Resin composition, cured product, prepreg, metal foil-clad laminate, resin composite sheet, printed wiring board, semiconductor device, and method for producing printed wiring board

Abstract

Provided are: a resin composition which is capable of suppressing backside exposure when formed into a cured product; and a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed wiring board, a semiconductor device, and a method for producing a printed wiring board, each of which uses the resin composition. A resin composition containing a thermosetting compound, the resin composition being formed into a cured product having a thickness of 30 [mu] m, the transmittance of g-rays (wavelength of 436 nm), the transmittance of h-rays (wavelength of 405 nm), and the transmittance of i-rays (wavelength of 365 nm) being 0.070% or less, each of the transmittance of g-rays (wavelength of 436 nm), the transmittance of h-rays (wavelength of 405 nm), and the transmittance of i-rays (wavelength of 365 nm).

Description

Technical Field

[0001] The present invention relates to a resin composition, a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed circuit board, a semiconductor device, and a method for producing a printed circuit board. Background Art

[0002] In recent years, semiconductor devices used in electronic devices, communication devices, etc., such as portable terminals, have been increasingly integrated and miniaturized. As a result, technologies that enable high-density mounting of semiconductor devices are being sought, and improvements are also being sought for printed circuit boards, which occupy an important position in the semiconductor devices.

[0003] Here, as the main final step of the printed circuit board processing method, the following method is used: a solder resist is applied to a printed circuit board on which a circuit is formed to form an insulating film that protects the circuit pattern. There are some known methods for forming a coating film using a solder resist, for example, in a method using a developing type solder resist, a solder resist is applied to the entire surface of the circuit pattern of the printed circuit board, a negative film (mask) having a predetermined circuit pattern is prepared, and the solder resist layer is exposed, and the uncured portion is developed.

[0004] However, if this method is used for a printed circuit board with electronic circuits formed on both sides, the light irradiated to one side will pass through the substrate of the printed circuit board and act on the solder resist layer on the opposite side, and sometimes resist residue will occur in the part that should be removed on the opposite side. This phenomenon in which the light irradiated to one side acts on the solder resist layer on the opposite side is called back exposure.

[0005] Here, Patent Document 1 discloses a composition for use as an insulating layer as a means for solving the above-mentioned back exposure, using the following composition: it is a composition for inhibiting the back exposure of a photosensitive composition cured by light of a wavelength of 350 to 420 nm, comprising a compound (A) having a naphthalene skeleton and a substituent bonded to at least the 2nd and / or 7th positions of the naphthalene ring contained in the aforementioned naphthalene skeleton.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: International Publication No. 2020 / 162278 Summary of the invention

[0009] Problem that the invention aims to solve

[0010] As described above, resin compositions that solve the problem of back exposure are known, but with recent technological innovations, the resin layer (insulating layer) used for printed circuit boards has become thinner, and the problem of back exposure has become more serious. Therefore, a new resin composition that can provide a resin layer (cured product) that can suppress back exposure is sought.

[0011] The present invention aims to solve this problem and aims to provide a resin composition capable of suppressing back exposure when a cured product is formed, as well as a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed circuit board, a semiconductor device, and a method for producing a printed circuit board using the above-mentioned resin composition.

[0012] Solutions for solving problems

[0013] The present inventors have studied the above problems and found that the above problems can be solved by preparing a resin composition having low transmittance for g-rays (wavelength 436nm), h-rays (wavelength 405nm) and i-rays (wavelength 365nm).

[0014] Specifically, the above problems can be solved by the following means.

[0015] <1> A resin composition comprising a thermosetting compound,

[0016] In a cured product formed from the resin composition with a thickness of 30 μm, the transmittances of g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm) are each 0.070% or less.

[0017] <2> The resin composition according to <1>, wherein the transmittance of a cured product formed into a 30 μm-thick product thereof to h-rays (wavelength: 405 nm) is 0.050% or less.

[0018] <3> The resin composition according to <1> or <2>, wherein the i-ray (wavelength: 365 nm) transmittance in a cured product formed into a 30 μm thickness is 0.040% or less.

[0019] <4> The resin composition according to any one of <1> to <3>, comprising an ultraviolet absorber and / or a non-metallic organic dye.

[0020] <5> The resin composition according to any one of <1> to <3>, comprising an ultraviolet absorber and a non-metallic organic pigment.

[0021] <6> The resin composition according to <4> or <5>, wherein the non-metallic organic coloring matter includes a dye.

[0022] <7> The resin composition according to any one of <4> to <6>, wherein the content of the ultraviolet absorber is more than 0 parts by mass and is 3.0 parts by mass or less based on 100 parts by mass of resin solid content in the resin composition.

[0023] <8> The resin composition according to any one of <4> to <7>, wherein the content of the non-metallic organic dye is more than 0 parts by mass and is 2.0 parts by mass or less per 100 parts by mass of resin solid content in the resin composition.

[0024] <9> The resin composition according to any one of <4> to <8>, wherein a mass ratio of the ultraviolet absorber to the non-metallic organic dye (ultraviolet absorber / non-metallic organic dye) is 0.15 to 4.0.

[0025] <10> The resin composition according to any one of <4> to <8>, wherein a mass ratio of the ultraviolet absorber to the non-metallic organic dye (ultraviolet absorber / non-metallic organic dye) is 0.4 to 1.5.

[0026] <11> The resin composition according to any one of <1> to <10>, wherein the thermosetting compound comprises one or more selected from the group consisting of maleimide compounds, epoxy compounds, phenolic compounds, oxetane resins, benzoxazine compounds, polyphenylene ether compounds containing two or more carbon-carbon unsaturated double bonds, polymers having a structural unit represented by formula (V), and cyanate compounds.

[0027]

[0028] (In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents a bonding position.)

[0029] <12> The resin composition according to any one of <1> to <11>, wherein a cured product of the resin composition has a dielectric loss tangent of 0.0001 or more and less than 0.0027.

[0030] <13> The resin composition according to any one of <1> to <12>, further comprising a filler.

[0031] <14> The resin composition according to <13>, wherein the content of the filler is 10 to 1000 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0032] <15> The resin composition according to any one of <1> to <14>, which is used for forming an insulating layer.

[0033] <16> The resin composition according to any one of <1> to <15>,

[0034] The transmittance of the cured product formed into a thickness of 30 μm is 0.050% or less for h-rays (wavelength 405 nm).

[0035] The i-ray (wavelength 365nm) transmittance of the cured product formed into a thickness of 30μm is 0.040% or less.

[0036] The resin composition comprises an ultraviolet absorber and a non-metallic organic pigment,

[0037] The aforementioned non-metallic organic pigments include dyes,

[0038] The content of the ultraviolet absorber is more than 0 parts by mass and less than 3.0 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition,

[0039] The content of the non-metallic organic pigment is more than 0 parts by mass and is 2.0 parts by mass or less relative to 100 parts by mass of the resin solid content in the resin composition,

[0040] The mass ratio of the ultraviolet absorber to the non-metallic organic pigment (ultraviolet absorber / non-metallic organic pigment) is 0.4 to 1.5,

[0041] The thermosetting compound comprises at least one selected from the group consisting of maleimide compounds, epoxy compounds, phenol compounds, oxetane resins, benzoxazine compounds, polyphenylene ether compounds containing two or more carbon-carbon unsaturated double bonds, polymers having a structural unit represented by formula (V), and cyanate compounds.

[0042]

[0043] (In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents a bonding position.)

[0044] <17> A cured product comprising the resin composition according to any one of <1> to <16>.

[0045] <18> A prepreg comprising a base material and the resin composition according to any one of <1> to <16>.

[0046] <19> A metal foil-clad laminate comprising: a layer formed from the resin composition according to any one of <1> to <16> and / or a layer formed from the prepreg according to <18>; and a metal foil disposed on one or both surfaces of the layer.

[0047] <20> A resin composite sheet comprising a support and a layer formed from the resin composition according to any one of <1> to <16> and disposed on a surface of the support.

[0048] <21> A printed wiring board comprising an insulating layer and a conductor layer disposed on a surface of the insulating layer, wherein the insulating layer comprises at least one of a layer formed from the resin composition according to any one of <1> to <16> and a layer formed from the prepreg according to <18>.

[0049] <22> The printed wiring board according to <21>, comprising an insulating layer having a thickness of 15 μm or less as the insulating layer.

[0050] <23> A semiconductor device comprising the printed circuit board described in <22>.

[0051] <24> A method for manufacturing a printed circuit board, comprising the following steps:

[0052] A step of preparing a substrate having laminated thereon: at least one insulating layer comprising a cured product of the resin composition described in any one of <1> to <16>; and at least one conductive layer in contact with the insulating layer;

[0053] A step of forming a photosensitive composition layer that is cured by light having a wavelength of 350 to 440 nm on both surfaces of the substrate; and

[0054] A step of disposing a mask pattern on at least one surface of the photosensitive composition layer and exposing the layer to light having a wavelength of 350 to 440 nm through the mask pattern.

[0055] <25> A method for manufacturing a printed circuit board, comprising the following steps:

[0056] A step of forming a photosensitive composition layer that is cured by light of a wavelength of 350 to 440 nm on both surfaces of a substrate, the substrate comprising: at least one insulating layer comprising a cured product of the resin composition described in any one of <1> to <16>, and at least one conductive layer in contact with the insulating layer; and

[0057] A step of disposing a mask pattern on at least one surface of the photosensitive composition layer and exposing the layer to light having a wavelength of 350 to 440 nm through the mask pattern.

[0058] <26> The method for producing a printed wiring board according to <24> or <25>, wherein the insulating layer has an insulating layer having a thickness of 15 μm or less.

[0059] Effects of the Invention

[0060] According to the present invention, there can be provided a resin composition capable of suppressing back exposure when a cured product is formed, and a cured product, a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed circuit board, a semiconductor device, and a method for producing a printed circuit board using the above-mentioned resin composition. DETAILED DESCRIPTION

[0061] A mode for implementing the present invention (hereinafter simply referred to as "this embodiment") will be described in detail below. It should be noted that the following this embodiment is an example for explaining the present invention, and the present invention is not limited to only this embodiment.

[0062] In the description of the group (atomic group) in this specification, when there is no description of substitution and unsubstituted, the group (atomic group) without a substituent and the group (atomic group) with a substituent are included. For example, "alkyl" not only includes alkyl without a substituent (unsubstituted alkyl), but also includes alkyl with a substituent (substituted alkyl). In this specification, the description without description of substitution and unsubstituted is preferably unsubstituted.

[0063] In the present specification, a (meth)allyl group represents both or either an allyl group and a methallyl group, a “(meth)acrylate” represents both or either an acrylate group and a methacrylate group, a “(meth)acrylic acid” represents both or either an acrylic acid group and a methacrylic acid group, and a “(meth)acryloyl group” represents both or either an acryloyl group and a methacryloyl group.

[0064] In this specification, the relative dielectric constant represents the ratio of the dielectric constant of a substance to the dielectric constant of a vacuum. It should be noted that in this specification, the relative dielectric constant may be simply referred to as "dielectric constant".

[0065] In addition, in this specification, "to" is used to mean that the numerical values ​​described before and after it are included as a lower limit and an upper limit.

[0066] In this specification, various physical property values ​​and characteristic values ​​are those at 23° C. unless otherwise specified.

[0067] In this specification, a "process" is not just an independent process. When it cannot be clearly distinguished from other processes, it is included in this term as long as the expected effect of the process can be achieved.

[0068] When the measurement methods and other information described in the standards in this manual differ from year to year, they are based on the standards as of January 1, 2022 unless otherwise specified.

[0069] In this specification, the resin solid content refers to the components excluding fillers (fillers such as inorganic fillers and resin fillers) and solvents, including thermosetting compounds, aromatic oligomers, thermoplastic elastomers, and other resin additive components (ultraviolet absorbers, non-metallic organic pigment additives, etc.).

[0070] The resin composition of the present embodiment is a resin composition containing a thermosetting compound, characterized in that the transmittance of g-ray (wavelength 436nm), h-ray (wavelength 405nm) and i-ray (wavelength 365nm) in a cured product formed to a thickness of 30μm is 0.070% or less. In the present embodiment, by making the transmittance of the aforementioned wavelengths 0.070% or less when the cured product is formed to a thickness of 30μm, back exposure can be effectively suppressed.

[0071] In addition, when the cured product formed by the conventional resin composition is used for the extremely thin insulating layer of the printed circuit board, there is a problem that the circuit pattern of the inner layer is detected as a defect in AOI (Automated Optical Inspection). This problem is easy to occur especially when the insulating layer does not contain a filler (especially an inorganic filler, and then glass cloth, filler, etc.). The resin composition of this embodiment can effectively avoid such a problem.

[0072] The resin composition of this embodiment is formed into a cured product with a thickness of 30 μm, and the g-ray (wavelength 436 nm) transmittance is 0.070% or less, preferably 0.069% or less, more preferably 0.068% or less, further preferably 0.067% or less, even more preferably 0.066% or less, and further preferably 0.065% or less. It is ideal that the lower limit of the g-ray (wavelength 436 nm) transmittance is 0%, but it is more practical to set it to 0.001% or more.

[0073] In addition, the resin composition of the present embodiment is formed into a cured product with a thickness of 30 μm, and the transmittance of H-ray (wavelength 405 nm) is 0.070% or less, preferably 0.050% or less, more preferably 0.045% or less, further preferably 0.040% or less, more preferably 0.038% or less, and further preferably 0.035% or less. It is ideal that the lower limit of the transmittance of H-ray (wavelength 405 nm) is 0%, but it is more practical to have a value of 0.001% or more.

[0074] Furthermore, in the cured product formed into a thickness of 30 μm by the resin composition of the present embodiment, the transmittance of i-ray (wavelength 365 nm) is 0.070% or less, more preferably 0.040% or less, further preferably 0.030% or less, still more preferably 0.025% or less, and further preferably 0.020% or less. It is ideal that the lower limit of the transmittance of i-ray (wavelength 365 nm) is 0%, but it is more practical to have a value of 0.001% or more.

[0075] As the means of realizing the low transmittance of the above-mentioned g-ray (wavelength 436nm), h-ray (wavelength 405nm) and i-ray (wavelength 365nm), for example, the kind of thermosetting compound selected to be mixed in the resin combination, the mode of adjusting other components can be enumerated. But if the kind of thermosetting compound is adjusted in order to suppress back exposure or various additives are mixed to the resin combination, the low dielectric properties (low dielectric constant and / or low dielectric loss tangent) of the cured product of the resin combination sometimes can be reduced. Therefore, in the present embodiment, preferably by making the resin combination comprising ultraviolet light absorber and / or non-metallic organic pigment, thus be adjusted to meet the above-mentioned transmittance. By being set to such a formation, the resin combination that can reach low dielectric properties and can effectively suppress back exposure can be provided. In particular, the resin combination that preferably comprises ultraviolet light absorber and non-metallic organic pigment is made in the present embodiment. By using ultraviolet light absorber and non-metallic organic pigment in combination, even if the total usage amount of the two components in the resin combination is relatively less, transmittance can still be effectively reduced, and the resin combination that can reach low dielectric properties and can effectively suppress back exposure can be provided. Furthermore, by precisely adjusting the content and mixing ratio of the ultraviolet absorber and the non-metallic organic pigment, a resin composition can be provided which has excellent heat resistance, can maintain low dielectric properties, and can effectively suppress back exposure.

[0076] <Thermosetting compounds>

[0077] The resin composition of the present embodiment contains a thermosetting compound. The thermosetting compound usually becomes the main component of the cured product of the present embodiment.

[0078] The thermosetting compound used in the present embodiment preferably includes one or more selected from the group consisting of maleimide compounds, epoxy compounds, phenol compounds, oxetane resins, benzoxazine compounds, (meth)allyl compounds, polyphenylene ether compounds containing two or more carbon-carbon unsaturated double bonds, polymers having a structural unit represented by formula (V), and cyanate compounds. It is more preferred that it includes one or more selected from the group consisting of maleimide compounds, epoxy compounds, phenol compounds, oxetane resins, benzoxazine compounds, polyphenylene ether compounds containing two or more carbon-carbon unsaturated double bonds, polymers having a structural unit represented by formula (V), and cyanate compounds. It is further preferred that it includes one or more selected from the group consisting of maleimide compounds, polyphenylene ether compounds containing two or more carbon-carbon unsaturated double bonds, and cyanate compounds. It is even more preferred that all of the maleimide compounds, polyphenylene ether compounds containing two or more carbon-carbon unsaturated double bonds, and cyanate compounds are included.

[0079]

[0080] (In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents a bonding position.)

[0081] <<Maleimide compounds>>

[0082] The resin composition of the present embodiment may also contain a maleimide compound. The resin composition of the present embodiment is not particularly limited as long as it is a compound having two or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, more preferably 2 or 3, preferably 2) maleimide groups in one molecule, and can be widely used. Compounds commonly used in the field of printed circuit boards can be used.

[0083] In the present embodiment, the maleimide compound is preferably a compound represented by formula (M0) to formula (M5), a maleimide compound (M6), or a compound represented by formula (M7), and more preferably a compound represented by formula (M0).

[0084]

[0085] (In formula (M0), R 51 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R 52 Each independently represents a hydrogen atom or a methyl group, and n1 represents an integer greater than 1.)

[0086] R 51 Preferred are hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group and phenyl group, more preferred are either a hydrogen atom or a methyl group, and still more preferred are hydrogen atom.

[0087] R 52 Preferred is methyl.

[0088] n1 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0089] The compound represented by formula (M0) may be a mixture of two or more compounds in addition to being a single compound. Examples of the mixture include a mixture of compounds having different n1, a mixture of compounds having different n1, and a mixture of compounds having different n1. 51 and / or R 52 The present invention also includes a mixture of compounds having different types of substituents, a mixture of compounds having different bonding positions (meta, para, or ortho) of the maleimide group and the oxygen atom relative to the benzene ring, and a mixture of compounds having two or more of the above different points. The same is true for the compounds represented by formula (M1) to formula (M5), the maleimide compound (M6), and the compound represented by formula (M7).

[0090]

[0091] (In formula (M1), R M1 , R M2 , R M3 and R M4 Each independently represents a hydrogen atom or an organic group. M5 and R M6 Each independently represents a hydrogen atom or an alkyl group. M represents a divalent aromatic group. A is a 4- to 6-membered alicyclic group. M7 and R M8 Each is independently an alkyl group. mx is 1 or 2, and lx is 0 or 1. M9 and R M10 Each independently represents a hydrogen atom or an alkyl group. M11 , R M12 , R M13 and R M14 Each independently represents a hydrogen atom or an organic group. M15 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group. px represents an integer of 0 to 3. nx represents an integer of 1 to 20.)

[0092] R in the formula M1 , R M2 , R M3 and R M4Each independently represents a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. M1 and R M3 Each independently preferably an alkyl group, R M2 and R M4 A hydrogen atom is preferred.

[0093] R M5 and R M6 Each independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group herein is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

[0094] Ar M Ar represents a divalent aromatic group, preferably phenylene, naphthalene diyl, phenanthrene diyl, anthracene diyl, more preferably phenylene, and still more preferably m-phenylene. M It may have a substituent, and as the substituent, an alkyl group is preferred, an alkyl group having 1 to 12 carbon atoms is more preferred, an alkyl group having 1 to 6 carbon atoms is further preferred, a methyl group, an ethyl group, a propyl group, or a butyl group is further preferred, and a methyl group is particularly preferred. M Preferably, there is no substitution.

[0095] A is a 4- to 6-membered alicyclic group, more preferably a 5-membered alicyclic group (preferably a group condensed with a benzene ring to form an indane ring). M7 and R M8 Each independently represents an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

[0096] mx is 1 or 2, preferably 2.

[0097] lx is 0 or 1, preferably 1.

[0098] R M9 and R M10 Each independently represents a hydrogen atom or an alkyl group, and an alkyl group is more preferred. The alkyl group herein is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, and a butyl group, and particularly preferably a methyl group.

[0099] R M11 , R M12 , R M13 and R M14 Each independently represents a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. M12and R M13 Each independently preferably an alkyl group, R M11 and R M14 A hydrogen atom is preferred.

[0100] R M15 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group, and is preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.

[0101] px represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and further preferably 0.

[0102] nx represents an integer of 1 to 20. nx may be an integer of 10 or less.

[0103] It should be noted that the resin composition of the present embodiment may include only one compound (M1) shown in the formula (M1) and at least a compound with different values ​​of nx, or may include more than two kinds. When including more than two kinds, for the average value (average number of repeating units) n of nx in the compound (M1) shown in the formula (M1) in the resin composition, in order to become a low melting point (low softening point) and a person with low melt viscosity and excellent handling properties, it is preferably more than 0.92, more preferably more than 0.95, further preferably more than 1.0, and more preferably more than 1.1. In addition, n is preferably less than 10.0, more preferably less than 8.0, further preferably less than 7.0, more preferably less than 6.0, and may also be less than 5.0. The same is true for formula (M1-2) etc. described later.

[0104] The compound (M1) represented by the formula (M1) is preferably a compound represented by the following formula (M1-1).

[0105]

[0106] (In formula (M1-1), R M21 , R M22 , R M23 and R M24 Each independently represents a hydrogen atom or an organic group. M25 and R M26 Each independently represents a hydrogen atom or an alkyl group. M27 , R M28 , R M29 and R M30 Each independently represents a hydrogen atom or an organic group. M31 and R M32 Each independently represents a hydrogen atom or an alkyl group. M33, R M34 , R M35 and R M36 Each independently represents a hydrogen atom or an organic group. M37 , R M38 and R M39 Each independently represents a hydrogen atom or an alkyl group. nx represents an integer of 1 to 20.

[0107] R in the formula M21 , R M22 , R M23 and R M24 Each independently represents a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. M21 and R M23 Preferably, alkyl, R M22 and R M24 A hydrogen atom is preferred.

[0108] R M25 and R M26 Each independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group herein is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

[0109] R M27 , R M28 , R M29 and R M30 Each independently represents a hydrogen atom or an organic group, preferably a hydrogen atom. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

[0110] R M31 and R M32 Each independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group herein is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

[0111] R M33 , R M34 , R M35 and R M36 Each independently represents a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

[0112] RM33 and R M36 Preferably, a hydrogen atom, R M34 and R M35 An alkyl group is preferred.

[0113] R M37 , R M38 and R M39 Each independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group herein is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

[0114] nx represents an integer of 1 to 20. nx may be an integer of 10 or less.

[0115] The compound represented by formula (M1-1) is preferably a compound represented by the following formula (M1-2).

[0116]

[0117] (In formula (M1-2), R M21 , R M22 , R M23 and R M24 Each independently represents a hydrogen atom or an organic group. M25 and R M26 Each independently represents a hydrogen atom or an alkyl group. M27 , R M28 , R M29 and R M30 Each independently represents a hydrogen atom or an organic group. M31 and R M32 Each independently represents a hydrogen atom or an alkyl group. M33 , R M34 , R M35 and R M36 Each independently represents a hydrogen atom or an organic group. M37 , R M38 , and R M39 Each independently represents a hydrogen atom or an alkyl group. nx represents an integer of 1 to 20.

[0118] In formula (M1-2), R M21 , R M22 , R M23 , R M24 , R M25 , R M26 , R M27 , R M28 , R M29 , R M30 , R M31 , R M32 , RM33 , R M34 , R M35 , R M36 , R M37 , R M38 , R M39 , and nx are each R in formula (M1-1) M21 , R M22 , R M23 , R M24 , R M25 , R M26 , R M27 , R M28 , R M29 , R M30 , R M31 , R M32 , R M33 , R M34 , R M35 , R M36 , R M37 , R M38 , R M39 , and nx have the same meanings and the preferred ranges are also the same.

[0119] The compound represented by the formula (M1-1) is preferably a compound represented by the following formula (M1-3), and more preferably a compound represented by the following formula (M1-4).

[0120]

[0121] (In formula (M1-3), nx represents an integer of 1 to 20.)

[0122] nx may be an integer less than 10.

[0123]

[0124] (In formula (M1-4), nx represents an integer of 1 to 20.)

[0125] nx may be an integer less than 10.

[0126] The molecular weight of the compound (M1) represented by the formula (M1) is preferably 500 or more, more preferably 600 or more, and further preferably 700 or more. By setting it to above the aforementioned lower limit, there is a tendency that the low dielectric properties and low water absorption of the obtained cured product are further improved. In addition, the molecular weight of the compound (M1) represented by the formula (M1) is preferably 10000 or less, more preferably 9000 or less, further preferably 7000 or less, more preferably 5000 or less, and further preferably 4000 or less. By setting it to below the aforementioned upper limit, there is a tendency that the heat resistance and handleability of the obtained cured product are further improved.

[0127]

[0128] (In formula (M2), R 54 Each independently represents a hydrogen atom or a methyl group, and n4 represents an integer greater than 1.)

[0129] n4 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably an integer of 1 to 3, more preferably 1 or 2, and may be 1.

[0130] The compound represented by formula (M2) may be a mixture of compounds having different n4, preferably a mixture. In addition, as described in the compound represented by formula (M0), it may be a mixture of compounds having different other parts.

[0131]

[0132] (In formula (M3), R 55 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n5 represents an integer of 1 to 10.

[0133] R 55 Preferred are hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group and phenyl group, more preferred are either a hydrogen atom or a methyl group, and still more preferred are hydrogen atom.

[0134] n5 is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1 or 2.

[0135] The compound represented by formula (M3) may be a mixture of compounds having different n5, preferably a mixture. In addition, as described in the compound represented by formula (M0), it may be a mixture of compounds having different other parts.

[0136]

[0137] (In formula (M4), R 56 Each independently represents a hydrogen atom, a methyl group or an ethyl group, and R 57 Each independently represents a hydrogen atom or a methyl group. )

[0138]

[0139] (In formula (M5), R 58 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R 59 Each independently represents a hydrogen atom or a methyl group, and n6 represents an integer greater than 1.)

[0140] R 58Preferred are hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group and phenyl group, more preferred are either a hydrogen atom or a methyl group, and still more preferred are hydrogen atom.

[0141] R 59 Preferred is methyl.

[0142] n6 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably an integer of 1 to 3, further preferably 1 or 2, and may be 1.

[0143] The compound represented by formula (M5) may be a mixture of compounds having different n6, preferably a mixture. In addition, as described in the compound represented by formula (M0), it may be a mixture of compounds having different other parts.

[0144] The maleimide compound (M6) is a compound having a structural unit represented by the formula (M6) and having maleimide groups at both ends of the molecular chain.

[0145]

[0146] (In formula (M6), R 61 R represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. 62 R represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. 63 Each independently represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. Each independently represents an integer of 0 to 10.

[0147] For details of the maleimide compound (M6) and a method for producing the same, reference may be made to paragraphs 0061 to 0066 of International Publication No. 2020 / 262577, the contents of which are incorporated herein by reference.

[0148] The maleimide compound (M6) may be a mixture of compounds having different other parts as described above with respect to the compound represented by the formula (M0).

[0149]

[0150] (In the above formula (M7), R 1 Each independently represents the aforementioned alkyl group, R 2 each independently represents an alkyl group, an alkoxy group or an alkylthio group having 1 to 10 carbon atoms; an aryl group, an aryloxy group or an arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group,

[0151] R 3 , R 4 , R 5 and R 6 Each independently represents a hydrogen atom or a methyl group, and R 3 and R 4 One of them is a hydrogen atom and the other is a methyl group, R 5 and R 6 One of them is a hydrogen atom and the other is a methyl group,

[0152] X 1 is a substituent represented by the following formula (x), and r is one of the substituents bonded to X. 1 The X of the benzene ring 1 , p represents an integer of 1 to 3, q ​​represents an integer of 0 to 4, and k represents an integer of 1 to 100.

[0153]

[0154] (In formula (x), R 7 and R 8 Each independently represents a hydrogen atom or a methyl group, and R 7 and R 8 One of them is a hydrogen atom and the other is a methyl group, R 9 Each independently represents an alkyl group, alkoxy group or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, and t represents an integer of 0 to 4.

[0155] In the above formula (1), when p is an integer greater than or equal to 2, the presence of a plurality of R 1 When q is an integer greater than 2, the presence of a plurality of R 2 When t is an integer greater than 2, the presence of a plurality of R 9 They are optionally the same as or different from each other.

[0156] The compound represented by formula (M7) may be a mixture of compounds having different k, preferably a mixture. In addition, as described in the compound represented by formula (M0), it may be a mixture of compounds having different other parts.

[0157] For details of the compound represented by formula (M7), reference can be made to the description of Japanese Patent No. 7160151, the contents of which are incorporated herein by reference.

[0158] The maleimide compound can be prepared by a known method, or a commercial product can be used. As commercial products, for example, as a compound represented by formula (M0), "BMI-80" manufactured by K.I. CHEMICAL INDUSTRY CO., LTD. can be cited, as a compound represented by formula (M1), "NE-X-9470S" manufactured by DIC Corporation can be cited, as a compound represented by formula (M2), "BMI-2300" manufactured by Daiwa Fine Chemicals Co., Ltd. can be cited, as a compound represented by formula (M3), "MIR-3000" manufactured by Nippon Kayaku Co., Ltd. can be cited, as a compound represented by formula (M4), K.I. CHEMICAL INDUSTRY CO., LTD. can be cited. CO., LTD., "BMI-70" manufactured by Nippon Kayaku Co., Ltd., as the compound represented by formula (M5), "MIR-5000" manufactured by Nippon Kayaku Co., Ltd., as the maleimide compound (M6), "MIZ-001" manufactured by Nippon Kayaku Co., Ltd., and as the compound represented by formula (M7), "NE-X-9500" manufactured by DIC Corporation.

[0159] In addition, as maleimide compounds other than the above, compounds having two or more maleimide groups can be exemplified, specifically, m-phenylene bismaleimide, 2,2-bis(4-(4-maleimidephenoxy)-phenyl)propane, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, and prepolymers thereof, prepolymers of these maleimides and amines, etc. can be cited.

[0160] In the case where the resin composition of the present embodiment includes a maleimide compound, the lower limit of its content is preferably 1 mass part or more, more preferably 5 mass parts or more, more preferably 10 mass parts or more, more preferably 15 mass parts or more, more preferably 20 mass parts or more, more preferably 25 mass parts or more, and particularly preferably 30 mass parts or more relative to 100 mass parts of resin solid components in the resin composition. By making the content of the maleimide compound be 1 mass part or more, there is a tendency that the flame retardancy of the obtained cured product is improved. In addition, the upper limit of the content of the maleimide compound is preferably 90 mass parts or less, more preferably 70 mass parts or less, more preferably 60 mass parts or less, more preferably 50 mass parts or less, and more preferably 40 mass parts or less relative to 100 mass parts of resin solid components in the resin composition. By making the content of the maleimide compound be 90 mass parts or less, there is a tendency that the metal foil peel strength and low water absorption are improved.

[0161] The resin composition in the present embodiment may contain only one maleimide compound or may contain two or more thereof. When containing two or more thereof, the total amount is preferably within the above range.

[0162] <<Epoxides>>

[0163] The resin composition of the present embodiment may contain an epoxy compound.

[0164] The epoxy compound is not particularly limited as long as it is a compound or resin having one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, more preferably 2 or 3, and even more preferably 2) epoxy groups in one molecule, and a wide range of compounds commonly used in the field of printed wiring boards can be used.

[0165] Examples of the epoxy compound include bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, bisphenol A novolac epoxy resin, glycidyl ester epoxy resin, aralkyl novolac epoxy resin, biphenyl aralkyl epoxy resin, naphthyl ether epoxy resin, cresol novolac epoxy resin, polyfunctional phenol epoxy resin, naphthalene epoxy resin, anthracene epoxy resin, naphthalene skeleton modified novolac epoxy resin, phenol aralkyl epoxy resin, naphthol aralkyl epoxy resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin, alicyclic epoxy resin, polyol epoxy resin, phosphorus-containing epoxy resin, glycidyl amine, glycidyl ester, compounds obtained by epoxidizing double bonds of butadiene or the like, compounds obtained by reacting hydroxyl-containing silicone resins with epichlorohydrin, and the like. By using these, the moldability and adhesion of the resin composition are improved. Among these, from the viewpoint of further improving flame retardancy and heat resistance, biphenyl aralkyl type epoxy resins, naphthyl ether type epoxy resins, multifunctional phenol type epoxy resins, and naphthalene type epoxy resins are preferred, and biphenyl aralkyl type epoxy resins are more preferred.

[0166] The resin composition of the present embodiment preferably includes epoxy compounds within the scope of not damaging the effect of the present invention. In the case where the resin composition of the present embodiment includes epoxy compounds, its content is preferably 0.1 mass parts or more, more preferably 1 mass parts or more, and further preferably 2 mass parts or more relative to 100 mass parts of resin solid components in the resin composition. By making the content of epoxy compounds more than 0.1 mass parts, there is a tendency for metal foil peeling strength and toughness to improve. For the upper limit of the content of epoxy compounds, in the case where the resin composition of the present embodiment includes epoxy compounds, relative to 100 mass parts of resin solid components in the resin composition, it is preferably 50 mass parts or less, more preferably 30 mass parts or less, further preferably 20 mass parts or less, more preferably 10 mass parts or less, and it can also be 8 mass parts or less, 5 mass parts or less. By making the content of epoxy compounds less than 50 mass parts, there is a tendency for the electrical properties of the obtained cured product to improve.

[0167] The resin composition in the present embodiment may contain only one epoxy compound or two or more epoxy compounds. When containing two or more epoxy compounds, the total amount is preferably within the above range.

[0168] In addition, the resin composition in the present embodiment may also be substantially free of epoxy compounds. Substantially free means that the content of epoxy compounds is less than 0.1 parts by mass, preferably less than 0.01 parts by mass, and further less than 0.001 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

[0169] <<Phenol compounds>>

[0170] The resin composition of the present embodiment may contain a phenol compound.

[0171] The phenol compound is not particularly limited as long as it has one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, further preferably 2 or 3, further preferably 2) phenolic hydroxyl groups in one molecule, and a wide range of compounds commonly used in the field of printed wiring boards can be used.

[0172] Examples of the phenolic compound include bisphenol A type phenolic resin, bisphenol E type phenolic resin, bisphenol F type phenolic resin, bisphenol S type phenolic resin, phenol novolac resin, bisphenol A novolac type phenolic resin, glycidyl ester type phenolic resin, aralkyl novolac phenolic resin, biphenyl aralkyl type phenolic resin, cresol novolac type phenolic resin, multifunctional phenolic resin, naphthol resin, naphthol novolac resin, multifunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified novolac type phenolic resin, phenol aralkyl type phenolic resin, naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin, alicyclic phenolic resin, polyol type phenolic resin, phosphorus-containing phenolic resin, hydroxyl-containing silicone resins, and the like. Among these, from the viewpoint of further improving the flame retardancy of the obtained cured product, at least one selected from the group consisting of biphenyl aralkyl phenol resins, naphthol aralkyl phenol resins, phosphorus-containing phenol resins and hydroxyl-containing silicone resins is preferred.

[0173] The resin composition of the present embodiment preferably includes a phenolic compound within a range that does not impair the effect of the present invention. When the resin composition of the present embodiment includes a phenolic compound, its content is preferably 0.1 mass parts or more, more preferably 1 mass parts or more, and further preferably 2 mass parts or more relative to 100 mass parts of the resin solid component in the resin composition. In addition, it is preferably 50 mass parts or less, more preferably 30 mass parts or less, further preferably 20 mass parts or less, more preferably 10 mass parts or less, and can also be 5 mass parts or less.

[0174] The resin composition in the present embodiment may contain only one phenol compound or two or more phenol compounds. When containing two or more phenol compounds, the total amount is preferably within the above range.

[0175] The resin composition in the present embodiment may also be configured to contain substantially no phenol compound. Substantially containing no phenol compound means that the content of the phenol compound is less than 0.1 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0176] <<Oxetane Resin>>

[0177] The resin composition of the present embodiment may contain an oxetane resin.

[0178] The oxetane resin is not particularly limited as long as it is a compound having one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, further preferably 2 or 3, further preferably 2) oxetane groups, and a wide range of compounds commonly used in the field of printed wiring boards can be used.

[0179] Examples of the oxetane resin include oxetane, alkyloxetane (e.g., 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, etc.), 3-methyl-3-methoxymethyloxetane, 3,3-bis(trifluoromethyl)oxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane, OXT-101 (manufactured by Toagosei Co., Ltd.), and OXT-121 (manufactured by Toagosei Co., Ltd.).

[0180] The resin composition of the present embodiment preferably includes an oxetane resin within the scope of not damaging the effect of the present invention. In the case where the resin composition of the present embodiment includes an oxetane resin, its content is preferably 0.1 mass parts or more, more preferably 1 mass parts or more, and further preferably 2 mass parts or more relative to 100 mass parts of the resin solids in the resin composition. By making the content of the oxetane resin more than 0.1 mass parts, there is a tendency for the metal foil peel strength and toughness to improve. For the upper limit of the content of the oxetane resin, in the case where the resin composition of the present embodiment includes an oxetane resin, relative to 100 mass parts of the resin solids in the resin composition, it is preferably less than 50 mass parts, more preferably less than 30 mass parts, more preferably less than 20 mass parts, more preferably less than 10 mass parts, and can also be less than 5 mass parts. By making the content of the oxetane resin less than 50 mass parts, there is a tendency for the electrical properties of the cured product obtained to improve.

[0181] The resin composition in the present embodiment may contain only one oxetane resin or two or more oxetane resins. When containing two or more oxetane resins, the total amount is preferably within the above range.

[0182] The resin composition in the present embodiment may also be configured to contain substantially no oxetane resin. Substantially containing no oxetane resin means that the content of the oxetane resin is less than 0.1 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0183] <<Benzoxazine compounds>>

[0184] The resin composition of the present embodiment may contain a benzoxazine compound.

[0185] The benzoxazine compound is not particularly limited as long as it is a compound having two or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, more preferably 2 or 3, and even more preferably 2) dihydrobenzoxazine rings in one molecule, and a wide range of compounds commonly used in the field of printed circuit boards can be used.

[0186] Examples of the benzoxazine compound include bisphenol A type benzoxazine BA-BXZ (manufactured by KONISHI CHEMICAL IND CO., LTD.), bisphenol F type benzoxazine BF-BXZ (manufactured by KONISHI CHEMICAL IND CO., LTD.), and bisphenol S type benzoxazine BS-BXZ (manufactured by KONISHI CHEMICAL IND CO., LTD.).

[0187] The resin composition of the present embodiment preferably contains a benzoxazine compound within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains a benzoxazine compound, the content thereof is preferably 0.1 parts by mass or more and preferably 50 parts by mass or less relative to 100 parts by mass of the resin solid content in the resin composition.

[0188] The resin composition in the present embodiment may contain only one benzoxazine compound or two or more benzoxazine compounds. When containing two or more benzoxazine compounds, the total amount is preferably within the above range.

[0189] The resin composition in the present embodiment may also be configured to contain substantially no benzoxazine compound. Substantially containing no benzoxazine compound means that the content of the benzoxazine compound is less than 0.1 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0190] <<Compounds containing a (meth)allyl group>>

[0191] The resin composition of the present embodiment preferably contains a (meth)allyl group-containing compound, and more preferably contains an allyl group-containing compound.

[0192] The (meth)allyl group-containing compound is preferably a compound containing two or more (meth)allyl groups, and more preferably a compound containing two or more allyl groups.

[0193] As the compound containing a (meth)allyl group, it is preferred that the compound contains at least one selected from the group consisting of an allyl isocyanurate compound, an allyl-substituted nadic imide compound, an allyl compound having a glycoluril structure, and diallyl phthalate. It is more preferred that the compound contains at least one selected from the group consisting of an allyl isocyanurate compound, an allyl-substituted nadic imide compound, and an allyl compound having a glycoluril structure. It is further preferred that the compound contains an allyl-substituted nadic imide compound, and it is further preferred that the compound contains an alkenyl nadic imide compound.

[0194] In the case where the resin combination of the present embodiment comprises the compound containing (methyl) allyl, its molecular weight is preferably more than 195, more preferably more than 300, further preferably more than 400, more preferably more than 500.By being set to more than the aforementioned lower limit, thus there is the tendency that the low dielectric properties of the cured product obtained and the thermotolerance further improve.In addition, the molecular weight of the compound containing (methyl) allyl is preferably less than 3000, more preferably less than 2000, further preferably less than 1000, more preferably less than 800.By being set to less than the aforementioned upper limit, thus there is the tendency that the low thermal expansion of the cured product obtained further improves.

[0195] In the case where the resin combination of the present embodiment includes the compound containing (meth) allyl, its content is preferably more than 1 mass part, more preferably more than 3 mass parts, more preferably more than 5 mass parts, or more than 10 mass parts relative to 100 mass parts of the resin solids in the resin combination.By setting the content of the compound containing (meth) allyl as more than the above-mentioned lower limit, there is a tendency that the excellent formability of the resin combination and the heat resistance of the cured product obtained are further improved.In addition, the upper limit of the content of the compound containing (meth) allyl is preferably less than 40 mass parts relative to 100 mass parts of the resin solids in the resin combination, more preferably less than 30 mass parts, more preferably less than 20 mass parts.By setting the content of the compound containing (meth) allyl as less than the above-mentioned upper limit, there is a tendency that the low thermal expansion of the cured product obtained is further improved.

[0196] The resin composition of the present embodiment may contain only one (meth)allyl group-containing compound or two or more thereof. When containing two or more thereof, the total amount is preferably within the above range.

[0197] The resin composition in the present embodiment may be substantially free of a (meth)allyl group-containing compound. Substantially free of a (meth)allyl group-containing compound means that the content of the (meth)allyl group-containing compound is less than 0.1 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0198] <<<Allyl isocyanurate compounds>>>

[0199] The allyl isocyanurate compound is not particularly limited as long as it is a compound having two or more allyl groups and an isocyanurate ring (urate skeleton), but a compound represented by the formula (TA) is preferred.

[0200] Formula (TA)

[0201]

[0202] (In formula (TA), R A represents a substituent).

[0203] In formula (TA), R A represents a substituent, and more preferably a substituent having a formula weight of 15 to 500.

[0204] R A The first example is an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms. By using an allyl compound having an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, a resin composition having excellent crosslinking properties and capable of obtaining a cured product having high toughness can be provided. Thus, even when the resin composition does not contain a substrate such as glass cloth, cracking can be suppressed during etching treatment or the like.

[0205] The carbon number of the alkyl group and / or alkenyl group is preferably 3 or more, more preferably 8 or more, from the viewpoint of improving the handling properties, and may be 12 or more, and preferably 18 or less. As a result, the resin fluidity of the resin composition becomes good, and it is considered that the circuit filling property when a multilayer circuit substrate is produced using the resin composition of the present embodiment will become more excellent.

[0206] R A A second example of is a group containing an allyl isocyanurate group. A When an allyl isocyanurate group is included, the compound represented by the formula (TA) is preferably a compound represented by the formula (TA-1).

[0207] Formula (TA-1)

[0208]

[0209] (In formula (TA-1), R A2 is a divalent linking group. )

[0210] In formula (TA-1), R A2It is preferably a divalent linking group with a formula weight of 54 to 250, more preferably a divalent linking group with a formula weight of 54 to 250 and carbon atoms at both ends, and further preferably an aliphatic hydrocarbon group with 2 to 20 carbon atoms (wherein the aliphatic hydrocarbon group may also contain an ether group and may also have a hydroxyl group).

[0211] More specifically, R A2 Preferably, it is a group represented by any of the following formulae (i) to (iii).

[0212]

[0213] (In formulas (i) to (iii), p c1 represents the number of repeating units of the methylene group, which is an integer from 2 to 18. c2 represents the number of repeating units of oxyethylene, which is 0 or 1. * represents the bonding site. )

[0214] The aforementioned c1 It is preferably an integer of 2-10, more preferably an integer of 3-8, and even more preferably an integer of 3-5.

[0215] The aforementioned c2 It can be 0 or 1, and is preferably 1.

[0216] R A2 The first example is preferred.

[0217] In the present embodiment, the reactive group (allyl group) equivalent of the compound represented by the formula (TA) is preferably 1000 or less. When the equivalent is 1000 or less, it is considered that a high Tg can be obtained more reliably.

[0218] Examples of the aforementioned alkyl group having 1 to 22 carbon atoms include linear or branched alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, and docosyl groups. Examples of the aforementioned alkenyl group having 2 to 22 carbon atoms include allyl and decenyl groups.

[0219] Specific examples of the compound represented by formula (TA) include triallyl isocyanurate, 5-octyl-1,3-diallyl isocyanurate, 5-dodecyl-1,3-diallyl isocyanurate, 5-tetradecyl-1,3-diallyl isocyanurate, 5-hexadecyl-1,3-diallyl isocyanurate, 5-octadecyl-1,3-diallyl isocyanurate, 5-eicosyl-1,3-diallyl isocyanurate, 5-docosyl-1,3-diallyl isocyanurate, 5-decenyl-1,3-diallyl isocyanurate, etc. These may be used alone or in combination of two or more, and may be used in the form of a prepolymer.

[0220] The method for producing the compound represented by formula (TA) is not particularly limited, and it can be obtained, for example, by reacting diallyl isocyanurate and an alkyl halide in an aprotic polar solvent such as N,N'-dimethylformamide in the presence of an alkaline substance such as sodium hydroxide, potassium carbonate, triethylamine, etc., at a temperature of about 60°C to 150°C.

[0221] In addition, the compound represented by formula (TA) can also use commercially available substances. As commercially available substances, there are no particular limitations, and for example, L-DAIC manufactured by SHIKOKU KASEI HOLDINGS CORPORATION can be cited. As triallyl isocyanurate, for example, TAIC manufactured by Mitsubishi Chemical Corporation can be cited. As the compound represented by formula (TA-1), for example, DD-1 manufactured by SHIKOKU KASEI HOLDINGS CORPORATION can be cited.

[0222] The molecular weight of the allyl isocyanurate compound (preferably the compound represented by formula (TA)) is preferably 200 or more, more preferably 300 or more, further preferably 400 or more, and even more preferably 500 or more. By setting the molecular weight to the above lower limit value or more, there is a tendency that the low dielectric properties and heat resistance of the obtained cured product are further improved. In addition, the molecular weight of the allyl isocyanurate compound (preferably the compound represented by formula (TA)) is preferably 3000 or less, more preferably 2000 or less, further preferably 1000 or less, and more preferably 800 or less. By setting the molecular weight to the above upper limit value or less, there is a tendency that the low thermal expansion of the obtained cured product is further improved.

[0223] When the resin composition of the present embodiment includes an allyl isocyanurate compound, its content is preferably more than 1 mass part, more preferably more than 3 mass parts, more preferably more than 5 mass parts, and can also be more than 10 mass parts relative to 100 mass parts of the resin solids in the resin composition. By setting the content of the allyl isocyanurate compound to more than the above-mentioned lower limit, there is a tendency that the moldability of the resin composition is excellent and the heat resistance of the obtained cured product is further improved. In addition, the upper limit of the content of the allyl isocyanurate compound is preferably less than 40 mass parts, more preferably less than 30 mass parts, and more preferably less than 20 mass parts relative to 100 mass parts of the resin solids in the resin composition. By setting the content of the allyl isocyanurate compound to less than the above-mentioned upper limit, there is a tendency that the low thermal expansion of the cured product obtained is further improved.

[0224] The resin composition of the present embodiment may contain only one kind of allyl isocyanurate or may contain two or more kinds. When containing two or more kinds, it is preferable that the total amount is within the above range.

[0225] <<<Allyl substituted nadic imide compounds>>>

[0226] The allyl-substituted nadic acid imide compound is not particularly limited as long as it is a compound having one or more allyl-substituted nadic acid imide groups in the molecule (preferably a compound having one or more nadic acid imide groups substituted by alkenyl groups in the molecule (alkenyl nadic acid imide compounds)). As a specific example thereof, a compound represented by the following formula (AN) can be cited.

[0227] Formula (AN)

[0228]

[0229] (In formula (AN), R1 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R2 represents an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, or a group represented by formula (AN-2) or (AN-3).

[0230] Formula (AN-2)

[0231]

[0232] (In formula (AN-2), R3 represents a group represented by methylene, isopropylidene, -C(=O)-, -O-, -S- or -S(=O)2-.)

[0233] Formula (AN-3)

[0234]

[0235] (In formula (AN-3), R4 each independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.)

[0236] In addition, the compound represented by formula (AN) can also use commercially available substances. As commercially available substances, there are no particular limitations, and for example, the compound represented by formula (AN-4) (BANI-M (made by Maruzen Petrochemical)), the compound represented by formula (AN-5) (BANI-X (made by Maruzen Petrochemical)), etc. can be cited. These can be used alone or in combination of two or more.

[0237] Formula (AN-4)

[0238]

[0239] Formula (AN-5)

[0240]

[0241] The molecular weight of the allyl-substituted nadic imide compound (preferably the compound shown in formula (AN)) is preferably 400 or more, more preferably 500 or more, and can be 550 or more. By setting the molecular weight of the allyl-substituted nadic imide compound to above the above lower limit, there is a tendency that the low dielectric properties, low thermal expansion and heat resistance of the obtained cured product are further improved. In addition, the molecular weight of the allyl-substituted nadic imide compound (preferably the compound shown in formula (AN)) is preferably 1500 or less, more preferably 1000 or less, further preferably 800 or less, and can also be 700 or less, 600 or less. By setting the molecular weight of the allyl-substituted nadic imide compound to below the above upper limit, there is a tendency that the moldability of the resin composition and the peel strength of the cured product obtained are further improved.

[0242] When the resin composition of the present embodiment includes an allyl-substituted nadic acid imide compound (preferably a compound shown in formula (AN)), its content is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass or more relative to 100 parts by mass of the resin solid content in the resin composition. In addition, it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and may also be 5 parts by mass or less. By setting the content of the allyl-substituted nadic acid imide compound to below the above upper limit, there is a tendency for the moldability of the resin composition and the peel strength of the obtained cured product to be further improved.

[0243] The resin composition of the present embodiment may contain only one kind of allyl-substituted nadic acid imide compound, or may contain two or more kinds. When containing two or more kinds, it is preferable that the total amount is within the above range.

[0244] The resin composition in the present embodiment may be configured to contain substantially no allyl-substituted nadic acid imide compound. Substantially containing no allyl-substituted nadic acid imide compound means that the content of the allyl-substituted nadic acid imide compound is less than 0.1 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0245] <<<Allyl compounds with glycoluril structure>>>

[0246] The allyl compound having a glycoluril structure is not particularly limited as long as it is a compound containing a glycoluril structure and two or more allyl groups, but a compound represented by formula (GU) is preferred.

[0247] Formula(GU)

[0248]

[0249] (In formula (GU), each R is independently a hydrogen atom or a substituent, and at least two of R are groups containing an allyl group.)

[0250] In the formula (GU), each R is independently preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms, preferably an alkenyl group having 2 to 5 carbon atoms, and preferably an allyl group.

[0251] In formula (GU), preferably 3 or 4 R are groups containing an allyl group, and more preferably 4 R are groups containing an allyl group.

[0252] Specific examples of the compound represented by formula (GU) include 1,3,4,6-tetraallyl glycoluril (a compound in which all Rs in formula (GU) are allyl groups).

[0253] In addition, commercially available compounds represented by formula (GU) may be used. Commercially available compounds are not particularly limited, and examples thereof include TA-G manufactured by SHIKOKU KASEI HOLDINGS CORPORATION.

[0254] The molecular weight of the allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)) is preferably 195 or more, more preferably 220 or more, further preferably 250 or more, and may be 300 or more, 400 or more. By setting the molecular weight of the allyl compound having a glycoluril structure to above the above lower limit, there is a tendency that the low dielectric properties and heat resistance of the obtained solidified material are further improved. In addition, the molecular weight of the allyl compound having a glycoluril structure (preferably a compound represented by formula (GU)) is preferably 1500 or less, more preferably 1000 or less, further preferably 800 or less, and may be 700 or less, 600 or less. By setting the molecular weight of the allyl compound having a glycoluril structure to below the above upper limit, there is a tendency that the low thermal expansion of the obtained solidified material is further improved.

[0255] In the case where the resin composition of the present embodiment includes an allyl compound (preferably a compound shown in formula (GU)) with a glycoluril structure, its content is preferably more than 1 mass part, more preferably more than 3 mass parts, more preferably more than 5 mass parts, or more than 10 mass parts relative to 100 mass parts of the resin solids in the resin composition. By setting the content of the allyl compound with glycoluril structure to more than the above-mentioned lower limit, there is a tendency that the low dielectric properties and heat resistance of the obtained solidified material are further improved. In addition, the upper limit of the content of the allyl compound (preferably a compound shown in formula (GU)) with glycoluril structure is preferably less than 40 mass parts, more preferably less than 30 mass parts, more preferably less than 25 mass parts, or less than 20 mass parts relative to 100 mass parts of the resin solids in the resin composition. By setting the content of the allyl compound with glycoluril structure to less than the above-mentioned upper limit, there is a tendency that the low thermal expansion of the obtained solidified material is further improved.

[0256] The resin composition of the present embodiment may contain only one kind of allyl compound having a glycoluril structure, or may contain two or more kinds. When containing two or more kinds, the total amount is preferably within the above range.

[0257] <<Polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds>>

[0258] The resin composition of the present embodiment may contain a polyphenylene ether compound having two or more carbon-carbon unsaturated double bonds.

[0259] The polyphenylene ether compound containing more than two carbon-carbon unsaturated double bonds is preferably a polyphenylene ether compound having more than two carbon-carbon unsaturated double bonds at the end, more preferably a polyphenylene ether compound having more than two groups selected from the group consisting of (meth) acryloyl, maleimide, (meth) allyl and vinyl benzyl at the end, and further preferably a polyphenylene ether compound having more than two groups selected from the group consisting of (meth) acryloyl, maleimide and vinyl benzyl. By using these polyphenylene ether compounds, there is a tendency to more effectively improve the low dielectric properties (low dielectric constant and / or low dielectric loss tangent) and low water absorption of printed circuit boards, etc.

[0260] The details of these are described below.

[0261] Examples of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds include compounds having a phenylene ether skeleton represented by the following formula (X1).

[0262]

[0263] (In formula (X1), R 24 , R 25 , R 26 and R 27 may be the same or different and represent an alkyl group, an aryl group, a halogen atom or a hydrogen atom having 6 or less carbon atoms.

[0264] The polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds may further contain a repeating unit represented by formula (X2) and / or a repeating unit represented by formula (X3).

[0265]

[0266] (In formula (X2), R 28 , R 29 , R 30 , R 34 and R 35 R may be the same or different and represent an alkyl group having 6 or less carbon atoms or a phenyl group. 31 , R 32 and R 33 They may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)

[0267]

[0268] (In formula (X3), R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 and R43 They may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A- is a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms. )

[0269] The polyphenylene ether compound containing more than two carbon-carbon unsaturated double bonds is preferably a modified polyphenylene ether compound (hereinafter, sometimes referred to as "modified polyphenylene ether compound (g)") in which a part or all of the terminal is functionalized by an ethylenically unsaturated group, more preferably a modified polyphenylene ether compound having two or more groups selected from the group consisting of (meth) acryloyl, maleimide, (meth) allyl and vinyl benzyl at the terminal, more preferably a modified polyphenylene ether compound having two or more groups selected from the group consisting of (meth) acryloyl, maleimide and vinyl benzyl at the terminal. By adopting such a modified polyphenylene ether compound (g), the dielectric loss tangent (Df) of the cured product of the resin composition can be further reduced, and low water absorption and metal foil peeling strength can be improved. These can be used 1 or in combination of 2 or more.

[0270] Examples of the modified polyphenylene ether compound (g) include polyphenylene ether compounds represented by formula (OP).

[0271]

[0272] (In formula (OP), X represents an aromatic group, -(YO) n1 - represents a polyphenylene ether structure, n1 represents an integer of 1 to 100, and n2 represents an integer of 1 to 4. Rx is a group represented by formula (Rx-1) or formula (Rx-2).

[0273]

[0274] (In formula (Rx-1) and formula (Rx-2), R 1 , R 2 and R 3 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group. * represents a bonding site with an oxygen atom. Mc each independently represents a hydrocarbon group having 1 to 12 carbon atoms. z represents an integer of 0 to 4. r represents an integer of 1 to 6.

[0275] When n1 and / or n2 are integers greater than or equal to 2, n1 structural units (YO) and / or n2 structural units may be the same or different.

[0276] In formula (Rx-1) and formula (Rx-2), R 1 , R 2 and R 3 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.

[0277] R 1 A hydrogen atom or an alkyl group is preferred, a hydrogen atom or a methyl group is more preferred, and a hydrogen atom is further preferred.

[0278] R 2 and R 3 Each independently is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.

[0279] As R 1 , R 2 and R 3 The carbon number of the alkyl, alkenyl or alkynyl group is preferably 5 or less, more preferably 3 or less.

[0280] r in the formula (Rx-1) represents an integer of 1 to 6, preferably an integer of 1 to 5, more preferably an integer of 1 to 4, further preferably an integer of 1 to 3, further preferably 1 or 2, and further preferably 1.

[0281] Mc in formula (Rx-1) each independently represents a hydrocarbon group having 1 to 12 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, further preferably a methyl group, ethyl group, isopropyl group, isobutyl group, tert-butyl group, pentyl group, octyl group or nonyl group, and even more preferably a methyl group, ethyl group, isopropyl group, isobutyl group or tert-butyl group.

[0282] In the formula (Rx-1), z represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, and even more preferably 0.

[0283] A specific example of the group represented by the formula (Rx-1) is a vinylbenzyl group, and a specific example of the group represented by the formula (Rx-2) is a (meth)acryloyl group.

[0284] As the modified polyphenylene ether compound (g), a compound represented by the formula (OP-1) is preferred.

[0285]

[0286] (In formula (OP-1), X represents an aromatic group, -(YO)n2- represents a polyphenylene ether structure, and R 1 , R 2 and R 3 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, n1 represents an integer of 1 to 6, n2 represents an integer of 1 to 100, and n3 represents an integer of 1 to 4.)

[0287] When n2 and / or n3 are integers greater than 2, n2 structural units (YO) and / or n3 structural units may be the same or different. n3 is preferably 2 or greater, more preferably 2.

[0288] The modified polyphenylene ether compound (g) in the present embodiment is preferably a compound represented by formula (OP-2).

[0289]

[0290] Here, -(OXO)- is preferably represented by Formula (OP-3) and / or Formula (OP-4).

[0291]

[0292] (In formula (OP-3), R 4 , R 5 , R 6 , R 10 and R 11 R may be the same or different and is an alkyl group having 6 or less carbon atoms or a phenyl group. 7 , R 8 and R 9 They may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)

[0293]

[0294] (In formula (OP-4), R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 They may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A- is a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

[0295] In addition, -(YO)- is preferably represented by formula (OP-5):

[0296]

[0297] (In formula (OP-5), R 20 , R 21 R may be the same or different and is an alkyl group having 6 or less carbon atoms or a phenyl group. 22 , R 23 may be the same or different and be a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. ) In particular, by making R 20 and R 21 Each independently being a group having one or more methyl and / or cyclohexyl groups, the rigidity of the obtained resin molecule becomes higher, and the mobility of molecules with high rigidity is lower than that of molecules with low rigidity, the relaxation time during dielectric relaxation becomes longer, and the low dielectric properties (Dk and / or Df) are improved, so it is preferred.

[0298] An example of formula (OP-5) has the following structure.

[0299]

[0300] Regarding the polyphenylene compound having the above structure, with reference to the description in Japanese Unexamined Patent Application Publication No. 2019-194312, this content can be incorporated into this specification.

[0301] In formula (OP-2), a and b each independently represent an integer from 0 to 100, and at least one of a and b is an integer from 1 to 100. a and b are each independently preferably an integer from 0 to 50, more preferably an integer from 1 to 30, and preferably an integer from 1 to 10. When a and / or b is an integer of 2 or more, two or more -(Y-O)- groups can be arranged in one structure independently, or can be arranged in blocks or randomly in two or more structures.

[0302] In addition, when a compound represented by formula (OP-2) is included in multiple types, the average value of a is preferably 1 < a < 10, and the average value of b is preferably 1 < b < 10.

[0303] As -A- in formula (OP-4), for example, divalent organic groups such as methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 1,4-phenylenebis(1-methylethylidene), 1,3-phenylenebis(1-methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, 1-phenylethylidene, etc. can be cited, but are not limited to these.

[0304] In the compound represented by the above formula (OP-2), preferably R 4 , R 5 , R 6 , R 10 , R 11 , R 20 and R 21 are alkyl groups having 3 or fewer carbon atoms, and R 7 , R 8 , R 9 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 22 , and R 23The polyphenylene ether compound is a hydrogen atom or an alkyl group with a carbon number of 3 or less, and it is particularly preferred that -(OXO)- represented by formula (OP-3) or formula (OP-4) is formula (OP-9), formula (OP-10), and / or formula (OP-11), and -(YO)- represented by formula (OP-5) is formula (OP-12) or formula (OP-13). When a and / or b is an integer greater than 2, two or more -(YO)- are each independently a structure in which two or more of formula (OP-12) and / or formula (OP-13) are arranged, or a structure in which formula (OP-12) and formula (OP-13) are arranged in blocks or randomly.

[0305]

[0306] (In formula (OP-10), R 44 , R 45 , R 46 and R 47 They may be the same or different and are hydrogen atoms or methyl groups. -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

[0307] As specific examples of -B-, the same ones as the specific examples of -A- in formula (OP-4) can be given.

[0308]

[0309] (In formula (OP-11), -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)

[0310] As specific examples of -B-, the same ones as the specific examples of -A- in formula (OP-4) can be given.

[0311]

[0312]

[0313] The polyphenylene ether compound used in the present embodiment is more preferably a compound represented by formula (OP-14) and / or a compound represented by formula (OP-15), and more preferably a compound represented by formula (OP-15).

[0314]

[0315] (In formula (OP-14), a and b each independently represent an integer of 0 to 100, and at least one of a and b is an integer of 1 to 100.)

[0316] a and b in formula (OP-14) have the same meanings as a and b in formula (OP-2) independently, and the preferred ranges are also the same.

[0317]

[0318] (In formula (OP-15), a and b each independently represent an integer of 0 to 100, and at least one of a and b is an integer of 1 to 100.)

[0319] a and b in formula (OP-15) have the same meanings as a and b in formula (OP-2) independently, and the preferred ranges are also the same.

[0320] The polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds can be manufactured by a known method, or a commercially available product can be used. As a commercially available product, for example, as a modified polyphenylene ether compound having a methacryloyl group at the end, "SA9000" manufactured by SABIC Innovative Plastics can be cited. In addition, as a modified polyphenylene ether compound having a vinyl benzyl group at the end, "OPE-2St1200" and "OPE-2st2200" manufactured by Mitsubishi Gas Chemical Co., Ltd. can be cited. In addition, as a modified polyphenylene ether compound having a vinyl benzyl group at the end, a polyphenylene ether compound having a hydroxyl group at the end, such as "SA90" manufactured by SABIC Innovative Plastics, modified to a vinyl benzyl group with vinyl benzyl chloride or the like can also be used.

[0321] In addition, details of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds can be referred to the descriptions in Japanese Patent Application Publication No. 2006-028111, Japanese Patent Application Publication No. 2018-131519, WO2019-138992, and WO2022-054303, and these contents are incorporated into this specification.

[0322] The polyphenylene ether compound (preferably a modified polyphenylene ether compound (g)) containing two or more carbon-carbon unsaturated double bonds preferably has a polystyrene-equivalent number average molecular weight (details are based on the method described in the examples described later) of 500 or more and 3,000 or less as measured by the GPC (gel permeation chromatography) method. By setting the number average molecular weight to be 500 or more, there is a tendency to further suppress the stickiness of the resin composition of the present embodiment when it is in the form of a coating film. By setting the number average molecular weight to be 3,000 or less, there is a tendency to further improve the solubility in a solvent.

[0323] In addition, the polyphenylene ether compound (preferably modified polyphenylene ether compound (g)) containing two or more carbon-carbon unsaturated double bonds has a polystyrene-converted weight average molecular weight based on GPC (details are based on the method described in the embodiments described later) of preferably 800 or more and 10,000 or less, and more preferably 800 or more and 5,000 or less. By setting it to above the lower limit, there is a tendency that the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition become lower, and by setting it to below the upper limit, there is a tendency that the solubility, low viscosity and moldability of the resin composition in a solvent when preparing a varnish described later, etc.

[0324] In addition, in the case of modified polyphenylene ether compound (g), the carbon-carbon unsaturated double bond equivalent of the terminal is preferably 400 to 5000 g per 1 carbon-carbon unsaturated double bond, more preferably 400 to 2500 g. By being set to above the above lower limit, the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to become lower. By being set to below the above upper limit, the solubility, low viscosity and formability of the resin composition in the solvent tend to be further improved.

[0325] In the case where the resin composition of the present embodiment includes a polyphenylene ether compound containing more than 2 carbon-carbon unsaturated double bonds, the lower limit of the content of the polyphenylene ether compound containing more than 2 carbon-carbon unsaturated double bonds is preferably more than 1 mass part, more preferably more than 5 mass parts, more preferably more than 10 mass parts, more preferably more than 15 mass parts, and more preferably more than 20 mass parts relative to 100 mass parts of resin solids in the resin composition.By being set to more than the aforementioned lower limit, there is a tendency that the low water absorption and low dielectric properties (Dk and / or Df) of the cured product obtained are further improved.In addition, the upper limit of the content of the polyphenylene ether compound containing more than 2 carbon-carbon unsaturated double bonds is preferably less than 70 mass parts, more preferably less than 60 mass parts, more preferably less than 50 mass parts, more preferably less than 40 mass parts, more preferably less than 35 mass parts, and further more preferably less than 30 mass parts relative to 100 mass parts of resin solids in the resin composition.By being set to less than the aforementioned upper limit, there is a tendency that the heat resistance and chemical resistance of the cured product obtained are further improved.

[0326] The resin composition in the present embodiment may contain only one polyphenylene ether compound having two or more carbon-carbon unsaturated double bonds, or may contain two or more. When containing two or more, the total amount is preferably within the above range.

[0327] <<Polymer (V) having a structural unit represented by formula (V)>>

[0328] The resin composition of this embodiment may include a polymer (V) having a structural unit represented by formula (V). By including a polymer (V) having a structural unit represented by formula (V), a resin composition having excellent low dielectric properties (low dielectric constant and / or low dielectric loss tangent) can be obtained.

[0329]

[0330] (In formula (V), Ar represents an aromatic hydrocarbon linking group. * represents a bonding position.)

[0331] The aromatic hydrocarbon linking group may be a group consisting only of an aromatic hydrocarbon optionally having a substituent, or may be a group consisting of a combination of an aromatic hydrocarbon optionally having a substituent and other linking groups. The aromatic hydrocarbon linking group is preferably a group consisting only of an aromatic hydrocarbon optionally having a substituent. It should be noted that the substituent optionally possessed by the aromatic hydrocarbon may include a substituent Z (for example, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a halogen atom, etc.). In addition, the above-mentioned aromatic hydrocarbon preferably has no substituent.

[0332] The aromatic hydrocarbon linking group is usually a divalent linking group.

[0333] Specific examples of the aromatic hydrocarbon linking group include phenylene, naphthalene diyl, anthracene diyl, phenanthrene diyl, biphenyl diyl, and fluorene diyl, which may have a substituent, and phenylene which may have a substituent is preferred. The substituent may be exemplified by the substituent Z mentioned above, and the phenylene group preferably has no substituent.

[0334] The structural unit represented by formula (V) more preferably includes at least one of the structural unit represented by the following formula (V1), the structural unit represented by the following formula (V2), and the structural unit represented by the following formula (V3). It should be noted that the * in the following formula represents a bonding position. In addition, the structural units represented by formulas (V1) to (V3) are sometimes collectively referred to as "structural units (a)".

[0335]

[0336] In formulas (V1) to (V3), L 1 It is an aromatic hydrocarbon linking group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms). Specifically, it includes phenylene, naphthalene diyl, anthracene diyl, phenanthrene diyl, biphenyl diyl, and fluorene diyl groups, which may have a substituent, and phenylene groups which may have a substituent are preferred. The substituent may be exemplified by the substituent Z mentioned above, and the above-mentioned phenylene groups preferably have no substituent.

[0337] As the compound forming the structural unit (a), a divinyl aromatic compound is preferably used, for example, divinylbenzene, bis(1-methylvinyl)benzene, divinylnaphthalene, divinylanthracene, divinylbiphenyl, divinylphenanthrene, etc. can be mentioned. Among them, divinylbenzene is particularly preferred. These divinyl aromatic compounds can be used alone, and two or more can be used as needed.

[0338] The polymer (V) having the structural unit represented by the formula (V) may be a homopolymer of the structural unit (a) as described above, or may be a copolymer with a structural unit derived from another monomer.

[0339] When the polymer (V) having the structural unit shown in formula (V) is a copolymer, the copolymerization preferably contains structural unit (a) of 3 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, and may be 15 mol% or more. As the upper limit, it is preferably 90 mol% or less, more preferably 85 mol% or less, further preferably 80 mol% or less, more preferably 70 mol% or less, further preferably 60 mol% or less, further more preferably 50 mol% or less, further preferably 40 mol% or less, particularly preferably 30 mol% or less, and further may be 25 mol% or less, or 20 mol% or less.

[0340] As the structural unit derived from other monomers, there can be exemplified a structural unit (b) derived from an aromatic compound having one vinyl group (monovinyl aromatic compound).

[0341] The structural unit (b) derived from a monovinyl aromatic compound is preferably a structural unit represented by the following formula (V4).

[0342]

[0343] In formula (V4), L 2 is an aromatic hydrocarbon linking group, and specific examples of preferred groups include the above-mentioned L 1 Example.

[0344] R V1 R is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (preferably an alkyl group). V1 When it is a hydrocarbon group, the carbon number is preferably 1 to 6, more preferably 1 to 3. V1 and L 2 It may optionally have the substituent Z described above.

[0345] When the polymer (V) having a structural unit represented by formula (V) is a copolymer containing a structural unit (b) derived from a monovinyl aromatic compound, examples of monovinyl aromatic compounds include vinyl aromatic compounds such as styrene, vinyl naphthalene, and vinyl biphenyl; ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, ortho-p-dimethylstyrene, ortho-ethylvinylbenzene, meta-ethylvinylbenzene, para-ethylvinylbenzene, methylvinylbiphenyl, and ethylvinylbiphenyl, etc., which are substituted with a core alkyl group. The monovinyl aromatic compounds exemplified herein may optionally and appropriately have the above-mentioned substituent Z. In addition, these monovinyl aromatic compounds may be used alone or in combination of two or more.

[0346] When the polymer (V) having the structural unit shown in formula (V) is a copolymer comprising the structural unit (b), the copolymerization ratio of the structural unit (b) is preferably 10 mol% or more, more preferably 15 mol% or more, and furthermore, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, or 75 mol% or more. As the upper limit, it is preferably 98 mol% or less, more preferably 90 mol% or less, and more preferably 85 mol% or less.

[0347] The polymer (V) having the structural unit shown in formula (V) may have other structural units other than structural units (a) and structural units (b). As other structural units, for example, structural units (c) derived from cycloolefin compounds can be cited. As cycloolefin compounds, hydrocarbons having double bonds in the ring structure can be cited. Specifically, in addition to monocyclic cyclic olefins such as cyclobutene, cyclopentene, cyclohexene, and cyclooctene, compounds having a norbornene ring structure such as norbornene, dicyclopentadiene, and aromatic rings such as indene and acenaphthene can also be cited. Cycloolefin compounds formed by condensation of aromatic rings, etc. As examples of norbornene compounds, compounds described in paragraphs 0037 to 0043 of Japanese Patent Publication No. 2018-039995 can be cited, and their contents are introduced into this specification. It should be noted that the cycloolefin compounds exemplified here can also have the above-mentioned substituent Z.

[0348] When the polymer (V) having the structural unit represented by formula (V) is a copolymer containing the structural unit (c), the copolymerization ratio of the structural unit (c) is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more. As the upper limit, it is preferably 90 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less, and can be 50 mol% or less, or can be 30 mol% or less.

[0349] The polymer (V) having the structural unit shown in formula (V) may further include structural units (d) derived from different polymerizable compounds (hereinafter also referred to as other polymerizable compounds). As other polymerizable compounds (monomers), for example, compounds containing three vinyl groups may be mentioned. Specifically, 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-trivinylcyclohexane may be mentioned. Alternatively, ethylene glycol diacrylate, butadiene, etc. may be mentioned. The copolymerization ratio (d) of the structural unit (d) derived from other polymerizable compounds is preferably 30 mol% or less, more preferably 20 mol% or less, and further preferably 10 mol% or less.

[0350] As an embodiment of the polymer (V) having a structural unit represented by formula (V), a polymer having structural unit (a) as an essential component and containing at least one of structural units (b) to (d) can be exemplified. Furthermore, an embodiment in which the total of structural units (a) to (d) accounts for 95 mol% or more, and further 98 mol% or more of all structural units can be exemplified.

[0351] As another embodiment of the polymer (V) having a structural unit represented by formula (V), it is preferred that the structural unit (a) is essential and that the structural units containing aromatic rings in all structural units except the terminal ones account for 90 mol % or more, more preferably 95 mol % or more, and may also be 100 mol %.

[0352] When calculating the mol % relative to all structural units, one structural unit is derived from one molecule of a monomer (e.g., a divinyl aromatic compound, a monovinyl aromatic compound, etc.) used to produce the polymer (V) having the structural unit represented by formula (V).

[0353] The manufacturing method of the polymer (V) having the structural unit shown in formula (V) is not particularly limited, and conventional methods can be used, for example, the raw material containing the divinyl aromatic compound (as required, the monovinyl aromatic compound, cycloolefin compound, etc. are coexisted) can be polymerized in the presence of a Lewis acid catalyst. As the Lewis acid catalyst, metal fluorides such as boron trifluoride or their complexes can be used.

[0354] The structure of the chain end of the polymer (V) having the structural unit represented by formula (V) is not particularly limited, but for the group derived from the above-mentioned divinyl aromatic compound, the structure of the following formula (E1) can be used. 1 The same as defined in the above formula (V1). * indicates a bonding position.

[0355] *-CH=CH-L 1 -CH=CH2(E1)

[0356] When the group derived from the monovinyl aromatic compound is a chain end, a structure of the following formula (E2) can be used. 2 and R V1 Each has the same meaning as defined in the above formula (V4). * represents a bonding position.

[0357] *-CH=CH-L 2 -R V1 (E2)

[0358] The molecular weight of the polymer (V) having the structural unit represented by the formula (V) is preferably 300 or more, more preferably 500 or more, further preferably 1,000 or more, and further preferably 1,500 or more in terms of number average molecular weight Mn. The upper limit is preferably 130,000 or less, more preferably 120,000 or less, further preferably 110,000 or less, and further preferably 100,000 or less.

[0359] The molecular weight of the polymer (V) with the structural unit shown in formula (V) is preferably 3,000 or more, more preferably 5,000 or more, and further preferably 10,000 or more in terms of weight average molecular weight Mw. By being set to above the aforementioned lower limit, the cured product of the resin composition can effectively exert the excellent low dielectric properties, particularly Df, and low dielectric properties after moisture absorption of the polymer (V) with the structural unit shown in formula (V). As the upper limit, it is preferably 130,000 or less, more preferably 100,000 or less, further preferably 80,000 or less, and more preferably 50,000 or less. By being set to below the aforementioned upper limit, there is a tendency that it is not easy to cause poor embedding when prepreg or resin sheet is laminated on the circuit forming substrate.

[0360] The monodispersity (Mw / Mn) represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn is preferably 100 or less, more preferably 50 or less, and even more preferably 20 or less. The lower limit is practically 1.1 or more, preferably 5 or more, more preferably 7 or more, and even more preferably 10 or more.

[0361] The above-mentioned Mw and Mn are measured according to the description in Examples described later.

[0362] When the resin composition of the present embodiment contains two or more polymers (V) having a structural unit represented by formula (V), it is preferred that Mw, Mn, and Mw / Mn of the mixture satisfy the above ranges.

[0363] The equivalent of the vinyl group of the polymer (V) having the structural unit shown in formula (V) is preferably 200 g / eq. or more, more preferably 230 g / eq. or more, and further preferably 250 g / eq. or more. In addition, the equivalent of the vinyl group is preferably 1200 g / eq. or less, more preferably 1000 g / eq. or less, and further can be 800 g / eq. or less, 600 g / eq. or less, 400 g / eq. or less, or 300 g / eq. or less. By setting it to above the above lower limit, there is a tendency that the storage stability of the resin composition is improved and the fluidity of the resin composition is improved. Therefore, it is not easy to produce pores when the formability is improved and the prepreg is formed, and there is a tendency that a printed circuit board with higher reliability can be obtained. On the other hand, by setting it to below the above upper limit, there is a tendency that the heat resistance of the obtained cured product is improved.

[0364] For the polymer (V) having a structural unit represented by formula (V) in the present specification, reference can be made to the compounds and their synthesis reaction conditions described in paragraphs 0029 to 0058 of International Publication No. 2017 / 115813, the compounds and their synthesis reaction conditions described in paragraphs 0013 to 0058 of JP-A-2018-039995, the compounds and their synthesis reaction conditions described in paragraphs 0008 to 0043 of JP-A-2018-168347, and the like. The compounds and their synthesis reaction conditions, etc., the compounds and their synthesis reaction conditions, etc. described in paragraphs 0014 to 0042 of Japanese Patent Application Laid-Open No. 2006-070136, the compounds and their synthesis reaction conditions, etc. described in paragraphs 0014 to 0061 of Japanese Patent Application Laid-Open No. 2006-089683, and the compounds and their synthesis reaction conditions, etc., described in paragraphs 0008 to 0036 of Japanese Patent Application Laid-Open No. 2008-248001, are incorporated into the present specification.

[0365] In the resin composition of the present embodiment, the content of the polymer (V) having the structural unit represented by the formula (V) is preferably 1 to 70 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0366] The lower limit of the content of the polymer (V) with the structural unit shown in formula (V) is more preferably 5 mass parts or more, more preferably 10 mass parts or more, more preferably 15 mass parts or more, can be 20 mass parts or more, or can be 25 mass parts or more. By setting the content of the polymer (V) with the structural unit shown in formula (V) to above the aforementioned lower limit, low dielectric properties, particularly low relative dielectric constant, can be effectively achieved. On the other hand, the upper limit of the content of the polymer (V) with the structural unit shown in formula (V) is more preferably 60 mass parts or less, more preferably 50 mass parts or less, more preferably 40 mass parts or less, or can be 35 mass parts or less, or 30 mass parts or less relative to 100 mass parts of the resin solids in the resin composition. By setting the content of the polymer (V) with the structural unit shown in formula (V) to below the aforementioned upper limit, the metal foil peel strength of the cured product obtained can be effectively improved.

[0367] The polymer (V) having a structural unit represented by formula (V) may be contained in the resin composition alone or in combination of two or more. When two or more polymers are contained, the total amount is preferably within the above range.

[0368] In addition, the resin composition in the present embodiment may also be composed of a polymer (V) substantially free of the structural unit represented by formula (V). Substantially free means that the content of the polymer (V) having the structural unit represented by formula (V) is less than 0.1 parts by mass, preferably less than 0.01 parts by mass, and further may be less than 0.001 parts by mass relative to 100 parts by mass of the resin solids in the resin composition.

[0369] <<Cyanate Ester Compounds>>

[0370] The resin composition of this embodiment preferably contains a cyanate compound. In this embodiment, even if a thermosetting compound having a particularly low Df and being easily affected by an ultraviolet absorber or a non-metallic organic pigment is used, a decrease in Df can be effectively suppressed.

[0371] The cyanate compound is not particularly limited as long as it contains one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, further preferably 2 or 3, further more preferably 2) cyanate groups (cyano groups) in one molecule, and a wide range of compounds commonly used in the field of printed circuit boards can be used. In addition, the cyanate compound is preferably a compound in which the cyanate group is directly bonded to an aromatic skeleton (aromatic ring).

[0372] As cyanate compound, for example, at least one selected from the group consisting of phenol novolac type cyanate compound, naphthol aralkyl type cyanate compound (naphthol aralkyl type cyanate), naphthol ether type cyanate compound, biphenyl aralkyl type cyanate compound, xylene resin type cyanate compound, trisphenol methane type cyanate compound, adamantane skeleton type cyanate compound, bisphenol M type cyanate compound, bisphenol A type cyanate compound and diallyl bisphenol A type cyanate compound can be cited. Among these, from the viewpoint of further improving the low water absorption of the obtained solidified material, at least one selected from the group consisting of phenol novolac type cyanate compound, naphthol aralkyl type cyanate compound, naphthol ether type cyanate compound, xylene resin type cyanate compound, bisphenol M type cyanate compound, bisphenol A type cyanate compound and diallyl bisphenol A type cyanate compound is preferably used, more preferably naphthol aralkyl type cyanate compound. These cyanate compounds can be prepared by known methods, and commercially available products can also be used. It should be noted that the cyanate ester compounds having a naphthol aralkyl skeleton, a naphthyl ether skeleton, a xylene skeleton, a triphenol methane skeleton or an adamantane skeleton have a large functional group equivalent number and a small number of unreacted cyanate groups, so the cured product of the resin composition using them tends to have a lower water absorption. In addition, mainly because they have an aromatic skeleton or an adamantane skeleton, the plating adhesion tends to be further improved.

[0373] The resin composition of the present embodiment preferably includes cyanate compounds within the scope of not damaging the effect of the present invention. In the case where the resin composition of the present embodiment includes cyanate compounds, the lower limit of its content is preferably more than 0.1 mass parts, more preferably more than 2 mass parts, more preferably more than 5 mass parts, more preferably more than 10 mass parts relative to 100 mass parts of the resin solids in the resin composition. By making the content of cyanate compounds more than 0.1 mass parts, there is a tendency for the heat resistance, combustion resistance, chemical resistance, low relative dielectric constant, low dielectric loss tangent, and insulation of the cured product obtained to improve. For the upper limit of the content of cyanate compounds, in the case where the resin composition of the present embodiment includes cyanate compounds, relative to 100 mass parts of the resin solids in the resin composition, preferably less than 70 mass parts, more preferably less than 50 mass parts, further preferably less than 40 mass parts, more preferably less than 30 mass parts, further more preferably less than 20 mass parts.

[0374] The resin composition in the present embodiment may contain only one cyanate compound or two or more cyanate compounds. When containing two or more cyanate compounds, the total amount is preferably within the above range.

[0375] The content (total amount) of the thermosetting compound in the resin composition of the present embodiment is preferably more than 1 mass part, more preferably more than 5 mass parts, further preferably more than 10 mass parts, more preferably more than 20 mass parts, and further more preferably more than 30 mass parts relative to 100 mass parts of resin solid components. By being set to more than the aforementioned lower limit, there is a tendency to further improve heat resistance, plating adhesion, low thermal expansion, etc. In addition, the upper limit of the content of the thermosetting compound is preferably less than 100 mass parts relative to 100 mass parts of resin solid components, more preferably less than 90 mass parts, more preferably less than 80 mass parts, or less than 70 mass parts.

[0376] The resin composition of the present embodiment may contain only one thermosetting compound or two or more thereof. When containing two or more thereof, the total amount is preferably within the above range.

[0377] <Ultraviolet light absorber>

[0378] The resin composition of the present embodiment preferably contains an ultraviolet absorber. By containing an ultraviolet absorber, the transmission of i-rays (wavelength 365 nm) and h-rays (wavelength 405 nm) can be effectively suppressed.

[0379] As an example of the ultraviolet absorber used in the present embodiment, there is a ultraviolet absorber having a maximum absorption (peak) in the wavelength region of 365nm±20nm, and a half-value width of the maximum absorption (peak) of 50nm or more. By using an ultraviolet absorber with a wide half-value width, there is a tendency to effectively suppress the absorption of h-rays (wavelength 405nm), which is preferred.

[0380] The type of ultraviolet absorber is not particularly limited. Examples of the ultraviolet absorber include benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, triazine ultraviolet absorbers, cyclic imino ester ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, conjugated diene ultraviolet absorbers, methyl dibenzoyl ultraviolet absorbers, coumarin ultraviolet absorbers, salicylate ultraviolet absorbers, acrylonitrile ultraviolet absorbers and benzodithiazole ultraviolet absorbers, preferably coumarin ultraviolet absorbers.

[0381] Examples of the benzotriazole-based ultraviolet absorber include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, and 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole. tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octyloxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazine-4-one), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidemethyl)-5-methylphenyl]benzotriazole, etc.

[0382] Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonyloxytrihydride benzophenone, and 2-hydroxy-4-methoxy-5-sulfoxytrihydride benzophenone. reitobenzophenone), 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc.

[0383] Examples of the triazine ultraviolet absorber include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol and 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-[(octyl)oxy]-phenol.

[0384] Examples of the cyclic iminoester-based ultraviolet absorbers include 2,2'-bis(3,1-benzoxazin-4-one), 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-m-phenylenebis(3,1-benzoxazin-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2,6-naphthalene)bis(3 ,1-benzoxazine-4-one), 2,2'-(1,5-naphthalene)bis(3,1-benzoxazine-4-one), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazine-4-one), 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazine-4-one) and 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazine-4-one).

[0385] Examples of the cyanoacrylate-based ultraviolet absorber include 1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

[0386] Examples of the coumarin-based ultraviolet absorber include 7-(diethylamino)coumarin, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), ketocoumarin, and carbonylbiscoumarin.

[0387] In addition, the descriptions in paragraphs 0065 to 0077 of Japanese Patent Application Laid-Open No. 2022-000700 and the descriptions in paragraphs 0019 to 0032 of Japanese Patent Application Laid-Open No. 2020-189783 can be referred to, and the contents thereof are incorporated into the present specification.

[0388] In the case where the resin combination of the present embodiment includes an ultraviolet light absorber, its content is preferably more than 0 mass parts relative to 100 mass parts of resin solids, more preferably more than 0.1 mass parts, more preferably more than 0.2 mass parts, more preferably more than 0.3 mass parts, and more preferably more than 0.4 mass parts. By being set to more than the aforementioned lower limit, there is the transmittance that can further reduce i-rays (wavelength 365nm) and then h-rays (wavelength 405nm), and the tendency of back exposure can be more effectively suppressed. In addition, the content of ultraviolet light absorber is preferably less than 3.0 mass parts relative to 100 mass parts of resin solids, more preferably less than 2.5 mass parts, more preferably less than 2.0 mass parts, more preferably less than 1.5 mass parts, more preferably less than 1.0 mass parts, and more preferably less than 0.8 mass parts. By being set to less than the aforementioned upper limit, there is the tendency that can further reduce the dielectric loss tangent of the cured product obtained.

[0389] The resin composition of the present embodiment may contain only one type of ultraviolet absorber, or may contain two or more types. When containing two or more types, it is preferable that the total amount is within the above range.

[0390] <Non-metallic organic pigments>

[0391] The resin composition of the present embodiment preferably contains a non-metallic organic dye. By containing a non-metallic organic dye, it is possible to effectively suppress the transmission of light mainly of g-rays (wavelength 436 nm).

[0392] The non-metallic organic coloring matter used in the present embodiment may be a dye or a pigment, and preferably includes a dye.

[0393] The non-metallic organic dye used in the present embodiment is preferably a dye having a maximum absorption (peak) in the wavelength range of 400 to 500 nm, and more preferably a dye having a maximum absorption (peak) in the wavelength range of 436 nm±30.

[0394] In addition, an example of the non-metallic organic pigment used in the present embodiment can enumerate the pigment that has maximum absorption (peak) and the half-value width of aforementioned maximum absorption (peak) is more than 50nm in the wavelength region of wavelength 436nm ± 30nm.By using the wide non-metallic organic pigment of half-value width like this, the tendency of the absorption that also can effectively suppress h-ray (wavelength 405nm) is arranged, is preferred.

[0395] The color of the non-metallic organic dye is not particularly limited, but is preferably black in appearance to human vision.

[0396] As non-metallic organic pigment, can exemplify cyanine pigment, triphenylmethane pigment, anthraquinone pigment, xanthene pigment, azo pigment, benzopyran pigment, indigo pigment, quinoline pigment, purple cyclic ketone (perinone) pigment and perylene pigment, preferably anthraquinone pigment and / or purple cyclic ketone pigment.The details of these non-metallic organic pigments can be with reference to the record of Japanese Unexamined Patent Publication No. 02-089683, the record of paragraph 0031 of Japanese Unexamined Patent Publication No. 2011-102384, these contents are incorporated in this specification sheets.

[0397] When the resin combination of the present embodiment comprises non-metallic organic pigment, its content preferably exceeds 0 mass parts, more preferably more than 0.2 mass parts, more preferably more than 0.3 mass parts, more preferably more than 0.4 mass parts, further more preferably more than 0.45 mass parts relative to resin solids 100 mass parts.By being set to more than the aforementioned lower limit, there is the transmittance that can further reduce g ray (wavelength 436nm) and then h ray (wavelength 405nm), can more effectively suppress the tendency of back exposure.In addition, the content of non-metallic organic pigment is preferably below 2.0 mass parts, more preferably below 1.75 mass parts, more preferably below 1.5 mass parts, more preferably below 1.25 mass parts, further more preferably below 1.0 mass parts relative to resin solids 100 mass parts.By being set to below the aforementioned upper limit, there is the tendency that can further reduce the dielectric loss tangent of the cured product obtained and the glass transition temperature further improves.

[0398] The resin composition of the present embodiment may contain only one non-metallic organic dye, or may contain two or more. When containing two or more, the total amount is preferably within the above range.

[0399] And then, in the present embodiment, the mass ratio (ultraviolet light absorber / non-metallic organic pigment) of ultraviolet light absorber and non-metallic organic pigment is preferably more than 0.15, in addition, is preferably below 4.0.By being set to such ratio, the transmittance of g ray (wavelength 436nm), h ray (wavelength 405nm) and i ray (wavelength 365nm) can be more effectively reduced, back exposure can be more effectively suppressed.Particularly, ultraviolet light absorber and non-metallic organic pigment have the tendency that the second order glass transition temperature of the cured product obtained by resin combination is reduced, and in the present embodiment, by using ultraviolet light absorber and non-metallic organic pigment in combination, the content of these compositions in the resin combination can be reduced relatively, the reduction of second order glass transition temperature can be effectively suppressed.

[0400] The mass ratio (ultraviolet light absorber / non-metallic organic pigment) of ultraviolet light absorber and non-metallic organic pigment is more preferably more than 0.2, further preferably more than 0.3, also can be more than 0.4.In addition, the mass ratio (ultraviolet light absorber / non-metallic organic pigment) of ultraviolet light absorber and non-metallic organic pigment is more preferably below 3.0, further preferably below 1.5, more preferably below 1.3, further more preferably below 1.2, and then more preferably below 1.1.

[0401] In the case where the resin combination of the present embodiment includes ultraviolet light absorber and non-metallic organic pigment, relative to 100 mass parts of resin solids, the total content of ultraviolet light absorber and non-metallic organic pigment preferably exceeds 0 mass parts, more preferably more than 0.2 mass parts, more preferably more than 0.4 mass parts, more preferably more than 0.6 mass parts, further more preferably more than 0.8 mass parts.By being set to more than the aforementioned lower limit, there is the transmittance that can further reduce g-ray (wavelength 436nm), h-ray (wavelength 405nm) and i-ray (wavelength 365nm), the tendency that can further suppress back exposure.In addition, relative to 100 mass parts of resin solids, the total content of ultraviolet light absorber and non-metallic organic pigment is preferably below 4.5 mass parts, more preferably below 4.0 mass parts, more preferably below 3.0 mass parts, more preferably below 2.0 mass parts, further more preferably below 1.75 mass parts.By being set to below the aforementioned upper limit, there is the tendency that can further reduce the dielectric loss tangent of the cured product obtained, and the glass transition temperature further improves.

[0402] The resin combination of the present embodiment can adopt the formation that does not contain carbon black in fact, and then does not contain conductive material in fact.Do not contain carbon black in fact, and then do not contain conductive material in fact, refer to, the content of carbon black (and then conductive material) is less than 10 mass % of the content of the non-metallic organic pigment included in the resin combination, preferably below 5 mass %, more preferably below 1 mass %, further preferably below 0.1 mass %.By being set to such formation, the insulating property of the resin combination and / or cured product obtained can be further improved.

[0403] <Filling material>

[0404] The resin composition of the present embodiment preferably contains a filler. By containing a filler, the dielectric properties (low dielectric constant, low dielectric loss tangent, etc.), flame retardancy, low thermal expansion, and other physical properties of the resin composition and its cured product can be further improved.

[0405] In addition, the filling material used in the present embodiment is more preferably excellent in low dielectric properties (low Dk and / or low Df). For example, the relative dielectric constant (Dk) of the filling material used in the present embodiment at a frequency of 10 GHz measured by the cavity resonator perturbation method is preferably 8.0 or less, more preferably 6.0 or less, and further preferably 4.0 or less. In addition, the lower limit of the relative dielectric constant is, for example, 2.0 or more, which is practical. In addition, the dielectric loss tangent (Df) of the filling material used in the present embodiment at a frequency of 10 GHz measured by the cavity resonator perturbation method is preferably 0.05 or less, and more preferably 0.01 or less. In addition, the lower limit of the dielectric loss tangent is, for example, 0.0001 or more, which is practical.

[0406] The filler used in the present embodiment is not particularly limited in type, and the materials commonly used in the present technical field can be appropriately used. Specifically, natural silica, fused silica, synthetic silica, amorphous silica, aerosil, hollow silica and other silicas, aluminum oxide, white carbon, titanium white, titanium oxide, zinc oxide, magnesium oxide, zirconium oxide and other metal oxides, zinc borate, zinc stannate, forsterite, barium titanate, strontium titanate, calcium titanate and other composite oxides, boron nitride, condensed boron nitride, silicon nitride, aluminum nitride and other nitrides, aluminum hydroxide, aluminum hydroxide heat-treated product (aluminum hydroxide is heat-treated to reduce a portion of crystal water), boehmite, magnesium hydroxide and other metal hydroxides (including hydrates), molybdenum oxide, zinc molybdate and other molybdenum compounds, barium sulfate, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE- Inorganic fillers (inorganic fillers) such as glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, short glass fibers (including glass fine powders such as E-glass, T-glass, D-glass, S-glass, and Q-glass), hollow glass, and spherical glass, and organic fillers (organic fillers) such as fluororesin fillers such as styrene-type, butadiene-type, and acrylic-type rubber powders, core-shell-type rubber powders, silicone resin powders, silicone rubber powders, silicone composite powders, polytetrafluoroethylene (PTFE) fillers, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) fillers, tetrafluoroethylene-hexafluoropropylene copolymer (FEP) fillers, tetrafluoroethylene-ethylene copolymer (ETFE) fillers, and polychlorotrifluoroethylene (PCTFE) fillers.

[0407] In the present embodiment, the filling material preferably includes an inorganic filling material and / or a fluororesin filler. As an inorganic filling material, it is preferably included in the group consisting of silicon dioxide, aluminum hydroxide, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, and calcium titanate. More than one, from the viewpoint of low dielectric properties (low Dk and / or low Df), more preferably including more than one selected from the group consisting of silicon dioxide and aluminum hydroxide, and more preferably including silicon dioxide. As a fluororesin filler, it is more preferably included in the group consisting of polytetrafluoroethylene (PTFE) filler and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) filler. More than one. By using these inorganic filling materials and fluororesin fillers, the heat resistance, dielectric properties, thermal expansion properties, dimensional stability, flame retardancy and other properties of the cured product of the resin composition are further improved.

[0408] The content of the filler in the resin combination of the present embodiment can be suitably set according to desired characteristics, is not particularly limited, relative to 100 mass parts of resin solids in the resin combination, preferably more than 10 mass parts, more preferably more than 20 mass parts, further preferably more than 40 mass parts, more preferably more than 60 mass parts, further more preferably more than 80 mass parts.By being set to more than the aforementioned lower limit, there is the tendency that low thermal expansion, low dielectric loss tangent further improve.In addition, the upper limit of the content of the filler is preferably less than 1000 mass parts, more preferably less than 800 mass parts, further preferably less than 500 mass parts, more preferably less than 300 mass parts, further more preferably less than 250 mass parts, also can be less than 200 mass parts, less than 150 mass parts.By being set to less than the aforementioned upper limit, there is the tendency that formability further improves.

[0409] In the resin composition of the present embodiment, as an example of a preferred embodiment, the content of the filler is 1 to 95% by mass of the components excluding the solvent, and the content of the filler is 30 to 80% by mass.

[0410] The resin composition of the present embodiment may contain only one filler, or may contain two or more fillers. When containing two or more fillers, the total amount is preferably within the above range.

[0411]

[0412] The resin composition of this embodiment may contain a low molecular weight vinyl compound (hereinafter sometimes referred to as "low molecular weight vinyl compound") having a molecular weight of less than 1000 and containing one organic group containing a carbon-carbon unsaturated bond in the molecule. By adding a low molecular weight vinyl compound, the moisture absorption heat resistance of the obtained cured product tends to be further improved.

[0413] Here, the carbon-carbon unsaturated bond constituting the aforementioned organic group containing a carbon-carbon unsaturated bond is a concept excluding the carbon-carbon unsaturated bond contained in the form of a part of an aromatic ring. On the other hand, it is a concept including the carbon-carbon unsaturated bond contained in the form of a part of a non-aromatic ring. Examples of carbon-carbon unsaturated bonds contained in the form of a part of a non-aromatic ring include cyclohexenyl and the like. In addition, it is a concept including the carbon-carbon unsaturated bond (e.g., vinylidene) contained in the part other than the end of a straight-chain or branched organic group.

[0414] In this embodiment, the organic group containing a carbon-carbon unsaturated bond preferably has a CH2=C(X)- (X is a hydrogen atom or a methyl group) structure. Thus, by using a compound containing a carbon-carbon unsaturated bond at the end of the molecule, it is possible to more effectively react with the vinyl group of the polymer (V) having the structural unit shown in formula (V).

[0415] The organic group containing a carbon-carbon unsaturated bond is more preferably one selected from the group consisting of a vinyl group, a (meth)allyl group, and a (meth)acryloyl group, and is further preferably a vinyl group.

[0416] In addition, the low molecular weight vinyl compound used in the present embodiment is preferably composed only of atoms selected from the group consisting of carbon atoms, hydrogen atoms, oxygen atoms, nitrogen atoms and silicon atoms, more preferably composed only of atoms selected from the group consisting of carbon atoms, hydrogen atoms, oxygen atoms and silicon atoms, and further preferably composed only of atoms selected from the group consisting of carbon atoms, hydrogen atoms and oxygen atoms.

[0417] In addition, the low molecular weight vinyl compound used in the present embodiment may or may not have a polar group. The low molecular weight vinyl compound used in the present embodiment preferably does not have a polar group. Examples of the polar group include amino, carboxyl, hydroxyl, and nitro groups.

[0418] In the present embodiment, the molecular weight of the low molecular weight vinyl compound is preferably more than 70, more preferably more than 80, and further preferably more than 90. By setting it to more than the aforementioned lower limit, there is a tendency that the low molecular weight vinyl compound can be suppressed from volatilizing from the resin combination of the present embodiment, its cured product, etc. The upper limit of the molecular weight of the low molecular weight vinyl compound is preferably less than 500, more preferably less than 400, further preferably less than 300, more preferably less than 200, and also less than 150. By setting it to less than the aforementioned upper limit, there is a tendency that the effect of improving the reactivity of the polymer (V) with the structural unit shown in the formula (V) is further improved.

[0419] When the resin composition of the present embodiment contains two or more low molecular weight vinyl compounds, the average molecular weight value of the low molecular weight vinyl compounds is preferably within the above range, and the molecular weight of each compound is more preferably within the above preferred range.

[0420] In the present embodiment, the boiling point of the low molecular weight vinyl compound is preferably above 110°C, more preferably above 115°C, and further preferably above 120°C. By setting it to above the aforementioned lower limit, the volatilization of the low molecular weight vinyl compound during the thermal curing of the resin composition can be suppressed, and the vinyl group possessed by the polymer (V) having the structural unit shown in formula (V) can be more effectively reacted with the low molecular weight vinyl compound. The boiling point of the low molecular weight vinyl compound is preferably below 300°C, more preferably below 250°C, and further preferably below 200°C. By setting it to below the aforementioned upper limit, it is not easy to remain in the cured product as a residual solvent.

[0421] When the resin composition of the present embodiment contains two or more low molecular weight vinyl compounds, the average value of the boiling points may fall within the above range, and the boiling points of the individual compounds are preferably within the above preferred range.

[0422] Examples of the low molecular weight vinyl compound include (meth)acrylate compounds, aromatic vinyl compounds (preferably styrene compounds), saturated fatty acid vinyl compounds, cyanide vinyl compounds, ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid anhydrides, ethylenically unsaturated dicarboxylic acid monoalkyl esters, ethylenically unsaturated carboxylic acid amides, vinyl silane compounds (e.g., vinyltrialkoxysilanes, etc.), acrylic silane compounds (e.g., acrylictrialkoxysilanes, etc.), methacrylic silane compounds (e.g., methacrylictrialkoxysilanes, etc.), styrylsilane compounds (e.g., styryltrialkoxysilanes, etc.), and the like.

[0423] The first embodiment of the low molecular weight vinyl compound is at least one selected from the group consisting of (meth)acrylate compounds, aromatic vinyl compounds, saturated fatty acid vinyl compounds, cyanide vinyl compounds, ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid anhydrides, ethylenically unsaturated dicarboxylic acid monoalkyl esters, and ethylenically unsaturated carboxylic acid amides.

[0424] The second embodiment of the low molecular weight vinyl compound is at least one selected from the group consisting of (meth)acrylate compounds, aromatic vinyl compounds, saturated fatty acid vinyl compounds, vinyl silane compounds, acryl silane compounds, methacryl silane compounds, and styryl silane compounds, preferably aromatic vinyl compounds and / or vinyl silane compounds.

[0425] Specific examples of the low molecular weight vinyl compound include methylstyrene, ethylvinylbenzene, vinyltrimethoxysilane, and vinyltriethoxysilane.

[0426] In the resin combination of the present embodiment, the content of low molecular vinyl compound is preferably more than 1 mass part, more preferably more than 2 mass parts, more preferably more than 2.5 mass parts relative to resin solids 100 mass parts.By being set to more than the aforementioned lower limit, there is the unreacted functional group in the cured product obtained to reduce, and the tendency of moisture absorption heat resistance improvement.In addition, the upper limit of the content of the aforementioned low molecular vinyl compound is preferably less than 30 mass parts, more preferably less than 20 mass parts, more preferably less than 10 mass parts, more preferably less than 8 mass parts, further more preferably less than 5 mass parts relative to resin solids 100 mass parts.By being set to below the aforementioned upper limit, there is the tendency that the low dielectric properties (Dk and / or Df) of the cured product obtained further improves.

[0427] The resin composition of the present embodiment may contain only one low molecular weight vinyl compound or may contain two or more thereof. When containing two or more thereof, the total amount is preferably within the above range.

[0428] <Aromatic oligomers>

[0429] The resin composition of the present embodiment may include an aromatic oligomer. An aromatic oligomer is an oligomer having a structural unit derived from an aromatic vinyl compound, and generally refers to a compound having a weight average molecular weight of less than 3000. In addition, an aromatic oligomer is generally a thermoplastic oligomer. It should be noted that the aromatic oligomer in the present embodiment does not include a polymer or an elastomer having a structural unit shown in formula (V).

[0430] As the aforementioned aromatic vinyl compound, for example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylanthracene, N, N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene and divinylbenzene etc. can be mentioned. These aromatic vinyl compounds can be used alone or in combination of two or more. Among these, styrene, α-methylstyrene, 4-methylstyrene are preferred, and α-methylstyrene is more preferred.

[0431] The aromatic oligomer may contain structural units derived from monomers other than aromatic vinyl compounds. Examples of the other monomers include (meth)acrylic acid, (meth)acrylic acid derivatives, (meth)acrylamide, (meth)acrylamide derivatives, (meth)acrylonitrile, isoprene, 1,3-butadiene, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, N-vinyl indole, N-vinyl phthalimide, N-vinyl pyrrolidone, N-vinyl carbazole, and N-vinyl caprolactam.

[0432] The content of the structural unit derived from the aromatic vinyl compound in the aromatic oligomer is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, further preferably 90% by mass or more, and still more preferably 95% by mass or more.

[0433] The weight average molecular weight (Mw) of the aromatic oligomer is preferably 300 or more, more preferably 500 or more, and further preferably 1,000 or more, and is usually less than 3,000, preferably 2,800 or less, more preferably 2,500 or less, and may be 2,000 or less. It should be noted that the weight average molecular weight (Mw) of the aromatic oligomer is a value obtained by gel permeation chromatography in terms of standard polystyrene.

[0434] Examples of the aromatic oligomer include polystyrene, polyα-methylstyrene, poly4-methylstyrene, styrene / α-methylstyrene copolymers, styrene / 4-methylstyrene copolymers, α-methylstyrene / 4-methylstyrene copolymers, and styrene / α-methylstyrene / 4-methylstyrene copolymers. It should be noted that the aromatic oligomer may be used alone or in combination of two or more.

[0435] As the aromatic oligomer, a commercially available product can be used. Examples of commercially available aromatic oligomers include aromatic polymers manufactured by Eastman Co., Ltd., such as Piccolastic A5 (polystyrene, softening point 5° C., Mw 350), Piccolastic A-75 (polystyrene, softening point 74° C., Mw 1300), Piccotex 75 (α-methylstyrene / 4-methylstyrene copolymer, softening point 75° C., Mw 1100), Piccotex LC (α-methylstyrene / 4-methylstyrene copolymer, softening point 91° C., Mw 1350), Kristalex 3070 (styrene / α-methylstyrene copolymer, softening point 70° C., Mw 950), Kristalex 3085 (styrene / α-methylstyrene copolymer, softening point 85° C., Mw 1150), and Kristalex 3100 (styrene / α-methylstyrene copolymer, softening point 100° C., Mw 1500), and YS Resin SX-100 (polystyrene, softening point 100°C, Mw 2500; manufactured by Yasuhara Chemical Co., Ltd.), FMR-0150 (styrene / aromatic hydrocarbon copolymer, softening point 145°C, Mw 2040; manufactured by Mitsui Chemicals, Inc.), FTR-6100 (styrene / aliphatic hydrocarbon copolymer, softening point 95°C, Mw 1210; manufactured by Mitsui Chemicals, Inc.), FTR-6110 (styrene / aliphatic hydrocarbon copolymer, softening point 110°C, Mw 1570; manufactured by Mitsui Chemicals, Inc.), FTR-6125 (styrene / aliphatic hydrocarbon copolymer Polymer, softening point 125°C, Mw 1950; manufactured by Mitsui Chemicals, Inc.), FTR-7100 (styrene / α-methylstyrene / aliphatic hydrocarbon copolymer, softening point 100°C, Mw 1440; manufactured by Mitsui Chemicals, Inc.), FTR-0100 (poly α-methylstyrene, softening point 100°C, Mw 1960; manufactured by Mitsui Chemicals, Inc.), FTR-2120 (styrene / α-methylstyrene copolymer, softening point 120°C, Mw 2630; manufactured by Mitsui Chemicals, Inc.), etc.

[0436] When the resin combination of the present embodiment includes an aromatic oligomer, its content is preferably more than 1 mass part, more preferably more than 2 mass parts, more preferably more than 3 mass parts, or more than 4 mass parts relative to 100 mass parts of resin solids. By being set to more than the aforementioned lower limit, there is a tendency to further reduce dielectric constant and dielectric loss tangent. In addition, the upper limit of the content of the aromatic oligomer is preferably less than 45 mass parts, more preferably less than 30 mass parts, more preferably less than 15 mass parts, more preferably less than 10 mass parts, or less than 8 mass parts relative to 100 mass parts of resin solids. By being set to less than the aforementioned upper limit, there is a tendency for chemical resistance to further improve.

[0437] The resin composition of the present embodiment may contain only one aromatic oligomer or two or more aromatic oligomers. When containing two or more aromatic oligomers, the total amount is preferably within the above range.

[0438] <<Elastomer>>

[0439] The resin composition of the present embodiment may contain an elastomer. The elastomer may be thermoplastic, thermosetting, or neither thermoplastic nor thermosetting, but is preferably thermoplastic.

[0440] The elastomer in this embodiment is not particularly limited, and for example, at least one selected from the group consisting of polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, styrene butadiene ethylene, styrene butadiene styrene, styrene isoprene styrene, styrene ethylene butylene styrene, styrene propylene styrene, styrene ethylene propylene styrene, fluororubber, silicone rubber, their hydrides, their alkyl compounds, and their copolymers can be cited.

[0441] In addition, as the elastomer, oligomers or polymers having a curable vinyl functional group and polybutadiene resins described in paragraphs 0044 and 0045 of JP-A-2019-194312 can also be exemplified, and these contents are incorporated into the present specification.

[0442] The number average molecular weight of the elastomer (preferably thermoplastic elastomer) used in the present embodiment is preferably more than 1000. By setting the number average molecular weight of the elastomer to more than 1000, there is a tendency that the low dielectric properties (Dk and / or Df, particularly low dielectric loss tangent) of the cured product obtained are more excellent. The number average molecular weight is preferably more than 1500, more preferably more than 2000, and according to the purposes, it can be more than 50,000, more than 60,000, more than 70,000, more than 80,000. The upper limit of the number average molecular weight of the elastomer is preferably less than 400,000, more preferably less than 350,000, and further preferably less than 300,000. By setting the number average molecular weight of the elastomer to less than the aforementioned upper limit value, there is a tendency that the solubility of the elastomer component in the resin composition is improved.

[0443] When the resin composition of the present embodiment contains two or more elastomers, it is preferred that the number average molecular weight of the mixture thereof satisfy the above range.

[0444] The elastomer used in the present embodiment may include a resin containing a polybutadiene structure. The polybutadiene structure may be partially or completely hydrogenated. As specific examples, B-1000, B-2000, B-3000, BI-2000, BI-3000 manufactured by Nippon Soda Co., Ltd., Ricon100, Ricon130, Ricon131, Ricon142, Ricon150, Ricon181, Ricon184, etc. manufactured by Cray Valley Co., Ltd. may be mentioned.

[0445] The elastomer used in the present embodiment may be a resin containing a poly(meth)acrylate structure, and specific examples thereof include TEISAN resin manufactured by Nagase ChemteX Corporation, and ME-2000, W-197C, KG-15, and KG-3000 manufactured by Negami Industries, Ltd.

[0446] The elastomer used in the present embodiment can include resins containing polycarbonate structures. Resins containing polycarbonate structures are sometimes referred to as "polycarbonate resins". As such resins, carbonate resins without reactive groups, carbonate resins containing hydroxyl groups, carbonate resins containing phenolic hydroxyl groups, carbonate resins containing carboxyl groups, carbonate resins containing anhydride groups, carbonate resins containing isocyanate groups, carbonate resins containing carbamate groups, and carbonate resins containing epoxy groups can be included. Reactive groups herein refer to functional groups that can react with other components, such as hydroxyl groups, phenolic hydroxyl groups, carboxyl groups, anhydride groups, isocyanate groups, carbamate groups, and epoxy groups.

[0447] Specific examples of the polycarbonate resin include FPC0220 and FPC2136 manufactured by Mitsubishi Gas Chemical Co., Ltd., and T6002 and T6001 (polycarbonate diol) manufactured by Asahi Kasei Chemicals Corp.

[0448] The elastomer used in the present embodiment may be a resin containing a polysiloxane structure, and specific examples thereof include SMP-2006, SMP-2003PGMEA, SMP-5005PGMEA, KR-510, and SMP-7014-3S manufactured by Shin-Etsu Silicones.

[0449] The elastomer used in the present embodiment may include a resin containing a polyalkylene structure and / or a polyalkyleneoxy structure. The polyalkyleneoxy structure is preferably a polyalkyleneoxy structure having 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure having 3 to 10 carbon atoms, and particularly preferably a polyalkyleneoxy structure having 5 to 6 carbon atoms. Specific examples of the resin containing a polyalkylene structure and / or a polyalkyleneoxy structure include PTXG-1000 and PTXG-1800 manufactured by Asahi Kasei Fibers Corp.

[0450] The elastomer used in the present embodiment may be a resin containing a polyisoprene structure, and specific examples thereof include KL-610 and KL613 manufactured by Kuraray Co., Ltd.

[0451] The elastomer used in the present embodiment may be a resin containing a polyisobutylene structure, and specific examples thereof include SIBSTAR-073T (styrene-isobutylene-styrene triblock copolymer) and SIBSTAR-042D (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation.

[0452] In the present embodiment, the elastomer (preferably a thermoplastic elastomer) is preferably an elastomer comprising a styrene monomer unit and a conjugated diene monomer unit (hereinafter referred to as "elastomer (e)"). By using such an elastomer (e), the low dielectric properties (Dk and / or Df, especially low dielectric loss tangent) of the obtained cured product are more excellent.

[0453] The elastomer (e) contains styrene monomer units. By containing styrene monomer units, the solubility of the elastomer (e) in the resin composition is improved. As styrene monomers, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene (vinyl styrene), N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, etc. can be exemplified. Among these, styrene, α-methylstyrene, and p-methylstyrene are preferred from the viewpoint of availability and productivity. Among these, styrene is particularly preferred.

[0454] The content of the styrene monomer unit in the elastomer (e) is preferably in the range of 10 to 80% by mass of all monomer units, more preferably in the range of 13 to 70% by mass, further preferably in the range of 15 to 50% by mass, and even more preferably in the range of 20 to 40% by mass. When the content of the styrene monomer unit is 80% by mass or less, the adhesion and adhesiveness to the substrate etc. become better. In addition, when it is 10% by mass or more, there is a tendency to suppress excessive adhesion, not easily produce residual adhesive, stop marks, and improve the easy peelability of the adhesive surfaces, so it is preferred.

[0455] The elastomer (e) may contain only one type of styrene monomer unit, or may contain two or more types. When containing two or more types, the total amount is preferably within the above range.

[0456] The method for measuring the content of the styrene monomer unit in the elastomer (e) of the present embodiment can refer to the description of International Publication No. 2017 / 126469, the contents of which are incorporated herein. The same applies to the conjugated diene monomer unit described later.

[0457] The elastomer (e) comprises a conjugated diene monomer unit. By comprising a conjugated diene monomer unit, the solubility of the elastomer (e) in the resin composition is improved. As a conjugated diene monomer, there is no particular limitation as long as it is a diene having a pair of conjugated double bonds. Examples of conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and farnesene, preferably 1,3-butadiene and isoprene, more preferably 1,3-butadiene.

[0458] The elastomer (e) may contain only one type of conjugated diene monomer unit, or may contain two or more types.

[0459] In the above-mentioned elastomer (e), the mass ratio of styrene monomer unit to conjugated diene monomer unit is preferably in the range of styrene monomer unit / conjugated diene monomer unit=5 / 95 to 80 / 20, more preferably in the range of 7 / 93 to 77 / 23, and further preferably in the range of 10 / 90 to 70 / 30. When the mass ratio of styrene monomer unit to conjugated diene monomer unit is in the range of 5 / 95 to 80 / 20, excessive adhesion can be suppressed and the adhesive force can be maintained at a high level, and the easy peelability of the adhesive surfaces becomes good.

[0460] In the above-mentioned elastomer (e), the conjugated diene bonds of the elastomer may be completely hydrogenated, partially hydrogenated, or not hydrogenated.

[0461] The elastomer (e) may or may not contain other monomer units in addition to the styrene monomer unit and the conjugated diene monomer unit. Examples of the other monomer units include aromatic vinyl compound units other than the styrene monomer unit.

[0462] In the elastomer (e), the total content of styrene monomer units and conjugated diene monomer units is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 97% by mass or more, and even more preferably 99% by mass or more of all monomer units.

[0463] As described above, the elastomer (e) may contain only one type of each of the styrene monomer unit and the conjugated diene monomer unit, or may contain two or more types. When containing two or more types, the total amount is preferably within the above range.

[0464] The elastomer (e) used in this embodiment may be a block polymer or a random polymer. In addition, it may be a hydrogenated elastomer in which the conjugated diene monomer units are hydrogenated, an unhydrogenated elastomer that is not hydrogenated, or a partially hydrogenated elastomer, preferably an unhydrogenated elastomer or a partially hydrogenated elastomer.

[0465] In one embodiment of the present embodiment, the elastomer (e) is a hydrogenated elastomer. Here, the hydrogenated elastomer refers to, for example, an elastomer in which the double bonds based on the conjugated diene monomer units are hydrogenated, and includes, in addition to an elastomer having a hydrogenation rate (hydrogenation rate) of 100%, an elastomer having a hydrogenation rate of 80% or more. The hydrogenation rate of the hydrogenated elastomer is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more. In the present embodiment, the hydrogenation rate is based on 1 The calculation was performed based on the measurement results of H-NMR spectroscopy.

[0466] In one embodiment of the present embodiment, the elastomer (e) is an unhydrogenated elastomer. Here, the unhydrogenated elastomer refers to an elastomer in which the proportion of double bonds based on conjugated diene monomer units in the elastomer that are hydrogenated, that is, the hydrogenation rate (hydrogenation rate) is 20% or less. The hydrogenation rate is preferably 15% or less, more preferably 10% or less, and further preferably 5% or less.

[0467] On the other hand, the partially hydrogenated elastomer refers to an elastomer in which a part of the double bonds based on the conjugated diene monomer units in the elastomer are hydrogenated, and generally refers to an elastomer in which the hydrogenation rate (hydrogenation ratio) is less than 80% and more than 20%.

[0468] Examples of commercially available products of the elastomer (e) used in this embodiment include SEPTON (registered trademark) 2104, V9461, and S8104 manufactured by Kuraray Co., Ltd., SOE (registered trademark) S1606, S1613, S1609, and S1605 manufactured by Asahi Kasei Corporation, H1041, H1043, P2000, and MP10 of Tuftec (registered trademark) manufactured by Asahi Kasei Corporation, and DYNARON (registered trademark) 9901P and TR2250 manufactured by JSR Corporation.

[0469] The elastomer used in this embodiment may also be a liquid diene. Liquid diene refers to a liquid elastomer containing a conjugated diene monomer unit. As conjugated diene monomers, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene and farnesene can be cited, preferably 1,3-butadiene and isoprene, more preferably 1,3-butadiene.

[0470] Examples of the liquid diene used in the present embodiment include liquid polybutadiene, liquid polyisoprene, modified products of liquid polybutadiene, modified products of liquid polyisoprene, liquid acrylonitrile-butadiene copolymers, and liquid styrene-butadiene copolymers.

[0471] The number average molecular weight of the liquid diene is not particularly limited as long as it is liquid at 20°C, but is preferably 500 or more and 10,000 or less.

[0472] When the resin combination of the present embodiment includes an elastomer (preferably including an elastomer (e)), its content is preferably more than 1 mass part, more preferably more than 2 mass parts, more preferably more than 3 mass parts, or more than 4 mass parts relative to 100 mass parts of resin solids. By being set to more than the aforementioned lower limit, there is a tendency that low dielectric properties (Dk and / or Df, particularly low dielectric loss tangent) are further improved. In addition, the upper limit of the content of the elastomer is preferably less than 45 mass parts relative to 100 mass parts of resin solids, more preferably less than 30 mass parts, more preferably less than 20 mass parts, more preferably less than 10 mass parts, or less than 8 mass parts. By being set to less than the aforementioned upper limit, there is a tendency that heat resistance is further improved.

[0473] The resin composition of the present embodiment may contain only one thermoplastic elastomer or two or more thermoplastic elastomers. When containing two or more thermoplastic elastomers, the total amount is preferably within the above range.

[0474] <Flame retardant>

[0475] The resin composition of the present embodiment may contain a flame retardant. Examples of the flame retardant include phosphorus-based flame retardants, halogen-based flame retardants, inorganic-based flame retardants, and silicone-based flame retardants, and phosphorus-based flame retardants are preferred.

[0476] As the flame retardant, known ones can be used, for example, brominated epoxy resin, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromobisphenol A, pentabromobenzyl (meth) acrylate, pentabromotoluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, chlorinated polystyrene, chlorinated paraffin and other halogen flame retardants, red phosphorus, tricresyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tri(dimethyl phthalate) phosphate, etc. Phosphorus-based flame retardants such as esters of toluene, trialkyl phosphates, dialkyl phosphates, tri(chloroethyl) phosphates, phosphazenes, 1,3-phenylenebis(2,6-di(xylyl) phosphate), 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, some boehmite, boehmite, zinc borate, antimony trioxide, and silicone-based flame retardants such as silicone rubber and silicone resin.

[0477] In the present embodiment, among these, 1,3-phenylenebis(2,6-di(xylyl)phosphate) is preferred from the viewpoint of not impairing the low dielectric properties.

[0478] When the resin composition of the present embodiment includes a flame retardant, its content is preferably 1 mass part or more, more preferably 5 mass parts or more, further preferably 10 mass parts or more, or 13 mass parts or more relative to 100 mass parts of the resin solid content in the resin composition. In addition, the lower limit of the content of the flame retardant is preferably 30 mass parts or less, more preferably 25 mass parts or less, or 20 mass parts or less.

[0479] The flame retardant may be used alone or in combination of two or more. When two or more flame retardants are used, the total amount is within the above range.

[0480] <Active ester compound>

[0481] The resin composition of the present embodiment may contain an active ester compound within a range that does not impair the effects of the present invention. The active ester compound is not particularly limited, and for example, reference may be made to paragraphs 0064 to 0066 of International Publication No. 2021 / 172317, the contents of which are incorporated herein.

[0482] When the resin composition of the present embodiment contains an active ester compound, the amount thereof is preferably 1 part by mass or more and preferably 50 parts by mass or less relative to 100 parts by mass of the resin solid content in the resin composition.

[0483] The resin composition in the present embodiment may contain only one active ester compound or two or more thereof. When containing two or more thereof, the total amount is preferably within the above range.

[0484] In addition, the resin composition in the present embodiment may also be configured to be substantially free of active ester compounds. Substantially free means that the content of active ester compounds is less than 1 part by mass, preferably less than 0.1 part by mass, and more preferably less than 0.01 part by mass, relative to 100 parts by mass of the resin solid content in the resin composition.

[0485] <Silane coupling agent>

[0486] The resin composition of the present embodiment may further contain a silane coupling agent. The resin composition of the present embodiment contains a silane coupling agent, which tends to further improve the dispersibility of the filler and further improve the bonding strength between the components of the resin composition of the present embodiment and the substrate described below.

[0487] The silane coupling agent is not particularly limited, and generally includes silane coupling agents used for surface treatment of inorganic substances, such as aminosilane compounds (e.g., γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxysilane compounds (e.g., γ-glycidoxypropyltrimethoxysilane, etc.), acrylic silane compounds (e.g., γ-acryloxypropyltrimethoxysilane, etc.), cationic silane compounds (e.g., N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), phenylsilane compounds, etc. Among these, the silane coupling agent is preferably an epoxysilane compound. As the epoxysilane compound, for example, "KBM-403", "KBM-303", "KBM-402", "KBE-403" and the like manufactured by Shin-Etsu Chemical Co., Ltd. can be mentioned.

[0488] In the case where the resin composition of the present embodiment includes a silane coupling agent, its content is preferably more than 0.1 mass parts, more preferably more than 0.5 mass parts, more preferably more than 1.0 mass parts, more preferably more than 1.5 mass parts, and more preferably more than 2.5 mass parts relative to 100 mass parts of resin solids. By being set to more than the aforementioned lower limit, there is a tendency that the dispersibility of the inorganic filler is further improved. In addition, the upper limit of the content of the silane coupling agent is preferably less than 10.0 mass parts relative to 100 mass parts of resin solids, more preferably less than 8.0 mass parts, more preferably less than 5.0 mass parts, and more preferably less than 4.0 mass parts. By being set to less than the aforementioned upper limit, there is a tendency that chemical resistance and heat resistance are further improved.

[0489] The resin composition of the present embodiment may contain only one silane coupling agent or may contain two or more silane coupling agents. When containing two or more silane coupling agents, the total amount is preferably within the above range.

[0490] <Dispersant>

[0491] The resin combination of the present embodiment may include a dispersant. As a dispersant, the dispersant used in the conventional coating can be appropriately used, and its type is not particularly limited. Preferably, a dispersant can be used as a wetting dispersant of a copolymer substrate, and as a specific example thereof, DISPERBYK (registered trademark) -110, 111, 161, 180, 2009, 2152, 2155, BYK (registered trademark) -W996, W9010, W903, W940 etc. made by BYK Japan KK can be cited.

[0492] When the resin composition of the present embodiment includes a dispersant, the lower limit of its content is preferably 0.01 mass parts or more, more preferably 0.1 mass parts or more, or 0.3 mass parts or more relative to 100 mass parts of the resin solid components in the resin composition. In addition, the upper limit of the content of the dispersant is preferably 10 mass parts or less, more preferably 5 mass parts or less, or 3 mass parts or less relative to 100 mass parts of the resin solid components in the resin composition.

[0493] The dispersant may be used alone or in combination of two or more. When two or more are used, the total amount is within the above range.

[0494] <Curing Accelerator>

[0495] The resin composition of this embodiment may also include a curing accelerator. The curing accelerator is not particularly limited, and examples thereof include imidazoles such as 2-ethyl-4-methylimidazole and triphenylimidazole; organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, di-tert-butyl diperphthalate, α,α'-di(tert-butylperoxide)diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxide)hexyne-3; azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, etc. Tertiary amines such as anthracene, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutylenediamine, and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, and catechol; high-temperature decomposition type free radical generators such as 2,3-dimethyl-2,3-diphenylbutane; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, manganese octoate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, and ferric acetylacetonate; those obtained by dissolving these organic metal salts in hydroxyl-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; organic tin compounds such as dioctyltin oxide, other alkyl tins, and alkyl tin oxides, etc.

[0496] Preferred curing accelerators are imidazoles and organic metal salts, and it is more preferred to use both imidazoles and organic metal salts in combination.

[0497] When the resin composition of the present embodiment includes a curing accelerator, the lower limit of its content is preferably 0.005 mass parts or more, more preferably 0.01 mass parts or more, and further preferably 0.1 mass parts or more relative to 100 mass parts of the resin solids in the resin composition. In addition, the upper limit of the content of the curing accelerator is preferably 10 mass parts or less, more preferably 5 mass parts or less, and further preferably 2 mass parts or less relative to 100 mass parts of the resin solids in the resin composition.

[0498] The curing accelerator may be used alone or in combination of two or more. When two or more are used, the total amount is within the above range.

[0499] <Solvent>

[0500] The resin composition of the present embodiment can contain a solvent, preferably an organic solvent. When containing a solvent, the resin composition of the present embodiment is at least a portion of the above-mentioned various resin solid components, preferably all dissolved or compatible with the form (solution or varnish) of the solvent. As a solvent, as long as it is a polar organic solvent or a non-polar organic solvent that can make at least a portion of the above-mentioned various resin solid components, preferably all dissolved or compatible, it is not particularly limited, as a polar organic solvent, for example, ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), cellosolves (for example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (for example, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), amides (for example, dimethoxyacetamide, dimethylformamide, etc.), as a non-polar organic solvent, aromatic hydrocarbons (for example, toluene, xylene, etc.) can be cited.

[0501] The solvent may be used alone or in combination of two or more. When two or more solvents are used, the total amount is within the above range.

[0502] <Other ingredients>

[0503] The resin composition of the present embodiment may contain various polymer compounds and various additives such as thermoplastic resins and oligomers thereof in addition to the above-mentioned components. As additives, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, thickeners, flow regulators, lubricants, defoamers, leveling agents, brighteners, polymerization inhibitors, etc. These additives may be used alone or in combination of two or more.

[0504] <Method for producing resin composition>

[0505] The manufacture method of the resin combination of the present embodiment is not particularly limited, for example, each component can be mixed with a solvent in sequence and fully stirred. At this time, in order to make each component dissolve or disperse uniformly, known processes such as stirring, mixing, and mixing can be carried out. Specifically, by using a stirring tank equipped with a stirrer with suitable stirring ability to carry out stirring and dispersing treatment, the dispersibility of the filler for the resin combination can be improved. The above-mentioned stirring, mixing, and mixing treatment can be appropriately carried out using a device such as a ball mill, a bead mill, etc. for the purpose of mixing, or a known device such as a mixing device of revolution or autogenous type.

[0506] <Purpose>

[0507] The resin combination of the present embodiment is used in the form of cured product. Specifically, the resin combination of the present embodiment can be suitable as low thermal expansion coefficient material, high relative dielectric constant material, low relative dielectric constant material, low dielectric loss tangent material, as the resin combination used for the insulating layer such as the insulating layer of a printed circuit board, and the electronic material resin combination used for semiconductor package. Wherein, it can be more suitable as low relative dielectric constant material and / or low dielectric loss tangent material, as the resin combination used for the insulating layer such as the insulating layer of a printed circuit board, and the electronic material resin combination used for semiconductor package. The resin combination of the present embodiment can be suitable as a prepreg, a metal foil laminated board, a resin composite sheet and a printed circuit board material used using a prepreg.

[0508] The dielectric loss tangent (Df) when the resin composition of the present embodiment is preferably made into a cured product is low. Specifically, the dielectric loss tangent (Df) at 10GHz measured according to the cavity resonator perturbation method is preferably less than 0.0028, more preferably less than 0.0027, and further preferably less than 0.0026. There is no particular limitation on the lower limit of the dielectric loss tangent (Df), for example, 0.0001 or more is practical.

[0509] In addition, the relative dielectric constant (Dk) of the resin composition of the present embodiment is preferably low when the cured product is made. Specifically, the relative dielectric constant (Dk) at 10 GHz measured by the cavity resonator perturbation method is preferably less than 3.0. There is no particular limitation on the lower limit of the relative dielectric constant (Dk), for example, more than 0.01 is practical.

[0510] Such low dielectric properties are achieved by using a thermosetting compound having low dielectric properties and precisely adjusting the amounts of the ultraviolet absorber and the non-metallic organic dye in the resin composition.

[0511] The relative dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product are more specifically measured by the method described in Examples described below.

[0512] The cured product of the resin composition of the present embodiment has a glass transition temperature (Tanδ) of preferably 245°C or more, more preferably 255°C or more, according to DMA (dynamic mechanical measurement). Such a high glass transition temperature is achieved by reducing the content of the ultraviolet absorber and the non-metallic organic pigment in the resin composition. The upper limit of the glass transition temperature is not particularly limited, for example, 350°C or less is practical.

[0513] More specifically, the glass transition temperature (Tan δ) is measured by the method described in the examples described later.

[0514] The resin composition of the present embodiment is suitable for use as a layered material (including a film, sheet, etc.) such as a prepreg, a resin composite sheet, etc., which is an insulating layer of a printed circuit board. When the layered material is used, the thickness of the layered material is preferably 0.1 μm or more. As the upper limit of the thickness, it can be less than 200 μm and less than 180 μm, but in terms of the material of the film that can also correspond to less than 100 μm, less than 80 μm, less than 50 μm, less than 30 μm, and less than 15 μm, the value of the present invention is high. It should be noted that the thickness of the above-mentioned layered material, for example, refers to the thickness of the glass cloth when the resin composition of the present embodiment is impregnated with the glass cloth.

[0515] The material formed from the resin composition of this embodiment can be used for applications where patterning is performed by exposure and development, or can be used for applications where exposure and development are not performed. The material is particularly suitable for applications where exposure and development are not performed.

[0516] <<Prepreg>>

[0517] The prepreg of the present embodiment is formed by a substrate (prepreg substrate) and a resin composition of the present embodiment. The prepreg of the present embodiment is obtained by, for example, applying (e.g., impregnating and / or coating) the resin composition of the present embodiment to a substrate, and then semi-curing it by heating (e.g., drying at 120 to 220° C. for 2 to 15 minutes, etc.). In this case, the amount of the resin composition attached to the substrate, i.e., the amount of the resin composition (including the filler) is preferably in the range of 20 to 99% by mass, more preferably in the range of 20 to 80% by mass, relative to the total amount of the semi-cured prepreg.

[0518] The substrate is not particularly limited as long as it is a substrate used in various printed circuit board materials. Examples of the material of the substrate include glass fibers (e.g., E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, spherical glass, etc.), inorganic fibers other than glass (e.g., quartz, etc.), and organic fibers (e.g., polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.). The form of the substrate is not particularly limited, and examples include woven fabrics, non-woven fabrics, rovings, chopped strand mats, surface-processed mats, and the like. These substrates may be used alone or in combination of two or more. Among these substrates, from the viewpoint of dimensional stability, woven fabrics subjected to super fiber opening treatment and hole filling treatment are preferred. From the viewpoint of strength and low water absorption, the substrate preferably has a thickness of less than 200 μm and a mass of 250 g / m 2 The following glass woven fabrics are preferably those surface-treated with silane coupling agents such as epoxysilane and aminosilane from the viewpoint of moisture absorption and heat resistance. From the viewpoint of electrical properties, low-dielectric glass fabrics formed of glass fibers such as L-glass, NE-glass, and Q-glass that exhibit low relative dielectric constant and low dielectric loss tangent are more preferred.

[0519] The substrate with low relative dielectric constant can be exemplified by a substrate with a relative dielectric constant of 5.0 or less (preferably 3.0 to 4.9). The substrate with low dielectric loss tangent can be exemplified by a substrate with a dielectric loss tangent of 0.006 or less (preferably 0.001 to 0.005). The relative dielectric constant and dielectric loss tangent are set to the values ​​measured by the perturbation method cavity resonator at a frequency of 10 GHz.

[0520] <<Metal foil clad laminate>>

[0521] The metal foil clad laminate of the present embodiment comprises a layer formed by the resin composition of the present embodiment and / or a layer formed by the prepreg of the present embodiment, and comprises a metal foil disposed on one side or both sides of the aforementioned layer. As a method for making a metal foil clad laminate of the present embodiment, for example, a method of disposing at least one (preferably overlapping more than 2) prepreg of the present embodiment, disposing a metal foil on one side or both sides thereof and performing stacking forming can be cited. In more detail, it can be made by disposing a metal foil such as copper or aluminum on one side or both sides of the prepreg and performing stacking forming. As the number of sheets of the prepreg, preferably 1 to 10 sheets, more preferably 2 to 10 sheets, and further preferably 2 to 9 sheets. As a metal foil, as long as it is a user in a printed circuit board material, it is not particularly limited, for example, copper foils such as rolled copper foil and electrolytic copper foil can be cited. The thickness of the metal foil (preferably copper foil) is not particularly limited and can be about 1.5 to 70 μm. In addition, when copper foil is used as the metal foil, as the copper foil, the roughness Rz of the copper foil surface measured in accordance with JIS B0601:2013 is preferably adjusted to 0.2 to 4.0 μm. By setting the roughness Rz of the copper foil surface to 0.2 μm or more, there is a tendency that the roughness of the copper foil surface becomes a moderate size and the peel strength of the copper foil is further improved. On the other hand, by setting the roughness Rz of the copper foil surface to 4.0 μm or less, there is a tendency that the roughness of the copper foil surface becomes a moderate size and the dielectric loss tangent characteristics of the obtained cured product are further improved. From the viewpoint of reducing the dielectric loss tangent, the roughness Rz of the copper foil surface is more preferably 0.5 μm or more, more preferably 0.6 μm or more, particularly preferably 0.7 μm or more, and more preferably 3.5 μm or less, more preferably 3.0 μm or less, and particularly preferably 2.0 μm or less.

[0522] As the lamination forming method, there can be mentioned the method generally used in forming laminated boards and multilayer boards for printed wiring boards, and more specifically, there can be mentioned the method using a multistage press, a multistage vacuum press, a continuous forming machine, an autoclave forming machine, etc., at a temperature of about 180 to 350° C., a heating time of about 100 to 300 minutes, a surface pressure of 20 to 100 kg / cm 2 A method for laminating and forming about. In addition, a multilayer board can also be made by laminating and forming the prepreg of the present embodiment and a wiring board for the inner layer prepared separately. As a method for manufacturing a multilayer board, for example, it is as follows: copper foil of about 35 μm is arranged on both sides of a prepreg of the present embodiment, and after laminating and forming by the above-mentioned forming method, an inner layer circuit is formed, and a blackening treatment is applied to the circuit to form an inner layer circuit board, and then, the inner layer circuit board and the prepreg of the present embodiment are alternately arranged one by one, and then copper foil is arranged on the outermost layer, and laminating and forming is preferably performed under vacuum under the above-mentioned conditions, thereby making a multilayer board. The metal foil-clad laminated board of the present embodiment can be suitably used as a printed circuit board.

[0523] As described above, the resin composition for electronic materials obtained using the resin composition of the present embodiment (resin composition formed by a combination of specific components) has low dielectric properties (low dielectric constant and / or low dielectric loss tangent) and excellent low thermal expansion of its cured product, and also has excellent heat resistance (glass transition temperature) and resistance to desmear.

[0524] <<Printed Circuit Board>>

[0525] The printed circuit board of this embodiment is a printed circuit board including an insulating layer and a conductor layer disposed on the surface of the insulating layer, wherein the insulating layer includes at least one of a layer formed from the resin composition of this embodiment and a layer formed from the prepreg of this embodiment. Such a printed circuit board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited.

[0526] More specifically, first, prepare a metal foil clad laminate (copper foil clad laminate, etc.). The surface of the metal foil clad laminate is subjected to etching to form an inner layer circuit and to make an inner substrate. The inner layer circuit surface of the inner substrate is subjected to a surface treatment for improving bonding strength as required, then, the cured product or prepreg of the resin composition of the present embodiment is overlapped on its inner layer circuit surface, and then the metal foil for the outer layer circuit is stacked on its outside, and heated and pressed to form an integral body. Thus, a laminate having an insulating layer formed by a cured product or prepreg of a resin composition between the metal foil for the inner layer circuit and the outer layer circuit is manufactured. Then, after drilling a through hole and a via hole is performed on the laminate, in order to remove the residue, i.e., smear, of the resin component contained in the cured product layer, a desmearing process is performed. Then, the plated metal film that makes the metal foil for the inner layer circuit and the outer layer circuit conduct is formed on the wall surface of the hole for through hole and via hole, and then the metal foil for the outer layer circuit is etched as needed to form the outer layer circuit. Alternatively, in the case of subtractive method, the through hole wall surface is electrolessly copper plated and electrolytic copper plated, and then a photoresist is used to form the circuit pattern. Thereafter, in order to protect the circuit pattern other than the position where each component is connected with the solder, solder resist is applied on both sides, and the opening processing of the position where the solder connection is required is performed. At this time, the opening processing is performed at different positions on the surface and back of the laminate, so the problem of back exposure will occur. Even if the cured product of the resin composition of the present embodiment is a cured product with a thickness of 30 μm, the transmittance of g-rays (wavelength 436nm), h-rays (wavelength 405nm) and i-rays (wavelength 365nm) is also low, so the problem of back exposure can be effectively suppressed.

[0527] After exposure, processing is performed as appropriate to manufacture a printed wiring board.

[0528] In addition, when a metal foil-clad laminate is not used, a conductor layer forming a circuit can be formed on the cured product or prepreg of the resin composition of this embodiment to produce a printed wiring board. In this case, the conductor layer can also be formed by chemical plating.

[0529] More specifically, the printed circuit board of the present embodiment can be manufactured, for example, by a method for manufacturing a printed circuit board comprising the following steps: a step of forming a photosensitive composition layer cured by light having a wavelength of 350 to 440 nm on both sides of a substrate having at least one insulating layer including a cured product of the resin composition of the present embodiment and having at least one conductor layer in contact with the insulating layer; and a step of disposing a mask pattern on at least one side of the photosensitive composition layer and exposing the layer to light having a wavelength of 350 to 440 nm through the mask pattern.

[0530] Furthermore, the printed circuit board of the present embodiment can also be manufactured by a method for manufacturing a printed circuit board having the following steps: a step of preparing a substrate on which is laminated at least one insulating layer comprising a cured product of the resin composition of the present embodiment and at least one conductive layer in contact with the insulating layer; a step of forming a photosensitive composition layer cured by light having a wavelength of 350 to 440 nm on both sides of the substrate; and a step of disposing a mask pattern on at least one side of the photosensitive composition layer and exposing the layer to light having a wavelength of 350 to 440 nm through the mask pattern.

[0531] It should be noted that, as the photosensitive composition layer, for example, a solder resist layer can be cited. As the solder resist, a commercially available material can be used. Regarding the exposure method, a known method can also be used, for example, it can be carried out by close exposure in which a mask pattern is closely attached to the photosensitive composition layer and exposed, or projection exposure in which the mask pattern is not closely attached to the photosensitive composition layer.

[0532] By using the resin composition of the present embodiment for the insulating layer of a printed circuit board, back exposure can be suppressed. The thickness of the insulating layer of the cured product of the resin composition of the present embodiment can be appropriately selected according to the intensity of the light used in the exposure, and is therefore not particularly limited, for example, less than 100 μm, less than 80 μm, less than 50 μm, less than 30 μm, or less than 15 μm. The lower limit of the thickness of the insulating layer is, for example, more than 0.1 μm, and may also be more than 5 μm, or more than 10 μm. As the insulating layer of the cured product of the resin composition of the present embodiment, a layer formed by the resin composition of the present embodiment and a layer formed by the prepreg of the present embodiment can be exemplified.

[0533] In the method for manufacturing a printed circuit board of the present embodiment, the insulating layer comprising the cured product of the resin composition of the present embodiment in the printed circuit board may be at least one layer, or may be two or more layers. In addition, the printed circuit board may be used in combination with an insulating layer comprising a cured product other than the resin composition of the present embodiment.

[0534] In addition, in the manufacturing method of a coreless printed circuit board, for example, the following steps are performed: replacing the step of preparing the above-mentioned printed circuit board as described above with the step of preparing a core substrate; and the step of obtaining a laminated body, which is: a laminated body having at least one insulating layer including the composition of the present embodiment and a conductor layer disposed on the outermost surface of the insulating layer laminated on the core substrate. That is, one or more insulating layers and one or more conductor layers are laminated on the core substrate, thereby obtaining a laminated body having a build-up layer formed on the core substrate. Thereafter, the core substrate is removed (peeled off), thereby forming a coreless printed circuit board (also referred to as a coreless substrate).

[0535] Then, the coreless substrate is subjected to the step of forming a photosensitive composition layer and the step of exposing the coreless substrate in the same manner as described above, thereby obtaining a coreless printed wiring board having a circuit pattern formed thereon.

[0536] In addition, this embodiment also relates to a semiconductor device including the printed circuit board. For details of the semiconductor device, reference can be made to paragraphs 0200 to 0202 of Japanese Patent Application Laid-Open No. 2021-021027, the contents of which are incorporated herein.

[0537] In addition, the insulating layer formed by the cured product of the resin composition of the present embodiment preferably makes the surface roughness of the insulating layer after the roughening treatment smaller. Specifically, the arithmetic mean roughness Ra of the surface of the insulating layer after the roughening treatment is preferably less than 200nm, more preferably less than 150nm, and particularly preferably less than 100nm. The lower limit of the arithmetic mean roughness Ra is not particularly limited, for example, it can be more than 10nm. For the determination of the arithmetic mean roughness Ra of the surface of the insulating layer, a shape measuring microscope (laser microscope, Keyence Corporation VK-X210 (trade name)) is utilized, and the object lens magnification is 150 times taken, and the height distribution on the straight line of the length 90μm randomly selected in the taken image is obtained by image processing.

[0538] <<Resin composite sheet>>

[0539] The resin composite sheet of the present embodiment includes: a support body, and a layer formed by the resin composition of the present embodiment disposed on the surface of the aforementioned support body. The resin composite sheet can be used as a laminated film or a dry film solder resist. There is no particular limitation on the method for manufacturing the resin composite sheet, and for example, the following method can be cited: a solution obtained by dissolving the resin composition of the present embodiment in a solvent is applied (coated) to the support body and dried to obtain a resin composite sheet.

[0540] Examples of the support used therein include polyethylene films, polypropylene films, polycarbonate films, polyethylene terephthalate films, ethylene tetrafluoroethylene copolymer films, release films having release agents coated on the surfaces of these films, organic film substrates such as polyimide films, conductor foils such as copper foil and aluminum foil, glass plates, SUS (Steel Use Stainless) plates, and plate-like objects such as FRP (Fiber-Reinforced Plastics), but are not particularly limited.

[0541] As a coating method (coating method), for example, a method of applying a solution of the resin composition of the present embodiment dissolved in a solvent to a support by a rod coater, a die coater, a scraper, a Baker applicator, etc. In addition, a single-layer sheet can be made by peeling off or etching the support from a resin composite sheet laminated with a support and a resin composition after drying. It should be noted that the solution obtained by dissolving the resin composition of the present embodiment in a solvent can also be supplied to a mold having a sheet-shaped cavity and dried, etc. to form a sheet, thereby obtaining a single-layer sheet without using a support.

[0542] It should be noted that in the preparation of the single-layer sheet or resin composite sheet of the present embodiment, the drying conditions when removing the solvent are not particularly limited, but if it is a low temperature, the solvent is likely to remain in the resin composition, and if it is a high temperature, the curing of the resin composition will proceed, so it is preferably dried at a temperature of 20°C to 200°C for 1 to 90 minutes. In addition, the single-layer sheet or resin composite sheet can be used in an uncured state where only the solvent is dried, or it can be used in a semi-cured (B-stage) state as needed. Furthermore, the thickness of the resin layer in the single-layer sheet or resin composite sheet of the present embodiment can be adjusted by the concentration and coating thickness of the solution of the resin composition of the present embodiment used in the coating (coating), and there is no particular limitation. Generally, if the coating thickness is thicker, the solvent is likely to remain during drying, so it is preferably 0.1μm or more. In addition, the upper limit can be 500μm or less, 200μm or less, 180μm or less, and it can also be made into a film of 100μm or less, 80μm or less, 30μm or less, and 15μm or less.

[0543] Example

[0544] The present invention will be described in more detail below by giving examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples may be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0545] If the measuring equipment used in the examples is difficult to obtain due to discontinuation of production, other equipment with equivalent performance may be used for measurement.

[0546] <Determination of Weight Average Molecular Weight and Number Average Molecular Weight>

[0547] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin and the compound were measured by gel permeation chromatography (GPC). A liquid delivery pump (LC-20AD manufactured by Shimadzu Corporation), a differential refractive index detector (RID-10A manufactured by Shimadzu Corporation), and a GPC column (GPCKF-801, 802, 803, 804 manufactured by Showa Denko K.K.) were used, tetrahydrofuran was used as the solvent, the flow rate was 1.0 mL / min, the column temperature was 40°C, and a calibration curve based on monodisperse polystyrene was used.

[0548] <Synthesis Example 1 Synthesis of Naphthol Aralkyl Cyanate Compound (SNCN)>

[0549] 300 g (1.28 mol in terms of OH group) of 1-naphthol aralkyl resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and 194.6 g (1.92 mol) of triethylamine (1.5 mol per 1 mol of hydroxyl group) were dissolved in 1800 g of dichloromethane to prepare Solution 1.

[0550] 125.9 g (2.05 mol) of cyanogen chloride (1.6 mol per 1 mol of hydroxyl groups), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol per 1 mol of hydroxyl groups), and 1205.9 g of water were added dropwise over 30 minutes while the liquid temperature was kept between -2°C and -0.5°C under stirring. After the addition of solution 1 was completed, stirring was performed at the same temperature for 30 minutes, and then a solution (solution 2) prepared by dissolving 65 g (0.64 mol) of triethylamine (0.5 mol per 1 mol of hydroxyl groups) in 65 g of dichloromethane was added dropwise over 10 minutes. After the addition of solution 2 was completed, stirring was performed at the same temperature for 30 minutes to terminate the reaction.

[0551] After that, the reaction solution was allowed to stand and the organic phase and the aqueous phase were separated. The obtained organic phase was washed five times with 1300 g of water. The conductivity of the waste water after the fifth washing was 5 μS / cm, confirming that the removable ionic compounds were sufficiently removed by washing with water.

[0552] The organic phase after washing was concentrated under reduced pressure and finally concentrated to dryness at 90°C for 1 hour to obtain 331 g of the target naphthol aralkyl cyanate compound (SNCN) (orange viscous substance). The weight average molecular weight of the obtained SNCN was 600. In addition, the IR spectrum of SNCN showed 2250 cm -1 (cyanate group) absorption, and does not show the absorption of hydroxyl group.

[0553] <Synthesis Example 2 Synthesis of Modified Polyphenylene Ether Compound>

[0554] <<Synthesis of Bifunctional Phenylene Ether Oligomer>>

[0555] 9.36 g (42.1 mmol) of CuBr2, 1.81 g (10.5 mmol) of N,N'-di-tert-butylethylenediamine, 67.77 g (671.0 mmol) of n-butyldimethylamine, and 2,600 g of toluene were placed in a 12 L vertical reactor equipped with a stirring device, a thermometer, an air inlet pipe, and a baffle. The mixture was stirred at a reaction temperature of 40°C, and nitrogen and air were mixed and adjusted to a mixed gas with an oxygen concentration of 8% by volume at a flow rate of 5.2 L / min. While bubbling, a mixed solution of 129.32 g (0.48 mol) of 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenol)-4,4'-diol, 878.4 g (7.2 mol) of 2,6-dimethylphenol, 1.22 g (7.2 mmol) of N,N'-di-tert-butylethylenediamine, and 26.35 g (260.9 mmol) of n-butyldimethylamine, which was previously dissolved in 2,300 g of methanol, was added dropwise over 230 minutes and stirred. After the addition was completed, 1,500 g of water in which 48.06 g (126.4 mmol) of tetrasodium ethylenediaminetetraacetate was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with a 1N aqueous hydrochloric acid solution and then washed with pure water. The obtained solution was concentrated to 50% by mass using an evaporator to obtain 1981 g of a toluene solution of a bifunctional phenylene ether oligomer (resin "A"). The number average molecular weight of resin "A" based on polystyrene conversion by GPC method was 1,975, the weight average molecular weight based on polystyrene conversion by GPC method was 3,514, and the hydroxyl equivalent was 990.

[0556] <<Synthesis of Modified Polyphenylene Ether Compounds>>

[0557] In a reactor equipped with a stirring device, a thermometer and a reflux tube, 833.4 g of a toluene solution of resin "A", 76.7 g of vinylbenzyl chloride (AGC Seimi Chemical Co., Ltd., "CMS-P"), 1,600 g of dichloromethane, 6.2 g of benzyldimethylamine, 199.5 g of pure water, and 83.6 g of a 30.5% by mass NaOH aqueous solution were added and stirred at a reaction temperature of 40°C. After stirring for 2 hours, the organic layer was washed with a 1N hydrochloric acid aqueous solution and then washed with pure water. The obtained solution was concentrated with an evaporator, added dropwise to methanol to solidify, and the solid was recovered by filtration and vacuum dried to obtain 450.1 g of a modified polyphenylene ether compound. The number average molecular weight of the modified polyphenylene ether compound based on the polystyrene conversion of the GPC method was 2,250, the weight average molecular weight based on the polystyrene conversion of the GPC method was 3,920, and the vinyl equivalent was 1189 g / vinyl.

[0558] Example 1

[0559] 15.0 parts by mass of the naphthol aralkyl type cyanate compound synthesized in Synthesis Example 1, 35.0 parts by mass of a bismaleimide represented by the following structure (BMI-80, manufactured by K.I Chemical Industry Co., Ltd.), 25.0 parts by mass of the modified polyphenylene ether compound obtained in Synthesis Example 2, 15.0 parts by mass of a phosphorus flame retardant (PX-200, manufactured by Daihachi Chemical Co., Ltd., 1,3-phenylenebis(2,6-di(xylyl)phosphate)), 5.0 parts by mass of a styrene oligomer (Kristalex 3085, manufactured by Eastman Chemical Co., Ltd.), 5.0 parts by mass of a thermoplastic elastomer (SEPS, manufactured by Kuraray Co., Ltd., SEPTON 2104), and 1.1 μm average particle size of ADMATECHS CO., LTD.) 62.5 parts by mass of SC4500SQ (classified product), 62.5 parts by mass of silica (average particle size 0.7 μm, SFP-130MC, manufactured by Denki Kagaku Kogyo Co., Ltd.), 1.0 parts by mass of a wetting and dispersing agent (DISPERBYK-161, manufactured by BYK), 3.0 parts by mass of a silane coupling agent (KBM403, manufactured by Shin-Etsu Silicones Co., Ltd.), 0.4 parts by mass of a wetting and dispersing agent (DISPERBYK-2009, manufactured by BYK), 0.5 parts by mass of an ultraviolet absorber (HR-1, manufactured by Chuo Synthetic Chemical Co., Ltd.), 0.5 parts by mass of a non-metallic organic pigment (Kayaset Black AN, manufactured by Nippon Kayaku Co., Ltd.), 0.005 parts by mass of manganese octoate, and 0.9 parts by mass of triphenylimidazole were dissolved and mixed in methyl ethyl ketone to obtain a varnish. It should be noted that the above-mentioned amounts of each addition represent the solid content.

[0560] BMI-80

[0561]

[0562] Me represents a methyl group.

[0563] <Manufacturing of Test Specimens of Cured Plates with a Thickness of 0.8 mm>

[0564] The solvent was evaporated from the obtained varnish to obtain a resin composition powder. The resin composition powder was filled into a mold with a side of 100 mm and a thickness of 0.8 mm, and copper foil (3EC-M2S-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) with a thickness of 12 μm was placed on both sides. 2 , vacuum pressing was performed at a temperature of 220°C for 120 minutes, and then the copper foils on both sides were removed by etching to obtain a cured plate with a side of 100 mm and a thickness of 0.8 mm.

[0565] The obtained cured plate was used to evaluate relative dielectric constant (Dk), dielectric loss tangent (Df), and glass transition temperature (Tanδ). The evaluation results are shown in Table 1.

[0566] <Manufacturing of Test Specimens of Cured Plates with a Thickness of 30 μm>

[0567] The obtained varnish was applied to a copper foil substrate (copper foil with a thickness of 1.5 μm (MT-FL, manufactured by Mitsui Mining & Smelting Co., Ltd.)) in such a manner that the thickness of the resin composition layer after drying was 30 μm, and the solvent was removed by drying at 150° C. for 3 minutes. A copper foil with a thickness of 12 μm (3EC-M2S-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) was arranged on the other side, and the mixture was dried under a pressure of 30 kg / cm 2 , vacuum pressing was performed at a temperature of 220°C for 120 minutes to obtain a copper-clad laminate with a side of 200 mm and a thickness of 30 μm. The copper foil of the obtained copper-clad laminate was removed by etching to obtain an evaluation sample (a cured plate with a thickness of 30 μm). The prepared evaluation sample was used to evaluate the transmittance of g-rays, h-rays and i-rays and back exposure. The evaluation results are shown in Table 1.

[0568] <Measurement Method and Evaluation Method>

[0569] (1) Measurement of the transmittance of g-rays (436 nm), h-rays (405 nm), and i-rays (365 nm)

[0570] The transmittance of the prepared evaluation sample having a thickness of 30 μm was measured at wavelengths of 365 nm, 405 nm, and 436 nm using a UV-vis measuring device (Hitachi Spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation).

[0571] The unit is expressed in %.

[0572] (2) Determination of relative dielectric constant (Dk) and dielectric loss tangent (Df)

[0573] The cured plate having a thickness of 0.8 mm obtained above was processed into a size of 1.0 mm×100 mm, dried at 120° C. for 60 minutes, and then the relative dielectric constant (Dk) and dielectric loss tangent (Df) after drying were measured at 10 GHz using a perturbation cavity resonator. The measurement temperature was set at 23° C.

[0574] Agilent 8722ES manufactured by Agilent Technologies, Inc. was used as the perturbation method cavity resonator.

[0575] Relative dielectric constant (Dk)

[0576] A: 3.0 or less

[0577] B: more than 3.0

[0578] Dielectric loss tangent (Df)

[0579] S: less than 0.0026

[0580] A: 0.0026 or more and less than 0.0027

[0581] B: 0.0027 or more but less than 0.0028

[0582] C: 0.0028 or more

[0583] (3) Determination of back exposure

[0584] A 15 μm thick film-shaped resist (PSR-800AUSSR1 manufactured by TAIYOHOLDINGS CO., LTD.) was laminated on both sides of the prepared 30 μm thick evaluation sample, and exposure was performed from one side (exposure side) under the following conditions. Then, the uncured resist on the side opposite to the exposure side (back side) was removed. It was confirmed whether resist residue remained on the back side due to back exposure from the exposure side.

[0585] Equipment: DI exposure machine made by ORC

[0586] Light source: 3 mixed (g-ray, h-ray, i-ray)

[0587] Exposure: 400mJ

[0588] A: No resist residue

[0589] B: There is resist residue

[0590] (4) Glass transition temperature (Tanδ)

[0591] The cured plate having a thickness of 0.8 mm obtained above was processed into a size of 12.7 mm × 30 mm, and the dynamic viscoelasticity was measured using a dynamic viscoelasticity measuring apparatus in accordance with JIS-K7244-4:1999 (Plastics - Test methods for dynamic mechanical properties - Part 4: Tensile vibration - Non-resonance method) at a starting temperature of 30°C, an end temperature of 400°C, a heating rate of 5°C / min, a measuring frequency of 1 Hz, and a nitrogen atmosphere. The temperature at which the loss tangent (Tanδ) obtained at this time is the maximum value is taken as the glass transition temperature.

[0592] As a dynamic viscoelasticity measuring apparatus, EXSTAR6000DMS6100 manufactured by Seiko Instruments Inc. was used.

[0593] Evaluation was performed as follows.

[0594] A: Above 255℃

[0595] B: 245℃ or higher but less than 255℃

[0596] C: less than 245℃

[0597] Example 2

[0598] In Example 1, the content of the non-metallic organic dye (Kayaset Black AN) was changed to 1.0 part by mass, and the other procedures were carried out in the same manner.

[0599] Example 3

[0600] In Example 1, the same procedures were followed except that the content of the ultraviolet absorber (HR-1) was changed to 1.0 part by mass and the content of the non-metallic organic dye (Kayaset Black AN) was changed to 1.0 part by mass.

[0601] Example 4

[0602] In Example 1, the ultraviolet absorber (HR-1) was not blended, the content of the non-metallic organic dye (Kayaset Black AN) was changed to 2.0 parts by mass, and the other procedures were carried out in the same manner.

[0603] Example 5

[0604] In Example 1, the content of the non-metallic organic dye (Kayaset Black AN) was changed to 2.0 parts by mass, and the other procedures were carried out in the same manner.

[0605] Example 6

[0606] In Example 1, the same procedures were followed except that the content of the ultraviolet absorber (HR-1) was changed to 3.0 parts by mass and the content of the non-metallic organic dye (Kayaset Black AN) was changed to 1.0 parts by mass.

[0607] Comparative Example 1

[0608] In Example 1, the ultraviolet absorber (HR-1) and the non-metallic organic dye (Kayaset Black AN) were not mixed, and the other procedures were carried out in the same manner.

[0609] Comparative Example 2

[0610] In Example 1, the non-metallic organic dye (Kayaset Black AN) was not blended, and the other procedures were carried out in the same manner.

[0611] Comparative Example 3

[0612] In Example 1, the same procedures were followed except that the content of the ultraviolet absorber (HR-1) was changed to 3.0 parts by mass and the non-metallic organic dye (Kayaset Black AN) was not blended.

[0613] Comparative Example 4

[0614] In Example 1, the ultraviolet absorber (HR-1) was not blended, the content of the non-metallic organic dye (Kayaset Black AN) was changed to 1.0 part by mass, and the other procedures were carried out in the same manner.

[0615] [Table 1]

[0616] Example 1 Example 2 Example 3 Example 4 Example 5 g-ray (436nm) transmittance (%) 0.064 0.059 0.040 0.039 0.027 h-ray (405nm) transmittance (%) 0.030 0.020 0.012 0.030 0.021 i-ray (365nm) transmittance (%) 0.011 0.006 0.006 0.016 0.018 Dk A A A A A Df s s A B B Determination of back exposure A A A A A Glass transition temperature(℃) A A A B B

[0617] [Table 2]

[0618] Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 g-ray (436nm) transmittance (%) 0.037 0.228 0.151 0.161 0.077 h-ray (405nm) transmittance (%) 0.005 0.110 0.044 0.029 0.048 i-ray (365nm) transmittance (%) 0.003 0.048 0.015 0.020 0.021 Dk A A A A A Df B s s c s Determination of back exposure A B B B B Glass transition temperature(℃) B A A A A

Claims

1. A resin composition comprising a thermosetting compound, In a cured product formed from the resin composition with a thickness of 30 μm, the transmittances of g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm) are each 0.070% or less.

2. The resin composition according to claim 1, wherein the transmittance of the cured product thereof formed into a 30 μm thick product is 0.050% or less to h-rays (wavelength: 405 nm). 3 . The resin composition according to claim 1 , wherein the i-ray (wavelength: 365 nm) transmittance in a cured product molded into a 30 μm thickness is 0.040% or less.

4. The resin composition according to claim 1 or 2, comprising an ultraviolet absorber and / or a non-metallic organic pigment.

5. The resin composition according to claim 1 or 2, comprising an ultraviolet absorber and a non-metallic organic pigment.

6. The resin composition according to claim 4, wherein The non-metallic organic pigment comprises a dye.

7. The resin composition according to claim 4, wherein The content of the ultraviolet absorber is more than 0 parts by mass and 3.0 parts by mass or less relative to 100 parts by mass of the resin solid content in the resin composition.

8. The resin composition according to claim 4, wherein The content of the non-metallic organic pigment is more than 0 parts by mass and is 2.0 parts by mass or less relative to 100 parts by mass of the resin solid content in the resin composition.

9. The resin composition according to claim 5, wherein The mass ratio of the ultraviolet absorber to the non-metallic organic pigment (ultraviolet absorber / non-metallic organic pigment) is 0.15 to 4.

0.

10. The resin composition according to claim 5, wherein The mass ratio of the ultraviolet absorber to the non-metallic organic pigment (ultraviolet absorber / non-metallic organic pigment) is 0.4 to 1.

5.

11. The resin composition according to claim 1 or 2, wherein The thermosetting compound comprises at least one selected from the group consisting of maleimide compounds, epoxy compounds, phenol compounds, oxetane resins, benzoxazine compounds, polyphenylene ether compounds containing two or more carbon-carbon unsaturated double bonds, polymers having a structural unit represented by formula (V), and cyanate compounds. In formula (V), Ar represents an aromatic hydrocarbon linking group, and * represents a bonding position.

12. The resin composition according to claim 1 or 2, wherein The dielectric loss tangent of a cured product of the resin composition is greater than or equal to 0.0001 and less than 0.0027. 13 . The resin composition according to claim 1 , further comprising a filler.

14. The resin composition according to claim 13, wherein The content of the filler is 10 to 1000 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

15. The resin composition according to claim 1 or 2, which is used for forming an insulating layer.

16. The resin composition according to claim 1, The transmittance of the cured product formed into a thickness of 30 μm is 0.050% or less for h-rays (wavelength 405 nm). The i-ray (wavelength 365nm) transmittance of the cured product formed into a thickness of 30μm is 0.040% or less. The resin composition comprises an ultraviolet absorber and a non-metallic organic pigment, The non-metallic organic pigment comprises a dye, The content of the ultraviolet absorber is more than 0 parts by mass and is 3.0 parts by mass or less relative to 100 parts by mass of the resin solid content in the resin composition, The content of the non-metallic organic pigment is more than 0 parts by mass and is 2.0 parts by mass or less relative to 100 parts by mass of the resin solid content in the resin composition, The mass ratio of the ultraviolet absorber to the non-metallic organic pigment (ultraviolet absorber / non-metallic organic pigment) is 0.4 to 1.5, The thermosetting compound comprises at least one selected from the group consisting of maleimide compounds, epoxy compounds, phenol compounds, oxetane resins, benzoxazine compounds, polyphenylene ether compounds containing two or more carbon-carbon unsaturated double bonds, polymers having a structural unit represented by formula (V), and cyanate compounds. In formula (V), Ar represents an aromatic hydrocarbon linking group, and * represents a bonding position. 17 . A cured product, which is a cured product of the resin composition according to claim 1 .

18. A prepreg comprising a substrate and the resin composition according to claim 1, 2 or 16. 19 . A metal foil-clad laminate comprising: a layer formed from the resin composition according to claim 1 ; and a metal foil disposed on one or both surfaces of the layer. 20 . A resin composite sheet comprising: a support; and a layer formed from the resin composition according to claim 1 , 2 or 16 and disposed on a surface of the support. 21 . A printed wiring board comprising an insulating layer and a conductor layer disposed on a surface of the insulating layer, wherein the insulating layer comprises a layer formed from the resin composition according to claim 1 . 22 . The printed circuit board according to claim 21 , having an insulating layer having a thickness of 15 μm or less as the insulating layer.

23. A semiconductor device comprising the printed circuit board according to claim 22.

24. A method for manufacturing a printed circuit board, comprising the following steps: A step of preparing a substrate, wherein the substrate is laminated with: at least one insulating layer comprising a cured product of the resin composition according to claim 1, 2 or 16, and at least one conductive layer in contact with the insulating layer; A step of forming a photosensitive composition layer that is cured by light with a wavelength of 350 to 440 nm on both surfaces of the substrate; and A step of disposing a mask pattern on at least one surface of the photosensitive composition layer and exposing the layer to light having a wavelength of 350 to 440 nm through the mask pattern.

25. A method for manufacturing a printed circuit board, comprising the following steps: A step of forming a photosensitive composition layer cured by light of a wavelength of 350 to 440 nm on both surfaces of a substrate, the substrate comprising: at least one insulating layer comprising a cured product of the resin composition according to claim 1, 2 or 16, and at least one conductive layer in contact with the insulating layer; and A step of disposing a mask pattern on at least one surface of the photosensitive composition layer and exposing the layer to light having a wavelength of 350 to 440 nm through the mask pattern. 26 . The method for manufacturing a printed circuit board according to claim 24 , comprising an insulating layer having a thickness of 15 μm or less as the insulating layer.

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