JP2005292279A - Radiation sensitive composition, laminate and method for manufacturing same, and electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation sensitive composition suitable for electronic components of an integrated circuit device, a liquid crystal display, a solid-state image sensor, etc., and giving a resin film excellent in sensitivity to radiation and excellent also in light resistance and dielectric characteristics, and to provide a laminate obtained by forming a resin film using the radiation sensitive composition on a substrate and a method for manufacturing the laminate. <P>SOLUTION: The radiation sensitive composition comprises a cycloolefin-base polymer, a crosslinking agent, a radiation sensitive compound and an amine antioxidant. The laminate consists of the substrate and the resin film formed using the radiation sensitive composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a radiation-sensitive composition suitable for production of electronic components such as an integrated circuit element, a liquid crystal display element, and a solid-state imaging device, a laminate having a resin film obtained from the radiation-sensitive composition on a substrate, and the laminate It relates to the manufacturing method.

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.
In recent years, with the increase in the density of wiring and devices, there has been a demand for radiation-sensitive compositions having excellent electrical properties and transparency required for resin films such as flattening films and insulating films. Yes.

In order to meet such various requirements, radiation-sensitive compositions using cyclic olefin polymers have been proposed.
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 for the production of electronic parts in the air for the purpose of increasing productivity, there is a problem that the transparency of the resulting resin film is lowered.
Patent Document 2 discloses a radiation-sensitive resin composition comprising an alicyclic olefin resin, an acid generator, a crosslinking agent, a specific phenol anti-aging agent and a solvent. However, in order to maintain the transparency of the resin after the heating step in the atmosphere using this radiation-sensitive resin composition, a large amount of a phenolic anti-aging agent must be added, and thus the sensitivity to radiation is low. In some cases, it did not function sufficiently as a radiation sensitive composition.

Japanese Patent Laid-Open No. 10-307388 WO03 / 100524

  The present invention has been made under such circumstances, and is a radiation-sensitive composition containing a cyclic olefin polymer, having excellent sensitivity to radiation, excellent light resistance, and excellent dielectric properties. Another object of the present invention is to provide a radiation-sensitive composition that provides a resin film, a laminate comprising a substrate and a resin film formed thereon from the radiation-sensitive composition, and a method for producing the same.

  As a result of intensive studies to solve the above problems, the present inventors have identified as an anti-aging agent in a radiation-sensitive composition containing a cyclic olefin polymer, a crosslinking agent, a radiation-sensitive compound and an anti-aging agent. It was found that the above object could be achieved by using this compound, and the present invention was completed based on this finding.

Thus, according to the present invention, there is provided a radiation-sensitive composition comprising a cyclic olefin polymer, a crosslinking agent, a radiation-sensitive compound and an amine-based antioxidant.
In the radiation-sensitive composition of the present invention, the amine-based anti-aging agent is preferably a hindered amine-based anti-aging agent.
In the radiation-sensitive composition of the present invention, the cyclic olefin-based polymer preferably contains a protic polar group.
Moreover, according to this invention, the laminated body which consists of a board | substrate and the resin film formed on it using said radiation sensitive composition is provided.
This laminate can be obtained by forming a resin film on a substrate using the radiation-sensitive composition and then crosslinking the resin as 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 above 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 manufacturing method of the laminated body of this invention, after forming a patterned resin film on a board | substrate, the crosslinking reaction of resin can be performed.
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 can be applied to various uses because it provides a resin film excellent in sensitivity, heat-resistant transparency and dielectric properties. In addition, since the laminate of the present invention is excellent in heat-resistant transparency and dielectric properties of the resin film, for example, electronic components such as display elements, integrated circuit elements, solid-state imaging elements, color filters, and black matrices are deteriorated. Protective film for preventing damage, flattening film for flattening the element surface and wiring, electric insulating film for maintaining electric insulation (thin transistor type liquid crystal display elements and electric insulating films for integrated circuit elements) It is suitable as a material for electronic parts such as an interlayer insulating film, a solder resist film, etc.), a microlens, and a spacer.

  The radiation-sensitive composition of the present invention comprises a cyclic olefin polymer, a crosslinking agent, a radiation-sensitive compound, and an amine-based antioxidant.

The cyclic olefin polymer is a polymer having a structural unit derived from a cyclic olefin monomer, and may have a structural unit derived from a monomer other than the cyclic olefin monomer.
The cyclic olefin polymer is a ring-opening (co) polymer of a cyclic olefin monomer, an addition copolymer of a cyclic olefin and a vinyl alicyclic hydrocarbon monomer or a vinyl aromatic hydrocarbon monomer, and These hydrogenated products are included.
In the present invention, the cyclic olefin polymer is a homopolymer or copolymer of a vinyl alicyclic hydrocarbon monomer (an alicyclic hydrocarbon having a vinyl group as a substituent) and other monomers. And a hydrogenated product of these, a hydrogenated product of these, a (co) polymer of a vinyl aromatic hydrocarbon monomer, and a copolymer of other monomers.
Further, these polymers may be either ring-opening polymers or addition polymers.
Among these, ring-opening (co) polymers of cyclic olefin monomers and hydrogenated products thereof, addition of cyclic olefin monomers and vinyl alicyclic hydrocarbon monomers or vinyl aromatic hydrocarbon monomers A copolymer and a hydrogenated product thereof, and a hydrogenated product of a vinyl aromatic hydrocarbon monomer polymer are preferable, and a hydrogenated product of a ring-opening (co) polymer of a cyclic olefin monomer is particularly preferable.

The cyclic olefin monomer for obtaining the cyclic olefin polymer is not particularly limited, and examples of the first group include a cyclic olefin monomer (a) containing 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.

An example of the second group of cyclic olefin monomers is a cyclic olefin monomer 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 (c) having another polar group (aprotic polar group). ) And can be shown separately.

Protic polar groups are heteroatoms, preferably atoms of groups 15 and 16 of the periodic table, more preferably atoms of groups 15 and 16 of the periodic table, and groups 1 and 2 of the periodic table, particularly preferably An atomic group in which hydrogen atoms are directly bonded to oxygen atoms.
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) 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.

  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 alkoxy group, a carbonyl group, a tertiary amino group, a sulfone group, a halogen atom, an acryloyl group and the like are shown. Of these, an ester group, an N-substituted imide group, and a cyano group are preferable, and an ester group and an N-substituted imide group are more preferable. In particular, an N-substituted imide group is preferable.

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- (4-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 and the like.

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 cyclic olefin containing 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 vinylcycloalkanes such as vinylcyclopropane, vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane; 3-methyl-1-vinylcyclohexane, 4 -Alkyl group-substituted vinylcycloalkanes such as methyl-1-vinylcyclohexane, 1-phenyl-2-vinylcyclopropane, 1,1-diphenyl-2-vinylcyclopropane;
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 Alkyl group-substituted vinyl aromatics 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;

  Other typical examples of the monomer copolymerizable with the cyclic olefin include a chain olefin (f). 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 Α-olefins having 2 to 20 carbon atoms such as hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, etc .; 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. 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.
The cyclic olefin polymer containing a protic polar group obtained by the above polymerization may be hydrogenated as necessary.

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, 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, rhodium, ruthenium, and the like, since side reactions such as modification of functional groups such as protic polar groups do not occur and carbon-carbon unsaturated bonds in the polymer can be selectively hydrogenated. And a ruthenium catalyst coordinated with a nitrogen-containing heterocyclic carbene compound or a phosphine having a high electron donating property is particularly preferable.

In the present invention, cyclic olefin polymers having different compositions can be used alone or in combination of two or more.
The cyclic olefin polymer used in the present invention preferably contains a polar group.
In the present invention, the number of polar groups contained in the cyclic olefin polymer containing a polar group is not particularly limited, and polar groups of different types may be contained.
In the present invention, the polar group contained in the cyclic olefin polymer containing a polar group is 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 the cyclic olefin monomer unit.
In the present invention, the cyclic olefin polymer preferably contains a protic polar group. The use of a cyclic olefin polymer containing a protic polar group (hereinafter referred to as “protic polar group-containing cyclic olefin polymer”) improves the sensitivity of the resulting radiation-sensitive composition to radiation. Is preferred.
These cyclic olefin-based polymers containing a protic polar group can be used individually or in combination of two or more in different compositions.

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

As a preferred method for producing a cyclic olefin polymer containing a protic polar group used in the present invention, the cyclic olefin monomer (b) containing a protic polar group is polymerized and hydrogenated as necessary. Method.
If necessary, the cyclic olefin monomer (b) containing a protic polar group is a monomer copolymerizable therewith (the above-mentioned monomers (a), (c) to (f)) and Can be copolymerized.

In addition, the protic polar group-containing cyclic olefin polymer used in the present invention is introduced into the cyclic olefin polymer not containing a protic polar group by a known method after introducing a protic polar group, if necessary. It can also be obtained by a method of hydrogenation. Hydrogenation may be performed on the polymer before introduction of the protic polar group.
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, an ester group may be used instead of the protic polar group.
The cyclic olefin polymer not containing a protic polar group can be obtained using the monomers (a) and (c) to (f). In this case, it goes without saying that a monomer containing a protic polar group may be used in combination.

  As a modifier for introducing a protic polar group, a compound having a carbon-carbon unsaturated bond reactive with a protic polar group 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 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. When the iodine value of the cyclic olefin polymer is in this range, it is particularly excellent in heat-resistant shape retention and suitable.

  In the present invention, as the crosslinking agent, those having two or more, preferably three or more functional groups capable of reacting with the cyclic olefin polymer in the molecule are used. The functional group is not particularly limited as long as it can react with the functional group, unsaturated bond, etc. in the cyclic olefin polymer. When the cyclic olefin polymer contains a protic polar group, preferred functional groups include, for example, an amino group, a carboxyl group, a hydroxyl group, an epoxy group, an isocyanate group, and more preferably an amino group, An epoxy group and an isocyanate group are preferable, and an epoxy group is particularly preferable.

  Specific examples of such a crosslinking agent include aliphatic polyamines such as hexamethylenediamine; aromatic polyamines such as 4,4′-diaminodiphenyl ether and diaminodiphenylsulfone; 2,6-bis (4′-azidobenzal) Azides such as cyclohexanone and 4,4′-diazidodiphenylsulfone; polyamides such as nylon, polyhexamethylenediamine terephthalamide and polyhexamethyleneisophthalamide; N, N, N ′, N ′, N ″, N Melamines such as "-(hexaalkoxymethyl) melamine; 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, those having an alicyclic skeleton, those having a cresol novolak skeleton, those having a phenol novolak skeleton, and a bisphenol A skeleton. And those having a naphthalene skeleton. 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.

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

  The radiation-sensitive compound used in the present invention is a compound that can absorb radiation such as ultraviolet rays and electron beams and cause a chemical reaction. In the present invention, when a cyclic olefin polymer having a protic polar group is used, those capable of controlling the alkali solubility are preferred. In the present invention, it is preferable to use a photoacid generator as the radiation-sensitive compound. When a photoacid generator is used, light resistance can be imparted without lowering the sensitivity to radiation by the combined use with an amine-based antiaging agent described later.

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 quinone diazide sulfonic acid halide include 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-benzoquinone diazide-5-sulfonic acid chloride, and the like.

Typical examples of the compound having a phenolic hydroxyl group include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1. -[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and the like.
Other compounds having a phenolic hydroxyl group include 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2-bis (4-hydroxyphenyl) propane, tris (4- Hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 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 in the range of 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 cyclic olefin polymer. When 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 unirradiated part becomes large, and patterning by development is possible. It is suitable because it is easy and the radiation sensitivity is high.

In the radiation sensitive composition of the present invention, it is essential to use an amine-based antioxidant. An amine-based antioxidant is one having at least one amino group in the molecule.
Examples of the amine-based anti-aging agent include primary amine compounds, secondary amine compounds, and tertiary amine compounds. However, tertiary amine compounds are preferable because they exhibit the most effective effects. is there. The amine-based anti-aging agent may be either a chain amine compound or a cyclic amine compound, but is preferably a cyclic amine compound, and a hindered amine-based anti-aging agent such as a nitrogen-containing heterocyclic amine compound is particularly preferable.

  Preferable specific examples of the amine anti-aging agent include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (ADK STAB LA-77; manufactured by Asahi Denka), bis (N-methyl-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, (2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate (Adekastab LA- 67, manufactured by Asahi Denka Co., Ltd.), (1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate (Adekastab LA-62, manufactured by Asahi Denka Co., Ltd.) ), [2,2,6,6-tetramethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9 {2,4,8,10-tetraoxaspiro (5, 5) Undecane Tyl] 1,2,3,4-butanetetracarboxylate (Adeka Stub 68, manufactured by Asahi Denka), [1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β ′ -Tetramethyl-3,9 {2,4,8,10-tetraoxaspiro (5,5) undecane} diethyl] 1,2,3,4-butanetetracarboxylate (Adeka Stub 63, manufactured by Asahi Denka) ,

  Poly [(6- (1,1,3,3-tetramethylbutyl) imino) -1,3,5-triazine / -2,4-diyl] [(2,2,6,6-tetramethyl-4 -Piperidyl) imino] hexamethylene (2,2,6,6-tetramethyl-4-piperidyl) iminol (CHIMASSORB 944, manufactured by Chimosa), bis (1-octyloxy-2,2,6,6-tetramethyl-4 -Piperidyl) sebacate (TINUVIN123; manufactured by Ciba Specialty Chemicals), dimethyl-1- (2-hydroxyethyl) 4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate (TINUVIN622, Ciba Special) Manufactured by Tea Chemicals), bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5 Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, tetrakis (2,2,6,6-tetra-methyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate And hindered amine compounds such as tetrakis (1,2,2,6,6-penta-methyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate.

  Examples of amine aging inhibitors other than hindered amine compounds include 2,2,4-trimethyl-1,2-dihydroquinoline and 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline. Alkylated diphenylamine compounds such as quinolines, diphenylamine, p- (p-toluenesulfonylamide) diphenylamine, N, N′-di-2-naphthyl-p-phenylenediamine, N-phenyl-1-naphthylamine, mercaptobenzimidazole, Examples thereof include benzotriazole compounds.

  These amine antioxidants can be used alone or in combination of two or more. The amount used is usually in the range of 0.001 to 50 parts by weight, preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the cyclic olefin polymer. is there.

In the present invention, an anti-aging agent other than the amine-based anti-aging agent can be used in combination.
Anti-aging agents that can be used in combination include: phenol-based anti-aging agents; benzophenone-based, quinone-based, lactone-based, salicylic acid ester-based and other oxygen-based anti-aging agents; nitrogen such as cyanoacrylate-based compounds Atom-containing antioxidants; sulfur atom-containing antioxidants such as thioether compounds and thiol compounds; phosphorus atom-containing antioxidants such as phosphate compounds; metal complex-based antioxidants; These anti-aging agents that can be used in combination can be used singly or in combination of two or more.
Among these, a phenolic anti-aging agent is preferable.

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

The radiation-sensitive composition of the present invention may contain a resin component other than the cyclic olefin polymer, other compounding agents, and the like as necessary.
Examples of other resin components include styrene resins, vinyl chloride resins, acrylic resins, polyphenylene ether resins, polyarylene sulfide resins, polycarbonate resins, polyester resins, polyamide resins, polyethersulfone resins, polysulfone resins, polyimide resins. , Rubbers and elastomers.

Examples of other compounding agents include sensitizers, surfactants, latent acid generators, adhesion assistants, antistatic agents, antifoaming agents, pigments, and dyes.
Examples of the sensitizer include 2H-pyrido- (3,2-b) -1,4-oxazin-3 (4H) -ones, 10H-pyrido- (3,2-b) -1,4- Preferred examples include benzothiazines, urazoles, hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, maleimides and the like.

  Surfactants are used for the purpose of preventing streaking and improving developability. For example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and other polyoxyethylenes are used. Ethylene alkyl ethers; polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; nonionic series such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate Surfactant; Fluorosurfactant; Silicone surfactant; (Meth) acrylic acid copolymer surfactant.

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

The radiation-sensitive composition of the present invention comprises, as essential components, a polymer having a polar group that reacts with the epoxy group, a crosslinking agent, a radiation-sensitive compound and an amine-based anti-aging agent. Is usually obtained by dissolving or dispersing in a solvent.
The solvent that can be used in the present invention is not particularly limited, and examples thereof include alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, Ethylene glycol mono-t-butyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl Ether, triethylene glycol Alkylene glycol monoethers such as methyl ether, triethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol Alkylene glycol dialkyl ethers such as diethyl ether, dipropylene glycol ethyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tripropylene glycol ethyl methyl ether;

Propylene glycol 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 -Alkylene glycol monoalkyl ether esters such as butyl ether acetate, propylene glycol mono sec-butyl ether acetate, propylene glycol mono t-butyl ether acetate; methyl ethyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, cyclohexanone , Cyclopentano Ketones such as methanol; alcohols such as methanol, ethanol, propanol, butanol and 3-methoxy-3-methylbutanol; cyclic ethers such as tetrahydrofuran and dioxane; cellosolv esters such as methyl cellosolve acetate and ethyl cellosolve acetate; benzene Aromatic hydrocarbons such as toluene, xylene; ethyl acetate, butyl acetate, ethyl lactate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate Esters such as methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, γ-butyrolactone S; N- methylformamide, N, N- dimethylformamide, N- methyl-2-pyrrolidone, N- methylacetamide, N, N- amides dimethylacetamide; dimethylsulfoxide; and the like.
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 to 1,000 parts by weight with respect to 100 parts by weight of the cyclic olefin polymer. Range.

The method for dissolving or dispersing the radiation-sensitive composition of the present invention in a solvent may be in accordance with a conventional method, for example, stirring using a stirrer and a magnetic stirrer, high-speed homogenizer, dispersion, planetary stirrer, biaxial stirrer, It can be performed using a ball mill, a triple roll, or the like.
The radiation-sensitive 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 dissolution stability, the coating property on the substrate, the film thickness uniformity and the flatness of the formed resin film are highly balanced and suitable.

The laminate of the present invention comprises a substrate and a resin film formed thereon using the radiation sensitive composition of the present invention.
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, for example, a printed wiring board, a silicon wafer substrate, a glass substrate, a plastic substrate, or the like can be used as the substrate. In addition, a glass substrate, a plastic substrate or the like used in the display field in which a thin transistor type liquid crystal display element, a color filter, a black matrix, or the like is formed is also preferably used.

The 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 in 1 to 30 minutes.

  The film lamination method is, for example, a method in which a radiation-sensitive composition dissolved or dispersed in a solvent is applied onto a substrate such as a resin film or a metal film, and then the solvent is removed by heating and 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.
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. A laminate in which a patterned resin film is formed on a substrate is useful as various electronic components.

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

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

After the desired patterned resin film is formed on the substrate in this way, the substrate is rinsed with a rinsing solution in order to remove development residues on the substrate, the back surface of the substrate, and the edge of the substrate, if necessary. Can do. After the rinse treatment, the remaining rinse liquid is removed with compressed air or compressed nitrogen.
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 on the substrate, the crosslinking reaction of the resin can be performed.
Crosslinking of the resin film formed on the substrate may be appropriately selected according to the type of the crosslinking agent, but is usually performed by heating. The heating method can be performed using, for example, a hot plate or an oven. The heating temperature is usually 180 to 250 ° C., and the heating time is appropriately selected depending on the size and thickness of the resin film and the equipment used. For example, when a hot plate is used, the oven is usually used for 5 to 60 minutes. When used, it is usually in the range of 30 to 90 minutes. Heating may be performed in an inert gas atmosphere as necessary. The inert gas is not particularly limited as long as it does not contain oxygen and does not oxidize the resin film. Examples thereof include nitrogen, argon, helium, neon, xenon, and krypton. Among these, nitrogen and argon are preferable, and nitrogen is particularly preferable. In particular, an inert gas having an oxygen content of 0.1% by volume or less, preferably 0.01% by volume or less, particularly nitrogen is suitable. These inert 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 (HLC-8020 manufactured by Tosoh Corporation), 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.

[sensitivity]
The radiation-sensitive composition is spin-coated on a glass substrate (Corning Corp., 1737 material) and then pre-baked at 95 ° C. for 2 minutes using a hot plate to form a resin film having a thickness of 2 μm.
This resin film is irradiated with ultraviolet rays having a light intensity at 365 nm of 5 mW / cm ² through the mask of 5 μm line and space pattern in the air for 40 seconds, 50 seconds and 60 seconds with different irradiation times. . Next, development processing was performed at 25 ° C. for 60 to 90 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide, followed by rinsing with ultrapure water for 30 seconds to form a positive line and space pattern.
Residual film ratio after development = 100 × film thickness after development / film thickness after pre-baking The minimum exposure time when the residual film ratio is 90% or more and the resin film in the exposed area is completely dissolved Is the sensitivity. Judge according to the following criteria.
○: Exposure time of less than 40 seconds Δ: Exposure time of 50 seconds or more, less than 60 seconds ×: Exposure time of 60 seconds or more

[Light resistance]
The resin film formed for the sensitivity evaluation and having a positive line and space pattern is heated at 230 ° C. for 1 hour using a clean oven. For the obtained sample, a light resistance tester (Suga Metalling Irradiation Tester, Suga Test Instruments Co., Ltd.) and a UV filter (L-39, manufactured by Asahi Techno Glass Co., Ltd.) were used. The film is irradiated with 50.000 lux at a temperature of 25 ° C. and a humidity of 40% RH for 50 hours, and the color change of the film is visually evaluated.
Compared with the sample which has not been irradiated with light, ◎ indicates that there is no change in the color of the film, and × indicates that the film is clearly yellowed.

[Dielectric properties of resin film]
After applying the radiation sensitive composition on the aluminum substrate using a spinner (manufactured by Mikasa Co., Ltd.), it was dried at 95 ° C. for 120 seconds on a hot plate, and a stylus type film thickness meter P-10 (manufactured by Tencor) ) To form a film so as to be 3 μm. 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 hot plate at 230 ° C. 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.
○: Dielectric constant is less than 3.
X: Dielectric constant is 3 or more.

[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 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 polymer. Mw of the obtained polymer in terms of polyisoprene was 5,500, and Mn was 3,200. The iodine value was 1.

[Example 1]
100 parts of the polymer obtained in Synthesis Example 1, 25 parts of an alicyclic structure-containing polyfunctional epoxy compound (molecular weight 2,700, number of epoxy groups 15, manufactured by Daicel Chemical Industries, EHPE 3150) as a crosslinking agent, 1 as a 1,2-quinonediazide compound , 1,3-Tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.5 mol) 25 parts by weight, (1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate as an anti-aging agent, 5 parts, Mix 5 parts of Sidoxypropyltrimethoxysilane and 0.05 part of silicone surfactant (KP341, manufactured by Shin-Etsu Chemical Co., Ltd.) After dissolving in a total amount of 400 parts of a solvent consisting of 200 parts of rumonoethyl ether acetate, 100 parts of diethylene glycol ethyl methyl ether and 100 parts of N-methyl-1-pyrrolidone, it was filtered through a polytetrafluoroethylene filter having a pore size of 0.45 μm. A radiation sensitive composition was prepared. This radiation sensitive composition was evaluated for sensitivity, heat-resistant transparency and dielectric properties. The results are shown in Table 1.

[Comparative Example 1]
A radiation-sensitive composition was prepared in the same manner as in Example 1 except that the antioxidant was changed to 5 parts of pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]. The radiation sensitive composition was evaluated for sensitivity, heat-resistant transparency and dielectric properties. The results are shown in Table 1.

[Footnotes in Table 1]
* 1
Amine system: (1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate Non-amine system: Pentaerythritol tetrakis [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate]

From the results in Table 1, it can be seen that the radiation-sensitive compositions of Examples using an amine-based anti-aging agent as an anti-aging agent are excellent in sensitivity, light resistance and dielectric properties.
On the other hand, it turns out that it is inferior to a sensitivity and light resistance in the comparative example 1 which did not use an amine type anti-aging agent as an anti-aging agent.

Claims (10)

A radiation-sensitive composition comprising a cyclic olefin polymer, a crosslinking agent, a radiation-sensitive compound, and an amine-based antioxidant. The radiation-sensitive composition according to claim 1, wherein the amine-based anti-aging agent is a hindered amine-based anti-aging agent. The radiation-sensitive composition according to claim 1, wherein the cyclic olefin polymer contains a protic polar group. A laminate comprising a substrate and a resin film formed thereon using the radiation-sensitive composition according to claim 1. The laminate according to claim 4, wherein the resin film is a patterned resin film. A method for producing a laminate comprising a substrate and a resin film formed thereon, wherein a resin film is formed on the substrate using the radiation-sensitive composition according to claim 1. . The manufacturing method of the laminated body of Claim 6 which bridge | crosslinks 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 any one of claims 1 to 3, and the resin film is irradiated with actinic radiation to form a latent image pattern in the resin film. The manufacturing method of the laminated body of Claim 5 which makes a latent image pattern actualize by making a developing solution contact a film | membrane, and forms patterned resin on a board | substrate. The manufacturing method of the laminated body of Claim 7 which performs the crosslinking reaction of resin after forming patterned resin on a board | substrate. An electronic component comprising the laminate according to claim 4.