JP2006265322A - Radiation-sensitive resin composition and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition capable of forming a resin film which has no thickness variation and maintain transparency even under high-temperature heating conditions. <P>SOLUTION: The radiation-sensitive resin composition comprises (A) an alicyclic olefin polymer having an acidic group, (B) a compound having two or more functional groups which react with an acidic group, (C) an onium salt, and (D) an oxidation inhibitor in an amount of 3-15 pts.wt. based on 100 pts.wt. of the polymer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a radiation-sensitive resin composition suitable for manufacturing electronic components such as an integrated circuit element, a liquid crystal display element, an organic electroluminescence element (hereinafter abbreviated as EL), a solid-state imaging element, and a printed board. The present invention relates to a transparent resin film using the same and a laminate formed by stacking the transparent resin films.

  For electronic components such as integrated circuit elements, liquid crystal display elements, organic EL elements, solid-state imaging elements, and printed circuit boards, protective films for preventing deterioration and damage of the components themselves, flatness for flattening the element surface and wiring Various resin films are provided as a pixel separation film for separating a light emitting portion, such as a conversion film, an electrical insulation film for maintaining electrical insulation, and an optical film for condensing and diffusing light. 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. As the wiring and devices are densified, a radiation-sensitive resin composition having excellent electrical characteristics and transparency for forming such a resin film is formed on the resin film such as the flattening film and the insulating film. It has come to be required. Recently, organic EL elements are provided with a pixel separation film and a resin film for flattening the element, and in order to extend the life of the light emitter, it has high insulation, excellent transparency, and low gas generation. A radiation-sensitive resin composition has been demanded.

In order to meet such various requirements, a radiation sensitive resin composition using an alicyclic olefin polymer has been proposed. For example, Patent Document 1 discloses a radiation-sensitive resin composition containing an alicyclic olefin polymer, an acid generator, and a crosslinking agent. Here, it is specifically shown that those using a triazine compound as an acid generator are excellent in heat resistant dimensional stability and heat discoloration. Evaluation regarding heat resistance in the publication is made under heating conditions of 220 ° C. for 60 minutes.
Patent Document 2 proposes blending a specific phenol compound with a radiation-sensitive resin composition containing an alicyclic olefin polymer, an acid generator, and a crosslinking agent. According to the publication, when a naphthoquinone diazide compound is used as an acid generator, when 1 part by weight of an antioxidant that is a phenol compound is added to 100 parts by weight of an alicyclic olefin polymer, 240 ° C., 60 minutes. It has been shown that transparency is maintained even under heating conditions.
As described above, radiation-sensitive resin compositions that exhibit good physical properties even under heating conditions at high temperatures have been provided, but with the diversification of display elements, more severe heating conditions are applied to display element manufacturing processes. Therefore, it has become difficult to obtain sufficient heat resistance even with the radiation-sensitive resin composition described in the above-mentioned literature. Accordingly, the present situation is that there is a demand for a film having a stable film thickness and transparency even under such conditions.

JP-A-11-052574 International Publication WO03 / 100524

  The present inventor has intensively studied to obtain a radiation-sensitive resin composition capable of forming a resin film having little film thickness fluctuation and maintaining transparency even under long-time high-temperature heating conditions. It has been found that this object is achieved when a salt is used and a predetermined amount of antioxidant is blended, and the present invention has been completed.

Thus, according to the present invention, A: an alicyclic olefin polymer having an acidic group, B: a compound having two or more functional groups that react with the acidic group, C: an onium salt, D: an antioxidant A radiation sensitive resin composition containing 3 to 15 parts by weight with respect to 100 parts by weight of the combined body is provided.
Moreover, the laminated body formed by laminating | stacking the said transparent resin film on the transparent resin film which uses the said radiation sensitive resin composition and a board | substrate is provided.

The present invention is described in detail below.
The radiation-sensitive resin composition of the present invention includes an alicyclic olefin polymer having an acidic group, a compound that functions as a crosslinking agent, a compound having two or more functional groups that react with the acidic group, an onium salt that functions as a radiation-sensitive agent, And an antioxidant.

The alicyclic olefin polymer having an acidic group used in the present invention is a ring-opening or addition polymer of an alicyclic olefin monomer using a metathesis polymerization catalyst or a Ziegler catalyst. Moreover, the hydride which hydrogenated such a polymer may be sufficient. In particular, a hydrogenated alicyclic olefin polymer obtained using an alicyclic olefin monomer and having an acidic group is suitable for use in combination with a photosensitizer to obtain a patterned transparent resin film. The alicyclic olefin monomer is a polymerizable monomer having a carbon-carbon double bond in the alicyclic structure. The alicyclic structure may be monocyclic or polycyclic (fused polycyclic, bridged ring, combination polycyclic, etc.). From the viewpoints of mechanical strength, heat resistance, etc., polycycles are preferred. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4-30, preferably 5-20, more preferably 5-15, when the heat resistance, and Various characteristics such as pattern properties are highly balanced and suitable.

The ratio of acidic groups bonded to the alicyclic olefin polymer is usually 30 to 100 mol%, preferably from the viewpoint of heat resistance, etc., based on the total number of moles of the repeating structural unit of the alicyclic olefin polymer, preferably It is 50-100 mol%, More preferably, it is 70-100 mol%.
The alicyclic olefin polymer having an acidic group may be polymerized by using an alicyclic olefin monomer having an acidic group together with an alicyclic olefin monomer having no acidic group, if necessary. After polymerizing the alicyclic olefin monomer not to be treated, an acidic group may be introduced by reacting a modifier. The modification reaction may be carried out in accordance with a conventional method, and is usually performed in the presence of a radical generator. In addition, the alicyclic olefin polymer having an acidic group is an alicyclic olefin monomer having an acidic group precursor that brings about an acidic group by a chemical change, such as an ester group or a cyano group, resulting in a carboxyl group by hydrolysis. Can be obtained by polymerizing with other alicyclic olefin monomers or the like, if necessary, and then chemically changing to give an acidic group.

Examples of the alicyclic olefin monomer having an acidic group include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene and 5-methyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene. Ene, 5-hydroxycarbonylmethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 8-methyl-8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-carboxymethyl-8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . Alicyclic olefin monomers having one carboxyl group, such as 1 ^7,10 ] dodec-3-ene; 5-exo-6-endo-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 8- Exo-9-endo-dihydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec- ³ -ene-8,9-dicarboxylic anhydride, hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] alicyclic olefin monomer having two carboxyl groups, such as heptadeca-4-ene-11,12-dicarboxylic acid anhydride; 5- (4-hydroxyphenyl) bicyclo [2.2.1] hept 2-ene, 5-methyl-5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 5-carboxymethyl-5- (4-hydroxyphenyl) bicyclo [2.2. 1] hept-2-ene, 8-methyl-8- (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-carboxymethyl-8- (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 . And cycloaliphatic olefin monomers having one hydroxyphenyl group such as ^{17, 10} ] dodec-3-ene.

Examples of the alicyclic olefin monomer having no polar group include 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] dodec-3-ene, 5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-2-ene (common name: norbornene), 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 (trivial name: dicyclopentadiene), tetracyclo ^{[8.4.0.1 11,14.} 0 ^2,8 ] tetradeca-3,5,7,12,11-tetraene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dec-3-ene (common name: tetracyclododecene), 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene, 8-phenyl-tetracyclo [4. 4.0.1 ^2,5 . 1 ^7,10 ] nonpolar alicyclic olefin monomers such as dodec-3-ene; N-substituted imide group-containing cyclic olefin monomers such as N-phenyl- (5-norbornene-2,3-dicarboximide); Cycloaliphatic olefin monomer having an ester group such as 5-acetoxybicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene; 8-cyanotetra Cyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-cyanotetracyclo [4.4.0.1 ^2,5 . Alicyclic olefin monomers having a cyano group such as 17, ¹⁰ ] dodec-3-ene and 5-cyanobicyclo [2.2.1] hept-2-ene;

  As a modifier for introducing an acidic group, a compound having an acidic group and a reactive carbon-carbon unsaturated bond in one molecule is usually used. Specific examples of such compounds include acrylic acid, methacrylic acid, angelic acid, tiglic acid, oleic acid, elaidic acid, erucic acid, brassic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, atropaic acid. Unsaturated carboxylic acids such as acid and cinnamic acid; allyl alcohol, methyl vinyl methanol, crotyl alcohol, methallyl alcohol, 1-phenylethen-1-ol, 2-propen-1-ol, 3-butene- 1-ol, 3-buten-2-ol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2- Such as methyl-3-buten-1-ol, 4-penten-1-ol, 4-methyl-4-penten-1-ol, 2-hexen-1-ol, etc. And the like can be given; saturated alcohols.

  In the present invention, different types of acidic groups may be included. The acidic group contained in the alicyclic olefin polymer containing an acidic group may be bonded to the alicyclic olefin monomer unit or may be bonded to a monomer unit other than the alicyclic olefin monomer. It is desirable that it is bonded to an alicyclic olefin monomer unit.

  In the alicyclic olefin polymer containing an acidic group used in the present invention, the acid value is preferably 50 to 250, more preferably 70 to 200. The acid value includes the acid group-containing monomer molecular weight: x, the other monomer molecular weight: y, the acid group-containing monomer weight ratio in the resin: a, the other monomer weight ratio: b, and the number of other monomers is n. It is a value calculated from an expression represented by (a / (x × a + y1 × b1 + y2 × b2 +... + Yn × bn)) × 56 × 1000.

The polymerization method of each monomer may be in accordance with a conventional method, and for example, a ring-opening polymerization method or an addition polymerization method is employed.
As the ring-opening polymerization catalyst, for example, a metal complex such as molybdenum, ruthenium, or osmium is 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, as a molar ratio of metal compound to alicyclic olefin in the polymerization catalyst. Preferably it is the range of 1: 1,000-1: 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, noble reactions such as functional group modification occur, and noble metal complex catalysts such as rhodium and ruthenium are preferred from the viewpoint that carbon-carbon unsaturated bonds in the polymer can be hydrogenated. A nitrogen-containing heterocyclic carbene compound or a ruthenium catalyst coordinated with a phosphine having a high donating property is particularly preferable.

The weight average molecular weight (Mw) of the alicyclic olefin polymer containing an acidic group used in the present invention is usually 1,000 to 1,000,000, preferably 1,500 to 100,000, more preferably. It is in the range of 2,000 to 10,000. The molecular weight distribution of the alicyclic olefin polymer containing an acidic group used in the present invention is usually 4 or less, preferably 3 or less, more preferably 2 in terms of weight average molecular weight / number average molecular weight (Mw / Mn) ratio. .5 or less.
The iodine value of the alicyclic olefin polymer containing an acidic 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 alicyclic olefin polymer containing an acidic group is in this range, the heat resistance is particularly excellent and suitable.

  The crosslinking agent used in the present invention is a compound having two or more functional groups that react with acidic groups. Examples of the functional group capable of reacting with an acidic group include an amino group, a carboxyl group, a hydroxyl group, an epoxy group, an oxetanyl group, and an isocyanate group. From the viewpoint of adhesion between the substrate and the resin film, an amino group, Epoxy groups and isocyanate groups are preferred, and epoxy groups and oxetanyl groups are particularly preferred. In the present invention, the compound used as the crosslinking agent may contain only one kind of these functional groups or may contain two or more kinds.

  Examples of the compound having two or more epoxy groups in a molecule as a functional group capable of reacting with an acidic group include SR-NPG, SR-16H, SRHL, SR-TMP, SR-MK3, SR-TPG, SR- Polyfunctional epoxy compounds having a chain structure such as 4PG, SR-2EG (product name; manufactured by Sakamoto Pharmaceutical Co., Ltd.); RE-310S (product name; manufactured by Nippon Kayaku Co., Ltd.), EXA7015 (product name: Dainippon) Ink Chemical Co., Ltd.), Epicoat 828 (product name: manufactured by Japan Epoxy Resin Co., Ltd.), SR-CF2 (product name: manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), etc .; ) And other bisphenol F type compounds such as Epicoat 506 (product name; manufactured by Japan Epoxy Resin Co., Ltd.) Epoxy compounds; phenol novolac type epoxy resins such as EPPN-201 (product name; manufactured by Nippon Kayaku Co., Ltd.); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-4500, EOCN-4600 (or above) Cresol novolac epoxy resins such as product name; manufactured by Nippon Kayaku Co., Ltd .; polyfunctional epoxy resins based on dicyclopentadiene such as XD-1000 (product name; manufactured by Nippon Kayaku Co., Ltd.); SR-HBA (product name) Manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), AK-601 (product name; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, Celoxide 2080, Celoxide 3000, Epolide GT300, Epolide GT400, EHPE3150 (above, product name; manufactured by Daicel Chemical Industries) Polyfunctional epoxy with alicyclic structure such as Compound; GAN, GOT (or, product name; manufactured by Nippon Kayaku Co., Ltd.) Epoxy compound having such amine structure; and the like.

  Examples of a compound having two or more oxetanyl groups in a molecule as a functional group capable of reacting with an acidic group include OXT-121, OXT-221, RSOX, 4, 4′-BPOX (above, product name; Toagosei Co., Ltd.) Bisoxetanes, such as Trisoxetane, PNOX-1009 (product name; manufactured by Toagosei Co., Ltd.), novolak-type oxetane, calixarene-type oxetane cardo-type oxetane, polyhydroxystyrene-type oxetane, silsesqui Examples include ether compounds with hydroxyl group-containing resins such as silicone resins such as oxane.

  Examples of compounds having a functional group other than an epoxy group or an oxetanyl group as a functional group capable of reacting with an acidic group include aliphatic polyamines such as hexamethylenediamine; aromatics such as 4,4′-diaminodiphenyl ether and diaminodiphenylsulfone Polyamines; azide compounds such as 2,6-bis (4′-azidobenzal) cyclohexanone and 4,4′-diazidodiphenylsulfone; polyamides such as nylon, polyhexamethylenediamine terephthalamide and polyhexamethyleneisophthalamide Melamines such as N, N, N ′, N ′, N ″, N ″-(hexaalkoxymethyl) melamine; glycols such as N, N ′, N ″, N ″ ′-(tetraalkoxymethyl) glycoluril; Urils; ethylene glycol di (meth) acrylate, Acrylate compounds such as xylacrylate polymers; isocyanate compounds such as hexamethylene diisocyanate polyisocyanate, isophorone diisocyanate polyisocyanate, tolylene diisocyanate polyisocyanate; hydrogenated diphenylmethane diisocyanate polyisocyanate; 1,4-di- (hydroxy Methyl) cyclohexane, 1,4-di- (hydroxymethyl) norbornane, 1,3,4-trihydroxycyclohexane and the like.

The compounds having a bifunctional or higher functional group used as a crosslinking agent in the present invention can be used alone or in combination of two or more.
The amount used is appropriately selected according to the purpose of use, but is usually 1 to 200 parts by weight, preferably 10 to 150 parts by weight, more preferably 100 parts by weight of the alicyclic olefin polymer having an acidic group. Is 20 to 100 parts by weight. When the amount used is in this range, the transparency and the amount of film reduction after heating of the resin film to be formed (the amount of film reduction is proportional to the amount of decomposition of the film) (hereinafter referred to as transparent after heating in the present invention) The properties and the amount of film reduction are collectively referred to as “heat resistance”), which is highly improved.

The onium salt used in the present invention is a reaction initiator for causing a crosslinking reaction between the functional group of the crosslinking agent and the acidic group of the alicyclic olefin polymer. It generates seeds or Lewis acids. When the functional group of the crosslinking agent is an oxetanyl group as an epoxy group, it is preferable because a transparent resin film having a sufficient crosslinking density can be provided while maintaining excellent transparency.
Specific examples of the onium salt include various kinds such as sulfonium salts, phosphonium salts, ammonium salts, iodonium salts, and the like. For example, diphenyliodonium, 4-methoxydiphenyliodonium, bis (4-methylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (dodecylphenyl) iodonium, triphenylsulfonium, diphenyl-4-thiophenoxyphenylsulfonium Bis [4- (diphenylsulfonio) -phenyl] sulfide, bis [4- (di (4- (2-hydroxyethyl) phenyl) sulfonio) -phenyl] sulfide, [eta] 5-2,4- (cyclopentageni L) [1,2,3,4,5,6-η- (methylethyl) benzene] -iron (1+) and the like, 4- (4- (2-chlorobenzoyl) phenylthio) phenylbis (4-fluorophenyl) ) Sulfonium onium ion and tetrafluorobore DOO, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, hexafluoroantimonate, compounds which consist of a combination of anions such hexachloroantimonate the like. Commercially available onium salts include Adekaoptomer SP-150, SP-152, SP-170, SP-172 (above, product name: manufactured by Asahi Denka Kogyo Co., Ltd.), Uvacure 1590, 1591 (above, product name: Daicel). UCB), Sun-Aid SI-110, SI-180, SI-100L, SI-80L, SI-60L (product name: manufactured by Sanshin Chemical Industry Co., Ltd.), and the like.
The amount of the onium salt used is appropriately selected according to the purpose of use of the transparent resin film to be formed, but is usually 0.5 to 15 parts by weight, preferably 100 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer having an acidic group. Is 1 to 10 parts by weight, more preferably 3 to 8 parts by weight. When the amount used is in this range, the heat resistance of the formed resin film is highly improved, which is preferable.

  As the antioxidant used in the present invention, phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, lactone antioxidants, etc. used as usual polymer blends are used. it can. 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) , Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], alkylated bisphenols, etc. It can be. 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. The amount used is appropriately selected according to the purpose of use, but is preferably 3 to 15 parts by weight, more preferably 5 to 12 parts by weight, based on 100 parts by weight of the alicyclic olefin polymer having an acidic group. . When the amount used is in this range, the heat resistance of the formed resin film is highly improved, which is preferable.

The radiation-sensitive resin composition of the present invention is usually used for resin film formation by mixing the above essential components with a solvent.
There is no particular limitation on the solvent used, for example, alkylene glycols such as propylene glycol and diethylene glycol; ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, Alkylene glycol monoethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether Alkylene glycol dialkyl ethers;

  Alkylene glycol monoalkyl ether esters such as propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; methyl ethyl ketone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, cyclohexanone, cyclo Ketones such as pentanone; alcohols such as methanol, ethanol, propanol, butanol and 3-methoxy-3-methylbutanol; cyclic ethers such as tetrahydrofuran and dioxane; cellosolv esters such as methyl cellosolve acetate and ethyl cellosolve acetate; Aromatic hydrocarbons such as benzene, toluene, xylene; ethyl acetate, butyl acetate, ethyl lactate, 2-hydroxy Esters such as methyl 2-methylpropionate and γ-butyrolactone; Amides such as N-methylformamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-methylacetamide, N, N-dimethylacetamide Dimethyl sulfoxide; and the like.

  These solvents can be used alone or in combination of two or more. The amount of the solvent used is usually 20 to 10,000 parts by weight, preferably 50 to 5,000 parts by weight, more preferably 100 to 3, parts by weight based on 100 parts by weight of the polymer having a polar group that reacts with an epoxy group. The range is 000 parts by weight.

  The radiation sensitive resin composition of the present invention may contain a curing accelerator, a surfactant, an adhesion assistant, a sensitizer, an antistatic agent, a storage stabilizer, an antifoaming agent, and the like.

The method for dissolving or dispersing the radiation-sensitive resin composition of the present invention in a solvent may be in accordance with a conventional method, for example, stirring using a stirrer and a magnetic stirrer, high-speed homogenizer, dispersion, planetary stirrer, biaxial stirrer , Ball mill, three rolls, etc. can be used.
The radiation-sensitive resin 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. Although obtained by mixing the radiation-sensitive resin composition of the present invention and a solvent, the solid content concentration is usually 1 to 70% by weight, preferably 3 to 60% by weight, more preferably 5 to 50% by weight. . When the solid content concentration is in this range, the coating property on the substrate, the film thickness uniformity and the flatness of the formed resin film are highly balanced and suitable.

The laminate of the present invention comprises a substrate and a resin film formed thereon using the radiation sensitive resin composition of the present invention. The thickness of one resin film is usually in the range of 0.1 to 100 μm, preferably 0.5 to 50 μm, more preferably 0.5 to 30 μm.
In the present invention, for example, a printed wiring board, a silicon wafer substrate, a glass substrate, a plastic substrate, or the like can be used as the substrate. In addition, a glass substrate, a plastic substrate or the like used in the display field in which a thin transistor type liquid crystal display element, a color filter, a black matrix, or the like is formed is also preferably used.

The laminate of the present invention can be obtained by forming a resin film on a substrate using the radiation sensitive resin composition of the present invention and then crosslinking the resin film as necessary.
The method for forming the resin film on the substrate is not particularly limited, and for example, a method such as a coating method or a film lamination method can be used. The application method is, for example, a method in which the radiation-sensitive resin composition is applied on a substrate and then dried by heating to remove the solvent. Examples of the method for applying the radiation-sensitive resin composition on the substrate include various methods such as a spray method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a spin coating method, a bar coating method, and a screen printing method. 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, more preferably What is necessary is just to perform for 1 to 30 minutes.

  The film laminating method is, for example, applying a radiation-sensitive resin composition mixed with a solvent on a base such as a resin film or a metal film, and then removing the solvent by heat drying to obtain a B stage film, In this method, the B-stage film is laminated on the substrate. The heating and drying conditions vary depending on the type and blending ratio of each component, but are usually 30 to 150 ° C., preferably 60 to 120 ° C., usually 0.5 to 90 minutes, preferably 1 to 60 minutes, more preferably What is necessary is just to perform for 1 to 30 minutes. The lamination of the film can be performed using a pressure bonding machine such as a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator or the like.

In a laminate comprising a substrate and a resin film formed on the substrate using the radiation sensitive resin composition of the present invention, the resin film may be patterned. The laminate of the present invention, particularly a laminate in which a patterned resin film is formed on a substrate, is useful as various electronic components.
The patterned resin film formed on the substrate, for example, exposes the resin film to actinic radiation to form a latent image pattern, and then exposes the developer film to the resin film having the latent image pattern to reveal the pattern. Can be obtained. A laminate in which a patterned resin film is formed on a substrate is useful as various electronic components.

The actinic radiation is not particularly limited as long as it can activate the radiation sensitive compound and change the solubility of the crosslinkable composition containing the radiation sensitive compound in an alkaline developer. 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 appropriately selected in the range of usually 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.

In the present invention, after forming the patterned resin on the substrate, the crosslinking reaction of the resin can be performed.
Crosslinking of the resin film formed on the substrate may be appropriately selected according to the type of the crosslinking agent, but is usually performed by heating. The heating method can be performed using, for example, a hot plate or an oven. The heating temperature is usually 180 to 250 ° C., and the heating time is appropriately selected depending on the size and thickness of the resin film and the equipment used. For example, when using a hot plate, the oven is usually used for 5 to 60 minutes. Is usually in the range of 10 to 90 minutes. Heating may be performed in an inert gas atmosphere as necessary.

  Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples. In addition, unless otherwise indicated, the part and% in each example are based on mass.

Each characteristic was evaluated by the following method.
[Weight average molecular weight (Mw) and number average molecular weight (Mn) of polymer]
Using gel permeation chromatography (manufactured by Tosoh Corporation; product name “HLC-8020”), the molecular weight was calculated as polyisoprene equivalent molecular weight.
[Hydrogenation rate]
The hydrogenation rate was 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]
It measured according to JIS K0070B.

[Method 1 of forming patterned resin film]
For Examples 1, 3 to 6 and Comparative Example 5, a patterned resin film was formed by the following method.
A radiation-sensitive resin composition is spin-coated on a glass substrate (product name “Corning 1737 Glass” manufactured by Corning), and dried at 90 ° C. for 120 seconds using a hot plate, so that the film thickness after drying is 1.2 μm. It forms into a film so that it may become. This resin film is irradiated with ultraviolet rays having a light intensity at 365 nm of 5 mW / cm ² for 20 seconds in air through a mask having a 10 μm line and space pattern. Subsequently, it heats at 130 degreeC for 60 second using a hotplate. Further, after developing for 75 seconds at 25 ° C. with a 0.5% solution of tetramethylammonium hydroxide, rinsing with ultrapure water for 30 seconds, a 10 μm line-and-space negative patterned resin film is obtained. Formed.

[Method 2 for forming patterned resin film]
In the case of Example 2 using a radiation-sensitive resin composition containing an epoxy compound as a cross-linking agent, a development process was performed at 25 ° C. for 100 seconds using a 0.5% tetramethylammonium hydroxide solution. In the same manner as in the patterned resin film forming method 1, a patterned resin film was formed on the substrate.

[Method 3 for forming patterned resin film]
In the case of Comparative Examples 1 to 3 using a radiation-sensitive resin composition containing a quinonediazide compound as a photosensitive agent, instead of forming a negative pattern, a positive patterned resin film is formed by the following method. did.
Except that the ultraviolet irradiation time was set to 40 seconds, heating was not performed after ultraviolet irradiation, and development was performed at 25 ° C. for 100 seconds using a 0.3% tetramethylammonium hydroxide solution. The patterned resin film was formed on the substrate in the same manner as in the formation method 1 of the patterned resin film.

[Method 4 for forming patterned resin film]
In the case of Comparative Example 4 using a radiation-sensitive resin composition containing a bisazide compound as a photosensitizer, the ultraviolet irradiation time is set to 40 seconds, and after ultraviolet irradiation, heating before development is not performed. A patterned resin film was formed on the substrate in the same manner as in the patterned resin film forming method 1 except that the development treatment was performed at 25 ° C. for 100 seconds using a 0.3% hydroxide solution.

[Pattern shape]
A case where a 10 μm line and space was formed was evaluated as ◯, and a case where a 10 μm line and space could not be formed was evaluated as x.

[Transparency, heat-resistant transparency, heat-resistant film reduction rate]
The substrate on which the patterned resin film is formed is heated in a clean oven at 230 ° C. in air (post-baking). After 30 minutes, the substrate is taken out of the oven and the substrate is returned to room temperature. (Initial transmittance) and film thickness (initial film thickness) were measured.
About this board | substrate again, a board | substrate is put into a clean oven, and it heats in air at 230 degreeC, and after 180 minutes, it takes out from oven and returns a board | substrate to room temperature, Then, the transmittance | permeability (transmittance after a heating) of a patterned resin film | membrane ) And film thickness (film thickness after heating).
The transmittance was measured at a wavelength of 400 nm to 700 nm using a spectrophotometer “V-560” (product name: manufactured by JASCO Corporation). The measured transmittance was converted to a transmittance of 1 μm based on the Lambert-Beer equation, and the ratio of the transmittance after heating to the initial transmittance was calculated.
The film thickness was measured using a stylus-type film thickness meter “P-10” (product name: manufactured by Tencor). The film reduction rate was calculated by the following formula based on the measured value.
Reduction ratio = ([initial film thickness] − [film thickness after heating]) / [initial film thickness] × 100

[Synthesis Example 1]
8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene 58 parts, N-phenyl- (5-norbornene-2,3-dicarboximide) 42 parts, 1,5-hexadiene 2.8 parts, (1,3-dimesi Tyrimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride 0.05 part and diethylene glycol ethyl methyl ether 400 parts were charged into a nitrogen-substituted pressure-resistant glass reactor and stirred at 80 ° C. for 2 hours with polymerization. And an alicyclic olefin polymer solution was obtained. The weight average molecular weight of the alicyclic olefin polymer was 3,200, the number average molecular weight was 1,900, and the polymerization conversion rate was 99.9% or more. Next, 0.1 parts of bis (tricyclohexylphosphine) ethoxymethylene ruthenium dichloride as a hydrogenation catalyst was added to the obtained polymer solution to carry out a hydrogenation reaction to obtain a solution of alicyclic olefin polymer hydride. It was. The obtained hydride had a weight average molecular weight of 4,430 and a number average molecular weight of 2,570. The hydrogenation rate was 99.9%. 1 part of activated carbon powder was added to the obtained alicyclic olefin polymer hydride solution, and hydrogen was dissolved at 150 ° C. under a pressure of 4 MPa for 3 hours while stirring in an autoclave. Next, the alicyclic olefin polymer hydride solution was filtered through a fluororesin filter having a pore size of 0.2 μm to separate the activated carbon to obtain 476 parts of the alicyclic olefin polymer hydride solution (1). Filtration was performed without any delay. The solid content concentration of the solution (1) was 20.6%. The acid value of the obtained polymer was about 150 calculated from the monomers used for the polymerization.

[Synthesis Example 2]
8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3-ene 40 parts and N-phenyl- (5-norbornene-2,3-dicarboximide) 60 parts, except that the polymerization reaction and hydrogenation reaction were carried out by the method of Synthesis Example 1. Then, a solution of alicyclic olefin polymer hydride was obtained. The obtained alicyclic olefin polymer hydride had a weight average molecular weight of 4,330, a number average molecular weight of 2,600, and a hydrogenation rate of 99.9%. The solution of the alicyclic olefin polymer hydride was filtered through a fluororesin filter having a pore size of 0.2 μm to separate the activated carbon to obtain 476 parts of the alicyclic olefin polymer solution. Filtration was performed without any delay. The filtered alicyclic olefin polymer solution was concentrated by a rotary evaporator to obtain an alicyclic olefin polymer solution (2) having a solid content concentration of 35.0%. The acid value of the obtained polymer was about 100 as calculated from the monomers used for the polymerization.

[Synthesis Example 3]
8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] Dodeca-3-ene 76 parts, N-phenyl- (5-norbornene-2,3-dicarboximide) 24 parts, except for changing the polymerization reaction and hydrogenation reaction by the method of Synthesis Example 1. Then, a solution of alicyclic olefin polymer hydride was obtained. The polymer hydride obtained had a weight average molecular weight of 4,450, a number average molecular weight of 2,700, and a hydrogenation rate of 99.9%. Except that this alicyclic olefin polymer hydride solution was used, it was filtered and concentrated in the same manner as in Synthesis Example 2 to obtain an alicyclic olefin polymer hydride solution (3% solids concentration 35.0%). ) The acid value of the obtained polymer was about 200 calculated from the monomers used for the polymerization.

[Examples 1-6, Comparative Examples 1-5]
In the alicyclic olefin polymer hydride solution obtained in the above synthesis example (amount in which the alicyclic olefin polymer hydride is 100 parts), the crosslinking agent, photosensitive agent, and antioxidant described in Table 1 are used. Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (product name “Irganox 1010” (phenolic antioxidant; product name: manufactured by Ciba Specialty Chemicals) And KP341 (silicone surfactant; product name; manufactured by Shin-Etsu Chemical Co., Ltd.) as a surfactant was added, followed by filtration with a Millipore filter having a pore size of 0.45 μm to obtain a radiation-sensitive resin composition. Using the obtained radiation-sensitive resin composition, a patterned resin film was formed, and the pattern shape, transparency, heat-resistant transparency and heat-resistant film reduction rate were evaluated.

  From the results shown in Table 1, a pattern film by radiation is obtained by using a radiation-sensitive resin composition comprising an alicyclic olefin polymer having an acidic group, a compound having a functional group that reacts with the acidic group, an onium salt, and an antioxidant. Can be formed, and maintains low transparency and transparency even after heat treatment in the atmosphere. Furthermore, high transparency and high residual film ratio (low decomposition rate) after subsequent heat treatment in the electronic component process ) Can be formed.

Claims (5)

A: Cycloaliphatic olefin polymer having an acidic group, B: Compound having two or more functional groups that react with the acidic group, C: Onium salt, D: 3 parts by weight of the antioxidant per 100 parts by weight of the polymer A radiation-sensitive resin composition comprising -15 parts by weight. The radiation-sensitive resin composition according to claim 1, wherein the functional group is an epoxy group or an oxetanyl group. D: The radiation-sensitive resin composition according to claim 1, wherein the antioxidant is a phenolic antioxidant. A transparent resin film using the radiation-sensitive resin composition according to claim 1. A laminate formed by laminating the transparent resin film according to claim 4 on a substrate.