of production of the polymer, and is usually 1,000 to 1,000,000, preferably 1,500 to 500,000, more preferably 2,000 to 50,000. The weight average molecular weight (Mw) of the above polymer is a value obtained by a gel permeation chromatography (GPC) in terms of polystyrene. When the Mw of the polymer is in the above range, heat resistance and solubility in a polar solvent can be further improved.

The polymer of the present invention may be obtained by (i) polymerizing one monomer represented by the above formula (1) alone; (ii) two or more monomers represented by the above formula (1). (iii) one obtained by copolymerizing at least one of the monomers represented by the above formula (1) with at least one of any other monomer copolymerizable therewith.

Examples of the other monomer which can be copolymerized include a cycloolefin monomer having a protic polar group (a) and a ring having a polar group other than the protic polar group of the monomer represented by the above formula (1). Olefin monomer (b); cycloolefin monomer (c) having no polar group; and monomer (d) other than cycloolefin (hereinafter referred to as monomers (a) to (d) ). Here, the monomer (d) may have a protic polar group or a polar group other than the polar group, or may have no polar group at all.

In the present invention, the polymer obtained by polymerizing the monomer represented by the above formula (1) is excellent in heat resistance and adhesion, and preferably has a protic polar group to copolymerize the above formula (1). The monomer shown is preferably a monomer having a protic polar group and a monomer (a). Further, a polymer having a protic polar group formed by copolymerizing a monomer represented by the above formula (1) and a monomer (a) may be used, and may be, for example, a monomer (b) to (d). And other polymers obtained by copolymerization of other monomers.

Specific examples of the monomer represented by the formula (1) include N-(1-methylbutyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylhydrazine. Amine, N-(2-methylbutyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, N-(1-methylpentyl)-bicyclo[2.2 .1]hept-5-alkenyl-2,3-dimethylimine, N-(2-methylpentyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethyl Yttrium, N-(1-ethylbutyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, N-(2-ethylbutyl)-bicyclo [2.2.1]hept-5-alkenyl-2,3-dimethylimine, N-(1-methylhexyl)-bicyclo[2.2.1]hept-5-enyl-2,3-di Formamidine, N-(2-methylhexyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, N-(3-methylhexyl)-bicyclo[ 2.2.1]hept-5-alkenyl-2,3-dimethylimine, N-(1-butylpentyl)-bicyclo[2.2.1]hept-5-enyl-2,3-di Formamidine, N-(2-butylpentyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, N-(1-methylheptyl)- Bicyclo[2.2.1]hept-5-alkenyl-2,3-carboximine, N-(2-methylheptyl)-bicyclo[2.2.1]hept-5-enyl-2,3 -dimethylimine, N-(3-methylheptyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, N-(4-methyl Heptyl)-bicyclo[2.2.1]hept-5-alkenyl-2,3-dimethylimine, N-(1-ethylhexyl)-bicyclo[2.2.1]hept-5-enyl- 2,3-dimethylimine, N-(2-ethylhexyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, N-(3-ethyl Hexyl)-bicyclo[2.2.1]hept-5-alkenyl-2,3-dimethylimine, N-(1-propylpentyl)-bicyclo[2.2.1]hept-5-enyl- 2,3-dimethylimine, N-(2-propylpentyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, N-(1-A Benzyl)-bicyclo[2.2.1]hept-5-alkenyl-2,3-carboximine, N-(2-methyloctyl)-bicyclo[2.2.1]hept-5-ene Base-2,3-dimethylimine, N-(3-methyloctyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, N-(4 -methyloctyl)-bicyclo[2.2.1]hept-5-alkenyl-2,3-dimethylimine, N-(1-ethylheptyl)-bicyclo[2.2.1]hept-5 -alkenyl-2,3-dimethylimine, N-(2-ethylheptyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, N- (3-ethylheptyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, N-(4-ethylheptyl)-bicyclo[2.2.1]g -5-alkenyl-2,3-dimethylimine, N-(1-propylhexyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, N -(2- Cyclohexyl)-bicyclo[2.2.1]hept-5-alkenyl-2,3-carboximine, N-(3-propylhexyl)-bicyclo[2.2.1]hept-5-enyl- 2,3-dimethylimine, N-(1-methylindenyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, N-(2-A Bismuthyl)-bicyclo[2.2.1]hept-5-alkenyl-2,3-dimethylimine, N-(3-methylindenyl)-bicyclo[2.2.1]hept-5-ene Base-2,3-dimethylimine, N-(4-methylindolyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, N-(5 -methylindenyl)-bicyclo[2.2.1]hept-5-alkenyl-2,3-dimethylimine, N-(1-ethyloctyl)-bicyclo[2.2.1]hept-5 -alkenyl-2,3-dimethylimine, N-(2-ethyloctyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, N- (3-ethyloctyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, N-(4-ethyloctyl)-bicyclo[2.2.1]g -5-alkenyl-2,3-dimethylimine, N-(1-methylindenyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, N-(1-methyldodecyl)-bicyclo[2.2.1]hept-5-enyl-2,3-carboximine, N-(1-methylundecyl)-bicyclo[2.2 .1]hept-5-alkenyl-2,3-dimethylimine, N-(1-methyldodecyto)-bicyclo[2.2.1]hept-5-enyl-2,3-di Hyperthyroidism Amine, N-(1-methyltridecyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, N-(1-methyltetradecyl)-bicyclo [2.2.1]hept-5-alkenyl-2,3-dimethylimine, N-(1-methylpentadecyl)-bicyclo[2.2.1]hept-5-enyl-2,3 - Dimethyl imine and the like. Further, these may be used alone or in combination of two or more.

The polymer of the present invention, in the case of a polymer having a protic polar group, a protonic polar group means a group in which a hydrogen atom is directly bonded to an atom belonging to Group 15 or Group 16 of the periodic table. An atom belonging to Group 15 or Group 16 of the periodic table, preferably having an oxygen atom, a nitrogen atom or a sulfur atom, in the first cycle or the second cycle of an atom belonging to Group 15 or Group 16 of the periodic table, particularly It is preferably an oxygen atom.

Specific examples of the protic polar group include a polar group having an oxygen atom such as a hydroxyl group, a carboxyl group (hydroxycarbonyl group), a sulfonic acid group or a phosphoric acid group; a primary amino group, a secondary amino group, a primary amidino group, and a second stage; A polar group having a nitrogen atom such as a mercapto group (eneimine group); a polar group having a sulfur atom such as a thiol group; Among these, those having an oxygen atom are preferred, and those having a carboxyl group are more preferred.

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

Specific examples of the cyclic olefin monomer (a) having a protic polar group include 5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene and 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 ]dodeca-4 - alkene, 9-methyl-9-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9,10-dihydroxycarbonyltetracyclo[6.2.1.1 ^{3, 6} .0 ^2,7 ]dodecyl-4-ene and the like having a carboxyl cyclic olefin; 5-(4-hydroxyphenyl)bicyclo[2.2.1]hept-2-ene, 5-methyl-5-( 4-hydroxyphenyl)bicyclo[2.2.1]hept-2-ene, 9-(4-hydroxyphenyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-Methyl-9-(4-hydroxyphenyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodecyl-4-ene and other cyclic olefins containing hydroxyl groups, etc., in order to improve the substrate and density It is preferred to use a cyclic olefin having a carboxyl group. The cyclic olefin monomer (a) having such a protic polar group may be used alone or in combination of two or more.

Specific examples of the cyclic olefin (b) having a polar group other than the protonic polar group, other than the monomer represented by the formula (1), may be an ester group and a monomer other than the formula (1). A cyclic olefin of an N-substituted quinone imine group, a cyano group or a halogen atom.

The cyclic olefin having an ester group may, for example, be 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 ]dodecyl-4-ene, 9-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[6.2.1.1 ^3,6 .0 ^{2, 7} ] Dodec-4-ene, 9-A Base-9-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene.

In addition to the monomer represented by the formula (1), a cyclic olefin having an N-substituted quinone imine may, for example, be N-phenylbicyclo[2.2.1]hept-5-ene-2,3-dimethyl Yttrium imine, N-(intra-bicyclo[2.2.1]hept-5-ene-2,3-diyldicarbonyl)methyl aspartate, and the like.

The cyclic olefin having a cyano group may, for example, be a 9-cyanotetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene or a 9-methyl-9-cyanotetracyclic ring. [6.2.1.1 ^3,6 .0 ^2,7 ]Dodecy-4-ene, 5-cyanobicyclo[2.2.1]hept-2-ene, and the like.

The cycloolefin having a halogen atom may, for example, be 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 ] ^Dodecene -4-ene, etc.

The cycloolefin monomer (b) having a polar group other than the protonic polar group other than the monomer represented by the formula (1) may be used alone or in combination of two or more.

Specific examples of the monomer (c) having a cyclic olefin having no polar group include bicyclo [2.2.1] hept-2-ene (also referred to as "norbornene"), 5-ethyl-bicyclo [ 2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1]hept-2-ene, 5-methylene -bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-1-ene, tricyclo[5.2.1.0 ^2,5 ]indole-3,8-diene (common name : dicyclopentadiene), tetracyclo[10.2.1.0 ^2,11 .0 ^4,9 ]tetradecyl-4,6,8,13-tetraene, tetracyclo[6.2.1.1 ^3,6 .0 ^{2 , 7} ] dodec-4-ene (also known as "tetracyclododecene".), 9-methyl-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]12-carbon-4- Alkene, 9-ethyl-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-methylene-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] dodec-4-ene, 9-ethylene-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 ] fifteen carbon-5,12-diene, cyclopentene, cyclopentadiene, 9-phenyl-tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] two-4-ene, tetracyclo [9.2.1.0 ^2,10 .0 ^3,8] Four-carbon -3,5,7,12- tetraene, pentacyclo [9.2.1.1 ^3,9 .0 ^2,10] pentadec-12-en and the like.

These cycloolefin monomers (c) having no polar group may be used alone or in combination of two or more.

Specific examples of the monomer (d) other than the cyclic olefin include ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, and 3-methyl- 1-pentene, 3-vinyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4, 4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-ten a 2 to 20 carbon atoms of tetraene, 1-hexadecene, 1-octadecene, 1-eicosene, etc.; 1,4-hexadiene, 4-methyl-1,4-hexanyl Non-conjugated dienes such as dienes, 5-methyl-1,4-hexadiene, 1,7-octadiene, and the like; and cyclobutene, cyclopentene, cyclohexene, a cycloolefin such as cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methylene-1H-indole or the like. Among these, α-olefins, particularly ethylene, are preferred.

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

Further, a method for obtaining a polymer having a protic polar group of the present invention is a method in which a polymer having no protic polar group is introduced into a protonic polar group by a known denaturing agent, and hydrogenation is carried out according to a desired method. . Further, when a protonic polar group is introduced by a denaturing agent, hydrogenation can also be carried out on the polymer before introduction of the protic polar group. Further, the protonic polar group may be further introduced by further denaturation of the polymer having a protic polar group.

The polymer having no protic polar group can be obtained by copolymerizing a monomer represented by the formula (1) and any combination of the above monomers (b) to (d).

A denaturing agent which introduces a protic polar group is usually used for a compound having a protonic polar group and a reactive carbon-carbon unsaturated bond in one molecule.

Specific examples of such a compound include acrylic acid, methacrylic acid, angelic acid, cis citric acid, oleic acid, elaidic acid, sinapic acid, basic acid, maleic acid, fumaric acid, citraconic acid, and the like. Unsaturated carboxylic acid such as benic acid, itaconic acid, belladonic acid, cinnamic acid; allyl alcohol, methyl vinyl methanol, crotyl alcohol, methacrylol, 1-phenylvinyl-1-ol, 2-propene -1-ol, 3-buten-1-ol, 3-buten-2-ol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol , 2-methyl-3-buten-2-ol, 2-methyl-3-buten-1-ol, 4-penten-1-ol, 4-methyl-4-pentene-1- An unsaturated alcohol such as an alcohol or 2-hexen-1-ol.

The denaturation reaction of the polymer using the denaturant can be carried out in accordance with a usual method, usually in the presence of a radical generator.

Next, the polymer of the present invention is classified into a ring-opening polymerization, and the case of the addition polymer.

(open-loop polymer and its manufacturing method)

The ring-opening polymer can be produced by ring-opening disproportionation polymerization of at least one of the monomers represented by the above formula (1) and a copolymerizable monomer used as required in the presence of a disproportionation reaction catalyst. .

The metathesis catalyst may be a transition metal compound of Groups 3 to 11 of the periodic table, as long as it is a catalyst capable of disproportionating polymerization of the polymerization unit represented by the above formula (1). For example, a disproportionation reaction catalyst can be used as described in Olefin Metathesis and Metathesis Polymerization (K. J. Ivln and J. C. Mol. Academic Press, San Diego 1997).

The disproportionation reaction catalyst may, for example, be a transition metal-carbene complex catalyst of Groups 3 to 11 of the periodic table. Among these, a ruthenium carbene complex catalyst is preferably used.

The transition metal-carbene complex catalyst of Groups 3 to 11 of the above periodic table may, for example, be a tungsten alkylene complex catalyst, a molybdenum alkylene complex catalyst, or a fluorinated alkylene complex. Catalyst, 钌alkylene complex catalyst, etc.

Specific examples of the above tungsten alkylene complex catalyst include W(N-2,6-Pr ⁱ ₂ C ₆ H ₃ )(CHBu ^t )(OBu ^t ) ₂ , W(N-2,6- Pr ⁱ ₂ C ₆ H ₃ )(CHBu ^t )(OCMe ₂ CF ₃ ) ₂ , W(N-2,6-Pr ⁱ ₂ C ₆ H ₃ )(CHBu ^t )(OCMe(CF ₃ ) ₂ ) ₂ , W(N-2,6-Pr ⁱ ₂ C ₆ H ₃ )(CHCMe ₂ Ph)(OBu ^t ) ₂ , W(N-2,6-Pr ⁱ ₂ C ₆ H ₃ )(CHCMe ₂ Ph)(OCMe ₂ CF ₃ ) ₂ , W(N-2,6-Pr ⁱ ₂ C ₆ H ₃ )(CHCMe ₂ Ph)(OCMe(CF ₃ ) ₂ ) ₂ or the like.

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

Specific examples of the fluorene alkylene complex catalyst include Re(CBu ^t )(CHBu ^t )(O-2,6-Pr ⁱ ₂ C ₆ H ₃ ) ₂ and Re(CBu ^t )(CHBu ^t ). (O-2-Bu ^t C ₅ H ₄ ) ₂ , Re(CBu ^t )(CHBu ^t )(OCMe ₂ CF ₃ ) ₂ , Re(CBu ^t )(CHBu ^t )(OCMe(CF ₃ ) ₂ ) ₂ , Re(CBu ^t )(CHBu ^t )(O-2,6-Me ₂ C ₆ H ₃ ) ₂ or the like.

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

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

[Chemical 3]

[Chemical 4]

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

Here, the carbene compound containing a hetero atom means a compound containing a carbene carbon and a hetero atom. Both of L ₁ and L ₂ or L ₁ are a carbene compound containing a hetero atom, and the carbene-containing carbon system is directly bonded to a ruthenium metal atom and bonded to a group containing a hetero atom.

L ₃ and L ₄ each independently represent an arbitrary anionic ligand. Further, two, three, four, five or six of R ₃ , R ₄ , L ₁ , L ₂ , L ₃ and L ₄ may be bonded to each other to form a multidentate chelating ligand. Further, specific examples of the hetero atom include N, O, P, S, As, and Se atoms. Among these, from the viewpoint of a stable carbene compound, N, O, P, S atoms and the like are preferred, and N atoms are particularly preferred.

In the above formula (2) and formula (3), the anionic ligands L ₃ and L ₄ have a negative charge when they are opened by a central atom, and examples thereof include a fluorine atom, a chlorine atom, and a bromine atom. And a halogen atom such as an iodine atom; an oxygen-containing hydrocarbon group such as a diketone group, an alkoxy group, an aryloxy group or a carboxyl group; an alicyclic hydrocarbon group substituted with a halogen atom such as a chlorocyclopentadienyl group; and the like. Among these, a halogen atom is preferred, and a chlorine atom is more preferred.

When L ₂ is a central electron supply compound, L ₂ may be any ligand having a neutral charge when the central atom is pulled apart. Specific examples thereof include carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, and thiocyanides. Among these, a phosphine or a pyridine is preferred, and a trialkylphosphine is more preferred.

The ruthenium complex catalyst represented by the above formula (2) may, for example, be benzylidene (1,3-bistrimethylimidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride. (1,3-bistrimethylimidazolin-2-ylidene)(3-methyl-2-butene-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene ( 1,3-bistrimethylphenyl-octahydrobenzimidazole-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-bis(1-phenylethyl)-4 -imidazolin-2-ylidene](tricyclohexylphosphine)phosphonium dichloride, benzylidene (1,3-dimethyl-2,3-dihydrobenzimidazole-2-ylidene) (tricyclic) Hexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole- 5-subunit) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene a ruthenium carbene complex of a hetero atom-containing carbene compound (1,3-1,3-trimethylidazolin-2-yl)pyridinium dichloride or the like and a neutral electron-donating compound; Benzyl bis(1,3-dicyclohexyl imidazolin-2-ylidene) ruthenium dichloride, benzylidene bis(1,3-diisopropyl-4-imidazolin-2-ylidene)dichloride Contains Carbon atoms 2 heteroatoms bonded alkenyl compound of ruthenium carbene complexes and the like.

The ruthenium carbene complex catalyst represented by the above formula (3) may, for example, be (1,3-bistrimethylimidazolidin-2-ylidene)(phenylvinylene) (tricyclohexylphosphine) ) ruthenium dichloride, (t-butylvinylidene) (1,3-diisopropyl-4-imidazolin-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, double (1 , 3-dicyclohexyl-4-imidazolin-2-ylidene)phenylvinylidene dichloride or the like.

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

The ring-opening polymerization using a disproportionation reaction catalyst can be carried out in a solvent or without a solvent. After the completion of the polymerization reaction, in the case where the produced polymer is not isolated and the hydrogenation reaction is carried out directly, polymerization in a solvent is preferred.

The solvent to be used is not particularly limited as long as it is a solvent which can dissolve the produced polymer and does not inhibit the polymerization reaction. The solvent to be used may, for example, be an aliphatic hydrocarbon such as n-pentane, n-hexane or n-heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane or trimethylcyclohexane. , alicyclic hydrocarbons such as ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydroindole, cyclooctane, etc.; benzene, toluene, xylene, trimethylbenzene, etc. Aromatic hydrocarbon; nitrogen-containing hydrocarbon such as nitromethane, nitrobenzene, acetonitrile, propionitrile, benzonitrile; ethers such as diethyl ether, tetrahydrofuran, dioxane; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentane Ketones such as ketone and cyclohexanone; esters of methyl acetate, ethyl acetate, ethyl propionate, methyl benzoate, etc.; chloroform, dichloromethane, 1,2-dichloroethane, chlorinated benzene a halogenated hydrocarbon such as dichlorobenzene or trichlorobenzene. Among these, aromatic hydrocarbons, alicyclic hydrocarbons, ethers, ketones or esters are preferred.

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

The disproportionation reaction catalyst is soluble in the solvent and added to the reaction system, or may be added directly without being dissolved. The solvent for modulating the catalyst solution may, for example, be the same solvent as the solvent used in the above polymerization.

Further, in the polymerization reaction, in order to adjust the molecular weight of the polymer, a molecular weight modifier may be added to the reaction system. As the molecular weight modifier, an α-olefin such as 1-butene, 1-pentene, 1-hexene or 1-octene; a styrene such as styrene or vinyl toluene; ethyl vinyl ether or the like can be used. An ether such as butyl vinyl ether or propylene glycidyl ether; a halogen-containing vinyl compound such as acrylonitrile chloride; an oxyethylene compound such as allyl acetate, allyl alcohol or glycidyl methacrylate; A nitrogen-containing vinyl compound such as a nitrile or acrylamide. By using a 0.05 to 50 mol% molecular weight modifier for the monomer composition containing the polymerization unit represented by the above formula (1), a polymer having a desired molecular weight can be obtained.

The polymerization temperature is not particularly limited, but is usually -100 ° C to +200 ° C, preferably -50 ° C to +180 ° C, 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.

(Addition polymer and its manufacturing method)

On the other hand, the addition polymer can be polymerized by using a conventional addition polymerization catalyst, at least one of the monomers represented by the above formula (1), and a copolymerizable monomer which is used as needed. Thus, the conventional addition polymerization catalyst, for example, a catalyst composed of a titanium, zirconium or palladium 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 in the range of 1:100 to 1:2,000,000 in the molar ratio of the metal compound:monomer in the polymerization catalyst.

(Hydrogen additive and its manufacturing method)

The hydrogen additive of the present invention is obtained by adding hydrogen to a carbon-carbon double bond of a main chain of the ring-opening polymer of the present invention. In the hydrogen additive of the present invention, the ratio of hydrogenated carbon-carbon double bonds (hydrogen addition rate) is usually 50% or more, and from the viewpoint of heat resistance, 70% or more is preferable, and 90% or more is more preferable. More preferably 95% or more.

The hydrogen addition rate of the hydrogen additive can be, for example, from the carbon intensity in the ¹ H-NMR spectrum of the hydrogen additive by comparing the peak intensity from the carbon-carbon double bond in the ¹ H-NMR spectrum of the ring-opening polymer. The peak intensity of the carbon double bond is obtained.

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

The hydrogenation catalyst to be used may be a homogeneous catalyst or a heterogeneous catalyst, and is not particularly limited, and those which are generally used for hydrogenation of an olefin compound can be suitably used.

The homogeneous catalyst may, for example, be cobalt acetate and triethyl aluminum, acetonitrile pyruvate and triisobutyl aluminum, a combination of dichlorotitanium and n-butyl aluminum, zirconocene dichloride and the first a Ziegler-type catalyst composed of a combination of a transition metal compound such as dibutyllithium, tetrabutoxytitanium and dimethylmagnesium and an alkali metal compound; as described in the above-mentioned part of the ring-opening disproportionation reaction catalyst Carbene complex catalyst, tris(triphenylphosphine) antimony dichloride, Japanese special open flat 7-2929, Japanese special open flat 7-149823, Japanese special open flat 11-109460, Japanese special open flat 11-158256, Japan special open flat A noble metal complex catalyst composed of a ruthenium compound described in JP-A-H11-109460, and the like.

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

Among these, a noble metal complex such as ruthenium or osmium is used in view of side reactions such as denaturation of a functional group in a ring-opening polymer and selective hydrogenation of a carbon-carbon double bond in the polymer. It is preferred that the catalyst and the palladium/carbon-based palladium act as a catalyst, and it is more preferable to use a ruthenium carbene complex catalyst or a palladium-supporting catalyst.

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

Further, when the ring-opening disproportionation reaction and the hydrogenation reaction are continuously carried out 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. In view of catalyst activation, a method of starting a hydrogenation reaction can also be preferably employed. Further, a method of increasing the activity by adding a base such as triethylamine or N,N-dimethylacetamide may be suitably employed.

The hydrogenation reaction is usually carried out in an organic solvent. The organic solvent can be appropriately selected depending on the solubility of the produced hydride, and the same organic solvent as the above-mentioned polymerization solvent can be used. Therefore, after the polymerization reaction, the solvent may be exchanged, and the reaction liquid or the filtrate obtained by filtering the disproportionation reaction catalyst from the reaction liquid may be reacted by adding a hydrogenation catalyst.

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

The time of the hydrogenation reaction is suitably selected to control the hydrogen addition rate. The reaction time is usually in the range of 0.1 to 50 hours, and 50% or more of the carbon-carbon double bonds of the main chain in the polymer may be hydrogenated, preferably 70% or more, more preferably 90% or more, and most preferably above 95.

The polymer and the hydrogen additive of the present invention obtained as described above are excellent in electrical properties such as heat resistance, low dielectric constant characteristics, low leakage current characteristics, high insulation breakdown voltage characteristics, low water absorption and adhesion, and reliability. It is high, has high transparency, and is excellent in pattern formation property in development. Therefore, the polymer and the hydrogen additive of the present invention can be suitably used for heat-resistant optical elements such as plastic lenses, spherical lenses, aspherical lenses, photocopier lenses, camera conversion lenses, optical disk sampling lenses, and vehicle component lenses. Material; material for optical semiconductor sealing, material for semiconductor underlayer, material for semiconductor protective film, material for liquid crystal sealing, circuit substrate material, material for circuit protection, material for planarization film, material for electrical insulating film, etc. The purpose of the use.

(resin composition)

The resin composition of the present invention comprises a polymer obtained by polymerizing a monomer represented by the above formula (1) and/or a hydrogen additive (A) thereof (hereinafter simply referred to as "polymer (A)"; and a solvent (B).

The solvent (B) to be used in the present invention is not particularly limited as long as it can dissolve the components contained in the resin composition well, and examples thereof include methanol, ethanol, propanol, butanol, and 3-methoxy group. Alcohols such as -3-methyl-butanol; cyclic ethers such as tetrahydrofuran and dioxane; and solubilized esters such as methyl cellosolve and ethyl cellosolve; ethylene glycol monoethyl ether and ethylene Glycol ethers such as alcohol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol ethyl methyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate (PGMEA); benzene, toluene, xylene Aromatic hydrocarbons; ketones such as methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone; ethyl 2-hydroxypropionate, 2-hydroxyl Ethyl 2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, methyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3- Ester of methyl methoxypropionate, methyl 3-ethoxypropionate, ethyl acetate, butyl acetate, ethyl lactate, etc.; N-methylformamide, N,N-dimethylmethyl Indoleamine, N-methyl-2-pyrrolidone, N-methylacetamide, N,N-dimethylacetamidine An aprotic polar solvent such as an amine, dimethyl hydrazine or γ-butyrolactone.

Among them, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate (PGMEA), cyclopentanone, N-methyl-2-pyrrolidone is preferred, diethylene glycol ethyl methyl ether, propylene glycol Monomethyl ether acetate (PGMEA) is more preferred, and diethylene glycol ethyl methyl ether is particularly preferred.

These solvents (B) may be used alone or in combination of two or more. The content of the solvent (B) of the resin composition of the present invention is usually 20 to 10,000 parts by weight, preferably 50 to 5,000 parts by weight, and 100 to 1,000 parts by weight, based on 100 parts by weight of the polymer (A). Better.

Further, the resin composition of the present invention preferably further contains a bridging agent (C). The bridging agent (C) may be a bridging structure formed by heating between the bridging agent molecules or a bridging structure formed by reacting with the polymer (A) to form a bridging structure. Specifically, it has a reactive group of 2 or more. Compound.

The reactive group may, for example, be an amine group, a carboxyl group, a hydroxyl group, an epoxy group or an isocyanate group, preferably an amine group, a carboxyl group or an isocyanate group, and more preferably an epoxy group. The epoxy group is preferably a terminal epoxy group or an alicyclic epoxy group, and more preferably an alicyclic epoxy group.

The molecular weight of the bridging agent (C) is not particularly limited and is usually from 100 to 100,000, preferably from 300 to 50,000, more preferably from 500 to 10,000.

Specific examples of the bridging agent (C) include aliphatic polyamines such as hexamethylenediamine and aromatics such as 4,4'-diaminodiphenyl ether and diaminodiphenyl hydrazine. Polyamines; azides of 2,6-bis((4'-azidobenzylidene)cyclohexanone, 4,4'-diazidediphenylfluorene; nylon, polyhexamethylene a polyamine such as an amine terephthalamide or polyhexamethylene metaxylamine; N, N, N', N', N", N"-(hexaalkyloxyalkyl) melamine Such as melamine which may have a methylol group or an imine group (trade name "CYMEL303, CYMEL325, CYMEL370, CYMEL232, CYMEL235, CYMEL272, CYMEL212, MYCOAT506" {above, CYTEC Industries, etc., CYMEL series, MYCOAT series); Glycolides such as N, N', N", N"'-(tetraalkoxyalkyl) glycoluril which may have a methylol group or an imine group (trade name "CYMEL1170" {above, CYTEC Industries, Inc. CYMEL series; acrylate compounds such as ethylene glycol di(meth)acrylate; hexamethylene diisocyanate polyisocyanate, isophorone diisocyanate polyisocyanate, toluene diisocyanate polyiso Isocyanate compound such as cyanate ester or hydrogenated diphenylmethane diisocyanate; 1,4-bis-(hydroxymethyl)cyclohexane, 1,4-bis-(hydroxymethyl)norbornane; 1,3 , 4-trihydroxycyclohexane, bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic epoxy resin, cresol novolac epoxy resin, polyphenol epoxy resin, cyclic aliphatic ring An epoxy compound such as an oxygen resin, an aliphatic glycidyl ether or an epoxy acrylate polymer.

Specific examples of the epoxy compound include a trifunctional epoxy compound having a structure of dicyclopentadiene (trade name "XD-1000", manufactured by Nippon Kayaku Co., Ltd.), and 2,2-bis(hydroxymethyl group). 1,2-epoxy-4-(2-oxocyclopentyl)cyclohexane adduct of 1-butanol (15-functional alicyclic ring having a cyclohexane skeleton and a terminal epoxy group) Oxygen resin. Trade name "EHPE3150", manufactured by Daicel Chemical Industry Co., Ltd.), epoxidized 3-cyclohexene-1,2-dicarboxylic acid bis(3-cyclohexenylmethyl) modified ε-caprolactone (fat Acyclic trifunctional epoxy resin, trade name "EPOLEAD GT301", manufactured by Daicel Chemical Industry Co., Ltd.), epoxidized butane tetracarboxylic acid tetrakis(3-cyclohexenemethyl) modified caprolactone (aliphatic ring) 4-functional epoxy resin, trade name "EPOLEAD GT401", manufactured by Daicel Chemical Industry Co., Ltd., etc., epoxy compound having an alicyclic structure; aromatic amine type polyfunctional epoxy compound (trade name "H-434", Dongdu Chemical resin company, cresol type polyfunctional epoxy compound (trade name "EOCN-1020", manufactured by Nippon Kasei Co., Ltd.), phenolic polyfunctional epoxy compound (EPICOAT 152, 154, Japanese epoxy tree) Co., Ltd., a polyfunctional epoxy compound having a naphthalene skeleton (trade name: EXA-4700, manufactured by Dainippon Ink and Chemicals Co., Ltd.), and a chain alkyl polyfunctional epoxy compound (trade name "SR-TMP", Sakamoto Pharmaceutical Co., Ltd. "Industrial company", polyfunctional epoxy polybutadiene (trade name "EPOLEAD PB3600", manufactured by Daicel Chemical Industry Co., Ltd.), glycidyl ether compound of glycerin (trade name "SR-GLG", manufactured by Sakamoto Pharmaceutical Co., Ltd.), A diglycerin polyglycidyl ether compound (trade name "SR-DGE", manufactured by Sakamoto Pharmaceutical Co., Ltd.), a polyglycerin polyglycidyl ether compound (trade name "SR-4GL", manufactured by Sakamoto Pharmaceutical Co., Ltd.), etc. An epoxy compound of a ring structure.

Among these, the bridging agent (C) is preferably a polyfunctional epoxy compound having two or more epoxy groups, and the resin film obtained by using the resin composition of the present invention has excellent heat-resistant shape retention property. A polyfunctional epoxy compound having an alicyclic structure and having 3 or more epoxy groups is particularly preferable. These bridging agents may be used alone or in combination of two or more.

The content of the bridging agent (C) of the resin composition of the present invention is not particularly limited, and may be arbitrarily set as long as the degree of heat resistance required for patterning the resin film obtained by using the resin composition of the present invention is considered. The weight of 100 parts of the polymer (A) is usually 1 to 200 parts by weight, preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight, and most preferably 25 to 75 parts by weight. The heat resistance of the resin film obtained by excessive or too little bridging agent (C) tends to be lowered.

Further, the resin composition of the present invention preferably further contains a radiation sensitive compound (D). The radiation sensitive compound (D) used in the present invention is a compound which can cause a chemical reaction by irradiation with radiation such as ultraviolet rays or electron beams. In the radiation sensitive compound (D) of the present invention, it is preferred to control the alkali solubility of the resin film formed of the resin composition, and in particular, a photoacid generator is preferably used.

The radiation sensitive compound (D) may, for example, be an azide compound such as an acetophenone compound, a triarylsulfonium salt or an azide compound, and is preferably an azide compound, and particularly preferably an azide compound.

As the azide hydrazine compound, for example, an ester compound of a sulfonium sulfonium halide and a compound having a phenolic hydroxyl group can be used. Specific examples of the azide sulfonium sulfonium halide include 1,2-azidoquinone-5-sulfonium chloride, 1,2-azido-naphthoquinone-4-sulfonium chloride, 1,2-azidobenzene.醌-5-sulfonyl chloride and the like. Representative examples of the compound having a phenolic hydroxyl group include 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane and 4,4'-[1- [4-[1-[4-Hydroxyphenyl]-1-methylethyl]-phenyl]ethylidene]bisphenol. Other compounds having a phenolic hydroxyl group other than these may, for example, be 2,3,4-trihydroxyphenol, 2,3,4,4'-tetrahydroxyphenol, 2-bis(4-hydroxyphenyl)propane, or the like. (4-hydroxyphenyl)methane, 1,1,1-tris(4-hydroxy-3-methylphenyl)ethane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, An oligomer of a phenol resin, an oligomer obtained by copolymerizing a compound having one or more phenolic hydroxyl groups, and dicyclopentadiene.

Among these, a condensate of 1,2-azidophthoquinone-5-sulfonyl chloride and a compound having a phenolic hydroxyl group is preferred, and 1,1,3-tris(2,5-dimethyl-) The condensate of 4-hydroxyphenyl)-3-phenylpropane (1 mol) and 1,2-azidophthoquinone-5-sulfonyl chloride (2.0 mol) is more preferred.

Photoacid generator, in addition to the azide compound, a phosphonium salt, a halogenated organic compound, an α,α'-bis(sulfonate) azide methane compound, α-carboxy-α'-sulfonium azide methane A conventional compound such as a compound, an anthraquinone compound, an organic acid ester compound, an organic acid decylamine compound, or an organic acid quinone imide compound.

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

The content of the radiation-sensitive compound (D) of the resin composition of the present invention is usually from 1 to 100 parts by weight, preferably from 5 to 80 parts by weight, based on 100 parts by weight of the polymer (A), and is 10 to 60 parts by weight. The range is better. When the content of the radiation-sensitive compound (D) is within this range, the resin film composed of the resin composition of the present invention can be formed on an arbitrary substrate, and when the pattern is formed, the radiation-irradiating portion and the radiation-unirradiated portion are applied to the developer. The difference in solubility is large, and the radiation sensitivity is high, and it is easy to be patterned by development.

The resin composition used in the present invention may contain, as desired, a sensitizer, a surfactant, a latent acid generator, an oxidation preventive agent, a coupling agent or a derivative thereof, as long as it does not inhibit the effects of the present invention. Other stabilizers such as light stabilizers, defoamers, pigments, dyes, fillers, etc.

Specific examples of the sensitizer include 2H-pyrido-(3,2-b)-1,4-oxazin-3(4H)-one, 10H-pyrido-(3,2-b) -1,4-benzothiazide, urinazole, carbendazim, barbituric acid, glycine anhydride, 1-hydroxybenzotriazole, alloxan, maleimide Wait.

The resin composition of the present invention preferably contains a surfactant.

The surfactant is used for the purpose of preventing the coating, the improvement of developability, and the like. Specific examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether and polyoxyethylene fluorenyl group; a polyoxyethylene aryl ether such as a phenyl ether; a nonionic surfactant such as a polyoxyethylene dialkyl ester such as polyoxyethylene dilaurate or polyoxyethylene distearate; or a fluorine-based surfactant; Surfactant; silicone surfactant; methacrylic copolymer surfactant: acrylic copolymer surfactant.

The latent acid generator is used for the purpose of improving the heat resistance and chemical resistance of the resin composition of the present invention. Specific examples thereof are an onium salt, a benzothiazole salt, an ammonium salt, a phosphonium salt or the like which are a cationic polymerization catalyst which generates an acid by heating. Among these, sulfonium salts and benzothiazole salts are preferred.

As the oxidation preventive agent, a phenolic oxidation inhibitor, a phosphorus oxidation inhibitor, a sulfur oxidation inhibitor, a lactone oxidation inhibitor, or the like which is generally used for the polymer can be used. For example, a phenolic oxidation inhibitor may be exemplified by 2,6-di-tert-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-tert-butylphenol), 2-third Butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 4,4'-butylene-bis-(3- Methyl-6-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), pentaerythritol tetra[3-(3,5-di Tributyl-4-hydroxyphenyl)propionate], alkylated bisphenol, and the like. Examples of the phosphorus-based oxidation inhibitor include triphenyl phosphite and tris(nonylphenyl) phosphite. As the sulfur-based oxidation preventing agent, dilauryl thiodipropionate can be mentioned.

The resin composition of the present invention preferably contains an acidic compound.

The acidic compound is not particularly limited as long as it has an acidic group, and an aliphatic compound, an aromatic compound, a heterocyclic compound or the like can be used. The acidic group may be an acidic functional group, and specific examples thereof include a strongly acidic group such as a sulfonic acid group or a phosphoric acid group; and a weakly acidic group such as a carboxyl group, a thiol group or a carboxymethylthio group. Among these, a carboxyl group, a thiol group or a carboxymethylthio group is preferred, and a carboxyl group is particularly preferred. Specific examples of the acidic compound include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, butyric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, glycolic acid, glyceric acid, and oxalic acid (also Known as "oxalic acid"), malonic acid (also known as "malic acid"), succinic acid (also known as "succinic acid"), glutaric acid, adipic acid (also known as "fat acid"), 1,2-cyclohexanedicarboxylic acid, 2-oxopropionic acid, 2-hydroxysuccinic acid, 2-hydroxypropanetricarboxylic acid, mercaptosuccinic acid, dimercaptosuccinic acid, 2,3-dimercapto-1 -propanol, 1,2,3-trimethylpropane, 2,3,4-trimercapto-1-butanol, 2,4-dimercapto-1,3-butanediol, 1,3,4-tri An aliphatic compound such as mercapto-2-butanol, 3,4-dimercapto-1,2-butanediol, 1,5-dimercapto-3-thiopentane; benzoic acid, p-hydroxybenzoic acid, O-hydroxybenzenecarboxylic acid, 2-naphthalenecarboxylic acid, methylbenzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, 3-phenylpropionic acid, 2-hydroxybenzoic acid, dihydroxybenzoic acid, dimethoxy Kean acid, benzene-1,2-dicarboxylic acid (also known as "phthalic acid"), benzene-1,3-dicarboxylic acid (also known as "isophthalic acid"), benzene -1,4-dicarboxylic acid (also known as "terephthalic acid"), benzene-1,2,3-tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, benzene-1,3, 5-tricarboxylic acid, benzene hexacarboxylic acid, biphenyl-2,2'-dicarboxylic acid, 2-(carboxymethyl)benzoic acid, 3-(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-mercapto-6-naphthocarboxylate Acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3-dioxylbenzene, 1,4-didecylbenzene, 1,4-naphthalene dithiol, 1,5-naphthalene Dithiol, 2,6-naphthalene dithiol, 2,7-naphthalene dithiol, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethyl Benzene, 1,2,3-tris(decylmethyl)benzene, 1,2,4-tris(decylmethyl)benzene, 1,3,5-tris(decylmethyl)benzene, 1,2,3- An aromatic compound such as tris(decylethyl)benzene, 1,2,4-tris(decylethyl)benzene, 1,3,5-tris(decylethyl)benzene; nicotine, iso-nicotine, citric acid , pyrrole-2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid, imidazole-2,4-dicarboxylic acid , imidazole-2,5-two a five-membered heterocyclic compound containing a nitrogen atom such as an acid, imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid or pyrazole-3,5-dicarboxylic acid; thiophene-2,3- Dicarboxylic acid, thiophene-2,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole-2,5- Dicarboxylic acid, thiazole-4,5-dicarboxylic acid, isothiazole-3,4-dicarboxylic acid, isothiazole-3,5-dicarboxylic acid, 1,2,4-thiazole-2,5-dicarboxylate Acid, 1,3,4-thiazole-2,5-dicarboxylic acid, 3-amino-5-mercapto-1,2,4-thiadiazole, 2-amino-5-mercapto-1,3, 4-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, 3-(5-mercapto-1,2 , 4-thiadiazol-3-ylsulfonyl)succinic acid, 2-(5-mercapto-1,3,4-thiadiazol-2-ylsulfonyl)succinic acid, (5-mercapto-1,2 , 4-thiadiazol-3-ylthio)acetic acid, (5-mercapto-1,3,4-thiadiazol-2-ylthio)acetic acid, 3-(5-mercapto-1,2,4 -thiadiazol-3-ylthio)propionic acid, 2-(5-mercapto-1,3,4-thiadiazol-2-ylthio)propionic acid, 3-(5-mercapto-1,2 , 4-thiadiazol-3-ylthio)succinic acid, 2-(5-mercapto-1,3,4-thiadiazol-2-ylthio)succinic acid, 4-(3-indolyl-1 , 2,4-thiadiazol-5-yl)thiobutanesulfonic acid, 4-(2-mercapto-1,3,4- a five-membered heterocyclic compound containing a nitrogen atom and a sulfur atom, such as oxazol-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-di Carboxylic acid, triazine-2,4-dicarboxylic acid, 2-diethylamino-4,6-dimercapto-s-triazine, 2-dipropylamino-4,6-dimercapto-s -triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-diphenylaminoamino-4,6-dimercapto-s-triazine, 2,4,6- A six-membered heterocyclic compound containing a nitrogen atom such as tridecyl-s-triazine or the like.

Among these, from the viewpoint that the adhesion of the resin film formed of the resin composition to the substrate is good, the number of the acidic groups is preferably two or more, and particularly preferably two.

A compound having two acidic groups, which may be mentioned: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, 1,2-cyclohexanedicarboxylic acid, benzene-1,2-dicarboxylate Acid (also known as "phthalic acid"), benzene-1,3-dicarboxylic acid (also known as "isophthalic acid"), benzene-1,4-dicarboxylic acid (also known as "p-benzene" Dicarboxylic acid"), biphenyl-2,2'-dicarboxylic acid, 2-(carboxymethyl)benzoic acid, 3-(carboxymethyl)benzoic acid, 4-(carboxymethyl)benzoic acid, 2-mercapto Benzoic acid, 4-mercaptobenzoic acid, 2-mercapto-6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-two An aromatic compound having two acidic groups such as mercaptobenzene, 1,4-naphthalene dithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol; pyrrole -2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid, imidazole-2,4-dicarboxylic acid, imidazole -2,5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, pyrazole-3,5-dicarboxylic acid, thiophene-2,3-dicarboxylic acid , thiophene-2,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole- 2,5-dicarboxylic acid, thiazole-4,5-dicarboxylic acid, isothiazole-3,4-dicarboxylic acid, isothiazole-3,5-dicarboxylic acid, 1,2,4-thiadiazole- 2,5-dicarboxylic acid, 1,3,4-thiadiazole-2,5-dicarboxylic acid, (5-mercapto-1,2,4-thiadiazol-3-ylthio)acetic acid, ( 5-mercapto-1,3,4-thiadiazol-2-ylthio)acetic acid, pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylate 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-dicarboxylic acid, triazine A heterocyclic compound having two acidic groups such as a 2,4-dicarboxylic acid is preferred.

By using these compounds, the effect of improving the adhesion of the resin film formed of the resin composition to the substrate can be obtained.

The resin composition of the present invention preferably contains a coupling agent or a derivative thereof.

As the coupling agent or a derivative thereof, a compound having one atom selected from a ruthenium atom, a titanium atom, an aluminum atom, or a zirconium atom, and having an alkoxy group or a hydroxyl group bonded to the atom can be used.

The coupling agent or a derivative thereof may, for example, be tetramethoxymethane, tetraethoxymethane, tetra-n-propoxymethane, tetraisopropylmethane or tetra-n-butoxymethane. Alkoxymethane methane; methyltrimethoxyanthracene methane, methyltriethoxymethane methane, ethyltrimethoxymethane, ethyltriethoxymethane, n-propyltrimethoxymethane, positive Propyltriethoxymethane, isopropyltrimethoxymethane, isopropyltriethoxymethane, n-butyltrimethoxymethane, n-butyltriethoxymethane, n-pentyl Trimethoxymethane, n-hexyltrimethoxymethane, n-heptyltrimethoxymethane, n-octyltrimethoxymethane, n-decyltrimethoxymethane, p-styryltrimethoxymethane , vinyl trimethoxymethane, vinyl triethoxymethane, cyclohexyltrimethoxymethane, cyclohexyltrimethoxymethane, cyclohexyltriethoxymethane, phenyltrimethoxyindole Phenyltriethoxymethane, 3-chloropropyltrimethoxymethane, 3-chloropropyltriethoxy Methane, 3,3,3-trifluoropropyltrimethoxymethane, 3,3,3-trifluoropropyltriethoxymethane, 3-aminopropyltrimethoxymethane, 3- Aminopropyltriethoxymethane, N-2-(aminoethyl)-3-aminopropyltrimethoxyindole methane, N-phenyl-3-aminopropyltrimethoxyindole methane , 2-hydroxyethyltrimethoxymethane, 2-hydroxyethyltriethoxymethane, 2-hydroxypropyltrimethoxymethane, 2-hydroxypropyltriethoxymethane, 3-hydroxyl Propyltrimethoxymethane, 3-hydroxypropyltriethoxymethane, 3-mercaptopropyltrimethoxymethane, 3-mercaptopropyltriethoxymethane, 3-isocyanatopropyl Trimethoxymethane, 3-isocyanatopropyltriethoxymethane, 3-glycidylpropyltrimethoxymethane, 3-glycidylpropyltriethoxymethane, 2-(3,4-epoxyhexyl)ethyltrimethoxyindole methane, 2-(3,4-epoxyhexyl)ethyltriethoxymethane, 3-(methyl)propenyloxypropyl Trimethoxymethane, 3-(methyl)propenyl methoxypropyltriethoxymethane, 3-ureidopropyltrimethoxy Methane, 3-ureidopropyltriethoxymethane, 3-ethyl(trimethoxyformamidopropyloxymethyl)epoxypropane, 3-ethyl(triethoxymethyl decyloxypropane) Of propylene oxide, 3-triethoxycarbamido-N-(1,3-dimethyl-butylene) propylamine, bis(triethoxymethyl sulfonylpropyl) tetrasulfide, etc. Alkoxymethane methane; dimethyldimethoxymethane, dimethyldiethoxymethane, diethyldimethoxymethane, diethyldiethoxymethane, di-n-propyl Dimethoxymethane, di-n-propyldiethoxymethane, diisopropyldimethoxymethane, diisopropyldiethoxymethane,di-n-butyldimethoxyfluorene Methane, di-n-pentyldimethoxymethane, di-n-pentyldiethoxymethane, di-n-hexyldimethoxymethane, di-n-hexyldiethoxymethane, di-n-heptyldimethyl Oxymethane, di-n-heptyldiethoxymethane, di-n-octyldimethoxymethane, di-n-octyldiethoxymethane, dicyclohexyldimethoxymethane, bicyclo Hexyldiethoxymethane, diphenyldimethyl Oxymethane, diphenyldiethoxymethane, 3-glycidylpropylmethyldiethoxymethane, 3-methylpropenyloxypropyldimethoxymethane, 3-propene醯Phenylpropyldimethoxymethane, 3-methylpropenyloxypropyldiethoxymethane, 3-propenyloxypropylmethyldiethoxymethane, N-2-( a dialkylhydrazine methane such as aminoethyl)-3-aminopropylmethyldimethoxymethane; and methyltriethoxymethane, dimethyldivinyloxymethane, A product containing a ruthenium atom such as X-12-414, KBP-44 (manufactured by Shin-Etsu Chemical Co., Ltd.), 217 FLAKE, 220 FLAKE, 233 FLAKE, z6018 (manufactured by TORAY-DOW-CORNING Co., Ltd.); Titanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexyloxy)titanium, isopropoxyoctyl titanate, diisopropoxy bis (acetylacetone) titanium, malon dioxygen Titanium bis(ethylacetamidineacetone), tri-n-butoxytitanium monostearate, titanium diisopropoxy distearate, titanium stearate, titanium diisopropoxy diisostearate, (2-n-butoxycarbonylbenzylideneoxy) tributoxytitanium a compound containing a titanium atom such as di-n-butoxy bis (triethanolamine) titanium; and a PLENACT series (manufactured by Ajinomoto Fine-Techno Co., Ltd.); (acetoloxy aluminum diisopropanol) a compound of aluminum atom; (tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetra-acetyl acetonide zirconium, tributoxy-acetonitrile, zirconium, monobutoxyacetamidine acetonide (ethyl acetoacetic acid) A zirconium atom-containing compound such as zirconium, butoxy bis(ethylacetamidineacetic acid) zirconium, tetraethylguanidinium zirconium or tributoxyzirconate.

By using these compounds, the effect of improving the adhesion of the resin film formed of the resin composition to the substrate can be obtained.

The resin composition of the present invention preferably contains a photostabilizer.

The light stabilizer can be captured by a UV absorber such as a benzophenone, a salicylate, a benzotriazole, a cyanoacrylate or a metal salt, or a hindered amine (HALS). The free radicals generated by light can be used. Among these, HALS is a compound having a piperidine structure, and the coloring of the resin composition of the present invention is small, and the stability is good. Specific compounds include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, 1,2,2,6,6,-pentamethyl-4-piperidin Pyridyl/trimethyl 1,2,3,4-butane tetracarboxylate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacic acid Ester and the like.

The method for preparing the resin composition of the present invention is not particularly limited as long as the components constituting the resin composition of the present invention are mixed by a known method.

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

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

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

(resin film)

The resin film of the present invention can be formed on a substrate by using the above-described resin composition of the present invention.

In the present invention, for example, a printed circuit board, a tantalum wafer substrate, a glass substrate, a plastic substrate, or the like can be used as the substrate. The substrate may be subjected to physical and/or chemical surface treatment on the surface of the substrate, or may have a multi-layer structure in which another film is formed on the surface of the substrate. Further, it is also possible to use an element such as a thin transistor type liquid crystal display element or a thin film transistor, a color filter, a black matrix, or the like which is used in a display field and a glass substrate or a plastic substrate.

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

The coating method is, for example, a method in which a resin composition is applied onto a substrate, followed by heating and drying to remove the solvent. The method of applying the resin composition to the substrate may be, for example, a spray coating 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, a screen printing method, or the like. method. The heating and drying conditions may vary depending on the type or blending ratio of each component contained in the resin composition, and the heating temperature is usually 30 to 150 ° C, preferably 60 to 120 ° C, and the heating time is usually 0.5 to 90 minutes, to 1 ~60 minutes is better, preferably 1~30 minutes.

In the film deposition method, the resin composition is applied onto a substrate for forming a B-stage (colloidal) film such as a resin film or a metal film, and then the solvent is removed by heat drying to obtain a B-stage film, and then the B is obtained. A method in which a film is laminated on the above substrate. The heating and drying conditions can be appropriately selected according to the kind or blending ratio of each component contained in the resin composition, and the heating temperature is usually 30 to 150 ° C, and the heating time is usually 0.5 to 90 minutes. The lamination of the film can be carried out using a press machine such as 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 usually 0.1 to 100 μm, preferably 0.5 to 50 μm, more preferably 0.5 to 30 μm.

In the case where the resin composition contains the bridging agent (C), the resin film can be bridged by forming a resin film on the substrate. The bridging of the resin film formed on the substrate may be carried out by heating according to the type of the bridging agent (C). The heating method can be carried out, for example, by heating a tray, an oven, or the like. The heating temperature is usually 180 to 250 ° C, and the heating time is appropriately selected depending on the size or thickness of the resin film. For example, when a heating plate is used, it is usually 5 to 60 minutes, and when the oven is used, it is usually 30 to 90. The range of minutes. Heating can also be carried out under an inert gas atmosphere as needed. The inert gas may be any one that does not contain oxygen and does not oxidize the resin film, and examples thereof include nitrogen, argon, helium, neon, krypton, xenon, and the like. Among these, nitrogen and argon are preferred, and nitrogen is particularly preferred. In particular, the oxygen content is 0.1% by volume or less, preferably 0.01% by volume or less, particularly preferably nitrogen. These inert gases may be used alone or in combination of two or more.

In the laminate comprising the resin film formed of the resin composition of the present invention on the substrate and the substrate, the resin film may be a patterned patterned resin film.

When the resin composition contains the radiation sensitive compound (D), for example, when the resin composition is formed on the substrate, the resin film formed of the resin composition is irradiated with active radiation to form a latent image pattern, and then the developer and the developer are The resin film having the latent image pattern is obtained by contacting the developed pattern.

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

Next, the latent image pattern formed on the resin film is developed to be developed. In the present invention, such a step is referred to as "patterning", and the patterned resin film is referred to as a "patterned resin film". For the developer, an aqueous solution of a basic compound is usually used. As the basic compound, for example, an alkali metal salt, an amine, or an ammonium salt can be used. The basic compound may be an inorganic compound or an organic compound. Specific examples of such compounds include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, and sodium metasilicate; aqueous ammonia; primary amines such as ethylamine and n-propylamine; and diethyl a secondary amine such as an amine or di-n-propylamine; a tertiary amine such as triethylamine or methyldiethylamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide or tetrabutylammonium hydroxide; a quaternary amine such as choline; an alcohol amine such as dimethylethanolamine or triethanolamine; pyrrole, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5- A cyclic amine such as diazabicyclo[4.3.0]non-5-ene or N-methylpyrrolidone. These basic compounds may be used alone or in combination of two or more.

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

A method of bringing the developer into contact with the resin film having the latent image pattern may be, for example, a paddle dissolution method, a spray method, or a dipping method. Development conditions, as long as the appropriate choice, the development temperature is usually

0~100°C, preferably 5~55°C, in the range of 10~30°C, the development time is usually suitable in the range of 30~180 seconds.

After the desired patterned resin film is formed on the substrate, the development residue on the substrate, the substrate back surface, and the substrate end portion can be removed as needed, and the substrate is wetted with a wetting liquid. After the wetting treatment, the remaining wetting liquid is removed by compressed air or compressed nitrogen.

Further, in order to inactivate the radiation sensitive compound (D), the substrate having the patterned resin film may be entirely irradiated with active radiation as needed. For the irradiation of the actinic radiation, the method exemplified by the method of forming the latent image pattern described above can be used. The resin film may be heated while irradiating the active radiation or after the irradiation. The heating method may, for example, be a method of heating the substrate in a heating pan or an oven. The heating temperature is usually 100 to 300 ° C, preferably in the range of 120 to 200 ° C.

In the present invention, after the patterned resin is formed on the substrate, a bridging reaction of the patterned resin is performed.

The bridging can be carried out in the same manner as the bridging of the resin film formed on the substrate described above.

The resin film of the present invention is obtained by using the polymer of the present invention and a resin composition containing a hydrogen additive, and thus has electrical properties such as heat resistance, low dielectric constant characteristics, low leakage current characteristics, and high insulation breakdown voltage characteristics. It is excellent in low water absorption and adhesion, high in reliability, high in transparency, and excellent in pattern formation property by development. Therefore, the laminate having the resin film and the substrate of the present invention, in particular, a laminate in which a patterned resin film is formed on a substrate, is used for various electronic components, particularly semiconductor devices.

[Examples]

Hereinafter, the present invention will be described in further detail by way of examples, but the invention is not limited by the examples.

In addition, in this embodiment, "part" and "%" are "weight part" and "weight%" unless otherwise mentioned.

<Evaluation method>

Each characteristic was evaluated in the following manner.

<Polymerization conversion rate>

The polymerization conversion rate was calculated by measuring the residual amount of the monomer in the reaction liquid after the completion of the polymerization reaction using a gas chromatograph.

<Hydrogen addition rate>

The hydrogen addition rate was determined by ¹ H-NMR spectrum, and the carbon number of carbon-carbon double bonds of hydrogenation was determined for the ratio of the number of carbon-carbon double bonds in the hydrogenation before hydrogenation. In the present example, the ratio of the hydrogenated carbon-carbon double bond was determined in mol% based on the pre-hydrogenation.

<weight average molecular weight ‧ number average molecular weight>

The weight average molecular weight and the number average molecular weight are obtained by using a gel permeation chromatograph (GPC, TOSO, model "HLC-8020", combined with three types of columns of TSKgel SuperH2000, TSKgel SuperH4000, TSKgel SuperH 5000) The molecular weight in terms of styrene was calculated. Further, the solvent is distilled using tetrahydrogen.

<Solubility to methyl isobutyl ketone>

The determination of whether the polymer or hydrogen additive is dissolved in methyl isobutyl ketone (MIBK) is evaluated by light transmittance measurement. The more the insoluble particles, the more the light transmittance is reduced by the light scattering of the particles. Therefore, the higher the light transmittance, the better the solubility.

The measurement of the light transmittance was carried out by using a spectrophotometer ("V-570 (product name)" manufactured by JASCO Corporation), and a solution in which one part of the polymer or hydrogen additive was dissolved in 100 parts of MIBK, and measured at 400 nm. The light penetration rate is carried out. Further, at the time of measurement, before measuring the light transmittance of the solution in which the polymer or the hydrogen additive was dissolved in MIBK, the light transmittance of the liquid having only MIBK was taken as 100%, and the spectrophotometer was subjected to the above spectrophotometer. Benchmarking.

From the light transmittance of the MIBK solution of the polymer or hydrogen additive, the solubility was judged as follows.

○: The light transmittance of the solution is 95% or more (the difference in light transmittance from MIBK is small, and the solubility is good.)

×: The light transmittance of the solution is less than 95% (the difference in light transmittance from MIBK is large, and the solubility is poor.)

<Water absorption>

[Production of sample for measuring water absorption]

The resin composition obtained in the following Examples and Comparative Examples was spin-coated on a silicon wafer having a diameter of 4 inches and a thickness of 0.52 mm, and then prebaked at 90 ° C for 2 minutes using a hot plate to form a film thickness of 2.5 μm. Resin film. Next, using a 0.4% by weight aqueous solution of tetramethylammonium hydroxide, development treatment was carried out at 25 ° C for 60 seconds, and then wetted with ultrapure water for 30 seconds. Then, the resin film was irradiated with ultraviolet rays having a light intensity of 5 mW/cm ² at 365 nm for 60 seconds in the air. Further, the oven was heated at 230 ° C for 60 minutes, and post-baking was carried out to obtain a tantalum wafer having a resin film. Then, a portion of the flat resin film at the center of the wafer was cut into a square shape having a corner of about 1 cm and a width of about 1 cm ² . Thereafter, the sample was placed in an atmosphere of 25° C. and a humidity of 50% for 30 minutes to obtain a sample for water absorption measurement.

[Method for measuring water absorption]

The measurement of water absorption was carried out as follows. In other words, the sample for water absorption measurement obtained above was heated to 230 ° C at 60 ° C / min using a temperature-raised desorption gas analyzer (TDS, model "WA1000S/W", manufactured by Electronic Science Co., Ltd.). The amount of moisture detected per unit area was taken as the value of water absorption for 30 minutes. The lower the value of water absorption, the more difficult it is to contain water, and it can be called a resin film which is highly insulating with water.

<adhesiveness>

[Production of Sample for Adhesion Measurement]

The resin composition obtained in the following Examples and Comparative Examples was spin-coated on a 10 cm square glass substrate [CORNING Corporation, CORNING 1737 (product name)], and then prebaked at 90 ° C for 2 minutes using a hot plate to form a film. A resin film having a thickness of 2.5 μm. Next, through the strip slits (corresponding to the spacing) having 10 parallel penetrable lights, the width and slit width between one slit of the slit and the adjacent slit (corresponding to the line) The same mask is exposed at a desired time with light of a desired intensity to the extent that a pattern can be formed. Next, in the evaluation, the slit width and the width between one slit of the slit and the adjacent slit are respectively 8 types of 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 10 μm, 25 μm, and 50 μm. A mask is prepared to prepare a sample. Next, the resin film to be exposed was subjected to development treatment at 23 ° C for 60 seconds by a paddle dissolution method using a 0.4% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution, and wetted with ultrapure water for 30 seconds. Further, the paddle-type dissolution method is a method in which a resin film is dropped on a resin film to be allowed to stand. As described above, a resin film having a pattern (line and space pattern) of the transfer mask pattern was formed on the glass substrate. In addition, in the resin film obtained by the following examples and the comparative examples, the portion having the slit portion of the mask corresponds to the portion where the resin film is removed. This part is called a spacer. On the other hand, a portion corresponding to one slit of the mask and the adjacent slit corresponds to a portion left by the resin film, and this portion is referred to as a line portion. Then, the thus obtained glass substrate on which the patterned resin film was formed was used as the adhesion measurement sample.

[Measurement method of adhesion]

The measurement of the adhesion was carried out in the following manner. In other words, the sample for the measurement of the adhesion property obtained above was observed by an optical microscope, and it was confirmed whether or not the line portion was peeled off from the substrate, and the adhesion property was measured. If the line is not peeled off, it can be said that the adhesion is high. Further, when the line portion was peeled off, it was confirmed that the line portion was peeled off to a maximum of several μm. The smaller the width of the line portion, the easier it is to peel off. Therefore, when it is confirmed that the line portion is peeled off from the substrate, the smaller the maximum width of the line portion (the value of the largest width among the line portions having the peeling off) is confirmed, the higher the adhesion is.

(Example 1)

100 parts of N-(1-methylpentyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, 2 parts of 1,5-hexadiene, 0.02 a portion of benzylidene (1,3-bistrimethylimidazolin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride (described in Org. Lett., Vol. 1, p. 953, 1999) The method of synthesizing) and 400 parts of diethylene glycol methyl ethyl ether were placed in a glass pressure-resistant reactor, and reacted at 80 ° C for 4 hours while stirring to obtain a polymerization reaction liquid of the polymer A1. The obtained polymer A1 had a polymerization conversion ratio of 99.6%, a weight average molecular weight of 5,660, a number average molecular weight of 3,510 and a molecular weight distribution of 1.49.

The solubility of methyl isobutyl ketone (MIBK) of polymer A1 was evaluated. The evaluation results are shown in Table 1. Polymer A1 was soluble in MIBK at 25 °C.

(Example 2)

The polymerization reaction liquid of the polymer A1 obtained in Example 1 was placed in a high pressure reactor, and hydrogenation reaction was carried out at 150 ° C under a hydrogen pressure of 4 MPa for 5 hours to obtain a hydrogen additive A2. The obtained hydrogen additive A2 had a weight average molecular weight of 7,010, a number average molecular weight of 4,590, a molecular weight distribution of 1.53, and a hydrogen addition ratio of 99.8%.

The solubility of methyl isobutyl ketone (MIBK) of hydrogen additive A2 was evaluated. The evaluation results are shown in Table 1. Hydrogen additive A2 is soluble in MIBK at 25 °C.

(Example 3)

According to the method described in JP-A-2006-016606, N-(1-methylpentyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine is added. Form polymer A3. The polymerization conversion ratio of the addition polymer A3 was 78.3%, the weight average molecular weight was 75,400, and the number average molecular weight was 36,200.

The solubility of methyl isobutyl ketone (MIBK) of polymer A3 was evaluated. The evaluation results are shown in Table 1. Polymer A3 is soluble in MIBK at 25 °C.

(Example 4)

Substituting N-(1-methylpentyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, using N-(2-ethylhexyl)-bicyclo[2.2. In the same manner as in Example 1, except that hept-5-alkenyl-2,3-dimethylimine, a polymerization reaction liquid was obtained, and a hydrogenation reaction was carried out in the same manner as in Example 2, using the obtained polymerization reaction liquid to obtain hydrogen. Additive A4. The obtained hydrogen addition A4 had a polymerization conversion ratio of 99.5%, a weight average molecular weight of 7,140, a number average molecular weight of 4,680, a molecular weight distribution of 1.53, and a hydrogen addition ratio of 99.8%.

The solubility of methyl isobutyl ketone (MIBK) of hydrogen additive A4 was evaluated. The evaluation results are shown in Table 1. Hydrogen additive A4 is soluble in MIBK at 25 °C.

(Example 5)

Substituting N-(1-methylpentyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, using N-(1-methyltri-dodeto)- A polymerization reaction liquid was obtained in the same manner as in Example 1 except for the bicyclo[2.2.1]hept-5-alkenyl-2,3-dimethylimine. The obtained polymerization reaction liquid was used to carry out hydrogenation in the same manner as in Example 2. The reaction was carried out to obtain a hydrogen additive A5. The obtained hydrogen addition A5 had a polymerization conversion ratio of 99.5%, a weight average molecular weight of 7,250, a number average molecular weight of 4,700, a molecular weight distribution of 1.54, and a hydrogen addition ratio of 99.7%.

The solubility of methyl isobutyl ketone (MIBK) of hydrogen additive A5 was evaluated. The evaluation results are shown in Table 1. Hydrogen additive A5 is soluble in MIBK at 25 °C.

(Example 6)

Replace 100 parts of N-(1-methylpentyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, using 80 parts of N-(2-ethylhexyl) -bicyclo[2.2.1]hept-5-alkenyl-2,3-dimethylimine, and 20-hydroxy 8-hydroxycarbonyl tetracyclo [4.4.0.1 ^2,5 ,1 ^7,10 ] twelve carbon In the same manner as in Example 1, a polymerization reaction liquid was obtained, and a hydrogenation reaction was carried out in the same manner as in Example 2 to obtain a hydrogen additive A6. The obtained hydrogen addition A6 had a polymerization conversion ratio of 99.6%, a weight average molecular weight of 6,900, a number average molecular weight of 4,570, a molecular weight distribution of 1.51, and a hydrogen addition ratio of 99.9%.

The solubility of methyl isobutyl ketone (MIBK) of hydrogen additive A6 was evaluated. The evaluation results are shown in Table 1. Hydrogen additive A6 is soluble in MIBK at 25 °C.

(Example 7)

Replace 100 parts of N-(1-methylpentyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, using 60 parts of N-(2-ethylhexyl) - bicyclo [2.2.1] hept-5-ene-2,3-dimethylbutyl (PEI), and 8-hydroxy-40-carbonyl group of tetracyclic [4.4.0.1 ^2,5, 1 ^7,10] dodecene A polymerization reaction liquid was obtained in the same manner as in Example 1 except for the 3-olefin. The obtained polymerization reaction liquid was subjected to a hydrogenation reaction in the same manner as in Example 2 to obtain a hydrogen additive A7. The obtained hydrogen addition A7 had a polymerization conversion ratio of 99.7%, a weight average molecular weight of 6,780, a number average molecular weight of 4,450, a molecular weight distribution of 1.52, and a hydrogen addition ratio of 99.9%.

The solubility of methyl isobutyl ketone (MIBK) of hydrogen additive A7 was evaluated. The evaluation results are shown in Table 1. Hydrogen additive A7 is soluble in MIBK at 25 °C.

(Comparative Example 1)

Substituting N-(1-methylpentyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, using N-(t-butyl)-bicyclo[2.2.1 In the same manner as in Example 1, except that hept-5-alkenyl-2,3-dimethylimine, a polymerization reaction liquid was obtained, and a hydrogenation reaction was carried out in the same manner as in Example 2, except that the obtained polymerization reaction liquid was used to obtain a hydrogen additive A8. . The obtained hydrogen addition A8 had a polymerization conversion ratio of 99.6%, a weight average molecular weight of 6,960, a number average molecular weight of 4,400, a molecular weight distribution of 1.58, and a hydrogen addition ratio of 99.8%.

The solubility of methyl isobutyl ketone (MIBK) of hydrogen additive A8 was evaluated. The evaluation results are shown in Table 1. Hydrogen additive A8 is insoluble in MIBK at 25 °C.

(Comparative Example 2)

Substituting N-(1-methylpentyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, using N-(intro-bicyclo[2.2.1]hept-5 A polymerization reaction liquid was obtained in the same manner as in Example 1 except that the methylene aspartate was used, and a hydrogenation reaction was carried out in the same manner as in Example 2 except that the obtained polymerization reaction liquid was used to obtain a hydrogen additive. A9. The obtained hydrogen addition A9 had a polymerization conversion ratio of 99.8%, a weight average molecular weight of 6,850, a number average molecular weight of 4,490, a molecular weight distribution of 1.53, and a hydrogen addition ratio of 99.7%.

The solubility of methyl isobutyl ketone (MIBK) of hydrogen additive A9 was evaluated. The evaluation results are shown in Table 1. Hydrogen additive A9 is insoluble in MIBK at 25 °C.

(Comparative Example 3)

Substituting 100 parts of N-(1-methylpentyl)-bicyclo[2.2.1]hept-5-enyl-2,3-dimethylimine, using 40 parts of N-(inward-bicyclic [2.2. 1] hept-5-ene-2,3-dicarboxy-yl) aspartic acid methyl ester, and 8-hydroxy group of 60-carbonyl tetracyclo [4.4.0.1 ^2,5, 1 ^7,10] dodecene - A polymerization reaction liquid was obtained in the same manner as in Example 1 except for the 3-ene. The obtained polymerization reaction liquid was subjected to a hydrogenation reaction in the same manner as in Example 2 to obtain a hydrogen additive A10. The obtained hydrogen addition A10 had a polymerization conversion ratio of 99.7%, a weight average molecular weight of 6,950, a number average molecular weight of 4,630, a molecular weight distribution of 1.50, and a hydrogen addition ratio of 99.7%.

The solubility of methyl isobutyl ketone (MIBK) of hydrogen additive A10 was evaluated. The evaluation results are shown in Table 1. Hydrogen additive A10 is insoluble in MIBK at 25 °C.

(Example 8)

100 parts by weight of the hydrogen additive A6 obtained in Example 6 was used as the polymer (A), 550 parts by weight of diethylene glycol ethyl methyl ether (EDM) as a solvent (B), and 50 parts by weight of epoxidized butyl Tetrakis(3-cyclohexenylmethyl)-modified ε-caprolactone (aliphatic cyclic tetrafunctional epoxy resin, trade name "EPOLEAD GT401", manufactured by Daicel Chemical Industry Co., Ltd.) as a bridging agent ( C) 0.05 weight part of a silicone-based surfactant ("KP-341 (product name)" manufactured by Shin-Etsu Chemical Co., Ltd.) as a surfactant, mixed and dissolved, and a filter made of polytetrafluoroethylene having a pore diameter of 0.45 μm The resin composition 1 was prepared by filtration.

The water repellency was evaluated using this resin composition 1. The results are shown in Table 2.

(Example 9, Comparative Example 4, 5)

The resin composition 2 was prepared in the same manner as in Example 8 except that the hydrogen additive A6 was used instead of the hydrogen additive A7 (Example 9), the hydrogen additive A9 (Comparative Example 4), and the hydrogen additive A10 (Comparative Example 5). 4.

The water repellency was evaluated using the resin compositions 2 to 4. The results are shown in Table 2.

(Embodiment 10)

100 parts by weight of the hydrogen additive A6 obtained in Example 6 was used as the polymer (A), and 550 parts of diethylene glycol ethyl methyl ether (EDM) was used as the solvent (B), and the weight of the 30 parts was 1,1. 3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane (1 mol) and 1,2-azidobenzoquinone-5-sulfonyl chloride (1.9 mol) The 1,2-azidobenzoquinone compound of the condensate is used as the radiation sensitive compound (D), and 0.05 weight part of a silicone-based surfactant ("KP-341 (product name)" manufactured by Shin-Etsu Chemical Co., Ltd.) is used as the interface activity. After mixing and dissolving, the mixture was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 μm to prepare a resin composition 5.

The water repellency was evaluated using this resin composition 5. The results are shown in Table 3.

(Example 11, Comparative Example 6, 7)

The resin composition 6 was prepared in the same manner as in Example 10 except that the hydrogen additive A6 was used instead of the hydrogen additive A7 (Example 11), the hydrogen additive A9 (Comparative Example 6), and the hydrogen additive A10 (Comparative Example 7). 8.

Water absorption was evaluated using these resin compositions 6 to 8. The results are shown in Table 3.

As shown in the examples, a polymer comprising a polymerization unit of the monomer represented by the general formula (1) was obtained. Further, a hydrogen additive obtained by hydrogenating a ring-opening polymer having a repeating unit in which the monomer represented by the above formula (1) is subjected to ring-opening polymerization is obtained. The obtained polymer and its hydrogen additive have high solubility in MIBK of a polar solvent, and it can be confirmed that it can be used for a wide range of applications (Examples 1 to 7). Further, as a result of the results of Tables 2 and 3, a resin composition having a polymer (hydrogen additive) obtained by polymerizing a monomer represented by the formula (1) has low water absorbability and is excellent in insulation properties because of adhesion. Highly high, it is possible to manufacture a resin film suitable for use in a wide range of applications. (Examples 8 to 11).

On the other hand, when the polymerization unit of the monomer represented by the formula (1) is not contained, the solubility in the MIBK of the polar solvent is lowered (Comparative Examples 1 to 3). Further, as a result of the results of Tables 2 and 3, a resin composition obtained by using a polymer (hydrogen additive) which does not contain a polymerization unit of the monomer represented by the general formula (1) has high water absorbability and poor adhesion. (Comparative Examples 4 to 7).

Claims (12)

A polymer comprising a polymerization unit of a monomer represented by the following formula (1): In the above formula (1), R ₁ represents a branched alkyl group having 5 to 16 carbon atoms. The polymer according to claim 1, which is obtained by copolymerizing a monomer represented by the above formula (1) with a monomer copolymerizable with the monomer. The polymer according to claim 2, wherein the copolymerizable monomer is a cycloolefin monomer having a protic polar group. The polymer according to claim 3, wherein the cycloolefin monomer having a protic polar group is a cycloolefin monomer having a carboxyl group. The polymer of claim 1, which is a ring-opening polymer. A hydrogen-added product of a ring-opening polymer formed by adding a hydrogen to a carbon-carbon double bond contained in a main chain of the ring-opening polymer described in claim 5 of the patent application. A resin composition comprising a polymer (A) and a solvent (B), wherein the polymer (A) is a polymer according to claim 1 of the patent application. A resin composition comprising a polymer (A) and a solvent (B), It is characterized in that the polymer (A) is a hydrogen additive of the ring-opening polymer described in claim 6 of the patent application. The resin composition according to claim 8 or 9, wherein the resin composition further comprises a bridging agent (C). The resin composition according to claim 8 or 9, wherein the resin composition further contains a radiation sensitive compound (D). A resin film formed by using the resin composition described in claim 8 or 9. An electronic component having the resin film described in claim 11 of the patent application.