JP4380702B2 - Radiation-sensitive composition, laminate, method for producing the same, and electronic component - Google Patents

Description

  The present invention relates to a radiation-sensitive composition and a laminate having a resin film obtained from the radiation-sensitive composition on a substrate, and more specifically, suitable for manufacturing electronic components such as display elements, integrated circuit elements, and solid-state imaging elements. A radiation-sensitive composition, a laminate having a resin film obtained from the radiation-sensitive composition on a substrate, and a method for producing the same.

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.
Conventionally, thermosetting resin materials such as epoxy resins have been widely used as resin materials for forming these resin films. However, with recent increases in the density of wiring and devices, these resin materials have been required to have fine electrical characteristics and excellent electrical characteristics.

  Several resin materials for meeting these requirements have been studied. For example, Patent Document 1 discloses an alkali-soluble cyclic polyolefin-based resin composition, a 1,2-quinonediazide compound, and a crosslinking agent having a functional group capable of forming a crosslinking agent (preferably glycolurils and, for example, bisphenol A type A radiation-sensitive composition containing a compound having at least two epoxy groups and having no radical polymerizability, such as an epoxy resin, is disclosed. However, when this radiation-sensitive composition is used, the film thickness during development or peeling of the developed film may occur, or the shape and transparency may be lost after the heating step. In addition, since the solvent resistance is not sufficient, the resin film formed from these radiation-sensitive compositions is not suitable for laminating, for example, a polyimide for a liquid crystal polarizing film on the resin film. It was.

Patent Document 2 discloses a radiation-sensitive composition comprising an alicyclic olefin resin, an acid generator, a crosslinking agent, and a solvent, and using a specific compound as a solvent. However, with this radiation-sensitive composition, there are cases in which the film thickness during development, the peel-off of the developed film, the shape and transparency change due to the heating process, and the like occur.
Furthermore, a curable composition comprising a ring structure-containing polymer having a polar group such as a carboxyl group, a polyfunctional epoxy resin, and a curing agent as required is disclosed (Patent Document 3). However, the curable composition disclosed herein is not suitable for efficiently forming a pattern by actinic radiation, and these requirements are required when heat-resistant shape retention and solvent resistance are highly required. Could not be satisfied sufficiently.

Japanese Patent Laid-Open No. 10-307388 JP 2003-156838 A WO01 / 04213 Publication

  The present invention has been made under such circumstances, has excellent electrical characteristics, does not cause a reduction in film thickness during development and does not cause peeling of the development film, and has high shape retention and transparency even after high-temperature heating. It is another object of the present invention to provide a radiation-sensitive composition excellent in chemical resistance, a laminate in which a resin film using the radiation-sensitive composition is formed on a substrate, and a method for producing the laminate.

  As a result of intensive studies to achieve the above object, the present inventors have a polymer having a polar group such as a carboxyl group having reactivity with an epoxy group, an alicyclic structure in the main chain structure, It has been found that a radiation-sensitive composition comprising a polyfunctional epoxy compound having three or more epoxy groups and a radiation-sensitive compound may be used, and further research is advanced based on these findings to complete the present invention. It was.

Thus, according to the present invention, a polymer containing a polar group that reacts with an epoxy group, a crosslinking agent comprising a polyfunctional epoxy compound having an alicyclic structure in the main chain structure and having three or more epoxy groups, and A radiation-sensitive composition comprising a radiation-sensitive compound is provided.
In the radiation-sensitive composition of the present invention, the polymer containing a polar group that reacts with an epoxy group is preferably a cyclic olefin polymer having a polar group that reacts with an epoxy group.
In the radiation-sensitive composition of the present invention, the cyclic olefin polymer having a polar group that reacts with an epoxy group preferably contains 10 to 90% by weight of a polar group-containing cyclic olefin unit.
Furthermore, in the present invention, the polar group that reacts with the epoxy group is preferably a protic polar group.
Furthermore, in the present invention, the main chain structure of the polyfunctional epoxy compound preferably has a branched alkylene chain.
Moreover, according to this invention, the laminated body formed by laminating | stacking the resin film which consists of said radiation sensitive composition on a board | substrate is provided.
This laminate can be obtained by a step of forming a resin film on the substrate using the radiation-sensitive composition and a step of crosslinking the resin if necessary.
In the present invention, the resin film may be a patterned resin film.
Furthermore, according to the present invention, a resin film is laminated on a substrate using the radiation sensitive composition, and the resin film is irradiated with actinic radiation to form a latent image pattern in the resin film, and then the resin film is formed. There is provided a method for producing the laminate, wherein a latent image pattern is exposed by bringing a developer into contact therewith to form a patterned resin on a substrate.
In the method for producing a laminate of the present invention, the resin can undergo a crosslinking reaction after the patterned resin is formed on the substrate.
Furthermore, according to this invention, the electronic component which consists of the said laminated body is provided.

  The radiation-sensitive composition of the present invention is excellent in electrical properties, improved in film thickness reduction during development and peeling of the developed film, has high shape retention after high-temperature heating, and is excellent in transparency and chemical resistance. Applicable to various uses. In addition, the laminate of the present invention is excellent in electrical characteristics, shape retention, transparency, and chemical resistance. For example, it can be used in electronic parts such as display elements, integrated circuit elements, solid-state imaging elements, color filters, and black matrices. Is a protective film for preventing deterioration and damage, a flattening film for flattening the element surface and wiring, and an electric insulating film for maintaining electrical insulation (for thin transistor type liquid crystal display elements and integrated circuit elements). It is suitable as a material for electronic parts such as an interlayer insulating film which is an electric insulating film, a solder resist film, etc.), a microlens, a spacer and the like.

The radiation-sensitive composition of the present invention comprises a polymer containing a polar group that reacts with an epoxy group, and a cross-link containing a polyfunctional epoxy compound having an alicyclic structure in the main chain structure and having three or more epoxy groups. It contains an agent and a radiation sensitive compound.
The polar group that reacts with the epoxy group is preferably a protic polar group, but may be a polar group other than the protic polar group (aprotic polar group).
In the present invention, the number of the polar groups that react with the epoxy groups contained in the polymer containing the polar group that reacts with the epoxy groups is not particularly limited. May be.

Protic polar groups are heteroatoms, preferably atoms of groups 15 and 16 of the periodic table, more preferably atoms of groups 1 and 2 of groups 15 and 16 of the periodic table, particularly preferably Is an atomic group in which a hydrogen atom is directly bonded to 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.

  There is no particular limitation on the skeleton of the polymer containing a polar group that reacts with the epoxy group used in the present invention. Examples thereof include a cyclic olefin polymer, a chain olefin polymer, an acrylate polymer, and the like. Can be mentioned. Among them, a cyclic olefin polymer and an acrylate polymer are preferable because of excellent dielectric properties, and a cyclic olefin polymer is particularly preferable.

  The protic polar group contained in the cyclic olefin polymer containing a protic polar group may be bonded to a monomer unit other than the cyclic olefin monomer, even if bonded to the cyclic olefin monomer unit. However, it is preferably bonded to a cyclic olefin monomer unit.

The cyclic olefin polymer constituting the portion other than the protic polar group of the cyclic olefin polymer containing a protic polar group (hereinafter sometimes referred to as “base portion”) is a homopolymer of cyclic olefin and Any of a copolymer and a copolymer of a cyclic olefin and another monomer may be used, and these hydrogenated products may also be used.
These cyclic olefin-based polymers containing a protic polar group can be used individually or in combination of two or more in different compositions.

  The cyclic olefin polymer containing a protic polar group used in the present invention is a polymer consisting only of monomer units derived from a cyclic olefin monomer (a) containing a protic polar group. Other monomer units that are copolymerizable with the monomer unit derived from the cyclic olefin monomer (a) containing a protic polar group and the cyclic olefin monomer (a) containing a protic polar group The copolymer which consists of a monomer unit induced | guided | derived from a body may be sufficient.

  In the cyclic olefin-based polymer containing a protic polar group used in the present invention, the ratio of a monomer unit containing a protic polar group to another monomer unit (a single unit containing a protic polar group). (Mer unit / other monomer unit) is usually in a range of 100/0 to 10/90, preferably 90/10 to 20/80, more preferably 80/20 to 30/70 in weight ratio. Selected to be.

Specific examples of the cyclic olefin monomer (a) containing a protic polar group include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo [2]. 2.1] hept-2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-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 . Carboxyl group-containing cyclic olefins such as 1 ^7,10 ] 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 hydroxy group-containing cyclic olefin such as ^{17, 10} ] dodec-3-ene. Among these, a carboxyl group-containing cyclic olefin is preferable. These protic polar group-containing cyclic olefins may be used alone or in combination of two or more.

As a monomer copolymerizable with the cyclic olefin monomer (a) containing a protic polar group, the cyclic olefin monomer (b) having a polar group other than the protic polar group has no polar group. There are no cyclic olefin monomers (sometimes referred to as “polar group-free cyclic olefin monomers”) (c), and monomers (d) other than cyclic olefins.
Among these, Preferably it is the cyclic olefin monomer (b) containing polar groups other than a protic polar group, and a polar group non-containing cyclic olefin monomer (c), More preferably, other than a protic polar group It is a cyclic olefin monomer (b) containing a polar group.

Specific examples of polar groups other than protic polar groups include ester groups (referred to generically as alkoxycarbonyl groups and aryloxycarbonyl groups), N-substituted imide groups, epoxy groups, halogen atoms, cyano groups, carbonyloxycarbonyls. Those having a group (an acid anhydride residue of a dicarboxylic acid), an alkoxyl group, a tertiary amino group, an acryloyl group and the like are shown.
Of these, ester groups, N-substituted imide groups and cyano groups are preferred, ester groups and N-substituted imide groups are more preferred, and N-substituted imide groups are particularly preferred.

Examples of the ester group-containing cyclic olefin include 5-acetoxybicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, and 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 N-substituted imide group-containing cyclic olefin include N-phenyl- (5-norbornene-2,3-dicarboximide).
Examples of the cyano group-containing cyclic olefin 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 halogen atom-containing cyclic olefin 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 olefins having polar groups other than protic polar groups may be used alone or in combination of two or more.

Specific examples of the non-polar group-containing cyclic olefin monomer (c) 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 (conventional 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 polar group-free cyclic olefin monomers (c) can be used alone or in combination of two or more.

  A typical example of the monomer (d) other than the cyclic olefin is 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. These monomers can be used alone or in combination of two or more.

Examples of a preferable production method of a cyclic olefin polymer containing a protic polar group include a method of polymerizing a cyclic olefin monomer (a) containing a protic polar group and hydrogenating as necessary. Can do.
If necessary, the cyclic olefin monomer (a) containing a protic polar group may be copolymerized with a monomer (the monomer (b), (c) or (d) described above). Can be copolymerized.

In the method for producing the protic polar group-containing cyclic olefin polymer, the protic polar group may be a precursor, and the precursor is subjected to a chemical reaction such as decomposition by light or heat, hydrolysis, etc. What is necessary is just to convert into a group. For example, when the protic polar group is a carboxyl group, a cyclic olefin polymer containing a protic polar group may be obtained by hydrolysis using a cyclic olefin containing an ester group instead of the protic polar group. it can.
The protic polar group-containing cyclic olefin polymer is obtained by introducing a protic polar group into a cyclic olefin polymer not containing a protic polar group by a known method, and then hydrogenating as necessary. Can also be obtained. Hydrogenation may be performed on the polymer before introduction of the protic polar group.

  The cyclic olefin polymer not containing a protic polar group can be obtained using the monomers (b) to (d). In this case, it goes without saying that a monomer containing a protic polar group may be used in 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 acid and cinnamic acid; allyl alcohol, methyl vinyl methanol, crotyl alcohol, methallyl alcohol, 1-phenylethen-1-ol, 2-propen-1-ol, 3-butene- 1-ol, 3-buten-2-ol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2- Such as methyl-3-buten-1-ol, 4-penten-1-ol, 4-methyl-4-penten-1-ol, 2-hexen-1-ol, etc. And the like can be given; saturated alcohols. The modification reaction may be carried out in accordance with a conventional method, and is usually performed in the presence of a radical generator.

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. 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 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.

  The acrylate polymer having a polar group that reacts with an epoxy group may be an acrylate copolymer having a protic polar group, but a carboxylic acid having an acrylic group, a carboxylic acid anhydride having an acrylic group, or an epoxy. A homopolymer or copolymer having at least one monomer selected from a group-containing acrylate compound as an essential component is preferred.

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) acryl” means “acryl” and / or “methacryl”.

  The acrylate polymer is copolymerizable with at least one monomer selected from unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, or epoxy group-containing unsaturated compound and other acrylate monomers or acrylates. It may be a copolymer with a monomer. 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, Examples thereof include vinyl group-containing radically polymerizable compounds such as vinyl benzyl methyl ether, vinyl glycidyl ether, styrene, α-methyl styrene, butadiene, and isoprene.
These compounds can be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the polymer containing a polar group that reacts with the epoxy group used in the present invention is usually 1,000 to 1,000,000, preferably 1,500 to 100,000, more preferably. Is in the range of 2,000 to 10,000.
The molecular weight distribution of the polymer containing a polar group that reacts with the epoxy group used in the present invention is usually 4 or less, preferably 3 or less, more preferably, in a weight average molecular weight / number average molecular weight (Mw / Mn) ratio. 2.5 or less.
The iodine value of the polymer containing a polar group that reacts with an epoxy group used in the present invention is usually 200 or less, preferably 50 or less, more preferably 10 or less. When the iodine value of a polymer containing a polar group that reacts with an epoxy group is in this range, a resin film formed using the obtained radiation-sensitive composition is excellent in heat resistance and suitable.
In the present invention, the polymer containing a polar group that reacts with an epoxy group may be used alone or in combination of two or more.

The crosslinking agent used in the present invention contains a polyfunctional epoxy compound having an alicyclic structure in the main chain structure and having three or more epoxy groups, preferably directly on the alicyclic structure portion. Or the epoxy compound which has 3 or more of epoxy groups couple | bonded through the bivalent coupling group is contained. The alicyclic structure may be obtained by hydrogenating an aromatic ring.
The proportion of the polyfunctional epoxy compound having an alicyclic structure in the main chain structure and having three or more epoxy groups in the crosslinking agent is preferably 50% by weight or more, more preferably 70% by weight or more.

  By using this cross-linking agent, the resin film formed from the radiation-sensitive composition of the present invention has excellent electrical characteristics, does not cause a reduction in film thickness or peeling of the developed film during development, and retains shape and transparency even after high-temperature heating. It is highly resistant and has excellent chemical resistance. Furthermore, it is preferable that the main chain structure of the polyfunctional epoxy compound further has an alkylene chain having a branched structure because the above properties are highly balanced. Here, the branched alkylene chain means one having tertiary or quaternary carbon in the alkylene chain. The number of epoxy groups in the polyfunctional epoxy compound is essential to be 3 or more, preferably 4 to 100, more preferably 5 to 50, and most preferably 10 to 30.

Examples of such epoxy compounds are hydrogenated bisphenol type epoxy resins, hydrogenated novolac type epoxy resins, glycidyl esters of alicyclic polyvalent carboxylic acids or epoxidized products of alicyclic olefins, and the like. The thing which has 3 or more (it is trifunctional or more) can be mentioned.
As a specific example of a polyfunctional epoxy compound having an alicyclic structure in the main chain structure and having 3 or more epoxy groups, a trifunctional epoxy compound having a dicyclopentadiene skeleton (trade name “XD-1000”). Nippon Kayaku Co., Ltd.). Examples of polyfunctional epoxy compounds having an alicyclic structure and a branched alkylene chain in the main chain structure and having 3 or more epoxy groups include 1 of [2,2-bis (hydroxymethyl) 1-butanol. , 2-Epoxy-4- (2-oxiranyl) cyclohexane adduct (15-functional alicyclic epoxy resin having a cyclohexane skeleton and a terminal epoxy group. Trade name “EHPE3150” manufactured by Daicel Chemical Industries, Ltd.), Epoxidation 3 -Cyclohexene-1,2-dicarboxylate bis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic trifunctional epoxy resin. Trade name “Epolide GT301”, manufactured by Daicel Chemical Industries, Ltd.), epoxidized butanetetra Carboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic tetrafunctional) Epoxy resin, trade name “Epolide GT401” (manufactured by Daicel Chemical Industries, Ltd.).

The molecular weight of the polyfunctional epoxy compound having an alicyclic structure in the main chain structure used in the present invention and having three or more epoxy groups is not particularly limited, but is usually 500 to 50,000, preferably 1,000. To 10,000, more preferably 1,500 to 5,000, particularly preferably 2,000 to 5,000. A molecular weight in this range is preferable from the viewpoint of stability during heating and gelation efficiency.
These polyfunctional epoxy compounds having an alicyclic structure in the main chain structure and having three or more epoxy groups can be used alone or in combination of two or more, and the amount used thereof depends on the purpose of use. Depending on the case, the polymer is usually selected in an amount of 1 to 200 parts by weight, preferably 10 to 100 parts by weight, more preferably 20 to 50 parts by weight per 100 parts by weight of the polymer containing a polar group that reacts with an epoxy group. It is. When the amount used is in this range, the heat resistance (heat-resistant shape retention and heat-resistant transparency) of the formed resin film is highly improved, which is preferable.

In the present invention, as the crosslinking agent, in addition to the polyfunctional epoxy compound having an alicyclic structure in the main chain structure and having three or more epoxy groups, other crosslinking agents can be used in combination.
As a crosslinking agent that can be used in combination, an epoxy compound having 3 or more epoxy groups but having no alicyclic structure in the main chain structure, an epoxy compound containing 2 epoxy groups, and 1 or less epoxy groups And / or a crosslinking agent having a total of two or more crosslinkable groups having the same reactivity as the epoxy group.

  As an epoxy compound having three or more epoxy groups but not having an alicyclic structure in the main chain structure, an epoxy compound having a cresol novolak structure in the main chain structure and having two or more epoxy groups, An epoxy compound having a phenol novolac structure and having two or more epoxy groups, an epoxy compound having a bisphenol A structure in the main chain structure and having two or more epoxy groups, and two or more having a naphthalene structure in the main chain structure And an epoxy compound having an epoxy group, a trimethylolpropane type epoxy compound having two or more epoxy groups, and the like.

  The cross-linking agent having a total of two or more crosslinkable groups having the same reactivity as the epoxy group and / or epoxy group of one or less is a total of two or more amino groups, carboxyl groups, hydroxyl groups, isocyanate groups, etc. The crosslinking agent which can be mentioned can be mentioned. Specific examples thereof include aliphatic polyamines such as hexamethylenediamine; aromatic polyamines such as 4,4′-diaminodiphenyl ether and diaminodiphenylsulfone; 2,6-bis (4′-azidobenzal) cyclohexanone, 4,4 Azide compounds such as' -diazidodiphenylsulfone; polyamides such as nylon, polyhexamethylenediamine terephthalamide, polyhexamethyleneisophthalamide; N, N, N ', N', N ", N"-(hexaalkoxy Melamines such as methyl) melamine; glycolurils such as N, N ′, N ″, N ″ ′-(tetraalkoxymethyl) glycoluril; acrylate compounds such as ethylene glycol di (meth) acrylate and epoxy acrylate polymers; Hexamethylene diisocyanate Isocyanate compounds such as polyisocyanates, isophorone diisocyanate polyisocyanates, tolylene diisocyanate polyisocyanates; hydrogenated diphenylmethane diisocyanate polyisocyanates; 1,4-di- (hydroxymethyl) cyclohexane, 1,4-di- (hydroxy Methyl) norbornane, 1,3,4-trihydroxycyclohexane and the like. Of these, those having an amino group or an isocyanate group are preferred. These crosslinkable groups may be the same or different.

  The radiation-sensitive compound used in the radiation-sensitive composition of the present invention is a compound that can absorb radiation such as ultraviolet rays and electron beams and cause a chemical reaction. Polymers having a polar group that reacts with the epoxy group used in the present invention, particularly those capable of controlling the alkali solubility of a cyclic olefin polymer having a protic polar group are preferred.

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

As the quinonediazide compound, for example, an ester compound of a quinonediazidesulfonic acid halide and a compound having a phenolic hydroxyl group can be used.
Examples of the quinonediazidesulfonic acid halide include 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-benzoquinonediazide-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, novolak resin oligomer, phenolic hydroxyl group Examples thereof include oligomers obtained by copolymerizing one or more compounds and dicyclopentadiene.
These radiation sensitive compounds can be used alone or in combination of two or more.

  The amount of the radiation sensitive compound used is usually 1 to 100 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the polymer containing a polar group that reacts with an epoxy group. Part range. When the amount of the radiation-sensitive compound 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 unirradiated part becomes large, and patterning by development is easy, and The radiation sensitivity is also high, which is preferable.

The radiation-sensitive composition of the present invention may contain a resin component (other resin component) other than a polymer containing a polar group that reacts with an epoxy group, other compounding agents, and the like, if necessary.
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 that do not contain polar groups that react with epoxy groups. , Polyethersulfone resin, polysulfone resin, polyimide resin, rubber, elastomer and the like.

Examples of other compounding agents include sensitizers, surfactants, latent acid generators, antioxidants, light stabilizers, adhesion aids, antistatic agents, antifoaming agents, pigments, dyes, and the like. Can do.
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 resistant shape retention and chemical resistance of the radiation-sensitive composition of the present invention. For example, the latent acid generator is a cationic polymerization catalyst that generates an acid by heating. Examples include zolium salts, ammonium salts, and phosphonium salts. Of these, sulfonium salts and benzothiazolium salts are preferred.

  As the antioxidant, there can be used phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, lactone antioxidants and the like used in ordinary polymers. For example, as phenol antioxidant, 2,6-di-t-butyl-4-methylphenol, p-methoxyphenol, styrenated phenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl) -4'-hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5'-methyl- 2'-hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 4,4'-thio-bis (3-methyl-6-t -Butylphenol), alkylated bisphenol and the like. Examples of the phosphorus antioxidant include triphenyl phosphite and tris phosphite (nonylphenyl), and examples of the sulfur antioxidant include dilauryl thiodipropionate. Among these, from the viewpoint of yellowing during heating, a phenol-based antioxidant is preferable, and among them, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] is preferable.

Light stabilizers include ultraviolet absorbers such as benzophenone-based, salicylic acid ester-based, benzotriazole-based, cyanoacrylate-based, and metal complex-based salts; hindered amine-based (HALS) and the like that capture radicals generated by light; Either is acceptable. Among these, HALS is a compound having a piperidine structure and is preferable because it is less colored and has good stability with respect to the composition of the present invention. Specific compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl 1,2,3,4 -Butanetetracarboxylate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.
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 composition of the present invention contains, as essential components, a polymer having a polar group that reacts with the epoxy group, a crosslinking agent, and a radiation-sensitive compound, and other components are added as necessary, and this is usually dissolved in a solvent. Alternatively, it can be obtained by dispersing.
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 Methyl ether, triethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, alkylene glycol monoethers such as tripropylene glycol monoethyl ether;

  Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tripropylene Alkylene glycol dialkyl ethers such as 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, Alkylene glycol monoalkyl ether esters such as pyrene glycol mono i-propyl ether acetate, propylene glycol mono n-butyl ether acetate, propylene glycol mono i-butyl ether 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; methyl cellosolve acetate, ethyl celloso Cellosolve esters such as blanking acetate;

Aromatic hydrocarbons such as benzene, toluene, xylene; ethyl acetate, butyl acetate, ethyl lactate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, hydroxyacetic acid Esters such as ethyl, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, γ-butyrolactone; N- Examples include amides such as methylformamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-methylacetamide, and N, N-dimethylacetamide; dimethyl sulfoxide;
These solvents can be used alone or in combination of two or more. The amount of the solvent used is usually 20 to 10,000 parts by weight, preferably 50 to 5,000 parts by weight, and more preferably 100 parts per 100 parts by weight of the polymer having a polar group that reacts with an epoxy group. It is the range of -1,000 weight part.

The mixing method of the radiation-sensitive composition of the present invention and the solvent may be in accordance with conventional methods. For example, stirring using a stirrer and a magnetic stirrer, high-speed homogenizer, dispersion, planetary stirrer, twin-screw stirrer, ball mill, three This can be done using a roll or the like.
The radiation-sensitive 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 0.5 μm.
The solid content concentration when the radiation-sensitive 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, and more preferably 10 to 40% by weight. When the solid content concentration is in this range, the coating property on the substrate, the film thickness uniformity and the flatness of the formed resin film are highly balanced and suitable.

The laminate of the present invention is formed by laminating a resin film made of a radiation sensitive composition on a substrate.
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. 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 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.

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

  Film lamination method, for example, by applying a mixture of a radiation sensitive composition and a solvent on a substrate such as a resin film or a metal film, the solvent is removed by heat drying to obtain a B stage film, In this method, the B-stage film is laminated on the substrate. The heating and drying conditions vary depending on the type and blending ratio of each component, but are usually 30 to 150 ° C., preferably 60 to 120 ° C., usually 0.5 to 90 minutes, preferably 1 to 60 minutes, and more. Preferably, it may be performed for 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.

In a laminate comprising a substrate and a resin film formed on the substrate using the radiation-sensitive composition of the present invention, the resin film may be patterned.
The laminate of the present invention, particularly a laminate in which a patterned resin film is formed on a substrate, is useful as various electronic components. Examples of the electronic component include a display element, an integrated circuit element, a solid-state imaging element, a color filter, and a black matrix.
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 radiation-sensitive compound and change the alkali solubility of the radiation-sensitive composition containing the radiation-sensitive compound. Specifically, single-wavelength ultraviolet rays such as g-line and i-line, mixed ultraviolet rays thereof, far-ultraviolet rays such as KrF excimer laser light and ArF excimer laser light; particle beams such as electron beams; Can be used. As a method of selectively irradiating these actinic radiations in a pattern to form a latent image pattern, it is sufficient to follow a conventional method. For example, with a reduction projection exposure apparatus or the like, a desired light beam such as ultraviolet rays or far ultraviolet rays can be obtained. A method of irradiating through a mask pattern, a method of drawing with a particle beam such as an electron beam, or the like can be used. When light is used as the active radiation, it may be single wavelength light or mixed wavelength light. Irradiation conditions may be appropriately selected depending on the active radiation to be used, for example, when using a light beam of wavelength 200 to 450 nm, the amount of irradiation is usually 10~1,000mJ / cm ^2, preferably 50 to 500 mJ / It is a range of cm ² and is determined according to irradiation time and illuminance. After irradiation with actinic radiation in this manner, the resin film is heat-treated at a temperature of about 60 to 130 ° C. for about 1 to 2 minutes as necessary.

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

As an aqueous medium of the aqueous solution of the alkaline compound, water; water-soluble organic solvents such as methanol and ethanol can be used. The aqueous solution of the alkaline compound may be one to which an appropriate amount of a surfactant or the like is added.
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.
Furthermore, if necessary, in order to deactivate the radiation-sensitive compound, the entire surface of the substrate having the patterned resin film can 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 in the range of 100 to 300 ° C, preferably 120 to 200 ° C.

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

  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 mass references | standards unless there is particular notice.

Each characteristic was evaluated by the following method.
[Weight average molecular weight (Mw) and number average molecular weight (Mn) of polymer]
Using gel permeation chromatography (manufactured by Tosoh Corporation, product name “HLC-8020”), the molecular weight is calculated as polyisoprene equivalent molecular weight.
[Hydrogenation rate]
A hydrogenation rate is calculated | required as a ratio with respect to the carbon-carbon double bond mole number before hydrogenation of the hydrogenated carbon-carbon double bond mole number by < ¹ > H-NMR spectrum.
[Iodine number]
Measured according to JIS K0070B.

[Formation of patterned resin film]
A radiation-sensitive composition is spin-coated on a glass substrate (product name “Corning 1737 Glass” manufactured by Corning) and dried at 95 ° C. for 120 seconds using a hot plate, resulting in a film thickness of 2.0 μm after drying. The film is formed as follows.
The resin film is irradiated with ultraviolet rays having a light intensity at 365 nm of 5 mW / cm ² in the air for 40 seconds through a mask having a 5 μm line and space pattern. Next, after developing for 60 to 90 seconds at 25 ° C. using a tetramethylammonium hydroxide 0.3% solution, rinsing with ultrapure water for 30 seconds to form a positive 5 μm line and space pattern A resin film is formed.

[Development residual film ratio]
Development residual film ratio = 100 × film thickness after development / film thickness after pre-baking, and the residual film ratio after 70 seconds of development is measured. Based on the measurement results, the following criteria are used.
A: The remaining film ratio is 95% or more (best)
B: 90% or more and less than 95% (good)
C: 85% or more and less than 90% (slightly inferior)
D: Less than 85% (inferior)

[Development margin (existence of pattern film peeling during development)]
When the development time is 70, 80, 90, and 100 seconds, the presence or absence of pattern peeling is observed, and the following criteria are used.
A: No pattern peeling (best) in all development times.
B: The pattern peels off in 100 seconds (good).
C: The pattern peels off (slightly inferior) in 90 seconds.
D: The pattern peels (inferior) in 80 seconds.

[Heat-resistant shape retention of resin film]
The entire surface of the patterned resin film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5 mW / cm ² in air for 60 seconds, and then the glass substrate on which this pattern was formed using a hot plate was heated at 160 ° C. for 2 seconds. First heat treatment (may be referred to as “middle baking”) for 1 minute. The cross section of the obtained pattern is observed with an electron microscope, and the width a of the lower end of the pattern is measured. Next, the glass substrate that has been subjected to the first heat treatment (middle baking) is subjected to a second heat treatment (sometimes referred to as “post-baking”) at 220 ° C. for 1 hour using a clean oven. The cross section of the pattern subjected to the second heat treatment is observed with an electron microscope, the shape of the upper end of the pattern is evaluated, and the lower end width b of the pattern is measured. The percentage (b / a) of the lower end width b of the pattern after the second heat treatment (post-bake) to the lower end width a of the pattern after the first heat treatment (middle bake) is determined and determined according to the following criteria.
A: The upper end is not rounded, and the above ratio is 110% or less (best).
B: The upper end is rounded, but the above ratio is 120% or less (good).
C: The upper end is rounded, and the above ratio exceeds 120% (slightly inferior).
D: The pattern is completely melted and fused with the adjacent pattern (inferior).

[Evaluation of heat-resistant transparency]
The transmittance of the patterned resin film is measured at a wavelength of 400 nm to 700 nm using a spectrophotometer (manufactured by JASCO Corporation, product name “V-560”). The measured value is converted into a transmittance of 2 μm based on the Lambert-Beer equation, and evaluated according to the following criteria.
A: The minimum transmittance is 90% or more (best)
B: 85% or more and less than 90% (good)
C: 80% or more and less than 85% (slightly inferior)
D: Less than 80% (inferior)

[Solvent resistance]
The swelling ratio of the patterned resin film when immersed in N-methyl-2-pyrrolidone (NMP) at 40 ° C. for 1 hour is defined as follows.
Membrane swelling rate (%) = 100 × (film thickness after NMP immersion / film thickness after post-baking) −100
This numerical value is used for determination according to the following criteria.
A: Swelling ratio is 2% or less (best)
B: 2% or more and less than 5% (good)
C: Less than 5-10% (somewhat inferior)
D: 10% or more (inferior)

[Dielectric properties of resin film]
After applying the radiation-sensitive composition using a spinner (Mikasa) on an aluminum substrate, it was dried on a hot plate at 95 ° C. for 120 seconds to obtain a stylus thickness meter (trade name, manufactured by Tencor). The film is formed so as to be 3 μm when measured in “P-10”). This film was not exposed to light and developed by immersing in a 0.3% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 100 seconds, followed by rinsing with ultrapure water for 1 minute, and then the entire surface of the resin film. The radiation sensitive compound is deactivated by irradiation with ultraviolet rays having a light intensity at 365 nm of 5 mW / cm ² . Thereafter, heating is performed on a 220 ° C. hot plate for 1 hour. An aluminum film having a thickness of 0.3 μm is formed on the resin film, and a dielectric constant of 1 MHz is measured in an environment at 23 ° C. Based on this dielectric constant, the following criteria are used for determination.
A: Dielectric constant is less than 3 (good).
D: Dielectric constant is 3 or more (inferior).

[Synthesis Example 1]
8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene 62.5 parts, N-phenyl- (5-norbornene-2,3-dicarboximide) 37.5 parts, 1-hexene 1.3 parts, 1,3-dimethyl Imidazolidine-2-ylidene (tricyclohexylphosphine) benzylidene ruthenium dichloride 0.05 part and 400 parts of tetrahydrofuran were charged into a nitrogen-substituted glass pressure-resistant reactor and reacted at 70 ° C. for 2 hours with stirring. 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 in which 1 part of activated carbon powder was added to 100 parts of the polymer solution B 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 diameter of 0.2 μm to separate 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 polymer (1). Mw of the obtained polymer (1) in terms of polyisoprene was 5,500, and Mn was 3,200. The iodine value was 1.

[Synthesis Example 2]
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene 100 parts, 1-hexene 1.3 parts, 1,3-dimethylimidazolidine-2-ylidene (tricyclohexylphosphine) benzylidene ruthenium dichloride 0.05 parts, and toluene 400 parts. Then, it was charged into a nitrogen-substituted glass pressure-resistant reactor and subjected to a polymerization reaction and a hydrogenation reaction in the same manner as in Synthesis Example 1 to obtain a hydrogenated polymer. Mw of the obtained hydrogenated polymer was 5,300, and Mn was 3,200. The iodine value was 1.
A hydrogenated polymer (100 parts), N-methylpyrrolidone (100 parts), propylene glycol (500 parts) and potassium hydroxide aqueous solution (85%) (84.5 parts) were charged into a reactor and stirred at 190 ° C. for 4.5 hours. The obtained reaction solution was poured into a large amount of a mixed solution of water, tetrahydrofuran and hydrochloric acid to coagulate the hydrolyzate. The coagulated polymer was washed with water, dried, and then a hydrolysis polymer (2) in which a methoxycarbonyl group was converted to a carboxyl group was obtained by hydrolysis. The hydrolysis rate of the obtained hydrolysis polymer was 95%.

[Example 1]
100 parts of the polymer (1) obtained in Synthesis Example 1, 200 parts of propylene glycol monoethyl ether acetate, 100 parts of diethylene glycol ethyl methyl ether and 100 parts of N-methyl-1-pyrrolidone as a solvent, 1,1 as a quinonediazide compound , 3-Tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.9 mol) 25 parts , 25 parts of a tetrafunctional epoxy resin having a alicyclic structure in the main chain as a crosslinking agent (molecular weight 400, product name “Epolide GT400”, manufactured by Daicel Chemical Industries), γ-glycidoxypropyltrimethoxy as an adhesion assistant 5 parts of silane, pentaerythritol tetrakis [3- (3,5-di-) as an antioxidant -Butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals, product name “Irganox 1010”) as a surfactant, a silicone-based surfactant (manufactured by Shin-Etsu Chemical Co., Ltd., product name “ KP341 ") 0.05 part was mixed and dissolved, and then filtered through a Millipore filter having a pore size of 0.45 µm to prepare a radiation-sensitive composition.
The radiation-sensitive composition was evaluated for the residual film ratio, development margin, heat-resistant shape retention after middle baking and post-baking, heat-resistant transparency after post-baking, solvent resistance and dielectric properties. The results are shown in Table 1.

[Example 2]
Example 1 is the same as Example 1 except that the cross-linking agent is changed to a 15-functional epoxy compound having a alicyclic structure in the main chain (molecular weight: about 2700, manufactured by Daicel Chemical Industries, product name “EHPE3150”). A radiation sensitive composition was prepared, and the same evaluation as in Example 1 was performed on this radiation sensitive composition. The results are shown in Table 1.

[Example 3]
In Example 1, a radiation sensitive composition was prepared in the same manner as in Example 1 except that the hydrolyzed polymer (2) was used instead of the polymer (1).
The radiation-sensitive composition was evaluated for the residual film ratio, development margin, heat-resistant shape retention after middle baking and post-baking, heat-resistant transparency after post-baking, solvent resistance and dielectric properties. The results are shown in Table 1.

[Example 4]
A radiation-sensitive composition was prepared in the same manner as in Example 3 except that the crosslinking agent was changed to that used in Example 2.
The radiation-sensitive composition was evaluated for the residual film ratio, development margin, heat-resistant shape retention after middle baking and post-baking, heat-resistant transparency after post-baking, solvent resistance and dielectric properties. The results are shown in Table 1.

[Comparative Example 1]
Except for using a bifunctional epoxy compound (molecular weight 352, manufactured by Dainippon Ink Co., Ltd., product name “EXA7015”) having an alicyclic structure in the main chain as a crosslinking agent, and changing the solvent to 400 parts of cyclohexanone, Examples In the same manner as in No. 1, a radiation sensitive composition was prepared.
The radiation-sensitive composition was evaluated for the residual film ratio, development margin, heat-resistant shape retention after middle baking and post-baking, heat-resistant transparency after post-baking, solvent resistance and dielectric properties. The results are shown in Table 1.

[Comparative Example 2]
A radiation-sensitive composition was prepared in the same manner as in Comparative Example 1 except that the crosslinking agent was changed to an aromatic amine type tetrafunctional epoxy compound (product name “H-434” manufactured by Tohto Kasei Co., Ltd.).
The radiation-sensitive composition was evaluated for the residual film ratio, development margin, heat-resistant shape retention after middle baking and post-baking, heat-resistant transparency after post-baking, solvent resistance and dielectric properties. The results are shown in Table 1.

[Comparative Example 3]
A radiation-sensitive composition was prepared in the same manner as in Comparative Example 1 except that the cross-linking agent was changed to a bifunctional bisphenol A type epoxy compound (molecular weight 340, manufactured by Dainippon Ink, product name “EXA850CRP”).
The radiation-sensitive composition was evaluated for the residual film ratio, development margin, heat-resistant shape retention after middle baking and post-baking, heat-resistant transparency after post-baking, solvent resistance and dielectric properties. The results are shown in Table 1.

From the results of Table 1, in the examples of the present invention using a polyfunctional epoxy compound having an alicyclic structure in the main chain structure and having three or more epoxy groups as a crosslinking agent, the residual film ratio and development margin It can be seen that the heat-resistant shape retention after middle baking and post-baking, heat-resistant transparency after post-baking, solvent resistance and dielectric properties are excellent.
In contrast, as a crosslinking agent, the main chain has an alicyclic structure but a bifunctional epoxy resin is used (Comparative Example 1) and a tetrafunctional epoxy compound, but the main chain structure has an alicyclic structure. It is found that when a material having no aliquot (Comparative Example 2) is used, these properties are inferior, and when using a bifunctional compound having no alicyclic structure, these various properties are remarkably inferior.

Claims (11)

A cross-linking agent and a radiation-sensitive compound containing a cyclic olefin polymer containing a polar group that reacts with an epoxy group, a polyfunctional epoxy compound having an alicyclic structure in the main chain structure and three or more epoxy groups A radiation-sensitive composition comprising the composition. The radiation-sensitive composition according to claim 1 , wherein the cyclic olefin polymer having a polar group that reacts with an epoxy group contains 10 to 90 wt% of a polar group-containing cyclic olefin unit. The radiation-sensitive composition according to claim 1 , wherein the polar group that reacts with the epoxy group is a protic polar group. The radiation-sensitive composition according to claim 1 , wherein the main chain structure of the polyfunctional epoxy compound has a branched alkylene chain. The laminated body formed by laminating | stacking the resin film which consists of a radiation sensitive composition of Claim 1 on a board | substrate. The laminate according to claim 5 , wherein the resin film is a patterned resin film. The manufacturing method of the laminated body which consists of a board | substrate and the resin film formed on it which has the process of forming a resin film on a board | substrate using the radiation sensitive composition of Claim 1 . The manufacturing method of the laminated body of Claim 7 which further has the process of bridge | crosslinking resin after forming a resin film on a board | substrate. A resin film is laminated on a substrate using the radiation-sensitive composition according to claim 1 , and the resin film is irradiated with actinic radiation to form a latent image pattern in the resin film, and then a developer is applied to the resin film. The manufacturing method of the laminated body of Claim 6 which makes a latent image pattern actualize by making it contact and forms a patterned resin film on a board | substrate. The manufacturing method of the laminated body of Claim 9 which further has the process of performing the crosslinking reaction of resin, after forming a patterned resin film on a board | substrate. An electronic component comprising the laminate according to claim 5 .