JP4771086B2 - Radiation sensitive resin composition, laminate and method for producing the same - Google Patents

Description

  The present invention provides a radiation-sensitive resin composition suitably used for the production of electronic components and optical components such as integrated circuit elements, liquid crystal display elements, and solid-state imaging elements, and the radiation-sensitive resin composition laminated on the substrate. The present invention relates to a laminate comprising a resin film made of a product, and a method for producing the laminate.

  For electronic components such as integrated circuit elements, liquid crystal display elements, solid-state image sensors, color filters, black matrices, protective films to prevent deterioration and damage, flattening films to flatten the element surface and wiring, Various resin films are provided as an electrical insulating film or the like for maintaining electrical 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.

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

  Furthermore, the resin film (patterned resin film) on which the pattern is formed is not limited to a shape having an angular cross section, and a gentle pattern may be required depending on the application. Examples thereof include microlenses having a lens diameter of about 2 to 10 μm as imaging optical system materials for on-chip color filters such as facsimiles, electronic copying machines, and solid-state image sensors, or optical system materials for optical fiber connectors. Can be mentioned.

An example of a method for forming a microlens using a radiation-sensitive resin composition is a method in which a dot pattern is formed and then the pattern is melt-flowed by heat treatment and used as a lens as it is. Such microlenses are subjected to a high temperature overheat treatment (melt flow) in the formation process or the formation process of peripheral devices such as wiring. At this time, if the heat resistant shape retention of the resin film made of the radiation sensitive resin material is insufficient, the lens shape may be deformed and the pattern shape cannot be maintained, and the function as a microlens may not be achieved. Moreover, if the resin film does not have a wide temperature margin to such an extent that a desired shape can be formed even when the heating temperature at the time of melt flow is away from the optimum temperature, stable production and yield of the product are reduced.
Also, with respect to other resin films such as an interlayer insulating film, heat resistant shape retention is important in order to stably form a desired deformation pattern when a process of deforming the pattern by melt flow is required.

  On the other hand, in the manufacture of integrated circuit elements and liquid crystal display devices, various substrates such as silicon substrates; glass substrates; metal film substrates such as aluminum, molybdenum and chromium; metal oxide film substrates such as ITO (tin-doped indium oxide); A thin film of a radiation sensitive resin composition is formed on the substrate, irradiated with an actinic ray such as ultraviolet rays through the mask pattern, developed, and the substrate is etched using the obtained resist pattern as a mask. Thus, a fine pattern is formed. In such photolithography, the radiation-sensitive resin composition is used as a resist material, and high resolution is required as its characteristics.

  Various resin film-forming materials used for electronic parts and the like are known, and as a resin composition containing a block type polyisocyanate compound, for example, the following compositions have been proposed.

  Patent Document 1 describes a chemically amplified resist composition containing a copolymer containing units derived from a styrene derivative or a methacrylic acid derivative, a photoacid generator, and a block polyisocyanate compound. According to this composition, it is described that dry etching resistance is good, sensitivity and resolution are high, and a highly accurate fine resist pattern can be stably formed.

Patent Document 2 describes a thermosetting resin composition comprising a copolymer having a unit derived from styrene or methacrylic acid having one or more carboxysilane groups and a glycidyl group, and a block polyisocyanate compound. Has been. According to this composition, a cured coating film having excellent glossiness, adhesion to a substrate, flatness and surface smoothness, spatter resistance, strong alkali resistance and strong acid resistance can be easily obtained. It is described.
JP 2001-27804 A JP 2001-81153 A

  However, the resin film forming materials as described above satisfy various characteristics such as heat resistance, chemical resistance, adhesion to a substrate, pattern formability, dry etching resistance, resist characteristics, etc. required for the material. Although the heat resistance shape retention of the resulting resin film may be insufficient, the temperature margin during melt flow may be narrow when forming a patterned resin film. We could not expect stable production and good yield of the products obtained.

  Therefore, the present invention is excellent in heat-resistant shape retention of the obtained resin film, has a wide temperature margin at the time of melt flow when forming a patterned resin film, and can be used suitably as a resist material. It is an object of the present invention to provide a laminate comprising an article, a substrate and a resin film comprising the radiation-sensitive resin composition laminated thereon, and a method for producing the laminate.

  As a result of intensive studies to solve the above problems, the present inventor has obtained a cyclic polyolefin polymer having a cyclic structure in the main chain, a radiation-sensitive compound, and a blocked polyisocyanate compound having a blocked isocyanate group. It has been found that the above object can be achieved by the radiation-sensitive resin composition contained, and the present invention has been completed based on this finding.

That is, the present invention
[1] Containing 100 parts by weight of a cyclic olefin polymer having a cyclic structure in the main chain, 1 to 100 parts by weight of a radiation sensitive compound, and 5 to 80 parts by weight of a block type polyisocyanate compound having a blocked isocyanate group. A radiation sensitive resin composition,
[2] The radiation-sensitive resin composition according to the above [1], wherein the cyclic olefin polymer has a protic polar group,
[3] A cyclic olefin polymer is a ring-opening polymer of a cyclic olefin monomer, a ring-opening copolymer of a cyclic olefin monomer and a hydrogenated product thereof; a cyclic olefin monomer and a vinyl alicyclic carbonization An addition copolymer of a hydrogen monomer and a hydrogenated product thereof; and an addition copolymer of a cyclic olefin monomer and a vinyl aromatic hydrocarbon monomer and a hydrogenated product thereof; The radiation-sensitive resin composition according to [1] or [2], which is at least one kind
[4] A laminate comprising a substrate and a resin film made of the radiation-sensitive resin composition according to any one of [1] to [3] laminated on the substrate,
[5] A method for producing a laminate including a step of forming a resin film on a substrate using the radiation-sensitive resin composition according to any one of [1] to [3],
[6] The laminate according to [4], wherein the resin film is a patterned resin film,
[7] A step of forming a resin film on the substrate using the radiation-sensitive resin composition according to any one of [1] to [3], wherein the resin film is irradiated with active radiation in the resin film The method for producing a laminate according to the above [6], comprising a step of forming a latent image pattern, and a step of patterning the resin film by exposing the latent image pattern by bringing a developer solution into contact with the resin film,
[8] The method for producing a laminate according to [7], further including a step of deforming a pattern shape by heating the patterned resin film formed on the substrate,
[9] The method for producing a laminate according to any one of [5], [7] and [8], further comprising a step of crosslinking a resin film formed on the substrate,
[10] An optical component comprising the laminate according to [4] or [6], and [11] an electronic component comprising the laminate according to [4] or [6],
Is to provide.

  The radiation-sensitive resin composition of the present invention is excellent in heat-resistant shape retention of the resin film obtained therefrom, and has a wide temperature margin during melt flow when forming a patterned resin film. For example, stable production of products obtained by patterning a resin film and improvement in yield can be achieved. Moreover, according to the radiation sensitive resin composition of the present invention, an excellent resolution resist pattern can be obtained.

The radiation-sensitive resin composition of the present invention comprises 100 parts by weight of a cyclic olefin polymer having a cyclic structure in the main chain, 1 to 100 parts by weight of a radiation-sensitive compound, and a blocked polyisocyanate compound 5 having a blocked isocyanate group. It contains ~ 80 parts by weight.
The radiation-sensitive resin composition of the present invention is characterized by using a combination of a cyclic olefin polymer having a cyclic structure in the main chain and a predetermined amount of a block-type polyisocyanate compound.

In the present specification, the cyclic olefin polymer may be referred to as “resin” and the film containing the cyclic olefin polymer may be referred to as “resin film”.
In this specification, “excellent heat-resistant shape retention” means that a patterned resin film (primary patterned resin film) obtained by patterning a resin film is melt-flowed to form a pattern of the primary patterned resin film. In the case of forming a patterned resin film (secondary patterned resin film) having a deformed shape, it is possible to easily form a desired pattern shape without excessively deforming the initial pattern shape, In the case where the secondary patterned resin film is exposed to a temperature higher than the temperature at the time of melt flow after the secondary patterned resin film is formed, it means that it has resistance to deformation of the desired pattern shape, Generally speaking, the pattern shape has high thermal controllability. Here, “deformation” means that the pattern shape changes to a level that can be visually recognized when the pattern shape is compared before and after heating the patterned resin film. On the other hand, “the temperature margin is wide” means that the allowable heating temperature range centering on the optimum temperature when the secondary patterned resin film is formed by melt-flowing the primary patterned resin film is wide. The above characteristics relating to the radiation-sensitive resin composition of the present invention can be evaluated according to the method described in Examples described later. In the present specification, the “patterned resin film” includes a primary patterned resin film and a secondary patterned resin film unless otherwise specified.

The cyclic olefin polymer used in the present invention is a homopolymer or copolymer of a cyclic olefin monomer having a cyclic structure (alicyclic ring or aromatic ring) of a cyclic olefin monomer unit in the main chain. . In the present invention, the cyclic olefin refers to an olefin monomer having a cyclic structure containing a carbon-carbon double bond capable of ring-opening polymerization. The cyclic olefin polymer may have a monomer unit other than the cyclic olefin monomer. The ratio of the cyclic olefin monomer unit in all the structural units 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.
Although it does not specifically limit as a cyclic olefin monomer used for this invention, For example, the below-mentioned cyclic olefin monomer (ac) is mentioned. On the other hand, the monomer other than the cyclic olefin monomer is not particularly limited, and examples thereof include a vinyl alicyclic hydrocarbon monomer (d) and a vinyl aromatic hydrocarbon monomer (e ) And chain olefin (f).
The cyclic olefin polymer of the present invention can be formed by polymerizing these monomers in any combination. Moreover, when the cyclic structure of the obtained polymer has an unsaturated bond, it can also be made into a saturated cyclic structure by hydrogenating it.

Examples of the first group of cyclic olefin monomers include cyclic olefin monomers (a) having no polar group. Specific examples thereof 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 . 110,13.0 ^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 may be used alone or in combination of two or more.

The second group of cyclic olefin monomers can include cyclic olefin monomers having a polar group.
These cyclic olefin monomers having a polar group may be used alone or in combination of two or more.

  The polar group can be divided into a protic polar group and another polar group. Therefore, the cyclic olefin monomer having a polar group includes a cyclic olefin monomer (b) having a protic polar group and a cyclic olefin monomer having a polar group other than the protic polar group (aprotic polar group). It can be shown separately from the body (c).

  In this specification, the protic polar group refers to an atomic group in which a hydrogen atom is directly bonded to an atom other than a carbon atom. Here, the atoms other than carbon atoms are preferably atoms belonging to Groups 15 and 16 of the periodic table, more preferably atoms belonging to the first and second periods of Groups 15 and 16 of the Periodic Table, More preferred are an oxygen atom, a nitrogen atom and a sulfur atom, and particularly preferred is an oxygen atom.

  Specific examples of the protic polar group include polar groups having an oxygen atom such as carboxyl group (hydroxycarbonyl group), sulfonic acid group, phosphoric acid group, hydroxyl group; primary amino group, secondary amino group, A polar group having a nitrogen atom such as a primary amide group or a secondary amide group (imide group); a polar group having a sulfur atom such as a thiol group; Among these, those having an oxygen atom are preferable, and a carboxyl group is more preferable.

Specific examples of the cyclic olefin monomer (b) having a protic polar group include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene and 5-methyl-5-hydroxycarbonylbicyclo [2. 2.1] Hept-2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-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 . Cyclic olefin having a carboxyl group such as 1 ^7,10 ] dodec-3-ene; 5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5- (4- Hydroxyphenyl) 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 cyclic olefin having a hydroxy group such as ^{17, 10} ] dodec-3-ene, among which a cyclic olefin having a carboxyl group is preferable.

  Specific examples of the aprotic polar group include an ester group (referred to generically as an alkoxycarbonyl group and an aryloxycarbonyl group), an N-substituted imide group, an epoxy group, a halogen atom, a cyano group, a carbonyloxycarbonyl group (dicarboxylic group). Acid anhydride residues), alkoxy groups, carbonyl groups, tertiary amino groups, sulfone groups, halogen atoms, acryloyl groups and the like. Of these, an ester group, an N-substituted imide group, a cyano group, and a halogen atom are preferred, and an ester group and an N-substituted imide group are more preferred. In particular, an N-substituted imide group is preferable.

  Specific examples of the cyclic olefin monomer (c) having an aprotic polar group include the following.

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 ] dodec-3-ene, 8- (2,2,2-trifluoroethoxycarbonyl) 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- (4-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.

  Examples of the vinyl alicyclic hydrocarbon monomer (d) include vinyl cycloalkanes such as vinyl cyclopropane, vinyl cyclobutane, vinyl cyclopentane, vinyl cyclohexane and vinyl cycloheptane; 3-methyl-1-vinyl And vinylcycloalkanes having substituents such as cyclohexane, 4-methyl-1-vinylcyclohexane, 1-phenyl-2-vinylcyclopropane, 1,1-diphenyl-2-vinylcyclopropane, and the like.

  Examples of the vinyl aromatic hydrocarbon monomer (e) include vinyl aromatics such as styrene, 1-vinylnaphthalene, 2-vinylnaphthalene and 3-vinylnaphthalene; 3-methylstyrene, 4-propylstyrene, 4 -Vinyl aromatics having a substituent such as cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene; m-divinylbenzene, p-divinylbenzene, bis (4- And polyfunctional vinyl aromatics such as vinylphenyl) methane;

  Examples of the chain olefin (f) include ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 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 An α-olefin having 2 to 20 carbon atoms such as hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; 1,4-hexadiene, 4- Non-conjugated dienes such as methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene and the like can be mentioned. These monomers can be used alone or in combination of two or more.

  The polymerization method of each monomer may be in accordance with a conventional method, for example, a 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. For example, a ring-opening polymer of a cyclic olefin monomer or a ring-opening copolymer of a cyclic olefin monomer (hereinafter, both are referred to as “a ring-opening (co) polymer of a cyclic olefin monomer”). When obtained, the amount of the polymerization catalyst is usually 1: 100 to 1: 2,000,000, preferably 1: 500 to 1: 1, in the molar ratio of the metal compound to the cyclic olefin monomer in the polymerization catalyst. It is in the range of 1,000,000, more preferably 1: 1,000 to 1: 500,000.

  The cyclic olefin polymer obtained by the above polymerization can be hydrogenated as desired. Hydrogenation 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, Ziegler type homogeneous catalysts, noble metal complex catalysts, supported noble metal catalysts and the like can be used. Among these hydrogenation catalysts, rhodium and ruthenium can be selectively hydrogenated to carbon-carbon unsaturated bonds in the polymer without causing side reactions such as modification of functional groups such as protic polar groups. And a ruthenium catalyst coordinated with a nitrogen-containing heterocyclic carbene compound or a phosphine having a high electron donating property is more preferable. The hydrogenation rate of the cyclic olefin polymer is preferably 80% or more, more preferably 90% or more.

The cyclic olefin polymer used in the present invention is not particularly limited, but is preferably a ring-opening (co) polymer of a cyclic olefin monomer and a hydrogenated product thereof; a cyclic olefin monomer and a vinyl alicyclic carbonization. An addition copolymer of a hydrogen monomer and a hydrogenated product thereof; and an addition copolymer of a cyclic olefin monomer and a vinyl aromatic hydrocarbon monomer and a hydrogenated product thereof; It is at least one, and more preferably a hydrogenated product of a ring-opening (co) polymer of a cyclic olefin monomer.
In the present invention, the cyclic olefin polymers having different compositions can be used alone or in combination of two or more.

  As the cyclic olefin polymer used in the present invention, those having a polar group are preferred. The number of polar groups contained in the cyclic olefin polymer having a polar group is not particularly limited, and the polar groups may include the same or different types. The 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, but is bonded to the cyclic olefin monomer unit. Is preferred.

  In the present invention, the cyclic olefin polymer preferably has a protic polar group. Sensitivity to radiation of the resulting radiation-sensitive resin composition by using a cyclic olefin polymer having a protic polar group (hereinafter sometimes referred to as “protic polar group-containing cyclic olefin polymer”). In addition, the adhesion of the composition to the substrate is improved, which is preferable. Protic polar group-containing cyclic olefin-based polymers having different compositions can be used alone or in combination of two or more.

  In the present invention, as the protic polar group-containing cyclic olefin polymer, those having a structural unit represented by the formula (I) as shown below are preferred, and the structural unit represented by the formula (I): And what has the structural unit represented by Formula (II) is more suitable. The structural unit represented by formula (I) and the structural unit represented by formula (II) are both cyclic olefin monomer units.

[In the formula (I), R ^{1 to} R ⁴ each independently represents 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), and at least one of R ^{1 to} R ⁴ is , R ′ is a —X _n —R ′ group, which is a protic polar group, and m is an integer of 0-2. ]

[In the formula (II), R ⁵ and R ⁶ together with the two carbon atoms to which they are bonded contain an oxygen atom or a nitrogen atom which may have a substituent. It forms a membered heterocyclic structure, and 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, such as a methyl group, an ethyl group, an n-propyl group, And isopropyl group. The aromatic group that 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 the protic polar group include the groups described above. Examples of substituents for alkyl groups and aromatic groups include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, etc. alkyl groups having 1 to 4 carbon atoms; phenyl groups, xylyl groups And aryl groups having 6 to 12 carbon atoms such as a group, a tolyl group and a naphthyl group.

In the general formula (II), R ⁵ and R ⁶ are formed together with two carbon atoms to which they are bonded to each other and include an oxygen atom or a nitrogen atom which may have a substituent 3 Examples of the membered heterocyclic structure include an epoxy structure. In addition, as a 5-membered heterocyclic structure formed by including an oxygen atom or a nitrogen atom, R ⁵ and R ⁶ together with two carbon atoms to which they are bonded may have a substituent, Examples thereof include a dicarboxylic anhydride structure [—C (O) —O—C (O) —] and a dicarboximide structure [—C (O) —N—C (O) —]. Examples of the substituent for the oxygen atom or nitrogen atom include a phenyl group, a naphthyl group, and an anthracenyl group.

  In the protic polar group-containing cyclic olefin polymer, 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) The body unit) is usually in the range of 100/0 to 10/90, preferably 90/10 to 20/80, and more preferably 80/20 to 30/70 by weight.

  As a preferable production method of the protic polar group-containing cyclic olefin polymer used in the present invention, a method of polymerizing the cyclic olefin monomer (b) having a protic polar group and optionally performing hydrogenation may be mentioned. Can do.

  In addition, the protic polar group-containing cyclic olefin polymer used in the present invention introduces a protic polar group into a cyclic olefin polymer having no protic polar group using a modifier by a known method. It can also be obtained by a method. At this time, hydrogenation may be performed on the polymer before and after introduction of the protic polar group.

  As a modifier for introducing a protic polar group into a cyclic olefin polymer having no protic polar group, a reactive carbon-carbon unsaturated bond and a protic polar group are usually contained in one molecule. The compound which has is 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 may be carried out in accordance with a conventional method, and is usually performed in the presence of a radical generator. These modifiers may be used alone or in combination of two or more.

In the method for producing the protic polar group-containing cyclic olefin polymer, a precursor thereof may be used in place of the protic polar group. That is, instead of a monomer having a protic polar group, a monomer having a precursor of the protic polar group may be used. Moreover, you may use the modifier which has the precursor instead of the protic polar group as a modifier. A precursor of a protic polar group is converted into a protic polar group by a chemical reaction such as decomposition or hydrolysis by light or heat according to the type.
For example, when a protic polar group in a protic polar group-containing cyclic olefin polymer is a carboxyl group, an ester group may be used as a precursor of the protic polar group, and then appropriately converted to a carboxyl group.

  On the other hand, the cyclic olefin polymer not having a protic polar group can be obtained by using, for example, the monomers (a) and (c) to (f) according to a conventional method.

  The weight average molecular weight (Mw) of the cyclic olefin polymer 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 cyclic olefin polymer used in the present invention is usually 4 or less, preferably 3 or less, and more preferably 2.5 or less in terms of a weight average molecular weight / number average molecular weight (Mw / Mn) ratio.

  The iodine value of the cyclic olefin polymer used in the present invention is usually 200 or less, preferably 50 or less, more preferably 10 or less. If the iodine value of the cyclic olefin polymer is within this range, it is particularly excellent in heat-resistant shape retention and suitable.

  The radiation-sensitive compound used in the present invention is a compound that can cause a chemical reaction by irradiation with radiation such as ultraviolet rays and electron beams. When a cyclic olefin polymer having a protic polar group is used in the present invention, the radiation sensitive compound is preferably one capable of controlling the alkali solubility of the cyclic olefin polymer. In the present invention, it is preferable to use a photoacid generator as the radiation-sensitive compound.

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

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

  The usage-amount of a radiation sensitive compound is 1-100 weight part normally with respect to 100 weight part of cyclic olefin polymers, Preferably it is the range of 5-50 weight part, More preferably, it is the range of 10-40 weight part. If the amount of the radiation-sensitive compound used is within this range, when the resin film formed on the substrate is patterned, the difference in solubility between the radiation-irradiated part and the radiation-unirradiated part in the developer increases. This is suitable because it can be easily patterned and the radiation sensitivity is high.

  The radiation-sensitive resin composition of the present invention contains a blocked polyisocyanate compound having a blocked isocyanate group in addition to the above components. The content of the block type polyisocyanate compound is 5 to 80 parts by weight with respect to 100 parts by weight of the cyclic olefin polymer.

  The content of the block-type polyisocyanate compound is preferably 10 to 60 parts by weight, more preferably 20 to 40 parts by weight with respect to 100 parts by weight of the cyclic olefin polymer.

  In the present invention, a cyclic olefin polymer having a cyclic structure in the main chain and a predetermined amount of a block type polyisocyanate compound are used in combination. Appropriate resistance to thermal deformation of the resin film is imparted by the temperature-dependent cross-linking action between the cyclic olefin polymer, preferably a protic polar group-containing cyclic olefin polymer and the block polyisocyanate compound. It is estimated that

  The block type polyisocyanate compound used in the present invention is a diisocyanate such as aliphatic diisocyanate or alicyclic diisocyanate; and an isocyanate group of a diisocyanate polymerized isocyanurate (diisocyanate trimer) blocking agent (protective agent) (Isocyanate group blocked). A block type polyisocyanate compound can be used individually or in combination of 2 or more types.

  The block type polyisocyanate compound itself is a known compound, and is called a blocked isocyanate or a blocked polyisocyanate in addition to the block type polyisocyanate, and is a compound that is stable at room temperature. When the block type polyisocyanate is heated, the blocking agent is dissociated to regenerate the original active isocyanate group.

  The diisocyanate and the isocyanurate are not particularly limited. Preferable specific examples include aliphatic or alicyclic diisocyanates such as 1,6-hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, and isophorone diisocyanate.

  As the blocking agent used to block the isocyanate group, a compound having active hydrogen is usually used. The compound having active hydrogen is not particularly limited. Specific examples thereof include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, cyclohexanol; phenol, o-nitro Phenols such as phenol, p-chlorophenol, o-cresol, m-cresol, p-cresol; thiols such as 1-dodecanethiol and benzenethiol; acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone Oximes such as oxime and benzophenone oxime; active methylene compounds such as diethyl malonate, ethyl acetoacetate and acetylacetone; lactams such as ε-caprolactam; It is below.

  Block type polyisocyanate compounds are commercially available. Examples thereof include the Death Module series (Desmodule BL3370, Deathmodule VPLS2253) and Clerant series (Cleran V1, Cleran VPLS2256) manufactured by Sumitomo Bayer Urethane, Ltd., Takeshi Mitsui Chemicals. Examples include Takenate series (B-815N, B-882N, B-874N) and Coronate series (Coronate L) manufactured by Nippon Polyurethane Industry. In the present invention, these block-type polyisocyanate compounds can be suitably used.

  In addition, the radiation-sensitive resin composition of the present invention is optionally blended with resin components other than cyclic olefin-based polymers, crosslinking agents, and other blends, as long as the desired effects of the present invention are not inhibited. Other components such as an agent may be included.

  As resin components other than the cyclic olefin polymer, for example, styrene resin, vinyl chloride resin, acrylic resin, polyphenylene ether resin, polyarylene sulfide resin, polycarbonate resin, polyester resin, polyamide resin, polyethersulfone resin, Examples include polysulfone resin, polyimide resin, rubber, and elastomer.

  As the crosslinking agent, one having two or more, preferably three or more functional groups capable of reacting with the cyclic olefin polymer in the molecule is used. The functional group possessed by the crosslinking agent is not particularly limited as long as it can react with the functional group or unsaturated bond in the cyclic olefin polymer. When the cyclic olefin polymer has a protic polar group, preferred functional groups capable of reacting with this polar group include, for example, an amino group, a carboxyl group, a hydroxyl group, an epoxy group, an isocyanate group, and the like. Are an amino group, an epoxy group and an isocyanate group, more preferably an epoxy group.

  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; N, N ', N", N "'-(tetraalkoxymethyl) glycolurils such as glycoluril; Acrylate compounds such as ethylene glycol di (meth) acrylate; Hexamethylene diisocyanate polyisocyanate 1, isocyanate compounds such as isophorone diisocyanate polyisocyanate, tolylene diisocyanate polyisocyanate, hydrogenated diphenylmethane diisocyanate; 1,4-di- (hydroxymethyl) cyclohexane, 1,4-di- (hydroxymethyl) norbornane; 1 , 3,4-trihydroxycyclohexane; various polyfunctional epoxy compounds;

  More specific examples of the polyfunctional epoxy compound include epoxy compounds having two or more epoxy groups, preferably three or more epoxy groups, having an alicyclic structure, having a cresol novolac skeleton, Examples thereof include those having a phenol novolac skeleton, those having a bisphenol A skeleton, those having a naphthalene skeleton, and the like. Among these, in view of good compatibility with the cyclic olefin polymer, a polyfunctional epoxy compound having an alicyclic structure and having two or more, more preferably three or more epoxy groups is preferable.

  As the crosslinking agent, a polyfunctional epoxy compound is particularly preferable. Specific examples thereof 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.

  Although the molecular weight of a crosslinking agent 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 crosslinking agent can be used individually or in combination of 2 types or more, respectively.

  Examples of other compounding agents include sensitizers, surfactants, latent acid generators, antistatic agents, antioxidants, adhesion assistants, antifoaming agents, pigments, and dyes.

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

  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 radiation-sensitive resin composition of the present invention. Specific examples thereof include sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts, which are cationic polymerization catalysts that generate an acid upon heating. Of these, sulfonium salts and benzothiazolium salts are preferred.

  In addition, a well-known thing is arbitrarily used as said compounding agent.

  The form of the radiation sensitive resin composition of this invention is not specifically limited, A solution or a dispersion liquid may be sufficient and a solid form may be sufficient. The radiation sensitive resin composition of the present invention is preferably used in the form of a solution or a dispersion.

  The preparation method of the radiation sensitive resin composition of the present invention is not particularly limited, and each component of the radiation sensitive resin composition of the present invention (a cyclic olefin polymer, a radiation sensitive compound and a block type polyisocyanate compound, If necessary, other components) may be mixed, but these components are preferably dissolved or dispersed in a solvent to obtain a solution or a dispersion. You may remove a solvent from the obtained solution or dispersion liquid as needed.

  The solvent used in the present invention is not particularly limited. Specific 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 monomethyl ether, triethylene glycol Alkylene glycol monoethers such as diethyl glycol ether, tripropylene glycol monomethyl ether, tripropylene glycol monomethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene Alkylene glycol dialkyl ethers such as glycol ethyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tripropylene glycol ethyl methyl ether; propylene glycol monomethyl 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 acetate, propylene glycol mono alkylene glycol monoalkyl ether esters such as sec-butyl ether acetate and propylene glycol mono t-butyl ether acetate; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, cyclohexanone and cyclopentanone Class: methanol, ethanol, propanol, pig Alcohols such as diol and 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, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3 -Esters such as methyl methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, γ-butyrolactone; N-methylformamide, N, N-dimethylformamide N- methyl-2-pyrrolidone, N- methylacetamide, N, N- amides dimethylacetamide; sulfoxides such as dimethyl sulfoxide; and the like.

  These solvents may be used alone or in combination of two or more. 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. It is.

  The method for dissolving or dispersing each component constituting the radiation-sensitive resin composition of the present invention in a solvent may be in accordance with a conventional method. Specifically, the stirring can be performed using a stirrer and a magnetic stirrer, a high-speed homogenizer, a dispersion, a planetary stirrer, a biaxial stirrer, a ball mill, a three-roller, or the like. 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 when each component constituting 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. 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 radiation-sensitive resin composition of the present invention has the characteristics that the obtained resin film has excellent heat-resistant shape retention and has a wide temperature margin during melt flow when forming a patterned resin film. Therefore, as one aspect of the present invention, a method for improving the heat-resistant shape retention of a resin film using the radiation-sensitive resin composition of the present invention, or a temperature margin during melt flow when forming a patterned resin film An enlargement method can also be provided.

  The laminate of the present invention is a laminate comprising a substrate and a resin film made of the radiation-sensitive resin composition of the present invention laminated thereon. 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.

  In the present invention, as the substrate, for example, a printed wiring substrate, a silicon wafer substrate, a glass substrate, a plastic substrate, or the like can be used. Further, 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 laminate of the present invention is usually composed of a substrate and a resin film made of the radiation-sensitive resin composition of the present invention directly laminated on the substrate, for example, through another film such as a planarizing film. A resin film may be indirectly laminated. Moreover, the laminated body of this invention also includes the multilayer laminated body which consists of a board | substrate and a resin film, and also another film depending on necessity other than the two-layer laminated body which consists of a board | substrate and a resin film.

  Moreover, the resin film may be patterned. The laminate of the present invention, particularly a laminate obtained by forming a patterned resin film on a substrate, is useful as various optical components and electronic components as described later.

  The laminate of the present invention can be produced, for example, by forming a resin film on a substrate using the radiation sensitive resin composition of the present invention.

  The method for forming the resin film on the substrate is not particularly limited, and for example, a method such as a coating method or a film lamination method can be used. The application method is, for example, a method in which a radiation-sensitive resin composition in the form of a solution or a dispersion 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 onto the substrate include various methods such as spraying, spin coating, roll coating, die coating, doctor blade method, spin coating, bar coating, and screen printing. This 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 under conditions of 1 to 30 minutes.

  In the film lamination method, for example, a radiation-sensitive resin composition in the form of a solution or dispersion is applied on a B-stage film-forming substrate such as a resin film or a metal film, and then the solvent is removed by heat drying. In this method, a stage film is obtained, and then this B stage film is transferred and laminated onto a laminate 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 under conditions of 1 to 30 minutes. Film lamination can be performed using a pressure bonding machine such as a pressure laminator, a press, a vacuum laminator, a vacuum press, or a roll laminator.

  A laminate comprising a substrate of the present invention and a patterned resin film comprising a radiation-sensitive resin composition laminated thereon, for example, a resin film substrate using the radiation-sensitive resin composition of the present invention. Laminate on this resin film to irradiate actinic radiation to form a latent image pattern in the resin film, and then bring the developer film into contact with the resin film to reveal the latent image pattern. It can be manufactured by patterning the membrane.

Lamination of the resin film comprising the radiation-sensitive resin composition of the present invention on the substrate may be performed according to the above method. The actinic radiation applied to the formed resin film is not particularly limited as long as it can activate the radiation-sensitive compound and change the alkali solubility of the radiation-sensitive resin composition containing the radiation-sensitive compound. . 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; In order to form a latent image pattern by selectively irradiating these actinic radiations on the resin film, it is sufficient to follow a conventional 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 way, the resin film is heat-treated at a temperature of about 60 to 130 ° C. for about 1 to 2 minutes as desired.

  Next, the latent image pattern formed on the resin film is developed to be manifested. In this specification, this process is referred to as “patterning”, and the patterned resin film is referred to as “patterned resin film”. . As the developer, an aqueous solution of an alkaline compound (alkaline aqueous solution) is usually used. The alkaline compound may be an inorganic compound or an organic compound. As the alkaline compound, for example, an alkali metal salt, an amine, or an ammonium salt can be used. Specific examples of these compounds include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate and sodium metasilicate; ammonia; primary amines such as ethylamine and n-propylamine; diethylamine; Secondary amines such as di-n-propylamine; tertiary amines such as triethylamine, methyldiethylamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, choline; Alcohol amines such as dimethylethanolamine and triethanolamine; pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5 En, N-methyl Cyclic amines such as pyrrolidone; 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 or a water-soluble organic solvent such as methanol or ethanol can be used. An appropriate amount of a surfactant or the like may be added to the alkaline aqueous solution.

  As a method for bringing the developer into contact with the resin film on which the latent image pattern is formed, for example, a paddle method, a spray method, a dipping method, or the like is used. The development conditions are usually selected appropriately 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.

  Thus, the intended patterned resin film is formed on the substrate. Then, if desired, the substrate may be rinsed with a rinse liquid such as ultrapure water in order to remove development residues on the substrate, the back surface of the substrate, and the edge of the substrate. After the rinse treatment, the remaining rinse liquid may be removed with compressed air or compressed nitrogen. Further, if desired, in order to deactivate the radiation-sensitive compound, the entire surface of the substrate having the patterned resin film may be irradiated with actinic radiation. 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 100 to 300 ° C, preferably 120 to 200 ° C, and the time is usually 1 minute to 120 minutes.

  Further, after obtaining the primary patterned resin film by the above method, this resin film may be heated to obtain a secondary patterned resin film in which the pattern shape before heating is deformed. By this deformation, for example, a pattern with a square cross-sectional shape is changed to a gentle pattern without corners. Specifically, for example, when a dot pattern is formed on the resin film, the resin film is melt-flowed to change the shape of the pattern from a dot shape to a hemispherical shape. Therefore, the present invention also includes a method for manufacturing a laminate, which further includes a step of heating the patterned resin film formed on the substrate to deform the pattern shape. Such a method for producing a laminate is useful, for example, for producing microlenses and the like.

  When manufacturing a secondary patterned resin film, the pattern of the primary patterned resin film is heated and melted to form a secondary patterned resin film having a desired pattern shape, and at the same time, cross-linking of the resin film proceeds in a balanced manner. In addition, it is presumed that a crosslinked structure of a degree necessary for maintaining the pattern shape of the secondary patterned resin film is formed. Therefore, according to the radiation-sensitive resin composition of the present invention, a secondary patterned resin film can be easily formed by melt flow, while the obtained secondary patterned resin film is exposed to a temperature higher than that during melt flow. However, resistance to deformation of the pattern shape can be exhibited. In addition, the temperature margin during the melt flow can be widened, and the secondary patterned resin film can be efficiently manufactured.

  The radiation sensitive resin composition of the present invention can be suitably used as, for example, a positive resist material. According to the above-described method for producing a laminate formed by forming a patterned resin film on a substrate, a resist pattern having excellent resolution can be obtained.

  As described above, the laminate of the present invention, in particular, a laminate comprising the substrate and the patterned resin film formed thereon is produced. In the present invention, after forming a resin film (including a patterned resin film) on the substrate, this film may be further cross-linked as desired. The present invention also includes a method for producing a laminate further comprising a step of crosslinking a resin film (including a patterned resin film) formed on a substrate.

  The resin film formed on the substrate may be cross-linked by, for example, an appropriate method depending on the type of the cross-linking agent used, but is usually performed by heating. The heating method can be performed using, for example, a hot plate or an oven. The heating temperature is usually 180 to 250 ° C., and the heating time is appropriately selected according to the size and thickness of the resin film and the equipment used. For example, when using a hot plate, it is usually in the range of 5 to 60 minutes, and when using an oven, it is usually in the range of 30 to 90 minutes. Heating may be performed in an inert gas atmosphere if desired. The inert gas may be any gas that 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.

  The laminate of the present invention obtained as described above is suitably used as an electronic component or an optical component such as an integrated circuit element, a liquid crystal display element, and a solid-state imaging element. These optical components and electronic components can be produced according to known methods using the radiation-sensitive resin composition or laminate of the present invention. The optical component and electronic component comprising the laminate of the present invention are included in the present invention.

  Hereinafter, the present invention will be described in more detail 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, the test and evaluation in the following were based on the following.

[Weight average molecular weight (Mw) and number average molecular weight (Mn) of polymer]
Tetrahydrofuran (THF) was used as an eluent, and the molecular weight was calculated as polyisoprene equivalent molecular weight by gel permeation chromatography using HLC-8020 manufactured by Tosoh Corporation as a gel permeation chromatograph.
[Hydrogenation rate]
Hydrogenation rate is the percentage (after hydrogenation / before hydrogenation) of the number of moles of hydrogenated carbon-carbon double bonds to the number of moles of carbon-carbon double bonds before hydrogenation according to ¹ H-NMR spectrum. As sought.
[Iodine number]
It measured according to JIS K0070B.

[Evaluation of radiation-sensitive resin composition]
(1) Formation of patterned resin film A silicon wafer substrate coated with a thermosetting resin film is spin-coated with a radiation-sensitive resin composition, dried at 100 ° C. for 120 seconds using a hot plate, and then dried. The film thickness was 1.2 μm.

This resin film was irradiated with i rays having a light intensity of 0.5 W / cm ² in air for 700 milliseconds through a mask having a pattern of 3.5 μm dots and 1.5 μm spaces. Next, after developing for 80 to 110 seconds at 23 ° C. using an aqueous solution of tetramethylammonium hydroxide 0.6 to 0.8%, rinsing with ultrapure water for 30 seconds, positive type 3.5 μm A dot-patterned resin film was formed. Note that W corresponds to J / sec.

(2) Heat resistant shape retention of patterned resin film The cross-sectional shape of the patterned resin film is observed with a scanning electron microscope (SEM), and the width a between dot patterns is measured based on the SEM image (magnification: 10,000 times). did. Next, the entire surface of the patterned resin film was irradiated with ultraviolet rays having a light wavelength at 365 nm of 5 mW / cm ² in air for 30 seconds, and then the substrate on which this pattern was formed using a hot plate was 140 to 170 ° C. The first heat treatment (middle bake 1) was performed for 10 minutes at the optimum temperature between and the patterned resin film was melted to deform the pattern from a dot shape to a hemispherical shape. Further, the substrate subjected to the middle bake 1 was subjected to a second heat treatment (post bake 1) at 230 ° C. for 10 minutes using a hot plate. The cross-sectional shape of the pattern after post-baking 1 was observed by SEM in the same manner as described above, and the width b between the dot patterns was measured based on the SEM image. The difference (ab) between the width a between the dot patterns after the formation of the patterned resin film and the width b between the dot patterns after the post bake 1 is obtained, and the heat resistant shape retention of the patterned resin film is determined according to the following evaluation criteria. evaluated.
〔Evaluation criteria〕
(Excellent): The pattern is hemispherical, and (ab) is 0.5 μm or less.
○ (good): The pattern is hemispherical, and (ab) is more than 0.5 μm and not more than 1 μm.
Δ (possible): The pattern is hemispherical, and (ab) is more than 1 μm and 1.5 μm or less.
X (impossible): The pattern is completely melted and fused with the adjacent pattern.

(3) Temperature margin during melt flow when forming the patterned resin film The cross-sectional shape of the patterned resin film is observed by SEM in the same manner as described above, and the width a ′ between the dot patterns is measured based on the SEM image. did. Next, the entire surface of the patterned resin film was irradiated with ultraviolet rays having a light wavelength at 365 nm of 5 mW / cm ² in air for 30 seconds, and then the substrate on which this pattern was formed was heated from 140 ° C. using a hot plate. The first heat treatment (middle bake 2) is performed for 10 minutes each at a temperature of 5 ° C. up to 170 ° C., and the patterned resin film is melted to deform the pattern from a dot shape to a hemispherical shape. It was. Further, the substrate subjected to the middle bake 2 was subjected to a second heat treatment (post bake 2) at 230 ° C. for 10 minutes using a hot plate. The cross-sectional shape of the pattern after post-baking 2 was observed with SEM in the same manner as described above, and the width b ′ between the dot patterns was measured based on the SEM image. The difference (a′−b ′) between the width a ′ between the dot patterns after the formation of the patterned resin film and the width b ′ between the dot patterns after the post-baking 2 is obtained, and the patterned resin film is obtained according to the following evaluation criteria. The temperature margin during melt flow during formation was evaluated.
〔Evaluation criteria〕
(Excellent): The pattern has a hemispherical shape, and the width of middle bake temperature where (a′−b ′) is 1 μm or less is 20 ° C. or more.
○ (good): The pattern has a hemispherical shape, and the width of middle bake temperature where (a′−b ′) is 1 μm or less is 10 ° C. or more and less than 20 ° C.
Δ (possible): The pattern has a hemispherical shape, and the width of middle bake temperature where (a′−b ′) is 1 μm or less is 5 ° C. or more and less than 10 ° C.
X (impossible): The width of the middle bake temperature where the pattern is hemispherical and (a′−b ′) is 1 μm or less is less than 5 ° C.

  In addition, “the width of the middle bake temperature” in the evaluation criteria is (a′−b ′) when the middle bake 2 is set at a temperature of 140 to 170 ° C. at intervals of 5 ° C. The difference between the lowest temperature and the highest temperature among the temperatures at which the value becomes a value (1 μm or less) defined in each evaluation standard.

[Synthesis Example 1]
8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] 62.5 parts dodec-3-ene, 37.5 parts N- (4-phenyl)-(5-norbornene-2,3-dicarboximide), 1.3 parts 1-hexene, , 3-dimethylimidazolidin-2-ylidene (tricyclohexylphosphine) benzylidene ruthenium dichloride (0.05 parts) and tetrahydrofuran (400 parts) were charged into a nitrogen-substituted glass pressure-resistant reactor and reacted at 70 ° C. for 2 hours with stirring. Thus, a polymer solution A (solid content concentration: about 20%) was obtained.

  A part of this polymer solution A is transferred to an autoclave equipped with a stirrer, and hydrogen is dissolved at a pressure of 4 MPa at 150 ° C. and reacted for 5 hours, and a polymer solution B containing a hydrogenated polymer (hydrogenation rate 100%). (Solid content concentration: about 20%) was obtained.

  A heat-resistant container to which 100 parts of the polymer solution B and 1 part of activated carbon powder were added was placed in an autoclave, and hydrogen was dissolved at 150 ° C. under a pressure of 4 MPa for 3 hours while stirring. 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 a polymer solution. Filtration was performed without any delay. The polymer solution was poured into ethyl alcohol to solidify, and the produced crumb was dried to obtain a cyclic olefin polymer. Mw of the obtained polymer in terms of polyisoprene was 5,500, Mn was 3,200, and Mw / Mn ratio was 1.7. The iodine value was 1.

[Example 1]
100 parts of a cyclic olefin polymer obtained in Synthesis Example 1; 200 parts of propylene glycol monoethyl ether acetate as solvent, 100 parts of diethylene glycol ethyl methyl ether and 100 parts of N-methyl-1-pyrrolidone; 1,1, as quinonediazide compound 25 parts of condensate of 3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.9 mol); As a crosslinking agent, an alicyclic structure-containing polyfunctional epoxy compound (molecular weight 2234, trade name “EHPE3150”, manufactured by Daicel Chemical Industries, Ltd.) 36 parts; block type polyisocyanate compound (trade name “Desmodur BL3370MPA”, Sumika Bayer Urethane Co., Ltd.) 5 parts; Pe as an antioxidant 6 parts of Taerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name Irganox 1010, manufactured by Ciba Specialty Chemicals); and a silicone-based surfactant A surfactant (trade name kp341, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.05 parts was mixed and dissolved, and then filtered through a fluororesin filter having a pore diameter of 0.45 μm to prepare a radiation-sensitive resin composition. According to the said method, the obtained radiation sensitive resin composition was evaluated. The temperature of middle bake 1 was 150 ° C. The results are shown in Table 1.

[Example 2]
In Example 1, a radiation sensitive resin composition was prepared and evaluated in the same manner except that the addition amount of the block type polyisocyanate compound was changed to 10 parts. The results are shown in Table 1.

[Example 3]
In Example 1, a radiation sensitive resin composition was prepared and evaluated in the same manner except that the addition amount of the block type polyisocyanate compound was changed to 20 parts. The results are shown in Table 1.

[Example 4]
In Example 1, a radiation sensitive resin composition was prepared and evaluated in the same manner except that the addition amount of the block type polyisocyanate compound was changed to 40 parts. The results are shown in Table 1.

[Example 5]
In Example 1, a radiation sensitive resin composition was prepared and evaluated in the same manner except that the addition amount of the block type polyisocyanate compound was changed to 60 parts. The results are shown in Table 1.

[Example 6]
In Example 1, a radiation sensitive resin composition was prepared and evaluated in the same manner except that the addition amount of the block type polyisocyanate compound was changed to 80 parts. The results are shown in Table 1.

[Comparative Example 1]
In Example 1, a radiation sensitive resin composition was prepared and evaluated in the same manner except that the addition amount of the block type polyisocyanate compound was changed to 1 part. The results are shown in Table 1.

[Comparative Example 2]
In Example 1, a radiation sensitive resin composition was prepared and evaluated in the same manner except that the addition amount of the block type polyisocyanate compound was changed to 90 parts. The temperature of middle bake 1 was 150 ° C. The results are shown in Table 1.

  From the result shown in Table 1, using the radiation sensitive resin composition of Examples 1-6 which contains a block type polyisocyanate compound in the range of 5-80 weight part with respect to 100 weight part of cyclic olefin polymers. It can be seen that the resulting patterned resin is excellent in heat resistant shape retention and has a wide temperature margin. In particular, it can be seen that an excellent effect is exhibited when the content of the block-type polyisocyanate compound is 10 to 60 parts by weight. On the other hand, the patterned resin film obtained using the radiation-sensitive resin composition of Comparative Example 1 in which the amount of the block-type polyisocyanate compound is less than 5 parts by weight or Comparative Example 2 in which the amount is more than 80 parts by weight It can be seen that the retention is poor and the temperature margin is narrow.

  INDUSTRIAL APPLICABILITY The present invention can contribute to the stabilization of the manufacture of electronic parts and optical parts such as integrated circuit elements, liquid crystal display elements, and solid-state imaging elements, and improvement in yield.

Claims (11)

  Radiation sensitivity comprising 100 parts by weight of a cyclic olefin polymer having a cyclic structure in the main chain, 1 to 100 parts by weight of a radiation sensitive compound, and 5 to 80 parts by weight of a blocked polyisocyanate compound having a blocked isocyanate group. Resin composition.   The radiation-sensitive resin composition according to claim 1, wherein the cyclic olefin polymer has a protic polar group.   The cyclic olefin polymer is a ring-opening polymer of a cyclic olefin monomer, a ring-opening copolymer of a cyclic olefin monomer and a hydrogenated product thereof; a cyclic olefin monomer and a vinyl alicyclic hydrocarbon monomer And at least one selected from the group consisting of: an addition copolymer of a cyclic olefin monomer and a vinyl aromatic hydrocarbon monomer; and a hydrogenated product thereof. The radiation-sensitive resin composition according to claim 1 or 2, which is a seed.   The laminated body which consists of a resin film which consists of a board | substrate and the radiation sensitive resin composition of any one of Claims 1-3 laminated | stacked on this.   The manufacturing method of the laminated body which has the process of forming a resin film on a board | substrate using the radiation sensitive resin composition of any one of Claims 1-3.   The laminate according to claim 4, wherein the resin film is a patterned resin film.   The process of forming a resin film on a board | substrate using the radiation sensitive resin composition of any one of Claims 1-3, Actinic radiation is irradiated to a resin film, and a latent image pattern is formed in a resin film The manufacturing method of the laminated body of Claim 6 which has the process of making a latent image pattern actualize by making a developing solution contact the resin film, and making the resin film into contact.   The manufacturing method of the laminated body of Claim 7 which further has the process of heating the patterned resin film formed on the board | substrate, and changing a pattern shape.   The manufacturing method of the laminated body of any one of Claim 5, 7, and 8 which further has the process of bridge | crosslinking the resin film formed on the board | substrate.   An optical component comprising the laminate according to claim 4 or 6.   An electronic component comprising the laminate according to claim 4.