JP2010224533A - Radiation-sensitive resin composition, resin film, and electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition allowing simple formation of a film, in a short time, to obtain a resin film maintaining high flatness and causing no film defect such as wrinkles, even if the film is subjected to other processings, such as, forming a conductive thin film on the resin film. <P>SOLUTION: The radiation-sensitive resin composition contains: a resin (A); a crosslinking agent (B) having an epoxy group; a crosslinking agent (C) having a triazine cyclic structure or a glycoluril structure and having at least one kind of functional group selected from among a group consisting of imino group, methylol group and alkoxybutyl group; and a radiation-sensitive compound (D). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a radiation-sensitive resin composition and a resin film obtained from the radiation-sensitive resin composition. More specifically, the present invention relates to a radiation-sensitive material suitable for manufacturing electronic components such as display elements, integrated circuit elements, and solid-state imaging elements. The present invention relates to a resin composition, a resin film obtained from the radiation-sensitive resin composition, and an electronic component having the resin film.

  Electronic components such as display elements, integrated circuit elements, solid-state imaging elements, color filters, thin film transistors, and black matrices are derived from the elements and wirings of the protective film, the substrate having the elements and wirings to prevent their deterioration and damage Various resin films are provided as a flattening film for flattening unevenness and an electric insulating film for maintaining electric insulation. An element such as a thin film transistor type liquid crystal display element or an integrated circuit element is provided with a resin film as an interlayer insulating film in order to insulate a plurality of wirings arranged in layers. In addition, the organic EL element generally has a configuration including an anode / hole injection transport layer / organic light emitting layer / electron injection layer / cathode as a configuration of the light emitting portion. A partition wall (also referred to as a pixel isolation film, a pixel definition film, or an element isolation film) is provided in order to electrically insulate from the elements and wirings, and a planarization film is provided between an active element such as a transistor and an anode. Is provided. Conventionally, various radiation-sensitive resin compositions have been used as materials for forming these resin films.

  For example, Patent Document 1 discloses a radiation-sensitive resin composition containing an alkali-soluble resin, a crosslinking agent having a triazine ring structure and having a methylol group or an alkoxyalkyl group, and a radiation-sensitive acid generator. Is disclosed. According to Patent Document 1, it is disclosed that this radiation-sensitive resin composition is excellent in various performances such as insulation, flatness, heat resistance, transparency, and chemical resistance.

  Patent Document 2 discloses a radiation-sensitive resin composition containing an alicyclic olefin resin, an acid generator, an epoxy group having a crosslinking agent as a reactive group of the crosslinking agent, and a crosslinking agent having a triazine ring structure. An epoxy group is disclosed as an example of the reactive group of the crosslinking agent, and a crosslinking agent having a triazine ring structure or a glycoluril structure is disclosed as a specific example of the crosslinking agent. According to Patent Document 2, it is disclosed that this radiation-sensitive resin composition is excellent in coating uniformity, storage stability, flatness, transparency and heat discoloration.

  Patent Document 3 discloses a radiation-sensitive material containing an alkali-soluble resin, a compound having a quinonediazide group, an epoxy resin, and a compound having a triazine ring structure and alkyl etherification of a part or all of a methylol group. A functional resin composition is disclosed. According to Patent Document 3, it is disclosed that this radiation-sensitive resin composition is excellent in resolution, insulation, thermal shock and adhesion, and can form a cured product with little change in pattern shape before and after post-baking. Has been.

  However, the radiation-sensitive resin compositions disclosed in these publications are flattened through other processes even though the resin film formed using the radiation-sensitive resin film is flat after formation. There was a problem that the property was remarkably deteriorated and a wrinkled pattern was formed on the film. For example, a conductive thin film such as a metal, ITO, or IZO is often formed on a resin film formed using the radiation-sensitive resin composition because of the structure of the member used. As described above, there is a problem that the flatness deteriorates when the conductive thin film is formed on the resin film. In particular, when trying to shorten the time required for the process for forming a resin film, the above problem appears remarkably.

JP 2002-249646 A JP 2003-195488 A JP 2007-079553 A

  Accordingly, an object of the present invention is to easily and quickly form a resin film that maintains high flatness and does not cause film defects such as wrinkles even after other processes such as forming a conductive thin film on the resin film. It aims at providing the radiation sensitive resin composition which can be formed into a film, the resin film obtained from this radiation sensitive resin composition, and the electronic component which has this resin film.

  As a result of intensive studies to achieve the above object, the present inventors have obtained a resin, a crosslinking agent having an epoxy group, a crosslinking agent having a specific structure and a specific functional group, a radiation-sensitive compound, The present inventors have found that a radiation-sensitive resin composition comprising a combination of is very effective, and have completed the present invention based on this finding.

  Thus, according to the present invention, the resin (A), the crosslinking agent (B) having an epoxy group, a triazine ring structure or a glycoluril structure, and an imino group, a methylol group and an alkoxybutyl group are selected. There is provided a radiation-sensitive resin composition having a crosslinking agent (C) having one or more functional groups and a radiation-sensitive compound (D).

  It is preferable that the molecular weight of the crosslinking agent (B) having an epoxy group is 200 or more.

  It is preferable that the crosslinking agent (B) having an epoxy group has at least two epoxy groups in the molecule.

  The radiation sensitive compound (D) is preferably a photoacid generator.

  The photoacid generator is preferably a quinonediazide compound.

  Moreover, according to this invention, the resin film formed using the radiation sensitive resin composition is provided.

  Moreover, according to this invention, the electronic component using the said resin film is provided.

  According to the present invention, a resin film that maintains high flatness even after other processes such as forming a conductive thin film on the resin film and does not cause film defects such as wrinkles can be easily formed in a short time. It is possible to provide a radiation sensitive resin composition that makes it possible. Thereby, it is possible to obtain an electronic component such as a high-definition display device in which no defect or display defect occurs.

  The radiation-sensitive resin composition of the present invention has a resin (A), a cross-linking agent (B) having an epoxy group, a triazine ring structure or a glycoluril structure, and an imino group, a methylol group and an alkoxybutyl group. It contains a crosslinking agent (C) having one or more functional groups selected from the above, and a radiation-sensitive compound (D).

  In the present invention, the resin (A) is not particularly limited, and examples thereof include cyclic olefin resins, acrylic resins, acrylamide resins, polysiloxanes, epoxy resins, phenol resins, cardo resins, polyimides, polyamideimides, polycarbonates, and polyethylene terephthalates. Can be mentioned. Among these, it is preferable to include at least one selected from the group consisting of a cyclic olefin resin, an acrylic resin, a cardo resin, a polysiloxane and a polyimide resin, and among these, high flatness and high transparency even after passing through other steps. In addition, the flatness due to other processes does not deteriorate even under a wide range of film formation conditions, so the yield can be improved and the production lead time can be reduced, and the flatness can be achieved even in a large area. The cyclic olefin resin is more preferable from the viewpoint of maintaining the properties, and the cyclic olefin resin having a protic polar group is particularly preferable. These resins may be used alone or in combination of two or more.

  In the present invention, the cyclic olefin resin is a homopolymer or copolymer of a cyclic olefin monomer having a cyclic structure (alicyclic ring or aromatic ring) and a carbon-carbon double bond. The cyclic olefin resin may have a unit derived from a monomer other than the cyclic olefin monomer. The ratio of the cyclic olefin monomer unit in the total structural units of the cyclic olefin resin is usually 30 to 100% by weight, preferably 50 to 100% by weight, and more preferably 70 to 100% by weight.

  In the cyclic olefin resin having a protic polar group, the protic polar group may be bonded to the cyclic olefin monomer unit or may be bonded to a monomer unit other than the cyclic olefin monomer, It is desirable that it is bonded to a cyclic olefin monomer unit.

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

  Specific examples of the protic polar group include polar groups having an oxygen atom such as a hydroxyl group, a carboxy group (hydroxycarbonyl group), a sulfonic acid group, and a phosphoric acid group; a primary amino group, a secondary amino group, and a primary group. A polar group having a nitrogen atom such as a secondary amide group or a secondary amide group (imide group); a polar group having a sulfur atom such as a thiol group; Among these, those having an oxygen atom are preferable, and a carboxy group is more preferable. In the present invention, the number of protic polar groups bonded to the cyclic olefin resin having a protic polar group is not particularly limited, and different types of protic polar groups may be included.

  As a monomer for constituting a cyclic olefin resin having a protic polar group, a cyclic olefin monomer having a protic polar group (a), a cyclic olefin monomer having a polar group other than a protic polar group (B), a cyclic olefin monomer having no polar group (c), and a monomer other than the cyclic olefin (d) (these monomers are hereinafter simply referred to as monomers (a) to (d)). .). Here, the monomer (d) may have a protic polar group or other polar group, or may not have a polar group at all. In the present invention, the cyclic olefin resin having a protic polar group is preferably composed of the monomer (a), the monomer (b) and / or the monomer (c). More preferably, it is composed of (a) and the monomer (b).

Specific examples of the monomer (a) include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene and 5-methyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene. Ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 9-hydroxycarbonyltetra Cyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9,10-dihydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . Carboxy group-containing cyclic olefin such as 0 ^2,7 ] dodec-4-ene; 5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5- (4-hydroxy Phenyl) bicyclo [2.2.1] hept-2-ene, 9- (4-hydroxyphenyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9- (4-hydroxyphenyl) tetracyclo [6.2.1.1 ^3,6 . Hydroxyl group-containing cyclic olefins such as 0 ^2,7 ] dodec-4-ene and the like are mentioned, among which carboxy group-containing cyclic olefins are preferable. These cyclic olefin monomers (a) having a protic polar group may be used alone or in combination of two or more.

  Specific examples of polar groups other than protic polar groups possessed by the cyclic olefin monomer (b) having polar groups other than protic polar groups are generically referred to as ester groups (alkoxycarbonyl groups and aryloxycarbonyl groups). .), N-substituted imide group, epoxy group, halogen atom, cyano group, carbonyloxycarbonyl group (acid anhydride residue of dicarboxylic acid), alkoxy group, carbonyl group, tertiary amino group, sulfone group, acryloyl group Etc. Among these, an ester group, an N-substituted imide group, and a cyano group are preferable, an ester group and an N-substituted imide group are more preferable, and an N-substituted imide group is particularly preferable.

Specific examples of the monomer (b) include the following cyclic olefins. Examples of the cyclic olefin having an ester group include 5-acetoxybicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl- 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 9-acetoxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-propoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-isopropoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-butoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-ethoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-n-propoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-isopropoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-n-butoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene and the like.

Examples of the cyclic olefin having an N-substituted imide group include N-phenylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -1-isopropyl. -4-methylbicyclo [2.2.2] oct-5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-[(2-ethylbutoxy) ethoxypropyl] -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (endobicyclo [2.2 .1] hept-5-ene-2,3-diyldicarbonyl) dimethyl aspartate and the like. Examples of the cyclic olefin having a cyano group include 9-cyanotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-cyanotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 5-cyanobicyclo [2.2.1] hept-2-ene and the like. Examples of the cyclic olefin having a halogen atom include 9-chlorotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-chlorotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene and the like. These cyclic olefin monomers (b) having a polar group other than the protic polar group may be used alone or in combination of two or more.

Specific examples of the cyclic olefin monomer (c) having no polar group include bicyclo [2.2.1] hept-2-ene (also referred to as “norbornene”), 5-ethyl-bicyclo [2. 2.1] Hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene- Bicyclo [2.2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 ^2,6 ] deca-3,8 - diene (common name: dicyclopentadiene), tetracyclo [10.2.1.0 ^2,11. 0 ^4,9 ] pentadeca-4,6,8,13-tetraene, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (also referred to as “tetracyclododecene”), 9-methyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-vinyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-propenyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, pentacyclo [9.2.1.1 ^3,9 . 0 ^2,10] pentadeca-5,12-diene, cyclopentene, cyclopentadiene, 9-phenyl - tetracyclo [6.2.1.1 ^{3, 6.} 0 ^2,7] dodeca-4-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene, pentacyclo [9.2.1.1 ^3,9 . 0 ^2,10] pentadeca-12-ene, and the like. These cyclic olefin monomers (c) having no polar group may be used alone or in combination of two or more.

  A specific example of the monomer (d) other than the cyclic olefin includes a chain olefin. Examples of the chain olefin include ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, C2-C20 α-olefins such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; 1,4-hexadiene, 4-methyl-1 , 4-hexadiene, 5-methyl-1,4-hexadiene, non-conjugated dienes such as 1,7-octadiene, and the like. Monomers (d) other than these cyclic olefins can be used alone or in combination of two or more.

  The cyclic olefin resin having a protic polar group used in the present invention is obtained by polymerizing the monomer (a) together with a monomer selected from the monomers (b) to (d) as desired. . The polymer obtained by polymerization may be further hydrogenated. A hydrogenated polymer is also included in the cyclic olefin resin having a protic polar group used in the present invention.

  In addition, the cyclic olefin resin having a protic polar group used in the present invention introduces a protic polar group into a cyclic olefin resin having no protic polar group using a known modifier, and optionally hydrogenated. It can be obtained also by the method of performing. Hydrogenation may be performed on the polymer before introduction of the protic polar group. Further, the cyclic olefin resin having a protic polar group may be further modified to introduce a protic polar group.

  A polymer having no protic polar group can be obtained by polymerizing the monomers (b) to (d) in any combination.

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

  The polymerization method for polymerizing the monomer (a) together with a monomer selected from the monomers (b) to (d) as desired may be in accordance with a conventional method, for example, ring-opening polymerization method or An addition polymerization method is employed. As the polymerization catalyst, for example, metal complexes such as molybdenum, ruthenium and osmium are preferably used. These polymerization catalysts can be used alone or in combination of two or more. The amount of the polymerization catalyst is usually from 1: 100 to 1: 2,000,000, preferably from 1: 500 to 1: 1,000,000, more preferably in the molar ratio of metal compound to cyclic olefin in the polymerization catalyst. Is in the range of 1: 1,000 to 1: 500,000. Hydrogenation of the polymer obtained by polymerizing each monomer is usually performed using a hydrogenation catalyst. As the hydrogenation catalyst, for example, those generally used for hydrogenation of olefin compounds can be used. Specifically, a Ziegler type homogeneous catalyst, a noble metal complex catalyst, a supported noble metal catalyst, and the like can be used. Among these hydrogenation catalysts, no side reactions such as functional group modification occur, and noble metals such as rhodium and ruthenium can be selectively hydrogenated from the main chain carbon-carbon unsaturated bonds in the polymer. A complex catalyst is preferable, and a nitrogen-containing heterocyclic carbene compound having a high electron donating property or a ruthenium catalyst coordinated with a phosphine is particularly preferable.

The hydrogenation rate of the main chain of the hydrogenated polymer is usually 90% or more, preferably 95% or more, more preferably 98% or more. When the hydrogenation rate is within this range, the resin (A) is particularly excellent in heat resistance and suitable. The hydrogenation rate of the resin (A) can be measured by ¹ H-NMR spectrum. For example, it can obtain | require as a ratio with respect to the carbon-carbon double bond mole number before hydrogenation of hydrogenated carbon-carbon double bond mole number.

In the present invention, as the cyclic olefin resin having a protic polar group, those having a structural unit represented by the formula (I) as shown below are particularly suitable, and a structure represented by the formula (I) What has a unit and the structural unit represented by Formula (II) is more suitable.

Wherein ^(I), R 1 ~R ⁴ are each independently a hydrogen atom or _-X n -R 'group (X is a divalent organic group; n is 0 or 1; R' Is an alkyl group which may have a substituent, an aromatic group which may have a substituent, or a protic polar group. At least one of R ^{1 to} R ⁴ is a —X _n —R ′ group in which R ′ is a protic polar group. m is an integer of 0-2. ]

[In formula (II), R < ⁵ > -R < ⁸ > is 3-5 membered heterocyclic ring which contains an oxygen atom or a nitrogen atom as a ring-constituting atom with two carbon atoms to which they are couple | bonded. A structure is formed, and this heterocyclic ring may have a substituent on the heterocyclic ring. k is an integer of 0-2. ]
In the general formula (I), examples of the divalent organic group represented by X include a methylene group, an ethylene group, and a carbonyl group.

  The alkyl group which may have a substituent represented by R ′ is usually a linear or branched alkyl group having 1 to 7 carbon atoms, and examples thereof include a methyl group, an ethyl group, n -A propyl group, an isopropyl group, etc. are mentioned. The aromatic group which may have a substituent is usually an aromatic group having 6 to 10 carbon atoms, and examples thereof include a phenyl group and a benzyl group. Examples of substituents for these alkyl groups and aromatic groups include alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl groups; phenyl groups And aryl groups having 6 to 12 carbon atoms such as xylyl group, tolyl group and naphthyl group. Examples of the protic polar group represented by R ′ include the groups described above.

In the general formula (II), examples of the 3-membered heterocyclic structure formed by R ^{5 to} R ⁸ together with two carbon atoms to which R ^{5 to} R ⁸ are bonded include an epoxy structure. Similarly, examples of the 5-membered heterocyclic structure include dicarboxylic anhydride structure [—C (═O) —O—C (═O) —], dicarboximide structure [—C (═O) —N— C (= O)-] and the like. Examples of the substituent bonded to the heterocyclic ring include phenyl group, naphthyl group, anthracenyl group, butyl group, pentyl group, hexyl group, 1-methylpentyl group, 1-ethylbutyl group, octyl group, 2-ethylhexyl group, Examples thereof include linear alkyl groups such as nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group and hexadecyl group, branched alkyl groups, and ester-containing groups such as dimethyl aspartate.

  The acrylic resin used in the present invention is not particularly limited, but a homopolymer having at least one selected from a carboxylic acid having an acrylic group, a carboxylic acid anhydride having an acrylic group, or an epoxy group-containing acrylate compound as an essential component. Or a copolymer is preferable.

  Specific examples of the carboxylic acid having an acrylic group include (meth) acrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutaconic acid, etc .; specific examples of the carboxylic acid anhydride having an acrylic group include maleic anhydride Acid, citraconic anhydride, etc .; specific examples of epoxy group-containing acrylate compounds include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n-butyl acrylic acid Glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6 7-epoxyheptyl; and the like. Of these, (meth) acrylic acid, maleic anhydride, glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl and the like are preferable. In the present invention, “(meth)” means either methacryl or acryl.

  The acrylic resin is a copolymer of at least one selected from an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride and an epoxy group-containing unsaturated compound and another acrylate monomer or a copolymerizable monomer other than an acrylate. It may be a polymer. Other acrylate monomers include methyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl ( Alkyl (meth) acrylates such as meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, etc. Hydroxyalkyl (meth) acrylates; phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate; Alkoxyalkyl (meth) acrylates such as xylethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxy polyethylene glycol Polyalkylene glycol (meth) acrylates such as (meth) acrylate; cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopenta Dienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meta Cycloalkyl (meth) acrylates such as acrylate; benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate. Of these, butyl (meth) acrylate, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and the like are preferable.

  The copolymerizable monomer other than the acrylate is not particularly limited as long as it is a compound copolymerizable with the carboxylic acid having an acrylic group, a carboxylic acid anhydride having an acrylic group, or an epoxy group-containing acrylate compound. And vinyl group-containing radical polymerizable compounds such as vinyl benzyl methyl ether, vinyl glycidyl ether, styrene, α-methyl styrene, butadiene, and isoprene. These compounds may be used alone or in combination of two or more. The monomer polymerization method may be in accordance with a conventional method, for example, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method or the like is employed.

A cardo resin is a resin having a cardo structure, that is, a skeletal structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure. A common cardo structure is a fluorene ring bonded to a benzene ring. Specific examples of the skeleton structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure include a fluorene skeleton, a bisphenol fluorene skeleton, a bisaminophenyl fluorene skeleton, a fluorene skeleton having an epoxy group, and an acrylic group. And a fluorene skeleton having the same. The cardo resin used in the present invention is formed by polymerizing the skeleton having the cardo structure by a reaction between functional groups bonded thereto. The cardo resin has a structure in which a main chain and bulky side chains are connected by one element (cardo structure), and has a ring structure in a direction substantially perpendicular to the main chain. An example of a cardo structure having an epoxy glycidyl ether structure is shown in Formula (III).

(In formula (III), n represents an integer of 0 to 10)
Monomers having a cardo structure include, for example, bis (glycidyloxyphenyl) fluorene type epoxy resin; condensate of bisphenol fluorene type epoxy resin and acrylic acid; 9,9-bis (4-hydroxyphenyl) fluorene, Cardio structure-containing bisphenols such as 9-bis (4-hydroxy-3-methylphenyl) fluorene; 9,9-bis (cyanoalkyl) fluorenes such as 9,9-bis (cyanomethyl) fluorene; -9,9-bis (aminoalkyl) fluorenes such as bis (3-aminopropyl) fluorene; The cardo resin is a polymer obtained by polymerizing a monomer having a cardo structure, but may be a copolymer with other copolymerizable monomers. The polymerization method of the monomer may be according to a conventional method, and for example, a ring-opening polymerization method or an addition polymerization method is employed.

The structure of the polysiloxane used in the present invention is not particularly limited, but preferably includes a polysiloxane obtained by mixing and reacting at least one organosilane represented by the formula (IV).

R _{9 in} formula (IV) represents any one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and the plurality of R ₉ are the same. It can be different. In addition, these alkyl groups, alkenyl groups, and aryl groups may all have a substituent, or may be unsubstituted without a substituent, and are selected according to the characteristics of the composition. it can. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 2,2 , 2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, 3-mercaptopropyl Group, 3-isocyanatopropyl group. Specific examples of the alkenyl group include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group. Specific examples of the aryl group include phenyl group, tolyl group, p-hydroxyphenyl group, 1- (p-hydroxyphenyl) ethyl group, 2- (p-hydroxyphenyl) ethyl group, 4-hydroxy-5- (p -Hydroxyphenylcarbonyloxy) pentyl group, naphthyl group.

R _{10 in} formula (IV) represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ₁₀ may be the same. It may be different. In addition, these alkyl groups and acyl groups may have a substituent or may be an unsubstituted form having no substituent, and can be selected according to the characteristics of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Specific examples of the acyl group include an acetyl group. Specific examples of the aryl group may include a phenyl group. N in the formula (IV) represents an integer of 0 to 3. A tetrafunctional silane when n = 0, a trifunctional silane when n = 1, a bifunctional silane when n = 2, and a monofunctional silane when n = 3.

  Specific examples of the organosilane represented by the formula (IV) include tetrafunctional silanes such as tetramethoxysilane and tetraethoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane Ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltri Methoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, p-hydroxyphenyltrimethoxysilane, 2- (p-hydroxy) Phenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Trifunctional silanes such as glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxy And bifunctional silanes such as silane, di-n-butyldimethoxysilane and diphenyldimethoxysilane; monofunctional silanes such as trimethylmethoxysilane and tri-n-butylethoxysilane.

  Of these organosilanes, trifunctional silanes are preferably used from the viewpoint of crack resistance and hardness of the resin film obtained from the resin composition of the present invention. These organosilanes may be used alone or in combination of two or more.

  The polysiloxane in the present invention can be obtained by hydrolysis and partial condensation of the above organosilane. A general method can be used for hydrolysis and partial condensation. For example, a solvent, water and, if necessary, a catalyst are added to the mixture, and the mixture is heated and stirred. During stirring, if necessary, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) may be distilled off by distillation.

  The polyimide used by this invention can be obtained by heat-processing the polyimide precursor obtained by making tetracarboxylic anhydride and diamine react. Examples of the precursor for obtaining the polyimide resin include polyamic acid, polyamic acid ester, polyisoimide, and polyamic acid sulfonamide. Specific examples of the acid dianhydride that can be used as a raw material for polyimide include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Anhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) ) No methane Bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2 , 5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9 , 10-perylenetetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride such as 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, butanetetracarboxylic dianhydride And aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-cyclopentanetetracarboxylic dianhydride. These acid dianhydrides can be used alone or in combination of two or more.

  Specific examples of diamines that can be used as raw materials for polyimide include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4 '-Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m- Phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl , Screw {4 (4-Aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4,4′- Diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-diethyl-4,4′-diaminobiphenyl, 2,2 ′, 3,3′-tetramethyl-4,4 ′ -Diaminobiphenyl, 3,3 ', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl, or aromatics thereof Examples include compounds substituted on the ring with an alkyl group or a halogen atom, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and the like. These diamines can be used alone or in combination of two or more.

  The polyimide used in the present invention is synthesized by a known method. That is, a tetracarboxylic dianhydride and a diamine are selectively combined, and these are combined with N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphorotriamide, It is synthesized by a known method such as reacting in a polar solvent such as γ-butyrolactone or cyclopentanone.

  The weight average molecular weight (Mw) of the resin (A) used in the present invention is usually 1,000 to 1,000,000, preferably 1,500 to 100,000, more preferably 2,000 to 10,000. 000 range. The molecular weight distribution of the resin (A) is a weight average molecular weight / number average molecular weight (Mw / Mn) ratio, and is usually 4 or less, preferably 3 or less, more preferably 2.5 or less. The weight average molecular weight (Mw) and molecular weight distribution of the resin (A) can be measured using gel permeation chromatography. For example, it can be determined as a molecular weight in terms of polystyrene using a solvent such as tetrahydrofuran as an eluent.

  The radiation sensitive resin composition of this invention has the crosslinking agent (B) which has an epoxy group as an essential component.

  The crosslinking agent (B) having an epoxy group is not particularly limited as long as it has an epoxy group and undergoes a crosslinking reaction with the crosslinking agent (B) itself or with another component different from the crosslinking agent (B). However, the weight average molecular weight is preferably 200 or more and 5000 or less, more preferably 500 or more and 4000 or less, still more preferably 700 or more and 3000 or less, and most preferably 1000 or more and 2800 or less. When the weight average molecular weight of the crosslinking agent (B) having an epoxy group is within the above range, the compatibility between the crosslinking agent (B) and the resin (A) is good, and the resulting resin film becomes a uniform film, Even when other processes such as forming a conductive thin film on the resin film are performed, it is excellent in the effect of maintaining high flatness and suppressing the occurrence of film defects such as wrinkles. In addition, the weight average molecular weight of a crosslinking agent (B) can be analyzed in accordance with conventional methods, such as measuring by polystyrene conversion using a gel permeation chromatography.

  In the crosslinking agent (B), the number of epoxy groups is preferably 2 or more, 30 or less, more preferably 3 or more and 25 or less, and most preferably 4 or more and 20 or less. If the number of epoxy groups is excessively high, uncrosslinked epoxy groups remain even after the cross-linking reaction step, and the water absorption rate of the resulting resin film deteriorates. If the number is too low, sufficient cross-linking cannot be obtained. In other processes such as forming a conductive thin film on the resin film, the effect of maintaining high flatness and suppressing the occurrence of film defects such as wrinkles is inferior.

  The crosslinking agent (B) preferably has an epoxy equivalent of 50 or more and 2000 or less, more preferably 80 or more and 250 or less, and most preferably 100 or more and 180 or less. In addition, the epoxy equivalent of a crosslinking agent (B) can be measured according to JISK7236 "how to obtain the epoxy equivalent of an epoxy resin". When the epoxy equivalent of the crosslinking agent (B) having an epoxy group is within the above range, the firing time at the time of forming the resin film is short and a high crosslinking effect appears even in a resin film obtained easily. In other processes such as forming a conductive thin film, it is excellent in the effect of maintaining high flatness and suppressing the occurrence of film defects such as wrinkles.

  The crosslinking agent (B) preferably has an alicyclic structure, more preferably a compound having an epoxy group bonded to the alicyclic structure portion directly or through a divalent linking group. The alicyclic structure may be obtained by hydrogenating an aromatic ring.

  Examples of such an epoxy group-containing crosslinking agent (B) include bisphenol type epoxy resins, hydrogenated bisphenol type epoxy resins, phenol novolac type epoxy resins, hydrogenated phenol novolak type epoxy resins, naphthalene ring-containing epoxy resins, and fluorenes. Examples thereof include a ring-containing epoxy resin and an alicyclic epoxy resin.

Specific examples of the crosslinking agent (B) having an epoxy group include the following. 3,4-epoxycyclohexylmethyl acrylate (trade name “Cyclomer A400”, manufactured by Daicel Chemical Industries, 1 epoxy, molecular weight 282, epoxy equivalent 282 g / eq.), 2,2-bis (hydroxymethyl) -1 -1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of butanol (an alicyclic epoxy resin having a cyclohexane skeleton and a terminal epoxy group. Trade name “EHPE3150”, manufactured by Daicel Chemical Industries, Ltd., having 15 epoxies , Molecular weight 2550, epoxy equivalent 170 g / eq.), Epoxidized butanetetracarboxylic acid tetrakis- (3-cyclohexenylmethyl) modified ε-caprolactone (trade name “Epolide GT401”, manufactured by Daicel Chemical Industries, Ltd. Molecular weight 880, epoxy equivalent 220). Poxylated 3-cyclohexene-1,2-dicarboxylate bis (3-cyclohexenylmethyl) -modified ε-caprolactone (trade name “Epolide GT301”, manufactured by Daicel Chemical Industries, Ltd. 3 epoxy, molecular weight 600, epoxy equivalent 200 g / eq.), 1,2,8,9-diepoxy limonene (trade name “Celoxide 3000”, manufactured by Daicel Chemical Industries, Ltd. 2, epoxy number 2, molecular weight 168, epoxy equivalent 84 g / eq.), (3 ′ , 4′-epoxycyclohexane) methyl 3,4-epoxycyclohexanecarboxylate (trade name “Celoxide 2021”, manufactured by Daicel Chemical Industries, Ltd., 2 epoxy, molecular weight 280, epoxy equivalent 140 g / eq.), 4-vinylcyclohexene Xene oxide (trade name "Celoxide 2000", manufactured by Daicel Chemical Industries, Ltd. 1 epoxy, molecular weight 124, epoxy equivalent 124 g / eq), trimethylolpropane polyglycidyl ether (trade name “SR-TMP”, manufactured by Sakamoto Pharmaceutical Co., Ltd. 3 epoxy, molecular weight 411, epoxy equivalent 137 g / eq .) In addition, as a cross-linking agent (B) available as a commercial product, Aposkawa Chemical Co., Ltd. Composeran E series and the like can be mentioned.
In addition, all the molecular weights mentioned here are weight average molecular weights.

  In the radiation sensitive resin composition of the present invention, the content of the crosslinking agent (B) is usually 10 to 100 parts by weight, preferably 20 to 80 parts by weight, more preferably 100 parts by weight of the resin (A). It is the range of 20-50 weight part. When the amount of the crosslinking agent (B) used is within this range, the compatibility between the crosslinking agent (B) and the resin (A) is good, and the resulting resin film becomes a uniform film, and a conductive thin film is formed on the resin film. The film is excellent in the effect of maintaining high flatness and suppressing the occurrence of film defects such as wrinkles when other processes such as forming are performed.

The radiation-sensitive resin composition of the present invention has, as an essential component, one or more functional groups selected from the group consisting of an imino group, a methylol group, and an alkoxybutyl group, having a triazine ring structure or a glycoluril structure. It has a crosslinking agent (C). The cross-linking agent (C) has a triazine ring structure as shown in the following formula (V) or a glycoluril structure as shown in the following formula (VI). Among them, a conductive thin film is formed on the resin film. From the viewpoint of maintaining high flatness and excellent in suppressing the occurrence of film defects such as wrinkles when other processes such as forming a melamine structure, the melamine structure (formula (VII)) is preferable. ) Or a guanamine structure (formula (VIII)) is more preferred, and a melamine structure is most preferred.

[In Formula (VI), Y _{1 to} Y ₄ are each independently hydrogen, an alkyl group that may have a functional group, or an aryl group, alkoxy group, or alkoxyalkyl group that may have a functional group. Selected from the group of ]

[In Formula (VII), R17 to R22 are each independently selected from the group consisting of hydrogen, an alkyl group that may have a functional group, an aryl group that may have a functional group, an alkoxy group, and an alkoxyalkyl group. To be elected. ]

[In Formula (VIII), R13 to R16 are each independently selected from the group consisting of hydrogen, an alkyl group that may have a functional group, an aryl group that may have a functional group, an alkoxy group, and an alkoxyalkyl group. It is. X is selected from the group consisting of hydrogen, an alkyl group that may have a functional group, or an aryl group that may have a functional group. ]
As an example of the industrial manufacturing method of the crosslinking agent (C) which has a melamine structure, the following methods are mentioned, for example.

(1) One-step method

[In Formula (IX), R1 to 6 are each independently selected from the group consisting of hydrogen, an alkoxymethyl group, and a methylol group. R is an alkyl group or an aryl group. ]
In the one-stage method, melamine, formaldehyde and alcohol are methylolated under acidic conditions, and under the same conditions, the alkoxylation reaction is carried out while distilling off excess alcohol, formaldehyde and water contained in formaldehyde, and the water produced. How to do it. Under acidic conditions, polynuclearization proceeds simultaneously under high temperature conditions where alcohol and water are distilled off. Moreover, the water produced | generated by reaction with the water in raw material formaldehyde makes the alkoxylation reaction incomplete. Thus, in the one-step method in which the two reactions of methylolation and alkoxylation are performed in one step, a cross-linking agent (C) having a melamine skeleton having a polynuclear resin structure with a residual methylol group and a high free formaldehyde content is obtained. .

(2) Multistage method

[In formula (X), R1-6 are each independently selected from the group consisting of hydrogen, an alkoxymethyl group, and a methylol group. R7 to R12 are each independently hydrogen or a methylol group. R is an alkyl group or an aryl group. ]
In the multi-stage method, after carrying out a methylolation reaction under alkaline conditions, an alkoxylation reaction is incompletely carried out at a relatively low temperature under acidic conditions, and again under alkaline conditions to prevent multinucleation, After distilling off alcohol, water and excess formaldehyde, adding alcohol again and conducting the alkoxylation reaction at a relatively low temperature under acidic conditions, the volatile components in the reaction solution are again distilled off, if necessary. Thus, a diluting solvent is added so as to obtain a predetermined concentration. As described above, the production method by the multistage method in which the methylolation reaction and the alkoxylation reaction are performed under different conditions and the reaction and distillation are repeated, the methylol group equivalent with less polynuclear body is controlled, and the free formaldehyde content is low. A crosslinking agent (C) having a small melamine skeleton is obtained.

  According to the said manufacturing method, a crosslinking agent (C) may become a mixture instead of a single compound completely. For example, it can be a mixture of different polynuclear bodies or a mixture of different functional groups. Here, the mixture of different polynuclear bodies can know the average of the polynuclear bodies of the mixture from the average degree of polymerization.

The crosslinking agent (C) has at least one functional group selected from the group consisting of an imino group, a methylol group and an alkoxybutyl group. Even in a crosslinking agent in which the main component does not contain the functional group, a mixture containing the functional group that is unintentionally produced in production may sometimes be included. Not applicable to C). Accordingly, in the present invention, the crosslinking agent (C) having a triazine ring structure or a glycoluril structure and having one or more functional groups selected from the group consisting of an imino group, a methylol group, and an alkoxybutyl group, It shall contain at least one imino group, methylol group and alkoxybutyl group as a functional group per triazine ring or glycoluril structure, preferably per triazine ring or one glycoluril structure. The average number is 2 to 6. The number of functional groups is determined by, for example, cross-linking agent (C) with dimethyl sulfoxide as described in the new edition of Polymer Analysis Handbook (published by Kinokuniya Shoten, the first edition issued on January 12, 1995). It can be dissolved in -d ₆ (DMSO-d ₆ ) and quantified from the proton peak or carbon peak of the desired functional group by proton nuclear magnetic resonance spectrum ( ¹ H NMR) or carbon nuclear magnetic resonance spectrum ( ¹³ C NMR). .

  The crosslinking agent (C) is not particularly limited as long as it has one or more functional groups selected from the group consisting of an imino group, a methylol group and an alkoxybutyl group, but contributes to high flatness even after passing through other steps. In addition, since flatness does not deteriorate due to other processes even under a wide range of film forming conditions, the yield can be improved and production lead time can be reduced, and the flatness can be maintained even in a large area. In particular, an imino group and a methylol group are preferable, and a methylol group is more preferable.

  The crosslinking agent (C) may further have a functional group other than an imino group, a methylol group, and an alkoxybutyl group. Examples of such a functional group include a methoxymethyl group and an ethoxymethyl group. In addition, a crosslinking agent (C) does not contain an epoxy group.

  In addition, the average degree of polymerization of the crosslinking agent (C) has an effect of maintaining high flatness and suppressing the occurrence of film defects such as wrinkles when other processes such as forming a conductive thin film on the resin film are performed. Is preferably 1.3 or more, 4.0 or less, more preferably 1.8 or more and 3.5 or less, still more preferably 2.0 or more and 3.0 or less, and most preferably 2.4 or more and 2.8 or less. preferable. Within this range, the film retains high flatness even after passing through other processes, and is excellent in the effect of maintaining high flatness even under a wide range of film formation conditions, so that the yield can be improved and the production lead time can be reduced. By doing so, the resin film can be manufactured at a lower cost.

  As the crosslinking agent (C) having a triazine ring structure used in the present invention, a material commercially available from each company can be used.

  Examples of the crosslinking agent having a triazine ring structure but not having one or more functional groups selected from the group consisting of an imino group, a methylol group and an alkoxybutyl group include “Cymel 300” (1.35), “Cymel”. 301 ”(1.50),“ Cymel 303 ”(1.70),“ Cymel 350 ”(1.60),“ Cymel 1123 ”(1.50) {from Cytec Industries, Inc.},“ Nikarak MW- ” 30 HM ”(1.30),“ Nicarak MW 390 ”(1.25) {manufactured by Sanwa Chemical Co., Ltd.}, and the like. The numbers in parentheses indicate the average degree of polymerization.

  As the crosslinking agent (C) having a triazine ring structure and having a methylol group, “Cymel 370” (2.60), “Cymel 771” (2.20), “Cymel 272” (2.50), “My Coat 102” (1.32) {above, manufactured by Cytec Industries, Inc.}, “Nikarac MX-750” (2.20), “Nikalac MX-706” (2.60) {above, Sanwa Chemical Co., Ltd. ) Made by company}. The numbers in parentheses indicate the average degree of polymerization.

  As a crosslinking agent (C) having a triazine ring structure and having an imino group, “Cymel 325” (2.30), “Cymel 327” (1.80), “Cymel 703” (1.90), Examples include “Cymel 712” (1.40), “My Coat 105” (1.32), “My Coat 106” (1.5) {manufactured by Cytec Industries, Inc.}. The numbers in parentheses indicate the average degree of polymerization.

  As the crosslinking agent (C) having a triazine ring structure and having an alkoxybutyl group, “Cymel 266” (1.40), “Cymel 267” (1.50), “Cymel 285” (1.50) "Cymel 232" (1.50), "Cymel 235" (1.40), "Cymel 236" (1.40), "Cymel 238" (1.60), "My Coat 506" (2.20 ) {The above, made by Cytec Industries, Inc.} and the like. The numbers in parentheses indicate the average degree of polymerization.

  Examples of the crosslinking agent (C) having a triazine ring structure and having a methylol group and an imino group include “Cymel 701” (1.80) {above, manufactured by Cytec Industries, Inc.}. The numbers in parentheses indicate the average degree of polymerization.

  Examples of the crosslinking agent (C) having a triazine ring structure and having a methylol group and an alkoxybutyl group include “Cymel 272” (2.50) {above, manufactured by Cytec Industries, Ltd.}. The numbers in parentheses indicate the average degree of polymerization.

  As the crosslinking agent (C) having a triazine ring structure and having an imino group and an alkoxybutyl group, “Cymel 212” (1.60), “Cymel 253” (1.90), “Cymel 254” (2 .30), “My Coat 508” (2.60), “Cymel 1128” (3.00), “My Coat 130” (1.77) {manufactured by Cytec Industries, Inc.}, and the like. . The numbers in parentheses indicate the average degree of polymerization.

  As the crosslinking agent (C) having a triazine ring structure and having a methylol group, an imino group, and an alkoxybutyl group, “Cymel 202” (2.10), “Cymel 207” (2.10) {above, Cytec Industries, Inc.} can be exemplified. The numbers in parentheses indicate the average degree of polymerization.

  As the crosslinking agent (C) having a glycoluril structure and not having one or more functional groups selected from the group consisting of an imino group, a methylol group and an alkoxybutyl group, “Nicarac MX-270” (1. 25) {Made by Sanwa Chemical Co., Ltd.} and the like. The numbers in parentheses indicate the average degree of polymerization.

  As the crosslinking agent (C) having a glycoluril structure and having one or more functional groups selected from the group consisting of an imino group, a methylol group, and an alkoxybutyl group, “Cymel 1170” (1.50) , “Cymel 1172” (2.00) {manufactured by Cytec Industries, Inc.} and the like. The numbers in parentheses indicate the average degree of polymerization.

  The crosslinking agent (C) used in the present invention is preferably one having a small amount of metal. Examples of a method for reducing the amount of metal in the cross-linking material (C) include a method by a metal reduction treatment (hereinafter, sometimes abbreviated as “low metalization treatment”). Examples of the method for the metallization treatment include a method using filtration using a filter such as a zeta filter, a method using a metallization treatment agent, and the like.

  An example of the filter used for filtration is a zeta filter. A zeta filter is a porous filter having a zeta potential, and is usually a porous matrix made of cellulose, polyester, polyethylene, polypropylene, and a modifier having a positive zeta potential in a neutral liquid. is there. The substance which comprises a porous matrix can be used individually or in combination of 2 or more types among these. Examples of the modifier include cationic colloidal silica and polymer having a positive zeta potential in a neutral liquid. The metallization process of a crosslinking agent (C) can be performed by filtering the solution containing a crosslinking agent using a zeta filter.

  As a specific method of metallization treatment using a zeta filter, for example, the above-mentioned “Cymel 370” (manufactured by Cytec Industries), which is a kind of a crosslinking agent (C) having a triazine ring structure and having a methylol group As an organic solvent, diethylene glycol ethyl methyl ether was added in an amount adjusted to a solid part concentration of 30%, mixed and stirred, and a zeta filter (trade name “B90-40QSH”, manufactured by Sumitomo 3M). The Na concentration in the crosslinking agent can be reduced to less than 100 ppb.

  As the metallizing agent, an ion exchange resin or an adsorbent having a large adsorbing power can be used, and examples thereof include magnesium silicate, aluminum oxide, magnesium oxide, activated carbon and the like. Add a solution containing a crosslinking agent to these metallization treatment agents, and after stirring, remove the metallization treatment agent by filtration, or add a solution containing the crosslinking agent to a column filled with the metallization treatment agent. The metallization treatment of the crosslinking agent can be performed by a method such as passing through.

  As a specific method of the metallization treatment of the cross-linking agent with an ion exchange resin, for example, an ion exchange resin (trade name “200CT / MSPS2-1” manufactured by Sumitomo 3M) was stirred and washed in diethylene glycol ethyl methyl ether. After removing the supernatant liquid, a 30% solution of “Cymel 370” (manufactured by Cytec Industries) in diethylene glycol ethyl methyl ether was added, and the mixture was further stirred for 50 minutes. Na concentration less than 50 ppb, Mg concentration less than 50 ppb, Al concentration less than 50 ppb, K concentration less than 50 ppb, Ca concentration less than 300 ppb, Cr concentration less than 50 ppb, Mn concentration less than 50 ppb, Fe concentration less than 50 ppb, Ni The concentration can be less than 50 ppb.

  As the metallization treatment with magnesium silicate, for example, magnesium silicate (trade name “Mizuka Life P-1”) is used instead of the ion exchange resin (trade name “200CT / MSPS2-1” manufactured by Sumitomo 3M). Except for using Mizusawa Chemical Co., Ltd.), the Na concentration in the cross-linking agent can be reduced to less than 5000 ppb by the same method as the metallization treatment of the cross-linking agent by the ion exchange resin described above.

  As the metallization treatment of the crosslinking agent with aluminum oxide, for example, instead of the ion exchange resin (trade name “200CT / MSPS2-1” manufactured by Sumitomo 3M), aluminum oxide (trade name “activated alumina CPN”. Mizusawa) Except for using Chemical Co., Ltd., the metal concentration can be reduced by a method equivalent to the above-described metallization treatment of the crosslinking agent by the ion exchange resin, and the Na concentration in the crosslinking agent can be reduced to less than 20000 ppb.

  In the radiation sensitive resin composition of the present invention, the content of the crosslinking agent (C) is usually 10 to 100 parts by weight, preferably 20 to 80 parts by weight, more preferably 100 parts by weight of the resin (A). It is the range of 30-50 weight part. When the amount of the crosslinking agent (C) is within this range, the compatibility between the crosslinking agent (C) and the resin (A) is good, and the resulting resin film becomes a uniform film, and a conductive thin film is formed on the resin film. The film is excellent in the effect of maintaining high flatness and suppressing the occurrence of film defects such as wrinkles when other processes such as forming are performed.

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

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

  As the quinonediazide compound, for example, an ester compound of a quinonediazidesulfonic acid halide and a compound having a phenolic hydroxyl group can be used. Specific examples of the quinone diazide sulfonic acid halide include 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-benzoquinone diazide-5-sulfonic acid chloride, and the like. Can be mentioned. Typical examples of the compound having a phenolic hydroxyl group include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1. -[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and the like. Other compounds having a phenolic hydroxyl group include 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2-bis (4-hydroxyphenyl) propane, tris (4- Hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, novolac resin oligomer, phenolic hydroxyl group Examples thereof include oligomers obtained by copolymerizing one or more compounds and dicyclopentadiene. Among these, a condensate of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and a compound having a phenolic hydroxyl group is preferable, and 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl)- A condensate of 3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.5 mol) is more preferred.

  Photoacid generators include quinonediazide compounds, onium salts, halogenated organic compounds, α, α′-bis (sulfonyl) diazomethane compounds, α-carbonyl-α′-sulfonyldiazomethane compounds, sulfone compounds, organic acids Known compounds such as ester compounds, organic acid amide compounds, and organic acid imide compounds can be used.

  These radiation-sensitive compounds can be used alone or in combination of two or more. Among these, a quinonediazide compound is preferable because a positive radiation-sensitive composition can be prepared. Content of the radiation sensitive compound (D) in the resin composition of this invention is 1-100 weight part with respect to 100 weight part of resin (A), Preferably it is 5-50 weight part, More preferably, it is 10-40 weight. Part range. When the amount of the radiation sensitive compound (D) used is within this range, when the resin film made of the resin composition of the present invention formed on an arbitrary substrate is patterned, the radiation irradiated part and the radiation non-irradiated part This is preferable because the difference in solubility in a developer is increased, patterning by development is easy, and radiation sensitivity is increased.

  If desired, the resin composition used in the present invention is a sensitizer, a surfactant, a latent acid generator, an antioxidant, a light stabilizer, and an antifoaming agent as long as the effects of the present invention are not inhibited. , Other compounding agents such as pigments and dyes;

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

  In this invention, it is preferable to contain surfactant as a component of a resin composition. The surfactant is used for the purpose of preventing striation (after application stripes) and improving developability. Specific examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Aryl ethers; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Fluorine surfactants; Silicone surfactants; Methacrylic acid copolymer surfactants Agents; acrylic acid copolymer surfactants; and the like.

  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 include sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts, which are cationic polymerization catalysts that generate an acid upon heating. Of these, sulfonium salts and benzothiazolium salts are preferred.

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

  In this invention, it is preferable to contain a light stabilizer as a component of a radiation sensitive resin composition. Light stabilizers include benzophenone-based, salicylic acid ester-based, benzotriazole-based, cyanoacrylate-based, metal complex salt-based ultraviolet absorbers, hindered amine-based (HALS), etc. that capture radicals generated by light, etc. But you can. Among these, HALS is a compound having a piperidine structure and is preferable because it is less colored and has good stability with respect to the composition of the present invention. Specific compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl 1,2,3,4 -Butanetetracarboxylate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.

  In the present invention, the radiation-sensitive resin composition has a resin (A), a crosslinking agent (B) having an epoxy group, a triazine ring structure or a glycoluril structure, and an imino group, a methylol group, and an alkoxybutyl group. A cross-linking agent (C) having at least one group selected from the group, and a radiation-sensitive compound (D) as essential components, other components are added as necessary, and this is usually dissolved or dispersed in a solvent. Can be obtained.

  The solvent that can be used in the present invention is not particularly limited. For example, alcohols such as methanol, ethanol, propanol, butanol and 3-methoxy-3-methylbutanol; cyclic ethers such as tetrahydrofuran and dioxane; methyl Cellosolve esters such as cellosolve acetate and ethyl cellosolve acetate; ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol ethyl methyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate (PGMEA ) Glycol ethers; aromatic hydrocarbons such as benzene, toluene, xylene; methyl ethyl ketone, Ketones such as clopentanone, cyclohexanone, 2-peptanone, 4-hydroxy-4-methyl-2-pentanone; ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropion Esters such as ethyl acetate, ethyl ethoxyacetate, methyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl acetate, butyl acetate, ethyl lactate; N- And aprotic polar solvents such as methylformamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-methylacetamide, N, N-dimethylacetamide, dimethylsulfoxide, and γ-butyllactone.

  Among these, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate (PGMEA), cyclopentanone, and N-methyl-2-pyrrolidone are preferable, and diethylene glycol ethyl methyl ether is particularly preferable.

  These solvents may be used alone or in combination of two or more. The amount of the solvent used is usually 20 to 10,000 parts by weight, preferably 50 to 5,000 parts by weight, and more preferably 100 to 1,000 parts by weight with respect to 100 parts by weight of the resin (A). is there.

  The preparation method of the radiation sensitive resin composition of this invention is not specifically limited, Each component of the radiation sensitive resin composition of this invention, ie, resin (A), the crosslinking agent (B) which has an epoxy group, A crosslinking agent (C) having a triazine ring structure or a glycoluril structure and having one or more groups selected from the group consisting of an imino group, a methylol group and an alkoxybutyl group, and a radiation sensitive compound (D) and a desired one Other components to be used may be mixed by a known method.

  The mixing method is not particularly limited, but it is preferable to mix a solution or dispersion obtained by dissolving or dispersing each component of the radiation-sensitive resin composition in a solvent. Thereby, the radiation sensitive resin composition of this invention is obtained with the form of a solution or a dispersion liquid.

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

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

  The amount of metal contained in the radiation-sensitive resin composition of the present invention is such that each concentration of Na, Mg, Al, K, Ca, Cr, Mn, Fe, and Ni is less than 500 ppb with respect to the radiation-sensitive resin composition. Preferably less than 200 ppb, most preferably less than 100 ppb.

  The resin film of the present invention can be obtained by forming it on a substrate using the radiation sensitive resin composition of the present invention.

  In the present invention, for example, a printed wiring board, a silicon wafer substrate, a glass substrate, a plastic substrate, or the like can be used as the substrate. In addition, a glass substrate, a plastic substrate or the like used in the display field in which a thin transistor type liquid crystal display element, a color filter, a black matrix, or the like is formed is also preferably used.

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

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

  In the film lamination method, the radiation-sensitive resin composition is applied onto a B-stage film-forming substrate such as a resin film or a metal film, and then the solvent is removed by heat drying to obtain a B-stage film. In this method, a B-stage film is laminated on the substrate. The heating and drying conditions can be appropriately selected according to the type and mixing ratio of each component, but the heating temperature is usually 30 to 150 ° C., and the heating time is usually 0.5 to 90 minutes. . Film lamination can be performed using a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator or the like.

  The thickness of the resin film formed on the substrate is usually 0.1 to 100 μm, preferably 0.5 to 50 μm, more preferably 0.5 to 30 μm.

  In the present invention, after the resin film is formed on the substrate, a resin crosslinking reaction can be performed.

  Crosslinking of the resin film formed on the substrate may be appropriately selected according to the type of the crosslinking agent, but is usually performed by heating. The heating method can be performed using, for example, a hot plate or an oven. The heating temperature is usually 180 to 250 ° C., and the heating time is appropriately selected depending on the size and thickness of the resin film and the equipment used. For example, when a hot plate is used, the oven is usually used for 5 to 60 minutes. When used, it is usually in the range of 30 to 90 minutes. Heating may be performed in an inert gas atmosphere as necessary. The inert gas is not particularly limited as long as it does not contain oxygen and does not oxidize the resin film. Examples thereof include nitrogen, argon, helium, neon, xenon, and krypton. Among these, nitrogen and argon are preferable, and nitrogen is particularly preferable. In particular, an inert gas having an oxygen content of 0.1% by volume or less, preferably 0.01% by volume or less, particularly nitrogen is suitable. These inert gases can be used alone or in combination of two or more.

  In the laminated body which consists of a board | substrate and the resin film formed on the board | substrate using the radiation sensitive resin composition of this invention, the resin film may be patterned.

  The patterned resin film formed on the substrate, for example, exposes the resin film to actinic radiation to form a latent image pattern, and then exposes the developer film to the resin film having the latent image pattern to reveal the pattern. Can be obtained.

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

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

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

  After the desired patterned resin film is formed on the substrate in this way, the substrate is rinsed with a rinsing solution in order to remove development residues on the substrate, the back surface of the substrate, and the edge of the substrate, if necessary. Can do. After the rinse treatment, the remaining rinse liquid is removed with compressed air or compressed nitrogen.

  Further, if necessary, the entire surface of the substrate having the patterned resin film can be irradiated with actinic radiation in order to deactivate the photoacid generator. For irradiation with actinic radiation, the method exemplified in the formation of the latent image pattern can be used. The resin film may be heated simultaneously with irradiation or after irradiation. Examples of the heating method include a method of heating the substrate in a hot plate or an oven. The temperature is usually in the range of 100 to 300 ° C, preferably 120 to 200 ° C.

  In this invention, after forming patterned resin on a board | substrate, the crosslinking reaction of patterned resin can be performed. The crosslinking may be performed in the same manner as the above-described crosslinking of the resin film formed on the substrate.

  The laminate of the present invention, particularly a laminate in which a patterned resin film is formed on a substrate, is useful as various electronic components, particularly semiconductor devices.

  Among the various electronic components, for example, it can be used as a partition material of a light emitting element of an organic EL display device. In the case of an active matrix organic EL display device, the partition material is located above the switching transistor of the active matrix substrate, and the light leakage current can be suppressed as the transparency is lower. Furthermore, both the active matrix organic EL display device and the passive matrix organic EL display device are preferable because the display contrast is improved. For example, the transparency of the partition material is preferably 20% or less in terms of light transmittance at a wavelength of 450 nm when the film thickness is 1.5 μm.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In this example, “parts” and “%” are “parts by weight” and “% by weight”, respectively, unless otherwise specified.

Each characteristic was evaluated by the following methods.
(1) Flatness 1 (wrinkle)
As one of the indicators of flatness, the measurement sample was observed with an optical microscope to confirm whether or not a wrinkle pattern was observed. The wrinkle pattern is generated when the flatness of the film is impaired. Therefore, the fact that no wrinkle pattern is observed means that the flatness of the film is good.
○: No wrinkle (good flatness)
×: wrinkle (poor flatness)
(2) Flatness 2 (light transmittance)
As another index of flatness, the measurement sample was measured using a spectrophotometer (manufactured by JASCO Corporation, “UV-visible spectrophotometer V-560 (product name)”). Here, the light transmittance is low because the flatness of the film is impaired and the light is refracted, and the light transmittance is high because the flatness of the film is good and the light is refracted. Therefore, it means that the higher the light transmittance, the better the flatness of the film and the less wrinkles. No wrinkles were observed in the observation under the optical microscope.
(3) Electrical characteristics (TFT off leak)
As one of the indicators of electrical characteristics, a protective film of the photosensitive resin composition of the present invention was formed on an active matrix substrate having an inverted staggered TFT, and the leakage current of the TFT immediately after film formation was measured. It can be said that the lower the leakage current, the better the characteristics as a protective film. The amount of current is preferably 1 × 10 ⁻¹⁰ A or less. Details are described below.

<Production of active matrix substrate>
On a glass substrate (trade name “Corning 1737”, manufactured by Corning), a sputtering apparatus is used to form chromium with a film thickness of 200 nm, patterning is performed by photolithography, and gate electrodes, gate signal lines, and gate terminal portions Formed. Next, the gate electrode and the gate electrode are covered with a CVD apparatus, the silicon nitride film serving as the gate insulating film is 450 nm thick, the a-Si layer (amorphous silicon layer) serving as the semiconductor layer is 250 nm thick, ohmic An n + Si layer to be a contact layer was continuously formed with a thickness of 50 nm, and the n + Si layer and the a-Si layer were patterned in an island shape. Further, chromium is formed to a thickness of 200 nm on the gate insulating film and the n + Si layer by a sputtering apparatus, and a source electrode, a source signal line, a drain electrode, and a data terminal portion are formed by photolithography, and the source electrode and the drain are formed. The unnecessary n + Si layer between the electrodes was removed to form a back channel having a source-drain line width of 14 μm and a distance between the source-drain electrodes of 3 μm, and a plurality of thin film transistors were formed on the glass substrate. An array substrate was obtained.

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

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

And the leakage current of TFT of the active matrix substrate was evaluated using the radiation sensitive resin composition obtained above. The gate voltage is swept from −10 V to +10 V, the drain voltage is +10 V, the source voltage is 0 V, the minimum drain current is the leakage current, and the evaluation is shown in Table 1 as follows.
○: Leakage current ≦ 1 × 10 ⁻¹⁰ A
×: Leakage current> 1 × 10 ⁻¹⁰ A

[Preparation of measurement sample]
A 10 cm square glass substrate [Corning, Corning 1737 (product name)] was spin-coated with the radiation-sensitive resin compositions obtained in the following Examples and Comparative Examples, and then heated at 90 ° C. for 2 minutes using a hot plate. Pre-baking was performed to form a resin film having a thickness of 2.5 μm. Next, a development treatment was performed at 25 ° C. for 60 seconds using a 0.4 wt% tetramethylammonium hydroxide aqueous solution, followed by rinsing with ultrapure water for 30 seconds. The resin film was irradiated with ultraviolet rays having a light intensity of 5 mW / cm ² at 365 nm in the air for 60 seconds. Furthermore, the post-baking which heats the desired time selected from 230 minutes at 230 degreeC for 30 minutes, 60 minutes, 90 minutes, and 120 minutes was performed. Here, it was confirmed that the obtained resin film was not observed to be wrinkled, the light transmittance was as high as 90% or more, and the flatness was sufficiently high.

  Next, an IZO thin film having a thickness of 90 nm was formed as a conductive thin film on the resin film at room temperature by sputtering. Furthermore, annealing was performed at 230 ° C. for 60 minutes using an oven to obtain a laminate as a measurement sample, and the flatness was evaluated by the above method.

[Production Example 1]
(Production of cyclic olefin polymer having a protic polar group)
As a cyclic olefin monomer having a protic polar group, 9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene 66.5 parts, N-phenylbicyclo [2.2.1] hept-5-ene-2 as cyclic olefin monomer having polar group other than protic polar group, 40 parts of 3-dicarboximide, 2.8 parts of 1,5-hexadiene, 0.05 part of (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride and diethylene glycol ethyl methyl ether 400 parts were charged into a nitrogen-substituted pressure-resistant glass reactor, and a polymerization reaction was carried out at 80 ° C. for 2 hours with stirring to obtain a polymerization reaction solution containing a ring-opening metathesis polymer a1. The polymerization conversion rate was 99.9% or more. The polymer a1 had a weight average molecular weight of 3,200, a number average molecular weight of 1,900, and a molecular weight distribution of 1.68. The weight average molecular weight, number average molecular weight, and molecular weight distribution were measured using three types of columns manufactured by Tosoh Corporation (model number: TSKgel SuperH2000, TSKgel SuperH4000, TSKgel SuperH5000), and measured in terms of polystyrene by gel permeation chromatography. Went.

  Next, 0.1 part of bis (tricyclohexylphosphine) ethoxymethylene ruthenium dichloride as a hydrogenation catalyst was added to the polymerization reaction solution, and hydrogen was dissolved at a pressure of 4 MPa for 5 hours to proceed the hydrogenation reaction. 1 part was added, hydrogen was dissolved at 150 ° C. under a pressure of 4 MPa for 3 hours while stirring in an autoclave. Subsequently, the solution was taken out and filtered through a fluororesin filter having a pore size of 0.2 μm to separate the activated carbon to obtain 476 parts of a hydrogenation reaction solution containing a hydride a2 of the ring-opening metathesis polymer a1. Filtration could be performed without any delay. The hydrogenation reaction solution containing the hydride a2 obtained here had a solid content concentration of 20.6%, and the yield of the hydride a2 was 98.1 parts. The obtained hydride a2 had a weight average molecular weight of 4,430, a number average molecular weight of 2,570, and a molecular weight distribution of 1.72. The hydrogenation rate was 99.9%.

  The obtained hydrogenation reaction solution of hydride a2 was concentrated by a rotary evaporator, the solid content concentration was adjusted to 35%, and a solution of hydride a2 (a cyclic olefin polymer having a carboxy group as a protic polar group) was prepared. Obtained. There was no change in yield, weight average molecular weight, number average molecular weight and molecular weight distribution of hydride before and after concentration.

[Production Example 2]
(Production of cyclic olefin polymer having a protic polar group)
As a cyclic olefin monomer having a protic polar group, 9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene 40 parts, N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene as a cyclic olefin monomer having a polar group other than a protic polar group -2,3-dicarboximide 60 parts, 1,5-hexadiene 2.8 parts, (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride 0.05 parts and diethylene glycol 400 parts of ethyl methyl ether was charged into a pressure-resistant glass reactor substituted with nitrogen, and a polymerization reaction was carried out at 80 ° C. for 2 hours with stirring to obtain a polymerization reaction solution containing a ring-opening metathesis polymer a3. The polymerization conversion rate was 99.6% or more. The polymer a3 had a weight average molecular weight of 6,260, a number average molecular weight of 4,410, and a molecular weight distribution of 1.49.

  Next, 0.1 part of bis (tricyclohexylphosphine) ethoxymethylene ruthenium dichloride as a hydrogenation catalyst was added to the polymerization reaction solution, and hydrogen was dissolved at a pressure of 4 MPa for 5 hours to proceed the hydrogenation reaction. 1 part was added, hydrogen was dissolved at 150 ° C. under a pressure of 4 MPa for 3 hours while stirring in an autoclave. Next, the solution was taken out and filtered through a fluororesin filter having a pore size of 0.2 μm to separate the activated carbon to obtain 476 parts of a hydrogenation reaction solution containing a hydride a4 of the ring-opening metathesis polymer a3. Filtration could be performed without any delay. The hydrogenation reaction solution containing hydride a4 obtained here had a solid content concentration of 20.6%, and the yield of hydride a4 was 98.1 parts. The obtained hydride a4 had a weight average molecular weight of 7,180, a number average molecular weight of 4,650, and a molecular weight distribution of 1.55. The hydrogenation rate was 99.8%.

  The obtained hydrogenation reaction solution of hydride a4 was concentrated with a rotary evaporator, the solid content concentration was adjusted to 35%, and a solution of hydride a4 (a cyclic olefin polymer having a carboxy group as a protic polar group) was prepared. Obtained. There was no change in yield, weight average molecular weight, number average molecular weight and molecular weight distribution of hydride before and after concentration.

[Production Example 3]
(Manufacture of polysiloxane)
A three-necked flask was charged with 74.91 parts of methyltrimethoxysilane, 69.41 parts of phenyltrimethoxysilane and 150.36 parts of diacetone alcohol (DAA), and 0.338 phosphoric acid was added to 55.8 parts of water while stirring at room temperature. A phosphoric acid aqueous solution in which a part (0.2 wt% with respect to the charged monomer) was dissolved was added over 10 minutes. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and the mixture was heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.). A total of 115 parts of methanol and water as by-products were distilled off. DAA was added to the obtained DAA solution of polysiloxane a5 so that the solid concentration was 35% by weight to obtain a resin solution containing polysiloxane a5.

[Production Example 4]
(Manufacture of cardo resin)
Equivalent reaction product of bisphenolfluorene type epoxy resin and acrylic acid in a four-necked flask with a reflux condenser (solid content concentration 50%, acid value 1.28 mgKOH / g in terms of solid content, epoxy equivalent 21,300. 198.53 parts of 50% propylene glycol monomethyl ether acetate solution manufactured by Nippon Steel Chemical Co., Ltd. (product name “ASF-400” solution), 39.54 parts of benzophenone tetracarboxylic dianhydride, 8.13 of succinic anhydride Part, 48.12 parts of propylene glycol monomethyl ether acetate and 0.45 part of triphenylphosphine, stirred for 1 hour under heating at 120 to 125 ° C., further heated and stirred at 75 to 80 ° C. for 6 hours, and then glycidyl 8.6 parts of methacrylate was added and further stirred at 80 ° C. for 8 hours. The obtained resin solution containing cardo resin a6 was concentrated by a rotary evaporator to obtain a resin solution containing cardo resin a6 having a solid content concentration of 35%.

[Low metallization method 1]
(Low cross-linking treatment of cross-linking agent by zeta filter)
Diethylene glycol ethyl methyl ether as an organic solvent is added to melamine (trade name “Cymel 370”, manufactured by Cytec Industries Co., Ltd.) in an adjusted amount so that the solid part concentration is 30%, and mixed and stirred to produce a zeta filter (product) The name “B90-40QSH” (manufactured by Sumitomo 3M) was filtered, and it was confirmed by ICP-MS (manufactured by Agilent) that the Na concentration in the melamine crosslinking agent was less than 100 ppb.

[Example 1]
As resin (A), 100 parts (in terms of solid content) of hydride a2 obtained in Production Example 1, and as a crosslinking agent (B) having an epoxy group, 2,2-bis (hydroxymethyl) -1-butanol 20 parts of 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct (15-functional alicyclic epoxy resin having a cyclohexane skeleton and a terminal epoxy group. Trade name “EHPE3150”, manufactured by Daicel Chemical Industries, Ltd.) As a crosslinking agent (C) having a triazine ring structure or a glycoluril structure and having one or more groups selected from the group consisting of an imino group, a methylol group, and an alkoxybutyl group, it has a triazine ring structure, In addition, 30 parts of a melamine having a methylol group (trade name “Cymel 370”, manufactured by Cytec Industries Co., Ltd.), a radiation-sensitive compound ( ), (1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane) (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 Mole) and 35 parts of a condensate (Toyo Gosei Co., Ltd., “TS200 (product name)”) as an anti-aging agent, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate] 3 parts, silicone surfactant (trade name “KP341”, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.05 parts, diethylene glycol ethyl methyl ether as an organic solvent, so that the solid part concentration is 24% Were added and mixed and stirred.

  After stirring for 30 minutes, the mixture became a homogeneous solution. This solution was filtered through a polytetrafluoroethylene filter having a pore diameter of 0.45 μm to prepare a radiation sensitive resin composition.

  Next, using this resin composition, a laminate was obtained by the preparation method of the data for the previous period measurement, and the wrinkle, light transmittance and electrical characteristics were evaluated by the previous period method. The results are shown in Table 1.

  In Table 1, the compounding amount of the binder resin (A) means 100 parts in terms of solid content.

[Examples 2 to 11]
In Example 1, as the resin (A), the crosslinking agent (B) and the crosslinking agent (C), the types and amounts of the crosslinking agent (B) and the crosslinking agent (C) shown in Table 1 were used, respectively. A resin composition was prepared in the same manner as in Example 1, and then a laminate was obtained. The resulting laminate was evaluated for wrinkles and light transmittance. The results are shown in Table 1.

Example 12
In Example 1, the resin composition was prepared in the same manner as in Example 1 except that the crosslinking agent (C) was metallized by the metallization method 1 and the Na content was 100 ppb or less. A laminate was obtained, and wrinkles, light transmittance, and electrical characteristics were measured for the obtained laminate. The results are shown in Table 1.

Example 13
In Example 12, a laminate was obtained in the same manner as in Example 12 except that post-baking was performed in the atmosphere at 300 ° C., and wrinkles and light transmittance were measured for the obtained laminate. The results are shown in Table 1.

[Comparative Examples 1-5]
In Example 1, as the crosslinking agent (B) and the crosslinking agent (C), the types and amounts of the crosslinking agent (B) and the crosslinking agent (C) shown in Table 1 were used, respectively. Then, a resin composition was prepared, and then a laminate was obtained. The resulting laminate was evaluated for wrinkles and light transmittance. The results are shown in Table 1.

  In addition, the kind of crosslinking agent (B), crosslinking agent (C), and other crosslinking agents used in Examples 1 to 13 and Comparative Examples 1 to 5 is as follows.

[Crosslinking agent (B)]
EHPE3150: polyfunctional epoxy compound having an alicyclic structure (1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, epoxy number 15, molecular weight 2550, epoxy equivalent 170 g / eq)
Epolede GT 401: polyfunctional epoxy compound having an alicyclic structure (epoxidized butanetetracarboxylic acid tetrakis- (3-cyclohexenylmethyl) -modified ε-caprolactone, epoxy number 4, molecular weight 880, epoxy equivalent 220 g / eq)
Celoxide 3000: polyfunctional epoxy compound having an alicyclic structure (1,2,8,9-diepoxy limonene, number of epoxies 2, molecular weight 168, epoxy equivalent 84 g / eq)
Cyclomer A400: monofunctional epoxy compound having an alicyclic structure (3,4-epoxycyclohexylmethyl acrylate, 1 epoxy, molecular weight 282, epoxy equivalent 282 g / eq)
[Crosslinking agent (C)]
Cymel 325: Melamine resin having an imino group (average degree of polymerization 2.30)
Cymel 701: Melamine resin having an methylol group and an imino group (average degree of polymerization 1.80)
Cymel 232: Melamine resin having an alkoxybutyl group (average polymerization degree 1.50)
Cymel 1170: glycoluril resin having an alkoxybutyl group (average polymerization degree 1.50)
Cymel 370: Melamine resin having a methylol group (average degree of polymerization 2.60)
[Other cross-linking agents]
Nicarak MW390: Melamine resin having no imino group, methylol group and alkoxybutyl group (average degree of polymerization 1.25)
MAPD: a compound (1-methylamino-2,3-propanediol) that does not have a triazine ring structure or glycoluril structure but has an imino group and a methylol group

  From the results of Table 1, the resin (A), the crosslinking agent (B) having an epoxy group, a triazine ring structure or a glycoluril structure, and selected from the group consisting of an imino group, a methylol group and an alkoxybutyl group, A resin film obtained by laminating a resin film on a substrate using the radiation-sensitive resin composition of Examples 1 to 8 having a crosslinking agent (C) having at least a group and a radiation-sensitive compound (D) Is sufficiently flat even after other processes such as forming a conductive thin film on the resin film. In addition, such a highly flat resin film can be formed in a short time.

  In contrast, Comparative Examples 1 to 3 in which only one of the crosslinking agent (B) or the crosslinking agent (C) is used, or a triazine ring structure is used instead of the crosslinking agent (C), but an imino group or a methylol group. And a group consisting of an imino group, a methylol group and an alkoxybutyl group instead of the crosslinking agent (C) selected from the group consisting of an alkoxybutyl group and one having no one or more groups In the case of Comparative Example 5 using one or more groups selected but not having a triazine ring structure or a glycoluril structure, the flatness of the resin film deteriorates through other steps. Even when the resin film formation process was changed, high flatness could not be obtained.

  Moreover, regarding electrical characteristics, Example 12 using the cross-linking agent (C) subjected to the low metallization treatment was compared with Example 1 using the cross-linking agent (C) not subjected to the low metallization treatment. The leakage current could be suppressed more effectively.

Claims (7)

Resin (A),
A crosslinking agent (B) having an epoxy group,
A crosslinking agent (C) having a triazine ring structure or a glycoluril structure and having at least one functional group selected from the group consisting of an imino group, a methylol group and an alkoxybutyl group;
And the radiation sensitive resin composition containing a radiation sensitive compound (D).   The radiation-sensitive resin composition according to claim 1, wherein the weight average molecular weight of the crosslinking agent (B) having an epoxy group is 200 or more.   The radiation sensitive resin composition according to claim 1 or 2, wherein the crosslinking agent (B) having an epoxy group has at least two epoxy groups in the molecule.   The radiation sensitive resin composition according to any one of claims 1 to 3, wherein the radiation sensitive compound (D) is a photoacid generator.   The radiation-sensitive resin composition according to claim 4, wherein the photoacid generator is a quinonediazide compound.   The resin film formed using the radiation sensitive resin composition of any one of Claims 1-5.   An electronic component using the resin film according to claim 6.