JP2005290093A - Crosslinkable resin composition, laminate and their producing method and electronic parts - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a crosslinkable resin composition that has excellent dissolution stability, in addition, gives resin film having uniform film thickness, flattened uneven parts, thermally resistant shape retention properties and excellent dielectric characteristics on the substrate and is suitable for electronic parts, for example, integrated circuit device, liquid crystal display, solid-state image sensing device, and provide a laminate body on the substrate by using the crosslinking resin composition and the method for producing this laminate. <P>SOLUTION: This is a crosslinkable resin composition comprising a ring olefin polymer bearing a protonic polar group, a crosslinking agent and a solvent in which the solvent comprises a mixture of a monoalkylene glycol compound and an oligoalkylene glycol compound where the weight ratio of the monoalkylene glycol to the oligoalkylene glycol is 10/90 to 50/50. Further, the laminate comprising a substrate and a resin film that is formed by using this crosslinking resin composition is provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a crosslinkable resin composition suitable for production of electronic components such as an integrated circuit element, a liquid crystal display element, and a solid-state imaging element, a laminate having a resin film obtained from the crosslinkable resin composition on a substrate, and this The present invention relates to an electronic component made of a laminate.

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.
Recently, as wiring and devices have higher density, the level of insulation and water absorption required for these flattening films and resin films such as insulating films has increased.
In order to meet such various demands, a crosslinkable resin composition using a cyclic olefin polymer has been proposed.

As a crosslinkable resin composition using a cyclic olefin polymer, for example, a crosslinkable resin composition containing an alicyclic olefin resin, an acid generator, a crosslinking agent, a specific phenol compound and a solvent is disclosed. (Patent Document 1). However, a resin film formed on a substrate using this crosslinkable resin composition may not be suitable when a high degree of film thickness uniformity or substrate unevenness planarization is required.
Patent Document 2 discloses a crosslinkable resin composition comprising an alicyclic olefin resin, an acid generator, a crosslinker, and a solvent, and containing a specific glycol solvent as a solvent. Has been. However, this crosslinkable resin composition has insufficient dissolution stability, and the film thickness uniformity and unevenness flatness of the resin film formed on the substrate may not be sufficiently obtained.

  Furthermore, Patent Document 3 discloses a crosslinkable resin composition comprising a cyclic olefin resin, an acid generator, a crosslinking agent, and a mixed solvent containing an aprotic polar solvent containing a nitrogen atom or a sulfur atom. Yes. However, the resin film obtained by forming this crosslinkable resin composition on a substrate has problems such as inferior film thickness uniformity, substrate unevenness planarization property, and heat resistant shape retention.

WO01 / 04213 Publication JP 2003-156838 A JP 2003-195488 A

  The present invention has been made under such circumstances, and is a crosslinkable resin composition containing a cyclic olefin polymer, which is excellent in dissolution stability and formed on a substrate from this composition. Crosslinkable resin composition having excellent film thickness uniformity, unevenness flattening property, heat resistance shape retention property, and excellent dielectric properties, and substrate, and resin film formed from the crosslinkable resin composition on the substrate It aims at providing the laminated body which consists of these.

  As a result of intensive studies in order to solve the above problems, the inventors of the present invention have identified two specific types of solvents as a solvent in a crosslinkable resin composition containing a cyclic olefin polymer having a protic polar group and a crosslinker. In combination with a specific ratio of the above compound, the dissolution stability is good, and the resin film to be formed on the substrate from now on has characteristics such as uniformity, unevenness flatness, heat-resistant shape retention and dielectric properties. Based on these findings, the present invention has been completed.

Thus, according to the present invention, there is provided a crosslinkable resin composition comprising a cyclic olefin polymer having a protic polar group, a crosslinking agent and a solvent, wherein the solvent comprises a monoalkylene glycol compound and an oligoalkylene glycol compound. A crosslinkable resin comprising a mixed solvent and having a weight ratio of monoalkylene glycol compound to oligoalkylene glycol compound (monoalkylene glycol compound: oligoalkylene glycol compound) of 10:90 to 50:50 A composition is provided.
In the crosslinkable resin composition of the present invention, the content of the protic polar group-containing cyclic olefin unit in the cyclic olefin polymer having a protic polar group is preferably 10 to 90% by weight.
In the crosslinkable resin composition of the present invention, the crosslinker preferably contains a polyfunctional epoxy compound having 3 or more epoxy groups.
The crosslinkable resin composition of the present invention can further contain a radiation sensitive compound.
Moreover, according to this invention, the laminated body which consists of a board | substrate and the resin film formed on it using said crosslinkable resin composition is provided.
This laminate can be obtained by forming a resin film on a substrate using the crosslinkable resin composition and then crosslinking the resin as necessary.
In the present invention, the resin film may be a patterned resin film.
According to the present invention, a resin film is further formed on a substrate using a crosslinkable resin composition containing a radiation-sensitive compound, and a latent image pattern is formed in the resin film by irradiating the resin film with active radiation. Then, the developer is brought into contact with the resin film to reveal the latent image pattern, and the patterned resin film is formed on the substrate. The substrate and the patterned resin film formed thereon are formed. A method for producing a laminate is provided.
In the manufacturing method of the laminated body, after forming the patterned resin film on the substrate, the crosslinking reaction of the resin can be performed.
Furthermore, according to this invention, the electronic component which consists of the said laminated body is provided.

  The crosslinkable resin composition of the present invention is excellent in dissolution stability and provides various resin films with extremely good properties such as film thickness uniformity, unevenness flattening, heat-resistant shape retention and dielectric properties. Applicable to usage. Moreover, since the laminate of the present invention is excellent in the film thickness uniformity of the resin film, the unevenness flatness, the heat resistant shape retention and the dielectric properties, for example, a display element, an integrated circuit element, a solid-state imaging element, a color filter For electronic parts such as black matrix, a protective film to prevent deterioration and damage, a flattening film to flatten the element surface and wiring, an electric insulating film to maintain electrical insulation (thin transistor type) It is suitable as a material for electronic parts such as a liquid crystal display element and an integrated circuit element (including an interlayer insulating film and a solder resist film), a microlens and a spacer.

  The crosslinkable resin composition of the present invention is a radiation-sensitive composition comprising a cyclic olefin polymer having a protic polar group, a crosslinker and a solvent, wherein two specific solvents are specified as the solvent. It is characterized by using a mixed solvent contained in a ratio.

In the cyclic olefin-based polymer containing a protic polar group used in the present invention, the protic polar group is a hetero atom, preferably an atom of Groups 15 and 16 of the periodic table, more preferably a periodic rule. It is an atomic group in which a hydrogen atom is directly bonded to an atom of Table 15 and Group 16 first and second period, particularly preferably 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.

In the present invention, the number of protic polar groups contained in the cyclic olefin polymer containing a protic polar group is not particularly limited, and different types of protic polar groups may be contained.
In the present invention, the protic polar group contained in the cyclic olefin-based polymer containing a protic polar group may be bonded to the cyclic olefin monomer unit but may be bonded to a monomer unit other than the cyclic olefin monomer. Although it may couple | bond, it is desirable to couple | bond with the cyclic olefin monomer unit.

In the present invention, 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 the cyclic olefin polymer. Any of a homopolymer and a copolymer, a copolymer of a cyclic olefin and another monomer may be used, or a hydrogenated product thereof may 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 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, 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.

As a preferred method for producing a cyclic olefin polymer containing a protic polar group used in the present invention, the cyclic olefin monomer (a) containing a protic polar group is polymerized and hydrogenated as necessary. Method.
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 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 (b) to (d). 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 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 weight average molecular weight (Mw) of the cyclic olefin polymer containing a protic polar group used in the present invention is usually 1,000 to 1,000,000, preferably 1,500 to 100,000. Preferably it is the range of 2,000-10,000.
The molecular weight distribution of the cyclic olefin polymer containing a protic polar group used in the present invention is usually 4 or less, preferably 3 or less, and more preferably 3 or less in terms of weight average molecular weight / number average molecular weight (Mw / Mn) ratio. Is 2.5 or less.
The iodine value of the cyclic olefin polymer containing a protic polar 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 the cyclic olefin polymer containing a protic polar group is in this range, it is particularly excellent in heat resistance and suitable.

In the present invention, as the crosslinking agent, those having 2 or more, preferably 3 or more functional groups in the molecule capable of reacting with the protic polar group of the cyclic olefin polymer containing a protic polar group are used. . Examples of the functional group capable of reacting with the protic polar group include an amino group, a carboxyl group, a hydroxyl group, an epoxy group, and an isocyanate group, preferably an amino group, an epoxy group, and an isocyanate group, and more preferably It is an epoxy group.
Specific examples of such a crosslinking agent include aliphatic polyamines such as hexamethylenediamine; aromatic polyamines such as 4,4′-diaminodiphenyl ether and diaminodiphenylsulfone; 2,6-bis (4′-azidobenzal) Azides such as cyclohexanone and 4,4′-diazidodiphenylsulfone; polyamides such as nylon, polyhexamethylenediamine terephthalamide and polyhexamethyleneisophthalamide; N, N, N ′, N ′, N ″, N Melamines such as "-(hexaalkoxymethyl) melamine; N, N ', N", N "'-(tetraalkoxymethyl) glycolurils such as glycoluril; Acrylate compounds such as ethylene glycol di (meth) acrylate; Hexamethylene diisocyanate polyisocyanate, iso Isocyanate compounds such as holon 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;

These cross-linking 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 100 wt% of a cyclic olefin polymer having a protic polar group. The amount is usually 1 to 1,000 parts by weight, preferably 5 to 500 parts by weight, and more preferably 10 to 100 parts by weight with respect to parts. When the amount used is in this range, the film thickness uniformity, unevenness flattening property and heat resistant shape retention property of the formed resin film are highly improved, which is preferable.
Although the molecular weight of 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, a polyfunctional epoxy compound having two or more epoxy groups is preferable as the cross-linking agent, and in particular, a polyfunctional epoxy compound having three or more epoxy groups is more preferable because of good film forming properties.
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.

  Specific examples of such an epoxy compound include a trifunctional epoxy compound having a dicyclopentadiene skeleton (trade name “XD-1000” manufactured by Nippon Kayaku Co., Ltd.), [2,2-bis (hydroxymethyl) 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 1-butanol (a 15-functional alicyclic epoxy resin having a cyclohexane skeleton and a terminal epoxy group. Trade name “EHPE3150”, manufactured by Daicel Chemical Industries, Ltd. ), Epoxidized 3-cyclohexene-1,2-dicarboxylic acid bis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic trifunctional epoxy resin, trade name “Epolide GT301”, manufactured by Daicel Chemical Industries, Ltd.) , Epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-capro A lactone (aliphatic cyclic tetrafunctional epoxy resin. Trade name “Epolide GT401” manufactured by Daicel Chemical Industries, Ltd.) can be mentioned.

  In addition, as an epoxy compound having 3 or more epoxy groups having no alicyclic structure, an aromatic amine type polyfunctional epoxy compound (trade name “H-434”, manufactured by Tohto Kasei Kogyo Co., Ltd.), a cresol novolac type polyfunctional compound Epoxy compound (trade name “EOCN-1020”, manufactured by Nippon Kayaku Co., Ltd.), phenol novolac type polyfunctional epoxy compound (Epicoat 152, 154, manufactured by Japan Epoxy Resin Co., Ltd.), polyfunctional epoxy compound having naphthalene skeleton (trade name EXA) -4700, Dainippon Ink Chemical Co., Ltd.), chain alkyl polyfunctional epoxy compound (trade name “SR-TMP”, Sakamoto Yakuhin Kogyo Co., Ltd.), polyfunctional epoxy polybutadiene (trade name “Epolide PB3600”, Daicel Chemical Industries) For example).

When the crosslinkable resin composition of the present invention contains a radiation sensitive compound, patterning of the formed resin film is facilitated, which is preferable. A radiation-sensitive compound is a compound that can absorb a radiation such as an ultraviolet ray and an electron beam and cause a chemical reaction, but controls alkali solubility of a cyclic olefin polymer having a protic polar group used in the present invention. What can be done is preferred.
Examples of such 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 1 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the cyclic olefin polymer containing a protic polar group. Part range. When the amount of 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 radiation-unirradiated part increases, and patterning by development is easy. In addition, the radiation sensitivity is high, which is preferable.
The crosslinkable resin composition of the present invention is characterized in that a solvent comprising a mixed solvent of a monoalkylene glycol compound and an oligoalkylene glycol compound is used as the solvent.
The monoalkylene glycol compound used in the present invention is not particularly limited as long as it is a compound having only one alkylene glycol chain in the molecule, but at least one of the terminal hydroxyl groups is esterified or etherified. Preferably, those having both terminal hydroxyl groups esterified or etherified are more preferable, and those having both terminal hydroxyl groups etherified are particularly preferable.

Examples of monoalkylene glycol compounds include monoalkylene glycols having hydroxyl groups at both ends, such as ethylene glycol and propylene glycol; ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono t-butyl ether, propylene glycol monoethyl ether Monoalkylene glycol monoethers in which one of both terminal hydroxyl groups such as propylene glycol monopropyl ether or propylene glycol monobutyl ether is etherified; mono-ester in which one of both terminal hydroxyl groups such as ethylene glycol acetate or propylene glycol acetate is esterified Alkylene glycol monoesters; ethylene glycol diethyl ether, propylene glycol dimethyl ether Monoalkylene glycol diethers in which both hydroxyl groups at both ends are etherified; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono n-propyl ether acetate, propylene glycol mono i-propyl ether acetate Monoalkylene in which one of the terminal hydroxyl groups is etherified and the other is esterified, such as 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 Glycol monoether esters; ethylene glycol diacetate, propylene glycol Monoalkylene glycol diester such as diacetate; and the like.
These monoalkylene glycol compounds can be used alone or in combination of two or more.

  The oligoalkylene glycol compound used in the present invention is not particularly limited as long as it has two or more alkylene glycol chains in the molecule, but the number of alkylene glycol chains is usually 2 to 10, preferably 2 to 2. 5, more preferably 2. From the viewpoint of availability and operability, those having a single alkylene glycol chain having 2 to 3 carbon atoms are preferred, and those having 2 are particularly preferred. The oligoalkylene glycol compound is preferably one in which at least one of the terminal hydroxyl groups is esterified or etherified, more preferably one in which both terminal hydroxyl groups are esterified or etherified, and both terminal hydroxyl groups are etherified. Are particularly preferred.

  Examples of the oligoalkylene glycol compound include oligoalkylene glycols having hydroxyl groups at both ends, such as diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, Oligoalkylene glycol monoethers in which one of both terminal hydroxyl groups is etherified, such as dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether ;

Oligoalkylene glycol monoesters in which one of both terminal hydroxyl groups is esterified, such as diethylene glycol monoacetate and dipropylene glycol monoacetate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether , Oligoalkyleneglycol in which both hydroxyl groups at both ends are etherified, dipropylene glycol ethyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether Diethers; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, oligoalkylene glycol ether esters either are etherified other terminal hydroxyl groups have been esterified, such as dipropylene glycol monomethyl ether acetate; and the like.
These oligoalkylene glycol compounds having two or more alkylene glycol chains can be used alone or in combination of two or more.
Among these, oligoalkylene glycol diethers in which both terminal hydroxyl groups are etherified are preferable, and dialkylene glycol diethers are particularly preferable.

The ratio of the monoalkylene glycol compound to the oligoalkylene glycol compound is 10/90 to 50/50, preferably 15/85 to 45/55, more preferably, by weight ratio (monoalkylene glycol compound: oligoalkylene glycol compound). It is in the range of 20/80 to 40/60. When the ratio of both solvents is within this range, it is preferable because the crosslinkable resin composition is excellent in dissolution stability and excellent in film thickness uniformity and unevenness flatness of the formed resin film.
The total amount of the monoalkylene glycol compound and the oligoalkylene glycol compound is appropriately selected according to the purpose of use, but is usually usually 20 with respect to 100 parts by weight of the cyclic olefin polymer having a protic polar group. The range is from 10,000 to 10,000 parts by weight, preferably from 50 to 5,000 parts by weight, and more preferably from 100 to 1,000 parts by weight.

  In the present invention, other solvents can be used as necessary. Other solvents include, for example, aliphatic hydrocarbons such as hexane, heptane, and octane: alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; methanol, ethanol Alcohols such as propanol and butanol; ethers such as dibutyl ether, diisoamyl ether, methylphenyl ether, tetrahydrofuran and dioxane; diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, dipropyl ketone, ethyl butyl ketone Chain ketones such as methyl amyl ketone, diisobutyl ketone and methyl hexyl ketone; cyclic ketones such as cyclohexanone and cyclopentanone; ethyl acetate, butyl acetate, ethyl lactate, 2-hydroxy-2-methyl Methyl lupropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Esters such as ethyl ethoxypropionate, methyl 3-ethoxypropionate and γ-butyrolactone; N-methylformamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-methylacetamide, N, N-dimethyl Amides such as acetamide; dimethyl sulfoxide; These other solvents can be used alone or in combination of two or more.

The crosslinkable resin composition of the present invention may contain a resin component other than the cyclic olefin polymer containing a protic polar group, other compounding agents, and the like, if necessary.
Examples of other resin components include cyclic olefin polymers having no protic polar groups, styrene resins, vinyl chloride resins, acrylic resins, polyphenylene ether resins, polyarylene sulfide resins, polycarbonate resins, polyester resins. , Polyamide resin, polyethersulfone resin, polysulfone resin, polyimide resin, rubber and elastomer.

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 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.

  As the antioxidant, there can be used phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, lactone antioxidants and the like used in ordinary polymers. For example, as phenols, 2,6-di-t-butyl-4-methylphenol, p-methoxyphenol, styrenated phenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4 '-Hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5'-methyl-2' -Hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 4,4'-thio-bis (3-methyl-6-tert-butylphenol) ), Alkylated bisphenol and the like. Examples of the phosphorus-based antioxidant include triphenyl phosphite and tris (nonylphenyl) phosphite. Examples of the sulfur-based 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 benzophenone-based, salicylic acid ester-based, benzotriazole-based, cyanoacrylate-based, metal complex salt-based ultraviolet absorbers, hindered amine-based (HALS), and the like that capture radicals generated by light. But you can. Among these, HALS is a compound having a piperidine structure and is preferable because it is less colored and has good stability with respect to the composition of the present invention. Specific compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl 1,2,3,4 -Butanetetracarboxylate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.
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 crosslinkable resin composition of the present invention comprises a cyclic olefin polymer having a protic polar group, a crosslinking agent and, if necessary, a radiation-sensitive compound and other components, and a monoalkylene glycol compound and an oligoalkylene glycol compound. It can be obtained by dissolving or dispersing in a mixed solvent. Methods for dissolving or dispersing each component in 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-roll Etc. can be used. 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 of the crosslinkable resin composition of the present invention is usually 1 to 70% by weight, preferably 5 to 50% by weight, more preferably 10 to 40% by weight. When the solid content concentration is in this range, the coating property on the substrate, the film thickness uniformity of the resin film to be formed, and the unevenness flattening property are excellent.

The laminate of the present invention comprises a substrate and a resin film formed thereon using the crosslinkable resin composition of the present invention.
In the present invention, for example, a printed wiring board, a silicon wafer substrate, a glass substrate, a plastic substrate, or the like can be used as the substrate. In addition, a glass substrate, a plastic substrate or the like used in the display field in which a thin transistor type liquid crystal display element, a color filter, a black matrix, or the like is formed is also preferably used.
The 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 crosslinkable resin composition of the present invention and then crosslinking the resin film. The resin film may be patterned.
The method for forming the resin film on the substrate is not particularly limited, and for example, a method such as a coating method or a film lamination method can be used. The application method is, for example, a method in which a crosslinkable resin composition is applied onto a substrate, then dried by heating to remove the solvent, and then cross-linked as necessary. Examples of the method for applying the crosslinkable resin 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. The method can be adopted. The heating and drying conditions vary depending on the type and blending ratio of each component, but are usually 30 to 150 ° C., preferably 60 to 120 ° C., usually 0.5 to 90 minutes, preferably 1 to 60 minutes, and more. Preferably it may be performed in 1 to 30 minutes.

  In the film lamination method, for example, the crosslinkable resin composition is applied on 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. It is the method of laminating. 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.

  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.

When the crosslinkable resin composition of the present invention contains a radiation sensitive compound, the resin film is patterned after the resin film is formed from the crosslinkable resin composition of the present invention on the substrate and before the resin film is crosslinked. It can be carried out. 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 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 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.

  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.

[Solution stability]
The crosslinkable resin composition is placed in a container and stirred at 150 RPM for 1 hour using a three-one motor. After this, the sample is divided into 2 minutes, each is allowed to stand at 20 ° C. and −5 ° C. for 1 day, and then the sample is returned to room temperature. At this time, the case where no precipitation occurs under any condition is defined as ◎ (excellent dissolution stability). About the crosslinkable resin composition in which precipitation occurs, the same operation is performed except that the stirring time is changed to 2 hours, and the determination is made according to the following criteria.
○ (Good): No precipitation was observed after storage at -20 ° C or 5 ° C.
Δ (possible): No precipitation is observed after storage at 5 ° C., but a precipitate is observed after storage at −20 ° C.
X (impossible): A precipitate is observed after storage at 5 ° C.

[Thickness uniformity of resin film (in-plane film thickness uniformity)]
After 50 ml of a crosslinkable resin composition was dropped on a glass substrate with a low-reflection Cr film of 550 × 650 × 0.7 mm and spin-coated, it was dried on a hot plate at 95 ° C. for 2 minutes to obtain a film thickness of 3 μm. A coated substrate is formed. Using an optical interference type film thickness measuring device VM-8000J (Dainippon Screen Co., Ltd.), measure the film thickness of 25 points set at approximately equal intervals in 5 rows vertically and horizontally, with 10 mm inside from the periphery of the coated substrate as the effective measurement area. Then, (in-plane film thickness fluctuation range) is calculated by the following formula.
In-plane film thickness fluctuation width = 100 × (maximum film thickness value−minimum film thickness value) / (average film thickness)
The in-plane film thickness uniformity is determined according to the following criteria based on the numerical value of the in-plane film thickness fluctuation range.
◎: Less than 10 ○: 10 or more and less than 15 △: 15 or more and less than 20 ×: 20 or more

[Flatness unevenness of resin film]
Using a spinner (manufactured by Mikasa Co., Ltd.) on a substrate in which an aluminum wiring having a grid pattern with a line width of 20 μm, a space of 300 μm and a height of 1.5 μm is formed on a glass substrate of 300 × 350 × 0.7 mm The resin composition is applied, dried using a hot plate at 95 ° C. for 120 seconds, and formed into a film having a dried film thickness (distance from the glass substrate) of 2.5 μm. Next, the film thickness (distance from the glass substrate) is measured using a contact-type film thickness meter P-10 (manufactured by Tencor). The difference in film thickness between the portion with and without the aluminum wiring is obtained by the following formula, and the determination is made according to the following criteria.
Difference in film thickness (%) = 100 × (film thickness in a part with wiring−film thickness in a part without wiring) / film thickness in a part without wiring ◎: film thickness difference is less than 5%
○: 5% or more and less than 10 △: 10% or more and less than 15% ×: 15% or more

[Heat-resistant shape retention of resin film]
A crosslinkable resin composition was applied onto a substrate in which an aluminum film having a step of 1.5 μm was formed on a 300 × 350 × 0.7 mm glass substrate using a spinner (manufactured by Mikasa), and a hot plate was used. It is used and dried at 95 ° C. for 120 seconds, and the film is formed so that the film thickness after drying is 2.5 μm. The entire surface of this 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 was heated at 160 ° C. for 2 minutes using a hot plate. First heat treatment is performed. 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 subjected to the first heat treatment is subjected to the second heat treatment at 230 ° 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 with respect to the lower end width a of the pattern after the first heat treatment is determined and determined according to the following criteria.
A: Roundness is not recognized at the upper end, and the above ratio is 110% or less.
○: The upper end is rounded, but the above ratio is 120% or less.
Δ: The upper end is rounded, and the above ratio exceeds 120%.
X: The pattern is completely melted and fused with the adjacent pattern.

[Dielectric properties of resin film]
After applying a crosslinkable resin composition on an aluminum substrate using a spinner (Mikasa), drying treatment was performed at 95 ° C. for 120 seconds on a hot plate, and a stylus 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 . Then, it heats with a 230 degreeC hotplate 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 60 parts, N-phenyl- (5-norbornene-2,3-dicarboximide) 40 parts, 1-hexene 1.3 parts, 1,3-dimethylimidazolidine-2 -0.05 part of ylidene (tricyclohexylphosphine) benzylidene ruthenium dichloride and 400 parts of tetrahydrofuran were charged into a pressure-resistant reactor made of nitrogen-substituted glass and reacted at 70 ° C for 2 hours with stirring to obtain a polymer solution A (solid content Concentration: about 20%).
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, a solvent having a total amount of 550 parts shown in Table 1, and 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1 as a 1,2-quinonediazide compound. -Methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.5 mol) condensate 25 parts by weight, alicyclic structure-containing polyfunctional as crosslinking agent 20 parts of an epoxy compound (molecular weight 2700, number of epoxy groups 15, manufactured by Daicel Chemical Industries, EHPE 3150), 1 part of γ-glycidoxypropyltrimethoxysilane as an adhesion assistant, silicone surfactant (manufactured by Shin-Etsu Chemical Co., Ltd., KP) -341) 0.05 part, and pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) as an antioxidant Propionate] After (Irganox 1010, Ciba Specialty Chemicals Inc.) 3 parts were mixed and dissolved to prepare a crosslinkable resin composition was filtered with a polytetrafluoroethylene filter with a pore size of 0.45 [mu] m. The crosslinkable resin composition was evaluated for dissolution stability, film thickness uniformity of the resin film after being laminated on the substrate, unevenness flatness, heat-resistant shape retention, and dielectric properties. The results are shown in Table 1.

[Examples 2-4, Comparative Examples 1-2]
A crosslinkable resin composition was prepared in the same manner as in Example 1 except that the solvent and the crosslinking agent were changed as shown in Table 1, and each characteristic was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Footnotes in Table 1]
* 1
HPE3150: Epoxy compound having an alicyclic structure and a branched structure having 15 epoxy groups and a molecular weight of 2700 (manufactured by Daicel Chemical Industries)
XD-1000: Epoxy compound having an alicyclic structure and a straight chain structure having 3 epoxy groups and a molecular weight of 714 (manufactured by Nippon Kayaku Co., Ltd.)
EXA-7015: Epoxy compound having an alicyclic structure and a straight chain structure having 2 epoxy groups and a molecular weight of 352 (Dainippon Ink Co., Ltd.)
* 2
EDM: Diethylene glycol ethyl methyl ether PGMEA: Propylene glycol monomethyl ether acetate * 3
Dissolution stability was poor and insoluble matter was present in the coating film.

  From the results of Table 1, in the examples of the present invention using a mixed solvent of a monoalkylene glycol compound and an oligoalkylene compound as a solvent, dissolution stability, in-plane film thickness uniformity, unevenness flatness, heat resistant shape It can be seen that the retention and dielectric properties are good, especially when the ratio of the monoalkylene glycol compound to the oligoalkylene compound is in the range of 15/85 to 45/55. In contrast, Comparative Example 1 using a mixed solvent in which the ratio of the monoalkylene glycol compound to the oligoalkylene compound is outside the scope of the present invention and Comparative Example 2 using the monoalkylene glycol compound alone have these characteristics. It turns out that all are remarkably inferior.

Claims (11)

A crosslinkable resin composition comprising a cyclic olefin polymer having a protic polar group, a crosslinking agent and a solvent, wherein the solvent comprises a mixed solvent of a monoalkylene glycol compound and an oligoalkylene glycol compound, And the weight ratio (monoalkylene glycol compound: oligoalkylene glycol compound) of a monoalkylene glycol compound and an oligoalkylene glycol compound is 10: 90-50: 50, The crosslinkable resin composition characterized by the above-mentioned. The crosslinkable resin composition according to claim 1, wherein the content of the protic polar group-containing cyclic olefin unit in the cyclic olefin polymer having a protic polar group is 10 to 90% by weight. The crosslinkable resin composition according to claim 1 or 2, wherein the crosslinking agent contains a polyfunctional epoxy compound having 3 or more epoxy groups. The crosslinkable resin composition according to any one of claims 1 to 3, further comprising a radiation sensitive compound. A laminate comprising a substrate and a resin film formed thereon using the crosslinkable resin composition according to any one of claims 1 to 4. The laminate according to claim 5, wherein the resin film is a patterned resin film. A resin film is formed on a substrate using the crosslinkable resin composition according to any one of claims 1 to 4, and a laminate comprising a substrate and a resin film formed thereon is produced. Method. The manufacturing method of the laminated body of Claim 7 which bridge | crosslinks resin after forming a resin film on a board | substrate. A resin film is formed on a substrate using the crosslinkable resin composition according to claim 4, and a latent image pattern is formed in the resin film by irradiating the resin film with active radiation. The laminated body according to claim 6, comprising a substrate and a patterned resin film formed thereon, wherein the latent image pattern is exposed by bringing the substrate into contact with each other to form a patterned resin film on the substrate. Production method. The manufacturing method of the laminated body of Claim 8 which performs 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.