JP2009251538A - Radiation-sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition excellent in patterning ability, especially developability, heat-resistant flowability, and adhesion in development. <P>SOLUTION: The radiation-sensitive resin composition contains an alkali soluble resin (A), a photoacid generator (B), and an acid phosphoric compound (C). The radiation-sensitive resin composition may further contain a crosslinking agent. It is desirable that the acid phosphoric compound (C) is a compound having one or two hydroxyl groups. It is desirable that the acid phosphoric compound (C) has a phosphate ester structure. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a radiation-sensitive resin composition suitable for production of electronic components such as integrated circuit elements, liquid crystal display elements, and solid-state imaging elements. More specifically, the present invention relates to a radiation sensitive resin composition comprising a specific compound and having excellent adhesion to a substrate.

  For electronic parts such as display elements, integrated circuit elements, solid-state image sensors, color filters, black matrices, etc., protective films to prevent deterioration and damage, flattening films to flatten the element surface and wiring, electrical Various resin films are provided as an electrical insulating film or the like for maintaining insulation. In addition, a resin film as an interlayer insulating film is provided in an element such as a thin film transistor type liquid crystal display element or an integrated circuit element in order to insulate between wirings arranged in layers.

Various radiation-sensitive resin compositions have been proposed to be applied to such various uses. Among them, the radiation sensitive resin composition using an alkali-soluble resin such as a cyclic polyolefin resin having a protic polar group is excellent in patterning performance such as resolution, exposure margin, remaining film rate, pattern shape, etc., and also has transparency and heat resistance. Excellent discoloration.
Film formation using these radiation-sensitive resin compositions is carried out by applying to a desired substrate and drying to form a resin film, and then irradiating with active energy rays to form a latent image, which is brought into contact with a developer. After the pattern is formed, heating is performed as desired.

  However, when the resin film on which the latent image is formed is processed with a developer, if the adhesion with the substrate is insufficient, the resin film may be peeled off from the substrate, so-called pattern peeling. For this reason, a method such as lowering the concentration of the developing solution may be employed, but it takes a long time for the development, thereby reducing productivity.

As countermeasures, several methods for improving the adhesion between the substrate and the resin film have been proposed. Patent Document 1 includes (A) a cyclic olefin resin having an acidic group, (B) a photoacid generator, and (C) a compound having a reactive group capable of binding to the acidic group of (A) at a temperature of 130 ° C. or higher. And (D) a photosensitive resin composition comprising a silane coupling agent having a sulfur atom in the molecule. According to the description of this gazette, the use of the component (D) improves the adhesion of the substrate and provides a resin composition that does not peel off the pattern during development.
Similarly, Patent Document 2 discloses (A) a cyclic olefin resin having an acidic group, (B) a photoacid generator, (C) a reactive group capable of binding to the acidic group of (A) at a temperature of 130 ° C. or higher. A photosensitive resin composition comprising a compound having a hydrogen atom, (D) a silane coupling agent, and (E) an antioxidant having a sulfur atom in the molecule is disclosed. According to the description of this publication, pattern peeling can be suppressed by using the component (E).
Patent Document 3 discloses an insulation containing an alkali-soluble resin (A) having a phenolic hydroxyl group, a radiation-sensitive acid generator (B), a crosslinking agent (C), an adhesion assistant (D), and an organic solvent (E). A radiation-sensitive resin composition for film formation is disclosed. In this radiation-sensitive resin composition, the adhesion assistant is a compound that improves the adhesion between the substrate and the insulating film, and specifically, a silane coupling agent or a thiol compound is used.

  As described above, the addition of various compounds has been studied to improve the adhesion of the radiation-sensitive resin composition. However, the present situation is that no sufficient effect has been found yet. .

JP 2007-078796 A JP 2007-078812 A Japanese Patent Application Laid-Open No. 2007-065488

  Accordingly, an object of the present invention is to provide a radiation-sensitive resin composition excellent in patterning performance, particularly developability, heat-resistant flow property and development adhesion, as well as excellent transparency and heat discoloration.

  As a result of intensive studies in order to solve the above-mentioned problems, the present inventor achieved the above object by using a specific compound in combination with a radiation-sensitive resin composition containing an alkali-soluble resin and a photoacid generator. Based on this finding, the present invention has been completed.

Thus, according to the present invention, there is provided a radiation-sensitive resin composition comprising an alkali-soluble resin (A), a photoacid generator (B) and an acidic phosphoric acid compound (C).
The radiation sensitive resin composition of the present invention preferably further comprises a crosslinking agent (D).
In the radiation sensitive resin composition of the present invention, the acidic phosphoric acid compound (C) is preferably a compound having 1 or 2 hydroxyl groups.
In the radiation-sensitive resin composition of the present invention, it is also preferable that the acidic phosphoric acid compound (C) has a phosphate ester structure.
Furthermore, in the radiation sensitive resin composition of the present invention, the acidic phosphoric acid compound (C) preferably has a partial structure in which a phosphorus atom and a carbon atom are directly bonded.
In the radiation sensitive resin composition of the present invention, the alkali-soluble resin (A) is preferably a cyclic olefin polymer having a protic polar group, an acrylic resin, a siloxane resin, or a cardo resin.

  The radiation-sensitive resin composition of the present invention can be applied to various uses because it provides a resin film that is excellent in heat-resistant flow properties, developability and adhesion, and has few film defects. In addition, various laminates obtained by laminating the radiation-sensitive resin composition of the present invention on a substrate are excellent in heat-resistant transparency and dielectric properties of the resin film.For example, display elements, integrated circuit elements, solid-state imaging elements, In electronic parts such as color filters and black matrices, protective films for preventing deterioration and damage, flattening films for flattening element surfaces and wiring, and electrical insulating films for maintaining electrical insulation (thin transistors) Suitable for materials for electronic parts such as microlenses, spacers, and the like.

  The radiation sensitive resin composition of the present invention comprises an alkali-soluble resin (A), a photoacid generator (B) and an acidic phosphoric acid compound (C).

The alkali-soluble resin (A) is not particularly limited, but is preferably a cyclic olefin polymer having a protic polar group, an acrylic resin, a siloxane resin, or a cardo resin, and among these, a cyclic olefin having a protic polar group Polymers are particularly preferred.
These alkali-soluble resins (A) may be used alone or in combination of two or more.

  The proton polar group refers to an atomic group 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 bonded to the alkali-soluble resin (A) 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 polar group having a nitrogen atom such as an amino group, a secondary amino group, a primary amide group or a secondary amide group (imide group); a polar group having a sulfur atom such as a thiol group; Among these, those having an oxygen atom are preferable, and a carboxy group is more preferable.
In the present invention, the number of protic polar groups bonded to the alkali-soluble resin (A) is not particularly limited, and different types of protic polar groups may be included.

In the present invention, the cyclic olefin polymer 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 polymer 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 unit of the cyclic olefin polymer 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 polymer having a protic polar group used in the present invention, the ratio of the monomer unit having a protic polar group to the other monomer unit (monomer unit having a protic polar group / The other monomer units) are generally in a weight ratio of 100/0 to 10/90, preferably 90/10 to 20/80, more preferably 80/20 to 30/70. Selected.
In the cyclic olefin polymer 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.

As monomers for constituting a cyclic olefin polymer having a protic polar group, a cyclic olefin monomer having a protic polar group (a), a cyclic olefin having a polar group other than a protic polar group Body (b), cyclic olefin monomer having no polar group (c), and monomer (d) other than cyclic olefin (hereinafter these monomers are simply referred to as monomers (a) to (d). Said). 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 polymer 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 the body (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-exo-6-endo-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 8 -Hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-exo-9-endo-dihydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . Carboxy group-containing cyclic olefins such as ^{17, 10} ] dodec-3-ene; 5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5- (4-hydroxy Phenyl) bicyclo [2.2.1] hept-2-ene, 8- (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 . And a hydroxyl group-containing cyclic olefin such as ^{17, 10} ] dodec-3-ene, among which a carboxy group-containing cyclic olefin is 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, 8-acetoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8- (2,2,2-trifluoroethoxy-carbonyl) tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.

Examples of the cyclic olefin having an N-substituted imide group include N-phenyl- (5-norbornene-2,3-dicarboximide).
Examples of the cyclic olefin having a cyano group include 8-cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5-cyanobicyclo [2.2.1] hept-2-ene, and the like.
Examples of the cyclic olefin having a halogen atom include 8-chlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-chlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-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 (common name: 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 [4.3.0.1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene), tetracyclo ^{[8.4.0.1 11,14.} 0 ^3,7 ] pentadeca-3,5,7,12,11-pentaene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dec-3-ene (common name: tetracyclododecene), 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, cyclopentene, cyclopentadiene, 1,4-methano -1,4,4a, 5,10,10a hexa hydro anthracene, 8-phenyl - tetracyclo [4.4. 0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), pentacyclo [7.4.0.1 ^{3 , 6} . 1 ^10,13 . 0 ^2,7] pentadeca-4,11-diene, pentacyclo [9.2.1.1 ^4,7. 0 ^2,10 . 0 ^3,8 ] pentadeca-5,12-diene 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 polymer 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. It is done. The polymer obtained by polymerization may be further hydrogenated. Hydrogenated polymers are also included in the cyclic olefin polymers having protic polar groups used in the present invention.

In addition, the cyclic olefin polymer having a protic polar group used in the present invention introduces a protic polar group into a cyclic olefin polymer having no protic polar group by using a known modifier. It can also be obtained by a method of hydrogenation. Hydrogenation may be performed on the polymer before introduction of the protic polar group. Moreover, the cyclic olefin polymer 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 polymer using this modifier may be carried out 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, side reactions such as functional group modification do not occur, and noble metal complex catalysts such as rhodium and ruthenium can be used because carbon-carbon unsaturated bonds in the polymer can be selectively hydrogenated. A nitrogen-containing heterocyclic carbene compound or a ruthenium catalyst coordinated with a phosphine having a high electron donating property is particularly preferable.

  In the present invention, as the cyclic olefin polymer having a protic polar group, those having a structural unit represented by the general formula (I) as shown below are particularly preferable. Those having a structural unit represented by formula (II) and a structural unit represented by formula (II) are more preferred.

[In General Formula (I), R ^{1 to} R ⁴ each independently represent a hydrogen atom or a —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 the general formula (II), R ^{5 to} R ⁸ are each an arbitrary combination of a 3- to 5-membered complex containing an oxygen atom or a nitrogen atom as a ring-constituting atom together with two carbon atoms to which they are bonded. A ring 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 a phenyl group, a naphthyl group, and an anthracenyl group.

  The acrylic resin is not particularly limited, but a homopolymer or copolymer 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. 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 both methacryl and 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, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl ( (Meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, ethylhexyl (meth) Acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) Acrylate, stearyl (meth) acrylate, alkyl (meth) acrylates such as isostearyl (meth) acrylate;

Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) Hydroxyalkyl (meth) acrylates such as acrylate; Phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxy Alkoxyalkyl (meth) acrylates such as ethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate and 2-methoxybutyl (meth) acrylate Relate; polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, Polyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate; cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, di Cyclopentanyl (meth) acrylate, Cycloalkyl (meth) acrylates such as cyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate; benzyl (meth) Examples thereof include acrylate and 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 structure of the polysiloxane used in the present invention is not particularly limited, but is preferably a polysiloxane obtained by mixing and reacting at least one organosilane represented by the general formula (III).

In General Formula (III), R ⁹ represents hydrogen or an optionally substituted alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. And when a plurality of R ⁹ are present, they may be the same or different.
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 and the like. Specific examples of the alkenyl group include a vinyl group, 3-acryloxypropyl group, 3-methacryloxypropyl group and the like. 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 and the like.

R ^{10 in the} general formula (III) represents hydrogen or an optionally substituted alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, When a plurality of R ¹⁰ are present, they may be the same or different.
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 include a phenyl group.

In the general formula (III), ^{R 9} and ^{R 10} may be selected depending on the properties of the composition.
In general formula (III), j represents an integer of 0 to 3. A tetrafunctional silane when j = 0, a trifunctional silane when j = 1, a bifunctional silane when j = 2, and a monofunctional silane when j = 3.

  Specific examples of the organosilane represented by the general formula (III) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyl Triisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyl Trimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3- Tacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ) Ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxy Silane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethyl Trifunctional silanes such as xysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxy And bifunctional silanes such as silane and diphenyldimethoxysilane; and 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 TFT passivation film. Moreover, these organosilanes may be used alone or in combination of two or more.

  The polysiloxane in the present invention can be obtained by hydrolyzing and partially condensing 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 the stirring, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) are distilled off as necessary.

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 is formed by polymerizing a 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 general formula (IV).

カルド構造を有する単量体は、例えば、ビス（グリシジルオキシフェニル）フルオレン型エポキシ樹脂；ビスフェノールフルオレン型エポキシ樹脂とアクリル酸との縮合物；９，９−ビス（４−ヒドロキシフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン等のカルド構造含有ビスフェノ−ル類；９，９−ビス（シアノメチル）フルオレン等の９，９−ビス（シアノアルキル）フルオレン類；９，９−ビス（３−アミノプロピル）フルオレン等の９，９−ビス（アミノアルキル）フルオレン類；等が挙げられる。
カルド樹脂は、カルド構造を有する単量体を重合して得られる重合体であるが、その他の共重合可能な単量体との共重合体であってもよい。
上記単量体の重合方法は、常法に従えばよく、例えば、開環重合法や付加重合法等が採用される。

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 weight average molecular weight (Mw) of the alkali-soluble 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.
The molecular weight distribution of the alkali-soluble resin (A) is usually 4 or less, preferably 3 or less, and more preferably 2.5 or less, as a weight average molecular weight / number average molecular weight (Mw / Mn) ratio.
The weight average molecular weight (Mw) and molecular weight distribution of the alkali-soluble resin (A) can be measured using gel permeation chromatography. For example, a solvent such as tetrahydrofuran can be used as an eluent, and the molecular weight can be determined as a polyisoprene equivalent molecular weight.
Moreover, the hydrogenation rate of alkali-soluble resin (A) is 90% or more normally, Preferably it is 95% or more, More preferably, it is 98% or more. When the hydrogenation rate is within this range, the alkali-soluble resin (A) is particularly excellent in heat resistance and suitable.
The hydrogenation rate of the alkali-soluble resin (A) can be measured by ¹ H-NMR spectrometry. 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.

  The photoacid generator used in the present invention is a substance that generates Bronsted acid or Lewis acid in response to light. The Bronsted acid or Lewis acid generated by light irradiation changes the acid dissociable group of the dissolution control agent into an acidic functional group. Since the dissolution control agent has an acidic functional group, it exhibits an action of attracting an alkaline aqueous liquid that has not been brought close to it because of its lipophilicity.

Examples of the photoacid generator include azide compounds such as acetophenone compounds, triarylsulfonium salts, and quinonediazide compounds, with azide compounds being preferred, and quinonediazide compounds being particularly preferred. These radiation sensitive compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
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.

  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.

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.

  The usage-amount of a photo-acid generator is 1-100 weight part normally with respect to 100 weight part of alkali-soluble resin (A), Preferably it is 5-50 weight part, More preferably, it is the range of 10-40 weight part. . When the amount of photoacid generator used is within this range, when patterning the resin film formed on the substrate, the difference in solubility between the radiation-irradiated part and the radiation-unirradiated part increases, and patterning is performed by development. Is easy and the radiation sensitivity is high, which is preferable.

一般式（Ｖ）において、Ｒ^１１及びＲ^１２は、水酸基、炭化水素オキシ基、炭化水素基又は水素原子である。但し、Ｒ^１１及びＲ^１２の少なくとも一方は、炭化水素オキシ基又は炭化水素基である。
炭化水素オキシ基は、特に限定されないが、その具体例としては、炭素数１〜１２のアルコキシ基、アルケニルオキシ基及びアルキニルオキシ基並びに炭素数６〜１２のアリーロキシ基を挙げることができる。これらの炭化水素オキシ基のうち、アルコキシ基が好ましく、特に炭素数３〜１０のアルコキシ基が好ましい。
また、炭化水素基は、特に限定されないが、その具体例としては、炭素数１〜１２のアルキル基、アルケニル基及びアルキニル基並びに炭素数６〜１２のアリール基を挙げることができる。これらの炭化水素基のうち、アルキル基が好ましく、特に炭素数３〜１０のアルキル基が好ましい。 The radiation-sensitive resin composition of the present invention contains an acidic phosphoric acid compound (C) as an essential component.
In the present invention, an acidic phosphoric acid compound refers to a phosphoric acid derivative in which at least one hydroxyl group is directly bonded to a phosphorus atom. The acidic phosphoric acid compound is represented by, for example, general formula (V).

In the general formula (V), R ¹¹ and R ¹² are a hydroxyl group, a hydrocarbon oxy group, a hydrocarbon group, or a hydrogen atom. However, at least one of R ¹¹ and R ¹² is a hydrocarbon oxy group or a hydrocarbon group.
The hydrocarbon oxy group is not particularly limited, and specific examples thereof include an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group, an alkynyloxy group, and an aryloxy group having 6 to 12 carbon atoms. Of these hydrocarbon oxy groups, an alkoxy group is preferable, and an alkoxy group having 3 to 10 carbon atoms is particularly preferable.
Moreover, although a hydrocarbon group is not specifically limited, As the specific example, a C1-C12 alkyl group, an alkenyl group, an alkynyl group, and a C6-C12 aryl group can be mentioned. Of these hydrocarbon groups, an alkyl group is preferable, and an alkyl group having 3 to 10 carbon atoms is particularly preferable.

The acidic phosphoric acid compound represented by the general formula (V) further includes acidic phosphoric acid ester derivatives represented by the general formulas (VIa) and (VIb), and acidic acids represented by the general formulas (VIIa) to (VIIc). It can be divided into phosphorous acid ester derivatives and hypophosphorous acid derivatives represented by general formulas (VIIIa) and (VIIIb).
In General Formulas (VIa) to (VIIIb), R ^{21 to} R ²⁴ are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, or 1 to 1 carbon atoms. A 20-alkylene group, an aralkyl group having 7 to 20 carbon atoms, and an alkaryl group having 7 to 20 carbon atoms, and these groups may have a substituent. R ^{21 to} R ²⁴ may be the same or different.

In these acidic phosphoric acid compounds, R ^{21 to} R ²⁴ may form a ring in any combination, and are represented by, for example, general formula (IX) via any atom or atomic group. A multimer such as a dimer may be formed.
In general formula (IX), X is a single bond or a divalent organic group. Examples of the divalent organic group include an alkylene group, an oxyalkylene group, and an oxyarylene group.

  Specific examples of the acidic phosphate ester derivative include acidic isopropyl phosphate, acidic butyl phosphate, acidic isopentyl phosphate, acidic octyl phosphate, acidic 2-ethylhexyl phosphate, acidic isodecyl phosphate, acidic diisodecyl phosphate, acidic phosphorus Acid tridecyl; acid diisopropyl phosphate, acid dibutyl phosphate, acid diisopentyl phosphate, acid dioctyl phosphate, acid bis (2-ethylhexyl) phosphate, acid bis (tridecyl) acid phosphate, methyl octyl phosphate, acid phosphate And methyl octadecyl.

Specific examples of the acidic phosphite derivative include: phosphonic acid; alkylphosphonic acid such as methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, cyclohexylphosphonic acid, octylphosphonic acid; phenylphosphonic acid, naphthylphosphonic acid Arylphosphonic acids such as;
Alkyl phosphonates such as methyl phosphonate, ethyl phosphonate, propyl phosphonate, butyl phosphonate, hexyl phosphonate, octyl phosphonate, 2-ethylhexyl phosphonate; aryl phosphonates such as phenyl phosphonate, naphthyl phosphonate; phosphonic acid Phospholic acid alkaryls such as tolyl and methoxyphenyl phosphonate; alkoxyalkyl phosphonates such as methoxyethyl phosphonate;
Methyl phosphonate, methyl phosphonate isopropyl, methyl phosphonate butyl, methyl phosphonate octyl, methyl phosphonate cyclohexyl, ethyl phosphonate, methyl butyl phosphonate, methyl octyl phosphonate, octyl phosphonate propyl, octyl phosphonate pentyl, octyl phosphonate octyl, Decyl octyl phosphonate, phenyl methyl phosphonate, phenyl propyl phosphonate, phenyl cyclohexyl phosphonate, phenyl octyl phosphonate, ethyl phenyl phosphonate, isopropyl phenyl phosphonate, hexyl phenyl phosphonate, octyl phenyl phosphonate; .

  Specific examples of hypophosphorous acid derivatives include diethylphosphinic acid, dibutylphosphinic acid, dioctylphosphinic acid, (hydroxyethyl) methylphosphinic acid, bis (hydroxyethyl) phosphinic acid, (methoxymethyl) methylphosphinic acid, bis (methoxy Methyl) phosphinic acid, 1,3-cyclobutylenephosphinic acid, 1-hydroxyphosphorane-1-oxide and the like.

  In the present invention, the acidic phosphoric acid compound preferably has two “PO” single bonds, and more preferably has one “PO—alkyl group” partial structure. From the viewpoint of adhesiveness to the substrate, those bonded to P atoms are preferably alkoxy groups, more preferably hydroxyl groups, rather than hydrocarbon groups. This is because when the hydroxyl group is present, the cross-linking reaction is likely to proceed, so that the heat resistant flow property is improved. Since the heat resistant flow property and developability (the amount of residue during development) are in a trade-off relationship, it is necessary to determine the structure in consideration of both characteristics.

  The acidic phosphoric acid compound may be used alone or in combination of two or more, and the amount used is appropriately selected according to the purpose of use, but 100 parts by weight of the alkali-soluble resin (A) The amount is usually 0.1 to 3 parts by weight, preferably 1 to 3 parts by weight. When the amount used is in this range, the development adhesion of the formed resin film is highly improved, and the post-baked shape is also maintained well. On the other hand, if the amount used is too large, the sensitivity is lowered and the developability is lowered.

The radiation sensitive resin composition of the present invention preferably contains a crosslinking agent.
As the crosslinking agent, those having two or more, preferably three or more functional groups capable of reacting with the alkali-soluble resin (A) in the molecule are used. A functional group will not be specifically limited if it can react with the functional group in an alkali-soluble resin (A), an unsaturated bond, etc. When the alkali-soluble resin (A) contains a protic polar group, preferred functional groups include, for example, an amino group, a carboxy group, a hydroxy group, an epoxy group, an isocyanate group, and more preferably an amino group. An epoxy group and an isocyanate group are more preferable, and an epoxy group is particularly preferable.

  Specific examples of such a crosslinking agent include aliphatic polyamines such as hexamethylenediamine; aromatic polyamines such as 4,4′-diaminodiphenyl ether and diaminodiphenylsulfone; 2,6-bis (4′-azidobenzal) Azides such as cyclohexanone and 4,4′-diazidodiphenylsulfone; polyamides such as nylon, polyhexamethylenediamine terephthalamide and polyhexamethyleneisophthalamide; N, N, N ′, N ′, N ″, N ″ -Melamines such as (hexaalkoxymethyl) melamine; glycolurils such as N, N ', N ", N"'-(tetraalkoxymethyl) glycoluril; acrylate compounds such as ethylene glycol di (meth) acrylate; Methylene diisocyanate polyisocyanate Isocyanate compounds such as isophorone diisocyanate polyisocyanate, tolylene diisocyanate polyisocyanate, hydrogenated diphenylmethane diisocyanate; 1,4-di- (hydroxymethyl) cyclohexane, 1,4-di- (hydroxymethyl) norbornane; 3,4-trihydroxycyclohexane; various polyfunctional epoxy compounds;

  More specific examples of the polyfunctional epoxy compound include epoxy compounds having two or more epoxy groups, those having an alicyclic skeleton, those having a cresol novolak skeleton, those having a phenol novolak skeleton, and a bisphenol A skeleton. And those having a naphthalene skeleton.

These crosslinking agents may be used alone or in combination of two or more, and the amount used is appropriately selected according to the purpose of use, but 100 parts by weight of the alkali-soluble resin (A) On the other hand, it is usually 1 to 1,000 parts by weight, preferably 5 to 500 parts by weight, and more preferably 10 to 100 parts by weight. When the amount used is in this range, the heat resistance of the formed resin film is highly improved, which is preferable.
Although the molecular weight of the crosslinking agent used by this invention is not specifically limited, Usually, it is 100-100,000, Preferably it is 500-50,000, More preferably, it is 1,000-10,000. A molecular weight in this range is preferable from the viewpoint of stability during heating and gelation efficiency.
In the present invention, the crosslinking agent is preferably a polyfunctional epoxy compound having two or more epoxy groups, and more preferably a polyfunctional epoxy compound having three or more epoxy groups.
Epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, polyphenol type epoxy resin, cyclic aliphatic epoxy resin, aliphatic glycidyl ether, epoxy acrylate polymer, etc. Can be mentioned.

In the radiation sensitive resin composition of the present invention, various anti-aging agents may be blended. By blending the anti-aging agent, not only the heat-resistant transparency of the resin film can be increased, but also the radiation sensitivity of the radiation-sensitive resin composition can be increased.
Anti-aging agent is not particularly limited, phenol-based anti-aging agent; hindered amine-based anti-aging agent; sulfur atom-containing anti-aging agent such as thioether compound and thiol compound; phosphorus atom-containing anti-aging agent such as phosphoric acid compound Etc. can be used.
These anti-aging agents may be used alone or in combination of two or more. The amount used is usually 0.001 to 10 parts by weight, preferably 0.01 to 8 parts by weight, more preferably 0.1 to 6 parts by weight, based on 100 parts by weight of the cyclic olefin polymer. is there.

  Specific examples of phenolic anti-aging agents include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) ) Propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3,4-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2 , 2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis- (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3 -T-butyl-4-hydroxy-5-methylphenyl) propionate, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) L) propionyloxy} 1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2-t-butyl-6- (3′-t-butyl-5′-) Examples include methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate and 4,4′-thio-bis (3-methyl-6-tert-butylphenol).

  Specific examples of the hindered amine anti-aging agent include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (ADK STAB LA-77, manufactured by Asahi Denka), bis (N-methyl-2,2 , 6,6-tetramethyl-4-piperidyl) sebacate, (2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate (Adekastab LA-67 Manufactured by Asahi Denka), (1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate (Adeka Stub LA-62, manufactured by Asahi Denka) [2,2,6,6-tetramethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9 {2,4,8,10-tetraoxaspiro (5,5 ) Undecane Diethyl] 1,2,3,4-butanetetracarboxylate (ADK STAB LA-68, manufactured by Asahi Denka Co., Ltd.), [1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9 {2,4,8,10-tetraoxaspiro (5,5) undecane} diethyl] 1,2,3,4-butanetetracarboxylate (ADK STAB LA-63, Asahi Manufactured by Denka Co., Ltd.), poly [(6- (1,1,3,3-tetramethylbutyl) imino) -1,3,5-triazine / -2,4-diyl] [(2,2,6,6 -Tetramethyl-4-piperidyl) imino] hexamethylene (2,2,6,6-tetramethyl-4-piperidyl) iminol (CHIMASSORB944, manufactured by Chimosa), bis (1-octyloxy-2,2,6,6) -Te Lamethyl-4-piperidyl) sebacate (TINUVIN123; manufactured by Ciba Specialty Chemicals), dimethyl-1- (2-hydroxyethyl) succinate 4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate ( TINUVIN622, manufactured by Ciba Specialty Chemicals), bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2 N-butyl malonate, tetrakis (2,2,6,6-tetra-methyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6- Penta-methyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate and the like.

The radiation sensitive resin composition of this invention may contain resin components other than alkali-soluble resin (A), another compounding agent, etc. as needed.
Other resin components include, for example, styrene resins, vinyl chloride resins, acrylic resins, polyphenylene ether resins, polyarylene sulfide resins, polycarbonate resins, polyester resins, polyamide resins, polyethersulfone resins, polysulfone resins, polyimide resins. , Rubbers and elastomers.

Examples of other compounding agents include sensitizers, surfactants, latent acid generators, adhesion assistants, antistatic agents, antifoaming agents, pigments, and dyes.
Examples of the sensitizer include 2H-pyrido- (3,2-b) -1,4-oxazin-3 (4H) -ones, 10H-pyrido- (3,2-b) -1,4- Preferred examples include benzothiazines, urazoles, hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, maleimides and the like.
Surfactants are used for the purpose of preventing streaking and improving developability. For example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and other polyoxyethylenes are used. Ethylene alkyl ethers; polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; nonionic series such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate Surfactant; Fluorosurfactant; Silicone surfactant; (Meth) acrylic acid copolymer surfactant.

The latent acid generator is used for the purpose of improving the heat resistance and chemical resistance of the radiation-sensitive resin composition of the present invention. For example, the latent acid generator is a cationic polymerization catalyst that generates an acid by heating, such as sulfonium salt, benzothiazo Examples thereof include a lithium salt, an ammonium salt, and a phosphonium salt. Of these, sulfonium salts and benzothiazolium salts are preferred.
Examples of the adhesion assistant include functional silane coupling agents, and specific examples thereof include trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, Examples include γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

  The radiation-sensitive resin composition of the present invention contains the alkali-soluble resin (A), photoacid generator (B) and acidic phosphoric acid compound (C) as essential components, and other components are added as necessary. Usually, it can be obtained by dissolving or dispersing in a solvent.

  The solvent that can be used in the present invention is not particularly limited, and examples thereof include alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, Ethylene glycol mono-t-butyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl Ether, triethylene glycol Alkylene glycol monoethers such as methyl ether, triethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol Alkylene glycol dialkyl ethers such as diethyl ether, dipropylene glycol ethyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tripropylene glycol ethyl methyl ether; propylene glycol mono Chill ether acetate, dipropylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono n-propyl ether acetate, propylene glycol mono i-propyl ether acetate, propylene glycol mono n-butyl ether acetate, propylene glycol mono i-butyl ether Alkylene glycol monoalkyl ether esters such as acetate, propylene glycol mono sec-butyl ether acetate, propylene glycol mono t-butyl ether acetate;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, cyclohexanone, cyclopentanone; alcohols such as methanol, ethanol, propanol, butanol, 3-methoxy-3-methylbutanol Cyclic ethers such as tetrahydrofuran and dioxane; cellosolv esters such as methyl cellosolve acetate and ethyl cellosolve acetate; aromatic hydrocarbons such as benzene, toluene and xylene; ethyl acetate, butyl acetate, ethyl lactate, 2-hydroxy-2; -Methyl methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate , Esters of ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, γ-butyrolactone; N-methylformamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone , N-methylacetamide, amides such as N, N-dimethylacetamide, dimethyl sulfoxide, and the like.

These solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
The amount of the solvent used is usually in the range of 20 to 10,000 parts by weight, preferably 50 to 5,000 parts by weight, more preferably 100 to 1,000 parts by weight with respect to 100 parts by weight of the cyclic olefin polymer. is there.

The method of dissolving or dispersing the radiation-sensitive resin composition of the present invention in a solvent may be according to a conventional method, for example, stirring using a stirrer and a magnetic stirrer, high-speed homogenizer, dispersion, planetary stirrer, biaxial stirrer, It can be performed using a ball mill, a triple roll, or the like.
The radiation-sensitive resin composition of the present invention is preferably used after being dissolved or dispersed in a solvent and then filtered using, for example, a filter having a pore size of about 0.05 μm.
The solid content concentration when the radiation-sensitive resin composition of the present invention is dissolved or dispersed in a solvent is usually 1 to 70% by weight, preferably 5 to 50% by weight, more preferably 10 to 40% by weight. When the solid content concentration is within this range, the dissolution stability, the coating property on the substrate, the film thickness uniformity and the flatness of the formed resin film are highly balanced and suitable.

After forming a resin film on a substrate using the radiation sensitive resin composition of the present invention, the resin film can be cross-linked as necessary to obtain a laminate.
The thickness of the resin film is usually in the range of 0.1 to 100 μm, preferably 0.5 to 50 μm, more preferably 0.5 to 30 μm.
As the substrate, for example, a printed wiring board, a silicon wafer substrate, a glass substrate, a plastic substrate, or the like can be used. 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 radiation-sensitive resin composition on the substrate include various methods such as spraying, spin coating, roll coating, die coating, doctor blade, spin coating, bar coating, and screen printing. The method can be adopted. Heat drying varies depending on the type and mixing ratio of each component, but is usually 30 to 150 ° C., preferably 60 to 120 ° C., usually 0.5 to 90 minutes, preferably 1 to 60 minutes, and more preferably. May be performed in 1 to 30 minutes.

The film lamination method, for example, obtained by dissolving or dispersing the radiation-sensitive resin composition in a solvent on a substrate such as a resin film or a metal film, and then removing the solvent by heat drying to obtain a B stage film. Next, this B stage film is laminated on the substrate. Heat drying varies depending on the type and mixing ratio of each component, but is usually 30 to 150 ° C., preferably 60 to 120 ° C., usually 0.5 to 90 minutes, preferably 1 to 60 minutes, and more preferably. May be performed in 1 to 30 minutes.
Film lamination can be performed using a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator or the like.

In a laminate comprising a substrate and a resin film formed on the substrate using the radiation sensitive resin composition of the present invention, the resin film may be patterned. A laminate in which a patterned resin film is formed on a substrate is useful as various electronic components.
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 radiation-sensitive resin 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;
A method of forming a latent image pattern by selectively irradiating these actinic radiations in a pattern may be in accordance with an ordinary method. 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.
As the developer, an aqueous solution of an alkaline compound is usually used. As the alkaline compound, for example, an alkali metal salt, an amine, or an ammonium salt can be used. The alkaline compound may be an inorganic compound or an organic compound. Specific examples of these compounds include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate and sodium metasilicate; ammonia water; primary amines such as ethylamine and n-propylamine; diethylamine Secondary amines such as di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and choline Alcohol alcohols such as dimethylethanolamine and triethanolamine; pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5 -En, N-Me Cyclic amines such as Rupiroridon; and the like. These alkaline compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

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 the present invention, after the patterned resin is formed on the substrate, the crosslinking reaction of the resin 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 gas may be used individually by 1 type, and may be used in combination of 2 or more type.

  Hereinafter, the present invention will be described more specifically with reference to synthesis examples and examples. In addition, the part and% in each example are a basis of weight unless there is particular notice. Moreover, various characteristics evaluation of a polymer and a radiation sensitive resin composition were based on the following method.

[Evaluation of radiation-sensitive resin composition]
(1) Formation of resin film A radiation-sensitive resin composition was spin-coated on a silicon nitride substrate subjected to UV / ozone treatment, ultrapure water cleaning, and HMDS treatment, and dried at 90 ° C. for 120 seconds using a hot plate. . Next, after developing for 60 seconds at 23 ° C. using a 0.4% aqueous solution of tetraammonium hydroxide, rinsing with ultrapure water for 30 seconds, the film thickness after development is 3.5 μm. The film is formed as follows.

(2) Development residue After development for 50 seconds and 120 seconds, the surface of each pattern is observed with a microscope to check for the presence of residue.
(3) Flow distance After measuring the width of the bottom of the pattern, the pattern is baked at 230 ° C. in nitrogen for 1 hour using an inert oven capable of controlling the atmosphere. The width of the bottom surface of the pattern after baking is measured, and the difference (the spread distance) of the width of the bottom surface of the pattern before and after baking is measured.
(4) Line width causing development peeling For line and space patterns of 5, 10, 25 and 50 microns, the pattern was observed after development for 50 seconds, and indicated by the line width at which development peeling occurred. The one that does not peel off is the best, but the smaller the pattern width, the better.

[Synthesis Example 1] (Production of cyclic olefin polymer having a protic polar group)
As a cyclic olefin monomer having a protic polar group, 8-carboxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene 60 parts, N-phenyl- (5-norbornene-2,3-dicarboximide) 40 parts as a cyclic olefin monomer having no protic polar group, 1,5 -Pressure-resistant glass reactor in which 2.8 parts of hexadiene, 0.05 part of (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride and 400 parts of diethylene glycol ethyl methyl ether were 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 the ring-opening metathesis polymer 1A. The polymerization conversion rate was 99.9% or more. The polymer 1A 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.

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 the hydride 1B of the ring-opening metathesis polymer 1A. Filtration could be performed without any delay. The hydrogenation reaction solution containing hydride 1B obtained here had a solid content concentration of 20.6%, and the yield of hydride 1B was 98.1 parts. The obtained hydride 1B 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 weight average molecular weight and number average molecular weight of the polymer and hydride were determined as polyisoprene equivalent molecular weight using gel permeation chromatography (product name: HLC-8020, manufactured by Tosoh Corporation) with tetrahydrofuran as an eluent. . The hydrogenation rate was determined by ¹ H-NMR spectrometry as the ratio of the number of moles of hydrogenated carbon-carbon double bonds to the number of moles of carbon-carbon double bonds before hydrogenation.

  The obtained hydrogenation reaction solution of hydride 1B was concentrated with a rotary evaporator, the solid content concentration was adjusted to 35%, and a solution of hydride 1C (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.

[Synthesis Example 2] (Production of cardo resin)
In a four-necked flask equipped with a reflux condenser, an equivalent equivalent reaction product of bisphenolfluorene type epoxy resin and acrylic acid (solid content concentration 50%, acid value 1.28 mgKOH / g in terms of solid content, epoxy equivalent 21,300, new) 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 parts of succinic anhydride , 48.12 parts of propylene glycol monomethyl ether acetate and 0.45 part of triphenylphosphine were added and stirred under heating at 120 to 125 ° C. for 1 hour, and further with heating and stirring at 75 to 80 ° C. for 6 hours, 8.6 parts of glycidyl methacrylate was added and further stirred at 80 ° C. for 8 hours to obtain a cardo resin.

[Synthesis Example 3] (Production of acrylic resin)
20 parts of styrene, 25 parts of butyl methacrylate, 25 parts of 2-ethylhexyl acrylate, 30 parts of methacrylic acid, 0.5 part of 2,2-azobisisobutyronitrile and 300 parts of propylene glycol monomethyl ether acetate are stirred in a nitrogen stream. The mixture was heated at 80 ° C. for 5 hours. The obtained resin solution was concentrated by a rotary evaporator to obtain an acrylic resin solution having a solid content concentration of 35%.

[Synthesis Example 4] (Production of siloxane resin)
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% by weight of 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 temperature of the oil bath was raised to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C. during this time). 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 so that the solid concentration was 35% to obtain a polysiloxane solution.

[Example 1]
100 parts of the cyclic olefin polymer obtained in Synthesis Example 1 as an alkali-soluble resin, 100 parts of diethylene glycol ethyl methyl ether as a solvent, and a quinonediazide compound {1,1,3-tris (2,5-dimethyl-4 as a photoacid generator) -Hydroxyphenyl) -3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) condensate} 30 parts, octyl phosphonate octylphosphoric acid compound 0 .5 parts, 50 parts of a polyfunctional aliphatic cyclic epoxy resin (manufactured by Daicel Chemical Industries, trade name “GT401”) as a crosslinking agent, pentaerythritol tetrakis [3- (3,5-di-t-) as an antioxidant Butyl-4-hydroxyphenyl) propionate] (Ciba Specialty Chemicals, 4 parts of the product name Irganox 1010) and 0.05 part of a silicone surfactant (trade name KP341, manufactured by Shin-Etsu Chemical Co., Ltd.) as a surfactant were mixed and dissolved, and then a filter (Millipore) with a pore size of 0.45 μm was dissolved. And a radiation sensitive resin composition (1) was prepared.
The radiation-sensitive composition (1) was spin-coated on a silicon substrate that had been subjected to UV / ozone treatment and ultrapure water cleaning, and dried at 90 ° C. for 120 seconds using a hot plate. Then, 5, 10, 25, and 50 micron line and space patterns were exposed using 365 nm and 405 nm mercury lamps. Next, after developing for 50 seconds at 23 ° C. using a 0.4% solution of tetraammonium hydroxide, the substrate was rinsed with ultrapure water for 30 seconds. About the obtained resin substrate with a pattern, the surface pattern shape was observed.
The results are shown in Table 1.

[Example 2]
A radiation sensitive resin composition was prepared in the same manner as in Example 1 except that the amount of octyl phosphonate was 1 part, and the pattern shape of the surface of the obtained resin substrate with a pattern was observed.
The results are shown in Table 1.

Example 3
A radiation-sensitive resin composition was prepared in the same manner as in Example 1 except that the crosslinking agent was not used, and the pattern shape of the surface of the obtained resin substrate with a pattern was observed.
The results are shown in Table 1.

Example 4
A radiation-sensitive resin composition was prepared in the same manner as in Example 1 except that octylphosphonic acid was used in place of octylphosphonate, and the pattern shape of the surface was observed for the resulting patterned resin substrate. It was.
The results are shown in Table 1.

Example 5
A radiation-sensitive resin composition was prepared in the same manner as in Example 1 except that dioctyl phosphinic acid was used instead of octyl phosphonate, and the pattern shape of the surface of the obtained patterned resin substrate was observed. It was.
The results are shown in Table 1.

Example 6
A radiation sensitive resin composition was prepared in the same manner as in Example 1 except that acidic dioctyl phosphate was used in place of octyl phosphonate, and the pattern shape of the surface was observed for the obtained resin substrate with pattern. I did it.
The results are shown in Table 1.

[Examples 7 to 9]
A radiation sensitive resin composition was prepared in the same manner as in Example 1 except that the cardo resin, acrylic resin and siloxane resin obtained in Synthesis Examples 2 to 4 were used instead of the cyclic olefin polymer, respectively. Then, the pattern shape of the surface of the obtained resin substrate with a pattern was observed.
The results are shown in Table 1.

[Comparative Example 1]
A radiation sensitive resin composition was prepared in the same manner as in Example 1 except that octyl phosphonate was not used, and a resin film was formed using the obtained radiation sensitive resin composition. The number of film defects was evaluated. The results are shown in Table 1.

[Comparative Example 2]
A radiation sensitive resin composition was prepared in the same manner as in Example 1 except that tributyl phosphate was used instead of octyl phosphonate, and a resin film was formed using the obtained radiation sensitive resin composition. The number of film defects during the exposure was evaluated. The results are shown in Table 1.

  From Table 1, it can be seen that the radiation-sensitive resin composition of the present invention using an acidic phosphoric acid compound is excellent in developability and heat resistant flow characteristics. In particular, when an acidic phosphite is used, the effect is remarkable.

Claims (6)

  A radiation-sensitive resin composition comprising an alkali-soluble resin (A), a photoacid generator (B), and an acidic phosphoric acid compound (C).   Furthermore, the radiation sensitive resin composition of Claim 1 formed by containing a crosslinking agent (D).   The radiation-sensitive resin composition according to claim 1 or 2, wherein the acidic phosphoric acid compound (C) is a compound having 1 or 2 hydroxyl groups.   The radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the acidic phosphoric acid compound (C) has a phosphate ester structure.   The radiation-sensitive resin composition according to any one of claims 1 to 4, wherein the acidic phosphoric acid compound (C) has a partial structure in which a phosphorus atom and a carbon atom are directly bonded.   The radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the alkali-soluble resin (A) is a cyclic olefin polymer having a protic polar group, an acrylic resin, a siloxane resin, or a cardo resin.