Negative photosensitive resin composition

Abstract

The present invention provides a negative photosensitive resin composition. The negative photosensitive resin composition contains a polymer and a photo radical generator. The polymer contains a structural unit (I) represented by the following formula (I) and a structural unit (II) represented by the following formula (II). In formula (I), R1 to R3 each independently represent a hydrogen atom, an alkyl group or an aromatic ring group, R1 to R3 can also combine 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, R5 to R8 can also combine to form a ring, and n represents 0, 1 or 2. #imgabs0#

Description

Technical Field

[0001] The present invention relates to a negative photosensitive resin composition. Background Art

[0002] In recent years, in electronic components such as integrated circuit elements and organic EL elements, various resin films are provided as: a protective film for preventing deterioration and damage of the component itself; a planarization film for planarizing the element surface and wiring; an electrical insulation film for maintaining electrical insulation; a pixel isolation film for separating light-emitting portions; an optical film for focusing and diffusing light, and the like.

[0003] Hitherto, as a photosensitive resin composition capable of forming the resin film as described above, for example, a resin composition containing a cyclic olefin resin having a polymerizable double bond-functional group in a side chain and a polymerization initiator has been proposed in Patent Document 1.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2006-156821. Summary of the Invention

[0007] Problems to be Solved by the Invention

[0008] Here, the photosensitive resin composition is required to have excellent developable pattern formability. In addition, the resin film obtained using the photosensitive resin composition is required to have excellent properties such as electrical properties such as dielectric loss tangent, chemical resistance, and stretchability.

[0009] However, the conventional photosensitive resin composition described in Patent Document 1 still has room for improvement in terms of improving the developable pattern formability and reducing the dielectric loss tangent of the obtained resin film, and further improving the chemical resistance and stretchability.

[0010] Therefore, an object of the present invention is to provide a negative photosensitive resin composition capable of improving the developable pattern formability, reducing the dielectric loss tangent of the obtained resin film, and further improving the chemical resistance and stretchability.

[0011] Means for Solving the Problems

[0012] The inventors of the present invention conducted in-depth research to achieve the above object. Then, the inventors found that by using a resin composition containing a polymer having a specific structural unit and a photo radical generator as a negative photosensitive resin composition, the pattern formability in development can be improved. Further, it was found that by forming a resin film using this resin composition, the dielectric loss tangent of the obtained resin film can be reduced, and the chemical resistance and stretchability can be improved. Then, based on these findings, the present invention was completed.

[0013] That is, the present invention aims to advantageously solve the above problems, and the negative photosensitive resin composition of the present invention is characterized by containing a polymer and a photo radical generator, and the polymer contains a structural unit (I) represented by the following formula (I) and a structural unit (II) represented by the following formula (II).

[0014] [Chemical formula 1]

[0015]

[0016] In formula (I), R1 to R3 each independently represent a hydrogen atom, an alkyl group or an aromatic ring group, R1 to R3 may also combine 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.

[0017] In formula (II), R5 to R8 each independently represent a hydrogen atom, an alkyl group or an aromatic ring group, R5 to R8 may also combine to form a ring, and n represents 0, 1 or 2.

[0018] Thus, according to the negative photosensitive resin composition containing a polymer having structural unit (I) and structural unit (II) and a photo radical generator, the pattern formability in development can be improved. Further, the dielectric loss tangent of the obtained resin film can be reduced, and the chemical resistance and stretchability of the resin film can be improved.

[0019] Here, in the negative photosensitive resin composition of the present invention, it is preferable that the photo radical generator is an acylphosphine oxide-based or oxime ester-based photo radical generator. If an acylphosphine oxide-based or oxime ester-based photo radical generator is used as the photo radical generator, the pattern formability in development can be further improved, and the dielectric loss tangent of the obtained resin film can be further reduced.

[0020] In addition, in the negative photosensitive resin composition of the present invention, the content of the above photo radical generator is preferably more than 0.5 parts by mass and 25 parts by mass or less with respect to 100 parts by mass of the above polymer. If the content of the photo radical generator is at least the above lower limit, the crosslinking reaction of the functional group possessed by the structural unit of the above formula (I) can proceed sufficiently, and thus the developability for forming a pattern can be made more excellent. In addition, if the content of the photo radical generator is at most the above upper limit, the dielectric loss tangent of the obtained resin film can be further reduced.

[0021] Furthermore, in the negative photosensitive resin composition of the present invention, the content ratio of the structural unit (I) in the above polymer is preferably 3 mol% or more and 70 mol% or less. If the content ratio of the structural unit (I) in the polymer is within the above range, the stretchability of the obtained resin film becomes excellent. Moreover, if the content ratio of the structural unit (I) in the polymer is at least the above lower limit, the chemical resistance of the resin film can be improved, and if it is at most the above upper limit, an increase in the dielectric loss tangent of the resin film can be suppressed.

[0022] In addition, in the present invention, the "content ratio of the structural unit" can be measured using 1 H-NMR, 13 C-NMR and other nuclear magnetic resonance (NMR) methods.

[0023] Advantages of the Invention

[0024] According to the present invention, a negative photosensitive resin composition capable of improving the developability for forming a pattern, reducing the dielectric loss tangent of the obtained resin film, and improving the chemical resistance and stretchability can be provided. Detailed Description of the Invention

[0025] Here, the negative photosensitive resin composition of the present invention is not particularly limited and can be used when forming a resin film that can be included in electronic components such as integrated circuit elements, organic EL elements, and semiconductor packages. In particular, the negative photosensitive resin composition of the present invention can be particularly preferably used in the production of insulating organic films such as organic EL and semiconductor packages. In addition, the actinic energy rays used for patterning the resin film formed using the negative photosensitive resin composition of the present invention are not particularly limited, and examples thereof include light having a single wavelength such as ultraviolet rays, g-rays, h-rays, and i-rays, light rays such as KrF excimer laser and ArF excimer laser, and particle beams such as electron beams. Among them, the negative photosensitive resin composition of the present invention can be particularly preferably used in the wavelength range of 200 nm to 500 nm, for example.

[0026] (Negative Photosensitive Resin Composition)

[0027] The negative photosensitive resin composition of the present invention needs to contain a polymer having a structural unit described below and a photo radical generator, and can optionally contain a solvent and an additive component. Moreover, according to the negative photosensitive resin composition of the present invention, the pattern formability in development can be improved, the dielectric loss tangent of the resin film formed using the negative photosensitive resin composition can be reduced, and the chemical resistance and stretchability can be improved.

[0028] <Polymer>

[0029] The polymer contained in the negative photosensitive resin composition of the present invention is a polymer having a functional group which can undergo a crosslinking reaction by radicals generated by irradiation with active energy rays in the presence of a photo radical generator. Moreover, 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 can contain structural units other than the structural unit (I) and the structural unit (II).

[0030] [Chemical formula 2]

[0031]

[0032] [Structural unit (I)]

[0033] Moreover, in the structural unit (I), in the above formula (I), R1 to R3 each independently represent a hydrogen atom, an alkyl group or an aromatic ring group, and R1 to R3 can also combine to form a ring.

[0034] Here, the alkyl group which can constitute R1 to R3 is not particularly limited, and examples thereof include an unsubstituted alkyl group having 1 to 5 carbon atoms. Among them, as the alkyl group which can constitute R1 to R3, a methyl group or an ethyl group is preferred.

[0035] In addition, the aromatic ring group which can constitute R1 to R3 is not particularly limited, and examples thereof include an aromatic ring having 4 to 30 carbon atoms, such as a benzene ring and a naphthalene ring.

[0036] Furthermore, the ring formed by the combination of R1 to R3 can be a monocyclic ring or a polycyclic ring.

[0037] In addition, in the formula (I), X represents an alkylene group having 1 to 10 carbon atoms. Here, the alkylene group having 1 to 10 carbon atoms which can constitute X is not particularly limited, and a chain-like alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a propylene group, a n-butylene group, and an isobutylene group is preferred, a linear alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a propylene group, and a n-butylene group is more preferred, a linear alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, and a propylene group is further preferred, and a methylene group is particularly preferred.

[0038] Further, in formula (I), m represents 0, 1 or 2, more preferably 0 or 1.

[0039] Moreover, in formula (I), R4 represents a hydrogen atom or an alkyl group. Here, the alkyl group that can form R4 is not particularly limited, and examples thereof include an unsubstituted alkyl group having 1 to 5 carbon atoms. Among them, as the alkyl group that can form R4, a methyl group or an ethyl group is preferred.

[0040] Moreover, as shown in formula (I), in the structural unit (I), a substituted or unsubstituted acryloyl group is bonded to the cyclic olefin structure via an alkylene group represented by X, so that the mobility of the functional group is improved. Therefore, in the presence of free radicals, the crosslinking reactivity of the functional group in the polymer containing the structural unit (I) is improved. Thus, the negative photosensitive resin composition of the present invention containing a polymer containing the structural unit (I) and the above structural unit (II) and a photo radical generator can improve the pattern formability in development, and can reduce the dielectric loss tangent of the obtained resin film and improve the stretchability of the resin film.

[0041] Moreover, with respect to the total of 100 mol% of the structural unit (I) and the structural unit (II), the content ratio of the structural unit (I) in the polymer is preferably 3 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more, preferably 70 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less. If the content ratio of the structural unit (I) in the polymer is within the above range, the stretchability of the obtained resin film becomes excellent. In addition, if the content ratio of the structural unit (I) in the polymer is at least the above lower limit, the chemical resistance of the resin film can be improved, and if it is at most the above upper limit, an increase in the dielectric loss tangent of the resin film can be suppressed.

[0042] [Structural unit (II)]

[0043] In addition, in the structural unit (II), in the above formula (II), R5 to R8 each independently represent a hydrogen atom, an alkyl group or an aromatic ring group, and R4 to R8 can also combine to form a ring.

[0044] Here, the alkyl group that can form R4 to R8 is not particularly limited, and examples thereof include the same alkyl groups as those that can form R1 to R3.

[0045] In addition, the aromatic ring group that can form R4 to R8 is not particularly limited, and examples thereof include the same aromatic ring groups as those that can form R1 to R3.

[0046] Furthermore, the ring formed by the combination of R4 to R8 is not particularly limited, and examples thereof include the same ring as the ring formed by the combination of R1 to R3.

[0047] Furthermore, in formula (II), n represents 0, 1 or 2, preferably 0 or 1.

[0048] Moreover, with respect to the total of 100 mol% of structural unit (I) and structural unit (II), the content ratio of structural unit (II) in the polymer is preferably 3 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, still more preferably 30 mol% or more, even more preferably 50 mol% or more, particularly preferably 60 mol% or more, preferably 97 mol% or less, more preferably 90 mol% or less, and further preferably 85 mol% or less.

[0049] [Properties of the polymer]

[0050] - Weight-average molecular weight -

[0051] Furthermore, the weight-average molecular weight (Mw) of the above polymer is preferably 3000 or more, more preferably 5000 or more, further preferably 10000 or more, preferably 500000 or less, more preferably 300000 or less, and further preferably 100000 or less. If the weight-average molecular weight of the polymer is above the above lower limit, the mechanical properties can be improved. In addition, if the weight-average molecular weight of the polymer is below the above upper limit, the solvent solubility can be improved.

[0052] - Molecular weight distribution -

[0053] The molecular weight distribution (Mw / Mn) of the above polymer is preferably 4 or less, more preferably 3 or less, and further preferably 2 or less. If the molecular weight distribution of the polymer is below the upper limit, the resolution can be improved. In addition, in the present invention, "molecular weight distribution (Mw / Mn)" refers to the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn). Moreover, in the present invention, the weight-average molecular weight of the polymer is determined as a polystyrene equivalent value by gel permeation chromatography (GPC).

[0054] (Synthesis method of the polymer)

[0055] The method for preparing the above polymer is not particularly limited. For example, it can be efficiently synthesized by a method including the following steps: a step of synthesizing a ring-opening polymer by ring-opening polymerization of a norbornene-based monomer, and a step of obtaining a hydrogenated ring-opening polymer by hydrogenating the obtained ring-opening polymer (hereinafter referred to as "ring-opening polymerization step"), and a step of obtaining a modified product of the hydrogenated ring-opening polymer by subjecting the obtained hydrogenated ring-opening polymer to a modification reaction (hereinafter referred to as "modification step"). Hereinafter, each step will be described in detail.

[0056] <Ring-opening polymerization process>

[0057] In the ring-opening polymerization process, first, a ring-opening polymer is synthesized by the ring-opening polymerization reaction of a norbornene-based monomer (I) capable of forming the above structural unit (I) and a norbornene-based monomer (II) capable of forming the above structural unit (II).

[0058] [Norbornene-based monomer (I)]

[0059] 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 dec-4,8-diene, 3-hydroxymethyltricyclo[5.2.1.0 2,6 dec-4,8-diene, 4-hydroxyquadricyclo[6.2.1.1 3,6 .0 2,7 dodec-9-ene, 4-hydroxymethylquadricyclo[6.2.1.1 3,6 .0 2,7 dodec-9-ene, 4,5-dihydroxymethylquadricyclo[6.2.1.1 3, 6 .0 2,7 dodec-9-ene, etc. The norbornene-based monomer (I) can be used alone or in combination of two or more.

[0060] [Norbornene-based monomer (II)]

[0061] Examples of the norbornene-based monomer (II) include quadricyclo[4.4.0.1 2,5 .1 7,10 dodec-3-ene (common name: quadricyclododecene), 8-ethylidene-quadricyclo[4.4.0.1 2,5 .1 7,10 dodec-3-ene (common name: ethylidenequadricyclododecene), tricyclo[5.2.1.0 2,6 dec-3,8-diene (common name: dicyclopentadiene), 1,4-methylen-1,4,4a-9a-tetrahydrofluorene (common name: methylenetetrahydrofluorene), 5-ethylidene-bicyclo[2.2.1]hept-2-ene (common name: ethylidene norbornene), 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-methylene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, quadricyclo[10.2.1.02,11 .0 4,9 Pentadec-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-methylene-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 Pentadec-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 .0 3,8 Tetradec-3,5,7,12-tetraene, pentacyclo[9.2.1.1 3,9 .0 2,10 .0 4,8 Pentadec-12-ene, and their derivatives etc. In addition, derivatives refer to derivatives having substituents in the ring structure. Moreover, as substituents that can be present in the ring structure, for example, alkyl groups, alkylene groups, vinyl groups, alkoxycarbonyl groups, alkylidene groups can be cited. Moreover, the ring structure of the derivatives can have one of these substituents or two or more.

[0062] Moreover, the norbornene-based monomer (II) can be used alone or in combination of two or more.

[0063] The ring-opening polymerization reaction can be carried out in a solvent according to a known method. At this time, the solvent is not particularly limited, and organic solvents such as tetrahydrofuran and toluene can be used. In addition, as the molecular weight regulator, the following can be used: ethylene; α-olefins having 3 or more and 20 or less 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, 1-eicosene; non-conjugated dienes such as 1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, and their derivatives. In addition, as the ring-opening polymerization catalyst, a metal catalyst containing metals such as molybdenum, tungsten, and ruthenium can be used, and among them, a metal catalyst containing ruthenium is preferred. Furthermore, the ring-opening polymerization time is usually 1 hour or more and 10 hours or less, preferably 2 hours or more and 5 hours or less. Moreover, the ring-opening polymerization temperature is usually 20 °C or more and 100 °C or less, preferably 90 °C or less.

[0064] Then, a hydrogenation reaction is carried out on the obtained ring-opening polymer to synthesize a hydrogenated ring-opening polymer.

[0065] At this time, the hydrogenation reaction can be carried out according to a known method. In addition, the hydrogenation reaction time, hydrogenation reaction temperature, and hydrogenation pressure in the hydrogenation reaction are not particularly limited. The hydrogenation reaction time is usually 1 hour or more and 10 hours or less, preferably 5 hours or less. In addition, the hydrogenation reaction temperature is usually 100 °C or more and 200 °C or less, preferably 180 °C or less. Moreover, the hydrogenation pressure is usually 1 MPa or more and 10 MPa or less, preferably 5 MPa or less.

[0066] <Modification step>

[0067] In the modification step, a modification reaction is carried out on the terminal part of the hydrogenated ring-opening polymer obtained in the ring-opening polymerization step by using a modifier to synthesize a modified product of the hydrogenated ring-opening polymer (i.e., a polymer containing the above structural unit (I) and structural unit (II)). Here, as the modifier, compounds having a methacryloyl group or an acryloyl group can be used, for example. Examples of the compound having a methacryloyl group include methacryloyl chloride and methacrylic anhydride. In addition, examples of the compound having an acryloyl group include acryloyl chloride and acrylic anhydride. Among these, from the viewpoint of efficiently carrying out the modification reaction, methacryloyl chloride or acryloyl chloride is more preferably used.

[0068] Here, the modification reaction is not particularly limited. For example, it can be carried out by reacting a hydrogenated ring-opening polymer with a modifier in a solvent in the presence of a modification reaction catalyst. At this time, the modification reaction catalyst is not particularly limited, and for example, triethylamine, pyridine, etc. can be used. In addition, the solvent is not particularly limited, and for example, the same solvent as that used in the ring-opening polymerization reaction can be used. In addition, the modification reaction temperature and the modification reaction time are not particularly limited. The modification reaction temperature is usually -10°C or higher and 15°C or lower, and the modification reaction time is usually 1 hour or longer and 15 hours or shorter.

[0069] <Photo radical generator>

[0070] As the photo radical generator, acylphosphine oxide-based, oxime ester-based, or aromatic ketone-based photo radical generators, etc. can be used. One type of photo radical generator can be used, or two or more types can be used in combination. Among them, from the viewpoints of being able to further improve the pattern formability of development and further reducing the dielectric loss tangent of the obtained resin film, as the photo radical generator, acylphosphine oxide-based or oxime ester-based photo radical generators are preferably used.

[0071] Moreover, as the acylphosphine oxide-based photo radical generator, for example, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyl phenylethoxyphosphine oxide, etc. can be used.

[0072] In addition, as the oxime ester-based photo radical generator, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyl oxime), etc. can be used.

[0073] In addition, as the aromatic ketone-based radical generator, benzophenone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, 2-hydroxy-2-methyl-1-phenyl-propanone, 2-methyl-1[4-methylthio)phenyl]-2-morpholinopropanone, methyl o-benzoylbenzoate, [4-(methylphenylthio)phenyl]phenylmethane, 1,4-dibenzoylbenzene, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyldiphenyl ether, benzyl, etc. can be used.

[0074] [Content of photo radical generator]

[0075] Moreover, with respect to 100 parts by mass of the polymer, the content of the photo radical generator is usually 0.3 parts by mass or more, preferably more than 0.5 parts by mass, more preferably 1 part by mass or more, usually 25 parts by mass or less, preferably less than 20 parts by mass, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less. If the content of the photo radical generator is above the above lower limit, the crosslinking reaction of the functional groups in the above structural unit (I) can proceed sufficiently, so that the pattern formability in development can be made more excellent. In addition, if the content of the photo radical generator in the negative photosensitive resin composition is below the above upper limit, the dielectric loss tangent of the obtained resin film can be further reduced.

[0076] <Solvent>

[0077] There is no particular limitation on the solvent that the negative photosensitive resin composition of the present invention can contain, 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, diisopentyl 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 can be used alone or in combination of two or more.

[0078] Moreover, the content of the solvent in the negative photosensitive resin composition is preferably an amount such that, with respect to the total mass of the negative photosensitive resin composition, the total amount excluding the solvent is preferably 10% by mass or more, more preferably 20% by mass or more, preferably 60% by mass or less, and more preferably 50% by mass or less.

[0079] <Additive components>

[0080] In addition, there is no particular limitation on the additive components that the negative photosensitive resin composition of the present invention can contain, and examples thereof include surfactants, antioxidants, sensitizers, adhesion aids, etc. These additive components can be used alone or in combination of two or more. Among them, from the viewpoint of improving the coatability of the negative photosensitive resin composition of the present invention and further improving the uniformity of the film thickness of the obtained resin film, a surfactant is preferably included as an additive component.

[0081] There is no particular limitation on the surfactant, and known silicone surfactants, fluorine surfactants, etc. can be used. Moreover, the content ratio of the surfactant in the negative photosensitive resin composition is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, with respect to the total mass of the negative photosensitive resin composition.

[0082] <Preparation method of negative photosensitive resin composition>

[0083] The negative photosensitive resin composition of the present invention can be prepared by mixing the above-mentioned essential components and various optional components by known methods. Here, the negative photosensitive resin composition of the present invention is, for example, used as a negative photosensitive resin composition obtained by dissolving each component in a solvent and filtering. When dissolving in a solvent, known mixers such as stirrers, ball mills, sand mills, bead mills, pigment dispersers, grinding crushers, ultrasonic dispersers, homogenizers, planetary mixers, and filmix can be used. In addition, during filtration, a usual filtration method using a filter material such as a filter can be adopted.

[0084] <Method for manufacturing a resin film>

[0085] The negative photosensitive resin composition of the present invention can form a resin film by using a known film-forming method (for example, refer to International Publication No. 2015 / 033901). Moreover, the obtained resin film is not particularly limited, and a resin film having a desired pattern can be formed by performing an exposure step of irradiating any active energy ray, such as light having a wavelength of 200 nm or more and 500 nm or less, and a development step. In addition, a pre-bake step can be performed before the exposure step as needed, or a post-exposure bake (PEB) step can be performed at a desired time after the start of the exposure step. Furthermore, in addition, a post-bake step can be performed after the development step as needed.

[0086] Here, the developer used in the above development step is not particularly limited. For example, solvents such as the solvents that the negative photosensitive resin composition of the present invention can contain can be used as the developer. These developers can be used alone or in combination of two or more.

[0087] Examples

[0088] Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In addition, in the following description, unless otherwise specified, "%" and "parts" representing amounts are based on mass.

[0089] In the examples and comparative examples, the dielectric loss tangent, the developed film residue rate, the chemical resistance, the tensile elongation rate, and the weight average molecular weight and molecular weight distribution of the polymer were measured or evaluated by the following methods, respectively.

[0090] <Dielectric loss tangent>

[0091] Using a sputtering device (manufactured by Shibaura Electronics Co., Ltd., "i-Miller CFS-4EP-LL"), the resin compositions prepared in each example and each comparative example were spin-coated on a 4-inch silicon wafer on which an aluminum film with a thickness of 50 nm was formed. Then, pre-baking was performed using a hot plate at 90 °C for 2 minutes to form a resin film composed of the resin composition. Next, using a mask aligner (MaskAligner, manufactured by Canon Inc., "PLA501F") with a g-h-i mixed line, exposure was carried out at an exposure dose of 1000 mJ / cm 2 After that, heating was performed in nitrogen at 180 °C for 1 hour to cure the resin film, and a silicon wafer with a 10-μm-thick resin film was obtained. The obtained silicon wafer with a resin film was immersed in a 0.1 mol% hydrochloric acid aqueous 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 short strips with a width of 2 mm and a length of 50 mm as test pieces, and the dielectric loss tangent at 10 GHz of the test pieces was measured by the cavity resonator method.

[0092] A: Dielectric loss tangent is less than 0.0075

[0093] B: Dielectric loss tangent is 0.0075 or more and less than 0.01

[0094] C: Dielectric loss tangent is 0.01 or more

[0095] <Developed residue film rate>

[0096] The resin compositions prepared in each example and each comparative example were applied on a silicon wafer by the spin-coating method, and heating and drying (pre-baking) were performed using a hot plate at 90 °C for 2 minutes to form a resin film with a thickness of 5.0 μm. Next, using a mask aligner (MaskAligner, manufactured by Canon Inc., "PLA501F"), exposure of the g-h-i mixed line was carried out at an exposure dose of 1000 mJ / cm 2 through a photomask having a line and space pattern with a line width of 100 μm.

[0097] Next, using toluene as a developer, after performing a 60-second development treatment, spin-drying was carried out to obtain a laminate composed of a resin film having a line and space pattern and a silicon wafer. Using an optical interference film thickness measurement device (manufactured by Dainippon Screen Mfg Co., Ltd., "LAMBDA ACE VM-1210"), the film thickness of the line pattern portion of the resin film after the development treatment was measured, and the developed residue film rate (%) was calculated according to the following formula. The larger the value of the developed residue film rate, the more excellent the pattern formation property of the development, and thus it is preferred.

[0098] Developed residual film rate (%) = (film thickness of the line pattern part of the resin film after development treatment) /

[0099] (film thickness of the resin film before development) × 100

[0100] A: The developed residual film rate is 80% or more

[0101] B: The developed residual film rate is 50% or more and less than 80%

[0102] C: The developed residual film rate is less than 50%

[0103] <Chemical resistance>

[0104] After spin-coating the resin compositions prepared in the respective examples and comparative examples on a silicon wafer, pre-baking is performed at 90 °C for 2 minutes using a hot plate to form a resin film composed of the resin composition. Then, after exposing the g-h-i mixed line with an exposure dose of 1000 mJ / cm 2 using a mask aligner (Mask Aligner, manufactured by Canon Inc., "PLA501F"), heating is performed in nitrogen at 180 °C for 1 hour to cure the resin film, thereby obtaining a silicon wafer with a 10-μm-thick resin film.

[0105] The obtained silicon wafer with a resin film is immersed in a flux cleaning solution (HC-FX-50 manufactured by Tosoh Corporation) at 23 °C for 15 minutes, and the film thickness change is calculated according to the following formula.

[0106] (Film thickness change (%) = (film thickness of the resin film after immersion - film thickness of the resin film before immersion) / film thickness before immersion × 100)

[0107] Based on the calculated film thickness change value (%), the chemical resistance of the resin film is evaluated according to the following criteria. The film has no cracks or peeling, and the smaller the film thickness change, the more excellent the chemical resistance of the resin film.

[0108] A: The film has no cracks or peeling, and the film thickness change is less than 3%

[0109] B: The film has no cracks or peeling, and the film thickness change is 3% or more

[0110] C: Cracks or peeling occur in the film

[0111] <Tensile elongation rate>

[0112] Using a sputtering device (manufactured by Shibaura Electronics Co., Ltd., "i-Miller CFS-4EP-LL"), after spin-coating the resin compositions prepared in each example and each comparative example on a 4-inch silicon wafer on which an aluminum film with a thickness of 50 nm was formed, pre-baking was performed using a hot plate at 90 °C for 2 minutes to form a resin film composed of the resin composition. Then, using a mask aligner (MaskAligner, manufactured by Canon Inc., "PLA501F"), g-h-i mixed lines were exposed with an exposure dose of 1000 mJ / cm 2 After that, the resin film was cured by heating in nitrogen at 180 °C for 1 hour to obtain a silicon wafer with a 10-μm-thick resin film. The obtained silicon wafer with the resin film was immersed in a 0.1 mol% hydrochloric acid aqueous solution for 12 hours to etch the aluminum, and thus after the resin film was peeled off from the silicon wafer with the resin film, it was dried in an oven at 110 °C for 1 hour.

[0113] The dried resin film was cut into short strips with a width of 5 mm and a length of 40 mm as test pieces, and the tensile elongation rate of the resin film was measured by performing a tensile test on the test pieces. Specifically, a tensile test was performed using a tensile testing machine (manufactured by Shimadzu Corporation, "AGS-10kNX") at 23 °C with a grip interval of 20 mm and a tensile speed of 2 mm / minute, and the elongation rate at the breaking point was measured. Eight test pieces were tested, and the average value of the top three points was taken as the tensile elongation rate of the resin film formed using the resin compositions obtained in each example and each comparative example. The larger the value of the tensile elongation rate, the higher the elongation property of the resin film. Moreover, the higher the elongation property of the resin film, the less likely it is to generate cracks and peeling during the temperature cycle test and the drop impact test, so it is preferred.

[0114] A: Tensile elongation rate is 10% or more

[0115] B: Tensile elongation rate is 5% or more and less than 10%

[0116] C: Tensile elongation rate is less than 5%

[0117] <Weight-average molecular weight and molecular weight distribution>

[0118] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymers obtained in the examples and comparative examples were measured using a gel permeation chromatograph, and the molecular weight distribution (Mw / Mn) was calculated.

[0119] Specifically, using a gel permeation chromatograph (manufactured by Tosoh, HLC-8220), using tetrahydrofuran as an eluent, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymer were obtained as standard polystyrene conversion values. Then, the molecular weight distribution (Mw / Mn) was calculated.

[0120] (Synthesis Example 1)

[0121] <Ring-opening polymerization step>

[0122] 100 parts of a monomer mixture composed of 65 mol% of 2-norbornene-5-methanol (hereinafter simply referred to as "NBMOH") as a norbornene monomer (I) and 35 mol% of tetracyclododecene (hereinafter simply referred to as "TCD") as a norbornene monomer (II), 3.0 parts of 1,5-hexadiene as a molecular weight regulator, 0.025 parts of (1,3-dimesitylimidazol-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 added to a glass pressure-resistant reactor purged with nitrogen, and the mixture was reacted at 80 °C for 4 hours with stirring to obtain a polymerization reaction solution.

[0123] The obtained polymerization reaction solution was added to an autoclave, and hydrogenation reaction was carried out at 150 °C and a hydrogen pressure of 4 MPa with stirring for 5 hours. Then, 300 parts of tetrahydrofuran as a solvent was added to the reaction solution. These were dropped into 8000 parts of methanol, and the formed precipitate was recovered by filtration and dried under reduced pressure at 50 °C to obtain a hydrogenated product of the ring-opening polymer (A-1).

[0124] <Modification step>

[0125] A three-necked flask equipped with a stirring blade and a thermometer was purged with nitrogen, and 100 parts of the hydrogenated product of the ring-opening polymer (A-1), 336.5 parts of triethylamine as a modification reaction catalyst, and 400 parts of tetrahydrofuran as a solvent were added. The reaction solution was cooled to 0 °C with an ice bath. While maintaining the temperature of the reaction solution at 10 °C or lower, 298.0 parts of methacryloyl chloride as a modifier was dropped, and the mixture was stirred for 2 hours. Further, the reaction solution was heated to room temperature and stirred for 12 hours. Then, 200 parts of tetrahydrofuran as a solvent was added to the reaction solution, and it was cooled to 0 °C. While maintaining the temperature of the reaction solution at 10 °C or lower, methanol in an amount of 0.5 times the mass of methacryloyl chloride was added, and the mixture was stirred at 0 °C for 1 hour and then heated to room temperature and stirred for 1 hour.

[0126] The reaction solution was dropped into 8000 parts of methanol, and the formed precipitate was recovered by filtration. The precipitate was washed 3 times with methanol and then dried under reduced pressure at 50 °C to obtain a modified product of the hydrogenated product of the ring-opening polymer (hereinafter referred to as "modified hydrogenated product of the ring-opening polymer") (B-1). The weight-average molecular weight of the modified hydrogenated product of the ring-opening polymer (B-1) measured by GPC was 14,600, and the molecular weight distribution was 1.7.

[0127] By1 By \(^1\)H-NMR measurement, it was confirmed that the methacryloyl modification rate of the ring-opening polymer hydride (A-1) was 100%, and the content of NBMOH after methacryloyl modification in the modified ring-opening polymer hydride (B-1) was 65 mol%. In addition, it was confirmed that the modified ring-opening polymer hydride (B-1) was a polymer containing 65 mol% of the structural unit represented by the following formula (I-1) and 35 mol% of the structural unit represented by the following formula (II-1).

[0128] [Chemical formula 3]

[0129]

[0130] (Synthesis Example 2)

[0131] In Synthesis Example 1, NBMOH was changed to 40 mol%, TCD was changed to 60 mol%, and the solvent was changed to toluene. Otherwise, the same operations as in Synthesis Example 1 were carried out to obtain a ring-opening polymer hydride (A-2).

[0132] Then, the ring-opening polymer hydride (A-1) was changed to the ring-opening polymer hydride (A-2), triethylamine was changed to 229.9 parts, methacryloyl chloride was changed to 176.2 parts, and the solvent was changed to toluene. Otherwise, the same operations as in Synthesis Example 1 were carried out to obtain a modified ring-opening polymer hydride (B-2). The weight-average molecular weight of the modified ring-opening polymer hydride (B-2) measured by GPC was 13,800, and the molecular weight distribution was 1.6.

[0133] By 1 \(^1\)H-NMR measurement, it was confirmed that the methacryloyl modification rate of the ring-opening polymer hydride (A-2) was 100%, and the content of NBMOH after methacryloyl modification in the modified ring-opening polymer hydride (B-2) was 40 mol%. In addition, it was confirmed that the modified ring-opening polymer hydride (B-2) was a polymer containing 40 mol% of the structural unit represented by the following formula (I-2) and 60 mol% of the structural unit represented by the following formula (II-2).

[0134] [Chemical formula 4]

[0135]

[0136] (Synthesis Example 3)

[0137] In Synthesis Example 1, NBMOH was changed to 5 mol%, TCD was changed to 95 mol%, and the solvent was changed to toluene. Otherwise, the same operations as in Synthesis Example 1 were carried out to obtain a ring-opening polymer hydride (A-3).

[0138] Then, the ring-opening polymer hydride (A-1) was changed to the ring-opening polymer hydride (A-3), triethylamine was changed to 22.4 parts, methacryloyl chloride was changed to 19.8 parts, and the solvent was changed to toluene. Otherwise, the same operations as in Synthesis Example 1 were carried out to obtain a modified ring-opening polymer hydride (B-3). The weight-average molecular weight of the modified ring-opening polymer hydride (B-3) measured by GPC was 13,500, and the molecular weight distribution was 1.6.

[0139] By 1 1H-NMR measurement, it was confirmed that the methacryloyl group modification rate of the ring-opening polymer hydride (A-3) was 100%, and the content of NBMOH after methacryloyl group modification in the modified ring-opening polymer hydride (B-3) was 5 mol%. In addition, it was confirmed that the modified ring-opening polymer hydride (B-3) was a polymer containing 5 mol% of the structural unit represented by the following formula (I-3) and 95 mol% of the structural unit represented by the following formula (II-3).

[0140] [Chemical formula 5]

[0141]

[0142] (Synthesis Example 4)

[0143] In Synthesis Example 1, NBMOH was changed to 15 mol%, and tetracyclododecene (hereinafter simply referred to as "ETD") in which TCD was changed from 90 mol% to 85 mol% was used. 3.0 parts of 1,5-hexadiene was changed to 1.0 part. Otherwise, the same operations as in Synthesis Example 1 were carried out to obtain a ring-opening polymer hydride (A-4).

[0144] Then, the ring-opening polymer hydride (A-1) was changed to the ring-opening polymer hydride (A-4), triethylamine was changed to 60.0 parts, and methacryloyl chloride was changed to 53.2 parts. Otherwise, the same operations as in Synthesis Example 1 were carried out to obtain a modified ring-opening polymer hydride (B-4). The weight-average molecular weight of the modified ring-opening polymer hydride (B-4) measured by GPC was 29,000, and the molecular weight distribution was 1.4.

[0145] By 1 1H-NMR measurement, it was confirmed that the methacryloyl group modification rate of the ring-opening polymer hydride (A-4) was 100%, and the content of NBMOH after methacryloyl group modification in the modified ring-opening polymer hydride (B-4) was 15 mol%. In addition, it was confirmed that the modified ring-opening polymer hydride (B-4) was a polymer containing 15 mol% of the structural unit represented by the following formula (I-4) and 85 mol% of the structural unit represented by the following formula (II-4).

[0146] [Chemical formula 6]

[0147]

[0148] (Synthesis Example 5)

[0149] In Synthesis Example 1, NBMOH was changed from 10 mol% to 30 mol%, and 90 mol% of TCD was changed to 70 mol% of ETD. Except for this, the same operations as in Synthesis Example 1 were carried out to obtain a hydrogenated ring-opening polymer (A-5).

[0150] Then, the hydrogenated ring-opening polymer (A-1) was changed to the hydrogenated ring-opening polymer (A-5), triethylamine was changed to 126.4 parts, and methacryloyl chloride was changed to 111.2 parts. Except for this, the same operations as in Synthesis Example 1 were carried out to obtain a modified hydrogenated ring-opening polymer (B-5). The weight-average molecular weight of the modified hydrogenated ring-opening polymer (B-5) measured by GPC was 14700, and the molecular weight distribution was 1.7.

[0151] By 1 1H-NMR measurement, it was confirmed that the methacryloyl modification rate of the hydrogenated ring-opening polymer (A-5) was 100%, and the content of NBMOH after methacryloyl modification in the modified hydrogenated ring-opening polymer (B-5) was 30 mol%. In addition, it was confirmed that the modified hydrogenated ring-opening polymer (B-5) was a polymer containing 30 mol% of the structural unit represented by the following formula (I-5) and 70 mol% of the structural unit represented by the following formula (II-5).

[0152] [Chemical formula 7]

[0153]

[0154] (Synthesis Example 6)

[0155] In Synthesis Example 1, NBMOH was changed from 10 mol% to 25 mol%, 90 mol% of TCD was changed to 75 mol% of dicyclopentadiene, and the solvent was changed to toluene. Except for this, the same operations as in Synthesis Example 1 were carried out to obtain a hydrogenated ring-opening polymer (A-6).

[0156] Then, the hydrogenated ring-opening polymer (A-1) was changed to the hydrogenated ring-opening polymer (A-6), triethylamine was changed to 136.0 parts, methacryloyl chloride was changed to 120.4 parts, and the solvent was changed to toluene. Except for this, the same operations as in Synthesis Example 1 were carried out to obtain a modified hydrogenated ring-opening polymer (B-6). The weight-average molecular weight of the modified hydrogenated ring-opening polymer (B-6) measured by GPC was 15000, and the molecular weight distribution was 1.6.

[0157] By 1By \(^1\)H-NMR measurement, it was confirmed that the methacryloyl modification rate of the ring-opened polymer hydride (A-6) was 100%, and the content of NBMOH after methacryloyl modification in the modified ring-opened polymer hydride (B-6) was 25 mol%. In addition, it was confirmed that the modified ring-opened polymer hydride (B-6) was a polymer containing 25 mol% of the structural unit represented by the following formula (I-6) and 75 mol% of the structural unit represented by the following formula (II-6).

[0158] [Chemical formula 8]

[0159]

[0160] (Synthesis Example 7)

[0161] In Synthesis Example 1, NBMOH was changed from 10 mol% to 35 mol%, and 90 mol% of TCD was changed to 65 mol% of ETD. Otherwise, the same operations as in Synthesis Example 1 were carried out to obtain a ring-opened polymer hydride (A-7).

[0162] Then, the ring-opened polymer hydride (A-1) was changed to the ring-opened polymer hydride (A-7), triethylamine was changed to 136.0 parts, and methacryloyl chloride was changed to 120.4 parts of acryloyl chloride. Otherwise, the same operations as in Synthesis Example 1 were carried out to obtain a modified ring-opened polymer hydride (B-7). The weight-average molecular weight of the modified ring-opened polymer hydride (B-7) measured by GPC was 13300, and the molecular weight distribution was 1.6.

[0163] By 1 \(^1\)H-NMR measurement, it was confirmed that the acryloyl modification rate of the ring-opened polymer hydride (A-7) was 100%, and the content of NBMOH after acryloyl modification in the modified ring-opened polymer hydride (B-7) was 35 mol%. In addition, it was confirmed that the modified ring-opened polymer hydride (B-7) was a polymer containing 35 mol% of the structural unit represented by the following formula (I-7) and 65 mol% of the structural unit represented by the following formula (II-7).

[0164] [Chemical formula 9]

[0165]

[0166] (Synthesis Example 8)

[0167] In Synthesis Example 1, NBMOH was changed from 10 mol% to 40 mol%, and 90 mol% of TCD was changed to 30 mol% of ethylidene norbornene (ENB) and 30 mol% of methylene tetrahydrofluorene (MTF). Otherwise, the same operations as in Synthesis Example 1 were carried out to obtain a ring-opened polymer hydride (A-8).

[0168] Then, the ring-opening polymer hydride (A-1) was changed to the ring-opening polymer hydride (A-8), triethylamine was changed to 201.8 parts, and methacryloyl chloride was changed to 154.7 parts. Otherwise, the same operations as in Synthesis Example 1 were carried out to obtain a modified ring-opening polymer hydride (B-8). The weight-average molecular weight of the modified ring-opening polymer hydride (B-8) measured by GPC was 14,100, and the molecular weight distribution was 1.7.

[0169] By 1 1H-NMR measurement, it was confirmed that the methacryloyl group modification rate of the ring-opening polymer hydride (A-8) was 100%, and the content of NBMOH after methacryloyl group modification in the modified ring-opening polymer hydride (B-8) was 40 mol%. In addition, it was confirmed that the modified ring-opening polymer hydride (B-8) was a polymer containing 40 mol% of the structural unit represented by the following formula (I-8), 30 mol% of the structural unit represented by the following formula (II-8a), and 30 mol% of the structural unit represented by the following formula (II-8b).

[0170] [Chemical formula 10]

[0171]

[0172] (Synthesis Example 9)

[0173] In Synthesis Example 1, 10 mol% of NBMOH was changed to 40 mol% of norbornenol, TCD was changed from 90 mol% to 60 mol%, 3.0 parts of 1,5-hexadiene was changed to 1.0 part, and the solvent was changed to toluene. Otherwise, the same operations as in Synthesis Example 1 were carried out to obtain a ring-opening polymer hydride (A-9).

[0174] Then, the ring-opening polymer hydride (A-1) was changed to the ring-opening polymer hydride (A-9), triethylamine was changed to 326.4 parts, methacryloyl chloride was changed to 250.3 parts, and the solvent was changed to toluene. Otherwise, the same operations as in Synthesis Example 1 were carried out to obtain a modified ring-opening polymer hydride (B-9). The weight-average molecular weight of the modified ring-opening polymer hydride (B-9) measured by GPC was 31,000, and the molecular weight distribution was 1.7.

[0175] By 1 1H-NMR measurement, it was confirmed that the methacryloyl group modification rate of the ring-opening polymer hydride (A-9) was 100%, and the content of NBMOH after methacryloyl group modification in the modified ring-opening polymer hydride (B-9) was 40 mol%. In addition, it was confirmed that the modified ring-opening polymer hydride (B-9) was a polymer containing 40 mol% of the structural unit represented by the following formula (I-9) and 60 mol% of the structural unit represented by the following formula (II-9).

[0176] [Chemical Formula 11]

[0177]

[0178] (Synthesis Example 10)

[0179] By the addition polymerization reaction of norbornene (NB), which is a norbornene-based monomer, and NBMOH, a norbornene / norbornene methanol copolymer as an addition polymer (A-10) was synthesized. Specifically, except that the scale was 20 times, the NB / NBMOH copolymer was synthesized according to the method described in Macromolecules 29, 2761 (1996). In addition, by 1 1H-NMR measurement, the content of NBMOH in the NB / NBMOH copolymer was 15 mol%.

[0180] Then, the ring-opening polymer hydride (A-1) was changed to the addition polymer (A-10), triethylamine was changed to 107.7 parts, methacryloyl chloride was changed to 82.6 parts, and further the reaction solvent was changed to toluene. Otherwise, the same operations as in Synthesis Example 1 were carried out to obtain a modified addition polymer (B-10).

[0181] By 1 1H-NMR measurement, it was confirmed that the methacryloyl modification rate of the addition polymer (A-10) was 100%, and the content of NBMOH after methacryloyl modification in the modified addition polymer (B-10) was 15 mol%. The weight-average molecular weight of the modified ring-opening polymer hydride (B-9) measured by GPC was 28,100, and the molecular weight distribution was 1.8. In addition, it was confirmed that the modified addition polymer (B-10) was a polymer containing 15 mol% of the structural unit represented by the following formula (I-10) and 85 mol% of the structural unit represented by the following formula (II-10).

[0182] [Chemical Formula 12]

[0183]

[0184] (Example 1)

[0185] (Preparation of Resin Composition)

[0186] 100 parts of the hydrogenated modified ring-opening polymer (B-1) obtained in Synthesis Example 1, 5 parts of an oxime ester-based photo radical generator (manufactured by BASF, "Irgacure OEX01", chemical formula: 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime), hereinafter referred to as "oxime ester-based radical generator (1)"), and toluene as a solvent (in an amount of 30% in total excluding the solvent with respect to the total mass of the resin composition) were mixed and dissolved. Then, a surfactant (manufactured by Shin-Etsu Silicone Co., Ltd., "KP-341", hereinafter referred to as "surfactant (1)") was added in an amount of 0.03% with respect to the total amount of the resin composition, and then filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm (hereinafter referred to as "filter (1)") to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1.

[0187] (Example 2)

[0188] 100 parts of the hydrogenated modified ring-opening polymer (B-2) obtained in Synthesis Example 2, 5 parts of the oxime ester-based photo radical generator (1), and toluene as a solvent (in an amount of 30% in total excluding the solvent with respect to the total amount of the resin composition) were mixed and dissolved. Then, the surfactant (1) was added in an amount of 0.03% with respect to the total amount of the resin composition, and then filtered through the filter (1) to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1.

[0189] (Example 3)

[0190] 100 parts of the hydrogenated modified ring-opening polymer (B-3) obtained in Synthesis Example 3, 5 parts of the oxime ester-based photo radical generator (1), and toluene as a solvent (in an amount of 30% in total excluding the solvent with respect to the total weight of the resin composition) were mixed and dissolved. Then, the surfactant (1) was added in an amount of 0.03% with respect to the total weight of the resin composition, and then filtered through the filter (1) to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1.

[0191] (Example 4)

[0192] 100 parts of the hydrogenated modified ring-opening polymer (B-4) obtained in Synthesis Example 4, 5 parts of an oxime ester-based photo-radical generator (manufactured by BASF, "Irgacure OEX02", chemical formula: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetoxime), hereinafter referred to as "oxime ester-based photo-radical generator (2)"), and toluene as a solvent (in an amount such that the total amount excluding the solvent is 30% relative to the total amount of the resin composition) were mixed and dissolved. Then, after adding surfactant (1) in an amount of 0.03% relative to the total amount of the resin composition, it was filtered through filter (1) to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1.

[0193] (Example 5)

[0194] 100 parts of the hydrogenated modified ring-opening polymer (B-5) obtained in Synthesis Example 5, 10 parts of an acylphosphine oxide-based photo-radical generator (manufactured by BASF, "Omnirad 819", chemical formula: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide), and toluene as a solvent (in an amount such that the total amount excluding the solvent is 30% relative to the total mass of the resin composition) were mixed and dissolved. Then, after adding surfactant (1) in an amount of 0.03% relative to the total amount of the resin composition, it was filtered through filter (1) to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1.

[0195] (Example 6)

[0196] 100 parts of the hydrogenated modified ring-opening polymer (B-5) obtained in Synthesis Example 5, 20 parts of the oxime ester-based photo-radical generator (1), and toluene as a solvent (in an amount such that the total amount excluding the solvent is 30% relative to the total amount of the resin composition) were mixed and dissolved. Then, after adding surfactant (1) in an amount of 0.03% relative to the total amount of the resin composition, it was filtered through filter (1) to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1.

[0197] (Example 7)

[0198] 100 parts of the hydrogenated modified ring-opening polymer (B-6) obtained in Synthesis Example 6, 5 parts of an oxime ester-based photo radical generator (2), and toluene as a solvent (in an amount of 30% in total excluding the solvent relative to the total amount of the resin composition) were mixed and dissolved. Subsequently, surfactant (1) was added in an amount of 0.03% relative to the total amount of the resin composition, and then filtered through filter (1) to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1.

[0199] (Example 8)

[0200] 100 parts of the hydrogenated modified ring-opening polymer (B-6) obtained in Synthesis Example 6, 0.5 parts of an oxime ester-based photo radical generator (2), and toluene as a solvent (in an amount of 30% in total excluding the solvent relative to the total amount of the resin composition) were mixed and dissolved. Subsequently, surfactant (1) was added in an amount of 0.03% relative to the total amount of the resin composition, and then filtered through filter (1) to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1.

[0201] (Example 9)

[0202] 100 parts of the hydrogenated modified ring-opening polymer (B-7) obtained in Synthesis Example 7, 3 parts of an oxime ester-based photo radical generator (1), and toluene as a solvent (in an amount of 30% in total excluding the solvent relative to the total amount of the resin composition) were mixed and dissolved. Subsequently, surfactant (1) was added in an amount of 0.03% relative to the total amount of the resin composition, and then filtered through filter (1) to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1.

[0203] (Example 10)

[0204] 100 parts of the hydrogenated modified ring-opening polymer (B-2) obtained in Synthesis Example 2, 5 parts of benzophenone as an aromatic ketone-based photo radical generator, and toluene as a solvent (in an amount of 30% in total excluding the solvent relative to the total amount of the resin composition) were mixed and dissolved. Subsequently, surfactant (1) was added in an amount of 0.03% relative to the total amount of the resin composition, and then filtered through filter (1) to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1.

[0205] (Example 11)

[0206] 100 parts of the hydrogenated modified ring-opening polymer (B-8) obtained in Synthesis Example 8, 5 parts of an oxime ester-based photo radical generator (2), and toluene as a solvent (in an amount of 30% in total excluding the solvent with respect to the total amount of the resin composition) were mixed and dissolved. Then, after adding surfactant (1) in an amount of 0.03% with respect to the total amount of the resin composition, it was filtered through filter (1) to prepare a resin composition.

[0207] Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1.

[0208] (Comparative Example 1)

[0209] 100 parts of the hydrogenated modified ring-opening polymer (B-9) obtained in Synthesis Example 9, 10 parts of the acylphosphine oxide-based photo radical generator used in Example 5, and toluene as a solvent (in an amount of 30% in total excluding the solvent with respect to the total amount of the resin composition) were mixed and dissolved. Then, after adding surfactant (1) in an amount of 0.03% with respect to the total amount of the resin composition, it was filtered through filter (1) to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1.

[0210] (Comparative Example 2)

[0211] 100 parts of the hydrogenated modified ring-opening polymer (B-2) obtained in Synthesis Example 2, 10 parts of the peroxide-based thermal radical generator dicumyl peroxide as a thermal radical generator, and toluene as a solvent (in an amount of 30% in total excluding the solvent with respect to the total amount of the resin composition) were mixed and dissolved. Then, after adding surfactant (1) in an amount of 0.03% with respect to the total amount of the resin composition, it was filtered through filter (1) to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1.

[0212] (Comparative Example 3)

[0213] 100 parts of the modified addition polymer (B-10) obtained in Synthesis Example 10, 5 parts of an oxime ester-based photo radical generator (1), and toluene as a solvent (in an amount of 30% in total excluding the solvent with respect to the total amount of the resin composition) were mixed and dissolved. Then, after adding surfactant (1) in an amount of 0.03% with respect to the total amount of the resin composition, it was filtered through filter (1) to prepare a resin composition. Then, using the obtained resin composition, various evaluations were carried out as described above. The results are shown in Table 1.

[0214] [Table 1]

[0215]

[0216] As can be seen from Table 1, the resin compositions (negative photosensitive resin compositions) of Examples 1 to 11 containing a polymer having a specified structural unit and a photo-radical generator are excellent in terms of the dielectric loss tangent, the remaining film rate after development, chemical resistance, and elongation at break.

[0217] In contrast, it can be seen that even in the resin composition of Comparative Example 1 using a polymer having a structural unit with a functional group, when using a polymer having a structure in which the functional group is directly bonded to the hydrogenated product of the ring-opening polymer, neither the remaining film rate after development nor the elongation at break can be improved.

[0218] Furthermore, it can be seen that in the resin composition of Comparative Example 2 using a thermal radical generator as the radical generator, the dielectric loss tangent decreases and the remaining film rate after development cannot be improved.

[0219] In addition, it can be seen that in the resin composition of Comparative Example 3 using a modified addition polymer, neither chemical resistance nor elongation at break can be improved.

[0220] Industrial Applicability

[0221] According to the present invention, a negative photosensitive resin composition capable of improving the pattern formability in development, reducing the dielectric loss tangent of the obtained resin film, and improving chemical resistance and stretchability can be provided.

Claims

1. A negative photosensitive resin composition comprising a polymer and a photo radical generator, wherein the polymer contains a structural unit (I) represented by the following formula (I) and a structural unit (II) represented by the following formula (II), the photo radical generator is at least one selected from acylphosphine oxide-based, oxime ester-based, and aromatic ketone-based photo radical generators, the content ratio of the structural unit (I) in the polymer is 5 mol% or more and 65 mol% or less, in formula (I), R1 to R3 each independently represent a hydrogen atom, an alkyl group, or an aromatic ring group, R1 to R3 may also combine to form a ring, R4 represents a hydrogen atom or an alkyl group, X represents an alkylene group having 1 to 10 carbon atoms, 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, R5 to R8 may also combine to form a ring, n represents 0, 1, or 2.

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

3. The negative photosensitive resin composition according to claim 1 or 2, wherein, The content of the photo radical generator is more than 0.5 part by mass and 25 parts by mass or less with respect to 100 parts by mass of the polymer.

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