JP4380703B2 - Radiation-sensitive composition, laminate, method for producing the same, and electronic component - Google Patents

Description

  The present invention relates to a radiation-sensitive composition and a laminate having a resin film obtained from the radiation-sensitive composition on a substrate, and more specifically, suitable for manufacturing electronic components such as display elements, integrated circuit elements, and solid-state imaging elements. A radiation-sensitive composition, a laminate having a resin film obtained from the radiation-sensitive composition on a substrate, a method for producing the laminate, and an electronic component comprising the 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. Such a resin film is required to have various properties such as insulation, heat resistance, transparency, water absorption resistance, and chemical resistance.
Recently, in such electronic components, multilayer wiring has been performed, and a material for forming a resin film that can maintain a high degree of insulation between the respective layers and has sufficient flatness is available. It has been demanded.

For this reason, a radiation-sensitive resin composition containing an alkali-soluble cyclic olefin resin having an ester group, a quinonediazide compound, and a crosslinking agent such as methylolmelamine has been proposed (Patent Document 1). However, although the resin film obtained using this radiation-sensitive resin composition has excellent properties as an insulating film such as low dielectric constant, heat resistance, flatness, transparency and solvent resistance, the entire substrate is seen. In some cases, the thickness of the formed resin film is not necessarily uniform, and it has been found that there is a problem in storage stability, such as polymer deposition during storage.
Patent Document 2 discloses a radiation-sensitive resin composition comprising a resin having an alicyclic skeleton and alkali-soluble by the action of an acid, a radiation-sensitive acid generator, and a specific solvent. The present invention seeks to form a resist film having a uniform thickness by combining a specific resin and a specific solvent with excellent properties such as sensitivity, resolution, and developability, and particularly excellent transparency to radiation. It is.
Patent Document 3 discloses a radiation-sensitive resin composition comprising an alicyclic olefin resin, an acid generator, a crosslinking agent, and a solvent, wherein the solvent contains at least a specific glycol compound. A characteristic radiation-sensitive resin composition has been proposed.

  However, with these radiation-sensitive resin compositions, the higher performance required for radiation-sensitive resin compositions with the recent reduction in size, thickness and performance of devices, specifically, the uniformity of the resin film. It is no longer possible to adequately cope with dissolution stability affecting the coating and reduction of coating unevenness affecting the light interference. At the same time, it is necessary to use safer compounds for environmental considerations. In particular, for a solvent contained in a large amount in the radiation sensitive resin composition, use of a solvent having lower toxicity is required.

Japanese Patent Laid-Open No. 10-307388 Japanese Patent Laid-Open No. 10-254139 JP 2003-156838 A

  The present invention has been made in order to cope with recent reduction in size and thickness of devices and improvement in safety, and has excellent electrical characteristics, good dissolution stability, no coating unevenness, and high safety. It is an object of the present invention to provide a practical radiation-sensitive composition, a laminate in which a resin film using the radiation-sensitive composition is formed on a substrate, and a method for producing the laminate.

  As a result of intensive studies to solve the above problems, the present inventors have found that in a radiation sensitive composition containing a cyclic olefin polymer containing a protic polar group, a radiation sensitive compound, a crosslinking agent and a solvent, When using a conventionally known solvent such as 2-heptanone, cyclohexanone, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether or diethylene glycol diethyl ether, the solution stability is not sufficient and uneven coating is observed, and the solvent When diethylene glycol ethyl methyl ether is used as a radiation-sensitive composition, it has been found that a highly radiation-stable composition with high solubility stability, no coating unevenness and high safety can be obtained, and the present invention is completed based on these findings. It came to.

Thus, according to the present invention, there is provided a radiation-sensitive composition comprising a cyclic olefin polymer containing a protic polar group, a radiation-sensitive compound, a crosslinking agent and a solvent, wherein the solvent is mutually contained in the same molecule. A radiation-sensitive composition comprising a diethylene glycol dialkyl ether having two different alkyl groups is provided.
In the radiation-sensitive composition of the present invention, the dialkylene glycol dialkyl ether having two different alkyl groups in the same molecule is preferably diethylene glycol dialkyl ether having two different alkyl groups in the same molecule.
In the radiation-sensitive composition of the present invention, the diethylene glycol dialkyl ether having two different alkyl groups in the same molecule is particularly preferably diethylene glycol ethyl methyl ether.

According to this invention, the laminated body which consists of a board | substrate and the resin film formed on it using the 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 laminate of the present invention, the resin film may be a patterned resin film.
According to the present invention, a resin film is further formed on the substrate using the radiation-sensitive composition, and a latent image pattern is formed in the resin film by irradiating the resin film with active radiation, and then a developer is applied to the resin film. A method for producing a laminate comprising a substrate and a patterned resin film formed thereon is provided, 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. .
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.

  According to the present invention, it is possible to obtain a radiation-sensitive composition that is excellent in dissolution stability and can provide a resin film with very little coating unevenness. A laminate in which a resin film is formed on a substrate using this radiation-sensitive composition has excellent electrical characteristics of the resin film and extremely little coating unevenness. For example, a display element, an integrated circuit element, a solid-state imaging element, a color Protective film for elements such as filters and black matrix, flattening film for flattening the element surface and wiring, insulating film for maintaining electrical insulation (electric insulating film for thin transistor type liquid crystal display elements and integrated circuit elements) It is suitable as a material for electronic components such as a microlens and a spacer.

  The radiation-sensitive composition of the present invention is a radiation-sensitive composition comprising a cyclic olefin polymer containing a protic polar group, a radiation-sensitive compound, a crosslinking agent, and a solvent, and a specific compound is used as the solvent. It is characterized by that.

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 a polar group having an oxygen atom such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a hydroxyl group; a primary amino group, a secondary amino group, a primary amide group, A polar group having a nitrogen atom such as a secondary amide group (imide group); a polar group having a sulfur atom such as a thiol group; and the like. 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 (a) containing a protic polar group include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene and 5-methyl-5-hydroxycarbonylbicyclo [2.2. 1] hept-2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-exo-6-endo-dihydroxycarbonylbicyclo [2.2.1] hept -2-ene, 8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-exo-9-endo-dihydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 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, the cyclic olefin monomer (b) containing a polar group other than the protic polar group and the non-polar group-containing cyclic olefin monomer (c) are preferable, and contain a polar group other than the protic polar group. The cyclic olefin monomer (b) is more 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. A group (an acid anhydride residue of dicarboxylic acid), an alkoxy group, a carbonyl group, a tertiary amino group, a sulfone group, a halogen atom, an acryloyl group, and the like.
Of these, ester groups, N-substituted imide groups and cyano groups are preferred, ester groups and N-substituted imide groups are more preferred, and N-substituted imide groups are particularly preferred.

Examples of the ester group-containing cyclic olefin include 5-acetoxybicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, and 5-methyl-5. -Methoxycarbonylbicyclo [2.2.1] hept-2-ene, 8-acetoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.

Examples of the N-substituted imide group-containing cyclic olefin include N-phenyl- (5-norbornene-2,3-dicarboximide).
Examples of the cyano group-containing cyclic olefin include 8-cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 5-cyanobicyclo [2.2.1] hept-2-ene, and the like.
Examples of the halogen atom-containing cyclic olefin include 8-chlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-chlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.
These cyclic olefins having polar groups other than protic polar groups may be used alone or in combination of two or more.

Specific examples of the non-polar group-containing cyclic olefin monomer (c) include bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethyl-bicyclo [2.2.1]. Hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2. 2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (conventional name: dicyclopentadiene), tetracyclo ^{[8.4.0.1 11,14.} 0 ^3,7 ] pentadeca-3,5,7,12,11-pentaene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dec-3-ene (common name: tetracyclododecene), 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, cyclopentene, cyclopentadiene, 1,4-methano -1,4,4a, 5,10,10a hexa hydro anthracene, 8-phenyl - tetracyclo [4.4. 0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), pentacyclo [7.4.0.1 ^{3 , 6} . 1 ^10,13 . 0 ^2,7] pentadeca-4,11-diene, pentacyclo [9.2.1.1 ^4,7. 0 ^2,10 . 0 ^3,8 ] pentadeca-5,12-diene and the like. These nonpolar cyclic olefins 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.

The radiation-sensitive compound used in the present invention is a compound capable of absorbing a radiation such as an ultraviolet ray or an electron beam and causing a chemical reaction, and a cyclic olefin type having a protic polar group used in the present invention. The alkali solubility of the polymer can be controlled.
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 quinonediazidesulfonic acid halide include 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-benzoquinonediazide-5-sulfonic acid chloride, and the like.
Typical examples of the compound having a phenolic hydroxyl group include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1. -[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and the like.
Other compounds having a phenolic hydroxyl group include 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2-bis (4-hydroxyphenyl) propane, tris (4- Hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, novolak resin oligomer, phenolic hydroxyl group Examples thereof include oligomers obtained by copolymerizing one or more compounds and dicyclopentadiene.
These radiation sensitive compounds can be used alone or in combination of two or more.

  The amount of the radiation-sensitive compound used is usually 1 to 100 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the cyclic olefin polymer containing a protic polar group. Part range. When the amount of the radiation sensitive compound used is within this range, when patterning the resin film formed on the substrate, the difference in solubility between the radiation irradiated part and the radiation non-irradiated part becomes large, and patterning by development is easy. In addition, the radiation sensitivity is increased, which is preferable.

  In the present invention, as the crosslinking agent, one having two or more, preferably three 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 is 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; glycolurils such as N, N ', N ", N"'-(tetraalkoxymethyl) glycoluril; acrylate compounds such as ethylene glycol di (meth) acrylate; Methylene diisocyanate polyisocyanate Isocyanate compounds such as isophorone diisocyanate polyisocyanate, tolylene diisocyanate polyisocyanate, hydrogenated diphenylmethane diisocyanate; 1,4-di- (hydroxymethyl) cyclohexane, 1,4-di- (hydroxymethyl) norbornane; 3,4-trihydroxycyclohexane; an epoxy compound having an alicyclic skeleton and having two or more epoxy groups, an epoxy compound having a cresol novolac skeleton and having two or more epoxy groups, a phenol novolac skeleton and Polyfunctional epoxy such as an epoxy compound having two or more epoxy groups, an epoxy compound having a bisphenol A skeleton and two or more epoxy groups, and an epoxy compound having a naphthalene skeleton and two or more epoxy groups Compounds; and the like. Among these, a polyfunctional epoxy compound is preferable, and a polyfunctional epoxy compound having an alicyclic skeleton and having two or more epoxy groups, more preferably three or more is particularly preferable because of good film forming properties. .

  These crosslinking agents can be used alone or in combination of two or more. The amount of the crosslinking agent used is usually 1 to 100 parts by weight, preferably 10 to 70 parts by weight, and more preferably 20 to 50 parts by weight with respect to 100 parts by weight of the cyclic olefin polymer containing a protic polar group. Range. When the cross-linking agent is in this range, the heat resistance is highly improved.

In the radiation-sensitive composition of the present invention, it is essential to use dialkylene glycol dialkyl ether having two different alkyl groups in the same molecule as a solvent. By using a dialkylene glycol dialkyl ether having two different alkyl groups in the same molecule as a solvent, dissolution stability is improved and coating unevenness can be reduced.
The alkyl group in the dialkylene glycol dialkyl ether having two different alkyl groups in the same molecule preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms.
Moreover, it is preferable that carbon number of one alkylene chain in the dialkylene glycol dialkyl ether which has two mutually different alkyl groups in the same molecule exists in the range of 1-4, More preferably, it is the range of 2-3.

Specific examples of diethylene glycol dialkyl ethers having two different alkyl groups in the same molecule include diethylene glycol ethyl methyl ether, diethylene glycol methyl propyl ether, diethylene glycol butyl methyl ether, diethylene glycol ethyl propyl ether, diethylene glycol butyl ethyl ether, diethylene glycol butyl propyl ether. Diethylene glycol dialkyl ether having two different alkyl groups in the same molecule, such as dipropylene glycol ethyl methyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethyl propyl ether, dipropylene glycol butyl ethyl And the like can be given; ether, dipropylene glycol dialkyl ether having mutually different two alkyl groups in the same molecule, such as dipropylene glycol butyl propyl ether.
Of these, diethylene glycol dialkyl ether having two different alkyl groups in the same molecule is preferable, and diethylene glycol ethyl methyl ether is particularly preferable.
The amount of dialkylene glycol dialkyl ether having two different alkyl groups in the same molecule is usually 20 to 10,000 parts by weight per 100 parts by weight of the cyclic olefin polymer containing a protic polar group. The range is preferably 50 to 5,000 parts by weight, more preferably 100 to 1,000 parts by weight.

In the present invention, dialkylene glycol dialkyl ether having two different alkyl groups in the same molecule may be used in combination with another solvent.
Examples of solvents that can be used in combination include chain and cyclic ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 4-hydroxy-4-methyl-2-pentanone; methanol, ethanol, propanol, butanol, and 3-methoxy-3. -Alcohols such as methylbutanol; cyclic ethers such as tetrahydrofuran and dioxane;
Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether; monoalkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether Monoalkylene glycol monoalkyl ether esters such as acetate (monoalkylene glycol monoether acetate);

  Ethylene glycol dimethyl ether, ethylene glycol diethyl ether; monoalkylene glycol dialkyl ethers such as propylene glycol dimethyl ether and propylene glycol diethyl ether; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether Dialkylene glycol monoalkyl ethers; diethylene glycol dimethyl ether, diethylene glycol diethyl ether; dialkylene glycol dialkyl ethers having the same two alkyl groups in the same molecule, such as dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether; Trialkylene glycol monoalkyl ethers such as coal monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether Trialkylene glycol dialkyl ethers such as tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol ethyl methyl ether; etc .;

Aromatic hydrocarbons such as benzene, toluene, xylene; ethyl acetate, butyl acetate, ethyl lactate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, hydroxyacetic acid Esters such as ethyl, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, γ-butyrolactone; N- Examples include amides such as methylformamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-methylacetamide, and N, N-dimethylacetamide; dimethyl sulfoxide;
These other solvents can be used alone or in combination of two or more, and the amount used is appropriately selected within a range not impairing the effects of the present invention.

The radiation-sensitive 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. These other resin components can be used alone or in combination of two or more, and the blending amount thereof is appropriately selected within a range not impairing the effects of the present invention.

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 a phenolic antioxidant, 2,6-di-t-butyl-4-methylphenol, p-methoxyphenol, styrenated phenol, n-octadecyl-3- (3 ′, 5′-di-t- Butyl-4′-hydroxyphenyl) propionate, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 2-tert-butyl-6- (3′-tert-butyl-5′-methyl) -2'-hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 4,4'-thio-bis (3-methyl-6- t-butylphenol), pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], alkylated bisphenol, etc. It can be mentioned. Examples of phosphorus antioxidants include triphenyl phosphite and tris phosphite (nonylphenyl). 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 radiation-sensitive composition of the present invention. Specific compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl 1,2,3,4 -Butanetetracarboxylate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.
Examples of the adhesion assistant include functional silane coupling agents, and specific examples thereof include trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, Examples include γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

The radiation-sensitive composition of the present invention comprises a cyclic olefin polymer containing a protic polar group, a radiation-sensitive compound and a cross-linking agent as essential components, and other components as necessary, and two different in the same molecule. It can be produced by dispersing or dissolving in a solvent containing a dialkylene glycol dialkyl ether having two alkyl groups. A method for dissolving or dispersing each component in the solvent may be in accordance with a conventional method, for example, by stirring using a stirrer and a magnetic stirrer, or by a high-speed homogenizer, dispersion, planetary stirrer, twin-screw stirrer, ball mill, It can be performed using 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 of the radiation-sensitive 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 dissolution stability is good and coating unevenness is reduced.

The laminate of the present invention comprises a substrate and a resin film formed thereon using the radiation sensitive 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 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 coating method is, for example, a method in which a radiation-sensitive composition is coated on a substrate, then dried by heating to remove the solvent, and then cross-linked as necessary. 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.
In the film lamination method, for example, after applying the radiation-sensitive composition on a substrate such as a resin film or a metal film, the solvent is removed by heat drying to obtain a B stage film, and then this B stage film is placed on the substrate. It is a 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.

In the present invention, the resin film may be a patterned resin film (hereinafter referred to as “patterned resin film”).
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 resin film patterned on the substrate can be formed as follows.
First, the resin film formed on the substrate as described above is irradiated with actinic radiation to form a latent image having a desired pattern. The actinic radiation is not particularly limited as long as it can activate the radiation-sensitive compound and change the alkali solubility of the radiation-sensitive composition. Specifically, ultraviolet rays, ultraviolet rays having a single wavelength such as g-line or i-line, light rays such as KrF excimer laser light and ArF excimer laser light; particle beams such as electron beams; In order to form a latent image pattern by selectively irradiating these actinic radiations in a pattern, it is sufficient to follow a conventional method. For example, ultraviolet rays, g rays, i rays, KrF excimers are 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 a light beam is used as the active radiation, the light beam 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. 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 conditions are usually selected appropriately in the range of 0 to 100 ° C., preferably 5 to 55 ° C., more preferably 10 to 30 ° C., and usually 30 to 180 seconds.
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.

After forming the patterned resin film on the substrate, the resin may be crosslinked.
Crosslinking of the patterned 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, the molecular weight is determined in terms of polyisoprene.
[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.

[Safety of solvent]
Judgment is made according to the following criteria based on the LD ₅₀ value obtained in the acute toxicity test by oral administration of the solvent to rats. The numerical values are based on product safety data sheets (Propylene glycol monomethyl ether acetate for Daicel Chemical Industries, and other solvents issued by Toho Chemical Industries).
○: 5,000 mg / kg or more ×: less than 5,000 mg / kg [dissolution stability]
The radiation-sensitive composition is stored separately for one day in a −20 ° C. environment and a 5 ° C. environment, and the presence or absence of precipitates is observed.
◯: No precipitate is observed after storage at -20 ° C or 5 ° C.
Δ: Precipitates are observed after storage at −20 ° C. environmental conditions, but no precipitates are observed after storage at 5 ° C. environmental conditions.
X: Precipitates are observed after both storage at -20 ° C and 5 ° C.

[Radiation-sensitive composition resin film formation and coating unevenness]
After 50 ml of a radiation sensitive 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 give a film thickness of 3 μm. A coated substrate is formed. Interference fringe inspection lamp HCN052NA (manufactured by TOSHIBA) is irradiated with light on the coated substrate, depending on the state of the interference fringes, a “dripping trace” where traces of dripping of the solution remain, and streaks generated when the solution spreads during spin coating The presence or absence of unevenness “muscle unevenness” is observed and judged according to the following criteria. These unevennesses all indicate a minute film thickness difference in a region that cannot be detected by the film thickness meter.
○: No unevenness is observed.
Δ: Only dripping marks are observed.
X: Both dripping marks and streaks are observed.

[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 . 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 diameter of 0.2 μm to separate activated carbon to obtain a polymer solution. Filtration was performed without any delay. The polymer solution was poured into ethyl alcohol to solidify, and the produced crumb was dried to obtain a polymer. 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, 550 parts of diethylene glycol ethyl methyl ether as a solvent, and 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1- as a 1,2-quinonediazide compound. 25 parts by weight of a condensate of methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.5 mol), an alicyclic structure-containing polyfunctional epoxy as a crosslinking agent 20 parts of a compound (molecular weight 2,700, epoxy group number 15, Daicel Chemical Industries, EHPE3150), 1 part of γ-glycidoxypropyltrimethoxysilane as an adhesion assistant, and a silicone surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) , KP-341) After mixing and dissolving 0.05 parts, a polytetrafluoroethylene-made film having a pore diameter of 0.45 μm was prepared. The radiation-sensitive composition was prepared by filtration through Luther. The radiation-sensitive composition was evaluated for dissolution stability, coating unevenness, and dielectric constant. The results are shown in Table 1.

[Comparative Examples 1-4]
Instead of diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate (Comparative Example 1), diethylene glycol dimethyl ether (Comparative Example 2), diethylene glycol diethyl ether (Comparative Example 3), 1: 1 of diethylene glycol monoethyl ether and propylene glycol monoethyl ether A radiation-sensitive composition was prepared in the same manner as in Example 1 except that 4 (weight ratio) mixed solvent (Comparative Example 4) was used. The radiation-sensitive composition was evaluated for dissolution stability, coating unevenness, and dielectric constant. The results are shown in Table 1.

[Footnotes in Table 1]
* 1 DEGEME: Diethylene glycol ethyl methyl ether PGMEA: Propylene glycol monomethyl ether acetate DEGDME: Diethylene glycol dimethyl ether DEGDEE: Diethylene glycol diethyl ether DEGEE: Diethylene glycol monoethyl ether PGEE: Propylene glycol monoethyl ether * 2 Insoluble in coating film Existed.

From the results in Table 1, when diethylene glycol ethyl methyl ether, which is a dialkylene glycol dialkyl ether having two different alkyl groups in the same molecule, is used as a solvent, there is no problem in safety and excellent dissolution stability. It can be seen that a radiation-sensitive composition free from coating unevenness is obtained, and that a resin film obtained using this composition is excellent in dielectric properties.
On the other hand, when other solvents are used, it is understood that the obtained radiation-sensitive composition has a problem in safety or shows an unsatisfactory result in either dissolution stability or coating unevenness. .

Claims (8)

A radiation-sensitive composition comprising a cyclic olefin polymer containing a protic polar group, a radiation-sensitive compound, a crosslinking agent, and a solvent, wherein the solvent contains diethylene glycol ethyl methyl ether A radiation-sensitive composition. 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 2 , wherein the resin film is a patterned resin film. The manufacturing method of the laminated body which consists of forming a resin film on a board | substrate using the radiation sensitive composition of Claim 1 , and consisting of a board | substrate and the resin film formed on it. The method for producing a laminate according to claim 4 , wherein the resin film is formed on the substrate and then the resin is crosslinked. A resin film is formed on a substrate using the radiation-sensitive composition according to claim 1 , an active radiation is irradiated to the resin film to form a latent image pattern in the resin film, and then a developer is applied to the resin film. 4. The method for producing a laminate according to claim 3 , comprising a substrate and a patterned resin film formed thereon, wherein the latent image pattern is exposed to contact to form a patterned resin film on the substrate. The manufacturing method of the laminated body of Claim 6 which performs cross-linking reaction of resin after forming a patterned resin film on a board | substrate. An electronic component comprising the laminate according to claim 2 .