Negative photosensitive resin composition

Abstract

Provided is a negative photosensitive resin composition. The negative photosensitive resin composition contains a polymer and a photo-radical generator, wherein the polymer includes a structural unit (I) represented by formula (I) and a structural unit (II) represented by formula (II). In formula (I), R1-R3 each independently represent a hydrogen atom, an alkyl group, or an aromatic ring group, R1-R3 may be bonded to each other to form a ring, R4 represents a hydrogen atom or an alkyl group, X represents a C1-C10 alkylene group, and m represents 0, 1, or 2. In formula (II), R5-R8 each independently represent a hydrogen atom, an alkyl group, or an aromatic ring group, R5-R8 may be bonded to each other to form a ring, and n represents 0, 1, or 2.

Description

[Technical Field]

[0001] The present invention relates to a negative-type photosensitive resin composition. [Background technology]

[0002] In recent years, electronic components such as integrated circuit elements and organic EL elements have been provided with various resin films, such as protective films for preventing deterioration and damage to the components themselves, planarizing films for planarizing the element surface and wiring, electrical insulating films for maintaining electrical insulation, pixel separation films for separating light-emitting parts, and optical films for condensing and diffusing light.

[0003] Conventionally, as a photosensitive resin composition capable of forming the above-mentioned resin film, for example, Patent Document 1 proposes a resin composition containing a cyclic olefin resin having a functional group with a polymerizable double bond in a side chain and a polymerization initiator. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-156821 Summary of the Invention [Problem to be solved by the invention]

[0005] Here, photosensitive resin compositions are required to have excellent pattern-forming properties upon development, and resin films obtained using the photosensitive resin compositions are required to have excellent electrical properties such as dielectric loss tangent, chemical resistance, and extensibility. However, conventional photosensitive resin compositions such as those described in Patent Document 1 have room for improvement in terms of improving pattern formability by development, reducing the dielectric loss tangent of the resulting resin film, and further improving chemical resistance and extensibility.

[0006] Therefore, an object of the present invention is to provide a negative photosensitive resin composition that can improve pattern formability by development, reduce the dielectric loss tangent of the resulting resin film, and further improve the chemical resistance and extensibility. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to achieve the above-mentioned object. They have found that by using a resin composition containing a polymer having a predetermined structural unit and a photoradical generator as a negative-tone photosensitive resin composition, it is possible to improve pattern formability by development. They have also found that by forming a resin film using the resin composition, it is possible to reduce the dielectric loss tangent of the resulting resin film and improve its chemical resistance and extensibility. Based on these findings, they have completed the present invention.

[0008] That is, an object of the present invention is to advantageously solve the above-mentioned problems, and the negative-type photosensitive resin composition of the present invention comprises a polymer and a photoradical generator, and the polymer comprises a structural unit (I) represented by the following formula (I) and a structural unit (II) represented by the following formula (II):

[0009] [ka]

[0010] In formula (I), R1 to R3 each independently represent a hydrogen atom, an alkyl group, or an aromatic ring group, and R1 to R3 may be bonded to form a ring; R4 represents a hydrogen atom or an alkyl group; X represents an alkylene group having 1 to 10 carbon atoms; and m represents 0, 1, or 2. In formula (II), R5 to R8 each independently represent a hydrogen atom, an alkyl group, or an aromatic ring group, and R5 to R8 may be bonded to form a ring, and n represents 0, 1, or 2. Thus, the negative-type photosensitive resin composition containing a polymer including the structural unit (I) and the structural unit (II) and a photoradical generator can improve pattern formability by development, reduce the dielectric loss tangent of the resulting resin film, and improve the chemical resistance and extensibility of the resin film.

[0011] In the negative-type photosensitive resin composition of the present invention, the photoradical generator is preferably an acylphosphine oxide-based or oxime ester-based photoradical generator. Use of an acylphosphine oxide-based or oxime ester-based photoradical generator as the photoradical generator can further improve pattern formability by development and further reduce the dielectric loss tangent of the resulting resin film.

[0012] Furthermore, in the negative-type photosensitive resin composition of the present invention, the content of the photoradical generator is preferably more than 0.5 parts by mass and not more than 25 parts by mass per 100 parts by mass of the polymer. If the content of the photoradical generator is not less than the above-mentioned lower limit, the crosslinking reaction of the functional groups possessed by the structural unit of formula (I) can be sufficiently promoted, thereby further improving the pattern formability by development. If the content of the photoradical generator is not more than the above-mentioned upper limit, the dielectric loss tangent of the resulting resin film can be further reduced.

[0013] Furthermore, in the negative-type photosensitive resin composition of the present invention, the content of the structural unit (I) in the polymer is preferably 3 mol % or more and 70 mol % or less. When the content of the structural unit (I) in the polymer is within the above range, the extensibility of the resulting resin film is excellent. When the content of the structural unit (I) in the polymer is equal to or more than the above lower limit, the chemical resistance of the resin film can be improved, and when it is equal to or less than the above upper limit, an increase in the dielectric loss tangent of the resin film can be suppressed. In the present invention, the "content ratio of structural units" is 1 H-NMR and 13 It can be measured using nuclear magnetic resonance (NMR) techniques such as C-NMR. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a negative photosensitive resin composition that can improve pattern formability by development, reduce the dielectric loss tangent of the resulting resin film, and improve the chemical resistance and extensibility. DETAILED DESCRIPTION OF THE INVENTION

[0015] The negative photosensitive resin composition of the present invention can be used, without particular limitation, to form resin films that can be used in electronic components such as integrated circuit devices, organic electroluminescent devices, and semiconductor packages. In particular, the negative photosensitive resin composition of the present invention can be particularly suitably used, for example, in the production of insulating organic films for organic electroluminescent devices and semiconductor packages. Furthermore, the active energy rays used in patterning a resin film formed using the negative photosensitive resin composition of the present invention are not particularly limited, and examples include single-wavelength light rays such as ultraviolet rays, g-rays, h-rays, and i-rays, light rays such as KrF excimer laser light and ArF excimer laser light, and particle beams such as electron beams. Among these, the negative photosensitive resin composition of the present invention can be particularly suitably used in a wavelength range of, for example, 200 nm to 500 nm.

[0016] (Negative-type photosensitive resin composition) The negative-tone photosensitive resin composition of the present invention must contain a polymer containing the structural units described below and a photoradical generator, and may optionally contain a solvent and additives. The negative-tone photosensitive resin composition of the present invention can improve pattern formability by development, reduce the dielectric loss tangent of a resin film formed using the negative-tone photosensitive resin composition, and improve chemical resistance and elongation.

[0017] <Polymer> The polymer contained in the negative-type photosensitive resin composition of the present invention is a polymer having functional groups capable of undergoing a crosslinking reaction by radicals generated by irradiation with active energy rays in the presence of a photoradical generator. The polymer of the present invention contains a structural unit (I) represented by the following formula (I) and a structural unit (II) represented by the following formula (II). Here, the polymer may contain structural units other than the structural units (I) and (II).

[0018] [ka]

[0019] Structural Units In the structural unit (I), R1 to R3 in the above formula (I) each independently represent a hydrogen atom, an alkyl group or an aromatic ring group, and R1 to R3 may be bonded to form a ring.

[0020] Here, the alkyl group that can constitute R1 to R3 is not particularly limited, and examples thereof include unsubstituted alkyl groups having 1 to 5 carbon atoms. Among these, the alkyl group that can constitute R1 to R3 is preferably a methyl group or an ethyl group.

[0021] The aromatic ring groups that can constitute R1 to R3 are not particularly limited, and examples thereof include aromatic rings having 4 to 30 carbon atoms, such as a benzene ring and a naphthalene ring.

[0022] Furthermore, the ring formed by combining R1 to R3 may be a monocyclic ring or a polycyclic ring.

[0023] In addition, in formula (I), X represents an alkylene group having 1 to 10 carbon atoms. Here, the alkylene group having 1 to 10 carbon atoms that can constitute X is not particularly limited, but is preferably a chain alkylene group having 1 to 6 carbon atoms such as a methylene group, ethylene group, propylene group, n-butylene group, or isobutylene group, more preferably a linear alkylene group having 1 to 6 carbon atoms such as a methylene group, ethylene group, propylene group, or n-butylene group, still more preferably a linear alkylene group having 1 to 3 carbon atoms such as a methylene group, ethylene group, or propylene group, and particularly preferably a methylene group.

[0024] Furthermore, in formula (I), m represents 0, 1 or 2, and 0 or 1 is more preferable.

[0025] In formula (I), R4 represents a hydrogen atom or an alkyl group. The alkyl group that can constitute R4 is not particularly limited, and examples thereof include unsubstituted alkyl groups having 1 to 5 carbon atoms. Among these, the alkyl group that can constitute R4 is preferably a methyl group or an ethyl group.

[0026] As shown in formula (I), the structural unit (I) has a substituted or unsubstituted acryloyl group as a functional group bonded to the cyclic olefin structure via an alkylene group represented by X, thereby enhancing the mobility of the functional group. Therefore, a polymer containing the structural unit (I) having such a functional group exhibits improved crosslinking reactivity of the functional group in the presence of radicals. This allows the negative-type photosensitive resin composition of the present invention, which contains a polymer containing the structural unit (I) and the structural unit (II) described above, and a photoradical generator, to improve pattern formability by development and reduce the dielectric loss tangent of the resulting resin film, thereby improving the extensibility of the resin film.

[0027] The content of the structural unit (I) in the polymer is preferably 3 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, and preferably 70 mol% or less, more preferably 50 mol% or less, and even more preferably 40 mol% or less, relative to 100 mol% of the total of the structural units (I) and (II). When the content of the structural unit (I) in the polymer is within the above range, the extensibility of the resulting resin film is excellent. When the content of the structural unit (I) in the polymer is equal to or greater than the above lower limit, the chemical resistance of the resin film can be improved, and when it is equal to or less than the above upper limit, an increase in the dielectric loss tangent of the resin film can be suppressed.

[0028] [Structural unit (II)] In the structural unit (II), R5 to R8 in the above formula (II) each independently represent a hydrogen atom, an alkyl group or an aromatic ring group, and R4 to R8 may be bonded to form a ring.

[0029] Here, the alkyl group that can constitute R4 to R8 is not particularly limited, and examples thereof include the same alkyl groups that can constitute R1 to R3.

[0030] The aromatic ring groups that can constitute R4 to R8 are not particularly limited, and examples thereof include the same aromatic ring groups that can constitute R1 to R3.

[0031] Furthermore, the ring formed by combining R4 to R8 is not particularly limited, and examples thereof include the same rings as those formed by combining R1 to R3.

[0032] Furthermore, in formula (II), n represents 0, 1 or 2, and is preferably 0 or 1.

[0033] The content of the structural unit (II) in the polymer is preferably 3 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, even more preferably 30 mol% or more, even more preferably 50 mol% or more, particularly preferably 60 mol% or more, and is preferably 97 mol% or less, more preferably 90 mol% or less, and even more preferably 85 mol% or less, relative to the total of the structural units (I) and (II), which is 100 mol%.

[0034] [Polymer properties] -Weight average molecular weight- Furthermore, the weight average molecular weight (Mw) of the above-mentioned polymer is preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more, and is preferably 500,000 or less, more preferably 300,000 or less, and even more preferably 100,000 or less. If the weight average molecular weight of the polymer is not less than the above lower limit, mechanical properties can be improved. Furthermore, if the weight average molecular weight of the polymer is not more than the above upper limit, solvent solubility can be improved.

[0035] -Molecular weight distribution- The molecular weight distribution (Mw / Mn) of the above-mentioned polymer is preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less. If the molecular weight distribution of the polymer is equal to or less than the upper limit, the resolution can be improved. In the present invention, the "molecular weight distribution (Mw / Mn)" refers to the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). In the present invention, the weight average molecular weight of the polymer is determined as a polystyrene equivalent value by gel permeation chromatography (GPC).

[0036] (Method of synthesizing polymer) The method for preparing the above-mentioned polymer is not particularly limited, and the polymer can be efficiently synthesized, for example, by a method including a step of synthesizing a ring-opening polymer by ring-opening polymerization of a norbornene monomer, and then subjecting the resulting ring-opening polymer to a hydrogenation reaction to obtain a hydrogenated ring-opening polymer (hereinafter referred to as the "ring-opening polymerization step"), and a step of subjecting the resulting hydrogenated ring-opening polymer to a modification reaction to obtain a modified hydrogenated ring-opening polymer (hereinafter referred to as the "modification step"). Each step will be described in detail below.

[0037] <Ring-opening polymerization process> In the ring-opening polymerization step, first, a ring-opening polymer is synthesized by a ring-opening polymerization reaction between a norbornene-based monomer (I) capable of forming the above-mentioned structural unit (I) and a norbornene-based monomer (II) capable of forming the above-mentioned structural unit (II).

[0038] [Norbornene-based monomers (I)] Here, examples of the norbornene-based monomer (I) include 2-norbornene-5-methanol, 2-methyl-2-hydroxymethylbicyclo[2.2.1]hept-5-ene, 2,3-dihydroxymethylbicyclo[2.2.1]hept-5-ene, 3-hydroxytricyclo[5.2.1.0 2,6 ]deca-4,8-diene, 3-hydroxymethyltricyclo[5.2.1.0 2,6 ]deca-4,8-diene, 4-hydroxytetracyclo[6.2.1.1 3,6 .0 2,7 ]dodec-9-ene, 4-hydroxymethyltetracyclo[6.2.1.1 3,6 .0 2,7 ]dodec-9-ene, 4,5-dihydroxymethyltetracyclo[6.2.1.1 3,6 .0 2,7 ]dodec-9-ene, etc. The norbornene-based monomer (I) can be used singly or in combination of two or more.

[0039] [Norbornene-based monomers (II)] Examples of the norbornene monomer (II) include tetracyclo[4.4.0.12,5 .1 7,10 ]dodec-3-ene (common name: tetracyclododecene), 8-ethylidene-tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodec-3-ene (common name: ethylidenetetracyclododecene), tricyclo[5.2.1.0 2,6 ]deca-3,8-diene (trivial name: dicyclopentadiene), 1,4-methano-1,4,4a-9a-tetrahydrofluorene (trivial name: methanotetrahydrofluorene), 5-ethylidenebicyclo[2.2.1]hept-2-ene (trivial name: ethylidenenobornene), bicyclo[2.2.1]hept-2-ene (also called "norbornene"), 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-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, tetracyclo[10.2.1.0 2,11 .0 4,9 ]pentadeca-4,6,8,13-tetraene, 9-methyl-tetracyclo[6.2.1.1 3,6 .0 2,7 ]dodec-4-ene, 9-ethyl-tetracyclo[6.2.1.1 3,6 .0 2,7 ]dodec-4-ene, 9-methylidene-tetracyclo[6.2.1.1 3,6 .0 2,7 ]dodec-4-ene, 9-ethylidene-tetracyclo[6.2.1.1 3,6 .0 2,7 ]dodec-4-ene, 9-vinyl-tetracyclo[6.2.1.1 3,6 .0 2,7 ]dodec-4-ene, 9-propenyl-tetracyclo[6.2.1.1 3,6 .0 2,7 ]dodec-4-ene, pentacyclo[9.2.1.1 3,9 .0 2,10 .0 4,8 ]Pentadeca-5,12-diene, 9-phenyl-tetracyclo[6.2.1.1 3,6 .0 2,7 ]dodec-4-ene, tetracyclo[9.2.1.0 2,10 .03,8 ]tetradeca-3,5,7,12-tetraene, pentacyclo[9.2.1.1 3,9 .0 2,10 .0 4,8 ]pentadec-12-ene and derivatives thereof. The derivatives refer to those having a substituent in the ring structure. Examples of the substituent that can be contained in the ring structure include an alkyl group, an alkylene group, a vinyl group, an alkoxycarbonyl group, and an alkylidene group. The ring structure of the derivative may have one or more of these substituents. The norbornene-based monomer (II) can be used alone or in combination of two or more.

[0040] The ring-opening polymerization reaction can be carried out in a solvent according to a known method. The solvent is not particularly limited, and examples thereof include organic solvents such as tetrahydrofuran and toluene. Further, as the molecular weight modifier, ethylene; α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; non-conjugated dienes, such as 1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 1,7-octadiene, and derivatives thereof, may be used. As the ring-opening polymerization catalyst, a metal catalyst containing a metal such as molybdenum, tungsten, or ruthenium can be used, with a metal catalyst containing ruthenium being preferred. Furthermore, the ring-opening polymerization time is typically 1 hour to 10 hours, preferably 2 hours to 5 hours. The ring-opening polymerization temperature is typically 20°C to 100°C, preferably 90°C or less.

[0041] The resulting ring-opened polymer is then subjected to a hydrogenation reaction to synthesize a hydrogenated ring-opened polymer.

[0042] The hydrogenation reaction can be carried out according to a known method. The hydrogenation reaction time, temperature, and pressure are not particularly limited, but the hydrogenation reaction time is usually 1 hour to 10 hours, and preferably 5 hours or less. The hydrogenation reaction temperature is usually 100°C to 200°C, and preferably 180°C or less. The hydrogenation pressure is usually 1 MPa to 10 MPa, and preferably 5 MPa or less.

[0043] <Denaturation process> In the modification step, a modification reaction is carried out on the terminals of the hydrogenated ring-opening polymer obtained in the ring-opening polymerization step using a modifying agent, thereby synthesizing a modified product of the hydrogenated ring-opening polymer (i.e., a polymer containing the structural units (I) and (II) described above). Here, as the modifying agent, for example, a compound having a methacryloyl group or an acryloyl group can be used. Examples of compounds having a methacryloyl group include methacrylic acid chloride and methacrylic acid anhydride. Furthermore, examples of compounds having an acryloyl group include acrylic acid chloride and acrylic acid anhydride. Among these, it is more preferable to use methacrylic acid chloride or acrylic acid chloride from the viewpoint of efficiently carrying out the modification reaction.

[0044] The modification reaction is not particularly limited, and can be carried out, for example, by reacting the hydrogenated ring-opening polymer with a modifying agent in a solvent in the presence of a modification catalyst. The modification catalyst is not particularly limited, and examples of suitable catalysts include triethylamine and pyridine. The solvent is also not particularly limited, and examples of suitable solvents include those used in the ring-opening polymerization reaction. The modification reaction temperature and modification reaction time are not particularly limited, but the modification reaction temperature is typically −10° C. to 15° C., and the modification reaction time is typically 1 hour to 15 hours.

[0045] <Photoradical generator> As the photoradical generator, an acylphosphine oxide-based, oxime ester-based, or aromatic ketone-based photoradical generator or the like can be used. One or more types of photoradical generators can be used in combination. Among them, from the viewpoints of further improving the pattern formability by development and further reducing the dielectric loss tangent of the resulting resin film, it is preferable to use an acylphosphine oxide-based or oxime ester-based photoradical generator as the photoradical generator.

[0046] As the acylphosphine oxide-based photoradical generator, for example, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, etc. can be used.

[0047] In addition, examples of oxime ester-based photoradical generators that can be used include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(o-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), and the like.

[0048] In addition, examples of aromatic ketone radical generators that can be used include benzophenone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1[4-methylthio]phenyl]-2-morpholinopropan-1-one, methyl o-benzoylbenzoate, [4-(methylphenylthio)phenyl]phenylmethane, 1,4-dibenzoylbenzene, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyldiphenyl ether, and benzyl.

[0049] [Photoradical generator content] The content of the photoradical generator is typically 0.3 parts by mass or more, preferably more than 0.5 parts by mass, and more preferably 1 part by mass or more, per 100 parts by mass of the polymer, and typically 25 parts by mass or less, preferably less than 20 parts by mass, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less. If the content of the photoradical generator is at least the above-mentioned lower limit, the crosslinking reaction of the functional groups in the structural unit (I) can be sufficiently promoted, thereby further improving the pattern formability by development. Furthermore, if the content of the photoradical generator in the negative-type photosensitive resin composition is at most the above-mentioned upper limit, the dielectric loss tangent of the resulting resin film can be further reduced.

[0050] <Solvent> The solvent that may be contained in the negative-type photosensitive resin composition of the present invention is not particularly limited, and examples thereof include aromatic solvents such as toluene, o-xylene, m-xylene, p-xylene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, and tetralin, hydrocarbons such as cyclohexane and decalin, ether solvents such as dibutyl ether, diisoamyl ether, tetrahydrofuran, and cyclopentyl methyl ether, ester solvents such as butyl acetate, hexyl acetate, and propylene glycol monomethyl ether acetate, and ketone solvents such as methyl ethyl ketone, diisobutyl ketone, and cyclopentanone. These solvents may be used alone or in combination of two or more.

[0051] The content of the solvent in the negative photosensitive resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, and is preferably 60% by mass or less, more preferably 50% by mass or less, based on the total mass of the negative photosensitive resin composition, in terms of the total amount of the solvent other than the solvent.

[0052] <Additional ingredients> The negative-tone photosensitive resin composition of the present invention may contain additional components, but these include, for example, surfactants, antioxidants, sensitizers, and adhesion aids. These additional components may be used alone or in combination of two or more. Among these, it is preferable to contain a surfactant as an additional component, from the viewpoint of improving the coatability of the negative-tone photosensitive resin composition of the present invention and further improving the uniformity of the film thickness of the resulting resin film.

[0053] The surfactant is not particularly limited, and known silicone surfactants, fluorine surfactants, etc. can be used. The content of the surfactant in the negative photosensitive resin composition is preferably 0.1% by mass or less, and more preferably 0.05% by mass or less, based on the total mass of the negative photosensitive resin composition.

[0054] <Method for preparing negative-type photosensitive resin composition> The negative-type photosensitive resin composition of the present invention can be prepared by mixing the above-mentioned essential components and various optional components by a known method. Here, the negative-type photosensitive resin composition of the present invention is used as a negative-type photosensitive resin composition obtained, for example, by dissolving the components in a solvent and filtering the resulting mixture. When dissolving the components in a solvent, known mixers such as a stirrer, ball mill, sand mill, bead mill, pigment disperser, crusher, ultrasonic disperser, homogenizer, planetary mixer, and Filmix can be used. When filtering, a general filtration method using a filter material such as a filter can be used.

[0055] <Method of manufacturing resin film> The negative photosensitive resin composition of the present invention can be used in a known film formation method (see, for example, International Publication No. 2015 / 033901) to form a resin film. The resulting resin film can then be subjected to an exposure step in which any active energy ray, for example, exposure light with a wavelength of 200 nm or more and 500 nm or less, is irradiated, without any particular limitation, and a development step, thereby forming a resin film having a desired pattern. If necessary, a pre-baking step may be performed prior to the exposure step, or a post-exposure bake (PEB) step may be performed at a desired timing after the start of the exposure step. Furthermore, if necessary, a post-baking step may be performed after the development step. The developer used in the developing step is not particularly limited, and for example, the solvents listed as solvents that can be contained in the negative photosensitive resin composition of the present invention can be used as the developer. These developers can be used alone or in combination of two or more. [Example]

[0056] The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. In the following description, "%" and "parts" representing amounts are based on mass unless otherwise specified. In the examples and comparative examples, the dielectric loss tangent, the developed residual film rate, the chemical resistance, the tensile elongation, and the weight average molecular weight and molecular weight distribution of the polymer were measured or evaluated using the following methods.

[0057] <Dielectric loss tangent> The resin compositions prepared in each example and comparative example were spin-coated onto a 4-inch silicon wafer on which a 50 nm thick aluminum film had been formed using a sputtering device (Shibaura Eletech Corporation, "i-Miller CFS-4EP-LL"), and then pre-baked on a hot plate at 90°C for 2 minutes to form a resin film made of the resin composition. Next, a mask aligner (Canon Inc., "PLA501F") was used to apply a ghi mixed beam at 1000 mJ / cm. 2 After exposure to a dose of 1000 kJ / cm, the resin film was cured by heating in nitrogen at 180°C for 1 hour, yielding a silicon wafer with a 10 μm-thick resin film. The resulting silicon wafer with the resin film was immersed in a 0.1 mol% hydrochloric acid solution for 12 hours to etch the aluminum, thereby peeling the resin film from the silicon wafer. After drying in an oven at 110°C for 1 hour, the dried resin film was cut into strips 2 mm wide and 50 mm long to prepare test pieces, and the dielectric loss tangent of these test pieces at 10 GHz was measured using a cavity resonator method. A: Dielectric tangent less than 0.0075 B: Dielectric tangent is 0.0075 or more and less than 0.01 C: Dielectric tangent is 0.01 or more

[0058] <Remaining film rate after development> The resin compositions prepared in each Example and Comparative Example were applied to a silicon wafer by spin coating, and then prebaked at 90°C for 2 minutes using a hot plate to form a resin film with a thickness of 5.0 μm. Next, using a mask aligner (Canon, "PLA501F"), the resin film was irradiated with a ghi mixed beam at 1000 mJ / cm through a photomask with a 100 μm line-and-space pattern. 2 The exposure was performed at a dose of 1000 ppm. Next, development was carried out for 60 seconds using toluene as a developer, and then the resulting film was shaken off and dried to obtain a laminate consisting of a resin film having a line and space pattern and a silicon wafer. The film thickness of the line pattern portion of the resin film after development was measured using an optical interference film thickness measuring device (Dainippon Screen Co., Ltd., "Lambda Ace VM-1210"), and the development residual film rate (%) was calculated according to the following formula. A higher value of the development residual film rate is preferable because it indicates better pattern formability by development. Residual film rate after development (%) = (film thickness of the line pattern part of the resin film after development) / (film thickness of the resin film before development) × 100 A: Residual film rate after development is 80% or more B: Residual film rate after development is 50% or more and less than 80% C: Residual film rate after development is less than 50%

[0059] <Chemical resistance> The resin compositions prepared in each Example and Comparative Example were spin-coated onto a silicon wafer, and then pre-baked at 90°C for 2 minutes using a hot plate to form a resin film made of the resin composition. Next, a mask aligner (Canon, "PLA501F") was used to apply a ghi mixed beam of 1000 mJ / cm 2 After exposure at an irradiation dose of 10 μm, the resin film was cured by heating at 180° C. for 1 hour in nitrogen, to obtain a silicon wafer with a resin film of 10 μm in thickness. The obtained silicon wafer with the resin film was immersed in a flux cleaning solution (HC-FX-50 manufactured by Tosoh Corporation) at 23° C. for 15 minutes, and the change in film thickness was calculated according to the following formula. (Film thickness change (%) = (resin film thickness after immersion - resin film thickness before immersion) / film thickness before immersion × 100) The chemical resistance of the resin film was evaluated based on the calculated film thickness change (%) according to the following criteria: The less cracks or peeling there were in the film and the smaller the film thickness change, the better the chemical resistance of the resin film. A: No cracks or peeling on the film, and the film thickness change is less than 3% B: No cracks or peeling in the film, and the film thickness change is 3% or more C: Cracks or peeling occurs on the film

[0060] <Tensile elongation> A 4-inch silicon wafer on which a 50 nm thick aluminum film had been formed using a sputtering device (Shibaura Eletech Corporation, "i-Miller CFS-4EP-LL") was spin-coated with the resin composition prepared in each Example and Comparative Example, and then pre-baked on a hot plate at 90°C for 2 minutes to form a resin film made of the resin composition. Next, a mask aligner (Canon Inc., "PLA501F") was used to apply a ghi mixed beam of 1000 mJ / cm 2 The resin film was then cured by heating at 180°C for 1 hour in nitrogen, yielding a silicon wafer with a 10 μm thick resin film. The resulting silicon wafer with the resin film was immersed in a 0.1 mol% aqueous hydrochloric acid solution for 12 hours to etch the aluminum, thereby peeling the resin film from the wafer with the resin film, and then dried in an oven at 110°C for 1 hour. The dried resin film was cut into a strip of 5 mm wide and 40 mm long to form a test piece, and a tensile test was performed on this test piece to measure the tensile elongation of the resin film. Specifically, a tensile test was performed using a tensile tester (Shimadzu Corporation, "AGS-10kNX") at 23°C, with a gripper spacing of 20 mm and a tensile speed of 2 mm / min, to measure the elongation at break. Eight test pieces were tested, and the average of the top three points was taken as the tensile elongation of the resin film formed using the resin composition obtained in each Example and Comparative Example. A higher tensile elongation value indicates higher extensibility of the resin film. Furthermore, a higher extensibility of the resin film is preferable because it is less likely to crack or peel during a temperature cycle test or a drop impact test. A: Tensile elongation is 10% or more B: Tensile elongation is 5% or more and less than 10% C: Tensile elongation less than 5%

[0061] <Weight average molecular weight and molecular weight distribution> The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymers obtained in the examples and comparative examples were measured by gel permeation chromatography, and the molecular weight distribution (Mw / Mn) was calculated. Specifically, using a gel permeation chromatograph (Tosoh Corporation, HLC-8220) and tetrahydrofuran as a developing solvent, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymer were determined in terms of standard polystyrene, and the molecular weight distribution (Mw / Mn) was calculated.

[0062] (Synthesis Example 1) <Ring-opening polymerization process> A monomer mixture (100 parts) consisting of 65 mol % of 2-norbornene-5-methanol (hereinafter abbreviated as "NBMOH") as the norbornene-based monomer (I) and 35 mol % of tetracyclododecene (hereinafter abbreviated as "TCD") as the norbornene-based monomer (II), 3.0 parts of 1,5-hexadiene as a molecular weight modifier, 0.025 parts of (1,3-dimesitylimidazolin-2-ylidene)(tricyclohexylphosphine)benzylidene ruthenium dichloride (synthesized by the method described in Org. Lett., Vol. 1, p. 953, 1999) as a ring-opening polymerization catalyst, and 300 parts of tetrahydrofuran as a solvent were charged into a nitrogen-purged glass pressure-resistant reactor and reacted at 80°C for 4 hours with stirring to obtain a polymerization reaction liquid. The resulting polymerization reaction solution was placed in an autoclave and stirred at 150°C under a hydrogen pressure of 4 MPa for 5 hours to carry out a hydrogenation reaction, after which 300 parts of tetrahydrofuran was added as a solvent to the reaction solution, which was then added dropwise to 8,000 parts of methanol, and the resulting precipitate was collected by filtration and dried under reduced pressure at 50°C to obtain a hydrogenated ring-opened polymer (A-1).

[0063] <Denaturation process> A three-neck flask equipped with a stirring blade and a thermometer was purged with nitrogen, and 100 parts of the hydrogenated ring-opened polymer (A-1), 336.5 parts of triethylamine as a modification reaction catalyst, and 400 parts of tetrahydrofuran as a solvent were charged. The reaction solution was cooled to 0 ° C. in an ice bath. While maintaining the temperature of the reaction solution at 10 ° C. or less, 298.0 parts of methacrylic acid chloride as a modifying agent was added dropwise and stirred for 2 hours. The reaction solution was then warmed to room temperature and stirred for 12 hours. Next, 200 parts of tetrahydrofuran as a solvent was added to the reaction solution, which was then cooled to 0 ° C. 0.5 parts by mass of methanol relative to the methacrylic acid chloride was added while maintaining the temperature of the reaction solution at 10 ° C. or less. The mixture was stirred at 0 ° C. for 1 hour, warmed to room temperature, and stirred for another 1 hour. The reaction solution was added dropwise to 8,000 parts of methanol, and the resulting precipitate was collected by filtration. The precipitate was washed three times with methanol and then dried under reduced pressure at 50°C to obtain a modified ring-opening polymer hydrogenation product (hereinafter referred to as "modified ring-opening polymer hydrogenation product") (B-1). GPC measurement of the modified ring-opening polymer hydrogenation product (B-1) revealed a weight-average molecular weight of 14,600 and a molecular weight distribution of 1.7. 1 H-NMR analysis confirmed that the methacryloyl modification rate of the hydrogenated ring-opening polymer (A-1) was 100%, and the content of methacryloyl-modified NBMOH in the modified hydrogenated ring-opening polymer (B-1) was 65 mol %. Furthermore, it was confirmed that the modified hydrogenated ring-opening polymer (B-1) was a polymer containing 65 mol % of structural units represented by the following formula (I-1) and 35 mol % of structural units represented by the following formula (II-1).

[0064] [ka]

[0065] (Synthesis Example 2) A ring-opened polymer hydrogenation product (A-2) was obtained in the same manner as in Synthesis Example 1, except that NBMOH was used in 40 mol %, TCD in 60 mol %, and the solvent was changed to toluene. A modified ring-opening polymer hydrogenation product (B-2) was obtained by the same procedure as in Synthesis Example 1, except that the ring-opening polymer hydrogenation product (A-1) was changed to the ring-opening polymer hydrogenation product (A-2), and the amounts of triethylamine and methacrylic acid chloride were changed to 229.9 parts and 176.2 parts, respectively, and the solvent was changed to toluene. The weight average molecular weight of the modified ring-opening polymer hydrogenation product (B-2) measured by GPC was 13,800, and the molecular weight distribution was 1.6. 1 H-NMR analysis confirmed that the methacryloyl modification rate of the hydrogenated ring-opening polymer (A-2) was 100%, and the content of methacryloyl-modified NBMOH in the modified hydrogenated ring-opening polymer (B-2) was 40 mol %. Furthermore, it was confirmed that the modified hydrogenated ring-opening polymer (B-2) was a polymer containing 40 mol % of structural units represented by the following formula (I-2) and 60 mol % of structural units represented by the following formula (II-2).

[0066] [ka]

[0067] (Synthesis Example 3) A ring-opened polymer hydrogenation product (A-3) was obtained in the same manner as in Synthesis Example 1, except that NBMOH was used at 5 mol %, TCD was used at 95 mol %, and the solvent was changed to toluene. The same procedure as in Synthesis Example 1 was repeated except that the ring-opening polymer hydrogenation product (A-1) was replaced with the ring-opening polymer hydrogenation product (A-3), and the amounts of triethylamine and methacrylic acid chloride were changed to 22.4 parts and 19.8 parts, respectively, and the solvent was changed to toluene, to obtain a modified ring-opening polymer hydrogenation product (B-3). The weight average molecular weight of the modified ring-opening polymer hydrogenation product (B-3) measured by GPC was 13,500, and the molecular weight distribution was 1.6. 1H-NMR analysis confirmed that the methacryloyl modification rate of the hydrogenated ring-opening polymer (A-3) was 100%, and the content of methacryloyl-modified NBMOH in the modified hydrogenated ring-opening polymer (B-3) was 5 mol %. Furthermore, it was confirmed that the modified hydrogenated ring-opening polymer (B-3) was a polymer containing 5 mol % of structural units represented by the following formula (I-3) and 95 mol % of structural units represented by the following formula (II-3).

[0068] [ka]

[0069] (Synthesis Example 4) A ring-opened polymer hydrogenation product (A-4) was obtained by the same procedure as in Synthesis Example 1, except that NBMOH was used at 15 mol%, TCD was changed from 90 mol% to 85 mol% of ethylidenetetracyclododecene (hereinafter abbreviated as "ETD"), and 1,5-hexadiene was used at 1.0 part instead of 3.0 parts. A modified ring-opening polymer hydrogenation product (B-4) was obtained by the same procedure as in Synthesis Example 1, except that the ring-opening polymer hydrogenation product (A-1) was changed to the ring-opening polymer hydrogenation product (A-4), and the amount of triethylamine was changed to 60.0 parts and the amount of methacrylic acid chloride was changed to 53.2 parts. The weight average molecular weight of the modified ring-opening polymer hydrogenation product (B-4) measured by GPC was 29,000, and the molecular weight distribution was 1.4. 1 H-NMR analysis confirmed that the methacryloyl modification rate of the hydrogenated ring-opening polymer (A-4) was 100%, and the content of methacryloyl-modified NBMOH in the modified hydrogenated ring-opening polymer (B-4) was 15 mol %. Furthermore, it was confirmed that the modified hydrogenated ring-opening polymer (B-4) was a polymer containing 15 mol % of structural units represented by the following formula (I-4) and 85 mol % of structural units represented by the following formula (II-4).

[0070] [ka]

[0071] (Synthesis Example 5) A ring-opened polymer hydrogenation product (A-5) was obtained by the same procedure as in Synthesis Example 1, except that NBMOH was changed from 10 mol% to 30 mol% and TCD was changed from 90 mol% to 70 mol%. A modified ring-opening polymer hydrogenation product (B-5) was obtained by the same procedure as in Synthesis Example 1, except that the ring-opening polymer hydrogenation product (A-1) was changed to the ring-opening polymer hydrogenation product (A-5), and the amount of triethylamine was changed to 126.4 parts and the amount of methacrylic acid chloride was changed to 111.2 parts. The weight average molecular weight of the modified ring-opening polymer hydrogenation product (B-5) measured by GPC was 14,700, and the molecular weight distribution was 1.7. 1 H-NMR analysis confirmed that the methacryloyl modification rate of the hydrogenated ring-opening polymer (A-5) was 100%, and the content of methacryloyl-modified NBMOH in the modified hydrogenated ring-opening polymer (B-5) was 30 mol %. Furthermore, it was confirmed that the modified hydrogenated ring-opening polymer (B-5) was a polymer containing 30 mol % of structural units represented by the following formula (I-5) and 70 mol % of structural units represented by the following formula (II-5).

[0072] [ka]

[0073] (Synthesis Example 6) The same procedure as in Synthesis Example 1 was carried out, except that NBMOH was changed from 10 mol% to 25 mol%, TCD was changed from 90 mol% to 75 mol% dicyclopentadiene, and the solvent was changed to toluene, to obtain a ring-opened polymer hydrogenation product (A-6). A modified ring-opening polymer hydrogenation product (B-6) was obtained by the same procedure as in Synthesis Example 1, except that the ring-opening polymer hydrogenation product (A-1) was changed to the ring-opening polymer hydrogenation product (A-6), and the amount of triethylamine was changed to 136.0 parts, the amount of methacrylic acid chloride was changed to 120.4 parts, and the solvent was changed to toluene. The weight average molecular weight of the modified ring-opening polymer hydrogenation product (B-6) measured by GPC was 15,000, and the molecular weight distribution was 1.6. 1H-NMR analysis confirmed that the methacryloyl modification rate of the hydrogenated ring-opening polymer (A-6) was 100%, and the content of methacryloyl-modified NBMOH in the modified hydrogenated ring-opening polymer (B-6) was 25 mol %. Furthermore, it was confirmed that the modified hydrogenated ring-opening polymer (B-6) was a polymer containing 25 mol % of structural units represented by the following formula (I-6) and 75 mol % of structural units represented by the following formula (II-6).

[0074] [ka]

[0075] (Synthesis Example 7) A ring-opened polymer hydrogenation product (A-7) was obtained by the same procedure as in Synthesis Example 1, except that NBMOH was changed from 10 mol% to 35 mol% and TCD was changed from 90 mol% to 65 mol%. A modified ring-opening polymer hydrogenation product (B-7) was obtained by the same procedure as in Synthesis Example 1, except that the ring-opening polymer hydrogenation product (A-1) was changed to the ring-opening polymer hydrogenation product (A-7), and the amount of triethylamine was changed to 136.0 parts and the amount of methacrylic acid chloride was changed to 120.4 parts of acrylic acid chloride. The weight average molecular weight of the modified ring-opening polymer hydrogenation product (B-7) measured by GPC was 13,300, and the molecular weight distribution was 1.6. 1 H-NMR analysis confirmed that the acryloyl modification rate of the hydrogenated ring-opening polymer (A-7) was 100%, and the content of acryloyl-modified NBMOH in the modified hydrogenated ring-opening polymer (B-7) was 35 mol %. Furthermore, it was confirmed that the modified hydrogenated ring-opening polymer (B-7) was a polymer containing 35 mol % of structural units represented by the following formula (I-7) and 65 mol % of structural units represented by the following formula (II-7).

[0076] [ka]

[0077] (Synthesis Example 8) The same procedure as in Synthesis Example 1 was carried out, except that NBMOH was changed from 10 mol% to 40 mol%, and TCD was changed to 90 mol% with 30 mol% of ethylidene nobornene (ENB) and 30 mol% of methanotetrahydrofluorene (MTF), to obtain a ring-opened polymer hydrogenation product (A-8). A modified ring-opening polymer hydrogenation product (B-8) was obtained by the same procedure as in Synthesis Example 1, except that the ring-opening polymer hydrogenation product (A-1) was changed to the ring-opening polymer hydrogenation product (A-8), and the amount of triethylamine was changed to 201.8 parts and the amount of methacrylic acid chloride was changed to 154.7 parts. The weight average molecular weight of the modified ring-opening polymer hydrogenation product (B-8) measured by GPC was 14,100, and the molecular weight distribution was 1.7. 1 H-NMR analysis confirmed that the methacryloyl modification rate of the hydrogenated ring-opening polymer (A-8) was 100%, and the content of methacryloyl-modified NBMOH in the modified hydrogenated ring-opening polymer (B-8) was 40 mol%. Furthermore, it was confirmed that the modified hydrogenated ring-opening polymer (B-8) was a polymer containing 40 mol% of structural units represented by the following formula (I-8), 30 mol% of structural units represented by the following formula (II-8a), and 30 mol% of structural units represented by the following formula (II-8b).

[0078] [ka]

[0079] (Synthesis Example 9) The same procedure as in Synthesis Example 1 was carried out except that in Synthesis Example 1, 10 mol% of NBMOH was changed to 40 mol% of norborneneol, TCD was changed from 90 mol% to 60 mol%, 1,5-hexadiene was changed from 3.0 parts to 1.0 part, and the solvent was changed to toluene, thereby obtaining a ring-opened polymer hydrogenation product (A-9). A modified ring-opening polymer hydrogenation product (B-9) was obtained by the same procedure as in Synthesis Example 1, except that the ring-opening polymer hydrogenation product (A-1) was changed to ring-opening polymer hydrogenation product (A-9), the amount of triethylamine was changed to 326.4 parts, the amount of methacrylic acid chloride was changed to 250.3 parts, and the solvent was changed to toluene. The weight average molecular weight of the modified ring-opening polymer hydrogenation product (B-9) measured by GPC was 31,000, and the molecular weight distribution was 1.7. 1 H-NMR analysis confirmed that the methacryloyl modification rate of the hydrogenated ring-opening polymer (A-9) was 100%, and the content of methacryloyl-modified NBMOH in the modified hydrogenated ring-opening polymer (B-9) was 40 mol %. Furthermore, it was confirmed that the modified hydrogenated ring-opening polymer (B-9) was a polymer containing 40 mol % of structural units represented by the following formula (I-9) and 60 mol % of structural units represented by the following formula (II-9).

[0080] [ka]

[0081] (Synthesis Example 10) A norbornene / norbornene methanol copolymer was synthesized as an addition polymer (A-10) by addition polymerization of norbornene (NB) as a norbornene-based monomer and NBMOH. Specifically, the NB / NBMOH copolymer was synthesized according to the method described in Macromolecules 29, 2761 (1996), except that the scale was increased by 20 times. 1 H-NMR measurement revealed that the NBMOH content in the NB / NBMOH copolymer was 15 mol %.

[0082] Then, the same operation as in Synthesis Example 1 was carried out, except that the ring-opening polymer hydrogenation product (A-1) was changed to an addition polymer (A-10), the amount of triethylamine was changed to 107.7 parts, the amount of methacrylic acid chloride was changed to 82.6 parts, and the reaction solvent was changed to toluene, to obtain a modified addition polymer (B-10). 1H-NMR measurement confirmed that the methacryloyl modification rate of addition polymer (A-10) was 100%, and the content of methacryloyl-modified NBMOH in modified addition polymer (B-10) was 15 mol%. GPC measurement confirmed that the weight average molecular weight of modified ring-opening polymer hydrogenation product (B-9) was 28,100, and the molecular weight distribution was 1.8. Furthermore, it was confirmed that modified addition polymer (B-10) was a polymer containing 15 mol% of structural units represented by the following formula (I-10) and 85 mol% of structural units represented by the following formula (II-10).

[0083] [ka]

[0084] Example 1 <Preparation of Resin Composition> 100 parts of the modified hydrogenated ring-opening polymer (B-1) obtained in Synthesis Example 1, 5 parts of an oxime ester-based photoradical generator (manufactured by BASF, "IrgacureOEX01", chemical formula: 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(o-benzoyloxime), hereinafter referred to as "oxime ester-based radical generator (1)"), and toluene as a solvent (an amount such that the total mass of the resin composition other than the solvent was 30%) were mixed and dissolved. Next, a surfactant (manufactured by Shin-Etsu Silicones, "KP-341", hereinafter referred to as "surfactant (1)") was added in an amount of 0.03% based on the total mass of the resin composition, and the mixture was filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm (hereinafter referred to as "filter (1)") to prepare a resin composition. The obtained resin composition was then subjected to various evaluations as described above. The results are shown in Table 1.

[0085] Example 2 100 parts of the modified ring-opening polymer hydrogenated product (B-2) obtained in Synthesis Example 2, 5 parts of the oxime ester photoradical generator (1), and toluene as a solvent (an amount such that the total amount of components other than the solvent was 30% of the total amount of the resin composition) were mixed and dissolved. Next, surfactant (1) was added to the resin composition so that the total amount was 0.03% of the total amount, and the resin composition was filtered through filter (1). The obtained resin composition was then subjected to various evaluations as described above. The results are shown in Table 1.

[0086] Example 3 100 parts of the modified ring-opening polymer hydrogenated product (B-3) obtained in Synthesis Example 3, 5 parts of the oxime ester photoradical generator (1), and toluene as a solvent (an amount such that the total amount of components other than the solvent was 30% of the total amount of the resin composition) were mixed and dissolved. Next, surfactant (1) was added to the resin composition so that the total amount was 0.03% by weight, and the resin composition was filtered through filter (1). The obtained resin composition was then subjected to various evaluations as described above. The results are shown in Table 1.

[0087] Example 4 100 parts of the modified hydrogenated ring-opening polymer (B-4) obtained in Synthesis Example 4, 5 parts of an oxime ester-based photoradical generator (manufactured by BASF, "IrgacureOEX02", chemical formula: ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), hereinafter referred to as "oxime ester-based photoradical generator (2)"), and toluene as a solvent (an amount such that the total amount of components other than the solvent was 30% of the total amount of the resin composition) were mixed and dissolved. Next, surfactant (1) was added to the resin composition so that the total amount was 0.03% of the total amount, and the mixture was filtered through filter (1) to prepare a resin composition. The obtained resin composition was then subjected to various evaluations as described above. The results are shown in Table 1.

[0088] Example 5 100 parts of the modified hydrogenated ring-opening polymer (B-5) obtained in Synthesis Example 5, 10 parts of an acylphosphine oxide photoradical generator (BASF's "Omnirad819", chemical formula: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide), and toluene as a solvent (amount such that the total amount of components other than the solvent was 30% of the total amount of the resin composition) were mixed and dissolved. Next, surfactant (1) was added to the resin composition so that the total amount was 0.03% of the total amount, and the resin composition was filtered through filter (1) to prepare a resin composition. The obtained resin composition was then subjected to various evaluations as described above. The results are shown in Table 1.

[0089] Example 6 100 parts of the modified hydrogenated ring-opening polymer (B-5) obtained in Synthesis Example 5, 20 parts of the oxime ester photoradical generator (1), and toluene as a solvent (amount such that the total amount of components other than the solvent was 30% of the total amount of the resin composition) were mixed and dissolved. Next, surfactant (1) was added to the resin composition so that the total amount was 0.03% of the total amount, and the resin composition was filtered through filter (1). The obtained resin composition was then subjected to various evaluations as described above. The results are shown in Table 1.

[0090] Example 7 100 parts of the modified hydrogenated ring-opening polymer (B-6) obtained in Synthesis Example 6, 5 parts of the oxime ester photoradical generator (2), and toluene as a solvent (amount such that the total amount of components other than the solvent was 30% of the total amount of the resin composition) were mixed and dissolved. Next, surfactant (1) was added to the resin composition in an amount of 0.03% by weight, based on the total amount of the resin composition, and the mixture was filtered through filter (1) to prepare a resin composition. The obtained resin composition was then subjected to various evaluations as described above. The results are shown in Table 1.

[0091] Example 8 100 parts of the modified hydrogenated ring-opening polymer (B-6) obtained in Synthesis Example 6, 0.5 parts of the oxime ester photoradical generator (2), and toluene as a solvent (amount such that the total amount of components other than the solvent was 30% of the total amount of the resin composition) were mixed and dissolved. Next, surfactant (1) was added to the resin composition so that the total amount was 0.03% of the total amount, and the resin composition was filtered through filter (1). The obtained resin composition was then subjected to various evaluations as described above. The results are shown in Table 1.

[0092] Example 9 100 parts of the modified hydrogenated ring-opening polymer (B-7) obtained in Synthesis Example 7, 3 parts of the oxime ester photoradical generator (1), and toluene as a solvent (amount such that the total amount of components other than the solvent was 30% of the total amount of the resin composition) were mixed and dissolved. Next, surfactant (1) was added to the resin composition so that the total amount was 0.03% of the total amount, and the resin composition was filtered through filter (1). The obtained resin composition was then subjected to various evaluations as described above. The results are shown in Table 1.

[0093] Example 10 100 parts of the modified hydrogenated ring-opening polymer (B-2) obtained in Synthesis Example 2, 5 parts of benzophenone as an aromatic ketone-based photoradical generator, and toluene as a solvent (an amount such that the total amount of components other than the solvent was 30% of the total amount of the resin composition) were mixed and dissolved. Next, surfactant (1) was added to the resin composition so that the total amount was 0.03% of the total amount, and the resin composition was filtered through filter (1). The obtained resin composition was then subjected to various evaluations as described above. The results are shown in Table 1.

[0094] Example 11 100 parts of the modified hydrogenated ring-opening polymer (B-8) obtained in Synthesis Example 8, 5 parts of the oxime ester photoradical generator (2), and toluene as a solvent (an amount such that the total amount of components other than the solvent was 30% of the total amount of the resin composition) were mixed and dissolved. Next, surfactant (1) was added to the resin composition so that the total amount was 0.03% of the total amount of the resin composition, and the mixture was filtered through filter (1) to prepare a resin composition. The resin composition thus obtained was subjected to various evaluations as described above. The results are shown in Table 1.

[0095] (Comparative Example 1) 100 parts of the modified hydrogenated ring-opening polymer (B-9) obtained in Synthesis Example 9, 10 parts of the acylphosphine oxide photoradical generator used in Example 5, and toluene as a solvent (an amount such that the total amount of components other than the solvent was 30% of the total amount of the resin composition) were mixed and dissolved. Next, surfactant (1) was added to the resin composition so that the total amount was 0.03% of the total amount, and the resin composition was filtered through filter (1). The obtained resin composition was then subjected to various evaluations as described above. The results are shown in Table 1.

[0096] (Comparative Example 2) 100 parts of the modified hydrogenated ring-opening polymer (B-2) obtained in Synthesis Example 2, 10 parts of dicumyl peroxide, a peroxide-based thermal radical generator, and toluene as a solvent (amount such that the total amount of the components other than the solvent was 30% of the total amount of the resin composition) were mixed and dissolved. Next, surfactant (1) was added to the resin composition in an amount of 0.03% based on the total amount, and the mixture was filtered through filter (1) to prepare a resin composition. The obtained resin composition was then subjected to various evaluations as described above. The results are shown in Table 1.

[0097] (Comparative Example 3) 100 parts of the modified addition polymer (B-10) obtained in Synthesis Example 10, 5 parts of the oxime ester photoradical generator (1), and toluene as a solvent (an amount such that the total amount of components other than the solvent was 30% of the total amount of the resin composition) were mixed and dissolved. Next, surfactant (1) was added to the resin composition so that the total amount was 0.03% of the total amount, and the resin composition was filtered through filter (1). The obtained resin composition was then subjected to various evaluations as described above. The results are shown in Table 1.

[0098] [Table 1]

[0099] Table 1 shows that the resin compositions (negative photosensitive resin compositions) of Examples 1 to 11, which contain a polymer containing a predetermined structural unit and a photoradical generator, are excellent in all of the dielectric loss tangent, development residual film rate, chemical resistance, and tensile elongation. In contrast, the resin composition of Comparative Example 1, which used a polymer containing a structural unit having a functional group but having a structure in which the functional group is directly bonded to a hydrogenated ring-opened polymer, was found to be unable to increase both the development residual film rate and the tensile elongation. Furthermore, it is clear that the resin composition of Comparative Example 2, which used a thermal radical generator as the radical generator, was unable to lower the dielectric loss tangent and increase the development residual film rate. It is also clear that the resin composition of Comparative Example 3, which used a modified addition polymer, was unable to improve both chemical resistance and tensile elongation. [Industrial Applicability]

[0100] According to the present invention, it is possible to provide a negative photosensitive resin composition that can improve pattern formability by development, reduce the dielectric loss tangent of the resulting resin film, and improve the chemical resistance and extensibility.

Claims

1. A polymer, and a photoradical generator, The polymer is a negative photosensitive resin composition containing a structural unit (I) represented by the following formula (I) and a structural unit (II) represented by the following formula (II): 【Chemistry 1】 (In formula (I), R １ ~R ３ each independently represents a hydrogen atom, an alkyl group, or an aromatic ring group; R １ ~R ３ may be bonded to form a ring, and R ４ represents a hydrogen atom or an alkyl group; X represents an alkylene group having 1 to 10 carbon atoms; and m represents 0, 1, or 2. In formula (II), R ５ ~R ８ each independently represents a hydrogen atom, an alkyl group, or an aromatic ring group; R ５ ~R ８ may be bonded to form a ring, and n represents 0, 1 or 2.

2. 2. The negative photosensitive resin composition according to claim 1, wherein the photoradical generator is an acylphosphine oxide-based or oxime ester-based photoradical generator.

3. 3. The negative photosensitive resin composition according to claim 1, wherein the content of the photoradical generator is more than 0.5 parts by mass and not more than 25 parts by mass per 100 parts by mass of the polymer.

4. 4. The negative photosensitive resin composition according to claim 1, wherein the content of the structural unit (I) in the polymer is 3 mol % or more and 70 mol % or less.

Images