resin composition

Abstract

A resin composition including a cycloolefin polymer having a styryl group in a side chain.

Description

[Technical Field]

[0001] The present invention relates to a resin composition. Specifically, the present invention relates to a resin composition that can be used to form a resin film. [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] Various studies have been conducted on resin compositions capable of forming the above-mentioned resin films. For example, Patent Document 1 proposes a cyclic olefin resin having a functional group with a polymerizable double bond in the side chain. Patent Document 1 proposes the synthesis of cyclic olefin resins using, as cyclic olefins having a functional group with a polymerizable double bond in a side chain, specifically, 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 5-(meth)acrylic acid-2-norbornene, (meth)acrylic acid 5-norbornene-2-methyl ester, (meth)acrylic acid 5-norbornene-2-ethyl ester, (meth)acrylic acid 5-norbornene-2-n-butyl ester, (meth)acrylic acid 5-norbornene-2-n-propyl ester, (meth)acrylic acid 5-norbornene-2-i-butyl ester, (meth)acrylic acid 5-norbornene-2-i-propyl ester, (meth)acrylic acid 5-norbornene-2-hexyl ester, (meth)acrylic acid 5-norbornene-2-octyl ester, (meth)acrylic acid 5-norbornene-2-decyl ester, etc. Furthermore, for example, Patent Document 2 proposes a resin composition containing a cyclic olefin copolymer having a plurality of crosslinkable double bonds in the side chain portion. Examples of the crosslinkable double bonds contained in the side chain of such a cyclic olefin copolymer are broadly exemplified by vinyl groups, alkenyl groups, acryloyl groups, and methacryloyl groups, and specifically, a resin composition containing LCOC-4 manufactured by Mitsui Chemicals, Inc. is proposed. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-156821 [Patent Document 2] JP 2018-39950 A Summary of the Invention [Problem to be solved by the invention]

[0005] Here, electronic components and the like having a resin film formed using a resin composition may be exposed to high temperature and high humidity conditions during use. Therefore, the resin film provided on the electronic components is required to exhibit stable performance before and after exposure to such conditions. However, the resin film obtained according to the above-mentioned conventional technology has room for improvement in this respect.

[0006] Therefore, an object of the present invention is to provide a resin composition capable of forming a resin film whose dielectric loss tangent value is unlikely to change before and after exposure to high-temperature and high-humidity conditions. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to achieve the above object, and have newly discovered that when a styryl group is introduced into the side chain of a cyclic olefin polymer, a resin composition can be obtained that can form a resin film whose dielectric loss tangent value is less likely to change before and after exposure to high-temperature and high-humidity conditions, and have completed the present invention.

[0008] The present invention aims to advantageously solve the above-mentioned problems by providing a resin composition comprising a cyclic olefin polymer having a styryl group in a side chain, and forming a resin film having a dielectric loss tangent that is less likely to change before and after exposure to high-temperature and high-humidity conditions.

[0009] In the resin composition of the present invention, the cyclic olefin polymer is preferably a ring-opening polymer, which makes it possible to form a resin film with high extensibility.

[0010] Furthermore, in the resin composition of the present invention, the cyclic olefin polymer preferably contains a structural unit represented by the following formula (I): [ka] where R 1 ~R 4each independently represents a hydrogen atom, an organic group having a styryl group, an alkyl group, or an aromatic ring group (excluding groups corresponding to the organic group having a styryl group), and R 1 ~R 4 At least one of the above is an organic group having a styryl group, and m is an integer of 0 to 4. When the cyclic olefin polymer has a structural unit represented by the above formula (I), it is possible to form a resin film whose dielectric loss tangent value is less likely to change before and after exposure to high-temperature and high-humidity conditions. In addition, R in the above formula (I) 1 ~R 4 The organic group having a styryl group capable of forming the formula (I) may have a substituent other than a styryl group. 1 ~R 4 The alkyl group and aromatic ring group capable of forming the formula (I) may each independently have a substituent.

[0011] Furthermore, in the resin composition of the present invention, the cyclic olefin polymer preferably further contains a structural unit represented by the following formula (II): [ka] where R 5 ~R 8 each independently represents a hydrogen atom, an alkyl group, or an aromatic ring group (excluding the above-mentioned organic group having a styryl group), and R 5 ~R 8 may be bonded to form a ring, and n is an integer of 0 to 4. If the cyclic olefin polymer has a structural unit represented by the above formula (II), it is possible to form a resin film whose dielectric loss tangent value is less likely to change before and after exposure to high-temperature and high-humidity conditions. In addition, R in the above formula (II) 5 ~R 8 The alkyl group and aromatic ring group capable of forming the formula (I) may each independently have a substituent.

[0012] Furthermore, the resin composition of the present invention may contain a polymerization initiator. The polymerization initiator is preferably an oxime ester-based photoradical generator. The inclusion of an oxime ester-based photoradical generator as the polymerization initiator allows for efficient production of a resin film. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a resin composition capable of forming a resin film whose dielectric loss tangent value is unlikely to change before and after exposure to high-temperature and high-humidity conditions. DETAILED DESCRIPTION OF THE INVENTION

[0014] Here, the resin composition of the present invention is not particularly limited and can be used when forming a resin film that can be provided on electronic components such as integrated circuit elements, organic electroluminescent elements, and semiconductor packages. In particular, the resin composition of the present invention can be particularly suitably used when producing insulating organic films such as organic electroluminescent elements, semiconductor packages, printed wiring boards, and solder resists. Furthermore, the resin composition of the present invention can be suitably used as a negative-type photosensitive resin composition in which the solubility of exposed areas in a developer is reduced, and the exposed areas remain after development. Furthermore, the active energy rays used when exposing a resin film formed using the resin composition of the present invention include, but are not limited to, 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.

[0015] (Resin composition) The resin composition of the present invention is required to contain a cyclic olefin polymer having a styryl group in a side chain, and may optionally contain a polymerization initiator, a solvent, and other additive components. The resin composition of the present invention can form a resin film whose dielectric loss tangent value is unlikely to change before and after exposure to high-temperature and high-humidity conditions.

[0016] <Polymer> The cyclic olefin polymer having a styryl group in a side chain contained in the resin composition of the present invention is a polymer in which a crosslinking reaction can proceed by radicals generated by irradiation with active energy rays in the presence of a polymerization initiator. Here, the cyclic olefin polymer having a styryl group in a side chain is an addition polymer or a ring-opening polymer. Among these, from the viewpoint of being able to form a resin film with good elongation, the cyclic olefin polymer having a styryl group in a side chain is preferably a ring-opening polymer.

[0017] The cyclic olefin polymer having a styryl group in a side chain preferably contains a structural unit (I) represented by the following formula (I) and a structural unit (II) represented by the following formula (II). When the polymer has such a structure, it is possible to form a resin film whose dielectric loss tangent value is less likely to change before and after exposure to high-temperature and high-humidity conditions. Furthermore, when the polymer has such a structure, it is possible to reduce the dielectric loss tangent value of the obtained resin film and improve the elongation of the obtained resin film.

[0018] [ka] [ka]

[0019] <<Structural unit (I)>> In the structural unit (I), R 1 ~R 4 each independently represents a hydrogen atom, an organic group having a styryl group, an alkyl group, or an aromatic ring group (excluding groups corresponding to an organic group having a styryl group), and R 1 ~R 4 At least one of the groups is an organic group having a styryl group, and m is an integer of 0 to 4.

[0020] where R 1 ~R 4 Examples of the organic group having a styryl group that can constitute the above include organic groups represented by the following formula (III).

[0021] [ka]

[0022] In the above formula (III), X and Z represent a single bond or an alkylene group having 1 to 10 carbon atoms, Y represents an oxygen atom or a sulfur atom, and R 9 is a hydrogen atom or a substituent, and p is an integer of 0-4.

[0023] The alkylene group having 1 to 10 carbon atoms which may be X and Z in the above formula (III) 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] In the above formula (III), R 9 Possible substituents include, but are not limited to, alkyl groups such as methyl and ethyl groups, and halogeno groups such as fluoro and chloro groups.

[0025] In the above formula (III), it is preferable that p is 0, that is, the styryl group has no substituent.

[0026] In addition, in the above formula (I), R 1 ~R 4 The alkyl group that can constitute the group is not particularly limited, and examples thereof include alkyl groups having 1 to 5 carbon atoms.

[0027] Furthermore, R 1 ~R 4 The aromatic ring group that can constitute the above is not particularly limited as long as it is a group other than the above-mentioned organic group having a styryl group, and examples thereof include aromatic ring groups having 4 to 30 carbon atoms.

[0028] Furthermore, in formula (I), m represents an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1.

[0029] In formula (I), R 1 ~R 4 Preferably, one of the structural units is an organic group having a styryl group, and the others are hydrogen atoms, because if the structural unit (I) is such a structural unit, synthesis is relatively easy and the production efficiency of the resin composition is improved.

[0030] Furthermore, since the structural unit (I) has an organic group having a styryl group, the polymer is less likely to be hydrolyzed even when the formed resin film is exposed to high-temperature, high-humidity conditions, and therefore, the change in the dielectric tangent value of the resin film before and after exposure to high-temperature, high-humidity conditions can be suppressed.

[0031] The content of the structural unit (I) in the polymer is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, and preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 55 mol% or less, based on the total structural units. When the content of the structural unit (I) in the polymer is within the above range, the resulting resin film is less susceptible to deterioration under high-temperature, high-humidity conditions, and the change in the dielectric loss tangent value between before and after exposure to high-temperature, high-humidity conditions can be more effectively suppressed. In particular, when the content of the structural unit (I) in the polymer is equal to or greater than the above lower limit, the glass transition temperature of the resulting resin film can be prevented from decreasing. Furthermore, when the content of the structural unit (I) in the polymer is equal to or less than the above upper limit, the elongation of the resulting resin film can be improved. In this specification, the "content ratio of structural units" means 1 H-NMR and 13 It can be measured using nuclear magnetic resonance (NMR) techniques such as C-NMR.

[0032] <<Structural unit (II)>> In the structural unit (II), R 5 ~R 8 each independently represents a hydrogen atom, an alkyl group, or an aromatic ring group (excluding groups corresponding to organic groups having a styryl group), and R 5 ~R 8 may be bonded to form a ring, and n is an integer of 0 to 4.

[0033] where R 5 ~R 8 The alkyl group that can constitute the group is not particularly limited, and examples thereof include the above-mentioned R 1 ~R 4 The alkyl group may be the same as the alkyl group that can constitute the above.

[0034] Also, R 5 ~R 8 The aromatic ring group that can constitute the above-mentioned R 1 ~R 4 The aromatic ring groups include the same as those that can constitute the above aromatic ring groups.

[0035] Furthermore, R 5 ~R 8 The ring formed by bonding may be a monocyclic ring or a polycyclic ring.

[0036] Furthermore, in formula (II), n represents an integer of 0 to 4, preferably 0, 1 or 2, and more preferably 0 or 1.

[0037] The content of the structural unit (II) in the polymer is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 45 mol% or more, and preferably 90 mol% or less, more preferably 80 mol%, and even more preferably 70 mol% or less, based on the total structural units. When the content of the structural unit (II) in the polymer is within the above range, the resulting resin film is more resistant to deterioration under high-temperature, high-humidity conditions, and the change in the dielectric loss tangent value between before and after exposure of the resin film to high-temperature, high-humidity conditions can be more effectively suppressed. In particular, when the content of the structural unit (II) in the polymer is equal to or greater than the above lower limit, the extensibility of the resulting resin film can be improved. Furthermore, when the content of the structural unit (II) in the polymer is equal to or less than the above upper limit, the glass transition temperature of the resulting resin film can be prevented from decreasing.

[0038] <<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 equal to or greater than the above-mentioned lower limit, the strength of the resulting resin film can be increased. Furthermore, if the weight-average molecular weight of the polymer is equal to or less than the above-mentioned upper limit, the solubility of the resulting resin film in a developer can be increased.

[0039] -Molecular weight distribution- The molecular weight distribution (Mw / Mn) of the above-mentioned polymer is preferably 4.0 or less, more preferably 3.0 or less. If the molecular weight distribution of the polymer is below the upper limit, the resolution can be improved when the resulting resin film is patterned. 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). The weight average molecular weight and number average molecular weight of the polymer are determined as polystyrene equivalent values ​​by gel permeation chromatography (GPC).

[0040] <<Polymer synthesis method>> The polymer described above is not particularly limited and can be prepared, for example, by subjecting a norbornene-based monomer to addition polymerization or ring-opening polymerization according to a conventional method to obtain a polymer, and then modifying the obtained polymer to introduce styryl groups into the side chains of the repeating units that constitute the polymer. In other words, a cyclic olefin polymer having styryl groups in the side chains can be prepared by subjecting a norbornene-based monomer to addition polymerization or ring-opening polymerization according to a conventional method to obtain a polymer, optionally subjecting the polymer to a hydrogenation reaction, and then subjecting the resulting polymer to a modification reaction. In particular, a cyclic olefin polymer having styryl groups in the side chains can be efficiently synthesized by a method including a step of synthesizing a ring-opening polymer by ring-opening polymerization of a norbornene-based monomer, and then subjecting the resulting ring-opening polymer to a hydrogenated ring-opening polymer (hereinafter referred to as the "ring-opening polymerization step"), and a step of modifying the resulting hydrogenated ring-opening polymer to obtain a modified hydrogenated ring-opening polymer (hereinafter referred to as the "modification step"). Each step will be described in detail below.

[0041] [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).

[0042] -Norbornene monomer (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 (trivial name: "tetracyclododecenemethanol"), 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.

[0043] -Norbornene monomer (II)- Examples of the norbornene monomer (II) include tetracyclo[4.4.0.1 2,5 .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: ethylidenenorbornene), 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 .0 3,8 ]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.

[0044] 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, and among these, a metal catalyst containing ruthenium is preferably used. Furthermore, the ring-opening polymerization time is usually from 1 hour to 10 hours, and preferably from 2 hours to 5 hours. The ring-opening polymerization temperature is usually from 20°C to 100°C, and preferably 90°C or less.

[0045] The resulting ring-opened polymer is then subjected to a hydrogenation reaction to synthesize a hydrogenated ring-opened polymer.

[0046] 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, preferably 5 hours or less. The hydrogenation reaction temperature is usually 100°C to 200°C, preferably 180°C or less. The hydrogenation pressure is usually 1 MPa to 10 MPa, preferably 5 MPa or less.

[0047] [Denaturation process] In the modification step, a modification reaction is carried out on the side chain portion of the hydrogenated ring-opening polymer obtained in the ring-opening polymerization step using a modifying agent to synthesize a modified product of the hydrogenated ring-opening polymer (i.e., a polymer containing the structural unit (I) described above). Here, for example, a compound having an aromatic vinyl group can be used as the modifying agent. Examples of compounds having an aromatic vinyl group include halogenated methylstyrenes such as 2-(fluoromethyl)styrene, 3-(fluoromethyl)styrene, 4-(fluoromethyl)styrene, 2-(chloromethyl)styrene, 3-(chloromethyl)styrene, 4-(chloromethyl)styrene, 2-(bromomethyl)styrene, 3-(bromomethyl)styrene, 4-(bromomethyl)styrene, 2-(iodomethyl)styrene, 3-(iodomethyl)styrene, and 4-(iodomethyl)styrene, as well as 2-(tosylmethyl)styrene, 3-(tosylmethyl)styrene, 4-(tosylmethyl)styrene, 2-(mesylmethyl)styrene, 3-(mesylmethyl)styrene, and 4-(mesylmethyl)styrene. Among these, from the viewpoint of efficiently carrying out the modification reaction, it is more preferable to use 4-(chloromethyl)styrene or 4-(bromomethyl)styrene.

[0048] The modification reaction is not particularly limited, and can be carried out, for example, by reacting the hydrogenated ring-opening polymer with a modifier in a solvent in the presence of a base. The base used is not particularly limited, and examples include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; and organic bases such as metal alkoxides of lithium t-butoxide, sodium t-butoxide, and potassium t-butoxide, triethylamine, pyridine, diazabicycloundecene, diazabicyclononene, and tetramethylguanidine. Among these, from the viewpoint of efficiently carrying out the modification reaction, it is preferable to use metal alkoxides of lithium t-butoxide, sodium t-butoxide, and potassium t-butoxide.

[0049] Furthermore, in the modification step, it is preferable to use a compound capable of generating iodide ions, such as potassium iodide or tetrabutylammonium iodide, as a catalyst. The addition of such a catalyst can promote the reaction in the modification step. The proportion of the catalyst capable of generating iodide ions to be added can be, for example, 1.0 part by mass or more and 10.0 parts by mass or less per 100 parts by mass of the polymer.

[0050] In the modification step, it is preferable to add a quinone polymerization inhibitor such as 2-tert-butyl-1,4-benzoquinone. The amount of the quinone polymerization inhibitor added may be, for example, 1.0 to 5.0 parts by mass per 100 parts by mass of the polymer.

[0051] The solvent is not particularly limited, and for example, the same solvent as that used in the ring-opening polymerization reaction can be used. The modification reaction temperature and modification reaction time are not particularly limited, but the modification reaction temperature is usually -10°C or higher and 100°C or lower, and the modification reaction time is usually 1 hour or higher and 15 hours or lower.

[0052] <Polymerization initiator> The resin composition of the present invention may contain a polymerization initiator. The polymerization initiator is not particularly limited, and a photoradical generator, a thermal radical generator, a photoacid generator, a photobase generator, etc. can be used. These polymerization initiators can be used alone or in combination of two or more.

[0053] <Photoradical generator> As the photoradical generator, an acylphosphine oxide-based, oxime ester-based, or aromatic ketone-based photoradical generator can be used. One or more types of photoradical generators can be used in combination. Among them, from the viewpoints of improving exposure sensitivity and improving the residual film rate after development, it is preferable to use an oxime ester-based photoradical generator as the photoradical generator.

[0054] Examples of acylphosphine oxide photoradical generators that can be used include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide.

[0055] Examples of oxime ester-based photoradical generators that can be used include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(o-benzoyloxime) (manufactured by BASF, distributed as "Irgacure (registered trademark) OXE01"); ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (manufactured by BASF, distributed as "Irgacure (registered trademark) OXE02"); and a compound (chemical formula not disclosed) distributed as "Irgacure (registered trademark) OXE03" manufactured by BASF.

[0056] 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.

[0057] <<Polymerization initiator content>> The content of the polymerization initiator is usually 0.3 parts by mass or more, preferably 1 part by mass or more, per 100 parts by mass of the polymer, and usually 25 parts by mass or less, preferably 15 parts by mass or less, and more preferably 10 parts by mass or less. If the content of the polymerization initiator is equal to or greater than the above-mentioned lower limit, the pattern formability of the resulting resin film when patterned can be improved. Furthermore, if the content of the polymerization initiator is equal to or less than the above-mentioned upper limit, the dielectric loss tangent of the resulting resin film can be reduced.

[0058] <Solvent> The solvent that may be contained in the 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.

[0059] The content of the solvent in the 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 resin composition, except for the solvent.

[0060] <Additional ingredients> The additive components that may be contained in the resin composition of the present invention are not particularly limited and include, for example, surfactants, antioxidants, sensitizers, adhesion aids, etc. These additive components may be used alone or in combination of two or more. Among them, it is preferable to contain a surfactant as an additive component from the viewpoint of improving the coatability of the resin composition of the present invention and further improving the uniformity of the film thickness of the resulting resin film.

[0061] The surfactant is not particularly limited, and known silicone surfactants, fluorine surfactants, etc. The content of the surfactant in the resin composition is preferably 0.1 mass % or less, and more preferably 0.05 mass % or less, based on the total mass of the resin composition.

[0062] <Method for preparing resin composition> The 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 resin composition of the present invention is used, for example, as a resin composition obtained 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 medium such as a filter can be used.

[0063] <Method of manufacturing resin film> The 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 having 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. [Example]

[0064] Hereinafter, the present invention will be specifically described 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 measurement of various attributes and various evaluations were each carried out by the following methods.

[0065] <Dielectric tangent> On a 4-inch silicon wafer on which an aluminum film with a thickness of 50 nm was formed using a sputtering apparatus (manufactured by Shibaura Electron Co., Ltd., “i-Miller CFS-4EP-LL”), the resin compositions prepared in each example and each comparative example were spin-coated, and then pre-baked at 90 °C for 2 minutes using a hot plate to form a film made of the resin composition. Next, after exposure with a g-h-i mixed line using a mask aligner (manufactured by Canon Inc., “PLA501F”) at an exposure dose of 1000 mJ / cm 2 ², the film was cured by heating at 180 °C for 1 hour in nitrogen to obtain a silicon wafer with a resin film having a thickness of 10 μm. The obtained silicon wafer with a resin film was immersed in a 0.1 mol% hydrochloric acid aqueous solution for 12 hours to perform aluminum etching, thereby peeling the resin film from the silicon wafer. After drying in an oven at 110 °C for 1 hour, this was cut into strips with a width of 2 mm and a length of 50 mm to obtain test pieces, and the value of the dielectric tangent at 10 GHz of these test pieces was measured by the cavity resonator method. As a result, it was confirmed that the value of the dielectric tangent of the obtained resin film was less than 0.006 in all cases through the examples and comparative examples.

[0066] <Change in the value of the dielectric tangent after HAST> Test pieces were prepared in the same manner as in the measurement of the dielectric tangent value, and the dielectric tangent at 10 GHz was measured using the cavity resonator method. The dielectric tangent value at this time was designated Df (initial). The silicon wafers with the resin film prepared by the above method were then placed in a highly accelerated life test (HAST) chamber at 130°C and 85% RH for 200 hours. The wafers were then immersed in a 0.1 mol% hydrochloric acid solution for 12 hours to etch the aluminum. The isolated resin film was then dried in an oven at 110°C for 1 hour, after which it was cut into strips measuring 2 mm wide and 50 mm long to prepare test pieces, and the dielectric tangent at 10 GHz was measured. The dielectric tangent value at this time was designated Df (after HAST). The rate of change in the dielectric tangent was calculated using the following formula and evaluated according to the following criteria. Rate of change of dielectric tangent = {Df (after HAST) - Df (initial)} / Df (initial) x 100 (%) A: The rate of change in dielectric tangent is less than 10% B: The rate of change of the dielectric tangent is 10% or more but less than 20% C: The rate of change of the dielectric tangent is 20% or more

[0067] <Glass transition temperature> 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 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. 2After exposure to a dose of 1000 kJ / cm, the wafer was heated in nitrogen at 180°C for 1 hour to obtain a resin film, yielding a silicon wafer with a 10 μm-thick resin film. The wafer was then immersed in a 0.1 mol% aqueous hydrochloric acid solution for 12 hours to etch the aluminum, removing the resin film from the wafer. The wafer was then dried in an oven at 110°C for 1 hour. Test specimens were cut into strips measuring 5 mm wide and 40 mm long, and the glass transition temperature was measured using a thermomechanical analysis (Mettler-Toledo, "TMA / SDTA841"). The measured glass transition temperature values ​​were evaluated according to the following criteria. A: 150℃ or higher B: 140℃ or higher but less than 150% C: Less than 140℃

[0068] <Tensile elongation> Test pieces were prepared in the same manner as in measuring the glass transition temperature, and a tensile test was performed on the test pieces to measure the tensile elongation. Specifically, a tensile test was performed using a tensile tester (Shimadzu Corporation, "AGS-10kNX") at 23°C, with a gripper distance of 2 cm and a tensile speed of 2 mm / min, and the elongation at break was measured. Eight test pieces were tested, and the average of the top three points was taken as the elongation of the resin film formed using the resin composition obtained in the Examples and Comparative Examples. A higher elongation value indicates higher extensibility of the resin film. Note that a resin film formed from a resin composition with higher extensibility is preferable because the resin film formed using the resin composition is less likely to crack or peel during a temperature cycle test or a drop impact test. A: Tensile elongation is 6% or more B: Tensile elongation is 3% or more and less than 6% C: Tensile elongation less than 3%

[0069] <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, a gel permeation chromatograph (HLC-8220, manufactured by Tosoh Corporation) was used with tetrahydrofuran as a developing solvent to determine the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymer in terms of standard polystyrene, and the molecular weight distribution (Mw / Mn) was calculated.

[0070] Example 1 <Preparation process of cyclic olefin polymer> 100 parts of a monomer mixture consisting of 15 mol% of 2-norbornene-5-methanol (NBMOH) as the norbornene-based monomer (I) and 85 mol% of ethylidenetetracyclododecene (ETD) as the norbornene-based monomer (II), 4.0 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 the mixture was reacted at 80°C for 4 hours with stirring to obtain a polymerization reaction liquid. The resulting polymerization reaction solution was then placed in an autoclave and stirred for 5 hours at 150°C under a hydrogen pressure of 4 MPa to carry out a hydrogenation reaction. 300 parts of tetrahydrofuran was added to the reaction solution, and this was added dropwise to 8,000 parts of methanol. The resulting precipitate was recovered by filtration and dried under reduced pressure at 50°C to obtain a cyclic olefin polymer (A-1).

[0071] <Cyclic Olefin Polymer Modification Process> A three-neck flask equipped with a stirrer tip and a thermometer was charged with 100 parts of the cyclic olefin polymer (A-1) obtained in Synthesis Example 1, 3.1 parts of tetrabutylammonium iodide as a catalyst, and 3.0 parts of 2-tert-butyl-1,4-benzoquinone as a polymerization inhibitor, and 900 parts of tetrahydrofuran was added to dissolve the mixture. 28.5 parts of potassium t-butoxide as a base were added in small portions, followed by stirring for 1 hour. The reaction solution was cooled to 0°C, and 51.7 parts of 4-(chloromethyl)styrene as a modifier was added dropwise. The mixture was stirred at room temperature for 12 hours. 528 parts of tetrahydrofuran was added to the reaction solution, which was then added dropwise to 9,000 parts of methanol, and the resulting precipitate was collected. This was suspended in 2,000 parts of methanol and subjected to suspension washing for 30 minutes. The solid matter was then filtered and dried under reduced pressure. The solid matter was diluted with tetrahydrofuran to a concentration of 7% by weight, and the solution was added dropwise to 10 times the amount of methanol while filtering through a cotton plug. The precipitate was collected and dried under reduced pressure at room temperature for 12 hours to obtain a cyclic olefin polymer (B-1) having styryl groups in the side chains (see formula below). The cyclic olefin polymer (B-1) having styryl groups in the side chains was a hydrogenated modified cyclic olefin ring-opening polymer having styryl groups in the side chains. The cyclic olefin polymer (B-1) having styryl groups in the side chains was measured by GPC according to the method described above to find that it had a weight average molecular weight of 32,000 and a molecular weight distribution of 2.6. 1 The modification rate measured by 1 H-NMR was 100%, and the content of styrene-modified NBMOH structural units (structural units (I)) in the polymer was 15 mol %.

[0072] [ka]

[0073] <Resin composition preparation process> As a cyclic olefin polymer having a styryl group in the side chain, 100 parts of the cyclic olefin polymer (B-1) obtained through the above process, 5 parts of Irgacure (registered trademark) OXE01 (manufactured by BASF) (C-1) as a polymerization initiator (C), and toluene as a solvent in an amount such that the total amount of the solvent other than the solvent was 30% by mass relative to the total mass of the resin composition were mixed and dissolved. Next, KP-341 (manufactured by Shin-Etsu Silicones Co., Ltd.) as a surfactant was added to the total mass of the resin composition so that it was 0.03% by mass, and then the resin composition was filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm 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.

[0074] Example 2 A cyclic olefin polymer (A-2) was obtained by the same procedure as in Example 1, except that in the <cyclic olefin polymer preparation step>, the composition of the monomer mixture was changed to 50 mol% NBMOH and 50 mol% ETD. Then, in the <cyclic olefin polymer modification step>, the cyclic olefin polymer (A-2) thus obtained was used, and the same procedure as in Example 1 was performed, except that the amount of tetrabutylammonium iodide was changed to 11.9 parts, t-butoxypotassium was changed to 108.2 parts, and the amount of 4-(chloromethyl)styrene added was changed to 196.2 parts, to obtain a cyclic olefin polymer (B-2) having styryl groups in the side chains (see the formula below). The weight average molecular weight of the cyclic olefin polymer (B-2) having styryl groups in the side chains, as obtained by GPC measurement according to the above, was 28,000, and the molecular weight distribution was 2.5. 1 The modification rate as measured by H-NMR was 100%, and the content of styrene-modified NBMOH in the polymer was 50 mol %.

[0075] [ka]

[0076] <Resin composition preparation process> As a cyclic olefin polymer having a styryl group in the side chain, 100 parts of the cyclic olefin polymer (B-2) having a styryl group in the side chain obtained as described above, 5 parts of Irgacure (registered trademark) OXE01 (manufactured by BASF) (C-1) as a polymerization initiator (C), and toluene as a solvent in an amount such that the total amount of the solvent other than the solvent is 30% by mass relative to the total mass of the resin composition were mixed and dissolved. Then, KP-341 (manufactured by Shin-Etsu Silicone Co., Ltd.) as a surfactant was added to the total mass of the resin composition so that it was 0.03% by mass, and then the resin composition was filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm 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.

[0077] Example 3 A cyclic olefin polymer (A-3) was obtained by the same procedure as in Example 1, except that in the <Cyclic olefin polymer preparation step>, the composition of the monomer composition was changed to 80 mol% NBMOH and 20 mol% ETD. Then, in the <Cyclic olefin polymer modification step>, the cyclic olefin polymer (A-3) thus obtained was used, and 21.5 parts of tetrabutylammonium iodide was changed to 139.3 parts of t-butoxypotassium, and the amount of 4-(chloromethyl)styrene was changed to 356.0 parts. A cyclic olefin polymer (B-3) having styryl groups in the side chains was obtained in the same manner as in Example 1, except for these points (see the formula below). The weight average molecular weight of the cyclic olefin polymer (B-3) having styryl groups in the side chains, obtained by GPC measurement according to the above, was 27,000, and the molecular weight distribution was 2.5. 1 The modification rate measured by 1 H-NMR was 100%, and the content of styrene-modified NBMOH in the polymer was 80 mol %.

[0078] [ka]

[0079] <Resin composition preparation process> As a cyclic olefin polymer having a styryl group in the side chain, 100 parts of the cyclic olefin polymer (B-3) having a styryl group in the side chain obtained as described above, 5 parts of Irgacure (registered trademark) OXE01 (manufactured by BASF) (C-1) as a photopolymerization initiator (C), toluene as a solvent in an amount such that the total amount of the solvent other than the solvent is 30% by mass relative to the total mass of the resin composition was mixed and dissolved. Then, KP-341 (manufactured by Shin-Etsu Silicone Co., Ltd.) as a surfactant was added so that it was 0.03% by mass relative to the total mass of the resin composition, and then the resin composition was filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare the resin composition. The resin composition thus obtained was subjected to various evaluations as described above. The results are shown in Table 1.

[0080] Example 4 A cyclic olefin polymer (A-4) was obtained by the same procedure as in Example 1, except that in the <cyclic olefin polymer preparation step>, the composition of the monomer mixture was changed to 50 mol% NBMOH and 50 mol% methanotetrahydrofluorene (MTF). Then, in the <cyclic olefin polymer modification step>, the cyclic olefin polymer (A-4) thus obtained was used, and the same procedure as in Example 1 was performed, except that 12.0 parts of tetrabutylammonium iodide was replaced with 109.6 parts of t-butoxypotassium, and the amount of 4-(chloromethyl)styrene added was changed to 198.7 parts, to obtain a cyclic olefin polymer (B-4) having styryl groups in the side chains (see the formula below). The weight average molecular weight of the cyclic olefin polymer (B-4) obtained by GPC measurement according to the above method was 31,000, and the molecular weight distribution was 2.5. 1 The modification rate as measured by H-NMR was 100%, and the content of styrene-modified NBMOH in the polymer was 50 mol %.

[0081] [ka] <Resin composition preparation process> As a cyclic olefin polymer having a styryl group in the side chain, 100 parts of the cyclic olefin polymer (B-4) having a styryl group in the side chain obtained as described above, 5 parts of Irgacure (registered trademark) OXE01 (manufactured by BASF) (C-1) as a photopolymerization initiator (C), toluene was mixed and dissolved as a solvent so that the total amount other than the solvent was 30% by weight relative to the total weight of the resin composition. Then, KP-341 (manufactured by Shin-Etsu Silicones Co., Ltd.) was added as a surfactant so that it was 0.03% by weight relative to the total weight of the resin composition, and then filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm 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.

[0082] Example 5 A cyclic olefin polymer (A-5) was obtained by the same procedure as in Example 1, except that in the <Cyclic olefin polymer preparation step>, the composition of the monomer mixture was changed to 15 mol% NBMOH, 50 mol% tetracyclododecenemethanol (TCDMOH), and 50 mol% ETD. Then, in the <Cyclic olefin polymer modification step>, the cyclic olefin polymer (A-5) thus obtained was used, and a cyclic olefin polymer (B-5) having styryl groups in the side chains was obtained by the same procedure as in Example 1, except that 9.9 parts of tetrabutylammonium iodide was changed to 90.4 parts of t-butoxypotassium, and the amount of 4-(chloromethyl)styrene added was changed to 163.9 parts. The weight average molecular weight of the cyclic olefin polymer (B-5) having styryl groups in the side chains obtained by GPC measurement according to the above procedure was 33,000, and the molecular weight distribution was 2.6. 1 The modification rate measured by H-NMR was 100%, and the content of styrene-modified TCDMOH in the polymer was 50 mol %.

[0083] [ka]

[0084] <Resin composition preparation process> As a cyclic olefin polymer having a styryl group in the side chain, 100 parts of the cyclic olefin polymer (B-5) having a styryl group in the side chain obtained as described above, 5 parts of Irgacure (registered trademark) OXE02 (manufactured by BASF) (C-2) as a photopolymerization initiator (C), toluene as a solvent in an amount such that the total amount other than the solvent is 30% by mass relative to the total weight of the resin composition was mixed and dissolved. Then, KP-341 (manufactured by Shin-Etsu Silicones Co., Ltd.) as a surfactant was added so that it was 0.03% by mass relative to the total mass of the resin composition, and then the resin composition was filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare a resin composition. The resin composition thus obtained was subjected to various evaluations as described above. The results are shown in Table 2.

[0085] Example 6 A cyclic olefin polymer (A-6) was obtained by the same procedure as in Example 1, except that in the <Cyclic olefin polymer preparation step>, the composition of the monomer mixture was changed to 50 mol% tetracyclododecenemethanol (TCDMOH) and 50 mol% dicyclopentadiene (DCPD). Then, in the <Cyclic olefin polymer modification step>, the cyclic olefin polymer (A-6) thus obtained was used, and a cyclic olefin polymer (B-6) having styryl groups in the side chains was obtained in the same manner as in Example 1, except that 11.5 parts of tetrabutylammonium iodide was changed to 104.4 parts of t-butoxypotassium, and the amount of 4-(chloromethyl)styrene added was changed to 189.3 parts (see the formula below). The weight average molecular weight of the cyclic olefin polymer (B-6) having styryl groups in the side chains, as obtained by GPC measurement according to the above, was 30,000, and the molecular weight distribution was 2.6. 1 The modification rate measured by H-NMR was 100%, and the content of styrene-modified TCDMOH in the polymer was 50 mol %.

[0086] [ka]

[0087] <Resin composition preparation process> As a cyclic olefin polymer having a styryl group in the side chain, 100 parts of the cyclic olefin polymer (B-6) having a styryl group in the side chain obtained as described above, 5 parts of Irgacure (registered trademark) OXE03 (manufactured by BASF) (C-3) as a photopolymerization initiator (C), toluene as a solvent was mixed and dissolved in an amount such that the total amount other than the solvent was 30% by mass relative to the total mass of the resin composition. Then, KP-341 (manufactured by Shin-Etsu Silicone Co., Ltd.) was added as a surfactant to be 0.03% by mass relative to the total mass of the resin composition, and then the resin composition was filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare a resin composition. The resin composition thus obtained was subjected to various evaluations as described above. The results are shown in Table 2.

[0088] Example 7 A cyclic olefin polymer (A-7) was obtained by the same procedure as in Example 1, except that in the <Cyclic olefin polymer preparation step>, the composition of the monomer mixture was changed so that TCDMOH was 50 mol% and MTF was 50 mol%. Then, in the <Cyclic olefin polymer modification step>, the cyclic olefin polymer (A-7) thus obtained was used, and a cyclic olefin polymer (B-7) having styryl groups in the side chains was obtained in the same manner as in Example 1, except that 9.9 parts of tetrabutylammonium iodide was replaced with 90.3 parts of t-butoxypotassium, and the amount of 4-(chloromethyl)styrene added was changed to 163.0 parts (see the formula below). The weight average molecular weight of the cyclic olefin polymer (B-7) having styryl groups in the side chains, as obtained by GPC measurement according to the above, was 35,000, and the molecular weight distribution was 2.5. 1 The modification rate measured by H-NMR was 100%, and the content of styrene-modified TCDMOH in the polymer was 50 mol %.

[0089] [ka]

[0090] <Preparation of Resin Composition> As a cyclic olefin polymer having a styryl group in the side chain, 100 parts of the cyclic olefin polymer (B-7) having a styryl group in the side chain obtained as described above, 5 parts of Irgacure (registered trademark) OXE01 (manufactured by BASF) (C-1) as a photopolymerization initiator (C), toluene as a solvent in an amount such that the total amount of the solvent other than the solvent was 30% by mass relative to the total mass of the resin composition was mixed and dissolved. Then, KP-341 (manufactured by Shin-Etsu Silicone Co., Ltd.) as a surfactant was added so that it was 0.03% by mass relative to the total mass of the resin composition, and then the resin composition was filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare a resin composition. The resin composition thus obtained was subjected to various evaluations as described above. The results are shown in Table 2.

[0091] Example 8 <Preparation process of cyclic olefin polymer> Cyclic olefin polymer (A-8), a norbornene (NB) / NBMOH addition polymer, was synthesized according to the method described in Macromolecules 29, 2761 (1996), except that the scale was increased by 20 times. Then, in the <Cyclic olefin polymer modification step>, the thus obtained cyclic olefin polymer (A-8) was used, and the solvent was changed from tetrahydrofuran to toluene, 5.6 parts of tetrabutylammonium iodide was replaced with 51.1 parts of t-butoxypotassium, and the amount of 4-(chloromethyl)styrene added was changed to 92.7 parts. Cyclic olefin polymer (B-8) having styryl groups in the side chains was obtained in the same manner as in Example 1 (see the formula below). The weight average molecular weight of the cyclic olefin polymer (B-8) having styryl groups in the side chains, as obtained by GPC measurement according to the above, was 45,000, and the molecular weight distribution was 2.4. 1 The modification rate as measured by H-NMR was 100%, and the content of styrene-modified NBMOH in the polymer was 15 mol %.

[0092] [ka]

[0093] <Resin composition preparation process> As a cyclic olefin polymer having a styryl group in the side chain, 100 parts of the cyclic olefin polymer (B-8) having a styryl group in the side chain obtained as described above, 0.5 parts of Irgacure (registered trademark) OXE01 (manufactured by BASF) (C-1) as a photopolymerization initiator (C), toluene as a solvent was mixed and dissolved in an amount such that the total amount of the solvent other than the solvent was 30% by mass relative to the total mass of the resin composition. Then, KP-341 (manufactured by Shin-Etsu Silicone Co., Ltd.) as a surfactant was added to the total mass of the resin composition so that it was 0.03% by mass, and then filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare a resin composition. The resin composition thus obtained was subjected to various evaluations as described above. The results are shown in Table 2.

[0094] (Comparative Example 1) <Preparation process of modified cyclic olefin polymer (B-9)> A three-neck flask equipped with a stirring blade and a thermometer was purged with nitrogen, and 100 parts of a cyclic olefin polymer (A-8) (an addition polymer), 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 were 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 addition polymer (B-9) (see the formula below). 1H-NMR measurement confirmed that the methacryloyl modification rate of the addition polymer, cyclic olefin polymer (A-8), was 100%, and the content of methacryloyl-modified NBMOH in the modified addition polymer (B-9) was 15 mol %. GPC measurement revealed that the weight average molecular weight of the modified addition polymer (B-9) was 28,100, and the molecular weight distribution was 1.8.

[0095] [ka]

[0096] <Resin composition preparation process> 100 parts of the modified addition polymer (B-9) obtained as described above, 5 parts of Irgacure (registered trademark) OXE01 (manufactured by BASF) (C-1) as a photopolymerization initiator (C), and toluene as a solvent in an amount such that the total amount other than the solvent was 30% by mass relative to the total mass of the resin composition were mixed and dissolved. Next, KP-341 (manufactured by Shin-Etsu Silicones Co., Ltd.) as a surfactant was added to the resin composition in an amount of 0.03% by mass, and the mixture was filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare a resin composition. The resin composition thus obtained was subjected to various evaluations as described above. The results are shown in Table 2.

[0097] [Table 1]

[0098] [Table 2]

[0099] Tables 1 and 2 show that in Examples 1 to 8, which used resin compositions containing cyclic olefin polymers having styryl groups in their side chains, it was possible to form resin films whose dielectric tangent values ​​were less likely to change before and after exposure to high-temperature, high-humidity conditions by HAST. On the other hand, Table 2 shows that in Comparative Example 1, which used a resin composition containing a cyclic olefin polymer not having styryl groups in its side chains, the dielectric tangent value of the formed resin film changed before and after exposure to high-temperature, high-humidity conditions by HAST. [Industrial Applicability]

[0100] According to the present invention, it is possible to provide a resin composition capable of forming a resin film whose dielectric loss tangent value is unlikely to change before and after exposure to high-temperature and high-humidity conditions.

Claims

1. A resin composition comprising a cyclic olefin polymer having a styryl group in a side chain.

2. The resin composition according to claim 1, wherein the cyclic olefin polymer is a ring-opening polymer.

3. The resin composition according to claim 1 or 2, wherein the cyclic olefin polymer contains a structural unit represented by the following formula (I): 【Chemistry 1】 Here, R １ ~R ４ each independently represents a hydrogen atom, an organic group having a styryl group, an alkyl group, an alkyl group having a substituent, or an aromatic ring group (excluding groups corresponding to the organic group having a styryl group), R １ ~R ４ At least one of the above is an organic group having a styryl group, and m is an integer of 0 to 4.

4. The resin composition according to claim 3 , wherein the cyclic olefin polymer further contains a structural unit represented by the following formula (II): 【Chemistry 2】 Here, R ５ ~R ８ each independently represents a hydrogen atom, an alkyl group, an alkyl group having a substituent, or an aromatic ring group (excluding the group corresponding to the organic group having a styryl group), R ５ ~R ８ may be bonded to form a ring, and n is an integer of 0 to 4.

5. The resin composition according to any one of claims 1 to 4, further comprising a polymerization initiator.

6. The resin composition according to any one of claims 1 to 5, wherein the polymerization initiator is an oxime ester-based photoradical generator.

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