TW200302399A - Irradiation-sensitive resin composition and pattern forming process - Google Patents

Abstract

The present invention provides a irradiation-sensitive resin composition comprising the alicyclic series olefin resin with acidic group, acidic generating agent, cross-linking agent, and solvent, characterized in that when the weight-average molecular weight of the alicyclic olefin resin with acidic group is less than 10000, the index number C1 indicated from formula (1) is more than 300; when the weight-average molecular weight of the alicyclic olefin resin with acidic group is more than 10000, the index number C2 indicated from formula (2) is more than 120.

Description

200302399-One ....................., .......-... ........-... ·, ： '-' -V. -V -l · '·' ·.… :: ........ ............ 发明 、 Explanation of the invention ...-............ ............ Two ...... Two .........- ^ ........ .....................................-............ ................... (The description of the invention should state: the technical field to which the invention belongs, the prior art, the content, the embodiment and the simple description of the drawings) ( A) The technical field to which the invention belongs The present invention relates to a radiation-sensitive resin composition, and more specifically, it relates to a solution which is dissolved in a developing solution of an alkaline solution by irradiation with active radiation such as particle rays or electron rays. Sexual radiation-sensitive resin composition. The radiation-sensitive resin composition of the present invention can form a resin film on which a pattern is formed by lithography. The radiation-sensitive resin composition of the present invention is suitable as a resin material for forming a resin film for electronic parts such as a protective film, a flattening film, and an electrical insulating film. (2) In the prior art, electronic parts such as liquid crystal display elements, integrated circuit elements, solid-state imaging elements, or color filters for liquid crystal displays are provided with a protective film to prevent deterioration or damage, and to make the surface or wiring of the element A flattened film, an electrically insulating film, and the like that maintain electrical insulation. Further, in order to insulate interlayer wiring provided in a layer form, an interlayer insulating film is provided on a thin film transistor type liquid crystal display element or an integrated circuit element. These protective films, planarizing films, interlayer insulating films, and the like use resin films for electronic parts having various functions. Conventionally, a thermosetting resin material such as an epoxy resin is generally used as a resin material when forming a resin film for electronic parts. However, when using a known thermosetting resin material conventionally used as a material for forming electronic parts, a sufficient flatness cannot be obtained. Resin film. Therefore, a 6-200302399 was developed in order to develop a resin material for the formation of a new-type radiation-resistant insulating film that can be finely patterned. In addition, in recent years, with the increase in the density of wiring and devices, these resin materials are required to have low dielectric properties. In response to this request, for example, a proposal was made to ring-open polymerize an orbornene-based monomer containing an ester group such as a methoxycarbonyl group, and hydrogenate the resulting ring-opened polymer to hydrolyze the hydrogenated product and convert the ester group partially A carboxyl group is formed, and a radiation-sensitive resin composition of the obtained alkali-soluble cyclic polyolefin resin is used (Japanese Patent Application Laid-Open No. 10-307 3 88 and Japanese Patent Application Laid-Open No. 1 1-52574). The radiation resin composition is a resin composition containing the above-mentioned alkali-soluble cyclic polyolefin resin, an acid generator (for example, a quinonediazide compound), and a crosslinking agent. More specifically, in these publications, the alkali-soluble cyclic polyolefin resin is based on a 8-methyl-8-methoxycarbonyl tetracyclic ring [[ΙΟ · 〖2 · 5.〗 7'10]-]- Resin formed by hydrolyzing the hydrogenation of dodecene ring-opening (co) polymer. However, as a result of the review by the present inventors, it can be seen that the resin film obtained by using the radiation-sensitive composition described in the above publication has dielectric properties, water absorption, flatness, transparency, solvent resistance, and heat-resistant dimensional stability. The better, but the resolution and the residual film rate are not good, and it is not easy to make a good pattern shape. (3) Summary of the invention The object of the present invention is to provide a radiation-sensitive resin composition containing an alicyclic olefin resin having an acidic group, an acid generator, a cross-linking agent, and a solvent, which has a low dielectric constant, heat resistance, and flatness. A radiation-sensitive resin composition having excellent fine pattern shape, which is excellent in transparency, transparency, and solvent resistance, and excellent in resolution and residual film rate. Furthermore, an object of the present invention is to provide a method for forming a pattern using a radiation-sensitive resin composition having various excellent characteristics-7-200302399. In addition, an object of the present invention is to provide a resin film for forming the pattern and a resin film for electronic parts using the resin film. As a result of intensive research to achieve the above-mentioned object, the inventors have found that the cycloaliphatic olefin resin having an acidic group is controlled by controlling the weight average molecular weight, molecular weight distribution, carbon number of the structural unit, and the proportion of the acidic group. Within a specific range, the solubility in the alkali imaging solution is reduced, and a strong dissolution-inhibiting effect in the unirradiated portion can be obtained. As a result, a radiation-sensitive resin composition having excellent resolution, residual film rate, and pattern shape can be obtained. The present invention has been completed based on this knowledge. Therefore, the present invention provides a radiation-sensitive resin composition containing (A) an alicyclic olefin resin having an acidic group, (B) an acid generator, (C) a crosslinking agent, and (D) a solvent In the radiation-sensitive resin composition, (A) the alicyclic olefin resin having an acidic group has a weight average molecular weight of less than 10,000 and has an index C1 represented by the following formula (1) of 300 or more and a weight of When the average molecular weight is 10,000 or more, it has the index C2 represented by the following formula (2): 1 2 0 or more (mw) ° * 5x (ac) 7 5 (Λ, C1 = ---— Χίο5 ⑴ (AG) 6X (MWD) 2 (where MW is the weight average molecular weight, AC is the average carbon number of the structural unit, AG is the mole number of acid groups in all structural units, and MWD is the molecular weight distribution), -8-(2 ) 200302399 (mw) 05x (ac) ag (ag) 2x (mwd) 3 (wherein the meaning of each symbol is the same as the formula (1). In addition, the present invention provides a substrate using a radiation-sensitive resin composition A resin film is formed on the resin film, and active radiation is irradiated in a pattern on the resin film to form a latent image pattern on the resin film. A pattern forming method in which a developing solution is brought into contact to develop a pattern. In addition, the present invention provides a resin film for forming a pattern by the above method, and a resin film for electronic parts using the resin film. BEST MODE The radiation-sensitive resin composition of the present invention is based on a resin containing (A) an alicyclic olefin resin having an acidic group, (B) an acid generator, (C) a crosslinking agent, and (D) a solvent. The radiation-sensitive resin composition is characterized in that (A) the alicyclic olefin resin having an acidic group has a weight average molecular weight of less than 1,000, and has an index C1 of 300 or more as shown in the following formula (1), When the weight average molecular weight is 10,000 or more, the index C2 is 120 or more (MW) a5X (AC) 7 (1) C 1 =-χΙΟ5 (AG) 6X (MWD) 2 (where , MW is the weight average molecular weight, AC is the average carbon number of the structural unit, AG is the mole number of the acidic group in all structural units, and MWD is the molecular weight distribution), 1-9 (2) (2) 200302399 ( MW) a5X (AC) 2 C2 =-ΧΙΟ3 (AG) 2X (MWD) 3 (where the meaning of each symbol and (1) The same). Index C1 is more than 300, the better is 400 or more, the better is 500 or more, the best is 600 or more. The index C2 is 120 or more, the better is 150 or more, the better It is 200 or more, and the most preferable is 2 50 or more. The weight average molecular weight, the average carbon number equivalent to the structural unit (hereinafter simply referred to as "average carbon number"), the mole percentage of acidic groups in all structural units (hereinafter referred to as acidity) Group ratio) and molecular weight distribution are factors that affect the solubility of an alicyclic olefin resin having an acidic group in an alkali developing solution. In the present invention, the solubility of an alicyclic olefin resin having an acidic group in an alkali developer is determined by an index C1 represented by formula (1) when the weight average molecular weight is less than 10,000 and the weight average molecular weight is 10,000 or more. The index C2 shown in equation (2) is judged. The weight-average molecular weight of the present invention is a polystyrene conversion 测定 measured by a gel-permeation-chromatography (GPC) method using tetrahydrofuran as a solvent, and 値 rounded to ten digits is an effective number 有效. When the alicyclic olefin resin having an acidic group is insoluble in tetrahydrofuran, chloroform or cyclohexane can be used. The upper limits of the index c 1 and the index C2 are not particularly limited, and are usually 10,000 or less, preferably 5,000 or less, more preferably 3,000 or less, and most preferably 1,500 or less. The upper limit of index C1 is mostly around 1,000. The upper limit of the index C2 is mostly around 500. The index C1 and the index C2 (hereinafter referred to as "index Ci") each satisfy the above-mentioned 200302399 pieces of alicyclic olefin resins having an acidic group, which have a low solubility in an alkali developing solution (that is, relatively poorly soluble in an alkali). Therefore, with the resin film obtained by using the radiation-sensitive resin composition containing the alicyclic olefin resin having an acidic group, the irradiated portion and the unirradiated portion of the active radiation have a large difference in solubility in the alkali imaging solution, and good results can be obtained. Resolution and residual film rate. In order to obtain an alicyclic olefin resin having an acidic group with an index ci in the above range, calculate the weight average molecular weight of the elements of formula (1) and formula (2) of the index Ci, the average carbon number of equivalent structural units, and the total structural units The mole% of the acidic group and the molecular weight distribution can be controlled by the production conditions of the alicyclic olefin resin having an acidic group. The molecular weight distribution of the alicyclic olefin resin having an acidic group in the present invention is a degree of dispersion represented by a weight average molecular weight / number average molecular weight (Mw / Mη). The number average molecular weight is the same as the weight average molecular weight, and is a polystyrene-equivalent 値 measured by GPC. In terms of excellent properties such as low dielectric constant, low water absorption, solvent resistance, resolution, residual film rate, and pattern shape, the weight average molecular weight is usually 500 to 20,000, preferably 1 000 to 1 50 0 0, more preferably 1 000 ~ 1 0000. Therefore, it is most preferable to use an alicyclic olefin resin having an acidic group having a weight-average molecular weight, which is suitable for using the formula (1). The method for controlling the weight-average molecular weight is not particularly limited, and for example, a method using a molecular weight adjuster described below can be used. Furthermore, when several resins having different weight-average molecular weights are mixed, the weight-average molecular weight is also determined by mixing the weight-average molecular weights of the resins. The method for controlling the molecular weight distribution is not particularly limited. For example, in order to obtain a molecular weight distribution of 3.3 or less, preferably 3.0 or less, more preferably 2.5 or less, and the best -11-200302399, the molecular weight distribution is 2.0 or less. Narrow resins are prepared by using conventional catalysts to adjust reaction conditions such as temperature or time, or by using the following catalysts with organic electron ruthenium compounds as the main component, which are neutral electron-donating ligands. . The average carbon number is calculated from the total amount of carbon atoms outside the carbon constituting the acidic > group of the constituent units constituting the resin and the ratio of each constituent unit. Here, the ratio of each constituent unit is 値 (mole) with respect to the structural unit of a total of 1 mole of the constituent resin. Therefore, for example, the structural unit (I) having a carbon number of 12 and the structural unit (II) having a carbon number of 6 except for the carbon constituting the polar group is 1: 1. The average carbon number of equivalent structural units in the presence of a molar ratio of 1: 1 is calculated as 1 2χ 0.5 + 6χ 0.5 = 9 〇 The ratio of the acidic group is the ratio (mole%) of the structural unit having an acidic group for all the structural units. The method of controlling the average carbon number or the proportion of acidic groups is not particularly limited. For example, it can be performed by adjusting the type or amount of monomers used in the production of the resin. (A) An alicyclic olefin resin having an acidic group used in the present invention is a polymer having a structural unit derived from an olefin monomer having an alicyclic structure (hereinafter referred to as "alicyclic olefin monomer"). . The polymer may also contain structural units other than the structural units derived from the alicyclic olefin monomer. As long as the acidic group is a group obtained by proton generation in water, specific examples thereof include a phenolic hydroxyl group, a carboxyl group (that is, a hydroxycarbonyl group), a dicarboxylic anhydride residue, a sulfonic acid residue, and a phosphoric acid residue. Among these, a carboxyl group and a dicarboxylic anhydride residue are preferable. The acidic group may exist in a structural unit derived from an alicyclic olefin monomer, or in a structural unit other than a structural unit derived from an alicyclic -12-200302399 olefin monomer. When the ratio of the acidic group is that a low-dielectric resin can be obtained and the solubility of the resin in an alkali developing solution can be easily controlled, it is usually 20 to 80 mol%, preferably 30 to 75 mol%, more The best is 30 to 70 mole%. The alicyclic olefin resin having an acidic group may have a polar group such as a hydroxyl group or an ester group other than the acidic group. The alicyclic structure contained in the alicyclic olefin monomer may be a monocyclic ring or a polycyclic ring (condensed polycyclic ring, crosslinked ring, polycyclic ring of these combinations, etc.). Polycyclic is preferred in terms of mechanical strength and heat resistance. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but it is usually 4 to 30, preferably 5 to 20, and more preferably 5 to 15 so that heat resistance and pattern formation can be achieved. The characteristics are highly balanced. The proportion of the structural unit derived from the alicyclic olefin monomer in the alicyclic olefin resin is appropriately selected depending on the purpose of use, and is usually 30 to 100% by weight, preferably 50 to 100% by weight, and more preferably 70 to Within 100%. When the structure ratio of the alicyclic olefin monomer is too small, heat resistance is not good, so it is not desirable. The alicyclic olefin resin is, for example, at least one kind selected from (i) a ring-opening (co) polymer of an alicyclic olefin monomer and a hydrogenated product thereof, (ii) addition (co) polymerization of an alicyclic olefin monomer Compounds, (iii) addition copolymers of alicyclic olefin monomers and ethylene compounds, (iv) monocyclic cycloolefin (co) polymers, (v) alicyclic conjugated diene (co) polymers, ( vi) Ethylene-based alicyclic hydrocarbon (co) polymers and hydrogenated products thereof, and (vii) aromatic ring hydrogenated products of aromatic olefin (co) polymers. The alicyclic olefin resin is preferably a hydrogenated product of a ring-opening (co) polymer of an alicyclic olefin monomer. The cycloaliphatic olefin resin is ring-opened (co-) with original norbornene monomer -13 — 200302399 Hydrogenated polymer is better. The orthobornene-based monomers are preferably the following tetracyclododecenes. An alicyclic olefin resin having an acidic group can be synthesized by modifying an alicyclic olefin resin with an acidic group-containing compound. Moreover, the alicyclic olefin resin having an acidic group can be used as an addition copolymer, an ring-opening copolymer, or the like of an alicyclic olefin monomer having an acidic group and an alicyclic olefin monomer having no acidic group. Hydrogen synthesis. In addition, the alicyclic olefin resin having an acidic group can make an alicyclic olefin monomer containing an ester group such as a methoxycarbonyl group, and a monomer having no ester group as needed (for example, a cyclic olefin monomer, ethylene Base monomers, etc.) addition (co) polymers, ring-opening (co) polymers, or these hydrogenates are decomposed and synthesized by hydrolysis. In the following, these points are explained in more detail. In the following description, in order to avoid complication, polymerization and copolymerization are expressed as "polymerization", and polymers and copolymers are expressed as "polymer" at the same time. In order to obtain an alicyclic olefin resin having an acidic group, for example, an alicyclic olefin monomer having no acidic group is subjected to addition polymerization or ring-opening polymerization with a monomer copolymerized with the material as needed, and It is required to synthesize an alicyclic olefin resin having no acidic group by hydrogenating an unsaturated bond portion, and to make the alicyclic olefin resin with acrylic acid, methacrylic acid, and α-ethyl in the presence of a radical initiator. Acrylic acid, 2-hydroxyethyl (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, internal cis-bicyclo [2 · 2 · 1] hept-5 -ene-2,3 -di Unsaturated carboxylic compounds such as carboxylic acids, methyl-endos-bicyclo [2.2.1] hept-5-ene-2, 3-dicarboxylic acids, and the like, or esters thereof; maleic anhydride, Unsaturated carboxylic acid anhydrides such as chlorinated maleic anhydride, butenyl succinic anhydride, tetrahydrophthalic anhydride, citraconic anhydride, etc.-14-200302399 are modified by a method (i) to synthesize them. Further, the alicyclic olefin resin having an acidic group can be obtained by a method (I I) of copolymerizing an alicyclic olefin monomer having no acidic group and an alicyclic olefin monomer having an acidic group. At this time, the form of polymerization is addition polymerization and ring-opening polymerization, and after the polymerization, addition may be performed as needed. In the method (I), the alicyclic olefin resin having no acidic group can be obtained by addition polymerization of aromatic olefins such as styrene, α-methylstyrene, divinylbenzene, vinylnaphthalene, and vinyltoluene. The aromatic ring of the polymer is hydrogenated to form a resin having the same structural unit as the structural unit derived from the alicyclic olefin monomer. The alicyclic olefin resin may be obtained by copolymerizing an alicyclic olefin monomer and a monomer copolymerizable therewith. When a monomer having an acidic group can be used as the copolymerizable monomer in the method (I), an alicyclic olefin resin having an acidic group can be directly obtained. In the above method (II), in particular, in the presence of a catalyst containing an organic ruthenium compound having a neutral electron-donating ligand as a main component, an alicyclic olefin monomer having no polar group and a lipid having a polar group are used. When the ring-opening olefin monomer is subjected to ring-opening metathesis copolymerization, and if necessary, the substituent is modified by hydrolysis or the like, an alicyclic olefin resin having a narrow molecular weight distribution can be obtained. The catalyst used in this method is a catalyst whose main component is an organic ruthenium compound coordinated with a neutral electron-supplying ligand. The neutral electron-supplying ligand constituting the organic ruthenium compound is a compound that coordinates a negatively charged anionic ligand when the ruthenium is decoupled from the central metal. At this time, there may be a counter anion, and it is also possible to have a ruthenium cation and an anion forming an ion pair as a counter ion. -15-200302399 Specific examples of monomers used in the preparation of the alicyclic olefin resin are described below. Cycloaliphatic olefin monomers without an acidic group such as bicyclo [2 · 2. .1] heptane-2-Huoxi (common name: pro-norbornene), 5-methyl-bicyclo [2 · 2 · 1] heptane -2 -ene, 5,5- dimethyl-bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-butyl-bicyclo [2.2.1] Hept-2-ene, 5-hexyl-bicyclo-2 -ene, 5-octyl-bicyclo [2.2.1] hept-2-ene, 5-octadecyl-bicyclo [ 2 · 2 · 1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylene-bicyclo [2.2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] heptan-2 · dilute, 5-propenyl-bicyclo [2.2.1] hept-2-ene, 5-methoxy-hydrocarbylmethyl-bicyclo [2 · 2 · 1] hept-2-ene, 5-cyano-bicyclo [2 · 2 · 1] hept-2-ene, 5-ethoxycarbonyl-bicyclo [2.2.1] hept-2-ene , Bicyclo [2.2.1] hept-5-enyl-2-methylpropionate, bicyclo [2 · 2 · 1] hept-5-enyl-2-methyloctanoate, 5_jing Methylmethylbicyclo [2.2.1] hept-2-ene, 5, 6-bis (hydroxymethyl) -bicyclo [2.21] hept-2-ene, 5-hydroxy-I-propylbicyclo [2.2 .1] hept-2-ene, 5,6-di-residue-bicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-2-enyl-5, 6-dijunction Acid imine, 5-ring Amyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexenyl-bicyclo [2 · 2 · 1] Hept-2-ene, 5'phenyl-bicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.12'5] dec-3,7-diene (common name: dicyclopentadiene ), Tricyclic [4 · 3 · 0 · 12, 5] dec-3 -ene, tricyclic [4.3.0.I2,5] eleven-3, 7-diene, tricyclic [4 · 3 · 0 I2,5] undec_ 3, 8-diene, tricyclic [4.3.0.I2,5] undec-3-ene, tetracyclic [7 · 4.0.11 (), 13.02 · 7] 13 _2,4,6-11-tetraene (alias: 1,4-methanol-tetrahydrofluorene), tetracyclic [Sj.O.l11'14 』2 · 8] fourteen-200302399

3,5,7,12-11-tetraene (alias: 1,4-methanol-1,4,4,5,10,103-hexahydroanthracene), tetracyclic [4 · 4. 0 · 12 '5. Γ · 1Q] dodec-3-ene (common name: tetrahydrocyclododecene), 8-methyl-tetracyclo [4.4.0.12,5 · Γ, 1 ()] dodec-3- Ene, 8-ethyl-tetracyclo [4.4.0.12'5.17'1Q] dodec-3-ene, 8-methylene-tetracyclo [4.4.0. I2, 5.17, 1G] dodec-3-ene , 8-ethylene-tetracyclo [4.4.0. I2'5.17'1G] dodec-3-ene, 8-vinyl-tetracyclo [4.4.0. I2'5.17'1G] dodec-3- Ene, 8-propenyl-tetracyclo [4.4.0.12,5.17'1G] dodec-3-ene, 8-methoxycarbonyl-tetracyclo [4.4.0. I2'5.17, 1Q] dodec-3- Ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0. I2,5.17'1G] dodec-3-ene, 8-hydroxymethyl-tetracyclo [4.4.0. I2,5.17 , 1Q] dodec-3-ene, 8-hydroxycarbonyl-tetracyclo [4.4.0. I2,5.17'1G] dodec-3-ene, 8-cyclopentyl-tetracyclo [4.4.0. I2 ' 5.17'1Q] dodec-3-ene, 8-cyclohexyl-tetracyclo [4.4.0.12'5.17'1G] dodec-3-ene, 8-cyclohexenyl-tetracyclo [4.4.0.12,5 · Γ'1 ()] dodec-3-ene, 8-phenyl-tetracyclic [4.4.0.12, 5.17, 1 ()] dodec-3-ene, pentacyclic [6.5. 1.1 3,6.0 2,7.0 9'13] Pentadec-3,10-diene, hexacyclo [7.4.0.13,6.11 (), 13.02,7] Penta-4,11-diene, 5-phenyl Bicyclo [2.2.1] hept-2-ene, tetracyclo [6.5.0. 12,5.08,13] tridecyl-3, 8,1 0,1 2 -tetraene (also known as 1,4-methanol -1,4, 4 a, 9 a -tetrahydrofluorene), tetracyclic [6 · 6 · 0 · 12,5 · 08,13] thirteen-3,8,10,12-tetraene (also known as 1,4-methanol-1,4,4 &, 5,10,1 (^-hexahydroanthracene), 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2- Methylbutyl) -1-cyclohexene, cyclooctene, 3 a, 5,6,7 a -tetrahydro-4,7 -methanol-1 fluorene -indene, monocyclic cycloolefins such as cycloheptene; Vinyl cyclohexene or ethylene cycloaliphatic hydrocarbon monomer of vinyl cyclohexene; -17-200302399 cyclopentadiene, cyclohexadiene alicyclic conjugated diene monomer, etc. Acidic group Cycloaliphatic olefin monomers having a hydroxycarbonyl group such as 5-hydroxycarbonylbicyclo [2 · 2.1.1] hept-2-ene, 5-hydroxycarbonylmethylbicyclo [2.2.1] heptan-2- Ene, 5,6-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5 -Dihydroxy Dicyclo [2.2.1] hept-2-ene, 5-hydroxycarbonyl-5-hydroxycarbonylmethylbicyclo [2.2.1] hept-2-ene, and other bicycloheptene derivatives; 5-hydroxycarbonyl Four rings [4 · 4 · 0. I2 · 5 · I7,1. ] Dodec-3-ene, 5-hydroxycarbonylmethyltetracyclo [4 · 4.0 · 12.5.17,1 ()] Dodec-3-ene, 5,6-dihydroxycarbonyltetracyclo [4.4. 0. I2.5. 17, 1G] dodec-3-ene, 5-methyl-5-hydroxycarbonyl tetracyclo [4 · 4 · 0.12 · 5.17, 1 ()] dodec-3-ene, 5- Hydroxycarbonyl-5-hydroxycarbonylmethyltetracyclo [4.4.0.12.5.17G] dodec-3-ene; 8-hydroxycarbonyltetracyclo [4.4.0.12.2.5.I7,1. ] Twelve-3-store, 8-mercaptomethyl tetracycline [4.4.0.12.5.17, 1 ()] dodec-3-ene, 8,9-dihydroxycarbonyl tetracyclic [4.4.0.125. Γ, 1 {)] dodec-3-ene, 8-methyl-8-hydroxycarbonyl tetracyclo [4.4.0.125.17'1 ()] dodec-3-ene, 8-methyl-8,9 -Dihydroxycarbonyltetracyclo [4 · 4.0.12.5 · Γ'1 ()] dodec-3-ene, 8-hydroxycarbonyl-8-hydroxycarbonylmethyltetracyclo [4.4.0.12 5.1 ?, 1 ()] Tetracyclododecene derivatives such as dodec-3-ene; 11-hydroxycarbonyl hexacyclic [6.6.l·l3'6 · 11 () '13 · 02 · 7 · 09, 14] 17-4- Alkenes, ll-hydroxycarbonylmethylhexacyclo [6 · 6 · 1 · l3'6.11 () 'l · 3 · 02 · 7 · 09, l · 4] hepta-4-ene, 11, 12-secondary Hexacyclic [6.6.1.13, 6.11 °, 13.〇27.09, 14] Hepta-4-ene, 11-methyl-11, 12-dihydroxycarbonyl hexacyclic + 11-hydroxycarbonyl- 11-Hydroxymethylhexacyclo-1 18-200302399 9,14] Hexadecene derivatives such as hepta-4-ene and the like. The alicyclic orthodontic monomers which are the two residual acid anhydride residues of the acidic group are, for example, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, 5-methylbicyclo [ 2 · 2 · 1] Bicycloheptane derivatives such as hept-2-en-5,6-di-anhydride, tetracyclo [4.4.0.12.5.17, 1 ()] dodec-3-ene-8, 9-dicarboxylic anhydride, 8-methyltetracyclo [4.4.0.12.5.17,1 ()] dodec-3-ene-8,9-dicarboxylic anhydride, tetracyclic dodecene derivatives, hexacyclic [ ^^^ renguang '㈠ ^ 人 ...' hepta-decene-11,12-dicarboxylic anhydride, U_methylhexacyclofluorene · 6 · 1 · 13'6 · 11 ^ '13 · 02 · 7 · 09 '14] Hexadecene 4-ene-1,1,2-dicarboxylic anhydride and other hexacycloheptadecene derivatives. The alicyclic olefin monomer can be used singly or in combination of two or more ° Monomers copolymerizable with the alicyclic olefin monomer such as ethylene, propylene, 1-butene, pentene, 1-hexene, 3-methyl Methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4- Dimethyl-buhexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene , 1-dodecene, 1-tetradecene, 1-hexadecene, octadecene, 1-icosene, etc. 2 or 20 carbon or ethylene olefins; 1,4-hexadiene, Non-conjugated dienes such as 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, etc .; and the like. These monomers can be used alone or in combination of two or more. A method for adjusting the weight-average molecular weight of the alicyclic fine warp polymer, for example, when the ring-opening polymerization of the alicyclic olefin is added to the total amount of the monomer, the molecular weight of the ethylene compound or the diene compound is 0.1. Method of adjusting the agent. When the molecular weight adjuster is used in a small amount, a poly-19-200302399 compound having a higher weight average molecular weight is prepared, and when it is excessive, a polymer having a lower weight average molecular weight is produced. Ethylene compounds used as molecular weight adjusters such as 1 -Α-olefin compounds such as butan, 1-pentene, 1-hexene, and 1-octene; styrene compounds such as styrene and vinyl toluene; ethyl vinyl ether, isobutyl vinyl ether, allyl Ether compounds such as glycidyl ether; halogen-containing ethylene compounds such as allyl chloride; oxygen-containing ethylene compounds such as allyl acetate, allyl alcohol, and glycidyl methacrylate; ammonium acrylate Etc. nitrogen-containing ethylene compounds; etc. Diene compounds such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl-1 Non-conjugated diene compounds such as 1,5-hexadiene; 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene Conjugated diene compounds such as alkene, 1,3-pentadiene, 1,3-hexadiene, and the like. Among these, an α-olefin compound of 1-hexene is more preferable. An alicyclic olefin resin obtained by using the monomer, such as a ring-opening polymer of an alicyclic olefin monomer, a hydrogenated product thereof, and an alicyclic ring Addition polymer of olefinic olefin monomer, addition polymer of alicyclic olefin monomer and ethylene compound, monocyclic cyclic olefin polymer, alicyclic conjugated diene polymer, ethylene alicyclic hydrocarbon polymer And its hydrogenated products, aromatic ring hydrogenated products of aromatic olefin polymers, and the like. Among these, ring-opening polymers with alicyclic olefin monomers and their hydrogenated products, addition polymers of alicyclic olefin monomers, addition polymers of alicyclic olefin monomers and ethylene compounds 2. The aromatic ring hydrogenation product of the aromatic olefin polymer is preferable, and the more preferable one is the hydrogenation product of the ring-opening polymer of the alicyclic olefin monomer. The alicyclic olefin resin can be used alone or in combination of two or more. -20- 200302399 (B) The acid generator used in the present invention is a compound that generates an acid by irradiation with active radiation. There is no particular limitation on the type of acid to be generated. In order to obtain a positive pattern, a compound having a weakly acidic group such as a carboxyl group or a phenolic hydroxyl group is preferred, and more preferably, a compound such as quinonediazide sulfonate is used. The carboxyl group produces an acidic compound. The method for preparing the quinonediazide sulfonate compound is not particularly limited. The 1,2-naphthoquinonediazide is made in a solvent such as acetone, dioxane, tetrahydrofuran and the like in the presence of a base such as triethylamine. Quinonediazidesulfonic acid halide with 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2-bis (4-hydroxyphenyl) propane, ginseng (4-hydroxyphenyl) methane, 1,1,1-ginseng (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-methyl (4-Hydroxyphenyl) ethane, 1,1,3-ginseng (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, phenolic resin, phenols and dicyclopentane An oligomer obtained by copolymerizing diene (Patent No. 3 09 09 9 1) and other phenol compounds having one or more phenolic hydroxyl groups are reacted. The esterification rate of the quinonediazidesulfonic acid ester compound is defined by the ratio of the hydrogen atom of the phenolic hydroxyl group of the phenol compound to the quinonediazidesulfonic acid residue. The esterification rate is usually 20 to 100 mol%, preferably 40 to 100 mol%, more preferably 50 to 100 mol%, and most preferably 60 to 100 mol%. If the esterification rate is too low, the dissolution inhibiting effect of the unexposed portion (unirradiated portion) is low, and the resolution and the residual film rate tend to decrease. Further, as the acid generator, carboxylic acids of diaryliodophosphonium salt, triarylphosphonium salt, phenyldiazo iron salt, sulfonyliminosulfonate derivative, tosylsulfonium compound, and benzyl derivative can be used. Ester compounds, halides of trioxane derivatives, etc.-21- 200302399 Organic halogen compounds, α, α, -bis (sulfofluorenyl) -diazomethane compounds, α-carbonyl-α-αsulfonamidyldiazo Methane compounds, maple compounds, organic phosphorus ester compounds, organic acid amine compounds, organic amine imine compounds and other strong acid-generating compounds can also form negative patterns. The amount of the acid generator is usually 0.5 to 100 parts by weight, preferably 1 to 50 parts by weight, and more preferably 10 to 30 parts by weight for 100 parts by weight of the alicyclic olefin resin having an acidic group. . If the amount of the acid generator is too small, the residual film rate or resolution deteriorates, while if it is too much, the heat resistance or light transmittance will decrease. The cross-linking agent of the component (C) used in the present invention has a function of reacting with an alicyclic olefin resin and forming a cross-linking structure between the alicyclic olefin resin, and specifically, one having two or more reactive groups Compound. Examples of the reactive group include an amino group, a carboxyl group, a hydroxyl group, an epoxy group, an isocyanate group, and a vinyl group. Specific examples of the cross-linking agent include aliphatic polyamines such as hexamethylenediamine; aromatic polyamines such as 4,4, -diaminodiphenyl ether and diaminodiphenyl maple; 2,6-bis ( 4'-azidobenzylidene) cyclohexanone, 4,4'-diazide diphenyl maple, and other azide compounds; Nylon, polyhexamethylene diamine terephthalate, polyhexamethylene Polyamines such as ammonium isophthalate; N, N, N ', N ,, N ,,, N ,,-(hexaalkoxymethyl) melamines, etc .; N, N' , N ", N- (tetraalkoxymethyl) acetylene urea and other acetylene ureas; ethylene glycol di (meth) acrylate, epoxy acrylate resins and other acrylate compounds; hexamethylidene Isocyanate-based polyisocyanates, isophorone diisocyanate-based polyisocyanates, xylyl diisocyanate-based polyisocyanates, and other isocyanate-based compounds; hydrogenated diphenylmethyl-k-isocyanate-based polyisocyanates; 1,4-di- ( Methylmethyl) cyclohexanone, 1,4-di- (hydroxymethyl) orbornorane; 1,3,4-trihydroxycyclohexanone; lipid-containing 22-22 200302399 epoxy of cyclic structure Compounds, resins, etc. These can be used as one or two or more mixtures. Among these crosslinking agents, N-alkoxymethylated melamine or N-alkoxymethyl is used in terms of heat resistance. The acetylated acetylene urea is preferred. These compounds include PL_ 丨 170, PL-1174, UFR65, CYMEL3 00, CYMEL303 (the above are made by Mitsui Seidick), BX-4000, Nikarak ) MW-30, MX290 (above manufactured by Sanwa Chemical Co., Ltd.) and other commercially available products are easy to obtain. In addition, in terms of better adhesion to substrates of resin films formed from radiation-sensitive resin compositions, An isocyanate-based compound is preferably used. The amount of the crosslinking agent is usually 1 to 100 parts by weight, preferably 5 to 80 parts by weight, and more preferably 10 to 70 parts by weight based on 100 parts by weight of the alicyclic olefin resin. It is preferably 20 to 50 parts by weight. If the amount of the cross-linking agent used is excessive, heat resistance, electrical characteristics, and water absorption are likely to be insufficient. The solvent of the component (D) used in the present invention may be used. If the above components are dissolved or dispersed, the solvent is, for example, methanol, ethanol, propanol, butanol , 3 -methoxy-3 -methyl butanol and other alcohols; cyclic ethers such as tetrahydrofuran, dioxane, etc .; methyl cellosolve acetate, ethyl cellosolve acetate, etc. Fiber esters; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono 3 -butyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, Alcohol ethers such as ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether; propylene glycol alkyl ether acetates such as propylene glycol propyl ether acetate; aromatics such as benzene, toluene, and xylene Ketones such as hydrocarbons, methyl ethyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-heptanone, etc .; ethyl 2-hydroxypropionate, 2-hydroxy-2- Ethyl methylpropionate, ethyl 2-hydroxy-2-methylpropionate-23- 200302399, ethyl ethoxyacetate, ethyl glycolate, 2-hydroxy-3 -methylbutyrate, 3 -Methyl methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3 -Methyl ethoxypropionate, ethyl acetate, butyl acetate, ethyl lactate, etc. Esters; N - methyl acyl amine, N, N - dimethylacetamide, dimethyl sulfoxide, [gamma] -butyrolactone, etc. aprotic polar solvent; and the like. These solvents are used in an amount sufficient to dissolve or disperse each component uniformly. The radiation-sensitive resin composition of the present invention may contain polyethylene oxide lauryl ether, polycycloethane dilaurate, etc. for the purpose of preventing streaks (after coating lines) and improving the developability. Non-ionic surfactants; Yefton cloth (transliteration) by Shin Akita Chemicals, Mekafak (transliteration) by Dainippon Ink Chemical Industry Co., Ltd., and Fronla by Sumitomo Seriyemu (transliteration) (Transliteration), fluorine-based surfactants such as Asahi Carton (transliteration) manufactured by Asahi Glass Company; silane-based surfactants such as organic silicone polymer KP series produced by Shin-Etsu Chemical Co .; Kyoeisha oil A variety of surfactants such as acrylic copolymer copolymer surfactants, such as polyfuron (transliteration), manufactured by Chemical Industry Corporation. The surfactant is usually 2 parts by weight or less, preferably 1 part by weight or less, based on 100 parts by weight of the solid content (components other than the solvent) of the radiation-sensitive resin composition, and is used as needed. In the radiation-sensitive resin composition of the present invention, for the purpose of improving adhesion to a substrate, a functional silane coupling agent such as γ-glycidoxypropyltrimethoxysilane may be added as an adhesion assistant. The amount of the bonding aid is usually 20 parts by weight or less, preferably 0.05 to 10 parts by weight, and more preferably 1 to 10 parts by weight for 100 parts by weight of the alicyclic olefin resin having an acidic group. -200302399 In addition, the radiation-sensitive resin composition of the present invention may contain a sensitizer, an antistatic agent, a storage stabilizer, an antifoaming agent, a pigment, a dye, and the like, as necessary. 2. The above components are mixed in a conventional manner, and dissolved or dispersed in a solvent to adjust the radiation-sensitive resin composition. The solid content concentration of the prepared radiation-sensitive resin composition of the present invention is not particularly limited, but it is usually 5 to 40% by weight. · The prepared radiation-sensitive resin composition is preferably a homogeneous solution. In this case, a filter of 0 · 2 to 1 μm is used to remove the foreign matter, and then it is preferably used. The radiation-sensitive resin composition of the present invention is suitable as a protective film for a device display device, an integrated circuit device, or the like, or a color filter for a liquid crystal display, a flattening film for flattening the surface of an element, or wiring, Materials for various types of resin films for electronic parts including electrically insulating insulating films (such as interlayer insulating films and soldering photoresist films for thin insulating liquid crystal display elements or integrated circuit elements). Φ The radiation-sensitive resin composition of the present invention is coated on a substrate to form a resin film ', and activated radiation is irradiated in a pattern on the resin film to form a latent image pattern on the resin film. By bringing a resin film having a latent image pattern into contact with a developing solution, the pattern can be developed. The method of forming a resin film on a substrate may be a method of coating the surface of the substrate with the radiation-sensitive resin composition of the present invention and drying it, and directly forming a resin film on the substrate, or a method of forming at least one side of A film made of a resin such as a diester film, a polypropylene film, a polyethylene film, or the like is coated on a body with a radiation-sensitive resin composition of the present invention and dried. After the resin film is formed on the carrier, A method in which a resin film of a carrier is superposed on a substrate. When the carrier-attached resin film is superposed on the substrate, it is preferable to heat and press the resin film using a pressure laminator, a pressure press, a vacuum laminator, a vacuum press, a roll laminator, or the like. The temperature during heating and pressure melting is usually 30 ~ 250 ° C, preferably 70 ~ 20 (TC, the pressure melting force is usually 10kPa ~ 20MPa, preferably 100kPa ~ 10MPa, and the pressure melting time is usually 30 seconds ~ 5 hours, preferably 1 minute to 3 hours, the atmospheric pressure is usually adjusted to 100 kPa to IPa, and preferably 40 kPa to 10 Pa when heating and pressing. The surface of the substrate or the carrier is coated with the radiation of the present invention. The method of the resin composition may be, for example, various methods such as a spray method, a roll coating method, and a spin coating method. Then, the obtained coating film is dried by heating to obtain a resin film having no fluidity. Directly on the substrate surface The heating conditions when forming the resin film vary depending on the type of each component, the mixing ratio, etc., and it is usually heated at 60 to 120 ° C for 10 to 600 seconds. The radiation-sensitive resin composition is coated on the surface of the substrate and dried. In the method of directly forming a resin film on a substrate, the heating for drying is generally referred to as pre-bake. The obtained resin film is irradiated with active radiation and a latent image pattern is formed on the resin film. Active radiation Of There are no special restrictions, such as ultraviolet, far ultraviolet, X-rays, electron rays, proton beams, etc. Among them, visible rays and ultraviolet rays are preferred. The amount of radiation can be arbitrarily set depending on the type or thickness of the resin film. The formation of the pattern can be A method of irradiating active radiation through a photomask 'a method capable of directly drawing by an electron beam, etc.-2 6-200302399 After radiation exposure, a resin film having a latent image pattern on a substrate is brought into contact with a developing solution' The irradiated part is removed and the latent image pattern is developed (developed). It can be heated before development (PEB treatment: post exposure bake). PEB treatment It can reduce development residues such as unnecessary resin components that must be removed when dissolved in the development solution. Cycloaliphatic olefin resins have alkali-soluble polar groups, especially when they have acidic groups, and it is easier to flow out through the development solution, so The developing solution is generally an aqueous solution in which alkali compounds are dissolved in water. The alkali compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methylsilicate, ammonium water, etc. Inorganic bases; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine, methyldiethylamine, and N-methylpyrrolidone ; Alcohol amines such as dimethylethanolamine, triethanolamine; Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, choline and other quaternary ammonium salts; pyrrole, piperidine, 1 Alicyclic amines such as 8-diazobicyclo [5 · 4 · 0] undec-7-ene, 1,5-diazobicyclo [4 · 3 · 0] non-5-ene; Etc. These alkali compounds can be used alone or in combination of two or more. A water-soluble organic solvent such as methanol, ethanol, or a surfactant can also be added to the developing solution in an appropriate amount. The imaging solution is dissolved at a rate of 1 μm / min or more at the irradiated portion of the resin film formed using the radiation-sensitive resin composition, and the undissolved portion of the resin film is dissolved at a rate of 0.5 μm / min or less. It is particularly good to obtain particularly excellent resolution and residual film ratio. From this point of view, when the radiation-sensitive resin composition of the present invention is used, the concentration of the developer used is 〇1〜1 · 〇 ％ by weight, preferably -27- 200302399 is 0 · 1 ~ 0 · 8% by weight. Tetramethylammonium hydroxide aqueous solution is suitable. The development time is usually 30 to 180 seconds. The method for contacting the developing solution with the resin film having a latent image pattern is not particularly limited, and for example, a stirring method, a spray method, or a dipping method can be used. The developing temperature is not particularly limited, but is usually 15 to 35 ° C, preferably 20 to 30 ° C. In this way, a resin film having a desired pattern is formed on the substrate. After a pattern is formed on the resin film by development, if it is necessary to remove unnecessary development residues remaining on the inner surface of the substrate and the end of the substrate, the substrate and the rinse solution can be contacted by a conventional method. The substrate in contact with the rinse liquid is usually dried by compressed air or compressed nitrogen to remove the rinse liquid from the substrate. If necessary, the entire surface of the patterned resin film may be irradiated with active radiation. After the pattern is formed on the resin film of the substrate ', the resin film can be hardened by heating if necessary. The heating method is performed by a heating device such as a hot plate and an oven. The heating temperature is usually 150 to 25 (TC, preferably 180 to 220 ° C). The heating time is usually 5 to 60 minutes when using a hot plate, and 30 to 90 minutes when using an oven. Post-baking is performed at a low temperature. It is preferable to carry out in an oxygen atmosphere, specifically, an oxygen concentration of 10 ppm or less. As described above, using the radiation-sensitive resin composition of the present invention, a resin film is formed on a substrate, and the resin film is irradiated in a pattern. Active radiation 'forms a latent image pattern on a resin film, and then forms a pattern on the resin film by a pattern forming method in which the resin film is brought into contact with a developing solution to develop the pattern. The resin film formed with the pattern is suitable for use as Protective film, flattening film, interlayer insulating film, etc. Resin film for electronic parts, etc. -28- 200302399 (4) Embodiments [Examples] The present invention will be described in more detail by means of synthesis examples and examples in the following. The parts and% in each example are based on weight (mass basis) when there is no particular limitation. [Synthesis Example 1] 70 parts of 8-hydroxycarbonyltetracyclo [4.4.0.12, 5.17, 1G] -dodeca-3 · ene , 30 copies of the four rings [4 · 4 · 0 I2'5 · 17'1G] -Dodecyl-3-ene '10 parts 1-hexene, 0.04 parts 1,3-di-Lylimidazolium-2-iridium) (tricyclohexylphosphine) benzyl methylene Ruthenium dichloride and 400 parts of tetrahydrofuran were placed in a glass pressure-resistant reaction vessel substituted with nitrogen, and heated to 70 ° C and stirred for 2 hours to prepare a reaction solution. It was confirmed by gas chromatography that no monomer remained in the reaction solution. The obtained reaction solution was poured into a large amount of n-hexane to precipitate a solid content. The obtained solid component was washed with n-hexane, and then dried under reduced pressure at 100 ° C. for 18 hours to obtain a ring-opening metathesis copolymer as a white solid. Add 1000 parts of the ring-opening metathesis copolymer, 400 parts of tetrahydrofuran, and 5 parts of platinum / carbon (10% platinum) as hydrogenation catalysts to a pressure cooker with a stirrer. Hydrogenated at 60 ° C for 8 hours. After the reaction solution was filtered, it was solidified and dried in a large amount of n-hexane in the same manner as described above to obtain an alicyclic olefin resin (polymer a) having an acidic group having a hydrogenation rate of 100% (measured by W-NMR spectrum). [Synthesis Example 2] Except changing each to 78 parts of 8-hydroxycarbonyltetracycline [4 · 4 · 0 · 12'5 · Γ'1 ()]-dodec-3-ene and 22 parts of tetracyclo [4.4 .0.12'5.17'1 ()]-dodecane-3-ene and 8 parts of 1-hexene were prepared in the same manner as in Synthesis Example 1 to obtain an alicyclic olefin resin having a hydrogenation rate of 100% and an acidic 200302399 group. (Polymer b) ° [Synthesis Example 3] Except changing each to 71 parts of 8-hydroxycarbonyl tetracyclo [4 · 4 · 0 · 12,5 · 17'1 ()]-dodec-3-ene, 29 Parts of tetracycline [4.4 · 0.12'5 · Γ'1 ()]-dodecane-3-storage, 20 parts of 1-hexene, the same hydrogenation rate as 100% was obtained in the same manner as in Synthesis Example 1, and acidity was obtained. Cycloaliphatic olefin resin (Polymer c) ° [Synthesis Example 4] Except changing each to 76 parts of 8-hydroxycarbonyltetracycline [4.4.0.12, 5.17, 1 ()]-dodec-3-ene, 24 parts of tetracycline [4 · 4 · 0 · 12,5.Γ, 1 ()]-dodec-3-ene and 8 parts of 1-hexene were prepared in the same manner as in Synthesis Example 1 to obtain a hydrogenation rate of 10. 0% alicyclic olefin resin (polymer d) with acid decadecyl. [Synthesis Example 5] In the method disclosed in Synthesis Example 5 of Japanese Patent Application Laid-Open No. 1 1-52574, the temperature of the catalyst was changed from 60 ° C to 80 ° C, and the polymerization holding temperature was changed from 80 ° C to At 110 ° C, using the method described in Synthesis Example 5 of this publication as a reference, an alicyclic olefin resin (polymer e) having an acidic group having a hydrogenation rate of 100% and a hydrolyzation rate of 75% can be obtained. Specifically, for example, polymer e is synthesized by the following method. 250 parts of 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.I2,5 "7,10] -3-dodecene, 180 parts of 1-hexene, and 750 parts of toluene were added In a reaction vessel substituted with nitrogen, heat to 80 ° C. To this was added 0.62 parts of a toluene solution of trimethylamine (1.5 mol / 1), and 3.7 parts of a 3-C4H5OH / CH3OH modified (3-C4H5OH / CH30 / W = 0.35 / 0.3 / l; Molar ratio) of WCU solution (concentration 0. 05 Molar / 1), heated and stirred at 110 ° C for 3 hours to prepare a soil solution of 200302399. The polymerization conversion rate of this polymerization reaction was 90%. 4,000 parts of the obtained polymer solution was placed in an autoclave, and 30.48 parts of RuHC1 (CO) [P (C6H5) 3] was added thereto under a hydrogen pressure of lO. 〇kg / cm2, reaction temperature of 16 5 ° C under heating and stirring for 3 hours. After the obtained reaction solution was cooled, the hydrogen was depressurized to prepare a hydrogenated polymer solution. The thus-obtained hydrogenated polymer was poured into a large amount of methanol to solidify the polymer. The hydrogenation rate of the obtained hydrogenated polymer was substantially 100%. 100 parts of the obtained hydrogenated polymer, 100 parts of N-methyl-2-pyrrolidone, 500 parts of propylene glycol, and 84.5 parts of potassium hydroxide (concentration 85%) were added to the reactor, and stirred at 190 ° C for 1.5 hours. The obtained reaction solution was poured into a large amount of a mixed solution of water, tetrahydrofuran and hydrochloric acid to coagulate the hydrolysate. The coagulated polymer was washed with water and dried to obtain polymer e as a hydrolyzed polymer. The hydrolyzation rate of the obtained hydrolyzable polymer was 75%. [Synthesis Example 6] An alicyclic olefin resin having an acidic group having a hydrogenation rate of 100% and a hydrolyzation rate of 75% was prepared in the same manner as in Synthesis Example 5 except that the polymerization holding temperature was changed from 110 ° C to 100 ° C. Polymer f). [Synthesis Example 7] A cycloaliphatic olefin resin having an acidic group having a hydrogenation rate of 100% and a hydrolytic decomposition rate of 75% was prepared in the same manner as in Synthesis Example 5 except that the polymerization holding temperature was changed from 110 ° C to 9 ° C ( Polymer g) [Comparative Synthesis Example 1] Based on the method disclosed in Synthesis Example 5 of JP-A No. 1 1-52 5 74, 8-methyl-8-methoxycarbonyl tetracyclic [4.4.0.12 , 5.17,1 ()]-3-twelve-31- 200302399 Ring-opening polymerization of ene was used to prepare a ring-opening polymer having a weight average molecular weight of 17,000. Then, after hydrogenating the obtained ring-opening polymer, Hydrolysis was performed for 1.5 hours to obtain an alicyclic olefin resin (polymer h) having a hydrogenation rate of 100%, a hydrolyzation rate of 75%, and an acid group. [Comparative Synthesis Example 2] Except for 90 parts each 8-hydroxycarbonyl tetracyclo [4.4.0. I2,5. 17,1G] dodec-3-ene, 10 parts of tetracyclo [4 · 4 · 0 · 12,5 · 17,1 ()] 12 Except for carbon-3-ene and 9 parts of 1-hexene, alicyclic olefin resin (Polymer I) having a hydrogenation rate of 1000%, a hydrolytic decomposition rate of 75%, and an acid group was prepared in the same manner as in Synthesis Example 1. The physical properties of the polymers a to I obtained in the above synthesis examples are shown in Table 1.

-3 2-200302399 Table 1 Polymer coating copolymerization ratio (mo 1%) Acid group ratio (mol%) Weight average molecular weight (Mw) Molecular weight distribution (Mw / Mn) Index Cl Index C2 Synthesis Example 1 a TCDC (70 ) TCD (30) 70 0.53x 104 1.81 677-Synthesis Example 2 b TCDC (78) TCD (22) 78 0.78χ 104 1.51 616 — Synthesis Example 3 c TCDC (71) TCD (29) 71 0 · 37χ IO04 1.71 582 A Synthesis Example 4 d TCDC (76) TCD (24) 76 0.81χ IO04 1.72 566 — Synthesis Example 5 e TCDE (100) — 75 1.65χ IO4 2.45 — 262 Synthesis Example 6 f TCDE (100) — 75 1.6χ ΙΟ4 2.92 —— 153 Synthesis Example 7 g TCDE (100) — 75 1 · 8χ IO4 3.15 — 129 Comparative Synthesis Example 1 h TCDE (100) — 75 1.7χ IO4 3.5-91 Comparative Synthesis Example 2 i TCDC (76) TCD (24 ) 90 0.68χ ΙΟ4 1.61 214 —

In Table 1, the symbols in the column of copolymerization ratio are as follows. TCDC: 8-hydroxycarbonyl tetracyclic [4.4.0.12, 5.17, 1G] Dodecane-3-ene is derived from the repeat unit spring TCD: tetracyclic [4.4.0 · I2'5. Γ'1 ()] twelve Derivative unit derived from carbon-3-ene TCDE ·· 8-methyl-8-methoxycarbonyl tetracyclic [4 · 4.0.12,5.Γ'1 ()]-derived from dodecyl-3-ene Repeating unit [Example 1] For 100 parts of the polymer a obtained in Synthesis Example 1, 550 parts of cyclohexanone and 20 parts by weight were used as 1,2, quinonediazide compounds. 2,5-Dimethyl-4-hydroxyphenyl) -3-phenylpropane (1 mole) and 丨, 2-naphthoquinone diazide-33- 200302399 nitrogen-5 -sulfonic acid chloride (1.9 Mol) condensate, 25 parts of CYMEL 3 0 as a cross-linking agent, 5 parts of r-glycidylpropyltrimethoxysilane as an adhesion aid, and 0.05 part of the meka method as a surfactant Grams (transliteration) F 172 [manufactured by Daiichi Ink Chemical Industry Co., Ltd.] after mixing and dissolving, a polytetrafluoroethylene filter with a pore size of 0.45 μm was used to prepare a radiation-sensitive photosensitive resin composition solution. The solution was spin-coated on a silicon substrate, a glass substrate, and a silicon oxide film substrate (hereinafter referred to as a "stepped substrate") having a step difference of 1 μm, and prebaked at 90 ° C on a hot plate. 〇μηι 的 涂膜。 Bake for 2 minutes to form a film thickness of 3. Ομηι. A mask having a predetermined pattern was placed on the obtained silicon substrate with a coating film, and ultraviolet rays with a wavelength of 3 65 nm and a light intensity of 5 mW / cm2 were irradiated in the air for 40 seconds. Secondly, a 0.3% aqueous solution of tetramethylammonium was used for development for 60 seconds at 25 ° C. Next, it was washed with ultrapure water for 1 minute to form a positive-shaped film having a pattern. Then, the entire surface was irradiated with ultraviolet light having a light intensity of 3 6 5 nm at 5 mW / cm 2 for 60 seconds. The silicon substrate, the glass substrate, and the silicon oxide film substrate having a 1 μm step difference were each heated on a hot plate at 200 ° C for 30 minutes, and then baked and patterned to obtain a patterned film. Silicon substrate, glass substrate and stepped substrate. [Examples 2 to 7] Except using polymer b (Example 2), polymer c (Example 3), polymer d (Example 4), polymer e (Example 5), polymer f (implementation Example) 6. Polymer g (Example 7) Substituting polymer a, a silicon substrate, a glass substrate, and a stepped base-34 — 200302399 plate with a patterned film formed thereon were prepared in the same manner as in Example 1. [Comparative Examples 1 and 2] Except that polymer h (Comparative Example 1) and polymer 丨 (Comparative Example 2) were used in place of Polymer a, silicon having a patterned thin film was prepared in the same manner as in Example 1: a substrate, Glass substrate and stepped substrate. : [Evaluation] The film thickness of each silicon substrate obtained above was heated in an oven at 220 ° C for 60 minutes, and the film thickness in the heating clamp was 95% or more. It can be confirmed that the heat resistance dimension stability is excellent. Each of the glass substrates obtained above was a UV-visible near-infrared spectrophotometer (V-5 70) manufactured by JASCO Corporation. The minimum light transmittance (t) at a wavelength of 400 to 80 Onm was 90%. All were good, and transparency was confirmed. Excellent. In addition to these evaluations, the dielectric ratio and water absorption of the alicyclic olefin resin (polymers a to i) used in each example were evaluated by the following methods, and the solvent resistance and resolution measured using the glass substrate obtained above were evaluated. , Residual film rate, and pattern shape. The results are shown in Table 2. · (1) Specific permittivity: The specific permittivity at 1 MHz (room temperature) was measured based on JIS C648 1 and evaluated based on the following criteria. A: ε < 2.60 Β: 2.60 ^ ε < 2.70 C: 2. 70 ^ ε < 2.80 D: 8 ^ 2.80-35- 200302399 (2) Water absorption rate: Measure the water absorption rate (w) based on IS C648 1 'Evaluated on the basis of the following. A: w < 0.05%. B * 0.05% ^ w < 〇.〇7% k C · 0.07% ^ w < 0.1% D * 0.1% ^ w

(3) Solvent resistance: I The glass substrate on which the patterned film was formed was immersed in a dimethylimine at 70 ° C for 30 minutes, and the film thickness change rate (S) 'was measured and evaluated on the basis of the following criteria.

A: 10% > S

B: 10% ^ SC: Swelling becomes large and peels from the substrate, and the thickness change rate cannot be measured (4) Resolution: _ Observing the patterned film formed on the glass substrate with a scanning electron microscope, the line and The minimum pattern size (W) formed by the gap with a line width of 1 ·· 1 is evaluated on the basis of the following. A · W ^ 5μιη Β ·· 5μιη < Ψ ^ ΙΟμπι D ·· W > 1 5μηι (5) Residual film rate:-3 6-200302399 With 0.3wt% tetramethylammonium hydroxide aqueous solution (25 ° C) Development was performed for 1 minute, and the film thickness of the unexposed portion before and after the development was measured using a contact-type film thickness measuring device. After the development (film thickness / film thickness before development) X 1 00 was used as the residual film rate (R), the following criteria were evaluated. Two A: R ^ 95%; B · 93% ^ R < 95% C: 90% ^ R < 9 3% D: 85% ^ R < 90% · E: R < 8 5% < 6) Pattern shape: Observe the patterned line and gap cross sections with a scanning electron microscope, and evaluate them with the following criteria. A: No residue from the radiation-sensitive resin composition, no rectangular shape cracks B: Only the interface between the resin pattern and the substrate is drawn slightly C: There are imaging residues in the gap part Spring-37- 200302399

Table 2 Polymer (parts by weight) Dielectric rate Water absorption Solvent resistance resolution Residual film rate pattern Example 1 a (100) AAAAAA Example 2 b (100) BAAAAA Example 3 c (100) AAABBA Example 4 d (100) BAABBA Example 5 e (100) CCBBBB Example 6 f (100) CCBBCB Example 7 g (100) CCBBDB Comparative Example 1 h (100) CCBDEB Comparative Example 2 i (100) CCBDEC From Table 2 The results show that the radiation-sensitive resin composition (Examples 1 to 7) of the present invention can maintain a balance of specific dielectric properties, water absorption resistance, heat resistance dimensional stability, flatness, and solvent resistance, and can Achieve excellent resolution, residual film rate, and pattern formation. Particularly, when an alicyclic olefin resin (polymers a and b) having an acidic group having a weight average molecular weight of less than 10,000, a molecular weight distribution of 2.0 or less, and an index C1 of 600 or more, excellent resolution and residual film ratio can be obtained. In addition, a repeating unit derived from tetradecyl-3-ene with 8-hydroxycarbonyl tetracyclo [4.4.0.1, 5.17, 1 g] and tetracyclyl [4.4.0.0.12, 5.17, 1G] twelve In the case of the alicyclic olefin resin (polymers a to d) having repeating units derived from carbon-3 ene (Examples 1 to 4), excellent water absorption resistance can be obtained. In addition, when using an alkali-soluble alicyclic olefin resin having a low index ci as described in JP 11-52574 or JP 10-307388 -38-200302399 (Comparative Examples 1 and 2), it is known that the specific dielectric The rate, water absorption, and solvent resistance are slightly poor, and the resolution, residual film rate, and pattern shape are poor. Industrial utilization value: The present invention can produce a radiation-sensitive resin composition having excellent properties, resolution, residual film rate, and pattern shape suitable for the formation of an electrical insulating film. The resin film formed using the radiation-sensitive resin composition of the present invention and the pattern-formed resin film can be suitably used as electronic components such as semiconductor elements, light-emitting diodes, various recordings, etc .; excess coating of hybrid IC, MCM, printed wiring boards, etc. Covering materials; interlayer insulating films for multilayer circuit boards; resin films for various electronic parts, such as the insulating layer of liquid crystal displays. (V) Schematic description: None

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Claims (1)

200302399 Patent application scope 1. A radiation-sensitive resin composition comprising (A) an alicyclic olefin resin having an acidic group, (B) an acid generator, (C) a cross-linking agent, and (D ) The solvent-containing radiation-sensitive resin composition is characterized in that (A) the alicyclic olefin-based resin having an acidic group has a weight average molecular weight of less than 10,000 'and has an index represented by the following formula (1) When C1 is 300 or more 'and the weight average molecular weight is 10,000 or more, the index C2 is 1 2 0 or more when the weight average molecular weight is 10,000 or more, Φ (1) (MW) a5x (AC) 7 · Cl =--XΙΟ5 (ag) 6x (mwd) 2 (where MW is the weight average molecular weight, AC is the average carbon number of the structural unit, AG is the mole number of acid groups in all structural units, and MWD is the molecular weight distribution), (MW) a5X (AC) 2 /, 2 =-X103 (2) (AG) 2X (MWD) 3 (wherein the meaning of each symbol is the same as that of formula (1)). 2. The radiation-sensitive property as described in item 1 of the scope of patent application. A resin composition in which (A) the alicyclic olefin resin having an acidic group has a weight average molecular weight of 500 to 20000. 3 The radiation-sensitive resin composition in which the acidic group is a phenolic hydroxyl group, a carboxyl group, a dicarboxylic anhydride residue, a sulfonic acid residue, or a phosphoric acid residue. -40-200302399 4. The radiation-sensitive resin composition according to item 3 of the patent application, wherein the acidic group is a carboxyl group. 5. The radiation-sensitive resin composition as described in the first item of the patent application, wherein the alicyclic olefin resin is at least one ring-opening (co) polymer selected from (i) an alicyclic olefin monomer and its hydrogenation Compounds, (1 1) addition (co) polymers of alicyclic olefin monomers, (iii) addition copolymers of alicyclic olefin monomers and ethylene compounds, (iv) (cyclo) polymerization of monocyclic cycloolefins Compounds, (v) alicyclic conjugated diene (co) polymers, (vi) ethylene alicyclic hydrocarbon (co) polymers and their hydrogenated products, and (vii) aromatic olefin (co) polymers Aromatic ring hydrogenated resin. 6. The radiation-sensitive resin composition according to item 5 of the patent application, wherein the alicyclic olefin resin is a hydrogenated product of a ring-opening (co) polymer of an alicyclic olefin monomer. 7. The radiation-sensitive resin composition according to item 6 of the application, wherein the alicyclic olefin resin is a hydrogenated product of a ring-opening (co) polymer of an original norbornene-based monomer. 8. The radiation-sensitive resin composition according to item 7 in the scope of the patent application, wherein the pro-norbornene-based monomer is tetracyclododecene. 9. The radiation-sensitive resin composition according to item 1 of the scope of patent application, wherein (A) the alicyclic olefin resin having an acidic group is a resin in which the alicyclic olefin resin is modified with a compound containing an acidic group. 10. The radiation-sensitive resin composition according to item 1 of the scope of the patent application, wherein the alicyclic olefin resin having an acidic group is an alicyclic 200302399 olefin monomer containing an acidic group and a monomer having no acidic group Addition (co) polymer, ring-opening (co) polymer, or the like. 1 1 · The radiation-sensitive resin composition according to item 丨 of the patent application, wherein (A) has an acidic group The cycloaliphatic olefin resin is an addition (co) polymer, a ring-opening (co) polymer that does not allow an alicyclic olefin monomer containing an ester group, and a monomer that does not have an ester group as required, or These hydrogenated products are formed by hydrolyzing. 1 2 · The radiation-sensitive resin composition according to item 丨 of the patent application, wherein the molecular weight distribution of the alicyclic olefin resin having an acidic group (A) is 3.3 or less. 1 3 · The radiation-sensitive resin composition according to item 1 of the scope of the patent application, wherein (A) the proportion of the structural unit having an acidic group in the alicyclic olefin resin having an acidic group is 20 to 80 mole%. 1 4 · Radiation sensitivity as described in the first patent application Aliphatic composition, in which the alicyclic olefin resin having an acidic group has a weight-average molecular weight of less than 10,000, a molecular weight distribution of 2.0 or less, and an index C1 of 600 or more. 1 5. The radiation sensitivity as described in item 1 of the scope of patent application A resin composition in which the (B) acid generator is quinonediazide sulfonate. 16. The radiation-sensitive resin composition according to item 1 of the patent application scope, wherein (C) the crosslinking agent has at least two A compound having a reactive group. 1 7 · —A pattern forming method characterized in that a resin film is formed on a substrate by using a radiation-sensitive resin composition as described in any one of claims 1 to 16 in the scope of patent application, and The resin film is irradiated with active radiation in a pattern, and a latent image pattern is formed on the resin film. Then, the pattern is visualized by contacting the resin film @, {{^^). 1 8. If applied The pattern formation method of item 17 of the patent scope, wherein the developing solution is a tetramethylammonium hydroxide aqueous solution having a concentration of 0.01 to 1.0% by weight. 1 9. A resin film characterized by, for example, an application Patent Scope 17 Method to form a pattern. 20-Application of a resin film for electronic parts which forms a resin film such as the pattern in item 19 of the patent application. 200302399 Lu, (1), the designated cutting chart in this case is: Figure (2), the representative symbols of the representative map are briefly explained: 柒 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: -4-