Photocurable resin composition, film, and cured film

Abstract

The present invention provides a photocurable resin composition that can produce a film with an improved balance of photocurability and low dielectric properties after photocuring. [Solution] A photocurable resin composition comprising an olefin polymer (A) having a crosslinkable group, a (meth)acryloyl compound (B) having two or more (meth)acryloyl groups, and a photoradical polymerization initiator (C).

Description

[Technical Field]

[0001] The present invention relates to a photocurable resin composition, a film, and a cured film. [Background technology]

[0002] From the perspective of miniaturizing and increasing the integration of semiconductor packages, semiconductor packages may sometimes be provided with a redistribution layer. Examples of technologies related to redistribution layers include those described in Patent Documents 1 and 2.

[0003] Patent Document 1 discloses a photosensitive resin composition that is low-temperature curable and whose cured product has a low dielectric loss tangent, comprising: a first polymer containing a polyimide represented by a predetermined formula; a second polymer having at least one substituted or unsubstituted maleimide group and different from the first polymer; a photosensitizer; and an antioxidant, wherein the antioxidant comprises at least one selected from hindered phenol compounds, thioether compounds, phosphite compounds, and phosphonite compounds.

[0004] Patent Document 2 discloses a curable resin composition that can be cured by light such as ultraviolet light and, if necessary, by heat, and whose cured product has low dielectric properties, and which contains (A) a compound having at least two or more styrene structures in the molecule, and (B) a photopolymerization initiator. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2024-024623 [Patent Document 2] Japanese Patent Publication No. 2023-130779 [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention provides a photocurable resin composition that can produce a film with an improved balance of photocurability and low dielectric properties after photocuring. [Means for solving the problem]

[0007] According to the present invention, the following photocurable resin composition, film, and cured film are provided.

[0008] [1] An olefin polymer (A) having a crosslinkable group, A (meth)acryloyl compound (B) having two or more (meth)acryloyl groups, A photocurable resin composition comprising a photoradical polymerization initiator (C). [2] The photocurable resin composition according to [1], wherein the (meth)acryloyl compound (B) comprises one or more selected from an alicyclic skeleton, an aromatic skeleton, and an aliphatic skeleton. [3] The photocurable resin composition according to [1] or [2], wherein the content of the (meth)acryloyl compound (B) is 1 part by mass or more and 100 parts by mass or less, when the content of the olefin polymer (A) is 100 parts by mass. [4] The photocurable resin composition according to any one of [1] to [3], wherein the photoradical polymerization initiator (C) has at least one maximum absorption wavelength in the wavelength region of 200 nm to 450 nm. [5] The photocurable resin composition according to any one of [1] to [4], wherein the photoradical polymerization initiator (C) comprises an oxime-based photoradical polymerization initiator. [6] The photocurable resin composition according to any one of [1] to [5], wherein the content of the photoradical polymerization initiator (C) is 0.1 parts by mass or more and 10 parts by mass or less, when the content of the olefin polymer (A) is 100 parts by mass. [7] The photocurable resin composition according to any one of [1] to [6] above, wherein the olefin polymer (A) contains a cyclic olefin copolymer (A1) having a crosslinkable group. [8] The cyclic olefin copolymer (A1) is a repeating unit (a1) represented by the following formula (I), and one or more repeating units (a2) selected from the group consisting of a repeating unit represented by the following formula (II), a repeating unit represented by the following formula (III), and a repeating unit represented by the following formula (IV), and a repeating unit (a3) represented by the following formula (V), and is the photocurable resin composition according to [7] above. [Chemical formula] (In the above formula (I), R 300 represents a hydrogen atom or a linear or branched alkyl group having 1 to 29 carbon atoms.) [Chemical formula] (In the above formula (II), u represents 0 or 1, v represents 0 or 1, w represents 0 or 1, R 61 to R 76 , R a1 , and R b1 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 102 and R 103 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 75 and R 76 may be bonded to each other to form a monocyclic or polycyclic ring.) [Chemical formula] [In formula (III) above, t represents a positive integer from 0 to 10, u represents 0 or 1, v represents 0 or a positive integer, w represents 0 or 1, R 61 ~R 76 , R a1 , and R b1 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 104 R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 75 and R 76 These may be bonded to each other to form a monocycle or polycycle. [ka] [In formula (IV) above, u represents 0 or 1, v represents 0 or 1, w represents 0 or 1, R 61 ~R 76 , R a1 , and R b1 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 75 and R 76 These may be bonded to each other to form a monocycle or polycycle. [ka] [In the above formula (V), u represents 0 or 1, v represents 0 or a positive integer, w represents 0 or 1, R 61 ~R 78 , R a1 , and R b1 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 75 and R 76 , R 76 and R77 , or R 77 and R 78 These may be bonded to each other to form a monocycle or polycycle. [9] The photocurable resin composition according to [8], wherein the olefin constituting the repeating unit (a1) contains ethylene.

[10] The cyclic non-conjugated diene constituting the repeating unit (a2) is 5-vinyl-2-norbornene, 8-vinyl-9-methyltetracyclo[4.4.0.1 2,5 .1 7,10 A photocurable resin composition according to [8] or [9], comprising one or more selected from the group consisting of ]-3-dodecene and 5-allyl-2-norbornene.

[11] The cyclic olefin constituting the repeating unit (a3) ​​is tetracyclo[4.4.0.1 2,5 .1 7,10 A photocurable resin composition according to any one of the above [8] to

[10] , comprising one or two selected from the group consisting of ]-3-dodecene and bicyclo[2.2.1]-2-heptene.

[12] The photocurable resin composition according to any one of [1] to

[11] , wherein the content of repeating units having crosslinkable groups in the olefin polymer (A) is 0.1 mol% or more and 50 mol% or less when the total content of repeating units in the olefin polymer (A) is 100 mol%.

[13] A photocurable resin composition according to any one of the above [1] to

[12] , further comprising a thermoplastic resin.

[14] The photocurable resin composition according to

[13] , wherein the thermoplastic resin comprises one or more selected from polyolefins, cyclic polyolefins, polyimides, polyamides, polyimidamides, polyesters, polyphenylene ethers, polyethersulfones, polyphenylene sulfides, polydicyclopentadienes, styrene-butadiene-styrene copolymers, and styrene-ethylene-butadiene-styrene copolymers.

[15] The photocurable resin composition according to

[13] or

[14] , wherein the content of the thermoplastic resin is 10 parts by mass or more and 200 parts by mass or less, when the content of the olefin polymer (A) is 100 parts by mass.

[16] A photocurable resin composition according to any one of [1] to

[15] above, wherein the reduction rate (100 × Df2 / Df1), which is the ratio of the dielectric loss tangent Df2 obtained by the following (Method 2) to the dielectric loss tangent Df1 obtained by the following (Method 1), is 99% or less. (Method 1) A coated film is prepared by applying a varnish containing the photocurable resin composition onto a PET film. Next, the coated film is dried at 150°C for 4 minutes under a nitrogen atmosphere to produce a dried film. Next, a 50mm x 50mm test piece 1 is prepared from the dried film. Next, the dielectric loss tangent Df1 of the test piece 1 is measured using a cylindrical cavity resonator at 23±2℃, 80%RH or less, and 10GHz. (Method 2) A coated film is prepared by applying a varnish containing the photocurable resin composition onto a PET film. Next, the coated film is dried at 150°C for 4 minutes under a nitrogen atmosphere to produce a dried film. Next, the illuminance of the dried film was measured using a 365nm wavelength illuminometer with a high-pressure mercury lamp output of 4000W, resulting in an illuminance of 20mW / cm². 2 Irradiation time 150 seconds, exposure amount 3000 mJ / cm² 2 By irradiating with light under atmospheric conditions, a cured film with a thickness of 35 ± 10 μm was produced. Next, a 50mm x 50mm test piece 2 is prepared from the cured film. Next, the dielectric loss tangent Df2 of the test piece 2 is measured using a cylindrical cavity resonator at 23±2℃, 80%RH or less, and 10GHz.

[17] A photocurable resin composition according to any of [1] to

[16] above, wherein the dielectric loss tangent Df2 determined by the following method (Method 2) is 0.013 or less. (Method 2) A coated film is prepared by applying a varnish containing the photocurable resin composition onto a PET film. Next, the coated film is dried at 150°C for 4 minutes under a nitrogen atmosphere to produce a dried film. Next, the illuminance of the dried film was measured using a 365nm wavelength illuminometer with a high-pressure mercury lamp output of 4000W, resulting in an illuminance of 20mW / cm². 2 Irradiation time 150 seconds, exposure amount 3000 mJ / cm² 2 By irradiating with light under atmospheric conditions, a cured film with a thickness of 35 ± 10 μm was produced. Next, a 50mm x 50mm test piece 2 is prepared from the cured film. Next, the dielectric loss tangent Df2 of the test piece 2 is measured using a cylindrical cavity resonator at 23±2℃, 80%RH or less, and 10GHz.

[18] A photocurable resin composition according to any of [1] to

[17] above, wherein X2 by the method described below (Method 3) is 0.019 or less. (Method 3) A coated film is prepared by applying a varnish containing the photocurable resin composition onto a PET film. Next, the coated film is dried at 150°C for 4 minutes under a nitrogen atmosphere to produce a dried film. Next, the illuminance of the dried film was measured using a 365nm wavelength illuminometer with a high-pressure mercury lamp output of 4000W, resulting in an illuminance of 20mW / cm². 2 Irradiation time 150 seconds, exposure amount 3000 mJ / cm² 2 By irradiating with light under atmospheric conditions, a cured film with a thickness of 35 ± 10 μm was produced. Next, a 50mm x 50mm test piece 2 is prepared from the cured film. Next, the relative permittivity Dk2 and dielectric loss tangent Df2 of the test piece 2 were measured using a cylindrical cavity resonator at 23±2℃, 80%RH or less, and 10GHz. Next, X2 is calculated using the following formula (X2). Formula (X2):X2=(Dk2) 0.5 ×Df2

[19] A photocurable resin composition according to any one of the above [1] to

[18] , which is in an uncured or semi-cured state.

[20] A photocurable resin composition according to any one of the above [1] to

[19] , used in a redistribution layer. [twenty one] A film comprising the photocurable resin composition described in any of the above [1] to

[20] . [twenty two] A cured film of the film described in

[21] above. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a photocurable resin composition that can produce a film with an improved balance of photocurability and low dielectric properties after photocuring.

[0010] The present invention will be described below based on embodiments. In these embodiments, unless otherwise specified, "A~B" indicating a numerical range represents A or greater and B or less. Furthermore, when a numerical range is described in steps, the upper and lower limits of each numerical range can be arbitrarily combined. In addition, the description "A and / or B" is a concept that includes the cases of A, B, and both A and B. In the notation of groups (atomic groups) in this embodiment, notations that do not specify whether they are substituted or unsubstituted include both groups that do not contain substituents and groups that do. For example, "alkyl group" includes not only alkyl groups that do not contain substituents (unsubstituted alkyl groups) but also alkyl groups that contain substituents (substituted alkyl groups). In this embodiment, the term "(meth)acrylic" represents a concept that encompasses both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate." Furthermore, each monomer constituting the "olefin polymer (A) having a crosslinkable group" in this embodiment may be a monomer obtained from fossil raw materials, a monomer obtained from animal or plant-based raw materials, or a monomer obtained from raw materials obtained by chemical recycling. Furthermore, in this embodiment, the -CH=CH2 group in the (meth)acrylic group is not included in the vinyl group. Furthermore, in this embodiment, crosslinking refers to the property in which the crosslinking groups of a compound undergo a curing reaction to form crosslinked bonds, thereby yielding a cured product.

[0011] [Photocurable resin composition] The photocurable resin composition of this embodiment comprises an olefin polymer (A) having a crosslinkable group, a (meth)acryloyl compound (B) having two or more (meth)acryloyl groups, and a photoradical polymerization initiator (C). According to the photocurable resin composition of this embodiment, a film can be obtained in which the balance between photocurability and low dielectric properties after photocuring is improved.

[0012] The reason for obtaining the above effects is not clear, but the following reasons can be inferred. In the photocurable resin composition of this embodiment, the olefin polymer (A), which has excellent low dielectric properties, has crosslinkable groups, so it is thought that the crosslinking of the olefin copolymer (A) can proceed appropriately by the photoreaction of a (meth)acryloyl compound (B) having two or more (meth)acryloyl groups with good compatibility and a photoradical polymerization initiator (C). As a result, it is thought that a film with an improved balance of photocurability and low dielectric properties after photocuring can be obtained.

[0013] Next, we will explain the components of photocurable resin compositions with specific examples. The photocurable resin composition of this embodiment (hereinafter also referred to as the resin composition) comprises an olefin polymer (A) having a crosslinkable group (hereinafter also referred to as polymer (A)), a (meth)acryloyl compound (B) having two or more (meth)acryloyl groups (hereinafter also referred to as compound (B)), and a photoradical polymerization initiator (C) (hereinafter also referred to as initiator (C)). The resin composition of this embodiment may consist of polymer (A), compound (B), and initiator (C), or may contain other components. The resin composition of this embodiment may also contain other components, such as a thermoplastic resin described later. The following sections will explain each component separately.

[0014] <Olefin polymer having crosslinkable groups (A)> The resin composition of this embodiment includes polymer (A) from the viewpoint of obtaining a film with an improved balance of photocurability and low dielectric properties after photocuring. Polymer (A) can be used without particular limitations as long as it has crosslinkable groups and contains repeating units derived from olefins. Polymer (A) may be a homopolymer or a copolymer.

[0015] The polymer (A) of this embodiment has a crosslinkable group in order to obtain a film with an improved balance of photocurability and low dielectric properties after photocuring. The crosslinkable group includes, for example, one or more selected from the group consisting of vinyl group; vinylidene group; vinylene group; vinyl group substituted with alkyl group, phenyl group or alkylphenyl group; vinylidene group substituted with alkyl group, phenyl group or alkylphenyl group; vinylene group substituted with alkyl group, phenyl group or alkylphenyl group; maleimide group; thiol group; thienyl group; silyl group; epoxy group; oxazoline group; (meth)acrylic group; carboxyl group; and hydrosilyl group. Polymer (A) preferably contains vinyl groups from the viewpoint of obtaining a film with a better balance of photocurability and low dielectric properties after photocuring.

[0016] Examples of polymer (A) in this embodiment include a cyclic olefin copolymer (A1) having a crosslinkable group (hereinafter also referred to as copolymer (A1)), a cyclic olefin homopolymer (A2) having a crosslinkable group (hereinafter also referred to as polymer (A2)), an olefin homopolymer having a crosslinkable group, and an olefin copolymer having a crosslinkable group.

[0017] Examples of polymer (A2) include ring-opening polymers of cyclic olefins and addition polymers of cyclic olefins having crosslinkable groups. Polymer (A2) may have, for example, a cyclic structure with four or more members, or an alicyclic structure.

[0018] Examples of olefin-based homopolymers having crosslinkable groups include polydivinylbenzene, polybutadiene, and polydicyclopentadiene. Examples of olefin copolymers having crosslinkable groups include polydivinylbenzene with introduced crosslinkable groups, polybutadiene with introduced crosslinkable groups, polydicyclopentadiene with introduced crosslinkable groups, polystyrene-polybutadiene-polystyrene block copolymer with introduced crosslinkable groups, polystyrene-polyethylene-polybutadiene-polystyrene block copolymer with introduced crosslinkable groups, styrene-butadiene copolymer with introduced crosslinkable groups, and polyacetylene with introduced crosslinkable groups.

[0019] In this embodiment, the content of repeating units having crosslinkable groups in polymer (A) is preferably 0.1 mol% or more, more preferably 1 mol% or more, even more preferably 10 mol% or more, and even more preferably 20 mol% or more, when the total content of repeating units in polymer (A) is 100 mol%, from the viewpoint of improving the crosslink density. In this embodiment, the content of repeating units having crosslinkable groups in polymer (A) is preferably 50 mol% or less, more preferably 45 mol% or less, even more preferably 40 mol% or less, and even more preferably 35 mol% or less, when the total content of repeating units in polymer (A) is 100 mol%, from the viewpoint of reducing the embrittlement of the resulting film. In this embodiment, the content of repeating units having crosslinkable groups in polymer (A) is preferably 0.1 mol% to 50 mol%, more preferably 1 mol% to 45 mol%, even more preferably 10 mol% to 40 mol%, and even more preferably 20 mol% to 35 mol%, when the total content of repeating units in polymer (A) is 100 mol%, from the viewpoint of improving the crosslink density and reducing the embrittlement of the resulting film.

[0020] The polymer (A) of this embodiment preferably includes a cyclic olefin polymer from the viewpoint of obtaining a film with improved low dielectric properties. Examples of cyclic olefin polymers include copolymer (A1) and polymer (A2).

[0021] (Cyclic olefin copolymer having crosslinkable groups (A1)) The polymer (A) of this embodiment will be described in detail below using copolymer (A1), but the polymer (A) of this embodiment is not limited to the following embodiments.

[0022] The polymer (A) of this embodiment includes copolymer (A1) from the viewpoint of obtaining a film with an improved balance of photocurability and low dielectric properties after photocuring. Copolymer (A1) can be used without particular limitations as long as it is a copolymer containing repeating units derived from a cyclic olefin.

[0023] The copolymer (A1) of this embodiment has a crosslinkable group in order to obtain a film with an improved balance of photocurability and low dielectric properties after photocuring. The crosslinkable group includes, for example, one or more selected from the group consisting of vinyl group; vinylidene group; vinylene group; vinyl group substituted with alkyl group, phenyl group or alkylphenyl group; vinylidene group substituted with alkyl group, phenyl group or alkylphenyl group; vinylene group substituted with alkyl group, phenyl group or alkylphenyl group; maleimide group; thiol group; thienyl group; silyl group; epoxy group; oxazoline group; (meth)acrylic group; carboxyl group; and hydrosilyl group. The copolymer (A1) preferably contains vinyl groups, from the viewpoint of obtaining a film with a better balance of photocurability and low dielectric properties after photocuring.

[0024] Next, the repeating units of the copolymer (A1) in this embodiment will be described.

[0025] The copolymer (A1) of this embodiment includes repeating units (a1), repeating units (a2), and repeating units (a3) ​​from the viewpoint of obtaining a film with improved low dielectric properties. The repeating unit (a1) is a repeating unit represented by the following formula (I). In other words, the repeating unit (a1) is a repeating unit derived from one or more olefins. The repeating unit (a2) is one or more repeating units selected from the group consisting of the repeating units represented by formula (II), formula (III), and formula (IV) below. In other words, the repeating unit (a2) is a repeating unit derived from one or more cyclic non-conjugated dienes. The repeating unit (a3) ​​is a repeating unit represented by the following formula (V). In other words, the repeating unit (a3) ​​is a repeating unit derived from one or more cyclic olefins.

[0026] In the following, the repeating unit represented by equation (II) will also be called the repeating unit (a22). Similarly, the repeating unit represented by equation (III) will also be called the repeating unit (a23). Furthermore, the repeating unit represented by equation (IV) will also be called the repeating unit (a24). In other words, repeating unit (a2) is one or more repeating units selected from the group consisting of repeating units (a22), repeating unit (a23), and repeating unit (a24).

[0027] [ka]

[0028] In equation (I), R 300 This represents a hydrogen atom or a linear or branched alkyl group having 1 to 29 carbon atoms.

[0029] [ka]

[0030] In equation (II), u represents 0 or 1, v represents 0 or 1, w represents 0 or 1, and R 61 ~R 76 , R a1 , and R b1 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 102 and R 103 Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 75 and R 76 These elements may be bonded to each other to form a monocycle or polycycle.

[0031] [ka]

[0032] In equation (III), t represents a positive integer between 0 and 10, u represents 0 or 1, v represents 0 or a positive integer, w represents 0 or 1, and R 61 ~R 76 , R a1 , and R b1 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 104 R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 75 and R 76 These elements may be bonded to each other to form a monocycle or polycycle.

[0033] [ka]

[0034] In equation (IV), u represents 0 or 1, v represents 0 or 1, w represents 0 or 1, and R 61 ~R 76 , R a1 , and R b1 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 75 and R 76 These elements may be bonded to each other to form a monocycle or polycycle.

[0035] [ka]

[0036] In equation (V), u represents 0 or 1, v represents 0 or a positive integer, w represents 0 or 1, and R 61 ~R 78 , R a1 , and R b1Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 75 and R 76 , R 76 and R 77 , or R 77 and R 78 These elements may be bonded to each other to form a monocycle or polycycle.

[0037] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, and tetradecyl groups. Examples of cycloalkyl groups having 3 to 15 carbon atoms include cyclopentyl groups and cyclohexyl groups. Furthermore, examples of alkyl halides having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms in which one or more halogen atoms substitute for hydrogen atoms. Examples of aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenyl, naphthyl, tolyl, xylyl, benzyl, and phenylethyl groups.

[0038] From the viewpoint of obtaining a film with improved low dielectric properties, the content of repeating units (a1) in the copolymer (A1) of this embodiment is preferably 10 mol% to 90 mol%, more preferably 30 mol% to 80 mol%, even more preferably 50 mol% to 75 mol%, and even more preferably 55 mol% to 70 mol%, when the total content of repeating units in the copolymer (A1) is 100 mol%.

[0039] From the viewpoint of obtaining a film with improved low dielectric properties, the content of repeating units (a2) in the copolymer (A1) of this embodiment is preferably 1 mol% to 60 mol%, more preferably 5 mol% to 50 mol%, even more preferably 10 mol% to 40 mol%, and even more preferably 20 mol% to 35 mol%, when the total content of repeating units in the copolymer (A1) is 100 mol%.

[0040] In this embodiment, the content of repeating units (a3) ​​in the copolymer (A1) is preferably 1 mol% to 40 mol%, more preferably 3 mol% to 30 mol%, even more preferably 5 mol% to 20 mol%, and even more preferably 8 mol% to 15 mol%, when the total content of repeating units in the copolymer (A1) is 100 mol%, from the viewpoint of obtaining a film with improved low dielectric properties.

[0041] Next, the raw materials for copolymer (A1) of this embodiment will be described.

[0042] Olefins, one of the raw materials for copolymer (A1), are monomers that undergo addition copolymerization to give repeating units (a1) represented by formula (I).

[0043] Examples of monomers that provide the repeating unit (a1) include olefins represented by the following formula (Ia) (hereinafter also referred to as olefin (Ia)).

[0044] [ka]

[0045] In equation (Ia), R 300 This represents a hydrogen atom or a linear or branched alkyl group having 1 to 29 carbon atoms.

[0046] Examples of olefins (Ia) include ethylene, 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. Furthermore, olefin (Ia) may be an olefin derived from biomass or an olefin derived from chemical recycling. Examples of biomass-derived olefins include biomass-derived ethylene and biomass-derived propylene.

[0047] From the viewpoint of obtaining a film with improved low dielectric properties, the olefin (Ia) preferably comprises one or more selected from the group consisting of ethylene and propylene, and more preferably comprises ethylene.

[0048] A cyclic non-conjugated diene, one of the raw materials for copolymer (A1), is a monomer that undergoes addition copolymerization to give one or more repeating units (repeating unit (a2)) selected from the group consisting of repeating units (a22) represented by formula (II), repeating units (a23) represented by formula (III), and repeating units (a24) represented by formula (IV).

[0049] Examples of monomers that provide the repeating unit (a22) include cyclic non-conjugated dienes represented by the following formula (IIa) (hereinafter also referred to as cyclic non-conjugated diene (IIa)). Examples of monomers that provide the repeating unit (a23) include cyclic non-conjugated dienes represented by the following formula (IIIa) (hereinafter also referred to as cyclic non-conjugated diene (IIIa)). Examples of monomers that provide the repeating unit (a24) include cyclic non-conjugated dienes represented by the following formula (IVa) (hereinafter also referred to as cyclic non-conjugated diene (IVa)). That is, examples of the monomer that provides the repeating unit (a2) include cyclic non-conjugated diene (IIa), cyclic non-conjugated diene (IIIa), cyclic non-conjugated diene (IVa), and the like.

[0050]

Chem.

[0051] In formula (IIa), u represents 0 or 1, v represents 0 or 1, w represents 0 or 1, and R 61 ~R 76 、R a1 、and R b1 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 102 and R 103 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 75 and R 76 may be bonded to each other to form a monocyclic or polycyclic ring.

[0052]

Chem.

[0053] In formula (IIIa), t represents a positive integer from 0 to 10, u represents 0 or 1, v represents 0 or a positive integer, w represents 0 or 1, and R 61 ~R 76 、R a1 、and R b1 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 104 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 75 and R 76They may be bonded to each other to form a monocyclic or polycyclic ring.

[0054]

Chemical formula

[0055] In formula (IVa), u represents 0 or 1, v represents 0 or 1, w represents 0 or 1, and R 61 ~R 76 、R a1 、and R b1 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 75 and R 76 may be bonded to each other to form a monocyclic or polycyclic ring.

[0056] Examples of the cyclic non-conjugated diene (IIa) include 5-ethylidene-2-norbornene, 5-n-propylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-ethylidene-6-methyl-2-norbornene, 8-ethylidene-9-methyltetracyclo[4.4.0.1 2,5 .1 7,10 -3-dodecene, and the like. Note that the cyclic non-conjugated diene (IIa) may be a biomass-derived cyclic non-conjugated diene or a chemical recycling-derived cyclic non-conjugated diene.

[0057] The cyclic non-conjugated diene (IIa) preferably contains 5-ethylidene-2-norbornene from the viewpoint of improving the performance balance of low dielectric characteristics and crosslinking characteristics.

[0058] Examples of the cyclic non-conjugated diene (IIIa) include cyclic non-conjugated dienes represented by the following chemical formulas, etc. Note that the cyclic non-conjugated diene (IIIa) may be a biomass-derived cyclic non-conjugated diene or a chemical recycling-derived cyclic non-conjugated diene.

[0059] [ka]

[0060] [ka]

[0061] From the viewpoint of improving the balance between low dielectric properties and crosslinking properties, the cyclic non-conjugated diene (IIIa) is preferably 5-vinyl-2-norbornene, 8-vinyl-9-methyltetracyclo[4.4.0.1 2,5 .1 7,10 It comprises one or more species selected from the group consisting of ]-3-dodecene and 5-allyl-2-norbornene.

[0062] Examples of cyclic non-conjugated dienes (IVa) include dicyclopentadiene and pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 Examples include ]-4,10-pentadecadiene. Furthermore, the cyclic non-conjugated diene (IVa) may be a cyclic non-conjugated diene derived from biomass, or a cyclic non-conjugated diene derived from chemical recycling.

[0063] From the viewpoint of improving the balance between low dielectric properties and crosslinking properties, the cyclic non-conjugated diene (IVa) preferably includes dicyclopentadiene.

[0064] The cyclic non-conjugated dienes constituting the repeating unit (a2) are preferably 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, and 8-vinyl-9-methyltetracyclo[4.4.0.1 2,5 .1 7,10]-3-dodecene and 5-allyl-2-norbornene comprise one or more selected from the group, more preferably 5-vinyl-2-norbornene, 8-vinyl-9-methyltetracyclo[4.4.0.1 2,5 .1 7,10 It comprises one or more species selected from the group consisting of ]-3-dodecene and 5-allyl-2-norbornene.

[0065] The copolymer (A1) can contain double bonds in its side chain portion by including repeating units (a2). Here, the side chain portion refers to the portion of copolymer (A1) other than the main chain.

[0066] One of the raw materials for copolymer (A1) is a cyclic olefin, which is a monomer that undergoes addition copolymerization to give a repeating unit (a3) ​​represented by formula (V).

[0067] Examples of monomers that provide the repeating unit (a3) ​​include cyclic olefins represented by the following formula (Va) (hereinafter also referred to as cyclic olefins (Va)).

[0068] [ka]

[0069] In equation (Va), u represents 0 or 1, v represents 0 or a positive integer, w represents 0 or 1, and R 61 ~R 78 , R a1 , and R b1 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R 75 and R 76 , R 76 and R 77 , or R 77 and R 78 These elements may be bonded to each other to form a monocycle or polycycle.

[0070] Examples of cyclic olefins (Va) include cyclic olefin monomers described in International Publication No. 2006 / 118261. Furthermore, the cyclic olefin (Va) may be a cyclic olefin derived from biomass, or a cyclic olefin derived from chemical recycling.

[0071] From the viewpoint of obtaining a film with improved low dielectric properties, cyclic olefins (Va) are preferably tetracyclo[4.4.0.1 2,5 .1 7,10 It contains one or more substances selected from the group consisting of ]-3-dodecene (hereinafter also called tetracyclododecene) and bicyclo[2.2.1]-2-heptene (hereinafter also called norbornene).

[0072] Next, we will describe the repeating units that the copolymer (A1) of this embodiment may further contain.

[0073] The copolymer (A1) of this embodiment may include repeating units other than repeating unit (a1), repeating unit (a2), and repeating unit (a3). Examples of repeating units other than repeating units (a1), (a2), and (a3) ​​include repeating units (a6) derived from a cyclic olefin represented by formula (VIa) (hereinafter also referred to as cyclic olefin (VIa)), repeating units (a7) derived from a cyclic olefin represented by formula (VIIa) (hereinafter also referred to as cyclic olefin (VIIa)), and repeating units (a8) derived from a linear polyene represented by formula (VIIIa) (hereinafter also referred to as linear polyene (VIIIa)).

[0074] [ka]

[0075] In equation (VIa), x and d are integers greater than or equal to 0. Also, y and z are integers between 0 and 2 (inclusive). 81 ~R 99 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group. Also, R 89 and R 90 They may be bonded to each other to form a monoring or polyring. Also, when both y and z are 0, R 95 and R 92 or R 95 and R 99 These elements may be bonded to each other to form monocyclic or polycyclic aromatic rings.

[0076] [ka]

[0077] In equation (VIIa), R 100 and R 101 Each of these independently represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms. Also, f represents an integer between 1 and 18.

[0078] [ka]

[0079] In equation (VIIIa), R 201 ~R 206 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Furthermore, P represents a direct bond or an alkylene group having 1 to 20 carbon atoms. P may also contain a double or triple bond.

[0080] Examples of cyclic olefins (VIa) include cyclic olefin monomers described in International Publication No. 2006 / 118261.

[0081] Examples of cyclic olefins (VIIa) include cyclic olefin monomers described in International Publication No. 2006 / 118261.

[0082] Examples of linear polyenes (VIIIa) include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 4,8-dimethyl-1,4,8-decatriene (DMDT), 1,3-butadiene, and 1,5-hexadiene.

[0083] From the viewpoint of improving the balance between low dielectric properties and crosslinking properties, the total content of repeating units (a6), repeating units (a7), and repeating units (a8) in the copolymer (A1) of this embodiment is preferably 10 mol% or less, more preferably 1 mol% or less, even more preferably 0.1 mol% or less, and even more preferably 0 mol%, when the total content of repeating units (a1), repeating units (a2), and repeating units (a3) ​​in the copolymer (A1) of this embodiment is set to 100 mol%.

[0084] (Method for producing copolymer (A1)) The copolymer (A1) of this embodiment can be produced, for example, according to the method for producing a cyclic olefin copolymer described in paragraphs 0075 to 0219 of International Publication No. 2012 / 046443. The method for producing the copolymer (A1) in this embodiment can be, for example, the method described in the example.

[0085] (Copolymerization catalyst) In the method for producing the copolymer (A1) of this embodiment, for example, a copolymer catalyst can be used. Examples of copolymer catalysts include transition metal compounds, organometallic compounds, organoaluminum oxy compounds, and compounds that react with transition metal compounds to form ion pairs. From the viewpoint of increasing the content of repeating units (a2) derived from cyclic non-conjugated dienes in the copolymer (A1), the copolymer catalyst preferably contains a transition metal compound, and more preferably contains a transition metal compound represented by the following formula (X).

[0086] [ka]

[0087] In formula (X), m is an integer from 1 to 4. Also, n is a number that satisfies the valency of Ti. Furthermore, R1 to R5 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. Furthermore, R6 represents an aliphatic hydrocarbon group in which the carbon atom bonded to the phenyl group in formula (X) is a primary, secondary, or tertiary carbon atom; an alicyclic hydrocarbon group in which the carbon atom bonded to the phenyl group in formula (X) is a primary, secondary, or tertiary carbon atom; or an aromatic group. Furthermore, X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. In equation (X), if m is 2 or greater, one of the R1-R6 groups in one ligand may be linked to one of the R1-R6 groups in another ligand. However, R1 groups cannot be linked to each other. Also, R1 groups, R2 groups, R3 groups, R4 groups, R5 groups, and R6 groups may be identical or different from each other. In equation (X), when n is 2 or greater, the multiple groups represented by X may be identical or different from each other. Furthermore, the multiple groups represented by X may be bonded together to form a ring.

[0088] From the viewpoint of obtaining a film with improved low dielectric properties, the content of polymer (A) in the resin composition of this embodiment is preferably 20% to 90% by mass, more preferably 30% to 80% by mass, and even more preferably 40% to 70% by mass, when the total amount of solids in the resin composition of this embodiment (total amount of components remaining as solids when cured) is taken as 100% by mass.

[0089] <Compound (B)> The resin composition of this embodiment includes compound (B) from the viewpoint of obtaining a film with an improved balance of photocurability and low dielectric properties after photocuring. Compound (B) of this embodiment has two or more (meth)acryloyl groups, from the viewpoint of obtaining a film with an improved balance of photocurability and low dielectric properties after photocuring. By having two or more (meth)acryloyl groups, compound (B) can crosslink polymer (A) and cure it. Compound (B) may have two (meth)acryloyl groups, or it may have three or more.

[0090] The compound (B) of this embodiment preferably has one or more selected from an alicyclic skeleton, an aromatic skeleton, and an aliphatic skeleton, and more preferably has one or more selected from an alicyclic skeleton and an aromatic skeleton, from the viewpoint of improving compatibility with the polymer (A). By having an alicyclic skeleton, an aromatic skeleton, or an aliphatic skeleton, the compatibility between the polymer (A) and compound (B) can be improved through interaction with the polymer (A) having a polyolefin skeleton. Furthermore, by improving the compatibility between the polymer (A) and compound (B), the homogeneity of the resin composition can be improved.

[0091] From the viewpoint of improving compatibility with polymer (A), the alicyclic skeleton preferably includes one or more selected from the group consisting of a cycloalkane skeleton, a cycloalkene skeleton, a dicyclopentadiene skeleton, a norbornane skeleton, and an adamantane skeleton.

[0092] The cycloalkane skeleton preferably comprises one or more selected from the group consisting of a cyclohexylene skeleton and a cyclohexyl skeleton. The cycloalkene skeleton preferably comprises one or more selected from the group consisting of cyclodecatrienediyl skeletons and cyclodecatriene skeletons. The dicyclopentadiene skeleton preferably comprises one or more selected from the group consisting of a tricyclodecanediyl skeleton, a dicyclopentanyl skeleton, and a dicyclopentenyl skeleton. The norbornane skeleton preferably comprises one or more selected from the group consisting of norbornanediyl skeleton, isobornanediyl skeleton, norbornyl skeleton, and isobornyl skeleton. The adamantane skeleton preferably comprises one or more selected from the group consisting of adamantanediyl skeletons and adamantyl skeletons.

[0093] From the viewpoint of improving compatibility with polymer (A), the aromatic skeleton preferably comprises one or more selected from the group consisting of aromatic hydrocarbon skeletons and heterocyclic skeletons, and more preferably comprises one or more selected from the group consisting of phenyl skeletons, biphenyl skeletons, triphenylmethane skeletons, naphthalene skeletons, anthracene skeletons, phenanthrene skeletons, fluorene skeletons, pyrene skeletons, thiophene skeletons, and furan skeletons.

[0094] From the viewpoint of improving compatibility with polymer (A), the aliphatic skeleton preferably includes one or more selected from the group consisting of a linear hydrocarbon skeleton and a branched hydrocarbon skeleton.

[0095] From the viewpoint of improving compatibility with polymer (A), compound (B) of this embodiment is preferably tricyclo[5.2.1.0 2,6This comprises one or more substances selected from the group consisting of decandimethanol diacrylate, [1,1'-biphenyl]-4,4'-diyl diacrylate, 4,4'-biphenol dimethacrylate, 1,3-adamantanediol dimethacrylate, tris(2-acryloyloxyethyl) isocyanurate, (((9H-fluorene-9,9-diyl)bis(4,1-phenylene))-bis(oxy)bis(ethane-2,1-diyl) diacrylate, 1,4-butanediol diacrylate, and 2,5-dimethylhexane-2,5-diylbis(2-methylacrylate).

[0096] From the viewpoint of improving crosslinking efficiency, the content of compound (B) in the resin composition of this embodiment is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, and even more preferably 12 parts by mass or more, when the content of polymer (A) in the resin composition of this embodiment is 100 parts by mass. From the viewpoint of obtaining a film with improved low dielectric properties, the content of compound (B) in the resin composition of this embodiment is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 70 parts by mass or less, and even more preferably 65 parts by mass or less, when the content of polymer (A) in the resin composition of this embodiment is 100 parts by mass. From the viewpoint of improving crosslinking efficiency and obtaining a film with further improved low dielectric properties, the content of compound (B) in the resin composition of this embodiment is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 5 parts by mass or more and 80 parts by mass or less, even more preferably 10 parts by mass or more and 70 parts by mass or less, and even more preferably 12 parts by mass or more and 65 parts by mass or less, when the content of polymer (A) in the resin composition of this embodiment is 100 parts by mass.

[0097] <Initiator (C)> The resin composition of this embodiment includes an initiator (C) from the viewpoint of obtaining a film with an improved balance of photocurability and low dielectric properties after photocuring. The initiator (C) in this embodiment is a compound that generates radicals upon light irradiation. Examples of light include ultraviolet light and visible light.

[0098] The initiator (C) of this embodiment has at least one maximum absorption wavelength in the wavelength range of 200 nm to 450 nm. In this embodiment, the wavelength range of the maximum absorption wavelength of the initiator (C) (however, if the initiator (C) has two or more maximum absorption wavelengths in the wavelength range of 450 nm or less, the wavelength range of the maximum absorption wavelength on the longest wavelength side in the wavelength range of 450 nm or less) is preferably 200 nm or more, more preferably 220 nm or more, even more preferably 240 nm or more, even more preferably 260 nm or more, even more preferably 280 nm or more, and even more preferably 300 nm or more, from the viewpoint of improving the economic efficiency of the light source used for photocuring. In this embodiment, the wavelength range of the maximum absorption wavelength of the initiator (C) (however, if the initiator (C) has two or more maximum absorption wavelengths in the wavelength range of 450 nm or less, the wavelength range of the maximum absorption wavelength on the longest wavelength side in the wavelength range of 450 nm or less) is preferably 450 nm or less, more preferably 440 nm or less, even more preferably 430 nm or less, even more preferably 420 nm or less, even more preferably 410 nm or less, and even more preferably 400 nm or less, from the viewpoint of improving the storage stability of the resin composition. In this embodiment, the wavelength range of the maximum absorption wavelength of the initiator (C) (however, if the initiator (C) has two or more maximum absorption wavelengths in the wavelength range of 450 nm or less, the wavelength range of the maximum absorption wavelength on the longest wavelength side in the wavelength range of 450 nm or less) is preferably 200 nm to 450 nm, more preferably 220 nm to 440 nm, even more preferably 240 nm to 430 nm, even more preferably 260 nm to 420 nm, even more preferably 280 nm to 410 nm, and even more preferably 300 nm to 400 nm.

[0099] Examples of initiators (C) in this embodiment include oxime-based photoradical polymerization initiators, acylphosphine oxide-based photoradical polymerization initiators, alkylphenone-based photoradical polymerization initiators, benzophenone-based photoradical polymerization initiators, benzyl ketal-based photoradical polymerization initiators, α-hydroxyketone-based photoradical polymerization initiators, and α-aminoketone-based photoradical polymerization initiators. Furthermore, examples of initiators (C) in this embodiment include thioxanthone, 2-benzyl-2-(dimethylamino)-4'-morpholinobtyrophenone, monoacylphosphine oxide (MAPO), and bisacylphosphine oxide (BAPO).

[0100] In this embodiment, the initiator (C) preferably includes an oxime-based photoradical polymerization initiator, and more preferably an oxime ester-based photoradical polymerization initiator, from the viewpoint of obtaining a film with a better balance of photocurability and low dielectric properties after photocuring.

[0101] From the viewpoint of obtaining a film with an improved balance of photocurability and low dielectric properties after photocuring, the content of initiator (C) in the resin composition of this embodiment is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.2 parts by mass or more and 8 parts by mass or less, even more preferably 0.4 parts by mass or more and 6 parts by mass or less, and even more preferably 0.5 parts by mass or more and 5 parts by mass or less, when the content of polymer (A) in the resin composition of this embodiment is 100 parts by mass.

[0102] <Other ingredients> The resin composition of this embodiment may contain other components, as long as they do not impede the effects of the invention of this embodiment. Examples of other components include resins other than polymer (A), additives, and so on. Examples of resins other than polymer (A) include thermoplastic resins and thermosetting resins other than polymer (A) (hereinafter also referred to as thermosetting resins). Examples of additives include photocationic initiators, light stabilizers, thermal radical polymerization initiators, sensitizers, antioxidants, inorganic fillers, organic fillers, heat-resistant stabilizers, weather-resistant stabilizers, radiation-resistant agents, plasticizers, lubricants, mold release agents, nucleating agents, friction and wear enhancers, flame retardants, foaming agents, antistatic agents, colorants, antifogging agents, antiblocking agents, impact-resistant agents, surface wetting improvers, hydrochloric acid absorbers, metal deactivators, leveling agents, and defoaming agents.

[0103] <Thermoplastic resin> The resin composition of this embodiment may further contain a thermoplastic resin, from the viewpoint of obtaining a film with an improved balance of photocurability and low dielectric properties after photocuring. The thermoplastic resin of this embodiment preferably comprises one or more selected from polyolefins, cyclic polyolefins, polyimides, polyamides, polyimidamides, polyesters, polyphenylene ethers, polyethersulfones, polyphenylene sulfides, polydicyclopentadienes, styrene-butadiene-styrene copolymers, and styrene-ethylene-butadiene-styrene copolymers, and more preferably comprises one or more selected from cyclic polyolefins and polyphenylene ethers.

[0104] From the viewpoint of obtaining a film with an improved balance of photocurability and low dielectric properties after photocuring, the content of thermoplastic resin in the resin composition of this embodiment is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 20 parts by mass or more and 100 parts by mass or less, even more preferably 30 parts by mass or more and 75 parts by mass or less, and even more preferably 40 parts by mass or more and 50 parts by mass or less, when the content of polymer (A) in the resin composition of this embodiment is 100 parts by mass or more and 200 parts by mass or less.

[0105] From the viewpoint of obtaining a film with an improved balance of photocurability and low dielectric properties after photocuring, the total content of polymer (A), compound (B), and initiator (C) in the resin composition of this embodiment is preferably 50% to 100% by mass, more preferably 55% to 95% by mass, even more preferably 60% to 90% by mass, even more preferably 65% ​​to 85% by mass, and even more preferably 70% to 80% by mass, when the total amount of solids in the resin composition of this embodiment (total amount of components remaining as solids when cured) is taken as 100% by mass.

[0106] From the viewpoint of obtaining a film with an improved balance of photocurability and low dielectric properties after photocuring, the total content of polymer (A), compound (B), initiator (C), and thermoplastic resin in the resin composition of this embodiment is preferably 50% to 100% by mass, more preferably 75% to 100% by mass, even more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, and even more preferably 95% to 100% by mass, when the total amount of solids in the resin composition of this embodiment (total amount of components remaining as solids when cured) is taken as 100% by mass.

[0107] <Method for preparing resin compositions> The resin composition of this embodiment can be prepared by mixing a polymer (A), a compound (B), an initiator (C), and, if necessary, other components such as a thermoplastic resin. As a mixing method, a solution blending method, in which the components are dissolved or dispersed in a solvent, can be employed. Examples of solvents include linear saturated hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and ketones. Examples of linear saturated hydrocarbons include heptane, hexane, and decane. Examples of alicyclic hydrocarbons include cyclohexane. Examples of aromatic hydrocarbons include toluene, benzene, and xylene. Examples of ketones include cyclohexanone.

[0108] The resin composition of this embodiment may be in an uncured or semi-cured state.

[0109] <Properties of resin compositions> The properties of the resin composition of this embodiment will be described below.

[0110] The relative permittivity Dk1 of the resin composition of this embodiment, as determined by the following method (Method 1a), is preferably 3.0 or less, more preferably 2.9 or less, even more preferably 2.8 or less, even more preferably 2.7 or less, and even more preferably 2.6 or less, from the viewpoint of obtaining a film with improved low dielectric properties. The lower limit of the relative permittivity Dk1 is not particularly limited, but for example, it may be 0.1 or greater, 0.5 or greater, or 1.0 or greater.

[0111] (Method 1a) A coated film is prepared by coating a PET film with a varnish containing a resin composition. Next, a dried film is prepared by drying the coated film at 150°C for 4 minutes under a nitrogen atmosphere. Then, a 50mm x 50mm test piece 1 is prepared from the dried film. Next, the relative permittivity Dk1 of test piece 1 is measured using a cylindrical cavity resonator at 23±2°C, 80% RH or less, and 10 GHz.

[0112] Here, the method for measuring the relative permittivity Dk1 of the resin composition of this embodiment can be, more specifically, the method described in the examples.

[0113] The relative permittivity Dk1 can be adjusted, for example, by adjusting the type of each component, the content of each component, the manufacturing conditions, etc., of the resin composition.

[0114] The dielectric loss tangent Df1 of the resin composition of this embodiment, as determined by the following (Method 1b), is preferably 0.020 or less, more preferably 0.018 or less, even more preferably 0.016 or less, even more preferably 0.015 or less, and even more preferably 0.014 or less, from the viewpoint of obtaining a film with improved low dielectric properties. The lower limit of the dielectric loss tangent Df1 is not particularly limited, but for example, it may be 0.0001 or greater, 0.0005 or greater, or 0.001 or greater.

[0115] (Method 1b) A coated film is prepared by coating a PET film with a varnish containing a resin composition. Next, a dried film is prepared by drying the coated film at 150°C for 4 minutes under a nitrogen atmosphere. Then, a 50mm x 50mm test piece 1 is prepared from the dried film. Next, the dielectric loss tangent Df1 of test piece 1 is measured using a cylindrical cavity resonator at 23±2°C, 80%RH or less, and 10GHz.

[0116] Here, the method for measuring the dielectric loss tangent Df1 of the resin composition of this embodiment can be more specifically the method described in the examples. Furthermore, the dielectric loss tangent Df1 can be adjusted, for example, by a method similar to the method for adjusting the relative permittivity Dk1.

[0117] In the resin composition of this embodiment, X1 prepared by the following method (Method 1c) is preferably 0.030 or less, more preferably 0.027 or less, even more preferably 0.025 or less, even more preferably 0.023 or less, and even more preferably 0.021 or less, from the viewpoint of obtaining a film with improved low dielectric properties. The lower limit of X1 is not particularly restricted, but for example, it may be 0.0001 or greater, 0.0005 or greater, or 0.001 or greater.

[0118] (Method 1c) A coated film is prepared by coating a PET film with a varnish containing a resin composition. Next, a dried film is prepared by drying the coated film at 150°C for 4 minutes under a nitrogen atmosphere. Then, a 50mm x 50mm test piece 1 is prepared from the dried film. Next, the relative permittivity Dk1 and dielectric loss tangent Df1 are measured for test piece 1 using a cylindrical cavity resonator at 23±2°C, 80%RH or less, and 10GHz. Then, X1 is calculated using the following formula (X1). Formula (X1):X1=(Dk1) 0.5 ×Df1

[0119] Here, the method for measuring X1 of the resin composition in this embodiment can be more specifically the method described in the examples. Furthermore, X1 can be adjusted, for example, by a method similar to the method for adjusting the relative permittivity Dk1.

[0120] The relative permittivity Dk2 of the resin composition of this embodiment, obtained by the following method (Method 2a), is preferably 3.0 or less, more preferably 2.8 or less, even more preferably 2.7 or less, even more preferably 2.6 or less, and even more preferably 2.5 or less, from the viewpoint of obtaining a film with improved low dielectric properties. The lower limit of the relative permittivity Dk2 is not particularly limited, but for example, it may be 0.1 or greater, 0.5 or greater, or 1.0 or greater.

[0121] (Method 2a) A coated film is prepared by applying a varnish containing a resin composition onto a PET film. Next, a dried film is prepared by drying the coated film at 150°C for 4 minutes under a nitrogen atmosphere. Finally, the dried film is subjected to an illuminance measurement of 20 mW / cm² using a 365 nm wavelength illuminometer with a 4000 W high-pressure mercury lamp. 2 Irradiation time 150 seconds, exposure amount 3000 mJ / cm² 2A cured film with a thickness of 35 ± 10 μm is prepared by light irradiation under atmospheric conditions. Next, a 50 mm × 50 mm test piece 2 is prepared from the cured film. Then, the relative permittivity Dk2 of test piece 2 is measured using a cylindrical cavity resonator at 23 ± 2 °C, 80% RH or less, and 10 GHz.

[0122] Here, the method for measuring the relative permittivity Dk2 of the resin composition in this embodiment can be more specifically the method described in the examples. Furthermore, the relative permittivity Dk2 can be adjusted, for example, by the same method as the method for adjusting the relative permittivity Dk1.

[0123] The dielectric loss tangent Df2 of the resin composition of this embodiment, obtained by the following method (2b), is preferably 0.013 or less, more preferably 0.011 or less, even more preferably 0.0090 or less, even more preferably 0.0070 or less, and even more preferably 0.0060 or less, from the viewpoint of obtaining a film with further improved low dielectric properties. The lower limit of the dielectric loss tangent Df2 is not particularly limited, but for example, it may be 0.0001 or greater, 0.0005 or greater, or 0.001 or greater.

[0124] (Method 2b) A coated film is prepared by applying a varnish containing a resin composition onto a PET film. Next, a dried film is prepared by drying the coated film at 150°C for 4 minutes under a nitrogen atmosphere. Finally, the dried film is subjected to an illuminance measurement of 20 mW / cm² using a 365 nm wavelength illuminometer with a 4000 W high-pressure mercury lamp. 2 Irradiation time 150 seconds, exposure amount 3000 mJ / cm² 2 A cured film with a thickness of 35 ± 10 μm is prepared by light irradiation under atmospheric conditions. Next, a 50 mm × 50 mm test piece 2 is prepared from the cured film. Then, the dielectric loss tangent Df2 of test piece 2 is measured using a cylindrical cavity resonator at 23 ± 2 °C, 80% RH or less, and 10 GHz.

[0125] Here, the method for measuring the dielectric loss tangent Df2 of the resin composition of this embodiment can be more specifically the method described in the examples. Furthermore, the dielectric loss tangent Df2 can be adjusted, for example, by a method similar to the method for adjusting the relative permittivity Dk1.

[0126] In the resin composition of this embodiment, X2 prepared by the following method (2c) is preferably 0.019 or less, more preferably 0.015 or less, even more preferably 0.012 or less, even more preferably 0.010 or less, and even more preferably 0.0090 or less, from the viewpoint of obtaining a film with improved low dielectric properties. The lower limit of X2 is not particularly restricted, but for example, it may be 0.0001 or greater, 0.0005 or greater, or 0.001 or greater.

[0127] (Method 2c) A coated film is prepared by applying a varnish containing a resin composition onto a PET film. Next, a dried film is prepared by drying the coated film at 150°C for 4 minutes under a nitrogen atmosphere. Finally, the dried film is subjected to an illuminance measurement of 20 mW / cm² using a 365 nm wavelength illuminometer with a 4000 W high-pressure mercury lamp. 2 Irradiation time 150 seconds, exposure amount 3000 mJ / cm² 2 A cured film with a thickness of 35 ± 10 μm is prepared by light irradiation under atmospheric conditions. Next, a 50 mm × 50 mm test piece 2 is prepared from the cured film. Then, the relative permittivity Dk2 and dielectric loss tangent Df2 of test piece 2 are measured using a cylindrical cavity resonator at 23 ± 2 °C, 80% RH or less, and 10 GHz. Next, X2 is calculated using the following formula (X2). Formula (X2):X2=(Dk2) 0.5 ×Df2

[0128] Here, the method for measuring X2 of the resin composition in this embodiment can be more specifically the method described in the examples. Furthermore, X2 can be adjusted, for example, by a method similar to the method for adjusting the relative permittivity Dk1.

[0129] The reduction ratio (100 × Dk2 / Dk1) of the resin composition of this embodiment, which is the ratio of the relative permittivity Dk2 obtained by (Method 2a) to the relative permittivity Dk1 obtained by (Method 1a), is preferably 120% or less, more preferably 110% or less, even more preferably 100% or less, even more preferably 99% or less, and even more preferably 98% or less, from the viewpoint of obtaining a film with further improved low dielectric properties. There is no particular lower limit to the reduction rate (100 × Dk2 / Dk1), but it may be, for example, 1% or more, 5% or more, or 10% or more.

[0130] The reduction ratio (100 × Df2 / Df1) of the resin composition of this embodiment, which is the ratio of the dielectric loss tangent Df2 obtained by (Method 2b) to the dielectric loss tangent Df1 obtained by (Method 1b), is preferably 99% or less, more preferably 95% or less, even more preferably 90% or less, even more preferably 87% or less, and even more preferably 85% or less, from the viewpoint of obtaining a film with further improved low dielectric properties. There is no particular lower limit to the reduction rate (100 × Df2 / Df1), but it may be 1% or more, 5% or more, or 10% or more.

[0131] The reduction ratio (100 × X2 / X1) of the resin composition of this embodiment, which is the ratio of X2 according to (Method 2c) to X1 according to (Method 1c), is preferably 99% or less, more preferably 95% or less, even more preferably 90% or less, even more preferably 87% or less, and even more preferably 85% or less, from the viewpoint of obtaining a film with further improved low dielectric properties. There is no particular lower limit to the reduction rate (100 × X² / X¹), but it may be, for example, 1% or more, 5% or more, or 10% or more.

[0132] <Uses of resin compositions> The applications of the resin composition of this embodiment are not particularly limited, and the resin composition of this embodiment can be applied to a variety of uses. The resin composition of this embodiment is suitable for use as a material for redistribution layers in semiconductor packages or substrates, for example, because it can produce films with an improved balance of photocurability and low dielectric properties after photocuring. In particular, the resin composition of this embodiment is suitable for use as a material for redistribution layers used in FOWLP (Fan-Out Wafer level Package).

[0133] [varnish] The varnish of this embodiment comprises a resin composition and a solvent. The solvent included in the varnish of this embodiment is not particularly limited as long as it does not impair the solubility or affinity of the polymer (A), compound (B), and initiator (C). Examples of solvents used in the varnish include linear saturated hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, alcohols, ketones, cellosolves, esters, halogenated hydrocarbons, ethers, and the like.

[0134] Examples of straight-chain saturated hydrocarbons include heptane, hexane, octane, and decane. Examples of alicyclic hydrocarbons include cyclohexane, methylcyclohexane, and decahydronaphthalene. Examples of aromatic hydrocarbons include toluene, benzene, xylene, mesitylene, and pseudocumene. Examples of alcohols include methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol. Examples of ketones include acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, acetophenone, and 4-methyl-2-pentanone. Examples of cellosolves include methyl cellosolve and ethyl cellosolve. Examples of esters include methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and butyl formate. Examples of halogenated hydrocarbons include trichloroethylene, dichloroethylene, and chlorobenzene. Examples of ethers include tetrahydrofuran and diethyl ether.

[0135] The solvent used in the varnish of this embodiment preferably comprises one or more selected from the group consisting of heptane, decane, cyclohexane, methylcyclohexane, decahydronaphthalene, toluene, benzene, xylene, mesitylene, pseudocumene, cyclohexanone, methyl ethyl ketone, and 4-methyl-2-pentanone, and more preferably comprises one or more selected from the group consisting of toluene and cyclohexane.

[0136] The solvent content in the varnish of this embodiment can be adjusted according to the coating method and the thickness of the film to be formed. From the viewpoint of improving the balance between the handling and coating properties of the varnish, the solvent content in the varnish of this embodiment is preferably 200 parts by mass or more and 1,000 parts by mass or less, and more preferably 400 parts by mass or more and 800 parts by mass or less, when the polymer (A) content in the varnish of this embodiment is 100 parts by mass.

[0137] The concentration of the total amount of solids in the varnish of this embodiment (the total amount of components that remain as solids when cured) is preferably 1% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and even more preferably 15% by mass or more and 35% by mass or less, when the total amount of varnish of this embodiment is 100% by mass, from the viewpoint of improving the balance between the handling and coating properties of the varnish.

[0138] Methods for producing varnish include, for example, mixing a resin composition with a solvent. Apparatus for producing varnish includes, for example, batch-type apparatus capable of stirring and mixing, and continuous-type apparatus capable of stirring and mixing. The temperature during varnish production can be arbitrarily selected within the range from room temperature to the boiling point of the solvent.

[0139] [film] The film of this embodiment includes the resin composition of this embodiment. The film of this embodiment can be produced by coating the resin composition onto a substrate.

[0140] The method of coating the resin composition is not particularly limited. Examples of coating methods include bar coating, spin coating, dip coating, spray coating, die coating, flow coating, curtain coating, roll coating, and gravure coating.

[0141] <Cured film> The cured film of this embodiment is obtained by curing the film of this embodiment. The cured film can be produced by crosslinking the film of this embodiment by irradiating it with light. There are no particular restrictions on the light irradiation conditions, but for example, using a high-pressure mercury lamp with a lamp output of 4000W, the illuminance measured with a wavelength 365nm illuminometer was 20mW / cm². 2 Irradiation time 150 seconds, exposure amount 3000 mJ / cm² 2 Examples include atmospheric conditions.

[0142] <Uses of film> The applications of the film of this embodiment are not particularly limited, and the film of this embodiment can be applied to a variety of uses. Because the film of this embodiment has an improved balance of photocurability and low dielectric properties after photocuring, it is suitable for use as an insulating resin layer in substrates for semiconductor packages, an insulating resin layer in redistribution layers in semiconductor packages, and so on. In particular, the film of this embodiment is suitable for use as an insulating resin layer in redistribution layers used in FOWLP (Fan-Out Wafer level Package). Examples of substrates for semiconductor packages include resin substrates, glass substrates, and glass / ceramic composite substrates.

[0143] <Rewiring layer> In this embodiment, the redistribution layer is located, for example, between the semiconductor chip and the substrate. The redistribution layer enables the connection of semiconductor chips and substrates with different dimensions and electrical connection densities. The redistribution layer of this embodiment includes the film of this embodiment or its cured film. The wiring layer of this embodiment preferably comprises a first resin layer including the film of this embodiment or its cured film, a second resin layer including the film of this embodiment or its cured film, and a metal layer located between the first resin layer and the second resin layer. In this case, the redistribution layer may comprise the first resin layer, the metal layer, and the second resin layer in this order.

[0144] The overall thickness of the redistribution layer, the thickness of each layer, and the overall shape of this embodiment can be appropriately adjusted according to the dimensions of the semiconductor chip and substrate, the electrical connection density, and so on. Examples of materials for the metal layer include copper.

[0145] The embodiments of the present invention have been described above, but these are merely examples, and various other configurations can also be adopted. Furthermore, the present invention is not limited to the embodiments described above, and any modifications, improvements, etc., that do not impair the effects of the present invention are included in the present invention. [Examples]

[0146] This embodiment will be described in detail below with reference to examples and other relevant information. However, this embodiment is not limited in any way to the descriptions of these examples.

[0147] First, I will explain the raw materials used in each example.

[0148] ·Polymer (A) (Copolymer (A1)) Copolymer 1: Synthesis Example 1 described below (content of repeating unit (a1): 62 mol%, content of repeating unit (a2): 27 mol%, content of repeating unit (a3): 11 mol%)

[0149] ·(Meth)acryloyl compound (B) Alicyclic (meth)acryloyl compound: Tricyclo[5.2.1.0 2,6 decane dimethanol diacrylate (CAS No.: 42594-17-2) (hereinafter also referred to as Compound 1). Aromatic (meth)acryloyl compound: [1,1'-biphenyl]-4,4'-diyl diacrylate (CAS No.: 84948-17-4) (hereinafter also referred to as Compound 2).

[0150] ·Photo radical polymerization initiator (C): Irgacure OXE-04 (manufactured by BASF) (hereinafter also referred to as Initiator 1). ·Photo cationic polymerization initiator: Irgacure 290 (manufactured by BASF) (hereinafter also referred to as Initiator 2).

[0151] ·Thermoplastic resin Cyclic olefin copolymer: APEL 6509T (manufactured by Mitsui Chemicals, Inc.) (hereinafter also referred to as Resin 1). ·Thermosetting resin Modified phenylene ether resin: OPE-2st-2200 (manufactured by Mitsubishi Gas Chemical Company, Inc.) (hereinafter also referred to as Resin 2). Epoxy resin: jER 828EL (manufactured by Mitsubishi Chemical Corporation) (hereinafter also referred to as Resin 3). ·Solvent Toluene (dehydrated toluene, manufactured by Kanto Chemical Co., Inc.) Cyclohexane (manufactured by Fujifilm Wako Pure Chemical Corporation)

[0152] Next, the production method of Copolymer 1 and the measurement method of the physical properties (content of each repeating unit) of Copolymer 1 will be described. First, the production method of Copolymer 1 will be described.

[0153] The following raw materials were used for the synthesis of Copolymer 1. ·Transition metal compounds (1): It was synthesized by the method described in Synthesis Example 1 of Japanese Patent Publication No. 2004-331965. • Modified methylaluminoxane (product name: MMAO-3A, ​​manufactured by Tosoh Finechem Co., Ltd.) (hereinafter also referred to as MMAO). • Ethylene (manufactured by Mitsui Chemicals, Inc.) • 5-Vinyl-2-norbornene (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter also referred to as VNB.) • Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene (manufactured by Mitsui Chemicals, Inc.) (hereinafter also referred to as TD.) • Toluene (dehydrated toluene, manufactured by Kanto Chemical Co., Ltd.) • Acetone (manufactured by Kanto Chemical Co., Ltd.) • Methanol (manufactured by Kanto Chemical Co., Ltd.)

[0154] Next, copolymer 1 was prepared by the following method.

[0155] [Synthesis example 1: Copolymer 1] In a 1000 mL stainless steel autoclave with a volume of SUS (stainless steel) that had been thoroughly purged with nitrogen, 455 mL of toluene, 29 mL of VNB, 16 mL of TD, and MMAO hexane solution (0.8 mmol in terms of aluminum atoms) and 446 mL of hydrogen were added. Then, ethylene was added to the SUS autoclave until the total pressure reached 0.6 MPa. Next, a toluene solution containing 0.028 mmol of transition metal compound (1) was added to the SUS autoclave, and polymerization was carried out at 35°C for 50 minutes. After that, polymerization was terminated by adding 1 mL of methanol. After polymerization was complete, deionized water was added to the resulting solution and stirred for 1 hour, after which the organic layer was filtered through filter paper. The filtered organic layer was added to a mixed solvent of acetone and methanol to precipitate the polymer. Next, the mixed solvent containing the precipitated polymer was stirred and filtered through filter paper. The resulting polymer was then dried under reduced pressure at 80°C for 10 hours to obtain copolymer 1.

[0156] (Method for measuring the content of each repeating unit) Using a nuclear magnetic resonance spectrometer (product name: EXcalibur270, manufactured by JEOL Ltd.), copolymer 1 was analyzed. 1 The H-NMR spectra were measured for each. 1 1H-NMR measurements were performed with 16 to 64 cumulative cycles at room temperature of 25°C. obtained 1 From the 1H-NMR spectrum, the content of repeating units (a1), (a2), and (a3) ​​was calculated based on the intensities of the peaks derived from hydrogen directly bonded to the double bond carbon and the peaks derived from other hydrogen atoms.

[0157] Next, the preparation methods for each example and each comparative example will be described.

[0158] [Example 1] (Varnish preparation) Each raw material was weighed to achieve the composition shown in Table 1. Next, the weighed raw materials were stirred in a solvent until fully dissolved to obtain the resin composition. Note that the units for the proportion of each raw material in Table 1 are parts by mass.

[0159] (Preparation of cured film) A coated film 1 was prepared by applying varnish 1 to a release-treated PET film using an automatic film coating machine (product name: PI-1210, manufactured by Tester Industries Co., Ltd.). The varnish 1 was applied under the following conditions: applicator gap of 350 μm, coating speed of 10 mm / second, and room temperature air (25°C, 80% RH or less). Next, the coated film 1 was dried using a dryer (product name: STPH-102M, manufactured by ESPEC Corporation) to obtain a dried film 1. The coated film 1 was dried at 150°C for 4 minutes under a nitrogen gas stream (nitrogen flow rate 30 L / min). Next, a cured film 1 (overall thickness 35 ± 10 μm) was obtained by irradiating the dried film 1 with light using an ultraviolet irradiation device (product name: SUV-4045H-MC, manufactured by San-ei Electric Works Co., Ltd.). The light irradiation of the dried film 1 was performed using a high-pressure mercury lamp with a lamp output of 4000 W, and the illuminance measured with an illuminometer at a wavelength of 365 nm was 20 mW / cm².2 , Irradiation time: 150 seconds, exposure dose: 3000 mJ / cm 2 , carried out under atmospheric conditions.

[0160] [Examples 2 - 4] Varnish and cured film were prepared in the same manner as in Example 1, except that the composition of the raw materials was changed to the composition shown in Table 1 corresponding to each example.

[0161] [Comparative Examples 1 - 5] Varnish and cured film were prepared in the same manner as in Example 1, except that the composition of the raw materials was changed to the composition shown in Table 1 corresponding to each example.

[0162] The properties of the film were measured or evaluated according to the following method. The obtained results are shown in Table 1.

[0163] [Measurement of Dielectric Properties before Light Irradiation] [Measurement of Relative Dielectric Constant Dk1] For the dry film of each example, the relative dielectric constant Dk1 was measured by the following method. A test piece 1 of 50 mm × 50 mm was prepared from the dry film. Then, for test piece 1, the relative dielectric constant Dk1 at 23 ± 2°C, 80% RH or less, and 10 GHz was measured using a cylindrical cavity resonator (product names: Synthesized Sweeper 8340B and Network Analyzer 8510B, both manufactured by YHP).

[0164] [Measurement of Dissipation Factor Df1] For the dry film of each example, the dissipation factor Df1 was measured by the following method. A test piece 1 of 50 mm × 50 mm was prepared from the dry film. Then, for test piece 1, the dissipation factor Df1 at 23 ± 2°C, 80% RH or less, and 10 GHz was measured using a cylindrical cavity resonator (product names: Synthesized Sweeper 8340B and Network Analyzer 8510B, both manufactured by YHP).

[0165] [Calculation of X1] For each dry film, X1 was calculated by the following formula (X1) using the relative permittivity Dk1 obtained from <Measurement of relative permittivity Dk1> and the dielectric loss tangent Df1 obtained from <Measurement of dielectric loss tangent Df1>. Formula (X1): X1 = (Dk1) 0.5 × Df1

[0166] [Measurement of dielectric properties after light irradiation] <Measurement of relative permittivity Dk2> For each cured film, the relative permittivity Dk2 was measured by the following method. Two test pieces of 50 mm × 50 mm were prepared from the cured film. Then, for the test piece 2, the relative permittivity Dk2 at 23 ± 2 °C, 80% RH or less, and 10 GHz was measured using a cylindrical cavity resonator (product names: Synthesized Sweeper 8340B and Network Analyzer 8510B, both manufactured by YHP).

[0167] <Measurement of dielectric loss tangent Df2> For each cured film, the dielectric loss tangent Df2 was measured by the following method. Two test pieces of 50 mm × 50 mm were prepared from the cured film. Then, for the test piece 2, the dielectric loss tangent Df2 at 23 ± 2 °C, 80% RH or less, and 10 GHz was measured using a cylindrical cavity resonator (product names: Synthesized Sweeper 8340B and Network Analyzer 8510B, both manufactured by YHP).

[0168] <Calculation of X2> For each cured film, X2 was calculated by the following formula (X2) using the relative permittivity Dk2 obtained from <Measurement of relative permittivity Dk2> and the dielectric loss tangent Df2 obtained from <Measurement of dielectric loss tangent Df2>. Formula (X2): X2 = (Dk2) 0.5 × Df2

[0169] [Calculation of reduction rate] For each example, the reduction ratio (100 × Dk2 / Dk1), which is the ratio of relative permittivity Dk2 to relative permittivity Dk1, the reduction ratio (100 × Df2 / Df1), which is the ratio of dielectric loss tangent Df2 to dielectric loss tangent Df1, and the reduction ratio (100 × X2 / X1), which is the ratio of X2 to X1, were calculated.

[0170] [Evaluation of photocurability] Fourier transform infrared spectroscopy (FT-IR) measurements were performed on the dried and cured films of each example under the following conditions. Instrument: FT / IR 4200 (manufactured by JASCO Corporation) Measurement method: Transmission method Measurement mode: Absorbance Total number of times: 16 Wavenumber resolution: 1cm -1 Measurement wavefrequency range: 600~4000cm -1

[0171] Regarding the dry film, wavenumber 1460cm ―1 Peak intensity and wavenumber 1637cm ―1 The peak intensities of each were determined. Next, for the dried film, the peak intensity ratio P1 was calculated using the following formula (P1). Formula (P1): P1=(wavenumber 1637cm ―1 (Peak intensity) / (Wavenumber 1460cm) ―1 (Peak intensity) Next, regarding the hardened film, wavenumber 1460 cm ―1 Peak intensity and wavenumber 1637cm ―1 The peak intensities of each were determined. Next, the peak intensity ratio P2 for the cured film was calculated using the following formula (P2). Formula (P2): P2=(wavenumber 1637cm ―1 (Peak intensity) / (Wavenumber 1460cm) ―1 (Peak intensity) Next, the rate of change ΔP of P2 with respect to P1 was calculated using the following formula (P3). Formula (P3): ΔP=[100×(P2−P1) / P1]

[0172] For each example, photocurability was evaluated as follows: A if the rate of change of P2 relative to P1 ΔP was greater than 20%, B if it was between 6% and 20%, and C if it was less than 6%.

[0173] [Table 1]

[0174] Table 1 shows that the cured film of the example had a better balance of photocurability and low dielectric properties compared to the cured film of the comparative example. In other words, the resin composition of this embodiment makes it possible to obtain a film with an improved balance of photocurability and low dielectric properties after photocuring.

Claims

1. An olefin polymer (A) having a crosslinkable group, A (meth)acryloyl compound (B) having two or more (meth)acryloyl groups, A photocurable resin composition comprising a photoradical polymerization initiator (C).

2. The photocurable resin composition according to claim 1, wherein the (meth)acryloyl compound (B) comprises one or more selected from an alicyclic skeleton, an aromatic skeleton, and an aliphatic skeleton.

3. The photocurable resin composition according to claim 1 or 2, wherein the content of the (meth)acryloyl compound (B) is 1 part by mass or more and 100 parts by mass or less, when the content of the olefin polymer (A) is 100 parts by mass.

4. The photocurable resin composition according to claim 1 or 2, wherein the photoradical polymerization initiator (C) has at least one maximum absorption wavelength in the wavelength region of 200 nm to 450 nm.

5. The photocurable resin composition according to claim 1 or 2, wherein the photoradical polymerization initiator (C) comprises an oxime-based photoradical polymerization initiator.

6. The photocurable resin composition according to claim 1 or 2, wherein the content of the photoradical polymerization initiator (C) is 0.1 parts by mass or more and 10 parts by mass or less, when the content of the olefin polymer (A) is 100 parts by mass.

7. The photocurable resin composition according to claim 1 or 2, wherein the olefin polymer (A) comprises a cyclic olefin copolymer (A1) having a crosslinkable group.

8. The cyclic olefin copolymer (A1) is The repeating unit (a1) is represented by the following formula (I), One or more repeating units (a2) selected from the group consisting of repeating units represented by the following formula (II), repeating units represented by the following formula (III), and repeating units represented by the following formula (IV), The photocurable resin composition according to claim 7, comprising a repeating unit (a3) ​​represented by the following formula (V). 【Chemistry 1】 [In the above formula (I), R ３００ This represents a hydrogen atom or a linear or branched alkyl group having 1 to 29 carbon atoms. 【Chemistry 2】 〔In the formula (II), u represents 0 or 1, v represents 0 or 1, w represents 0 or 1, and R ６１ ~R ７６ , R ａ１ , and R ｂ１ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R １０２ and R １０３ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ７５ and R ７６ may be bonded to each other to form a monocyclic or polycyclic ring.〕 【Transformation 3】 [In formula (III) above, t represents a positive integer from 0 to 10, u represents 0 or 1, v represents 0 or a positive integer, w represents 0 or 1, R ６１ ~R ７６ , R ａ１ , and R ｂ１ Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R １０４ R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ７５ and R ７６ These may be bonded to each other to form a monocycle or polycycle. 【Chemistry 4】 [In formula (IV) above, u represents 0 or 1, v represents 0 or 1, w represents 0 or 1, R ６１ ~R ７６ , R ａ１ , and R ｂ１ Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ７５ and R ７６ These may be bonded to each other to form a monocycle or polycycle. 【Transformation 5】 [In the above formula (V), u represents 0 or 1, v represents 0 or a positive integer, w represents 0 or 1, R ６１ ~R ７８ , R ａ１ , and R ｂ１ Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ７５ and R ７６ , R ７６ and R ７７ , or R ７７ and R ７８ These may be bonded to each other to form a monocycle or polycycle.

9. The photocurable resin composition according to claim 8, wherein the olefin constituting the repeating unit (a1) contains ethylene.

10. The cyclic non-conjugated diene constituting the repeating unit (a2) is 5-vinyl-2-norbornene, 8-vinyl-9-methyltetracyclo[4.4.0.1 ２，５ 1. ７，１０ The photocurable resin composition according to claim 8, comprising one or more selected from the group consisting of ]-3-dodecene and 5-allyl-2-norbornene.

11. The cyclic olefin constituting the repeating unit (a3) ​​is tetracyclo[4.4.0.1 ２，５ 1. ７，１０ The photocurable resin composition according to claim 8, comprising one or two selected from the group consisting of ]-3-dodecene and bicyclo[2.2.1]-2-heptene.

12. The photocurable resin composition according to claim 1 or 2, wherein the content of repeating units having crosslinkable groups in the olefin polymer (A) is 0.1 mol% or more and 50 mol% or less when the total content of repeating units in the olefin polymer (A) is 100 mol%.

13. The photocurable resin composition according to claim 1 or 2, further comprising a thermoplastic resin.

14. The photocurable resin composition according to claim 13, wherein the thermoplastic resin comprises one or more selected from polyolefins, cyclic polyolefins, polyimides, polyamides, polyimidamides, polyesters, polyphenylene ethers, polyethersulfones, polyphenylene sulfides, polydicyclopentadienes, styrene-butadiene-styrene copolymers, and styrene-ethylene-butadiene-styrene copolymers.

15. The photocurable resin composition according to claim 13, wherein the content of the thermoplastic resin is 10 parts by mass or more and 200 parts by mass or less, when the content of the olefin polymer (A) is 100 parts by mass.

16. The photocurable resin composition according to claim 1 or 2, wherein the reduction rate (100 × Df2 / Df1), which is the ratio of the dielectric loss tangent Df2 obtained by the following method (Method 2) to the dielectric loss tangent Df1 obtained by the following method (Method 1), is 99% or less. (Method 1) A coated film is prepared by applying a varnish containing the photocurable resin composition onto a PET film. Next, the coated film is dried at 150°C for 4 minutes under a nitrogen atmosphere to produce a dried film. Next, a 50 mm x 50 mm test piece 1 is prepared from the dried film. Next, the dielectric loss tangent Df1 of the test piece 1 is measured using a cylindrical cavity resonator at 23±2°C, 80% RH or less, and 10 GHz. (Method 2) A coated film is prepared by applying a varnish containing the photocurable resin composition onto a PET film. Next, the coated film is dried at 150°C for 4 minutes under a nitrogen atmosphere to produce a dried film. Next, the illuminance of the dried film was measured using a 365 nm wavelength illuminometer with a high-pressure mercury lamp output of 4000 W, resulting in an illuminance of 20 mW / cm². ２ Irradiation time 150 seconds, exposure amount 3000 mJ / cm² ２ By irradiating with light under atmospheric conditions, a cured film with a thickness of 35 ± 10 μm was produced. Next, a 50 mm x 50 mm test piece 2 is prepared from the cured film. Next, the dielectric loss tangent Df2 of the test piece 2 is measured using a cylindrical cavity resonator at 23±2°C, 80% RH or less, and 10 GHz.

17. The photocurable resin composition according to claim 1 or 2, wherein the dielectric loss tangent Df2 obtained by the following method (method 2) is 0.013 or less. (Method 2) A coated film is prepared by applying a varnish containing the photocurable resin composition onto a PET film. Next, the coated film is dried at 150°C for 4 minutes under a nitrogen atmosphere to produce a dried film. Next, the illuminance of the dried film was measured using a 365 nm wavelength illuminometer with a high-pressure mercury lamp output of 4000 W, resulting in an illuminance of 20 mW / cm². ２ Irradiation time 150 seconds, exposure amount 3000 mJ / cm² ２ By irradiating with light under atmospheric conditions, a cured film with a thickness of 35 ± 10 μm was produced. Next, a 50 mm x 50 mm test piece 2 is prepared from the cured film. Next, the dielectric loss tangent Df2 of the test piece 2 is measured using a cylindrical cavity resonator at 23±2°C, 80% RH or less, and 10 GHz.

18. The photocurable resin composition according to claim 1 or 2, wherein X2 by the method described below (Method 3) is 0.019 or less. (Method 3) A coated film is prepared by applying a varnish containing the photocurable resin composition onto a PET film. Next, the coated film is dried at 150°C for 4 minutes under a nitrogen atmosphere to produce a dried film. Next, the illuminance of the dried film was measured using a 365 nm wavelength illuminometer with a high-pressure mercury lamp output of 4000 W, resulting in an illuminance of 20 mW / cm². ２ Irradiation time 150 seconds, exposure amount 3000 mJ / cm² ２ By irradiating with light under atmospheric conditions, a cured film with a thickness of 35 ± 10 μm was produced. Next, a 50 mm x 50 mm test piece 2 is prepared from the cured film. Next, the relative permittivity Dk2 and dielectric loss tangent Df2 of the test piece 2 were measured using a cylindrical cavity resonator at 23±2℃, 80%RH or less, and 10GHz. Next, X2 is calculated using the following formula (X2). Equation (X2): X2 = (Dk2) ０．５ ×Df2

19. The photocurable resin composition according to claim 1 or 2, which is in an uncured or semi-cured state.

20. A photocurable resin composition according to claim 1 or 2, used in a redistribution layer.

21. A film comprising the photocurable resin composition described in claim 1.

22. A cured film of the film according to claim 21.

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