Resin composition

Abstract

The present invention relates to a resin composition comprising a cyclic olefin polymer having a styryl group in the side chain.

Description

Technical Field

[0001] This invention relates to resin compositions. More specifically, this invention relates to resin compositions capable of forming resin films. Background Technology

[0002] In recent years, various resin films have been used in electronic components such as integrated circuits and organic EL components as protective films to prevent the components from deteriorating or being damaged, as planarization films to flatten the surface of components and wiring, as electrical insulating films to maintain electrical insulation, as pixel separation films to separate the light-emitting parts, and as optical films to focus and diffuse light.

[0003] Various studies have been conducted on resin compositions capable of forming resin films as described above. For example, Patent Document 1 proposes a cyclic olefin resin containing functional groups with polymerizable double bonds in its side chains. In Patent Document 1, as a cyclic olefin containing a functional group with polymerizable double bonds in the side chain, specifically, the use of 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 5-(meth)acrylate-2-norbornene, (meth)acrylate-5-norbornene-2-methyl ester, (meth)acrylate-5-norbornene-2-ethyl ester, (meth)acrylate-5-norbornene-2-n-butyl ester, (meth)acrylate-5-norbornene-2-n-propyl ester, (meth)acrylate-5-norbornene-2-isobutyl ester, (meth)acrylate-5-norbornene-2-isopropyl ester, (meth)acrylate-5-norbornene-2-hexyl ester, (meth)acrylate-5-norbornene-2-octyl ester, and (meth)acrylate-5-norbornene-2-decyl ester are proposed to synthesize cyclic olefin resins. Furthermore, for example, Patent Document 2 discloses a resin composition containing a cyclic olefin copolymer with multiple crosslinking double bonds in the side chain portion. Examples of crosslinking double bonds in the side chain of this cyclic olefin copolymer include vinyl, alkenyl, acryloyl, and methacryloyl groups. Specifically, a resin composition formulated with LCOC-4 manufactured by Mitsui Chemicals Co., Ltd. is disclosed.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2006-156821;

[0007] Patent Document 2: Japanese Patent Application Publication No. 2018-39950. Summary of the Invention

[0008] The problem the invention aims to solve

[0009] Here, electronic components and the like, which have resin films formed using resin compositions, are sometimes exposed to high temperature and high humidity conditions during use. Therefore, it is required that the resin film of the electronic components maintain stable performance both before and after exposure to such operating conditions. However, there is room for improvement in this regard for the resin films obtained according to the prior art described above.

[0010] Therefore, the object of the present invention is to provide a resin composition that can form a resin film whose dielectric loss tangent value does not change significantly before and after exposure to high temperature and high humidity conditions.

[0011] Solution for solving the problem

[0012] To achieve the above-mentioned objectives, the inventors conducted in-depth research. Then, the inventors made a new discovery: by introducing styrene groups into the side chains of a cyclic olefin polymer, a resin composition capable of forming a resin film whose dielectric loss tangent does not easily change before and after exposure to high temperature and high humidity conditions can be obtained, thus completing the present invention.

[0013] That is, the object of the present invention is to advantageously solve the above-mentioned problems. The resin composition of the present invention is characterized by comprising a cyclic olefin polymer having styrene groups in the side chains. According to this resin composition, it is possible to form a resin film whose dielectric loss tangent value does not change significantly before and after exposure to high temperature and high humidity conditions.

[0014] Furthermore, the resin composition of the present invention preferably uses an open-ring polymer as the cyclic olefin polymer. If the cyclic olefin polymer is an open-ring polymer, a resin film with high elongation can be formed.

[0015] Furthermore, in the resin composition of the present invention, the cyclic olefin polymer preferably comprises the structural unit represented by the following formula (I).

[0016] [Chemical Formula 1]

[0017]

[0018] Here, R 1 ~R 4 Each independently represents a hydrogen atom, an organic group having a styrene group, an alkyl group, or an aromatic cyclic group (wherein the aromatic cyclic group does not contain a group equivalent to the aforementioned organic group having a styrene group), R 1 ~R 4 At least one of them is an organic group having the above-mentioned styrene group, and m represents an integer from 0 to 4.

[0019] If the cyclic olefin polymer has the 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.

[0020] In addition, R can be formed in the above formula (I). 1 ~R 4 The organic group containing a styrene group can also have substituents other than styrene. Furthermore, it is possible to form R in the above formula (I). 1 ~R 4 The alkyl and aromatic cyclic groups can also have substituents independently.

[0021] Furthermore, in the resin composition of the present invention, the above-mentioned cyclic olefin polymer preferably also contains the structural unit represented by the following formula (II).

[0022] [Chemical Formula 2]

[0023]

[0024] Here, R 5 ~R 8 Each independently represents a hydrogen atom, an alkyl group, or an aromatic cyclic group (wherein the aromatic cyclic group does not contain a group equivalent to the organic group having a styrene group mentioned above), R 5 ~R 8 They can combine to form a ring, where n is an integer from 0 to 4.

[0025] If the cyclic olefin polymer has the 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.

[0026] In addition, R can be formed in the above formula (II). 5 ~R 8 The alkyl and aromatic cyclic groups can also have substituents independently.

[0027] Furthermore, the resin composition of the present invention may contain a polymerization initiator. Moreover, an oxime ester-based photoradical generator is preferably used as the polymerization initiator. If an oxime ester-based photoradical generator is included as the polymerization initiator, the resin film can be manufactured efficiently.

[0028] Invention Effects

[0029] According to the present invention, a resin composition is provided that can form a resin film whose dielectric loss tangent value does not change significantly before and after exposure to high temperature and high humidity conditions. Detailed Implementation

[0030] Here, the resin composition of the present invention is not particularly limited, and can be used in forming resin films that can be present in electronic components such as integrated circuit elements, organic EL elements, and semiconductor packages. In particular, the resin composition of the present invention is especially suitable for use in manufacturing insulating organic films such as organic EL, semiconductor packages, printed wiring substrates, and solder resists. Furthermore, the resin composition of the present invention can be suitably used as a negative photosensitive resin composition, wherein the exposed areas of the negative photosensitive resin composition have low solubility in the developer, and the exposed areas remain after development. In addition, the active energy rays used for exposing the resin film formed using the resin composition of the present invention are not particularly limited, and examples include single-wavelength light such as ultraviolet rays, gamma rays, h rays, i rays, KrF excimer lasers, ArF excimer lasers, and particle beams such as electron beams.

[0031] (Resin Composition)

[0032] The resin composition of the present invention needs to contain a cyclic olefin polymer with styrene groups on the side chains, and can optionally contain polymerization initiators, solvents, and other additives. Furthermore, the resin composition according to the present invention can form a resin film whose dielectric loss tangent value does not easily change before and after exposure to high temperature and high humidity conditions.

[0033] <Polymer>

[0034] The cyclic olefin polymer with styrene groups in the resin composition of the present invention is a polymer that can undergo a crosslinking reaction by generating free radicals through irradiation with active energy rays in the presence of a polymerization initiator. Here, the cyclic olefin polymer with styrene groups in the side chain is an addition polymer or a ring-opening polymer. From the viewpoint of being able to form a resin film with good elongation, the cyclic olefin polymer with styrene groups in the side chain is preferably a ring-opening polymer.

[0035] Furthermore, the cyclic olefin polymer with styrene groups in the side chains preferably contains structural units (I) represented by formula (I) and (II) represented by formula (II). By giving the polymer this structure, a resin film can be formed whose dielectric loss tangent value is less prone to change before and after exposure to high temperature and high humidity conditions. In addition, by giving the polymer this structure, the dielectric loss tangent value of the obtained resin film can be reduced, and the obtained resin film can have good elongation.

[0036] [Chemical Formula 3]

[0037]

[0038] [Chemical Formula 4]

[0039]

[0040] <<Structural Unit (I)>>

[0041] Furthermore, in structural unit (I), in the above equation (I), R 1 ~R 4 Each independently represents a hydrogen atom, an organic group having a styrene group, an alkyl group, or an aromatic cyclic group (wherein the aromatic cyclic group does not contain a group equivalent to an organic group having a styrene group), R 1 ~R 4 At least one of them is an organic group having a styrene group, and m represents an integer from 0 to 4.

[0042] Here, as can constitute R 1 ~R 4 Organic groups containing styrene groups can be exemplified by the organic groups represented by formula (III).

[0043] [Chemical Formula 5]

[0044]

[0045] Here, in formula (III) above, X and Z represent single bonds or alkylene groups with 1 to 10 carbon atoms, Y represents an oxygen atom or a sulfur atom, and R represents... 9 It can be a hydrogen atom or a substituent, and p is an integer from 0 to 4.

[0046] In the above formula (III), the alkylene group having 1 to 10 carbon atoms, which can be X and Z, is not particularly limited, but preferably is a chain alkylene group having 1 to 6 carbon atoms, such as methylene, ethylene, propylene, n-butylene, or isobutylene. More preferably is a straight-chain alkylene group having 1 to 6 carbon atoms, such as methylene, ethylene, propylene, or n-butylene. Even more preferably is a straight-chain alkylene group having 1 to 3 carbon atoms, such as methylene, ethylene, or propylene. Methylene is particularly preferred.

[0047] In equation (III) above, it can be used as R 9 The substituents are not particularly limited, and examples include alkyl groups such as methyl and ethyl, and halogen groups such as fluorine and chloro.

[0048] Furthermore, in the above formula (III), p is preferably 0, that is, the styrene group preferably does not have substituents.

[0049] Furthermore, in the above formula (I), as a form capable of constituting R 1 ~R 4 Alkyl groups are not particularly limited, but examples include alkyl groups having 1 to 5 carbon atoms.

[0050] Furthermore, as a component of R 1 ~R4 The aromatic ring group is not particularly limited as long as it does not contain an organic group equivalent to the styrene group mentioned above. Examples of aromatic ring groups with 4 to 30 carbon atoms are given.

[0051] Furthermore, in formula (I), m represents an integer from 0 to 4, preferably an integer from 0 to 2, and more preferably 0 or 1.

[0052] Moreover, in equation (I), R is preferred. 1 ~R 4 One of them is an organic group with a styrene group, and the others are hydrogen atoms. This is because if the structural unit (I) is such a structural unit, the synthesis is easier and the production efficiency of the resin composition is improved.

[0053] Furthermore, by including organic groups with styrene groups in the structural unit (I), the polymer is not easily hydrolyzed even when the formed resin film is exposed to high temperature and high humidity conditions. Therefore, the change in the dielectric loss tangent of the resin film before and after exposure to high temperature and high humidity conditions can be suppressed.

[0054] Furthermore, relative to all structural units, the content of structural unit (I) in the polymer is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 55 mol% or less. If the content of structural unit (I) in the polymer is within the above range, the resulting resin film is less prone to further deterioration under high temperature and high humidity conditions, and the change in dielectric loss tangent before and after exposure of the resin film to high temperature and high humidity conditions can be suppressed more effectively. In particular, if the content of structural unit (I) in the polymer is at or above the lower limit value, the decrease in the glass transition temperature of the resulting resin film can be suppressed. In addition, if the content of structural unit (I) in the polymer is at or below the upper limit value, the elongation of the resulting resin film is good.

[0055] Additionally, in this specification, the "proportion of structural units" can be used 1 H-NMR, 13 The measurements were performed using nuclear magnetic resonance (NMR) methods such as C-NMR.

[0056] <<Structural Unit (II)>>

[0057] In structural unit (II), R 5 ~R 8 Each independently represents a hydrogen atom, alkyl group, or aromatic cyclic group (wherein the aromatic cyclic group does not contain a group equivalent to an organic group having a styrene group), R 5 ~R 8They can also combine to form a ring, where n is an integer from 0 to 4.

[0058] Here, as can constitute R 5 ~R 8 Alkyl groups, without particular limitation, can be exemplified by those that can form the above-described R. 1 ~R 4 The same alkyl group as the alkyl group.

[0059] Furthermore, as a component of R 5 ~R 8 The aromatic ring group, without particular limitation, can be exemplified by those that can form the above-mentioned R. 1 ~R 4 The aromatic ring group is the same as the aromatic ring group.

[0060] Furthermore, R 5 ~R 8 The resulting ring can be a single ring or multiple rings.

[0061] Furthermore, in equation (II), n represents an integer from 0 to 4, preferably 0, 1 or 2, and more preferably 0 or 1.

[0062] Furthermore, relative to all structural units, the content of structural unit (II) in the polymer is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 45 mol% or more, preferably 90 mol% or less, more preferably 80 mol%, and even more preferably 70 mol% or less. If the content of structural unit (II) in the polymer is within the above range, the resulting resin film is less prone to further deterioration under high temperature and high humidity conditions, and the change in the dielectric loss tangent before and after exposing the resin film to high temperature and high humidity conditions can be suppressed more effectively. In particular, if the content of structural unit (II) in the polymer is at or above the lower limit value, the elongation of the resulting resin film can be improved. In addition, if the content of structural unit (II) in the polymer is at or below the upper limit value, the decrease in the glass transition temperature of the resulting resin film can be suppressed.

[0063] <<Properties of Polymers>>

[0064] -weight-average molecular weight-

[0065] Furthermore, the weight-average molecular weight (Mw) of the polymer is preferably 3,000 or more, more preferably 5,000 or more, even more preferably 10,000 or more, 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 above or below the aforementioned lower limit, the strength of the obtained resin film can be improved. In addition, if the weight-average molecular weight of the polymer is below or below the aforementioned upper limit, the solubility of the obtained resin film in the developing solution can be improved.

[0066] -Molecular weight distribution-

[0067] The molecular weight distribution (Mw / Mn) of the polymer described above 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 when patterning the obtained resin film can be improved. Furthermore, in this invention, "molecular weight distribution (Mw / Mn)" refers to the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn). Moreover, the weight-average molecular weight and number-average molecular weight of the polymer are determined by gel permeation chromatography (GPC) in the form of polystyrene equivalents.

[0068] <<Methods for the Synthesis of Polymers>>

[0069] The polymers described above are not particularly limited. For example, polymers can be obtained by addition polymerization or ring-opening polymerization of norbornene monomers using conventional methods, and the obtained polymers can be modified by introducing styrene groups into the side chains of the repeating units constituting the polymer. In other words, cyclic olefin polymers with styrene groups in the side chains can be prepared as follows: after obtaining a polymer by addition polymerization or ring-opening polymerization using conventional methods, the polymer is arbitrarily subjected to a hydrogenation reaction, and the obtained polymer is modified. Cyclic olefin polymers with styrene groups in the side chains can be efficiently synthesized by a method comprising the following steps: ring-opening polymerization of norbornene monomers to synthesize a ring-opening polymer; hydrogenation reaction of the obtained ring-opening polymer to obtain a hydrogenated ring-opening polymer (hereinafter referred to as the "ring-opening polymerization step"); and modification reaction of the obtained 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.

[0070] [Ring-open polymerization process]

[0071] In the ring-opening polymerization process, firstly, a ring-opening polymer is synthesized by a ring-opening polymerization reaction between a norbornene monomer (I) capable of forming the above-mentioned structural unit (I) and a norbornene monomer (II) capable of forming the above-mentioned structural unit (II).

[0072] -norbornene monomers (I)-

[0073] Here, examples of norbornene monomers (I) include, for instance: 2-norbornene-5-methanol, 2-methyl-2-hydroxymethylbicyclo[2.2.1]hept-5-ene, 2,3-dihydroxymethylbicyclo[2.2.1]hept-5-ene, and 3-hydroxytricyclo[5.2.1.0]hept-5-ene. 2,6 [Dec-4,8-diene, 3-hydroxymethyltricyclo[5.2.1.0]] 2,6 [6.2.1.1] Dec-4,8-diene, 4-hydroxytetracyclo[6.2.1.1] 3,6 .0 2,7 [6.2.1.1 Dodecyl-9-ene, 4-hydroxymethyltetracyclo[6.2.1.1]] 3,6 .0 2,7 Dodecyl-9-ene (common name: "tetracyclododecylene methanol"), 4,5-dihydroxymethyltetracyclo[6.2.1.1] 3,6 .0 2,7 Dodecyl-9-ene, etc. Norbornene monomers (I) can be used alone or in combination of two or more.

[0074] -norbornene monomers (II)-

[0075] Examples of norbornene monomers (II) include tetracyclic [4.4.0.1] 2,5 .1 7,10 Dodecyl-3-ene (common name: tetracyclic dodecylene), 8-ethylidene-tetracyclic [4.4.0.1] 2,5 .1 7,10 Dodecyl-3-ene (common name: ethylidene tetracyclododecene), tricyclic [5.2.1.0] 2,6 ] Dec-3,8-diene (common name: dicyclopentadiene), 1,4-methylene-1,4,4a,9a-tetrahydrofluorene (common name: bridged methylene tetrahydrofluorene), 5-ethylidene bicyclo[2.2.1]hept-2-ene (common name: ethylidene norbornene), bicyclo[2.2.1]hept-2-ene (also known as "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, tetracyclo[10.2.1.0 2,11 .0 4,9 [Pentadecyl-4,6,8,13-tetraene, 9-methyl-tetracyclo[6.2.1.1]] 3,6 .0 2,7 [6.2.1.1] Dodecyl-4-ene, 9-ethyl-tetracyclo[6.2.1.1] 3,6 .0 2,7 [6.2.1.1] Dodecyl-4-ene, 9-methylene-tetracyclo[6.2.1.1] 3,6 .02,7 [6.2.1.1] Dodecyl-4-ene, 9-ethylidene-tetracyclo[6.2.1.1] 3,6 .0 2,7 [6.2.1.1] Dodecyl-4-ene, 9-vinyl-tetracyclo[6.2.1.1] 3,6 .0 2,7 [6.2.1.1] Dodecyl-4-ene, 9-propenyl-tetracyclo[6.2.1.1] 3,6 .0 2,7 [Dodecyl-4-ene, pentacyclic [9.2.1.1]] 3,9 .0 2,10 .0 4,8 [Pentadecyl-5,12-diene, 9-phenyl-tetracyclo[6.2.1.1]] 3,6 .0 2,7 [Dodecyl-4-ene, tetracyclo[9.2.1.0]] 2,10 .0 3,8 [Tetradecane-3,5,7,12-tetraene, pentacyclic [9.2.1.1]] 3,9 .0 2,10 .0 4,8 [15-carbon-12-ene and its derivatives, etc. Furthermore, a derivative refers to a substance having substituents in its ring structure. Examples of substituents that can be present in the ring structure include alkyl, alkylene (Alkylene group), vinyl, alkoxycarbonyl, and alkylene (Alkylidene group). Moreover, the ring structure of a derivative may have one or more of these substituents.]

[0076] Moreover, norbornene monomers (II) can be used alone or in combination of two or more.

[0077] Ring-opening polymerization can be carried out in a solvent according to known methods. In this case, there are no particular limitations on the solvent, and organic solvents such as tetrahydrofuran and toluene can be used. In addition, as molecular weight regulators, the following can be used: ethylene; α-olefins with 3 or more but less than 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-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; and 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, as well as their derivatives. Furthermore, metal catalysts containing metals such as molybdenum, tungsten, and ruthenium can be used as ring-opening polymerization catalysts, with ruthenium-containing metal catalysts being preferred. The ring-opening polymerization time is typically 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 typically 20°C or more and 100°C or less, preferably 90°C or less.

[0078] Then, the obtained ring-opening polymer is subjected to a hydrogenation reaction to synthesize the ring-opening polymer hydrogenated product.

[0079] At this point, the hydrogenation reaction can be carried out according to known methods. Furthermore, the hydrogenation reaction time, temperature, and pressure are not particularly limited; the hydrogenation reaction time is typically 1 hour or more and 10 hours or less, preferably 5 hours or less. The hydrogenation reaction temperature is typically 100°C or more and 200°C or less, preferably 180°C or less. Moreover, the hydrogenation pressure is typically 1 MPa or more and 10 MPa or less, preferably 5 MPa or less.

[0080] [Modification Process]

[0081] In the modification process, the side chain portion of the ring-opening polymer hydrogenated product obtained in the ring-opening polymerization process is modified by using a modifier to synthesize a modified version of the ring-opening polymer hydrogenated product (i.e., a polymer containing the above-described structural unit (I)). Here, as a modifier, a compound having aromatic vinyl groups can be used, for example. Examples of compounds containing aromatic vinyl groups include 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, 4-(iodomethyl)styrene, and halogenated methylstyrene, 2-(toluenesulfonylmethyl)styrene, 3-(toluenesulfonylmethyl)styrene, 4-(toluenesulfonylmethyl)styrene, 2-(methanesulfonylmethyl)styrene, 3-(methanesulfonylmethyl)styrene, and 4-(methanesulfonylmethyl)styrene. Among these, 4-(chloromethyl)styrene or 4-(bromomethyl)styrene is more preferred from the viewpoint of efficiently carrying out the modification reaction.

[0082] Here, the modification reaction is not particularly limited; for example, the modification reaction can be carried out by reacting the hydrogenated ring-opening polymer with the modifier in a solvent in the presence of a base. In this case, the base is not particularly limited, and can be: alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; metal alkoxides such as lithium tert-butoxy, sodium tert-butoxy, and potassium tert-butoxy; and organic bases such as triethylamine, pyridine, diazabicycloundecene, nonene diazabicyclo, and tetramethylguanidine. Among these, from the viewpoint of efficiently carrying out the modification reaction, metal alkoxides such as lithium tert-butoxy, sodium tert-butoxy, and potassium tert-butoxy are preferred.

[0083] Furthermore, in the modification process, compounds such as potassium iodide and tetrabutylammonium iodide, which can serve as sources of iodide ion generation, are preferably used as catalysts. By incorporating such catalysts, the reaction in the modification process can be promoted. The proportion of the catalyst capable of generating iodide ions can, for example, be 1.0 parts by mass or more and 10.0 parts by mass or less per 100 parts by mass of polymer.

[0084] Furthermore, in the modification process, quinone-based polymerization inhibitors such as 2-tert-butyl-1,4-benzoquinone are preferably incorporated. The proportion of the quinone-based polymerization inhibitor can be, for example, 1.0 part by weight or more and 5.0 parts by weight or less per 100 parts by weight of polymer.

[0085] Furthermore, there are no particular limitations on the solvent used; for example, the same solvent used in ring-opening polymerization can be used. Additionally, there are no particular limitations on the modification reaction temperature and time; the modification reaction temperature is generally above -10°C and below 100°C, and the modification reaction time is generally above 1 hour and below 15 hours.

[0086] <Polymerization Initiator>

[0087] The resin composition of the present invention may contain a polymerization initiator. There are no particular limitations on the polymerization initiator; photoradioactive agents, thermal radical generators, photoacid generators, photobase generators, etc., can be used. One of these polymerization initiators can be used alone, or two or more can be used in combination.

[0088] <Photoradical generator>

[0089] As a photoradical generator, acylphosphine oxide-based, oxime ester-based, or aromatic ketone-based photoradical generators can be used. One or more photoradical generators can be used. From the viewpoint of further improving exposure sensitivity and increasing the residual film yield after development, oxime ester-based photoradical generators are preferred.

[0090] As acylphosphine oxide-based photoradical generators, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide can be used.

[0091] As oxime ester-based photoradical generators, examples include: 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(o-benzoyl oxime) (manufactured by BASF and commercially available under the trademark "Irgacure OXE01"); acetone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(o-acetyl oxime) (manufactured by BASF and commercially available under the trademark "Irgacure OXE02"); and a compound manufactured by BASF and commercially available under the trademark "Irgacure OXE03" (chemical formula not disclosed).

[0092] In addition, as aromatic ketone free radical generators, benzophenone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone-1,2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2-methyl-1-[4-methylthio]phenyl]-2-morpholinylpropane-1-one, methyl o-benzoylbenzoate, [4-(methylphenylthio)phenyl]phenylmethane, 1,4-dibenzoylbenzene, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyldiphenyl ether, benzoylayl, etc.

[0093] <<Content of Polymerization Initiator>>

[0094] Furthermore, relative to 100 parts by mass of polymer, the content of the polymerization initiator is typically 0.3 parts by mass or more, preferably 1 part by mass or more, typically 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 at or above the aforementioned lower limit, the resulting resin film can exhibit excellent pattern-forming properties during patterning. In addition, if the content of the polymerization initiator is at or below the aforementioned upper limit, the dielectric loss tangent of the resulting resin film can be reduced.

[0095] <Solvent>

[0096] The solvents that can be included in the resin composition of the present invention are not particularly limited, and examples include: aromatic solvents such as toluene, o-xylene, m-xylene, p-xylene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, and tetrahydronaphthalene; hydrocarbons such as cyclohexane and decahydronaphthalene; ether solvents such as dibutyl ether, diisopentyl ether, tetrahydrofuran, and cyclopentylmethyl 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. One of these solvents can be used alone, or two or more can be used in combination.

[0097] Furthermore, the solvent content in the resin composition, relative to the total mass of the resin composition excluding the solvent, is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 60% by mass or less, and more preferably 50% by mass or less.

[0098] <Added Ingredients>

[0099] Furthermore, there are no particular limitations on the additives that can be included in the resin composition of the present invention, and examples include surfactants, antioxidants, sensitizers, and adhesion promoters. These additives can be used alone or in combination of two or more. 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 obtained resin film, surfactants are preferably included as additives.

[0100] There are no particular limitations on the surfactant used; known organosilicon surfactants, fluorinated surfactants, etc., can be used. Moreover, the proportion of the surfactant in the resin composition relative to the total mass of the resin composition is preferably 0.1% by mass or less, more preferably 0.05% by mass or less.

[0101] <Preparation Method of Resin Composition>

[0102] The resin composition of the present invention can be prepared by mixing the aforementioned necessary components and various arbitrary components using known methods. Here, the resin composition of the present invention is provided for use, for example, as a resin composition obtained by dissolving the components in a solvent and then filtering. When dissolving in a solvent, known mixers such as stirrers, ball mills, sand mills, bead mills, pigment dispersers, grinders, ultrasonic dispersers, homogenizers, planetary mixers, and FILMIX can be used. Furthermore, when filtering, conventional filtration methods using filter media such as filters can be employed.

[0103] <Method for manufacturing resin film>

[0104] Furthermore, the resin composition of the present invention can be used to form a resin film using a known film-forming method (e.g., refer to International Publication No. 2015 / 033901). Moreover, there are no particular limitations on the resulting resin film; a resin film with a desired pattern can be formed by performing an exposure step and a development step involving irradiation with any active energy radiation, such as light with a wavelength of 200 nm or more and 500 nm or less. Furthermore, a prebake step can be performed before the exposure step, or a post-exposure baking (PEB) step can be performed at a desired time after the start of the exposure step, if desired. Additionally, a post-baking step can be performed after the development step, if desired.

[0105] Example

[0106] The present invention will now be specifically described based on embodiments, but the present invention is not limited to these embodiments. Furthermore, in the following description, unless otherwise stated, "%" and "parts" refer to quantities based on mass.

[0107] In the examples and comparative examples, the measurement of various properties and various evaluations were carried out by the following methods respectively.

[0108] <Dielectric loss tangent>

[0109] Using a sputtering device (manufactured by SHIBAURA ELETEC CORPORATION, "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 film thickness of 50 nm was formed. Then, using a hot plate, pre-baking was carried out at 90 °C for 2 minutes to form a film formed from the resin composition. Next, after exposure with a g-h-i mixed ray at an exposure dose of 1000 mJ / cm 2 using a mask aligner (manufactured by Canon Inc., "PLA501F"), the film was cured by heating in nitrogen at 180 °C for 1 hour to obtain a resin film, and a silicon wafer with a 10-μm-thick resin film was obtained. 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 the resin film was peeled off from the silicon wafer. After drying in an oven at 110 °C for 1 hour, it was cut into a rectangle with a width of 2 mm and a length of 50 mm as a test piece, and the value of the dielectric loss tangent of the test piece at 10 GHz was measured by the cavity resonator method. As a result, it was confirmed by the examples and comparative examples that the values of the dielectric loss tangent of the obtained resin films were all less than 0.006.

[0110] <Change in the value of the dielectric loss tangent after HAST>

[0111] A test piece was fabricated in the same manner as when measuring the value of the dielectric loss tangent, and the dielectric loss tangent at 10 GHz was measured by the cavity resonator method. The value of the dielectric loss tangent at this time was taken as Df (initial). In addition, the silicon wafer with the resin film fabricated by the above method was placed in a highly accelerated stress test (HAST) chamber under the conditions of 130 °C and 85% RH for 200 hours. After that, it was immersed in a 0.1 mol% hydrochloric acid aqueous solution for 12 hours to etch the aluminum, and the separated resin film was dried in an oven at 110 °C for 1 hour, and then cut into a rectangle with a width of 2 mm and a length of 50 mm as a test piece, and the dielectric loss tangent at 10 GHz was measured. The value of the dielectric loss tangent at this time was taken as Df (after HAST). The change rate of the dielectric loss tangent was calculated according to the following formula and evaluated according to the following criteria.

[0112] Change rate of dielectric loss tangent = [Df (after HAST) - Df (initial)] / Df (initial) × 100 (%)

[0113] A: The change rate of the dielectric loss tangent is less than 10%

[0114] B: The rate of change of the dielectric loss tangent is greater than 10% and less than 20%.

[0115] C: The rate of change of the dielectric loss tangent is over 20%.

[0116] <Glass transition temperature>

[0117] The resin compositions prepared in the various examples and comparative examples were spin-coated onto a 4-inch silicon wafer with a 50 nm thick aluminum film formed on it using a sputtering apparatus (manufactured by SHIBAURA ELETEC CORPORATION, "i-Miller CFS-4EP-LL"). The wafers were then pre-baked at 90°C for 2 minutes using a hot plate to form a film from the resin composition. Next, a mask aligner (manufactured by Canon Corporation, "PLA501F") was used with a ghi mixed beam at 1000 mJ / cm². 2 After exposure to nitrogen, the wafer was heated at 180°C for 1 hour to obtain a resin film, resulting in a silicon wafer with a 10 μm thick resin film. The wafer was then immersed in a 0.1 mol% hydrochloric acid aqueous solution for 12 hours to etch aluminum, thereby peeling off the resin film. It was then dried in an oven at 110°C for 1 hour. The wafer was cut into rectangles 5 mm wide and 40 mm long as test pieces, and the glass transition temperature was determined by thermomechanical analysis (Mettler-Toledo, “TMA / SDTA841”). The determined glass transition temperature values ​​were evaluated according to the following criteria.

[0118] A: Above 150℃

[0119] B: Temperature above 140℃ and below 150℃

[0120] C: Less than 140℃

[0121] <Elongation at break>

[0122] Test pieces were prepared in the same manner as those used for determining the glass transition temperature, and tensile tests were performed on these test pieces to determine the tensile elongation. Specifically, tensile tests were conducted at 23°C with a clamp spacing of 2 cm and a tensile speed of 2 mm / min using a tensile testing machine (manufactured by Shimadzu Corporation, "AGS-10kNX"). The elongation at the point of fracture was measured. Eight test pieces were tested, and the average of the three highest values ​​was taken as the elongation of the resin film formed from the resin composition obtained in the usage examples and comparative examples. A higher elongation value indicates a greater elongation of the resin film. Furthermore, a greater elongation of the resin film formed from the resin composition means that the resin film formed using this resin composition is less prone to cracking and peeling during temperature cycling tests and drop impact tests, which is therefore preferable.

[0123] A: Elongation at break of 6% or more

[0124] B: Elongation at break of 3% or more but less than 6%

[0125] C: Elongation at break less than 3%

[0126] <Weight-average molecular weight and molecular weight distribution>

[0127] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymers obtained in the examples and comparative examples were determined using gel permeation chromatography, and the molecular weight distribution (Mw / Mn) was calculated.

[0128] Specifically, gel permeation chromatography (Tosoh, HLC-8220) was used with tetrahydrofuran as the elution solvent to determine the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymer in the form of standard polystyrene conversion values. Then, the molecular weight distribution (Mw / Mn) was calculated.

[0129] (Example 1)

[0130] <Preparation process of cyclic olefin polymers>

[0131] 100 parts of a monomer mixture consisting of 15 mol% of 2-norbornene-5-methanol (NBMOH) as norbornene monomer (I) and 85 mol% of ethylidene tetracyclododecene (ETD) as norbornene monomer (II), 4.0 parts of 1,5-hexadiene as a molecular weight regulator, 0.025 parts of (1,3-bis(trimethyl)-methylimidazoline-2-ethylenedimethyl)(tricyclohexylphosphine)benzyl ruthenium dichloride (synthesized using 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 nitrogen-replaced glass pressure reactor and reacted at 80°C for 4 hours with stirring to obtain a polymerization reaction solution.

[0132] Next, the obtained polymerization reaction solution was added to an autoclave and stirred at 150°C and 4 MPa for 5 hours to carry out a hydrogenation reaction. 300 parts of tetrahydrofuran were added to the reaction solution and then added dropwise to 8000 parts of methanol. The precipitate generated was recovered by filtration and dried under reduced pressure at 50°C to obtain the cyclic olefin polymer (A-1).

[0133] <Modification process of cyclic olefin polymers>

[0134] In a three-necked flask equipped with a stirrer and thermometer, 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 were added, followed by 900 parts of tetrahydrofuran to dissolve it. 28.5 parts of potassium tert-butoxy as a base were added in small amounts each time, and the mixture was stirred for 1 hour. The reaction solution was cooled to 0°C, and 51.7 parts of 4-(chloromethyl)styrene as a modifier were added dropwise, while the mixture was stirred at room temperature for 12 hours. 528 parts of tetrahydrofuran were added to the reaction solution, and then added dropwise to 9000 parts of methanol to recover the precipitate. The precipitate was suspended in 2000 parts of methanol and washed for 30 minutes. The solid was then filtered and dried under reduced pressure. The mixture was diluted with tetrahydrofuran and filtered through cotton plugs until the solid content was 7% by weight, then added dropwise to 10 times its volume of methanol. The precipitate was recovered and dried under reduced pressure at room temperature for 12 hours to obtain a cyclic olefin polymer (B-1) with styrene side chains (refer to the following formula). The cyclic olefin polymer (B-1) with styrene side chains is a hydrogenated modified cyclic olefin ring-opening polymer with styrene side chains. For the cyclic olefin polymer (B-1) with styrene side chains, the weight-average molecular weight was 32,000 and the molecular weight distribution was 2.6, as determined by GPC using the above method.

[0135] use 1 The modification rate determined by H-NMR was 100%, and the content of styrene-modified NBMOH structural units (structural unit (I)) in the polymer was 15 moles.

[0136] [Chemical Formula 6]

[0137]

[0138] <Preparation process of resin composition>

[0139] 100 parts of the cyclic olefin polymer (B-1) obtained through the above process, which is a cyclic olefin polymer having styrene groups as side chains, 5 parts of Irgacure (registered trademark) OXE01 (manufactured by BASF) (C-1) as a polymerization initiator (C), and toluene as a solvent, with a total addition amount of 30% by weight relative to the total mass of the resin composition, excluding solvent, were mixed and dissolved. Next, K-341 (manufactured by Shin-Etsu Silicone Co., Ltd.) as a surfactant was added at a rate of 0.03% by weight relative to the total mass of the resin composition, and the mixture was filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare the resin composition.

[0140] The resulting resin composition was then subjected to various evaluations as described above. The results are shown in Table 1.

[0141] (Example 2)

[0142] In the <Preparation Step of Cyclic Olefin Polymer>, the composition of the monomer mixture was changed so that NBMOH and ETD were 50 mol% each, and the same operation as in Example 1 was performed to obtain cyclic olefin polymer (A-2). Then, in the <Modification Step of Cyclic Olefin Polymer>, using the thus obtained cyclic olefin polymer (A-2), 11.9 parts of tetrabutylammonium iodide were changed to 108.2 parts of potassium tert-butoxy, and the amount of 4-(chloromethyl)styrene was changed to 196.2 parts, and the same operation as in Example 1 was performed to obtain cyclic olefin polymer (B-2) with styrene side chains (refer to the following formula). According to the above method, the weight-average molecular weight of the cyclic olefin polymer (B-2) with styrene side chains obtained by GPC was 28,000, and the molecular weight distribution was 2.5. Furthermore, using... 1 The modification rate determined by H-NMR was 100%, and the content of styrene-modified NBMOH in the polymer was 50 moles.

[0143] [Chemical Formula 7]

[0144]

[0145] <Preparation process of resin composition>

[0146] 100 parts of a cyclic olefin polymer with styrene side chains (B-2), obtained according to the above method, 5 parts of Irgacure (registered trademark) OXE01 (manufactured by BASF) (C-1), serving as a polymerization initiator (C), and toluene, as a solvent, were mixed and dissolved in an amount totaling 30% by weight relative to the total mass of the resin composition, excluding the solvent. Next, KP-341 (manufactured by Shin-Etsu Silicone Co., Ltd.), serving as a surfactant, was added at 0.03% by weight relative to the total mass of the resin composition, and the mixture was then filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare the resin composition.

[0147] The resulting resin composition was then subjected to various evaluations as described above. The results are shown in Table 1.

[0148] (Example 3)

[0149] In the <Preparation Step of Cyclic Olefin Polymer>, the composition of the monomer composition was changed so that NBMOH was 80 mol% and ETD was 20 mol%, and the same operation as in Example 1 was performed to obtain cyclic olefin polymer (A-3). Then, in the <Modification Step of Cyclic Olefin Polymer>, using the cyclic olefin polymer (A-3) thus obtained, 21.5 parts of tetrabutylammonium iodide were changed to 139.3 parts of potassium tert-butoxy, and the amount of 4-(chloromethyl)styrene was changed to 356.0 parts. Except for these aspects, the same operation as in Example 1 was performed to obtain cyclic olefin polymer (B-3) with styrene side chains (refer to the following formula). The weight-average molecular weight of the cyclic olefin polymer (B-3) with styrene side chains obtained by GPC according to the above method was 27,000, and the molecular weight distribution was 2.5. Furthermore, using 1 The modification rate, as determined by H-NMR, was 100%, and the content of styrene-modified NBMOH in the polymer was 80 mol%.

[0150] [Chemical Formula 8]

[0151]

[0152] <Preparation process of resin composition>

[0153] One hundred parts of a cyclic olefin polymer with styrene side chains (B-3), obtained according to the above method, which is a cyclic olefin polymer with styrene side chains, and five parts of Irgacure (registered trademark) OXE01 (manufactured by BASF) (C-1), which is a photopolymerization initiator (C), and toluene, which is added as a solvent, in an amount totaling 30% by weight relative to the total mass of the resin composition, excluding solvent, were mixed and dissolved. Next, KP-341 (manufactured by Shin-Etsu Silicone Co., Ltd.), which is added as a surfactant, was added in an amount of 0.03% by weight relative to the total mass of the resin composition, and then the mixture was filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare the resin composition.

[0154] The resulting resin composition was then subjected to various evaluations as described above. The results are shown in Table 1.

[0155] (Example 4)

[0156] In the <Preparation Step of Cyclic Olefin Polymer>, the composition of the monomer mixture was changed so that NBMOH was 50 mol% and brined methylene tetrahydrofluorene (MTF) was 50 mol%, and the same operation as in Example 1 was performed to obtain cyclic olefin polymer (A-4). Then, in the <Modification Step of Cyclic Olefin Polymer>, using the cyclic olefin polymer (A-4) thus obtained, 12.0 parts of tetrabutylammonium iodide were changed to 109.6 parts of potassium tert-butoxy, and the amount of 4-(chloromethyl)styrene was changed to 198.7 parts, and the same operation as in Example 1 was performed to obtain cyclic olefin polymer (B-4) with styrene side chains (refer to the following formula). The weight-average molecular weight of the cyclic olefin polymer (B-4) obtained by GPC according to the above method was 31,000 and the molecular weight distribution was 2.5. Furthermore, using 1 The modification rate determined by H-NMR was 100%, and the content of styrene-modified NBMOH in the polymer was 50 moles.

[0157] [Chemical Formula 9]

[0158]

[0159] <Preparation process of resin composition>

[0160] One hundred parts of a cyclic olefin polymer with styrene side chains (B-4), obtained according to the above method, which is a cyclic olefin polymer with styrene side chains, and five parts of Irgacure (registered trademark) OXE01 (manufactured by BASF) (C-1), which is a photopolymerization initiator (C), were mixed and dissolved with toluene as a solvent, which, excluding solvent, totaled 30% by weight relative to the total weight of the resin composition. Next, KP-341 (manufactured by Shin-Etsu Silicone Co., Ltd.), as a surfactant, was added at 0.03% by weight relative to the total weight of the resin composition, and the mixture was filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare the resin composition.

[0161] The resulting resin composition was then subjected to various evaluations as described above. The results are shown in Table 1.

[0162] (Example 5)

[0163] In the <Preparation Step of Cyclic Olefin Polymer>, the composition of the monomer mixture was changed by replacing NBMOH with 15 mol%, tetracyclododecene methanol (TCDMOH) with 50 mol%, and ETD with 50 mol%. Otherwise, the same operation as in Example 1 was performed to obtain the cyclic olefin polymer (A-5). Then, in the <Modification Step of Cyclic Olefin Polymer>, using the thus obtained cyclic olefin polymer (A-5), 9.9 parts of tetrabutylammonium iodide were replaced with 90.4 parts of potassium tert-butoxy, and the amount of 4-(chloromethyl)styrene was changed to 163.9 parts. Otherwise, the same operation as in Example 1 was performed to obtain the cyclic olefin polymer (B-5) with styrene side chains. The weight-average molecular weight of the cyclic olefin polymer (B-5) with styrene side chains obtained by GPC according to the above method was 33,000, and the molecular weight distribution was 2.6. Furthermore, using… 1 The modification rate, as determined by H-NMR, was 100%, and the content of styrene-modified TCDMOH in the polymer was 50 mol%.

[0164] [Chemical Formula 10]

[0165]

[0166] <Preparation process of resin composition>

[0167] 100 parts of a cyclic olefin polymer with styrene side chains (B-5), obtained according to the above method, and 5 parts of Irgacure OXE02 (manufactured by BASF) (C-2), used as a photopolymerization initiator (C), were mixed and dissolved with toluene as a solvent, excluding solvent, in an amount totaling 30% by weight relative to the total weight of the resin composition. Next, KP-341 (manufactured by Shin-Etsu Silicone Co., Ltd.), used as a surfactant, was added at 0.03% by weight relative to the total weight of the resin composition. The mixture was then filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare the resin composition.

[0168] The resulting resin composition was then subjected to various evaluations as described above. The results are shown in Table 2.

[0169] (Example 6)

[0170] In the <Preparation Step of Cyclic Olefin Polymer>, the composition of the monomer mixture was changed so that tetracyclododecene methanol (TCDMOH) was 50 mol% and dicyclopentadiene (DCPD) was 50 mol%, and the same operation as in Example 1 was performed to obtain cyclic olefin polymer (A-6). Then, in the <Modification Step of Cyclic Olefin Polymer>, using the cyclic olefin polymer (A-6) thus obtained, 11.5 parts of tetrabutylammonium iodide were changed to 104.4 parts of potassium tert-butoxy, and the amount of 4-(chloromethyl)styrene was changed to 189.3 parts, and the same operation as in Example 1 was performed to obtain cyclic olefin polymer (B-6) with styrene side chains (refer to the following formula). The weight-average molecular weight of the cyclic olefin polymer (B-6) with styrene side chains obtained by GPC according to the above method was 30,000, and the molecular weight distribution was 2.6. Furthermore, using 1 The modification rate, as determined by H-NMR, was 100%, and the content of styrene-modified TCDMOH in the polymer was 50 mol%.

[0171] [Chemical Formula 11]

[0172]

[0173] <Preparation process of resin composition>

[0174] One hundred parts of a cyclic olefin polymer with styrene side chains (B-6), obtained according to the above method, and five parts of Irgacure OXE03 (manufactured by BASF) (C-3), used as a photopolymerization initiator (C), were mixed and dissolved with toluene as a solvent, excluding solvent, in an amount totaling 30% by mass relative to the total mass of the resin composition. Next, KP-341 (manufactured by Shin-Etsu Silicone Co., Ltd.), used as a surfactant, was added at 0.03% by mass relative to the total mass of the resin composition, and the mixture was filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare the resin composition.

[0175] The resulting resin composition was then subjected to various evaluations as described above. The results are shown in Table 2.

[0176] (Example 7)

[0177] In the <Preparation Step of Cyclic Olefin Polymer>, the composition of the monomer mixture was changed so that TCDMOH was 50 mol% and MTF was 50 mol%, and the same operation as in Example 1 was performed to obtain cyclic olefin polymer (A-7). Then, in the <Modification Step of Cyclic Olefin Polymer>, using the cyclic olefin polymer (A-7) thus obtained, 9.9 parts of tetrabutylammonium iodide were changed to 90.3 parts of potassium tert-butoxy, and the amount of 4-(chloromethyl)styrene was changed to 163.0 parts, and the same operation as in Example 1 was performed to obtain cyclic olefin polymer (B-7) with styrene side chains (refer to the following formula). The weight-average molecular weight of the cyclic olefin polymer (B-7) with styrene side chains obtained by GPC according to the above method was 35,000, and the molecular weight distribution was 2.5. Furthermore, using 1 The modification rate, as determined by H-NMR, was 100%, and the content of styrene-modified TCDMOH in the polymer was 50 mol%.

[0178] [Chemical Formula 12]

[0179]

[0180] <Preparation of Resin Compositions>

[0181] 100 parts of a cyclic olefin polymer with styrene side chains (B-7), obtained according to the above method, and 5 parts of Irgacure OXE01 (manufactured by BASF) (C-1), used as a photopolymerization initiator (C), were mixed and dissolved with toluene as a solvent, excluding solvent, in an amount totaling 30% by mass relative to the total mass of the resin composition. Next, KP-341 (manufactured by Shin-Etsu Silicone Co., Ltd.), used as a surfactant, was added at 0.03% by mass relative to the total mass of the resin composition, and the mixture was filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare the resin composition.

[0182] The resulting resin composition was then subjected to various evaluations as described above. The results are shown in Table 2.

[0183] (Example 8)

[0184] <Preparation process of cyclic olefin polymers>

[0185] The scale was increased 20-fold, and the cyclic olefin polymer (A-8) was synthesized as a norbornene (NB) / NBMOH addition polymer according to the method described in Macromolecules 29,2761 (1996). Then, in the <Cyclic Olefin Polymer Modification Step>, using the thus obtained cyclic olefin polymer (A-8), the solvent was changed from tetrahydrofuran to toluene, 5.6 parts of tetrabutylammonium iodide was changed to 51.1 parts of potassium tert-butoxy, and the amount of 4-(chloromethyl)styrene was changed to 92.7 parts. Otherwise, the process was carried out in the same manner as in Example 1, yielding a cyclic olefin polymer (B-8) with styrene side chains (refer to the following formula). The weight-average molecular weight of the cyclic olefin polymer (B-8) with styrene side chains obtained by GPC according to the above method was 45,000, and the molecular weight distribution was 2.4. Furthermore, using… 1 The modification rate determined by H-NMR was 100%, and the content of styrene-modified NBMOH in the polymer was 15 moles.

[0186] [Chemical Formula 13]

[0187]

[0188] <Preparation process of resin composition>

[0189] 100 parts of the cyclic olefin polymer with styrene side chains (B-8), obtained according to the above method, and 0.5 parts of Irgacure OXE01 (manufactured by BASF) (C-1), which serves as a photopolymerization initiator (C), were mixed and dissolved with toluene as a solvent, excluding solvent, in an amount totaling 30% by mass relative to the total mass of the resin composition. Next, KP-341 (manufactured by Shin-Etsu Silicone Co., Ltd.), as a surfactant, was added at 0.03% by mass relative to the total mass of the resin composition, and the mixture was filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare the resin composition.

[0190] The resulting resin composition was then subjected to various evaluations as described above. The results are shown in Table 2.

[0191] (Comparative Example 1)

[0192] <Preparation process of modified cyclic olefin polymer (B-9)>

[0193] A three-necked flask equipped with a stirrer and thermometer was nitrogen-purged. 100 parts of a cyclic olefin polymer (A-8) as an addition polymer, 336.5 parts of triethylamine as a catalyst for modification, and 400 parts of tetrahydrofuran as a solvent were added. The reaction solution was cooled to 0°C in an ice bath. While maintaining the temperature of the reaction solution below 10°C, 298.0 parts of methacrylamide chloride as a modifier were added dropwise, and the mixture was stirred for 2 hours. The reaction solution was then further heated to room temperature and stirred for another 12 hours. Next, 200 parts of tetrahydrofuran as a solvent were added to the reaction solution, and the mixture was cooled to 0°C. While maintaining the temperature of the reaction solution below 10°C, methanol in an amount equal to 0.5 parts by mass relative to methacrylamide chloride was added. The mixture was stirred at 0°C for 1 hour, then heated to room temperature and stirred for another hour.

[0194] The reaction solution was added dropwise to 8000 parts of methanol, and the resulting precipitate was recovered by filtration. After washing the precipitate three times with methanol, it was dried under reduced pressure at 50°C to obtain the modified addition polymer (B-9) (see the following formula).

[0195] pass 1 ¹H-NMR analysis confirmed that the methacryloyl modification rate of the cyclic olefin polymer (A-8) as an addition polymer was 100%, and the content of NBMOH after methacryloyl modification in the modified addition polymer (B-9) was 15 mol%. The weight-average molecular weight and molecular weight distribution of the modified addition polymer (B-9) determined by GPC were 28,100 and 1.8, respectively.

[0196] [Chemical Formula 14]

[0197]

[0198] <Preparation process of resin composition>

[0199] 100 parts of the modified addition polymer (B-9) obtained according to the above method, 5 parts of Irgacure (registered trademark) OXE01 (manufactured by BASF) (C-1) as photopolymerization initiator (C), and toluene as solvent, in an amount totaling 30% by mass relative to the total mass of the resin composition (excluding solvent), were mixed and dissolved. Next, KP-341 (manufactured by Shin-Etsu Silicone Co., Ltd.) as surfactant was added at 0.03% by mass relative to the total mass of the resin composition, and the mixture was filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare the resin composition.

[0200] The resulting resin composition was then subjected to various evaluations as described above. The results are shown in Table 2.

[0201] [Table 1]

[0202]

[0203] [Table 2]

[0204]

[0205] As shown in Tables 1-2, in Examples 1-8 using a resin composition containing a cyclic olefin polymer with styrene side chains, a resin film with a dielectric loss tangent that does not easily change before and after exposure to high temperature and high humidity conditions can be formed by HAST. On the other hand, as shown in Table 2, in Comparative Example 1 using a resin composition containing a cyclic olefin polymer without styrene side chains, the dielectric loss tangent of the resin film formed by HAST changes before and after exposure to high temperature and high humidity conditions.

[0206] Industrial availability

[0207] According to the present invention, a resin composition is provided that can form a resin film whose dielectric loss tangent value does not change significantly before and after exposure to high temperature and high humidity conditions.

Claims

1. A resin composition comprising a cyclic olefin polymer having styrene groups in its side chains, The cyclic olefin polymer comprises structural units represented by formula (I) and structural units represented by formula (II). Here, R 1 ~R 4 Each independently represents a hydrogen atom, an organic group having a styrene group, an alkyl group, or an aromatic cyclic group, wherein, The aromatic cyclic group does not contain a group equivalent to the organic group having a styrene group, R 1 ~R 4 At least one of them is the organic group having a styrene group, where m represents an integer from 0 to 4. Here, R 5 ~R 8 Each independently represents a hydrogen atom, an alkyl group, or an aromatic cyclic group, wherein the aromatic cyclic group does not contain a group equivalent to the organic group having a styrene group, R 5 ~R 8 They can combine to form a ring, where n is an integer from 0 to 4.

2. The resin composition according to claim 1, wherein, The resin composition also includes a polymerization initiator.

3. The resin composition according to claim 2, wherein, The polymerization initiator is an oxime ester-based photoradical generator.

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