Resin composition, resin sheet, multilayer printed wiring board, and semiconductor device

Abstract

A resin composition according to the present invention comprises: a maleimide compound (A) comprising a structural unit represented by formula (1) and maleimide groups located at both ends of a molecular chain; a dicyclopentadiene phenol type epoxy (meth) acrylate (B) comprising one or more carboxyl groups; and a photocuring initiator (C). # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a resin composition, a resin sheet, a multilayer printed circuit board and a semiconductor device. Background Art

[0002] Active research is underway to reduce the thickness of laminates used in multilayer printed circuit boards by miniaturizing and increasing their density. This thinning also requires thinner insulation layers, such as resin sheets and metal-clad sheets that do not contain glass cloth.

[0003] Furthermore, various properties required of resin sheets and metal-clad foil sheets used in insulating layers have also become more diverse and stringent. One of the required properties is dielectric properties (low dielectric constant and low dielectric loss tangent).

[0004] Furthermore, the resin composition as the material of the insulating layer is mainly composed of thermosetting resins, but the opening for obtaining conduction between the insulating layers is usually performed by laser processing. The opening using laser processing has the problem that the higher the number of holes in the high-density substrate, the longer the processing time becomes. Therefore, in recent years, it is required to use a resin composition that can cure the exposed portion (exposure process) and remove the unexposed portion (development process) by irradiation with light, etc., and to perform opening processing in the exposure and development processes together to produce a resin sheet for a high-density substrate.

[0005] The exposure method uses a mercury lamp as a light source, performing exposure through a photomask. Materials that can be properly exposed to the mercury lamp's light source are required. Exposure methods using this mercury lamp as a light source utilize GHI mixed radiation (a wavelength of 436 nm for g-rays, 405 nm for h-rays, and 365 nm for i-rays), and a general-purpose photocuring initiator can be selected. Furthermore, in recent years, exposure methods using i-rays (365 nm wavelength), which have less chromatic aberration than GHI mixed radiation, as a light source have been increasingly introduced to achieve higher-definition patterns.

[0006] As a development method, alkali development is used because a high-definition pattern can be obtained.

[0007] Patent Document 1 describes a resin composition containing a bismaleimide compound (curable resin) and a photoradical curing initiator (curing agent) as a photosensitive resin composition for use in laminates and resin sheets.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: WO2018 / 56466A1 Summary of the Invention

[0011] Problems to be solved by the invention

[0012] However, in patent documentation 1, bismaleimide compounds are used as curable resins, but the light transmittance of maleimide compounds is poor usually, so if maleimide compounds are included, light cannot fully reach photocuring initiator, and photocuring initiator is difficult to produce free radicals, and its reactivity is very low. In addition, in patent documentation 1, when using the active energy ray of the i-ray comprising a wavelength of 365nm to carry out photocuring, because the i-ray transmittance of maleimide compounds is low, there is a problem of low degree of cure. Thus, in patent documentation 1, maleimide compounds are cured by adding heating before development, but due to being accompanied by heating, it is impossible to obtain high-precision insulating layer, resist pattern. In addition, the resin composition recorded in patent documentation 1 is originally alkali developable and is not sufficient, so unexposed resin composition is also left after development. Therefore, in patent documentation 1, it is impossible to obtain insulating layer, high-precision resist pattern with low dielectric constant and low dielectric loss tangent and high-precision, it is impossible to use for the manufacture of high-density printed circuit boards.

[0013] The present invention has been made in view of the above-mentioned problems in the prior art, and its object is to provide a resin composition and a resin sheet that have excellent photocurability to various active energy rays, particularly to active energy rays including i-rays having a wavelength of 365 nm, in the exposure step when producing a multilayer printed wiring board, and that can impart excellent alkali developability in the development step; and a resin composition and a resin sheet that can provide a cured product having a low relative dielectric constant and a low dielectric loss tangent, a high-definition insulating layer having a low relative dielectric constant and a low dielectric loss tangent, a high-density printed wiring board having a high-definition resist pattern, and a semiconductor device.

[0014] Solutions for solving problems

[0015] The present inventors have conducted intensive studies and have discovered that a resin composition and a resin sheet comprising a specific maleimide compound (A), a dicyclopentadienol-type epoxy (meth)acrylate containing one or more carboxyl groups (B), and a photocuring initiator (C) have excellent photocurability to various active energy rays, particularly to active energy rays including i-rays having a wavelength of 365 nm, during the exposure step in the production of a multilayer printed circuit board. Furthermore, the resin composition and a resin sheet can be imparted with excellent alkali developability during the development step. By using these resin compositions, a cured product having a lower relative dielectric constant and dielectric loss tangent can be obtained, and thus, a high-definition insulating layer with a low relative dielectric constant and dielectric loss tangent, a high-density printed circuit board having a high-definition resist pattern, and a semiconductor device can be obtained. The present invention has been completed.

[0016] That is, the present invention includes the following contents.

[0017] [1] A resin composition comprising: a bismaleimide compound (A) comprising a structural unit represented by the following formula (1) and maleimide groups located at both ends of the molecular chain; a dicyclopentadienol-type epoxy (meth)acrylate (B) comprising one or more carboxyl groups; and a photocuring initiator (C).

[0018]

[0019] (In formula (1), R1 represents a straight-chain or branched alkylene group having 1 to 16 carbon atoms, or a straight-chain or branched alkenylene group having 2 to 16 carbon atoms. R2 represents a straight-chain or branched alkylene group having 1 to 16 carbon atoms, or a straight-chain or branched alkenylene group having 2 to 16 carbon atoms. R3 each independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 16 carbon atoms, or a straight-chain or branched alkenyl group having 2 to 16 carbon atoms. n1 each independently represents an integer from 1 to 10.).

[0020] [2] The resin composition according to [1], wherein the content of the bismaleimide compound (A) is 5.0 to 90 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition, the content of the epoxy (meth)acrylate (B) is 5.0 to 90 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition, and the content of the photocuring initiator (C) is 0.1 to 50 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

[0021] [3] The resin composition according to [1] or [2], further comprising a maleimide compound (D) other than the bismaleimide compound (A), wherein the content of the maleimide compound (D) is 1.0 to 25 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

[0022] [4] The resin composition according to any one of [1] to [3], further comprising one or more resins or compounds (E) selected from the group consisting of modified polyphenylene ether compounds, cyanate compounds, phenolic resins, oxetane resins, benzoxazine compounds and epoxy resins, wherein the total content of the resins or compounds (E) is 1.0 to 25 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

[0023] [5] The resin composition according to any one of [1] to [4], further comprising a filler (F), wherein the content of the filler (F) is 5.0 to 100 parts by mass relative to 100 parts by mass of the total resin solid content in the resin composition.

[0024] [6] A resin sheet comprising a support and a resin layer disposed on one or both surfaces of the support, wherein the resin layer comprises the resin composition according to any one of [1] to [5].

[0025] [7] The resin sheet according to [6], wherein the resin layer has a thickness of 1 to 50 μm.

[0026] [8] A multilayer printed wiring board comprising an insulating layer and a conductor layer formed on one or both surfaces of the insulating layer, wherein the insulating layer comprises the resin composition according to any one of [1] to [5].

[0027] [9] A semiconductor device comprising the resin composition according to any one of [1] to [5].

[0028] Effects of the Invention

[0029] According to the present invention, a photocurable film having excellent photocurability to various active energy rays, particularly to active energy rays including i-rays having a wavelength of 365 nm, can be provided in the exposure step in the production of a multilayer printed circuit board. Furthermore, excellent alkali developability can be imparted in the development step. By using such a film, a cured product having a lower relative dielectric constant and dielectric loss tangent can be obtained, and thus, a high-definition insulating layer with a low relative dielectric constant and dielectric loss tangent, a high-definition resist pattern, and a high-density printed circuit board and a semiconductor device can be provided. DETAILED DESCRIPTION

[0030] Hereinafter, a method for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail. The following embodiments are examples for illustrating the present invention and are not intended to limit the present invention to the following contents. The present invention can be implemented by appropriately deforming within the scope of its purpose.

[0031] It should be noted that "(meth)acrylic acid" in this specification refers to both "acrylic acid" and its corresponding "methacrylic acid." Furthermore, in this specification, unless otherwise specified, "resin solids" or "resin solids in a resin composition" refers to the components in the resin composition excluding the photocuring initiator (C), filler (F), silane coupling agent, wetting and dispersing agent, crosslinking agent, additives listed in other components, and organic solvent. "100 parts by mass of resin solids" refers to the total of 100 parts by mass of the components in the resin composition excluding the photocuring initiator (C), filler (F), silane coupling agent, wetting and dispersing agent, crosslinking agent, additives listed in other components, and organic solvent.

[0032] In this specification, Mw represents the mass average molecular weight, Mn represents the number average molecular weight, and Mw / Mn represents the molecular weight distribution. Mw, Mn, and Mw / Mn can be determined by conversion to polystyrene standards based on gel permeation chromatography (GPC).

[0033] In this specification, the substituent is not particularly limited, and examples thereof include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms, a hydroxyl group, a cyano group, a nitro group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aryl group, an aralkyl group, an alkoxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an alkanoyloxy group, an aroyloxy group, and an alkylsilyl group. Specific examples of these substituents can be found in the examples of the groups described in this specification.

[0034] [Resin composition]

[0035] The resin composition of the present embodiment comprises: a maleimide compound (A) (also referred to as component (A) or bismaleimide compound (A)) comprising a structural unit represented by formula (1) and maleimide groups located at both ends of the molecular chain, a dicyclopentadienol-type epoxy (meth)acrylate (B) (also referred to as component (B) or epoxy (meth)acrylate (B)) comprising one or more carboxyl groups, and a photocuring initiator (C) (also referred to as component (C) or initiator (C)). The resin composition of the present embodiment comprises a specific bismaleimide compound (A), a specific epoxy (meth)acrylate (B) and an initiator (C), and is suitable for use in the production of multilayer printed circuit boards. By using the resin composition, in the exposure process in the production of multilayer printed circuit boards, it has excellent photocurability to various active energy rays, particularly to active energy rays including i-rays with a wavelength of 365 nm, and can impart excellent alkali developability in the development process. In addition, by using the resin composition and the resin sheet, a cured product with a lower relative dielectric constant and dielectric loss tangent can be obtained, and high-definition, high-density printed wiring boards and semiconductor devices having high-definition insulating layers with low relative dielectric constant and dielectric loss tangent, and high-definition resist patterns can be obtained.

[0036] Bismaleimide compound (A)

[0037] The resin composition of the present embodiment contains a maleimide compound (A) containing a structural unit represented by formula (1) and maleimide groups located at both ends of the molecular chain.

[0038]

[0039] In formula (1), R1 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. R2 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. R3 each independently represents a hydrogen atom, 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. n1 each independently represents an integer of 1 to 10.

[0040] The present inventors have found that by including the epoxy (meth)acrylate (B) and the photocuring initiator (C) described later, along with the bismaleimide compound (A), the resin composition exhibits excellent photocurability to various active energy rays, particularly to active energy rays including i-rays having a wavelength of 365 nm. The reason for this is not yet clear, but the present inventors presume it to be as follows. However, the reason is not limited to this.

[0041] Maleimide compounds generally have poor light transmittance. Therefore, if a resin composition contains a maleimide compound, light cannot adequately reach the photoinitiator dispersed in the resin composition, making it difficult for the photoinitiator to generate free radicals. Consequently, photoradical reactions of maleimide compounds are generally difficult to proceed, and even if free radical polymerization or dimerization of the maleimide monomer proceeds, the reactivity is very low.

[0042] However, the bismaleimide compound (A) has a structural unit shown in formula (1), i.e., an alicyclic skeleton with little light absorption, and therefore has very excellent light transmittance. In addition, epoxy (meth) acrylate (B) has an alicyclic skeleton with little light absorption in its structure, and therefore has very excellent light transmittance. Therefore, light fully reaches the photocuring initiator, effectively causing the photoradical reaction of maleimide, the polymerization reaction of the ethylenically unsaturated groups contained in epoxy (meth) acrylate, and the reaction of the ethylenically unsaturated groups contained in maleimide and epoxy (meth) acrylate, etc., and can be used together with the bismaleimide compound (A), epoxy (meth) acrylate (B), photocuring initiator (C), the maleimide compound (D) described later as needed, resin or compound (E), filling material (F), etc. to perform photocuring. Therefore, by using the resin composition and the resin sheet, a cured product with a lower relative dielectric constant and dielectric loss tangent can be suitably obtained, and a high-definition insulating layer with a low relative dielectric constant and dielectric loss tangent, a high-density printed wiring board having a high-definition resist pattern, and a semiconductor device can be suitably manufactured.

[0043] A chloroform solution containing a bismaleimide compound (A) at 1% by mass is prepared, and an active energy ray containing a wavelength of 365nm (i-ray) is used. When the transmittance of the chloroform solution containing a bismaleimide compound (A) at 1% by mass is measured, the transmittance is 5% or more, showing very excellent light transmittance. Therefore, even if active energy rays containing a wavelength of 365nm (i-ray) are used, photocuring can be appropriately performed. From the perspective of showing more excellent light transmittance, the transmittance at a wavelength of 365nm (i-ray) is preferably 8% or more, more preferably 10% or more. The upper limit of the transmittance at a wavelength of 365nm (i-line) is, for example, 99.9% or less. It should be noted that, in this specification, the cuvette (cell) length (path length during measurement) when measuring transmittance and absorbance is 1 cm.

[0044] It should be noted that photocuring initiators tend to have a reduced absorbance with respect to active energy rays having a wavelength of 365 nm (i-rays). Therefore, the photocuring initiator (C) is preferably one having an absorbance of 0.1 or greater with respect to light having a wavelength of 365 nm (i-rays) when measuring the absorbance of a chloroform solution containing the photocuring initiator (C) at a concentration of 0.01% by mass, indicating very excellent light absorption.

[0045] Furthermore, maleimide compounds generally have extremely low water solubility and lack reactivity with the alkali component in an alkali developer, making it difficult to achieve alkali developability. However, by including epoxy (meth)acrylate (B) along with the bismaleimide compound (A), the resin composition exhibits excellent photocurability and very good alkali developability. The reason for this is not yet clear, but the present inventors speculate as follows.

[0046] That is, epoxy (meth) acrylate (B) has an alicyclic structure and an ethylenically unsaturated group capable of polymerization in the structure, so in the exposure process, it does not hinder the photocuring reaction and has excellent photocurability. By using such epoxy (meth) acrylate (B) together with the bismaleimide compound (A), the obtained cured product, insulating layer and anti-etching pattern have a high crosslinking density. Furthermore, epoxy (meth) acrylate (B) has a plurality of polar groups such as carboxyl groups, ester bonds and ether bonds in the structure, and has an alicyclic structure with high flexibility, so in the development process, the alkaline developer easily flows into the unexposed part (resin composition), can give the resin composition excellent alkali developability, and can appropriately control the water solubility of the unexposed part. In addition, the bismaleimide compound (A) has a relatively long chain and soft structure, and on this basis, does not have a structure that causes interaction with the alkaline component in the alkaline developer. Therefore, in the developing process, when the alkali developer flows into the unexposed portion (resin combination), it will not be hindered by the bismaleimide compound (A), and the alkali component in the alkali developer has a high affinity with the polar group in the epoxy (meth) acrylate (B), and the alkali component and the carboxyl group in the epoxy (meth) acrylate (B) can quickly and appropriately form a salt. Therefore, the water solubility of the unexposed portion (resin combination) is improved. Both the bismaleimide compound (A) and the epoxy (meth) acrylate (B) have a high alicyclic skeleton with flexibility, so their compatibility is very high. Therefore, the bismaleimide compound (A) in the alkali developer, along with the dissolution of the epoxy (meth) acrylate (B) in the alkali developer, can be dissolved in the alkali developer in a manner of being involved with the epoxy (meth) acrylate (B). Based on such reasons, it is inferred that the resin combination has excellent alkali developability.

[0047] Then, utilize light to further heat such resin combination as required, solidify thus, thereby can obtain the low cured product of relative dielectric constant and dielectric loss tangent.Therefore, by using resin combination and the resin sheet obtained by resin combination, can obtain the lower cured product of relative dielectric constant and dielectric loss tangent, can obtain high-precision and have the high-density printed circuit board (PCB) and the semiconductor device of the insulating layer that relative dielectric constant and dielectric loss tangent are low, high-precision resist pattern.Its reason is still uncertain, but the inventor etc. infer as follows.

[0048] That is, as mentioned above, resin combination has excellent light curing property and alkali developability.Therefore, resin combination can have excellent resolution, can obtain very high fine insulating layer and resist pattern.That is, bismaleimide compound (A) is due to maleimide skeleton, and relative dielectric constant and dielectric loss tangent are lower.And then, relative dielectric constant and dielectric loss tangent of the dicyclopentadiene skeleton as the main skeleton of epoxy (meth) acrylate (B) are also lower.On the other hand, bismaleimide compound (A) has maleimide skeleton, and epoxy (meth) acrylate (B) has polar group, so the molar polarization of these compounds is relatively large.Therefore, it is believed that if these compounds are mixed, the influence of molar polarization (molar polarization) becomes large, and the dielectric constant of mixture and dielectric loss tangent become high compared with bismaleimide compound (A) or epoxy (meth) acrylate (B). But, as mentioned above, these compounds all have the high alicyclic structure of flexibility, so compatibility is very high, and solidified material can have high cross-linking density.Therefore, in solidified material, the influence of molar polarization tapers off, and solidified material can have excellent dielectric properties.Thus infer, solidified material has excellent light curing property and alkali development, and relative dielectric constant and dielectric loss tangent decrease.Based on such reason, infer by using resin combination and the resin sheet obtained by resin combination, can suitably obtain the lower solidified material of relative dielectric constant and dielectric loss tangent, can obtain high fine and have the low insulating layer of relative dielectric constant and dielectric loss tangent, the high-density printed circuit board and the semiconductor device of high fine resist pattern.But reason is not limited to this.

[0049] Furthermore, the obtained cured product is also excellent in heat resistance, insulation reliability, and thermal stability. Therefore, according to this embodiment, protective films, insulating layers, and resist patterns in multilayer printed wiring boards and semiconductor devices can be suitably formed.

[0050] The bismaleimide compound (A) is not particularly limited as long as it exhibits the effects of the present invention. From the perspective of obtaining a more suitable viscosity and further suppressing an increase in the viscosity of the varnish, the mass average molecular weight (Mw) is preferably 100 to 5000, more preferably 300 to 4500.

[0051] Next, the structure of the bismaleimide compound (A) will be described.

[0052] In the formula (1) of the bismaleimide compound (A), R1 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. From the perspective of obtaining a more suitable viscosity and further controlling the increase in viscosity of the varnish, R1 is preferably a linear or branched alkylene group, and more preferably a linear alkylene group.

[0053] The number of carbon atoms of the alkylene group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint of obtaining a more suitable viscosity and further suppressing the increase in viscosity of the varnish.

[0054] Examples of the linear or branched alkylene group include methylene, ethylene, propylene, 2,2-dimethylpropylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, undecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, neopentylene, dimethylbutylene, methylhexylene, ethylhexylene, dimethylhexylene, trimethylhexylene, methylheptylene, dimethylheptylene, trimethylheptylene, tetramethylheptylene, ethylheptylene, methyloctylene, methylenenonylene, methylenedecylene, methylenedodecylene, methylundecylene, methyltridecylene, methyltetradecylene, and methylpentadecylene.

[0055] The number of carbon atoms in the alkenylene group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint of obtaining a more appropriate viscosity and further suppressing the increase in viscosity of the varnish.

[0056] Examples of the linear or branched alkenylene group include vinylene, 1-methylvinylene, allylene, propenylene, isopropenylene, 1-butenylene, 2-butenylene, 1-pentenylene, 2-pentenylene, isopentenylene, cyclopentenylene, cyclohexenylene, and dicyclopentadienylene.

[0057] In formula (1), R2 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. From the perspective of obtaining a more suitable viscosity and further controlling the increase in viscosity of the varnish, R2 is preferably a linear or branched alkylene group, and more preferably a linear alkylene group.

[0058] The number of carbon atoms of the alkylene group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint of obtaining a more suitable viscosity and further suppressing the increase in viscosity of the varnish.

[0059] As the linear or branched alkylene group, the above-mentioned R1 can be referred to.

[0060] The number of carbon atoms in the alkenylene group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint of obtaining a more appropriate viscosity and further suppressing the increase in viscosity of the varnish.

[0061] As the linear or branched alkenylene group, the above-mentioned R1 can be referred to.

[0062] In the formula (1), R1 and R2 may be the same or different, but are preferably the same from the viewpoint of easier synthesis of the bismaleimide compound (A).

[0063] In formula (1), R3 each independently represents a hydrogen atom, 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. From the perspective of obtaining a more suitable viscosity and further controlling the viscosity increase of the varnish, R3 each independently preferably represents a hydrogen atom or a linear or branched alkyl group having 1 to 16 carbon atoms. More preferably, 1 to 5 groups (R3) in R3 are linear or branched alkyl groups having 1 to 16 carbon atoms, and the remaining groups (R3) are hydrogen atoms. Even more preferably, 1 to 3 groups (R3) in R3 are linear or branched alkyl groups having 1 to 16 carbon atoms, and the remaining groups (R3) are hydrogen atoms.

[0064] The number of carbon atoms in the alkyl group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint of obtaining a more appropriate viscosity and further suppressing the increase in viscosity of the varnish.

[0065] Examples of the linear or branched alkyl group include methyl, ethyl, n-propyl, isopropyl, 1-ethylpropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, sec-hexyl, tert-hexyl, n-heptyl, n-octyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylpentan-3-yl, and n-nonyl.

[0066] The number of carbon atoms in the alkenyl group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint of obtaining a more appropriate viscosity and further controlling the increase in viscosity of the varnish.

[0067] Examples of the linear or branched alkenyl group include vinyl, allyl, 4-pentenyl, isopropenyl, isopentenyl, 2-heptenyl, 2-octenyl, and 2-nonenyl.

[0068] In formula (1), n1 each independently represents an integer of 1 to 10.

[0069] The bismaleimide compound (A) has a maleimide group at both ends of the molecular chain. Both ends refer to the two ends in the molecular chain of the bismaleimide compound (A). For example, when the structural unit represented by formula (1) is located at the end of the molecular chain of the bismaleimide compound (A), it means that there is a maleimide group at the end of the molecular chain of R1, or at the end of the molecular chain in the N atom of the maleimide ring, or at both ends. The bismaleimide compound (A) may also have a maleimide group other than at both ends of the molecular chain.

[0070] The maleimide group is represented by formula (2), and the N atom is bonded to the molecular chain of the bismaleimide compound (A). The maleimide groups bonded to the bismaleimide compound (A) may all be the same or different, but preferably the maleimide groups at both ends of the molecular chain are the same.

[0071]

[0072] In formula (2), R 24 Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. 24 Preferably, both are hydrogen atoms.

[0073] The number of carbon atoms in the alkyl group is preferably 1 to 3, more preferably 1 to 2, from the viewpoint of more suitable photocuring.

[0074] As the linear or branched alkyl group, the above-mentioned R3 can be referred to.

[0075] Examples of such bismaleimide compounds (A) include maleimide compounds represented by formula (3). These may be used alone or in combination of two or more compounds having different repeating numbers of a in formula (3).

[0076]

[0077] In formula (3), a represents an integer of 1 to 10. From the viewpoint of obtaining a more appropriate viscosity and being able to further control the increase in viscosity of the varnish, a is preferably an integer of 1 to 6.

[0078] A commercially available bismaleimide compound (A) may be used. An example of a commercially available bismaleimide compound is MIZ-001 (trade name, a mixture containing a maleimide compound of formula (3) where a is an integer of 1 to 6) manufactured by Nippon Kayaku Co., Ltd.

[0079] Relative to 100 parts by mass of the resin solids in the resin composition, the content of the bismaleimide compound (A) is preferably 5.0 to 90 parts by mass, more preferably 10 to 80 parts by mass, further preferably 15 to 70 parts by mass, and even more preferably 20 to 65 parts by mass. By making the content of the bismaleimide compound (A) within the above range, a cured product having the bismaleimide compound as the main component can be obtained, the photocurability can be further improved, and there is a tendency to obtain more excellent dielectric properties (low dielectric constant and low dielectric loss tangent), heat resistance and thermal stability.

[0080] The bismaleimide compound (A) can be used alone or in combination of two or more.

[0081] (Method for producing bismaleimide compound (A))

[0082] The bismaleimide compound (A) can be produced by a known method. For example, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, a monomer containing a diamine such as a dimer diamine, and maleic anhydride are subjected to a polyaddition reaction at a temperature of generally about 80°C to 250°C, preferably about 100°C to 200°C, for generally about 0.5 hours to 50 hours, preferably about 1 hour to 20 hours, to obtain an addition polymer. Thereafter, the addition polymer is subjected to an imidization reaction, i.e., a dehydration ring-closure reaction, at a temperature of generally about 60°C to 120°C, preferably about 80°C to 100°C, for generally about 0.1 hours to 2 hours, preferably about 0.1 hours to 0.5 hours, to obtain the bismaleimide compound (A).

[0083] Dimer diamine can be obtained, for example, by a reductive amination reaction of dimer acid. The amination reaction can be carried out, for example, by a known method such as a reduction method using ammonia and a catalyst (e.g., the method described in Japanese Patent Application Laid-Open No. 9-12712). Dimer acid refers to a dibasic acid obtained by dimerizing unsaturated fatty acids through an intermolecular polymerization reaction. Although it also depends on the synthesis conditions and refining conditions, it usually contains a small amount of monomeric acid, trimer acid, etc. in addition to dimer acid. After the reaction, double bonds remain in the obtained molecule, but in this embodiment, substances in which the double bonds present in the molecule are reduced to saturated dibasic acids through hydrogenation are also included in the dimer acid. Dimer acid can be obtained, for example, by using Lewis acid and Bronsted acid as catalysts to polymerize unsaturated fatty acids. Dimer acid can be manufactured by a known method (e.g., the method described in Japanese Patent Application Laid-Open No. 9-12712). Examples of the unsaturated fatty acid include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, eicosapentaenoic acid, docosapentaenoic acid, carassic acid, tetracosapentaenoic acid, docosahexaenoic acid, and nisinic acid. The number of carbon atoms in the unsaturated fatty acid is generally 4 to 24, and preferably 14 to 20.

[0084] In the production of the bismaleimide compound (A), a monomer containing a diamine is preferably dissolved or dispersed in an organic solvent in a slurry form in an inert atmosphere such as argon or nitrogen to prepare a monomer solution containing the diamine. Furthermore, 1,2,4,5-cyclohexanetetracarboxylic dianhydride is preferably added to the monomer solution containing the diamine after being dissolved or dispersed in an organic solvent in a slurry form, or in a solid state.

[0085] By adjusting the number of moles of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and the number of moles of the total amount of the monomer including the diamine and the maleimide compound, any bismaleimide compound (A) can be obtained.

[0086] Various known solvents can be used in the polyaddition reaction and the imidization reaction. Examples of the solvent include amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; esters such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, ethyl lactate, methyl acetate, ethyl acetate, and butyl acetate; and aliphatic alcohols having 1 to 10 carbon atoms such as methanol, ethanol, and propanol. phenols containing aromatic groups, such as phenol and cresol; alcohols containing aromatic groups, such as benzyl alcohol; glycols such as ethylene glycol and propylene glycol; or glycol ethers such as monoethers or diethers of these glycols with methanol, ethanol, butanol, hexanol, octanol, benzyl alcohol, phenol, and cresol, or esters of these monoethers; cyclic ethers such as dioxane and tetrahydrofuran; carbonates such as ethylene carbonate and propylene carbonate; aliphatic and aromatic hydrocarbons such as toluene and xylene; and aprotic polar solvents such as dimethyl sulfoxide. These solvents can be used alone or in combination of two or more, as needed.

[0087] In the imidization reaction, a catalyst is preferably used. Examples of catalysts include tertiary amines and dehydration catalysts. Heterocyclic tertiary amines are preferred, and examples include pyridine, picoline, quinoline, and isoquinoline. Examples of dehydration catalysts include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride.

[0088] The amount of the tertiary amine added is preferably 0.5 to 5.0 times the molar equivalent of the amide group. The amount of the dehydration catalyst added is preferably 0.5 to 10.0 times the molar equivalent of the amide group.

[0089] After the imidization reaction is completed, the solution can be used as a bismaleimide compound (A) solution, or a poor solvent can be added to the reaction solvent to convert the bismaleimide compound (A) into a solid. Examples of the poor solvent include water, methanol, ethanol, 2-propanol, ethylene glycol, triethylene glycol, 2-butanol, 2-pentanol, 2-hexanol, cyclopentanol, cyclohexanol, phenol, and tert-butanol.

[0090] [Dicyclopentadienol-type epoxy (meth)acrylate (B) containing one or more carboxyl groups]

[0091] The resin composition of the present embodiment contains dicyclopentadienol-type epoxy (meth)acrylate (B) having one or more carboxyl groups in its structure.

[0092] Epoxy (meth)acrylate (B) has a molecular structure obtained by acid-modifying dicyclopentadienol-type epoxy (meth)acrylate and contains one or more carboxyl groups in its structure. Epoxy (meth)acrylate (B) can be used alone or in combination of two or more.

[0093] The epoxy (meth)acrylate (B) may have a hydroxyl group, an alkyl group, an alkoxy group, an aryloxy group, an aryl group, an aminoalkyl group, a carboxyalkyl group, a (meth)acryloyl group, or the like in the molecule.

[0094] Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropyloxy, n-butoxy, isobutoxy, tert-butoxy, n-hexyl, and 2-methylpropoxy. Examples of aryloxy groups include phenoxy and p-tolyloxy. Examples of aryl groups include phenyl, tolyl, benzyl, methylbenzyl, xylyl, mesityl, naphthyl, and anthracenyl. Examples of aminoalkyl groups include aminomethyl, aminoethyl, aminopropyl, aminodimethyl, aminodiethyl, aminodipropyl, aminobutyl, aminohexyl, and aminononyl. Examples of carboxyalkyl groups include carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, carboxyhexyl, and carboxynonyl.

[0095] The carboxyl group in epoxy (meth) acrylate (B) can be a salt such as a sodium salt and a potassium salt. When there is one carboxyl group in the molecule, it can be in the form of an anhydride formed by the carboxyl group and other groups such as a carboxymethyl group being connected to each other. When two or more carboxyl groups are contained in the molecule, it can be in the form of an anhydride formed by two of the two or more carboxyl groups being connected to each other, or in the form of an anhydride formed by the carboxyl group and other groups such as a carboxymethyl group being connected to each other, or it can have both of these anhydrides. When epoxy (meth) acrylate (B) has two or more carboxylalkyl groups in the molecule, it can be in the form of an anhydride formed by these groups being connected to each other.

[0096] A chloroform solution containing 1% by mass of epoxy (meth) acrylate (B) was prepared. When the transmittance of the chloroform solution containing 1% by mass of epoxy (meth) acrylate (B) was measured using active energy rays having a wavelength of 365 nm (i-ray), the transmittance was 40% or more, showing very excellent light transmittance. Therefore, even when active energy rays having a wavelength of 365 nm (i-ray) are used, photocuring can be appropriately performed. From the perspective of showing even better light transmittance, the transmittance at a wavelength of 365 nm (i-ray) is preferably 45% or more, more preferably 50% or more. The upper limit of the transmittance at a wavelength of 365 nm (i-line) is, for example, 99.9% or less.

[0097] The epoxy (meth)acrylate (B) is not particularly limited as long as it exhibits the effects of the present invention. However, from the perspectives of obtaining a more suitable viscosity, further suppressing the increase in the viscosity of the varnish, and further obtaining a cured product having a lower relative dielectric constant and dielectric loss tangent, and obtaining a higher-definition insulating layer with a lower relative dielectric constant and dielectric loss tangent, and a high-density printed wiring board and semiconductor device having a higher-definition resist pattern, the weight average molecular weight (Mw) is preferably 300 to 50,000, more preferably 400 to 30,000, even more preferably 500 to 10,000, even more preferably 700 to 5,000, and even more preferably 1,000 to 3,000.

[0098] From the perspective of further improving the developability and obtaining a higher-precision insulating layer and an anti-etching pattern, the acid value of epoxy (meth) acrylate (B) is preferably 30 mgKOH / g or more. From the perspective of further improving the developability and obtaining a higher-precision insulating layer and an anti-etching pattern, the acid value of epoxy (meth) acrylate (B) is more preferably 50 mgKOH / g or more. In addition, from the perspective of being able to more appropriately prevent dissolution caused by a developer after being cured by active energy rays, the acid value of epoxy (meth) acrylate (B) is preferably 160 mgKOH / g or less. From the perspective of being able to further appropriately prevent dissolution caused by a developer after being cured by active energy rays, the acid value of epoxy (meth) acrylate (B) is more preferably 150 mgKOH / g or less, and further preferably 140 mgKOH / g or less. It should be noted that, in this specification, "acid value" means a value measured by a method based on JIS K 0070: 1992.

[0099] Epoxy (meth) acrylate (B) can be obtained by the following method, for example. First, a dicyclopentadienol type epoxy resin (i) (also referred to as epoxy resin (i)) with a structure shown in formula (30), a carboxylic acid compound (ii) (also referred to as carboxylic acid compound (ii)) containing an ethylenically unsaturated group and a carboxyl group that can be polymerized, and a compound (iii) (also referred to as compound (iii)) containing a hydroxyl group and a carboxyl group in a structure as needed are reacted to obtain a compound (iv) (also referred to as compound (iv)) containing more than one hydroxyl group. Then, at least one of the compounds (v) (also referred to as compound (v)) selected from the group consisting of a carboxylic acid compound and an acid anhydride containing a carboxylic acid compound and the hydroxyl group in the compound (iv) is subjected to an addition reaction, and more than one carboxyl group is introduced by an ester bond to obtain epoxy (meth) acrylate (B). Carboxylic acid compound (ii), compound (iii) and compound (v) may be the same or different.

[0100]

[0101] In formula (30), R1 each independently represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms. 21 Each independently represents an integer from 1 to 4. 22 Each independently represents an integer of 1 to 3. n2 represents an integer of 1 to 20. The epoxy resin (i) may be a mixture of compounds having different numbers of repetitions of n2. In the case of a mixture, the number of repetitions of n2 is the average value of the mixture and is in the range of 1 to 20.

[0102] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0103] Examples of the linear or branched alkyl group having 1 to 6 carbon atoms in R1 include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, sec-hexyl, tert-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, and 2-methylpent-3-yl. From the perspective of obtaining a cured product having a lower relative dielectric constant and dielectric loss tangent, a finer insulating layer having a lower relative dielectric constant and dielectric loss tangent, or a high-density printed wiring board and semiconductor device having a finer resist pattern, R1 is preferably a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, methyl, ethyl, n-propyl, 2-butyl, isobutyl, tert-butyl or n-pentyl, further preferably a hydrogen atom, methyl, ethyl or n-propyl, and still more preferably a hydrogen atom.

[0104] The carboxylic acid compound (ii) is not particularly limited as long as it is a compound containing one or more polymerizable ethylenically unsaturated groups and carboxyl groups in its structure. Examples of such carboxylic acid compounds (ii) include (meth)acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, and reaction products of saturated or unsaturated dibasic acids and unsaturated group-containing monoglycidyl compounds. Examples of the (meth)acrylic acid include (meth)acrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, (meth)acrylic acid dimer, monocarboxylic acid compounds containing one carboxyl group per molecule, such as half esters of an equimolar reaction product of a saturated or unsaturated dibasic acid anhydride and a (meth)acrylate derivative having one hydroxyl group per molecule, half esters of an equimolar reaction product of a saturated or unsaturated dibasic acid and a monoglycidyl (meth)acrylate derivative, polycarboxylic acid compounds having multiple carboxyl groups per molecule, such as half esters of an equimolar reaction product of a saturated or unsaturated dibasic acid anhydride and a (meth)acrylate derivative having multiple hydroxyl groups per molecule, and half esters of an equimolar reaction product of a saturated or unsaturated dibasic acid and a glycidyl (meth)acrylate derivative having multiple epoxy groups.

[0105] The compound (iii) is not particularly limited as long as it contains one or more hydroxyl groups and one or more carboxyl groups in its structure. Examples of such compound (iii) include hydroxypropionic acid, hydroxybutyric acid, hydroxystearic acid, dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutyric acid, and hydroxyphthalic acid.

[0106] Examples of the compound (v) include the following chain aliphatic polycarboxylic acids, alicyclic polycarboxylic acids, aromatic compounds containing two or more carboxyl groups, and hetero compounds containing two or more carboxyl groups. Specific examples of these compounds are described below.

[0107] A known method can be used for the reaction of the epoxy resin (i), the carboxylic acid compound (ii), and the compound (iii) as required.

[0108] The reaction temperature and reaction time are not particularly limited, but are usually 50° C. to 150° C. and 5 minutes to 60 hours.

[0109] Regarding the charging amount of the epoxy resin (i), the carboxylic acid compound (ii) and the compound (iii), the total amount of the carboxylic acid compound (ii) and the compound (iii) is usually 10 to 150 equivalent % based on 1 equivalent of the epoxy resin (i).

[0110] A catalyst is preferably used in the reaction. The amount of the catalyst used is generally 0.1 to 10 parts by mass relative to 100 parts by mass of the total reactants. Examples of the catalyst include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylantimony, methyltriphenylantimony, chromium octoate, and zirconium octoate.

[0111] The reaction can be carried out in the absence of a solvent or in the presence of a solvent.

[0112] Examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane and decane; mixtures thereof such as petroleum ether, white gasoline, solvent naphtha, etc.; ester solvents, ether solvents and ketone solvents.

[0113] Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate; cyclic esters of γ-butyrolactone; polycarboxylic acid alkyl esters such as ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, butylene glycol monomethyl ether acetate, polyalkylene glycol monoalkyl ether monoacetates, and dialkyl glutarate, dialkyl succinate, and dialkyl adipate.

[0114] Examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether; glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether; and cyclic ethers such as tetrahydrofuran.

[0115] Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

[0116] The solvent is usually used so as to have a solid content of 30 to 90% by mass.

[0117] During the reaction, a polymerization inhibitor may be used as needed. Examples of the polymerization inhibitor include hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazyl, diphenylamine, and 3,5-di-tert-butyl-4-hydroxytoluene.

[0118] The addition reaction of compound (iv) and compound (v) can be carried out by a known method. Examples of such a reaction method include a method in which compound (v) is added to a reaction solution containing compound (iv).

[0119] The amount of compound (v) added to the reaction solution containing compound (iv) is not particularly limited, but is preferably prepared so that the acid value of epoxy (meth)acrylate (B) falls within the above range.

[0120] The addition reaction temperature and the addition reaction time are not particularly limited, but are usually 50° C. to 150° C. and 5 minutes to 60 hours.

[0121] A catalyst is preferably used in the addition reaction. The amount of the catalyst used is usually 0.1 to 10 parts by mass based on 100 parts by mass of the total reactants. The catalyst may be any of the catalysts exemplified in the reaction of compound (iv) above.

[0122] The reaction can be carried out without a solvent or with a solvent. The solvent and the amount thereof used can refer to the solvents and amounts exemplified in the reaction of compound (iv) above.

[0123] As epoxy (meth)acrylate (B), the epoxy (meth)acrylate (B) which has the structure represented by formula (31) is mentioned, for example.

[0124]

[0125] In formula (31), R2 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. R3 represents a residue of a polycarboxylic acid. R4 each independently represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms. R5 represents a group represented by formula (32) or a group represented by formula (33). n3 each independently represents an integer of 1 to 3. n4 represents an integer of 1 to 20. n5 represents an integer of 0 to 19. The total number of n4 and n5 (the number of n4 + n5) represents an integer of 1 to 20. The epoxy (meth)acrylate (B) having the structure represented by formula (31) may be a mixture of compounds in which the number of repetitions of n4 and n5 is different. In the case of a mixture, the number of repetitions of n4 and n5 is the average value of the mixture, n4 is in the range of 1 to 20, n5 is in the range of 0 to 19, and the total number of n4 and n5 (the number of n4 + n5) is in the range of 1 to 20.

[0126]

[0127] In formula (32), R2, R3, R4 and n3 have the same meanings as R2, R3, R4 and n3 in formula (31). In formula (32), -* represents the end of the bond directly bonded to the carbon atom of R5 in formula (31).

[0128] In formula (33), R2, R3, R4 and n3 have the same meanings as R2, R3, R4 and n3 in formula (31). In formula (33), -* represents the end of the bond directly bonded to the carbon atom of R5 in formula (31).

[0129] In epoxy (meth)acrylate (B), in the structural units in n4 and / or n5, any one or more of R2, R3, R4, and n3 may further include a structural unit different from R2, R3, R4, and n3. For example, in the structural unit in n4, the residue of R3 may include a different structural unit. In this case, the repetition number of n4 is the sum of the average repetition number of the structural unit in n4 and the average repetition number of the different structural units, and the total is an integer of 1 to 20.

[0130] As the linear or branched alkyl group having 1 to 6 carbon atoms in R2 of formula (31) to (33), for example, reference can be made to the examples of the groups described in this specification. As R2, it is preferably a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, a 2-butyl group, an isobutyl group, a tert-butyl group or an n-pentyl group, further preferably a hydrogen atom, a methyl group, an ethyl group or a n-propyl group, and further preferably a hydrogen atom. By making R2 the above-mentioned group, the reactivity of photocuring can be further improved, so there is a tendency to obtain a cured product having a lower relative dielectric constant and a lower dielectric loss tangent. In addition, there is a tendency to obtain a higher density printed circuit board and a semiconductor device having a higher precision and an insulating layer having a lower relative dielectric constant and a lower dielectric loss tangent, and a higher precision anti-etching pattern.

[0131] R3 in formulas (31) and (32) represents a residue of a polycarboxylic acid. In this specification, the residue of a polycarboxylic acid refers to an organic group obtained by removing one carboxyl group from a polycarboxylic acid, and the organic group includes a carboxylic acid in which the total number of carboxylic acids contained in the polycarboxylic acid is -1. It should be noted that when the polycarboxylic acid is oxalic acid (oxalic acid), R3 is a carboxylic acid (-COOH). R3 can also be represented by -Z-(COOH) m Here, Z represents an organic group after removing the carboxylic acid and carboxyl groups from the residue of a polycarboxylic acid, and m represents the total number of carboxylic acids, where the total number of carboxylic acids contained in the polycarboxylic acid is -1. For example, when the polycarboxylic acid is malonic acid (malonic acid), Z represents a methyl group, and m is 1. It should be noted that when the polycarboxylic acid is oxalic acid, Z represents a single bond, and m is 1.

[0132] The polycarboxylic acid may have groups such as hydroxyl, alkyl, alkoxy, aryloxy, aryl, aminoalkyl, amino, carboxyalkyl, and (meth)acryloyl groups. Specific examples of these groups can refer to the examples of the groups described in this specification.

[0133] The polycarboxylic acid may be an acid anhydride formed by mutually linking two carboxyl groups in the molecule. In the case of a carboxyalkyl group in the molecule, the polycarboxylic acid may be an acid anhydride formed by mutually linking a carboxylalkyl group and a carboxyl group. In the case of two or more carboxyalkyl groups in the molecule, the polycarboxylic acid may be an acid anhydride formed by mutually linking these groups.

[0134] Examples of the polycarboxylic acid include chain aliphatic polycarboxylic acids, alicyclic polycarboxylic acids, aromatic compounds containing two or more carboxyl groups, and hetero compounds containing two or more carboxyl groups.

[0135] Examples of the chain aliphatic polycarboxylic acid include ethanedioic acid (oxalic acid), malonic acid (betaine acid), methylmalonic acid, succinic acid (succinic acid), methylsuccinic acid, 2-hydroxysuccinic acid (malic acid), methylhydroxysuccinic acid, glutaric acid (gum acid), methylglutaric acid, methylhydroxyglutaric acid, adipic acid (adipic acid), pimelic acid (syrup acid), suberic acid (suberic acid), azelaic acid (azelaic acid), sebacic acid (sebacic acid), dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, 2-hydroxy-1,2,3-tricarboxylic acid (citric acid), 2,3-dihydroxysuccinic acid (tartaric acid), maleic acid, fumaric acid, citraconic acid, mesaconic acid, 2-glutaconedioic acid, methylenesuccinic acid, allylmalonic acid, isopropylidenesuccinic acid, 2,4-hexadienedioic acid, and acetylene dicarboxylic acid.

[0136] Examples of the alicyclic polycarboxylic acid include cyclopropanedicarboxylic acid, hydroxycyclopropanedicarboxylic acid, cyclopropylenedicarboxylic acid, cyclopropanetricarboxylic acid, hydroxycyclopropanetricarboxylic acid, cyclopropylenetricarboxylic acid, cyclobutanedicarboxylic acid, hydroxycyclobutanedicarboxylic acid, cyclobutenedicarboxylic acid, cyclobutanetricarboxylic acid, cyclobutenetricarboxylic acid, cyclobutanetetracarboxylic acid, cyclobutenetetracarboxylic acid, cyclopentanedicarboxylic acid, cyclopentenedicarboxylic acid, cyclopentanetricarboxylic acid, cyclopentenetricarboxylic acid, cyclopentanetetracarboxylic acid, cyclopentenetetracarboxylic acid, cyclopentanepentacarboxylic acid, cyclopentenepentacarboxylic acid, cyclohexanedicarboxylic acid, and cyclohexene-1,2-dicarboxylic acid. Monocyclic carboxylic acids such as cyclohexene dicarboxylic acid, cyclohexane tricarboxylic acid, cyclohexene tricarboxylic acid, cyclohexane tetracarboxylic acid, cyclohexene tetracarboxylic acid, cyclohexane pentacarboxylic acid, cyclohexene pentacarboxylic acid, cyclohexane hexacarboxylic acid, cyclohexene hexacarboxylic acid, cycloheptane dicarboxylic acid, cycloheptene dicarboxylic acid, cyclooctane dicarboxylic acid, and cyclooctene dicarboxylic acid; and polycyclic or bridged alicyclic dicarboxylic acids such as norbornane dicarboxylic acid, hydroxynorbornane dicarboxylic acid, tricyclodecane dicarboxylic acid, tetracyclododecanedicarboxylic acid, adamantane dicarboxylic acid, hydroxyadamantanedicarboxylic acid, methyladamantanedicarboxylic acid, ethyladamantanedicarboxylic acid, and butyladamantanedicarboxylic acid.

[0137] As aromatic compounds comprising more than two carboxyl groups, for example, phenylacetic acid, hydroxyphenylacetic acid, phthalic acid, trimellitic acid, pyromellitic acid, pentacarboxylbenzene, hexacarboxylbenzene, naphthalene dicarboxylic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, oxydiphthalic acid, diphenylmethane tetracarboxylic acid, hydroxynaphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, benzene pentacarboxylic acid, benzene hexacarboxylic acid, anthracene dicarboxylic acid, anthracene tricarboxylic acid, anthracene tetracarboxylic acid, and anthracene pentacarboxylic acid. Aromatic compounds can have groups such as hydrogen atoms, and alkyl, alkoxy, aryloxy, aryl, aminoalkyl, hydroxyl, amino, and carboxylalkyl groups on the aromatic rings of these parent skeletons. In addition, when these compounds have more than two carboxyl groups in the molecule, they can be anhydrides formed by the mutual connection of two carboxyl groups in the molecule. When these compounds have carboxyl alkyl in the molecule, they can be anhydrides formed by the mutual connection of carboxyl alkyl and carboxyl groups. When these compounds have more than two carboxyl alkyl in the molecule, they can be anhydrides formed by the mutual connection of two carboxyl groups. For specific examples of these groups, reference can be made to the examples of the groups described in the present specification.

[0138] As the hetero compound comprising more than two carboxyl groups, for example, compounds comprising more than two carboxyl groups in heterocycles such as furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thianthrene, phenothiazine, phenoxazine, xanthene, acridine, phenazine and carbazole can be listed. The hetero compound can have, for example, a hydrogen atom and a substituent such as an alkyl, alkoxy, aryloxy, aryl, aminoalkyl, hydroxyl, amino and carboxylalkyl on these parent skeletons. In addition, when these compounds have more than two carboxyl groups in the molecule, they can be an acid anhydride formed by the mutual connection of two carboxyl groups in the molecule. When these compounds have carboxylalkyl in the molecule, they can be an acid anhydride formed by the mutual connection of carboxylalkyl and carboxyl. When these compounds have more than two carboxylalkyl in the molecule, they can be an acid anhydride formed by the mutual connection of two carboxyl groups. For specific examples of these groups, reference can be made to the examples of the groups described in the present specification.

[0139] As polycarboxylic acid, preferably cyclohexene dicarboxylic acid, cyclohexane tricarboxylic acid, cyclohexane tetracarboxylic acid, trimellitic acid, naphthalene tricarboxylic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, oxygen bisphthalic acid, diphenylmethane tetracarboxylic acid, naphthalene tetracarboxylic acid, anthracene tetracarboxylic acid, benzene pentacarboxylic acid and mellitic acid or their acid anhydride, more preferably cyclohexene dicarboxylic acid or cyclohexene dicarboxylic acid anhydride.By making R3 be the residue of these polycarboxylic acids, the cured product that relative dielectric constant and dielectric loss tangent are lower can be obtained, can obtain more higher fine and there is the insulating layer that relative dielectric constant and dielectric loss tangent are lower or the high-density printed circuit board (PCB) and the semiconductor device of more higher fine resist pattern.In addition, unexposed portion integral body is more likely to collapse, and in addition, alkali developer is more likely to flow into, and therefore has the tendency that the stripping property after being able to give more excellent alkali developability, development further improves to resin combination.

[0140] As R3, it is further preferably a group shown in formula (34). The group shown in formula (34) is a residue of cyclohexene-1,2-dicarboxylic acid or a residue of cyclohexene-1,2-dicarboxylic anhydride. By R3 being a group shown in formula (34), a cured product with a lower relative dielectric constant and dielectric loss tangent can be obtained, and then a high-density printed circuit board and a semiconductor device with a high precision and a lower insulating layer with a relative dielectric constant and dielectric loss tangent or a higher precision resist pattern can be obtained. In addition, the unexposed portion as a whole is more likely to collapse, and in addition, the alkali developer is more likely to flow in, so there is a tendency that the resin composition can be given a more excellent alkali developability, the peelability after development is further improved.

[0141]

[0142] In formula (34), -* represents a bonding end to the carbon atom directly bonded to R3 in formula (31) and / or (32).

[0143] As the halogen atom and the linear or branched alkyl group having 1 to 6 carbon atoms in R4 of formula (31) to (33), for example, reference can be made to the examples of the groups described in this specification. As R4, from the perspective of obtaining a cured product with a lower relative dielectric constant and dielectric loss tangent, a higher-precision insulating layer with a lower relative dielectric constant and dielectric loss tangent, or a high-density printed circuit board and semiconductor device with a higher-precision resist pattern, it is preferably a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, methyl, ethyl, n-propyl, 2-butyl, isobutyl, tert-butyl or n-pentyl, further preferably a hydrogen atom, methyl, ethyl or n-propyl, and even more preferably a hydrogen atom.

[0144] As R5, preferably the group shown in formula (32).By making R5 be this group, the cured product that relative dielectric constant and dielectric loss tangent are lower can be obtained, more high-precision and there is the insulating layer that relative dielectric constant and dielectric loss tangent are lower or the high-density printed circuit board (PCB) and semiconductor device of more high-precision resist pattern can be obtained.In addition, unexposed portion overall body is more likely to collapse, and in addition, alkali developer is more likely to flow into, therefore has the tendency that the stripping property after being able to give more excellent alkali developability, development to resin combination further improves.

[0145] Epoxy (meth) acrylate (B) preferably contains a structural unit in n5. In this case, n4 is preferably an integer of 1 to 19, n5 is an integer of 1 to 19, and the total number of n4 and n5 (n4 + n5) is an integer of 2 to 20. In addition, the epoxy (meth) acrylate (B) containing the structural unit in n5 is also preferably a mixture of compounds in which the number of repetitions of n4 and n5 are different. In the case of a mixture, the number of repetitions of n4 and n5 is the average value of their mixture, n4 is in the range of 1 to 19, n5 is in the range of 1 to 19, and the total number of n4 and n5 (n4 + n5) is in the range of 2 to 20. By using such an epoxy (meth) acrylate (B), there is a tendency to obtain a cured product with a lower relative dielectric constant and dielectric loss tangent, and to obtain a higher-precision insulating layer with a lower relative dielectric constant and dielectric loss tangent, a high-density printed circuit board with a higher-precision resist pattern, and a semiconductor device. Furthermore, the unexposed portion as a whole is more likely to collapse, and an alkali developer is more likely to flow in, thereby imparting more excellent alkali developability to the resin composition and tending to further improve the releasability after development.

[0146] As epoxy (meth) acrylate (B), preferably include the epoxy (meth) acrylate shown in formula (35), more preferably include the epoxy (meth) acrylate shown in formula (36).By using these epoxy (meth) acrylates as epoxy (meth) acrylate (B), there is the tendency that can further improve the reactivity of photocuring reaction, the heat resistance of cured product, developability and the stripping property after development.Therefore, there is the tendency that can obtain the cured product that relative dielectric constant and dielectric loss tangent are lower, heat resistance is more excellent, more higher precision, relative dielectric constant and dielectric loss tangent are lower, heat resistance is more excellent, the high density printed circuit board and semiconductor device of the resist pattern with higher precision, heat resistance is excellent.And then, there is following tendency: developability is more excellent, unexposed portion overall body is more likely to collapse, and alkali developer is more likely to flow into, can give more excellent alkali developability to resin combination, and the stripping property after development is further improved.

[0147]

[0148] In formula (35), R6 each independently represents a hydrogen atom, a methyl group, an ethyl group or an n-propyl group. R7 each independently represents a residue of cyclohexene dicarboxylic acid, a residue of cyclohexane tetracarboxylic acid, a residue of trimellitic acid, a residue of naphthalene tricarboxylic acid, a residue of benzophenone tetracarboxylic acid, a residue of biphenyl tetracarboxylic acid, a residue of oxydiphthalic acid, a residue of diphenylmethane tetracarboxylic acid, a residue of naphthalene tetracarboxylic acid, a residue of anthracene tetracarboxylic acid, a residue of benzene pentacarboxylic acid or a residue of benzene hexacarboxylic acid. n6 represents an integer of 1 to 19. n7 represents an integer of 1 to 19. The total number of n6 and n7 (the number of n6 + n7) represents an integer of 2 to 20. The epoxy (meth)acrylate represented by formula (35) may be a mixture of compounds in which the number of repetitions of n6 and n7 is different. In the case of a mixture, the repetition numbers of n6 and n7 are respectively the average values ​​of the mixture, n6 is in the range of 1 to 19, n7 is in the range of 1 to 19, and the total number of n6 and n7 (n6 + n7) is in the range of 2 to 20. R7 preferably contains a residue of cyclohexenedicarboxylic acid.

[0149] In formula (35), regarding R6, R7, n6 and n7, reference can be made to R2, R3, n4 and n5 in formula (31), respectively.

[0150]

[0151] In formula (36), n8 represents an integer of 1 to 19. n9 represents an integer of 1 to 19. The total number of n8 and n9 (the number of n8 + n9) represents an integer of 2 to 20. The epoxy (meth)acrylate represented by formula (36) may be a mixture of compounds having different numbers of repetitions of n8 and n9. In the case of a mixture, the numbers of repetitions of n8 and n9 are respectively the average values ​​of the mixture, n8 is in the range of 1 to 19, n9 is in the range of 1 to 19, and the total number of n8 and n9 (the number of n8 + n9) is in the range of 2 to 20.

[0152] As the compound represented by formula (36), commercially available products can also be used. Examples of commercially available products include ZXR-1889H (trade name, a mixture of compounds having different numbers of repetitions of n8 and n9, n8 being in the range of 1 to 19, n9 being in the range of 1 to 19, and the total number of n8 and n9 being in the range of 2 to 20, with a mass average molecular weight (Mw) of 2250 and an acid value of 111 mgKOH / g) and ZXR-1807H (trade name, a mixture of compounds having different numbers of repetitions of n8 and n9, n8 being in the range of 1 to 19, n9 being in the range of 1 to 19, and the total number of n8 and n9 being in the range of 2 to 20, with a mass average molecular weight (Mw) of 2270 and an acid value of 100 mgKOH / g) manufactured by Nippon Kayaku Co., Ltd.

[0153] Relative to 100 parts by mass of the resin solids in the resin composition, the content of epoxy (meth) acrylate (B) is preferably 5.0 to 90 parts by mass, more preferably 10 to 80 parts by mass, further preferably 15 to 70 parts by mass, and even more preferably 20 to 65 parts by mass. By making the content of epoxy (meth) acrylate (B) the above range, there is a tendency to further improve the reactivity of the photocuring reaction, the heat resistance, developability and peelability of the cured product after development. Therefore, there is a tendency to obtain a cured product having a lower relative dielectric constant and a lower dielectric loss tangent and better heat resistance, an insulating layer having a higher precision, a higher relative dielectric constant and a lower dielectric loss tangent and better heat resistance, a high-density printed circuit board and a semiconductor device having a resist pattern having a higher precision and better heat resistance. Furthermore, there is a tendency that developability is better, the unexposed portion as a whole is more likely to collapse, and the alkali developer is more likely to flow in, and a more excellent alkali developability can be given to the resin composition.

[0154] In the resin composition, the mass ratio ((A) / (B)) of the bismaleimide compound (A) relative to the epoxy (meth) acrylate (B) is preferably 0.1 to 1.5, more preferably 0.5 to 1.4, further preferably 0.6 to 1.3, and further preferably 0.7 to 1.2. By making the mass ratio within the above range, there is a tendency to further improve the reactivity of the photocuring reaction, the heat resistance, developability and peelability of the cured product after development. Therefore, there is a tendency to obtain a cured product having a further lower relative dielectric constant and dielectric loss tangent and better heat resistance, and further a higher precision, a lower relative dielectric constant and dielectric loss tangent, and a better heat resistance insulating layer, and a higher precision, higher heat resistance resist pattern of a high-density printed circuit board and a semiconductor device. It has a better developability, the unexposed part as a whole is more likely to collapse, and the alkali developer is more likely to flow in, which can give the resin composition a better alkali developability.

[0155] [Photocuring initiator (C)]

[0156] The resin composition of the present embodiment includes a photocuring initiator (C). The photocuring initiator (C) is not particularly limited, and a photocuring initiator commonly known in the field of photocurable resin compositions can be used. The photocuring initiator (C) is used together with the bismaleimide compound (A), epoxy (meth)acrylate (B), the maleimide compound (D) described later, which is mixed as needed, the resin or compound (E), the filler (F), etc. to perform photocuring using various active energy rays.

[0157] Examples of the photocuring initiator (C) include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, and di-tert-butyl-diperoxyphthalate; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, benzoyl-diphenyl-phosphine oxide, and bisbenzoyl-phenyl oxide. Phosphine and other acylphosphine oxides; acetophenones such as acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and 4,4'-dimethylaminobenzophenone; 1,2-octanedione-1-[4-(phenylthio)phenyl-2-(O-benzoyloxime)], and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetooxime)ethanone Free radical photocuring initiators such as oxime esters, diazonium salts of Lewis acids such as p-methoxyphenyldiazonium fluorophosphate and N,N-diethylaminophenyldiazonium hexafluorophosphate; iodonium salts of Lewis acids such as diphenyliodonium hexafluorophosphate and diphenyliodonium hexafluoroantimonate; sulfonium salts of Lewis acids such as triphenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluoroantimonate; phosphonium salts of Lewis acids such as triphenylphosphonium hexafluoroantimonate; other halides; triazine initiators; borate initiators; cationic photocuring initiators such as other photoacid generators.

[0158] The photocuring initiator (C) may be a commercially available product. Examples thereof include Omnirad (registered trademark) 369 (trade name) manufactured by IGM Resins BV, Omnirad (registered trademark) 819 (trade name) manufactured by IGM Resins BV, Omnirad (registered trademark) 819DW (trade name) manufactured by IGM Resins BV, Omnirad (registered trademark) 907 (trade name) manufactured by IGM Resins BV, Omnirad (registered trademark) TPO (trade name) manufactured by IGM Resins BV, Omnirad (registered trademark) TPO-G (trade name) manufactured by IGM Resins BV, Omnirad (registered trademark) 784 (trade name) manufactured by IGM Resins BV, Irgacure (registered trademark) OXE01 (trade name) manufactured by BASF Japan Ltd., Irgacure (registered trademark) OXE02 (trade name) manufactured by BASF Japan Ltd., and Omnirad (registered trademark) 907 (trade name) manufactured by IGM Resins BV. Ltd., Irgacure (registered trademark) OXE03 (trade name), and BASF Japan Ltd., Irgacure (registered trademark) OXE04 (trade name), etc.

[0159] These photocuring initiators (C) can be used alone or in combination of two or more.

[0160] A chloroform solution containing a photocuring initiator (C) at 0.01% by mass is prepared. When the absorbance of the chloroform solution containing the photocuring initiator (C) at 0.01% by mass is measured using active energy rays having a wavelength of 365 nm (i-ray), the absorbance is preferably 0.1 or more. Such a photocuring initiator (C) exhibits very excellent light absorptivity. From the perspective of being able to obtain a resin composition having even better photocurability, the absorbance at a wavelength of 365 nm (i-ray) is more preferably 0.15 or more, and further preferably 0.2 or more. The upper limit of the absorbance at a wavelength of 365 nm (i-line) is, for example, 99.9 or less.

[0161] As the photocuring initiator (C), oxime esters and acylphosphine oxides are preferred, and oxime esters are more preferred, from the viewpoint of higher sensitivity to various active energy rays.

[0162] As the oxime esters, 1,2-octanedione-1-[4-(phenylthio)phenyl-2-(O-benzoyloxime)] is preferred because it can provide a cured product having higher sensitivity to various active energy rays, better solvent solubility, lower relative dielectric constant and dielectric loss tangent, and an insulating layer having lower relative dielectric constant and dielectric loss tangent.

[0163] As the acylphosphine oxides, compounds represented by formula (4) are preferred because they have higher absorbance to various active energy rays, particularly active energy rays including i-rays having a wavelength of 365 nm.

[0164]

[0165] In formula (4), R 23 Each independently represents a group represented by formula (5) or a phenyl group.

[0166]

[0167] In formula (5), R 24 Each independently represents a hydrogen atom or a methyl group. In formula (5), -* represents a group directly bonded to R in formula (4). 23 The bonding end of the phosphorus atom (P).

[0168] For the compound represented by formula (4), a chloroform solution containing the compound at 0.01% by mass is prepared, and when the absorbance of the chloroform solution is measured using active energy rays having a wavelength of 365 nm (i-ray), the absorbance for light having a wavelength of 365 nm (i-ray) is 0.1 or more, which is very excellent absorbance. Therefore, the compound appropriately generates free radicals for light having a wavelength of 365 nm (i-line). The absorbance is preferably 0.15 or more, more preferably 0.2 or more. The upper limit is, for example, 10.0 or less, 5.0 or less, or 2.0 or less.

[0169] In formula (4), R 23 Each independently represents a group represented by formula (5) or a phenyl group. 23 Among them, preferably one or more groups are represented by formula (5).

[0170] In formula (5), R 24 Each independently represents a hydrogen atom or a methyl group. 24 Among them, preferably one or more are methyl groups, and more preferably all are methyl groups.

[0171] Examples of the compound represented by formula (4) include acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Among them, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide is preferred due to its superior light transmittance. These compounds may be used alone or in combination of two or more.

[0172] Relative to 100 parts by mass of the resin solid component in the resin composition, the content of the photocuring initiator (C) is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 30 parts by mass, further preferably 0.3 to 10 parts by mass, further preferably 0.5 to 9.0 parts by mass, and further preferably 1.0 to 8.0 parts by mass. By making the content of the photocuring initiator (C) the above range, there is a tendency to more fully perform photocuring in the resin composition without hindering the photocuring reaction and making the exposed portion more fully insoluble in alkali developability. In addition, there is a tendency to obtain a cured product with a lower relative dielectric constant and a dielectric loss tangent and an insulating layer with a lower relative dielectric constant and a dielectric loss tangent.

[0173] [Maleimide compound (D)]

[0174] The resin composition of the present embodiment preferably further contains a maleimide compound (D) (also referred to as component (D) or compound (D)) other than the bismaleimide compound (A) of the present embodiment, in order to obtain a cured product having a lower relative dielectric constant and dielectric loss tangent, and to obtain a higher-definition insulating layer having a lower relative dielectric constant and dielectric loss tangent, a high-density printed wiring board having a higher-definition resist pattern, and a semiconductor device.

[0175] As the maleimide compound (D), unlike the bismaleimide compound (A), there is no particular limitation as long as it is a compound having one or more maleimide groups in the molecule. As such maleimide compound (D), for example, a compound represented by formula (6), a compound represented by formula (7), a compound represented by formula (8), a compound represented by formula (9), a compound represented by formula (10), a compound represented by formula (11), a compound represented by formula (12), N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-anilinophenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, 6-maleimidocaproic acid, 4-maleimidobutyric acid, bis(4-maleimidophenyl)methane, 2,2-bis(4- (4-maleimidophenoxy)-phenyl) propane, 4,4-diphenylmethane bismaleimide, bis(3,5-dimethyl-4-maleimidophenyl) methane, bis(3-ethyl-5-methyl-4-maleimidophenyl) methane, bis(3,5-diethyl-4-maleimidophenyl) methane, phenylmethane maleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene biscitraconimide, m-phenylene biscitraconimide, p-phenylene biscitraconimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl) propane, 3,3-dimethyl-5,5-diethyl-4 ,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,2-bismaleimide ethane, 1,4-bismaleimide butane, 1,5-bismaleimide pentane, 1,5-bismaleimide-2-methylpentane, 1,6-bismaleimide hexane, 1,6-bismaleimide-(2,2,4-trimethyl) hexane, 1,8-bismaleimide-3,6-dioxaoctane, 1,11-bismaleimide-3,6,9-trioxaundecane, 1,3-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, 4,4-diphenylmethane biscitraconimide, 2,2-bis[4-(4-citraconimidephenoxy)phenyl]propane, bis(3,5-dimethyl-4-citraconimidephenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidephenyl)methane, bis(3,5-diethyl-4-citraconimidephenyl)methane, polyphenylmethane maleimide, fluorescein-5-maleimide, prepolymers of these maleimide compounds, and prepolymers of maleimide compounds and amine compounds. These maleimide compounds (D) can be used alone or in combination of two or more.

[0176] As the maleimide compound (D), a compound having excellent light transmittance is preferably used. More preferably, the maleimide compound (D) is a compound that makes the resin composition photosensitized and photocured when exposed to various active energy rays, particularly active energy rays having a wavelength of 365 nm (i-rays).

[0177] From the perspective of being able to more suitably photocurable even when using active energy rays comprising a wavelength of 365 nm (i-ray), the transmittance of the maleimide compound (D) is preferably 0.5% or more when preparing a chloroform solution containing the maleimide compound (D) at 1% by mass and measuring the transmittance of the chloroform solution containing the maleimide compound (D) at 1% by mass using active energy rays comprising a wavelength of 365 nm (i-ray). From the perspective of showing better light transmittance, the transmittance is more preferably 0.8% or more, and further preferably 1.0% or more. The upper limit of the transmittance at a wavelength of 365 nm (i-line) is, for example, 99.9% or less.

[0178] Relative to 100 parts by mass of the resin solids in the resin composition, the content of maleimide compound (D) is preferably 1.0 to 25 parts by mass, more preferably 3.0 to 20 parts by mass, and further preferably 5.0 to 15 parts by mass. By making the content of maleimide compound (D) be the above range, a cured product having a lower relative dielectric constant and dielectric loss tangent can be obtained, with the tendency of obtaining a higher and finer insulating layer having a lower relative dielectric constant and dielectric loss tangent, a high-density printed circuit board and a semiconductor device having a higher and finer resist pattern. And then, there is the tendency of being able to give more excellent alkali developability, not hindering the photocuring reaction in the resin composition and being able to show better curability.

[0179] As the maleimide compound (D), from the perspective of obtaining a cured product having a lower relative dielectric constant and dielectric loss tangent, and further obtaining a high-definition insulating layer having a lower relative dielectric constant and dielectric loss tangent, and further obtaining a high-density printed wiring board and a semiconductor device having a high-definition resist pattern, it is preferred that the maleimide compound (D) contain one or more selected from the group consisting of the compound represented by formula (6), the compound represented by formula (7), the compound represented by formula (8), the compound represented by formula (9), the compound represented by formula (10), the compound represented by formula (11) and the compound represented by formula (12), more preferably contain one or more selected from the group consisting of the compound represented by formula (6), the compound represented by formula (7) and the compound represented by formula (8), and even more preferably contain the compound represented by formula (6).

[0180] (Compound represented by formula (6))

[0181] The resin composition of this embodiment preferably further contains a compound represented by formula (6) in order to obtain a cured product having a lower relative dielectric constant and dielectric loss tangent, and to obtain an insulating layer having a higher precision and a lower relative dielectric constant and dielectric loss tangent, a high-density printed circuit board having a higher precision anti-etching pattern, and a semiconductor device.

[0182]

[0183] In formula (6), Ra each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 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, or an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group. q represents an integer of 0 to 4. When q is an integer of 2 to 4, Ra may be the same or different within the same ring. Rb each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 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, 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. r represents an integer of 0 to 3. When r is 2 or 3, Rb may be the same or different in the same ring. n is the average number of repeating units and represents a value of 0.95 to 10.0.

[0184] The reason why a cured product having lower relative dielectric constant and dielectric loss tangent can be obtained by further containing the compound represented by formula (6) in the resin composition of the present embodiment is not yet clear, but the present inventors speculate as follows.

[0185] That is, the compound shown in formula (6) has a relatively low relative dielectric constant and dielectric loss tangent due to the maleimide skeleton. In addition, the compound shown in formula (6) has a relatively rigid structure due to the presence of a benzene ring, and on the other hand, it also has flexibility due to the presence of an isopropylidene group. Moreover, the compound shown in formula (6) also has excellent photocurability due to the presence of a cyclopentane ring and an isopropylidene group in the structure. Therefore, the compound shown in formula (6) has very high compatibility with bismaleimide compound (A) and epoxy (meth) acrylate (B), and can be suitably photocured together with a photocuring initiator (C), and the resulting cured product can have a higher crosslinking density. On this basis, it is possible to impart a relatively rigid structure caused by the benzene ring and a large volume structure of the cured product caused by the bulky indane skeleton, thereby further reducing the relative dielectric constant and dielectric loss tangent of the cured product. It is thus inferred that if the resin composition further includes a compound shown in formula (6), a cured product with a lower relative dielectric constant and dielectric constant can be obtained. However, the reason is not limited to this.

[0186] The content of the compound represented by formula (6) is preferably 1.0 to 25 parts by mass, more preferably 3.0 to 20 parts by mass, and even more preferably 5.0 to 15 parts by mass relative to a total of 100 parts by mass of the resin solids in the resin composition. By setting the content of the compound represented by formula (6) within the above range, a cured product with a lower relative dielectric constant and dielectric loss tangent can be obtained, and there is a tendency to obtain a higher-definition insulating layer with a lower relative dielectric constant and dielectric loss tangent, a high-density printed wiring board with a higher-definition resist pattern, and a semiconductor device.

[0187] Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, 1-ethylpropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, sec-hexyl, tert-hexyl, n-heptyl, n-octyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylpentan-3-yl, n-nonyl, isononyl, and n-decyl.

[0188] Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentoxy group, and an n-hexoxy group.

[0189] Examples of the alkylthio group having 1 to 10 carbon atoms include a methylthio group and an ethylthio group.

[0190] Examples of the aryl group having 6 to 10 carbon atoms include phenyl, cyclohexylphenyl, phenol, cyanophenyl, nitrophenyl, naphthyl, biphenyl, anthracenyl, naphthacene, anthracenyl, pyrenyl, peryl, pentacene, benzopyrenyl, phenyl, pyrenyl and triphenylene.

[0191] Examples of the aryloxy group having 6 to 10 carbon atoms include a phenoxy group and a p-tolyloxy group.

[0192] Examples of the arylthio group having 6 to 10 carbon atoms include a phenylthio group and a p-tolylthio group.

[0193] Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

[0194] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0195] In formula (6), Ra is preferably each independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

[0196] In formula (6), q is preferably 2 or 3, more preferably 2. It should be noted that the groups other than Ra directly bonded to the benzene ring are hydrogen atoms. That is, for example, when q is 0, it means that all Ra are hydrogen atoms. Preferably, all Ra are hydrogen atoms.

[0197] In formula (6), it is preferred that all Rb are hydrogen atoms. It is also preferred that r is an integer of 1 to 3, and that each Rb is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. It should be noted that groups other than Rb directly bonded to the benzene ring are hydrogen atoms. That is, for example, when r is 0, it means that all Rb are hydrogen atoms.

[0198] The compound represented by formula (6) can be produced by a known method. Specific production methods include, for example, the method described in WO2020 / 217679.

[0199] As the compound represented by formula (6), commercially available products can be used, for example, NE-X-9470S (trade name, DIC Corporation, in formula (6), Ra has two methyl groups (q=2) at each ortho position relative to the N-maleimide group, Rb are all hydrogen atoms (r=0), and n is an integer greater than or equal to 1 and less than or equal to 10).

[0200] (Compound represented by formula (7))

[0201] The compound represented by formula (7) is the following compound.

[0202]

[0203] In formula (7), R 12 、R 13 and R 14 Each independently represents a hydrogen atom or an optionally substituted linear or branched alkyl group having 1 to 8 carbon atoms.

[0204] Examples of the linear or branched alkyl group having 1 to 8 carbon atoms and optionally having a substituent include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2,2-dimethylpropyl, cyclopentyl, hexyl, and heptyl. The hydrogen atoms in these alkyl groups may be substituted with halogen atoms such as fluorine and chlorine atoms, as well as cyano groups. Examples of substituents include halogen atoms, hydroxyl groups, cyano groups, nitro groups, thiol groups, heterocyclic groups, linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, cyclic aliphatic hydrocarbon groups, aryl groups, aralkyl groups, alkoxy groups, alkenyl groups, acyl groups, alkoxycarbonyl groups, alkanoyloxy groups, aroyloxy groups, and alkylsilyl groups. Among these alkyl groups, methyl, ethyl, isopropyl and tert-butyl groups are preferred, methyl, ethyl and isopropyl groups are more preferred, and methyl groups are even more preferred, from the perspectives of superior photocurability, heat resistance and thermal stability, better solubility in solvents, low melting point, low water absorption and better compatibility with other resins.

[0205] As the compound represented by formula (7), the compound represented by formula (13) is more preferable.

[0206]

[0207] (Compound represented by formula (8))

[0208] The compound represented by formula (8) is the following compound.

[0209]

[0210] In formula (8), R 15 、R 16 and R 17 Each independently represents a hydrogen atom, a hydroxyl group, or an optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms. n3 represents an integer of 1 to 10.

[0211] As linear or branched alkyl groups having 1 to 6 carbon atoms, for example, reference can be made to the examples of groups described in this specification. Alkyl groups are preferably methyl, ethyl, n-propyl, and isopropyl groups, with methyl being more preferred, from the perspectives of exhibiting better solubility in solvents, a low melting point, low water absorption, and better compatibility with other resins. Substituents include halogen atoms, hydroxyl groups, cyano groups, nitro groups, thiol groups, heterocyclic groups, linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, cyclic aliphatic hydrocarbon groups, aryl groups, aralkyl groups, alkoxy groups, alkenyl groups, acyl groups, alkoxycarbonyl groups, alkanoyloxy groups, aroyloxy groups, and alkylsilyl groups.

[0212] In addition, in R 15 、R 16 and R 17Among them, from the viewpoint of showing more excellent solubility in solvents, R 15 and R 17 is a linear or branched alkyl group having 1 to 6 carbon atoms and R 16 The preferred alkyl groups are as described above.

[0213] n3 is preferably an integer of 1 to 10, more preferably an integer of 1 to 6, from the viewpoint of achieving better solubility in a solvent, obtaining a more appropriate viscosity, and further suppressing the increase in viscosity of the varnish.

[0214] As the compound represented by formula (8), commercially available products can be used, for example, the compound represented by formula (14) (BCPH01 (trade name, Mw / Mn = 1.0 to 1.8) manufactured by Gun Ei Chemical Industry Co., Ltd., BCPH13 (trade name, Mw / Mn = 1.0 to 1.6) manufactured by Gun Ei Chemical Industry Co., Ltd.) and the compound represented by formula (15) (BMCX426 (trade name) manufactured by Gun Ei Chemical Industry Co., Ltd.) can be cited.

[0215]

[0216] In formula (14), n 21 An integer from 1 to 5.

[0217]

[0218] In formula (15), n 22 An integer from 1 to 10.

[0219] (Compound represented by formula (9))

[0220] The compound represented by formula (9) is the following compound.

[0221]

[0222] In formula (9), R 18 Each independently represents a hydrogen atom, a methyl group or an ethyl group, R 19 Each independently represents a hydrogen atom or a methyl group.

[0223] As R 18 A methyl group or an ethyl group is preferred from the viewpoints of better solubility in solvents, a low melting point, low water absorption, and better compatibility with other resins.

[0224] As R 19A hydrogen atom is preferred from the viewpoints of exhibiting better solubility in solvents, a low melting point, low water absorption, and better compatibility with other resins.

[0225] As the maleimide compound represented by formula (9), a commercially available product can be used, and an example thereof is BMI-70 (trade name) manufactured by K.I. Chemical Industry Co., Ltd. represented by formula (16).

[0226]

[0227] (Compound represented by formula (10))

[0228] The compound represented by formula (10) is the following compound.

[0229]

[0230] In formula (10), R 20 Each independently represents a hydrogen atom or a methyl group. n4 represents an integer of 1 to 10.

[0231] As the maleimide compound represented by formula (10), a commercially available product can be used, and an example thereof is MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd. represented by formula (17).

[0232]

[0233] In formula (17), n 31 An integer from 1 to 10.

[0234] (Compound represented by formula (11))

[0235] The compound represented by formula (11) is the following compound.

[0236]

[0237] In formula (11), R 21 Each independently represents a hydrogen atom, a methyl group or an ethyl group.

[0238] As R 21 A methyl group or an ethyl group is preferred from the viewpoints of better solubility in solvents, a low melting point, low water absorption, and better compatibility with other resins.

[0239] As the maleimide compound represented by formula (11), a commercially available product can be used, and an example thereof is BMI-80 (trade name) manufactured by K.I. Chemical Industry Co., Ltd. represented by formula (18).

[0240]

[0241] (Compound represented by formula (12))

[0242] The compound represented by formula (12) is the following compound.

[0243]

[0244] In formula (12), R 22 Each independently represents a hydrogen atom or a methyl group. n5 represents an integer of 1 to 10.

[0245] As R 22 A hydrogen atom is preferred from the viewpoints of exhibiting better solubility in solvents, a low melting point, low water absorption, and better compatibility with other resins.

[0246] As n5, an integer of 1 to 5 is more preferable from the viewpoints of better solubility in a solvent, obtaining a more appropriate viscosity, and being able to further suppress the increase in viscosity of the varnish.

[0247] As the maleimide compound represented by formula (12), a commercially available product can be used, and an example thereof is BMI-2300 (trade name) manufactured by Daiwa Kasei Industry Co., Ltd. represented by formula (19).

[0248]

[0249] In formula (19), n 41 An integer from 1 to 4.

[0250] [Resin or compound (E)]

[0251] The resin composition of this embodiment preferably further comprises one or more resins or compounds (E) selected from the group consisting of modified polyphenylene ether compounds, cyanate compounds, phenolic resins, oxetane resins, benzoxazine compounds, and epoxy resins (also referred to as component (E), or "resin or compound (E)") in order to obtain a cured product with a lower relative dielectric constant and dielectric loss tangent, thereby obtaining a higher-definition insulating layer with a lower relative dielectric constant and dielectric loss tangent, a high-density printed circuit board with a higher-definition resist pattern, and a semiconductor device. The resin or compound (E) may be used alone or in combination of two or more.

[0252] In addition, in this specification, the resin or compound (E) is different from the bismaleimide compound (A), epoxy (meth)acrylate (B), the photocuring initiator (C), and the maleimide compound (D).

[0253] The resin combination of present embodiment preferably comprises modified polyphenylene ether compound.If the resin combination of present embodiment further comprises modified polyphenylene ether compound, then there is the tendency that can obtain the lower cured product of relative dielectric constant and dielectric loss tangent and then obtain high-precision and the insulating layer lower of relative dielectric constant and dielectric loss tangent, the high-density printed circuit board (PCB) and semiconductor device of more high-precision resist pattern.In addition, there is the tendency that can obtain cured product, insulating layer and the resist pattern with more excellent flame retardancy, heat resistance and thermal expansion characteristics.

[0254] As the resin or compound (E), a resin or compound having excellent light transmittance is preferably used. More preferably, the resin or compound (E) is a resin or compound that is photosensitized and photocured when exposed to various active energy rays, particularly active energy rays having a wavelength of 365 nm (i-rays).

[0255] From the perspective of being able to photocure more appropriately even when using active energy rays containing a wavelength of 365nm (i-ray), a chloroform solution containing 1% by mass of the resin or compound (E) is prepared, and when the transmittance of the chloroform solution containing 1% by mass of the resin or compound (E) is measured using active energy rays containing a wavelength of 365nm (i-ray), the transmittance is preferably 10% or more. From the perspective of showing better light transmittance, the transmittance is more preferably 15% or more, and even more preferably 20% or more. The upper limit of the transmittance at a wavelength of 365nm (i-line) is, for example, 99.9% or less.

[0256] The total content of the resin or compound (E) is preferably 1.0 to 25 parts by mass, more preferably 3.0 to 20 parts by mass, and even more preferably 5.0 to 15 parts by mass, relative to 100 parts by mass of the resin solids in the resin composition. By adjusting the content of the resin or compound (E) to the above range, a cured product with a lower relative dielectric constant and dielectric loss tangent can be obtained, and further, a high-definition insulating layer with a lower relative dielectric constant and dielectric loss tangent, as well as a high-density printed wiring board and semiconductor device with a higher-definition resist pattern can be obtained.

[0257] <Modified polyphenylene ether compound>

[0258] The resin composition of this embodiment preferably further contains a modified polyphenylene ether compound in order to obtain a cured product with a lower relative dielectric constant and dielectric loss tangent, thereby enabling the production of a high-definition insulating layer with a lower relative dielectric constant and dielectric loss tangent, a high-density printed wiring board with a higher-definition resist pattern, and a semiconductor device.

[0259] The modified polyphenylene ether compound may be any known modified polyphenylene ether compound, as long as some or all of the terminals of the polyphenylene ether compound are modified, without particular limitation. It should be noted that, in this specification, the term "modified" in the modified polyphenylene ether compound refers to substitution of some or all of the terminals of the polyphenylene ether compound with reactive functional groups such as carbon-carbon unsaturated double bonds. The modified polyphenylene ether compound may be used alone or in combination of two or more.

[0260] The reason why a cured product having lower relative dielectric constant and dielectric loss tangent can be obtained by further including a modified polyphenylene ether compound in the resin composition of the present embodiment is not yet clear, but the present inventors speculate as follows.

[0261] That is, the modified polyphenylene ether compound has a low relative dielectric constant and dielectric loss tangent due to the polyphenylene ether skeleton. In addition, the modified polyphenylene ether compound has a high and rigid structure of planarity due to the presence of phenylene groups. On the other hand, due to the presence of an ether bond, it also has rotational flexibility. In addition, a portion or all of the ends of the polyphenylene ether compound have reactive functional groups such as carbon-carbon unsaturated double bonds that are highly reactive to light. Therefore, the compatibility of the bismaleimide compound (A) and epoxy (meth) acrylate (B) of the modified polyphenylene ether compound is very high, and it is possible to suitably photocure with a photocuring initiator (C), and the resulting cured product can have a higher crosslinking density. Moreover, due to the large polyphenylene ether skeleton, a large structure can be given to the cured product, and therefore the relative dielectric constant and dielectric loss tangent of the cured product can be further reduced. It is thus inferred that if the resin composition further includes a modified polyphenylene ether compound, a cured product with a lower relative dielectric constant and dielectric constant can be obtained. However, the reason is not limited thereto.

[0262] Examples of the polyphenylene ether compound involved in the modified polyphenylene ether compound include polymers containing one or more structural units selected from the group consisting of the structural unit represented by formula (20), the structural unit represented by formula (21), and the structural unit represented by formula (22).

[0263]

[0264] In formula (20), R8, R9, R 10 and R 11 Each independently represents an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom or a hydrogen atom.

[0265]

[0266] In formula (21), R 12 、R 13 、R 14 、R 18 、R19 Each independently represents an alkyl group having 6 or less carbon atoms or a phenyl group. 15 、R 16 、R 17 Each independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.

[0267]

[0268] In formula (22), R 20 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 Each independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A- represents a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

[0269] As -A- in formula (22), 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, and 1-phenylethylidene can be mentioned, but the present invention is not limited to these.

[0270] Preferred modified polyphenylene ether compounds include, for example, polyphenylene ether compounds in which a part or all of the terminals are modified with ethylenically unsaturated groups such as vinylbenzyl groups, epoxy groups, amino groups, hydroxyl groups, mercapto groups, carboxyl groups, methacryloyl groups, and silyl groups.

[0271] Examples of the modified polyphenylene ether compound having a hydroxyl group at the end include SA90 (trade name, SABIC Innovative Plastics Co., Ltd.).

[0272] Examples of the modified polyphenylene ether compound having a methacryloyl group at the end include SA9000 (trade name, SABIC Innovative Plastics Co., Ltd.) and the like.

[0273] The method for producing the modified polyphenylene ether compound is not particularly limited as long as the effects of the present invention can be obtained. For example, the modified polyphenylene ether compound can be produced by the method described in Japanese Patent No. 4591665.

[0274] The modified polyphenylene ether compound more preferably includes a modified polyphenylene ether compound having an ethylenically unsaturated group at the terminal. Examples of the ethylenically unsaturated group include alkenyl groups such as vinyl, allyl, acryloyl, methacryloyl, propenyl, butenyl, hexenyl, and octenyl; cycloalkenyl groups such as cyclopentenyl and cyclohexenyl; and alkenylaryl groups such as vinylbenzyl and vinylnaphthyl. Among these, vinylbenzyl is preferred.

[0275] The terminal ethylenically unsaturated groups may be single or multiple, and may be the same or different.

[0276] From the perspective of being able to obtain a cured product with a lower relative dielectric constant and dielectric loss tangent, an insulating layer with higher precision and a lower relative dielectric constant and dielectric loss tangent, a high-density printed circuit board with a higher-precision anti-etching pattern, and a semiconductor device, the modified polyphenylene ether compound having an ethylenically unsaturated group at the end is preferably a compound represented by formula (23).

[0277]

[0278] In formula (23), X represents an aromatic group, -(YO) m - represents a polyphenylene ether moiety. R1, R2, and R3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group, m represents an integer from 1 to 100, n represents an integer from 1 to 6, and q represents an integer from 1 to 4. m is preferably an integer from 1 to 50, more preferably an integer from 1 to 30. n is preferably an integer from 1 to 4, more preferably 1 or 2, and ideally 1. q is preferably an integer from 1 to 3, more preferably 1 or 2, and ideally 2.

[0279] Examples of the aromatic group represented by X in formula (23) include groups obtained by removing q hydrogen atoms from a ring structure selected from the group consisting of a benzene ring structure, a biphenyl ring structure, an indenyl ring structure, and a naphthalene ring structure (e.g., a phenylene group, a biphenylene group, an indenyl group, and a naphthylene group). Among them, a biphenylene group is preferred.

[0280] Here, the aromatic group represented by X may include a diphenyl ether group in which an aryl group is bonded via an oxygen atom, a benzophenone group in which an aryl group is bonded via a carbonyl group, or a 2,2-diphenylpropane group in which an aryl group is bonded via an alkylene group.

[0281] The aromatic group may be substituted with a common group such as an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably a methyl group), an alkenyl group, an alkynyl group, or a halogen atom. However, since the aromatic group is substituted on the polyphenylene ether moiety via an oxygen atom, the maximum number of common groups depends on the number of polyphenylene ether moieties.

[0282] As the polyphenylene ether moiety in formula (23), the structural units represented by formula (20), formula (21), and formula (22) described above can be used. Among them, it is more preferable to contain the structural unit represented by formula (20).

[0283] In addition, as the modified polyphenylene ether compound represented by formula (23), the number-average molecular weight (Mn) is preferably 500 to 7000. From the aspects of obtaining a cured product with a lower relative dielectric constant and dielectric loss tangent, obtaining an insulating layer with higher fineness and a lower relative dielectric constant and dielectric loss tangent, a high-density printed circuit board with a higher-fineness resist pattern, and a semiconductor device, in formula (23), the number-average molecular weight (Mn) is more preferably 700 to 7000. The number-average molecular weight (Mn) is further preferably 1000 to 3000.

[0284] As the modified polyphenylene ether compound, in formula (23), the compound represented by formula (24) is preferred.

[0285]

[0286] In formula (24), X is an aromatic group, -(Y-O) m - and -(O-Y) m - respectively represent the polyphenylene ether moiety, and m represents an integer of 1 to 100. m is preferably an integer of 1 to 50, and more preferably an integer of 1 to 30.

[0287] X, -(Y-O) in formula (24) m - and m have the same meanings as in formula (23). -(O-Y) in formula (24)[[ID=2,2]] m - has the same meaning as -(Y-O) in formula (23). m -

[0288] X in formula (23) and formula (24) is formula (25), formula (26), or formula (27), and -(Y-O) in formula (23) and formula (24) m - and -(O-Y) m - are preferably a structure formed by arranging formula (28) or formula (29), or a structure formed by block or random arrangement of formula (28) and formula (29).

[0289]

[0290] In formula (26), R 28 、R 29 、R 30 and R 31 each independently represent a hydrogen atom or a methyl group. -B- is a divalent hydrocarbon group that is linear, branched, or cyclic and has 20 or fewer carbon atoms.

[0291] As specific examples of -B-, the same specific examples as those of -A- in formula (22) can be given.

[0292]

[0293] In formula (27), -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

[0294] As specific examples of -B-, the same specific examples as those of -A- in formula (22) can be given.

[0295]

[0296]

[0297] The method for producing the modified polyphenylene ether compound having the structure represented by formula (24) is not particularly limited. For example, it can be produced by vinylbenzyl etherifying the terminal phenolic hydroxyl group of a bifunctional phenylene ether oligomer obtained by oxidative coupling of a bifunctional phenol compound and a monofunctional phenol compound.

[0298] As the modified polyphenylene ether compound having the structure represented by formula (24), commercially available products can be used, and for example, OPE (registered trademark)-2St1200 and OPE (registered trademark)-2st2200 (these are trade names, Mitsubishi Gas Chemical Co., Ltd.) can be preferably used.

[0299] The content of the modified polyphenylene ether compound is preferably 1.0 to 25 parts by mass, more preferably 3.0 to 20 parts by mass, and even more preferably 5.0 to 15 parts by mass relative to a total of 100 parts by mass of the resin solids in the resin composition. By adjusting the content of the modified polyphenylene ether compound within the above range, a cured product having a lower relative dielectric constant and dielectric loss tangent can be obtained, which tends to result in a higher-definition insulating layer with a lower relative dielectric constant and dielectric loss tangent, and a high-density printed wiring board and semiconductor device having a higher-definition resist pattern.

[0300] <Cyanate Compound>

[0301] The cyanate compound is not particularly limited as long as it is a resin having at least one aromatic moiety substituted with a cyanooxy group (cyanate group) in its molecule.

[0302] For example, the compound represented by formula (37) can be mentioned.

[0303]

[0304] In formula (37), Ar1 represents a benzene ring, a naphthalene ring, or a group formed by two benzene rings being singly bonded. When there are multiple groups, they may be the same or different. Ra each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a group formed by an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms being bonded. The aromatic ring in Ra may have a substituent, and the substituents in Ar1 and Ra may be selected at any position. p represents the number of cyano groups bonded to Ar1, and is independently an integer from 1 to 3. q represents the number of Ra bonded to Ar1, and is 4-p when Ar1 is a benzene ring, 6-p when it is a naphthalene ring, and 8-p when two benzene rings are singly bonded. t represents the average number of repetitions, and is an integer from 0 to 50. The cyanate ester compound may be a mixture of compounds having different t. When there are multiple Xs, each independently represents a single bond, a divalent organic group having 1 to 50 carbon atoms (the hydrogen atom may be substituted by a heteroatom), a divalent organic group having 1 to 10 nitrogen atoms (for example, -NRN-, where R represents an organic group), a carbonyl group (-CO-), a carboxyl group (-C(=O)O-), a carbonyldioxy group (-OC(=O)O-), a sulfonyl group (-SO2-), a divalent sulfur atom, or a divalent oxygen atom.

[0305] The alkyl group in Ra of formula (37) may have any of a linear or branched chain structure and a cyclic structure (eg, a cycloalkyl group).

[0306] Furthermore, the hydrogen atoms in the alkyl group in formula (37) and the aryl group in Ra may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, or a cyano group.

[0307] Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2,2-dimethylpropyl, cyclopentyl, hexyl, cyclohexyl, and trifluoromethyl.

[0308] Specific examples of the alkenyl group include vinyl, (meth)allyl, isopropenyl, 1-propenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 2-methyl-2-propenyl, 2-pentenyl, and 2-hexenyl.

[0309] Specific examples of the aryl group include phenyl, xylyl, mesityl, naphthyl, phenoxyphenyl, ethylphenyl, o-m- or p-fluorophenyl, dichlorophenyl, dicyanophenyl, trifluorophenyl, methoxyphenyl, and o-m- or p-tolyl.

[0310] Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group.

[0311] Specific examples of the divalent organic group having 1 to 50 carbon atoms in X of formula (37) include methylene, ethylene, trimethylene, cyclopentylene, cyclohexylene, trimethylcyclohexylene, biphenylmethylene, dimethylmethylene-phenylene-dimethylmethylene, fluorenediyl, and phthalenediyl. The hydrogen atoms in the divalent organic group may be substituted with halogen atoms such as fluorine and chlorine atoms, alkoxy groups such as methoxy and phenoxy, and cyano groups.

[0312] Examples of the divalent organic group having 1 to 10 nitrogen atoms in X in formula (37) include an imino group and a polyimide group.

[0313] In addition, examples of the organic group represented by X in formula (37) include a group having a structure represented by formula (38) or a group having a structure represented by formula (39).

[0314]

[0315] In formula (38), Ar2 represents a benzene diyl group, a naphthalene diyl group, or a biphenyl diyl group, and when u is an integer greater than 2, they may be the same or different. Rb, Rc, Rf, and Rg each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or an aryl group having at least one phenolic hydroxyl group. Rd and Re each independently represent any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. u represents an integer from 0 to 5.

[0316]

[0317] In formula (39), Ar3 represents a phenylenediyl group, a naphthalenediyl group, or a biphenylenediyl group. When v is an integer greater than 2, they may be the same or different. Ri and Rj each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a trifluoromethyl group, or an aryl group substituted with at least one cyanooxy group. v represents an integer from 0 to 5, but a mixture of compounds having different v's may also be used.

[0318] Furthermore, as X in formula (37), a divalent group represented by the following formula can be mentioned.

[0319]

[0320] Here, in the formula, z represents an integer of 4 to 7. Rk each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0321] Specific examples of Ar2 of formula (38) and Ar3 of formula (39) include: a benzene diyl group in which two carbon atoms represented by formula (38) or two oxygen atoms represented by formula (39) are bonded to the 1,4 position or the 1,3 position; a biphenyl diyl group in which two carbon atoms or two oxygen atoms are bonded to the 4,4' position, the 2,4' position, the 2,2' position, the 2,3' position, the 3,3' position or the 3,4' position; and a naphthalene diyl group in which two carbon atoms or two oxygen atoms are bonded to the 2,6 position, the 1,5 position, the 1,6 position, the 1,8 position, the 1,3 position, the 1,4 position or the 2,7 position.

[0322] The alkyl and aryl groups in Rb, Rc, Rd, Re, Rf and Rg of formula (38) and Ri and Rj of formula (39) are the same as those in formula (37).

[0323] Specific examples of the cyano-substituted aromatic compound represented by formula (37) include cyanobenzene, 1-cyano-2-, 1-cyano-3-, or 1-cyano-4-methylbenzene, 1-cyano-2-, 1-cyano-3-, or 1-cyano-4-methoxybenzene, 1-cyano-2,3-, 1-cyano-2,4-, 1-cyano-2,5-, 1-cyano-2,6-, 1-cyano-3,4-, or 1-cyano-3,5-dimethylbenzene, cyanoethylbenzene, cyanobutylbenzene, cyanooctylbenzene, cyanononylbenzene, 2-(4-cyanophenyl)-2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyano-4-cyclohexylbenzene, 1-cyano- 1-cyano-4-vinylbenzene, 1-cyano-2- or 1-cyano-3-chlorobenzene, 1-cyano-2,6-dichlorobenzene, 1-cyano-2-methyl-3-chlorobenzene, cyanonitrobenzene, 1-cyano-4-nitro-2-ethylbenzene, 1-cyano-2-methoxy-4-allylbenzene (cyanate of eugenol), methyl (4-cyanophenyl) sulfide, 1-cyano-3-trifluoromethylbenzene, 4-cyanobiphenyl, 1-cyano-2- or 1-cyano-4-acetylbenzene, 4-cyanobenzaldehyde, methyl 4-cyanobenzoate, phenyl 4-cyanobenzoate, 1-cyano-4-acetamidobenzene, 4-cyanobenzophenone, 1-cyano-2,6-di-tert-butylbenzene, 1,2-dicyanobenzoyl Benzene, 1,3-dicyanobenzene, 1,4-dicyanobenzene, 1,4-dicyano-2-tert-butylbenzene, 1,4-dicyano-2,4-dimethylbenzene, 1,4-dicyano-2,3-dimethylbenzene, 1,3-dicyano-2,4,6-trimethylbenzene, 1,4-dicyano-2,3,6-trimethylbenzene, 1,3-dicyano-5-methylbenzene, 1-cyano or 2-cyano naphthalene, 1-cyano-4-methoxynaphthalene, 2-cyano-6-methoxynaphthalene, 2-cyano-7-methoxynaphthalene, 2,2'-dicyano-1,1'-binaphthyl, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-dicyanonaphthalene, 2, 2'- or 4,4'-dicyanobiphenyl, 4,4'-dicyanooctafluorobiphenyl, 2,4'- or 4,4'-dicyanodiphenylmethane, bis(4-cyano-3,5-dimethylphenyl)methane, 1,1-bis(4-cyanophenyl)ethane, 1,1-bis(4-cyanophenyl)propane, 2,2-bis(4-cyanophenyl)propane, 2,2-bis(4-cyanophenyl-3-methylphenyl)propane, 2,2-bis(2-cyano-5-biphenyl)propane, 2,2-bis(4-cyanophenyl)hexafluoropropane, 2,2-bis(4-cyanophenyl-3,5-dimethylphenyl)propane, 1,1-bis(4-cyanophenyl)butane, 1,1-bis(4-cyanophenyl)iso ...1-bis(4-cyanophenyl)pentane, 1,1-bis(4-cyanophenyl)-3-methylbutane, 1,1-bis(4-cyanophenyl)-2-methylbutane, 1,1-bis(4-cyanophenyl)-2,2-dimethylpropane, 2,2-bis(4-cyanophenyl)butane, 2,2-bis(4-cyanophenyl)pentane, 2,2-bis(4-cyanophenyl)hexane, 2,2-bis(4-cyanophenyl)-3-methylbutane, 2,2-bis(4-cyanophenyl)-4-methylpentane, 2,2-bis(4-cyanophenyl)-3,3-dimethylbutane, 3,3-bis(4-cyanophenyl)hexane, 3,3-bis(4-cyanophenyl)heptane, 3,3-bis(4-cyanophenyl) phenyl) octane, 3,3-bis(4-cyanophenyl)-2-methylpentane, 3,3-bis(4-cyanophenyl)-2-methylhexane, 3,3-bis(4-cyanophenyl)-2,2-dimethylpentane, 4,4-bis(4-cyanophenyl)-3-methylheptane, 3,3-bis(4-cyanophenyl)-2-methylheptane, 3,3-bis(4-cyanophenyl)-2,2-dimethylhexane, 3,3-bis(4-cyanophenyl)-2,4-dimethylhexane, 3,3-bis(4-cyanophenyl)-2,2,4-trimethylpentane, 2,2-bis(4-cyanophenyl)-1,1,1,3,3,3-hexafluoropropane, bis(4-cyanophenyl)phenylmethane, 1,1-bis( 4-cyanophenyl)-1-phenylethane, bis(4-cyanophenyl)biphenylmethane, 1,1-bis(4-cyanophenyl)cyclopentane, 1,1-bis(4-cyanophenyl)cyclohexane, 2,2-bis(4-cyanophenyl-3-isopropylphenyl)propane, 1,1-bis(3-cyclohexyl-4-cyanophenyl)cyclohexane, bis(4-cyanophenyl)diphenylmethane, bis(4-cyanophenyl)-2,2-dichloroethylene, 1,3-bis[2-(4-cyanophenyl)-2-propyl]benzene, 1,4-bis[2-(4-cyanophenyl)-2-propyl]benzene, 1,1-bis(4-cyanophenyl)-3,3,5-trimethylcyclohexane, 4-[bis(4-cyanophenyl)methyl]biphenyl, 4 , 4-dicyanobenzophenone, 1,3-bis(4-cyanophenyl)-2-propen-1-one, bis(4-cyanophenyl) ether, bis(4-cyanophenyl) sulfide, bis(4-cyanophenyl) sulfone, 4-cyanophenyl 4-cyanobenzoate (4-cyanophenyl-4-cyanobenzoate), bis-(4-cyanophenyl) carbonate, 1,3-bis(4-cyanophenyl)adamantane, 1,3-bis(4-cyanophenyl)-5,7-dimethyladamantane, 3,3-bis(4-cyanophenyl)isobenzofuran-1(3H)-one (cyanate of phenolphthalein), 3,3-bis(4-cyano-3-methylphenyl)isobenzofuran-1(3H)-one (cyanate of o-cresolphthalein), 9,9'-bis(4-cyanophenyl)fluorene, 9,9-bis(4-cyano-3-methylphenyl)fluorene, 9,9-bis(2-cyano-5-biphenyl)fluorene, tris(4-cyanophenyl)methane, 1,1,1-tris(4-cyanophenyl)ethane, 1,1,3-tris(4-cyanophenyl)propane, α,α,α'-tris(4-cyanophenyl)-1-ethyl-4-isopropylbenzene, 1,1,2,2-Tetrakis(4-cyanophenyl)ethane, Tetrakis(4-cyanophenyl)methane, 2,4,6-tris(N-methyl-4-cyanoanilino)-1,3,5-triazine, 2,4-bis(N-methyl-4-cyanoanilino)-6-(N-methylanilino)-1,3,5-triazine, bis(N-4-cyanophenyl)-2-methylphenyl)-4,4'-oxydiphthaloyl imide, bis(N-3-cyano-4-methylphenyl)-4,4'-oxydiphthalimide, bis(N-4-cyanophenyl)-4,4'-oxydiphthalimide, bis(N-4-cyano-2-methylphenyl)-4,4'-(hexafluoroisopropylidene)diphthalimide, tris(3,5-dimethyl-4-cyanobenzyl) isocyanurate, 2-phenyl-3,3- Bis(4-cyanophenyl)phthalimide, 2-(4-methylphenyl)-3,3-bis(4-cyanophenyl)phthalimide, 2-phenyl-3,3-bis(4-cyanophenyl-3-methylphenyl)phthalimide, 1-methyl-3,3-bis(4-cyanophenyl)indolin-2-one, and 2-phenyl-3,3-bis(4-cyanophenyl)indolin-2-one.

[0324] These cyanate ester compounds can be used alone or in combination of two or more.

[0325] Specific examples of the cyanate compound represented by formula (37) include phenol novolac resins and cresol novolac resins (products obtained by reacting phenol, alkyl-substituted phenol or halogen-substituted phenol with a formaldehyde compound such as formalin or paraformaldehyde in an acidic solution by a known method), trisphenol novolac resins (products obtained by reacting hydroxybenzaldehyde with phenol in the presence of an acidic catalyst), fluorene novolac resins (products obtained by reacting a fluorenone compound with 9,9-bis(hydroxyaryl) fluorenes in the presence of an acidic catalyst), phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins, and biphenyl aralkyl resins (substances obtained by reacting a dihalogenated methyl compound represented by Ar4-(CH2Y)2 (Ar4 represents a phenyl group, Y represents a halogen atom, and the same shall apply to this paragraph below) with a phenol compound in the presence of an acidic catalyst or in the absence of a catalyst, and a bis(alkyl) compound represented by Ar4-(CH2OR)2 (R represents an alkyl group). The present invention also includes a phenolic resin obtained by reacting a bis(hydroxymethyl) compound represented by Ar4-(CH2OH)2 with a phenolic compound in the presence of an acidic catalyst, a bis(hydroxymethyl) compound represented by Ar4-(CH2OH)2 with a phenolic compound in the presence of an acidic catalyst, or a condensation product of an aromatic aldehyde compound, an aralkyl compound, and a phenolic compound), a phenol-modified xylene formaldehyde resin (a xylene formaldehyde resin and a phenolic compound are reacted in the presence of an acidic catalyst by a known method), a modified naphthalene formaldehyde resin (a naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound are reacted in the presence of an acidic catalyst by a known method), a phenol-modified dicyclopentadiene resin, or a phenolic resin having a polynaphthalene ether structure (a polyhydroxynaphthalene compound having two or more phenolic hydroxy groups in one molecule is subjected to dehydration condensation in the presence of a basic catalyst by a known method), and prepolymers thereof. These cyanate compounds can be used alone or in combination of two or more.

[0326] The production method of these cyanate ester compounds is not particularly limited, and known methods can be used. Specifically, a method of obtaining or synthesizing a hydroxyl-containing compound having a desired backbone and then modifying the hydroxyl group using known methods to form a cyanate ester is exemplified. Examples of methods for cyanating a hydroxyl group include the method described in Ian Hamerton, "Chemistry and Technology of Cyanate Ester Resins," Blackie Academic & Professional.

[0327] Cured products using these cyanate ester compounds tend to have more excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion.

[0328] <Phenolic resin>

[0329] As the phenolic resin, any commonly known phenolic resin can be used as long as it has two or more hydroxyl groups in one molecule, such as bisphenol A phenolic resin, bisphenol E phenolic resin, bisphenol F phenolic resin, bisphenol S phenolic resin, phenol novolac resin, bisphenol A novolac phenolic resin, glycidyl ester phenolic resin, aralkyl novolac phenolic resin, biphenyl aralkyl phenolic resin, cresol novolac phenolic resin, multifunctional phenolic resin, naphthol resin, naphthol novolac resin, multifunctional naphthol resin, anthracene phenolic resin, naphthalene skeleton-modified novolac phenolic resin, phenol aralkyl phenolic resin, naphthol aralkyl phenolic resin, dicyclopentadiene phenolic resin, biphenyl phenolic resin, alicyclic phenolic resin, polyol phenolic resin, phosphorus-containing phenolic resin, phenolic resin containing a polymerizable unsaturated hydrocarbon group, and hydroxyl-containing silicone resins. These phenol resins can be used alone or in combination of two or more.

[0330] <Oxetane resin>

[0331] As the oxetane resin, a generally known oxetane resin can be used. Examples include oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane and other alkyloxetanes, 3-methyl-3-methoxymethyloxetane, 3,3-bis(trifluoromethyl)perfluorooxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane, OXT-101 (manufactured by Toagosei Co., Ltd., trade name), OXT-121 (manufactured by Toagosei Co., Ltd., trade name), and OXT-221 (manufactured by Toagosei Co., Ltd., trade name). These oxetane resins can be used alone or in combination of two or more.

[0332] <Benzoxazine Compounds>

[0333] As a benzoxazine compound, as long as it is a compound having two or more dihydrobenzoxazine rings in one molecule, a commonly known compound can be used. For example, bisphenol A benzoxazine BA-BXZ (trade name, manufactured by Konishi Chemical Industry Co., Ltd.), bisphenol F benzoxazine BF-BXZ (trade name, manufactured by Konishi Chemical Industry Co., Ltd.), bisphenol S benzoxazine BS-BXZ (trade name, manufactured by Konishi Chemical Industry Co., Ltd.), Pd benzoxazine (trade name, manufactured by Shikoku Chemical Industry Co., Ltd.), Fa benzoxazine (trade name, manufactured by Shikoku Chemical Industry Co., Ltd.) and phenolphthalein benzoxazine can be listed. These benzoxazine compounds can be used alone or in combination of two or more.

[0334] <Epoxy resin>

[0335] The epoxy resin is not particularly limited, and commonly known epoxy resins can be used. For example, bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol A novolac epoxy resin, biphenyl epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, xylene novolac epoxy resin, multifunctional phenol epoxy resin, naphthalene epoxy resin, naphthalene skeleton modified novolac epoxy resin, naphthyl ether epoxy resin, phenol aralkyl epoxy resin, anthracene epoxy resin, trifunctional phenol epoxy resin, quadrifunctional phenol epoxy resin, triglycidyl isocyanurate Acid esters, glycidyl ester epoxy resins, alicyclic epoxy resins, dicyclopentadiene novolac epoxy resins, biphenyl novolac epoxy resins, phenol aralkyl novolac epoxy resins, naphthol aralkyl novolac epoxy resins, aralkyl novolac epoxy resins, naphthol aralkyl epoxy resins, dicyclopentadiene epoxy resins, polyol epoxy resins, phosphorus-containing epoxy resins, glycidylamine, butadiene and other double bond epoxidized compounds, compounds obtained by the reaction of hydroxyl-containing silicone resins with epichlorohydrin, and halides thereof. These epoxy resins can be used alone or in combination of two or more.

[0336] As epoxy resins, commercially available products can be used, for example, the epoxy resin represented by formula (40) (NC-3000FH (trade name) manufactured by Nippon Kayaku Co., Ltd., in which n5 is approximately 4) and the naphthalene-type epoxy resin represented by formula (41) (HP-4710 (trade name) manufactured by DIC Corporation).

[0337]

[0338] These epoxy resins can be used alone or in combination of two or more.

[0339] <Other compounds>

[0340] The resin composition of the present embodiment may contain other compounds other than the bismaleimide compound (A), epoxy (meth)acrylate (B), photocuring initiator (C), maleimide compound (D), and resin or compound (E) as long as the effects of the present invention are exhibited.

[0341] Examples of such other compounds include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether; styrenes such as styrene, methylstyrene, ethylstyrene, and divinylbenzene; triallyl isocyanurate, trimethylallyl isocyanurate, and bisallyl nadicimide. These other compounds may be used alone or in combination of two or more.

[0342] The content of other compounds is usually 1.0 to 25 parts by mass relative to 100 parts by mass of the total resin solid content in the resin composition.

[0343] [Filling material (F)]

[0344] The resin combination of the present embodiment is for the cured product that can obtain relative dielectric constant and dielectric loss tangent lower, it is possible to obtain higher fine and relative dielectric constant and dielectric loss tangent lower insulating layer, there is the high-density printed circuit board and semiconductor device of the more fine anti-etching pattern, the aspect that each characteristic such as film coating, heat resistance further improves, preferably further includes filling material (F).As filling material (F), preferably there is insulation, does not hinder the material of the permeability of the various active energy rays used in photocuring.As filling material (F), more preferably inorganic filling material.Filling material (F) is different from bismaleimide compound (A), epoxy (methyl) acrylate (B), photocuring initiator (C), maleimide compound (D) and resin or compound (E).Filling material (F) can be used alone 1 kind or suitably mixed and used more than 2 kinds.

[0345] The average particle size of the filler (F) is not particularly limited. From the perspective of further obtaining the ultraviolet light transmittance of the resin composition, it is usually 0.005 to 10 μm, preferably 0.01 to 1.0 μm. It should be noted that, in the present invention, the "average particle size" of the filler (F) refers to the median particle size of the filler (F). Here, the median particle size refers to the particle size at which the volume of the particles on the side with a larger particle size and the volume of the particles on the side with a smaller particle size each account for 50% of the total powder when the particle size distribution of the powder is divided into two parts based on a certain particle size. The average particle size (median particle size) of the filler (F) is measured by a wet laser diffraction scattering method.

[0346] Examples of the filler (F) include silica (e.g., natural silica, fused silica, amorphous silica, and hollow silica), aluminum compounds (e.g., boehmite, aluminum hydroxide, aluminum oxide, and aluminum nitride), boron compounds (e.g., boron nitride), magnesium compounds (e.g., magnesium oxide, and magnesium hydroxide), calcium compounds (e.g., calcium carbonate), molybdenum compounds (e.g., molybdenum oxide, and zinc molybdate), barium compounds (e.g., barium sulfate, and barium silicate), talc (e.g., natural talc, and calcined talc), mica, glass (e.g., short fiber glass, spherical glass, fine powder glass, E glass, T glass, and D glass), silicone powder, fluororesin-based fillers, polyurethane resin-based fillers, (meth)acrylic resin-based fillers, polyethylene-based fillers, styrene-butadiene rubber, and silicone rubber.

[0347] Wherein, filling material (F) preferably includes more than one selected from the group consisting of silica, boehmite, barium sulfate, organosilicon powder, fluororesin filling material, polyurethane resin filling material, (methyl) acrylic resin filling material, polyethylene filling material, styrene-butadiene rubber and silicone rubber, more preferably includes more than one selected from the group consisting of silica, styrene-butadiene rubber and silicone rubber, further preferably includes silica. By making resin combination include these filling materials (F), there is the cured product that relative dielectric constant and dielectric loss tangent are lower, and then high-precision and relative dielectric constant and dielectric loss tangent lower insulating layer, more high-precision resist pattern high-density printed circuit board and semiconductor device can be obtained, the tendency that each characteristic such as film coating, heat resistance further improves.

[0348] These fillers (F) can be surface-treated with a silane coupling agent described later. As the silane coupling agent for the surface treatment of the filler (F), there is no particular limitation as long as it is a silane coupling agent commonly used for the surface treatment of inorganic or organic substances. For example, 3-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, [3-(6-aminohexylamino)propyl]trimethoxysilane and [3-(N,N-dimethyl Aminosilanes such as [(amino)-propyl]trimethoxysilane; γ-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldiethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and [8-(glycidyloxy)-n-octyl]trimethoxysilane; vinyltri(2-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trimethoxy(7-octen-1-yl)silane and trimethoxy(7-octen-1-yl)silane. Vinyl silanes such as methoxy(4-vinylphenyl)silane; methacryl silanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyldiethoxymethylsilane; acryl silanes such as 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane; isocyanate silanes such as 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane; isocyanurate silanes such as tris-(trimethoxysilylpropyl)isocyanurate; 3-mercaptopropyltrimethoxysilane and Mercaptosilanes such as 3-mercaptopropyldimethoxymethylsilane; ureidosilanes such as 3-ureidopropyltriethoxysilane; styrylsilanes such as p-styryltrimethoxysilane; cationic silanes such as N-β-(N-vinylbenzylaminoethyl-γ-aminopropyltrimethoxysilane hydrochloride); acid anhydrides such as [3-(trimethoxysilyl)propyl]succinic anhydride; phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane and p-tolyltrimethoxysilane; arylsilanes such as trimethoxy(1-naphthyl)silane. These silane coupling agents may be used alone or in combination of two or more.

[0349] As silane coupling agent, preferably include one or more in the group selected from epoxy silane system silane coupling agent, vinyl silane system silane coupling agent, phenyl amino silane system silane coupling agent and phenyl silane system silane coupling agent, more preferably include epoxy silane system silane coupling agent.In epoxy silane system silane coupling agent, further preferably γ-glycidyl ether oxypropyl trimethoxy silane.By using these silane coupling agents, can well with bismaleimide compound (A) and epoxy (methyl) acrylate (B), the maleimide compound (D) mixed as needed, with resin or compound (E) etc. reaction, there is the cured product that relative dielectric constant and dielectric loss tangent are lower, and then can obtain high fine and relative dielectric constant and dielectric loss tangent lower insulating layer or with more high fine resist pattern high density printed circuit board and semiconductor device, the tendency that each characteristic such as coating property or heat resistance further improves.

[0350] From the perspective of obtaining a cured product with a lower relative dielectric constant and dielectric loss tangent, and further obtaining a high-definition insulating layer with a lower relative dielectric constant and dielectric loss tangent, and further obtaining a high-density printed circuit board and semiconductor device with a high-definition anti-etching pattern, and further improving the coating properties and heat resistance, fused silica is more preferred as silica. Specific examples of silica include SFP-120MC (trade name) and SFP-130MC (trade name) manufactured by Denka Co., Ltd.; 3SE-CM1 (trade name), 3SM-CM4 (trade name), K180SE-CM1 (trade name), 5SM-CM2 (trade name), 0.3μmSX-CM1 (trade name), 0.3μmSX-EM1 (trade name), 0.3μmSV-EM1 (trade name), SC1050-MLQ (trade name), SC 2050-MNU (trade name), SC2050-MTX (trade name), SC2050-MB (trade name), SC1050-MLE (trade name), 2.2μm SC6103-SQ (trade name), SE2053-SQ (trade name), Y50SZ-AM1 (trade name), YA010C-MFN (trade name), YA050C-MJE (trade name), YA050C-MJM (trade name), YA050C-MJF (trade name) and YA050C-MJA (trade name).

[0351] The content of the filler (F) is preferably 5.0 to 100 parts by mass, more preferably 10 to 70 parts by mass, even more preferably 15 to 50 parts by mass, and even more preferably 20 to 35 parts by mass, relative to a total of 100 parts by mass of the resin solids in the resin composition. By adjusting the content of the filler (F) within the above range, a cured product with a lower relative dielectric constant and dielectric loss tangent can be obtained, and a high-density printed wiring board and semiconductor device with a finer insulation layer having a lower relative dielectric constant and dielectric loss tangent can be obtained, and various properties such as coating properties and heat resistance tend to be further improved.

[0352] [Silane coupling agent and wetting and dispersing agent]

[0353] In order to further improve the dispersibility of the filler (F) and the bonding strength between the bismaleimide compound (A) and epoxy (meth)acrylate (B), the maleimide compound (D) and the resin or the compound (E) and the filler (F) if blended as needed, the resin composition of the present embodiment may contain one or more selected from the group consisting of silane coupling agents and wetting dispersants.

[0354] There are no particular limitations on these silane coupling agents as long as they are silane coupling agents commonly used for surface treatment of inorganic or organic substances. Examples include 3-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, [3-(6-aminohexylamino)propyl]trimethoxysilane, and [3-(N,N-dimethyl Aminosilanes such as [(amino)-propyl]trimethoxysilane; γ-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldiethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and [8-(glycidyloxy)-n-octyl]trimethoxysilane; vinyltri(2-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trimethoxy(7-octen-1-yl)silane and trimethoxy(7-octen-1-yl)silane. Vinyl silanes such as methoxy(4-vinylphenyl)silane; methacryl silanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyldiethoxymethylsilane; acryl silanes such as 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane; isocyanate silanes such as 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane; isocyanurate silanes such as tris-(trimethoxysilylpropyl)isocyanurate; 3-mercaptopropyltrimethoxysilane and Mercaptosilanes such as 3-mercaptopropyldimethoxymethylsilane; ureidosilanes such as 3-ureidopropyltriethoxysilane; styrylsilanes such as p-styryltrimethoxysilane; cationic silanes such as N-β-(N-vinylbenzylaminoethyl-γ-aminopropyltrimethoxysilane hydrochloride); acid anhydrides such as [3-(trimethoxysilyl)propyl]succinic anhydride; phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane and p-tolyltrimethoxysilane; arylsilanes such as trimethoxy(1-naphthyl)silane. These silane coupling agents may be used alone or in combination of two or more.

[0355] The content of the silane coupling agent is usually 0.1 to 10 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

[0356] As a wetting dispersant, there is no particular limitation as long as it is a dispersion stabilizer for coating applications. As specific examples, for example, DISPERBYK (registered trademark)-110 (trade name), 111 (trade name), 118 (trade name), 180 (trade name), 161 (trade name), BYK (registered trademark)-W996 (trade name), W9010 (trade name), and W903 (trade name) manufactured by BYK-Chemie Japan Co., Ltd. can be mentioned. These wetting dispersants can be used alone or in combination of two or more.

[0357] The content of the wetting and dispersing agent is usually 0.1 to 10 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

[0358] [Crosslinking agent]

[0359] The resin combination of the present embodiment is for obtaining a cured product having a relative dielectric constant and a dielectric loss tangent lower, it is possible to obtain a higher and finer insulating layer having a relative dielectric constant and a dielectric loss tangent lower, with a high-density printed circuit board (PCB) and a semiconductor device of a higher and finer resist pattern, preferably also including a cross-linking agent. Cross-linking agent is different from bismaleimide compound (A), epoxy (methyl) acrylate (B), photocuring initiator (C), maleimide compound (D), resin or compound (E) and filling material (F). Cross-linking agent can be used alone or two or more are suitably mixed for use.

[0360] As a crosslinking agent, from the perspective of obtaining a cured product having a lower relative dielectric constant and dielectric loss tangent, and thus obtaining a high-definition insulating layer having a lower relative dielectric constant and dielectric loss tangent, and further obtaining a high-density printed wiring board and semiconductor device having a high-definition resist pattern, it is preferred to contain one or more selected from the group consisting of melamine compounds, allyl compounds, and urea compounds, and more preferably a melamine compound.

[0361] Examples of the melamine compound include hexamethylolmelamine, hexamethoxymethylmelamine, compounds in which 1 to 6 methylol groups of hexamethylolmelamine are methoxymethylated, and mixtures thereof.

[0362] Commercially available melamine compounds may be used, for example, the compound represented by formula (a) (Nikalac (registered trademark) MW-100LM (trade name), manufactured by Sanwa Chemical Co., Ltd.) and the compound represented by formula (b) (Nikalac (registered trademark) MX270 (trade name), manufactured by Sanwa Chemical Co., Ltd.).

[0363]

[0364] Examples of allyl compounds include diallyl isocyanurate, triallyl isocyanurate, and tetraallyl isocyanurate. Commercially available allyl compounds may also be used. Examples of commercially available allyl compounds include triallyl isocyanurate (TAIC (registered trademark), TAIC (registered trademark), Mitsubishi Chemical Corporation).

[0365] Examples of the urea compound include tetramethylurea and tetramethoxymethylurea.

[0366] The content of the cross-linking agent is usually 0.1 to 10 parts by mass, preferably 1.0 to 8.0 parts by mass, relative to 100 parts by mass of the resin solid content in the resin composition.

[0367] [Compounds containing one or more carboxyl groups]

[0368] The resin composition of the present embodiment may include a compound containing one or more carboxyl groups as long as it exerts the effect of the present invention. The compound containing one or more carboxyl groups includes one or more carboxyl groups in its structure. The compound containing one or more carboxyl groups is different from a bismaleimide compound (A), epoxy (meth) acrylate (B), a photocuring initiator (C), a maleimide compound (D), a resin or compound (E), a filler (F) and a cross-linking agent. The carboxyl group may be a salt such as a sodium salt and a potassium salt. When two or more carboxyl groups are included in the molecule, it may be in the form of an acid anhydride formed by two or more carboxyl groups being connected to each other. The compound containing one or more carboxyl groups may be used alone or in a suitable mixture of two or more.

[0369] From the viewpoint of obtaining more excellent alkali developability, the compound containing one or more carboxyl groups preferably contains an integer of 2 to 20 carboxyl groups in the molecule.

[0370] From the viewpoint of further improving developability, the molecular weight of the compound containing one or more carboxyl groups is preferably 50 to 10,000, more preferably 100 to 8,000, even more preferably 130 to 6,000, and even more preferably 150 to 5,000.

[0371] From the viewpoint of further improving developability, the mass average molecular weight (Mw) of the compound containing one or more carboxyl groups is preferably 50 to 10,000, more preferably 100 to 8,000, and even more preferably 150 to 5,000.

[0372] The content of the compound containing one or more carboxyl groups is generally 0.1 to 30 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition, in order to impart more excellent alkali developability and to exhibit good curability in the resin composition without inhibiting the photocuring reaction.

[0373] [Organic solvents]

[0374] The resin combination of the present embodiment may include an organic solvent as needed. If an organic solvent is used, the viscosity during the preparation of the resin combination may be adjusted to a more suitable range. The type of organic solvent is not particularly limited as long as it can dissolve a part or all of the resin in the resin combination. One organic solvent may be used alone or two or more may be suitably mixed.

[0375] Examples of the organic solvent include halogen solvents such as dichloromethane, chloroform, dichloroethane, and chlorobenzene; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, and acetonitrile; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; cellosolve solvents such as 2-ethoxyethanol and propylene glycol monomethyl ether; aliphatic alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; phenol solvents containing aromatic groups such as phenol and cresol; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, methyl methoxypropionate, methyl hydroxyisobutyrate, γ-butyrolactone, and propylene glycol monomethyl ether acetate; aromatic hydrocarbon solvents such as toluene and xylene, etc.

[0376] Among these, aprotic polar solvents, ketone solvents, cellosolve solvents, and ester solvents are preferred from the perspective of exhibiting superior solubility in the bismaleimide compound (A), epoxy (meth)acrylate (B), initiator (C), optionally compounded compound (D), resin or compound (E), filler (F), silane coupling agent, wetting dispersant, crosslinking agent, compound containing one or more carboxyl groups, and other resins and compounds. Aprotic polar solvents, ketone solvents, and ester solvents are more preferred from the perspective of exhibiting superior solubility.

[0377] As the aprotic polar solvent, dimethylacetamide is preferred. As the ketone solvent, methyl ethyl ketone is preferred. As the cellosolve solvent, propylene glycol monomethyl ether is preferred. As the ester solvent, butyl acetate, γ-butyrolactone, and propylene glycol monomethyl ether acetate are preferred.

[0378] [Other ingredients]

[0379] In the resin composition of the present embodiment, various polymer compounds such as thermosetting resins, thermoplastic resins and oligomers thereof, and elastomers that have not been listed heretofore; flame retardant compounds that have not been listed heretofore; additives, etc. can also be used in combination, within the scope that does not impair the characteristics of the present embodiment. There is no particular limitation as long as they are commonly used substances. For example, among the flame retardant compounds, there can be listed: nitrogen-containing compounds such as melamine and benzoguanamine; compounds containing oxazine rings; phosphorus compounds such as phosphate compounds of phosphorus compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters. As additives, there can be listed ultraviolet absorbers, antioxidants, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, lubricants, defoaming agents, surface conditioners, glossing agents, polymerization inhibitors, and thermosetting accelerators such as imidazole compounds. These components can be used alone or in combination of two or more. As imidazole, commercially available products can also be used. Examples of commercially available products include 2-phenyl-4-methylimidazole (Curezol (registered trademark) 2P4MZ (trade name, SHIKOKU CHEMICALS CORPORATION)).

[0380] In the resin composition, the content of components other than additives among other components is usually 0.01 to 10 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

[0381] In the resin composition, the content of the additives among other components is usually 0.01 to 10 parts by mass, respectively, based on 100 parts by mass of the resin solid content in the resin composition.

[0382] [Resin composition and method for producing varnish]

[0383] The resin composition of the present embodiment can be prepared by appropriately mixing a bismaleimide compound (A), an epoxy (meth)acrylate (B), and a photocuring initiator (C) with, as needed, a maleimide compound (D), a resin or compound (E), a filler (F), a crosslinking agent, a compound containing one or more carboxyl groups and other compounds, an organic solvent, and additives. The resin composition can be prepared by, for example, sequentially mixing the above components into a solvent and stirring thoroughly.

[0384] When manufacturing resin combination, known processing (stirring, mixing and mixing treatment etc.) for making each component dissolve or disperse uniformly can be carried out as needed. Specifically, by using the stirring tank that is equipped with the stirrer with suitable stirring ability to carry out stirring and dispersing treatment, the dispersibility of each component in the resin combination can be improved. Stirring, mixing and mixing treatment can be suitably carried out using known devices such as stirring devices for the purpose of dispersion, three-roller machine, ball mill, bead mill and sand mill, or mixing devices for the purpose of mixing, or revolution or autogenous type mixing devices, etc., for example, using ultrasonic homogenizer. In addition, when preparing resin combination, organic solvent can be used as needed. The type of organic solvent is not particularly limited as long as it can dissolve the resin in the resin combination, and its specific example is as described above.

[0385] The resin composition can be suitably used in the form of a varnish when making the resin sheet of the present embodiment described later. The varnish can be obtained by a known method. For example, the varnish can be obtained by adding 10 to 900 parts by mass, preferably 30 to 500 parts by mass, of an organic solvent to 100 parts by mass of the components other than the organic solvent in the resin composition, and performing the above-mentioned known treatments (stirring, mixing, and kneading treatment, etc.). It should be noted that the organic solvent used in the preparation of the varnish is not particularly limited, and its specific examples are as described above.

[0386] [use]

[0387] The resin combination of present embodiment can be suitable for the making of multilayer printed circuit board (PCB), can be preferably used for the purposes of the resin combination needing insulation.For example, can be used for photosensitive film, with the photosensitive film of support, prepreg, resin sheet, circuit substrate (laminate purposes, multilayer printed circuit board (PCB) purposes etc.), solder resist, bottom filling material, chip bonding material, semiconductor sealing material, hole-filling resin and parts embedding resin etc.Wherein, resin combination can obtain the lower cured product of relative dielectric constant and dielectric loss tangent, and light curing property and alkali developability are excellent, therefore can be suitable for the insulating layer of multilayer printed circuit board (PCB) with or solder resist with.

[0388] [cured material]

[0389] A cured product is obtained by curing a resin composition. For example, the cured product can be obtained by melting or dissolving the resin composition in a solvent, pouring it into a mold, and curing it with light under conventional conditions. The wavelength of the light is preferably within the range of 100 to 500 nm, which is effective for curing with a photoinitiator or the like.

[0390] [Resin sheet]

[0391] The resin sheet of this embodiment comprises a support and a resin layer disposed on one or both surfaces of the support. The resin layer comprises the resin composition of this embodiment. The resin sheet can be produced by coating the resin composition onto the support and drying it. The resin layer in the resin sheet has excellent photocurability and alkali developability.

[0392] The support may be any known support without particular limitation, but is preferably a resin film. Examples of the resin film include polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polyethylene naphthalate film, polyvinyl alcohol film, and triacetoacetate film. Among these, PET film is preferred.

[0393] To facilitate peeling from the resin layer, the resin film is preferably coated with a peeling agent on its surface. The thickness of the resin film is preferably 5 to 100 μm, more preferably 10 to 50 μm. If the thickness is 5 μm or more, the support tends to be less likely to break when peeling the support before alkali development. If the thickness is 100 μm or less, the resolution tends to be less likely to decrease when exposing the support. Therefore, when the thickness is within the above range, a better resin film tends to be obtained. In this specification, the thickness can be measured using a micrometer, for example.

[0394] Furthermore, in order to reduce light scattering during exposure, the resin film is preferably a film having excellent transparency.

[0395] Furthermore, in the resin sheet, the resin layer may be protected by a protective film.

[0396] By protecting the resin layer side with a protective film, it is possible to further prevent dust and the like from adhering to and damaging the surface of the resin layer. As the protective film, a film made of the same material as the resin film can be used. The thickness of the protective film is preferably 1 to 50 μm, more preferably 5 to 40 μm. If the thickness is 1 μm or more, there is a tendency that the operability of the protective film is not easily reduced. If the thickness is 50 μm or less, there is a tendency that it is advantageous in terms of cost. It should be noted that the protective film preferably has a smaller adhesive force between the resin layer and the protective film than between the resin layer and the support.

[0397] Examples of the method for producing a resin sheet include a method of applying a resin composition to a support such as a PET film and drying the resulting film to remove an organic solvent.

[0398] The coating method can be carried out by a known method using, for example, a roll coater, comma coater, gravure coater, die coater, bar coater, lip coater, knife coater, or extrusion coater. Drying can be carried out, for example, by heating in a dryer at 60 to 200° C. for 1 to 60 minutes.

[0399] To further prevent diffusion of the organic solvent in subsequent steps, the amount of organic solvent remaining in the resin layer is preferably 5% by mass or less relative to the total mass of the resin layer. To further improve workability, the thickness of the resin layer is preferably 1 to 50 μm.

[0400] The resin sheet can be preferably used for producing an insulating layer of a multilayer printed circuit board.

[0401] [Multilayer printed circuit board]

[0402] The multilayer printed circuit board of the present embodiment has an insulating layer and a conductor layer formed on one or both sides of the insulating layer, and the insulating layer comprises the resin composition of the present embodiment. The insulating layer can also be obtained by, for example, overlapping and curing more than one resin sheet. The number of stacking layers of the insulating layer and the conductor layer can be appropriately set according to the target application. In addition, the order of the insulating layer and the conductor layer is not particularly limited. As the conductor layer, it can be a metal foil used in various printed circuit board materials, for example, metal foils such as copper and aluminum can be listed. As the copper metal foil, copper foil such as rolled copper foil and electrolytic copper foil can be listed. The thickness of the conductor layer is generally 1 to 100 μm. Specifically, it can be manufactured by the following method.

[0403] (Lamination process)

[0404] In the lamination process, a vacuum laminator is used to laminate the resin layer side of the resin sheet onto the single or double sides of the circuit substrate. As the circuit substrate, for example, a glass epoxy substrate, a metal substrate, a ceramic substrate, a silicon substrate, a semiconductor sealing resin substrate, a polyester substrate, a polyimide substrate, a BT resin substrate and a thermosetting polyphenylene ether substrate etc. can be cited. It should be noted that the circuit substrate refers to a substrate having a conductor layer (circuit) patterned on the single or double sides of the substrate as described above. In addition, in the multilayer printed circuit board in which the conductor layer and the insulating layer are alternately stacked, the substrate having the conductor layer (circuit) patterned on the single or double sides of the outermost layer of the multilayer printed circuit board is also included in the circuit substrate. It should be noted that the insulating layer stacked on the multilayer printed circuit board can be an insulating layer obtained by overlapping and curing the resin sheets of more than one embodiment, or an insulating layer obtained by overlapping the resin sheet of the present embodiment and a known resin sheet different from the resin sheet of the present embodiment. It should be noted that the overlapping method of the resin sheet of the present embodiment and the known resin sheet that is different from the resin sheet of the present embodiment is not particularly limited. It is also possible to implement roughening treatment on the conductor layer surface in advance by blackening treatment and / or copper etching. In the lamination process, when the resin sheet has a protective film, after the protective film is peeled off and removed, the resin sheet and the circuit substrate are preheated as needed, while the resin layer of the resin sheet is pressurized and heated while being pressed onto the circuit substrate. In the present embodiment, it is preferably used that the resin layer of the resin sheet is laminated to the circuit substrate under reduced pressure by vacuum lamination.

[0405] Under the conditions of the lamination process, the pressing temperature (lamination temperature) is preferably 50° C. to 140° C. The pressing pressure is preferably 1 to 15 kgf / cm 2 . The pressing time is preferably 5 to 300 seconds. The air pressure is preferably under reduced pressure, more preferably 20 mmHg or less. In addition, the lamination process can be intermittent or continuous using rollers. The vacuum lamination method can be carried out using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a two-stage stacking laminator manufactured by Nikko-Materials Co., Ltd. can be cited.

[0406] (Exposure Process)

[0407] In the exposure step, after the resin layer is formed on the circuit board in the lamination step, various active energy rays are irradiated as a light source to cure the resin layer in the irradiated area. The bismaleimide compound (A) does not inhibit the photocuring reaction in the exposure step.

[0408] Irradiation can be performed through a mask pattern or by direct irradiation. Examples of active energy rays include ultraviolet rays, visible light rays, electron beams, and X-rays. The wavelength of the active energy rays is, for example, in the range of 200 to 600 nm. When ultraviolet rays are used, the irradiation dose is approximately 5 to 1000 mJ / cm 2 In addition, when a printed circuit board having high-density and high-precision wiring formation (pattern) is manufactured using a stepper that performs projection exposure in a step-and-repeat manner, it is preferable to use active energy rays having a wavelength of 365 nm (i-rays), for example. In this case, the irradiation dose is approximately 5 to 10,000 mJ / cm 2 In addition, when using direct writing exposure to manufacture printed circuit boards with high-density and high-precision wiring patterns, active energy rays with a wavelength of 365 nm (i-rays) can also be used. In this case, the irradiation dose is approximately 5 to 10,000 mJ / cm 2 .

[0409] Exposure methods using a mask pattern include contact exposure, where the mask pattern is brought into close contact with the multilayer printed circuit board, and non-contact exposure, where projection exposure is performed using lenses or mirrors without close contact. Either method can be used. Furthermore, when a support is present on the resin layer, exposure can be performed from above the support or after the support is peeled off.

[0410] (Alkali Development Process)

[0411] When no support is present on the resin layer, the non-photocured portion (unexposed portion) can be removed by alkali development directly after the exposure step, and then developed to form a pattern of the insulating layer.

[0412] When a support is present on the resin layer, after the exposure step, the support is removed, and then the uncured portion (unexposed portion) is removed by alkali development and then developed to form a pattern of the insulating layer.

[0413] The unexposed resin layer comprising the resin composition of this embodiment contains the bismaleimide compound (A) and the epoxy (meth)acrylate (B), and therefore has excellent alkali developability, enabling rapid removal of the unexposed resin composition. Consequently, a printed wiring board having a high-definition pattern can be obtained.

[0414] In the case of alkali development, the developer is not particularly limited as long as it selectively dissolves the unexposed portion, and alkali developers such as tetramethylammonium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution, sodium hydroxide aqueous solution, and potassium hydroxide aqueous solution can be used. In this embodiment, tetramethylammonium hydroxide aqueous solution is more preferably used. These alkali developers can be used alone or in combination of two or more.

[0415] In addition, as an alkali development method, for example, it can be carried out by known methods such as dipping, puddle, spraying, shaking dipping, brushing, and scraping. In pattern formation, these development methods can also be used in combination as needed. In addition, as a development method, the use of high-pressure spraying further improves the resolution and is therefore preferred. When using a spray method, the spray pressure is preferably 0.02 to 0.5 MPa.

[0416] (Post-baking process)

[0417] In this embodiment, after the alkali development process is completed, a post-baking process is performed to form an insulating layer (cured product). As the post-baking process, an ultraviolet irradiation process using a high-pressure mercury lamp or a heating process using a clean oven can be listed, and these can also be used in combination. In the case of ultraviolet irradiation, the irradiation amount can be adjusted as needed, for example, 0.05 to 10 J / cm 2 The heating conditions can be appropriately selected as needed, but are preferably in the range of 150 to 220°C for 20 to 180 minutes, and more preferably in the range of 160 to 200°C for 30 to 150 minutes.

[0418] (Conductor Layer Forming Step)

[0419] After forming the insulating layer (cured product), a conductive layer is formed on the surface of the insulating layer by dry plating.

[0420] It should be noted that when forming the conductor layer, the surface of the insulating layer may be subjected to a surface modification treatment before dry plating. As the surface modification treatment, known methods such as plasma etching, reverse sputtering, and corona treatment can be used.

[0421] As dry plating, known methods such as evaporation, sputtering, and ion plating can be used. Evaporation (vacuum evaporation) methods, for example, involve placing a multilayer printed circuit board in a vacuum chamber, heating and evaporating the metal, and thereby forming a metal film on the insulating layer. Sputtering methods, for example, involve placing a multilayer printed circuit board in a vacuum chamber, introducing an inert gas such as argon, applying a DC voltage, and causing the ionized inert gas to collide with a target metal, thereby using the ejected metal to form a metal film on the insulating layer.

[0422] Next, a conductor layer is formed by chemical plating, electroplating, etc. As a method for subsequent patterning, for example, a subtractive process, a semi-additive process, etc. can be used.

[0423] [Semiconductor devices]

[0424] The semiconductor device of this embodiment includes the resin composition of this embodiment. Specifically, it can be manufactured by the following method. The semiconductor device can be manufactured by mounting a semiconductor chip on a conductive portion of a multilayer printed circuit board. Here, the conductive portion refers to the portion of the multilayer printed circuit board that transmits electrical signals, and this portion can be either surface or embedded. Furthermore, the semiconductor chip is not particularly limited as long as it is a circuit element made of a semiconductor.

[0425] The method for mounting semiconductor chips during semiconductor device manufacturing is not particularly limited as long as the semiconductor chips function effectively. Specifically, examples include wire bonding, flip-chip mounting, bumpless build-up (BBUL), anisotropic conductive film (ACF), and non-conductive film (NCF).

[0426] Furthermore, semiconductor devices can be manufactured by forming an insulating layer comprising a resin composition on a semiconductor chip or a substrate on which the semiconductor chip is mounted. The substrate on which the semiconductor chip is mounted can be in the form of a wafer or a panel. Once formed, the insulating layer can be manufactured using the same method as the multilayer printed circuit board described above.

[0427] Example

[0428] Hereinafter, this embodiment will be described in more detail using examples and comparative examples. This embodiment is not limited to the following examples.

[0429] [Evaluation of raw materials]

[0430] [Transmittance and absorbance]

[0431] As the bismaleimide compound (A), MIZ-001 (trade name, mass average molecular weight (Mw): 3000) manufactured by Nippon Kayaku Co., Ltd. was used. A chloroform solution containing MIZ-001 (trade name) at 1% by mass was prepared, and the transmittance at a wavelength of 365 nm was measured using a UV-vis spectrophotometer (Hitachi High-Technologies Corp., Hitachi U-4100 (trade name)). It should be noted that a quartz cuvette with a cuvette length (path length during measurement) of 1 cm was used for the transmittance measurement.

[0432] Similarly, the transmittance at a wavelength of 365 nm was measured for each of ZXR-1889H (trade name) manufactured by Nippon Kayaku Co., Ltd. and ZXR-1807H (trade name) manufactured by Nippon Kayaku Co., Ltd. as epoxy (meth)acrylate (B).

[0433] Similarly, the transmittance at a wavelength of 365 nm was measured for NE-X-9470S (trade name) manufactured by DIC Corporation as the maleimide compound (D).

[0434] Similarly, the transmittance at a wavelength of 365 nm was measured for Mitsubishi Gas Chemical Co., Ltd. OPE (registered trademark)-2St1200 (trade name) as the resin or compound (E).

[0435] As the photocuring initiator (C), Irgacure (registered trademark) OXE01 (trade name) manufactured by BASF Japan Ltd. was used. A chloroform solution containing 0.01% by mass of Irgacure (registered trademark) OXE01 (trade name) was prepared, and the absorbance at a wavelength of 365 nm was measured using a UV-vis measurement device (U-4100 (trade name)). A quartz cuvette with a cuvette length (path length during measurement) of 1 cm was used for the absorbance measurement.

[0436] Similarly, as a photocuring initiator (C), Irgacure (registered trademark) OXE03 (trade name) manufactured by BASF Japan Ltd. and Omnirad (registered trademark) 819 (trade name) manufactured by IGM Resins BV were used, and the absorbance at a wavelength of 365 nm was measured.

[0437] These results are shown in Table 1.

[0438] [Table 1]

[0439]

[0440] [Example 1]

[0441] (Production of Resin Composition and Resin Sheet)

[0442] 40 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A) and ZXR-1889H (trade name, a compound represented by formula (36), a mixture of compounds having different numbers of repetitions of n8 and n9; n8 is in the range of 1 to 19, n9 is in the range of 1 to 19, and the total number of n8 and n9 is in the range of 2 to 20, having a mass average molecular weight (Mw) of 2250 and an acid value of 111 mgKOH) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) were mixed. / g) (non-volatile content 66.0%)) 30.3 parts by mass (20 parts by mass as non-volatile content conversion) of ZXR-1807H (trade name, a mixture of a compound represented by formula (36), n8 and n9 having different numbers of repetitions, n8 being in the range of 1 to 19, n9 being in the range of 1 to 19, and the sum of n8 and n9 being in the range of 2 to 20, with a mass average molecular weight (Mw) of 2270 and an acid value of 100 mgKOH / g) (non-volatile content 66.0%)) manufactured by Nippon Kayaku Co., Ltd. as epoxy (meth)acrylate (B) 30.3 parts by mass (20 parts by mass as non-volatile content conversion) of BASF 5.0 parts by mass of Irgacure (registered trademark) OXE03 (trade name, oxime esters) manufactured by Japan Ltd., 16.3 parts by mass of NE-X-9470S (trade name, compound represented by formula (6)) manufactured by DIC Corporation as the maleimide compound (D) (non-volatile content 61.0%) (10 parts by mass as non-volatile content conversion), 15.3 parts by mass of OPE (registered trademark)-2St1200 (trade name, modified polyphenylene ether compound having a structure represented by formula (24)) (non-volatile content 65.0%) manufactured by Mitsubishi Gas Chemical Co., Ltd. as the resin or compound (E), and Admatechs Co., Ltd. as the filler (F). 41.3 parts by mass (25 parts by mass, calculated as nonvolatile content) of a MEK (methyl ethyl ketone) solution (60.5% nonvolatile content) of 3SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 300 nm) and 5.0 parts by mass of NIKALAC (registered trademark) MW-100LM (trade name, compound represented by formula (a)) manufactured by Sanwa Chemical Co., Ltd. as a crosslinking agent were mixed, and 42 parts by mass of MEK was added to obtain a varnish (resin composition). The mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) in the varnish (resin composition) was 1.This varnish was dripped onto a 25 μm thick PET film (Unipeel (registered trademark) TR1-25 (trade name) manufactured by UNITIKAL TD.) and formed into a coating film using a bar coater (K ​​Control Roller (trade name) manufactured by Matsuo Sangyo Co., Ltd., a tabletop printing tester). The resulting coating film was dried at 80°C for 5 minutes to obtain a resin sheet having a resin layer with a thickness of 15 μm and a PET film as a support.

[0443] (Preparation of Evaluation Laminate)

[0444] On a substrate of a glass non-woven fabric substrate BT resin double-sided copper foil-clad laminate (copper foil thickness: 18 μm, thickness: 0.2 mm, CCL-HL832NS manufactured by Mitsubishi Gas Chemical Co., Ltd.) roughened on both sides with CZ8101 (trade name) manufactured by MEC COMPANY LTD, the obtained resin sheet was placed with the resin surface facing the substrate, and vacuumed (5.0 hPa or less) for 30 seconds using a vacuum laminator (manufactured by Nikko-Materials Co., Ltd.). Then, the laminate was pressed at a pressure of 10 kgf / cm 2 The laminate molding was performed at a temperature of 70°C for 30 seconds. 2 Lamination molding was performed at a temperature of 70° C. for 60 seconds to obtain a laminate for evaluation in which the copper-clad laminate, the resin layer, and the support were laminated.

[0445] (Preparation of Evaluation Laminated Resin Sheet)

[0446] The two obtained resin sheets were laminated with the resin surfaces facing each other, and vacuum laminator (made by Nikko-Materials Co., Ltd.) was used to evacuate the sheets to 5.0 hPa or less for 30 seconds. 2 After lamination molding at 70°C for 30 seconds, the pressure was further increased to 7 kgf / cm 2 , and a temperature of 70°C for 60 seconds to obtain a laminate (a). After peeling off the support on one side of the obtained laminate (a), the laminate (a) was folded in half with the resin side from which the support was peeled facing each other, and the resin sides were bonded together. A vacuum laminator (made by Nikko-Materials Co., Ltd.) was used to evacuate the laminate (below 5.0 hPa) for 30 seconds. Then, the laminate was pressed under a pressure of 10 kgf / cm 2 After lamination molding at 70°C for 30 seconds, the pressure was further increased to 7 kgf / cm 2, and a temperature of 70°C for 60 seconds to obtain a laminate (b). After peeling off the support on one side of the obtained laminate (b), the laminate (b) was folded in half with the resin side from which the support was peeled facing each other, and the resin sides were bonded together. A vacuum laminator (made by Nikko-Materials Co., Ltd.) was used to evacuate the laminate (below 5.0 hPa) for 30 seconds. Then, the laminate was heated at a pressure of 10 kgf / cm 2 , lamination molding was performed at a temperature of 70°C for 30 seconds, and then at a pressure of 7 kgf / cm 2 The laminated resin sheet for evaluation having supports on both sides was obtained by laminating at 70° C. for 60 seconds. The thickness of the resin layer in each of the obtained laminated resin sheets for evaluation was 80 μm or more.

[0447] [Example 2]

[0448] 20 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 15.15 parts by mass (10 parts by mass as non-volatile matter conversion) of ZXR-1889H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B), 30.3 parts by mass (20 parts by mass as non-volatile matter conversion) of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B), and BASF Japan Ltd., 5.0 parts by mass of Irgacure (registered trademark) OXE03 (trade name, oxime esters), 16.3 parts by mass of NE-X-9470S (trade name, compound represented by formula (6)) (non-volatile content 61.0%) manufactured by DIC Corporation as the maleimide compound (D) (10 parts by mass as converted to non-volatile content), 15.3 parts by mass of OPE (registered trademark)-2St1200 (trade name, modified polyphenylene ether compound having a structure represented by formula (24)) (non-volatile content 65.0%) manufactured by Mitsubishi Gas Chemical Co., Ltd. as the resin or compound (E), and Admatechs Co., Ltd. as the filler (F). A varnish (resin composition) was prepared by adding 41.3 parts by mass (25 parts by mass as nonvolatile content) of a MEK (methyl ethyl ketone) solution (nonvolatile content 60.5%) of 3SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 300 nm) and 5.0 parts by mass of NIKALAC (registered trademark) MW-100LM (trade name, compound represented by formula (a)) manufactured by SANWA CHEMICAL CO., LTD. as a crosslinking agent. 42 parts by mass of MEK was added to obtain the varnish (resin composition). The mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) in the varnish (resin composition) was 0.67.

[0449] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0450] [Example 3]

[0451] 60 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 45.45 parts by mass (30 parts by mass as non-volatile matter conversion) of ZXR-1889H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B), 30.3 parts by mass (20 parts by mass as non-volatile matter conversion) of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B), and BASF Japan Co., Ltd. as a photocuring initiator (C) were mixed. Ltd., 5.0 parts by mass of Irgacure (registered trademark) OXE03 (trade name, oxime esters), 16.3 parts by mass of NE-X-9470S (trade name, compound represented by formula (6)) (non-volatile content 61.0%) manufactured by DIC Corporation as the maleimide compound (D) (10 parts by mass as converted to non-volatile content), 15.3 parts by mass of OPE (registered trademark)-2St1200 (trade name, modified polyphenylene ether compound having a structure represented by formula (24)) (non-volatile content 65.0%) manufactured by Mitsubishi Gas Chemical Co., Ltd. as the resin or compound (E), and Admatechs Co., Ltd. as the filler (F). A varnish (resin composition) was prepared by adding 41.3 parts by mass (25 parts by mass as nonvolatile content) of a MEK (methyl ethyl ketone) solution (nonvolatile content 60.5%) of 3SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 300 nm) and 5.0 parts by mass of NIKALAC (registered trademark) MW-100LM (trade name, compound represented by formula (a)) manufactured by SANWA CHEMICAL CO., LTD. as a crosslinking agent. To this was added 42 parts by mass of MEK to obtain the varnish (resin composition). The mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) in the varnish (resin composition) was 1.2.

[0452] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0453] [Example 4]

[0454] 40 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1889H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), and BASF Japan Ltd. Irgacure (registered trademark) OXE01 (trade name, 1,2-octanedione-1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)]) 5.0 parts by mass, DIC Corporation NE-X-9470S (trade name, compound represented by formula (6)) (non-volatile content 61.0%) as the maleimide compound (D) 16.3 parts by mass (10 parts by mass as non-volatile content conversion) of DIC Corporation NE-X-9470S, Mitsubishi Gas Chemical Co., Ltd. OPE (registered trademark)-2St1200 (trade name, modified polyphenylene ether compound having a structure represented by formula (24)) (non-volatile content 65.0%) as the resin or compound (E), Admatechs Co., Ltd. as the filler (F) A varnish (resin composition) was prepared by adding 41.3 parts by mass (25 parts by mass as nonvolatile content) of a MEK (methyl ethyl ketone) solution (nonvolatile content 60.5%) of 3SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 300 nm) and 5.0 parts by mass of NIKALAC (registered trademark) MW-100LM (trade name, compound represented by formula (a)) manufactured by Sanwa Chemical Co., Ltd. as a crosslinking agent. 42 parts by mass of MEK was added to the mixture. The mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) in the varnish (resin composition) was 1.

[0455] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0456] [Example 5]

[0457] 40 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1889H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), and BASF Japan Ltd. Irgacure (registered trademark) OXE01 (trade name, 1,2-octanedione-1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)]) manufactured by Ltd., 3.0 parts by mass of Irgacure (registered trademark) OXE03 (trade name, oxime esters) manufactured by BASF Japan Ltd. as a photocuring initiator (C), 16.3 parts by mass (10 parts by mass in terms of non-volatile content) of NE-X-9470S (trade name, compound represented by formula (6)) manufactured by DIC Corporation as a maleimide compound (D), and OPE (registered trademark)-2St1200 (trade name, having a structure represented by formula (24) manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a resin or compound (E) A varnish (resin composition) was prepared by adding 15.3 parts by mass (10 parts by mass as a nonvolatile component) of a modified polyphenylene ether compound (nonvolatile content 65.0%), 41.3 parts by mass (25 parts by mass as a nonvolatile component) of a MEK (methyl ethyl ketone) solution (nonvolatile content 60.5%) of Admatechs 3SE-CM1 (trade name, epoxysilane surface-treated slurry (fused) silica, average particle size: 300 nm) manufactured by Admatechs Co., Ltd. as a filler (F), and 5.0 parts by mass of NIKALAC (registered trademark) MW-100LM (trade name, compound represented by formula (a)) manufactured by Sanwa Chemical Co., Ltd. as a crosslinking agent. 42 parts by mass of MEK were added to obtain a varnish (resin composition). It should be noted that in the varnish (resin composition), the mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) was 1.

[0458] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0459] [Example 6]

[0460] 40 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1889H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), and BASF Japan Ltd. Irgacure (registered trademark) OXE03 (trade name, oxime esters) 4.0 parts by mass, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM Resins 1.0 parts by mass of Omnirad (registered trademark) 819 (trade name) manufactured by BV Co., Ltd., 16.3 parts by mass of NE-X-9470S (trade name, compound represented by formula (6)) (non-volatile content 61.0%) manufactured by DIC Corporation as a maleimide compound (D) (10 parts by mass as converted to non-volatile content), 15.3 parts by mass of OPE (registered trademark)-2St1200 (trade name, modified polyphenylene ether compound having a structure represented by formula (24)) (non-volatile content 65.0%) manufactured by Mitsubishi Gas Chemical Co., Ltd. as a resin or compound (E), and 10 parts by mass of Admatechs Co., Ltd. as a filler (F). A varnish (resin composition) was prepared by adding 41.3 parts by mass (25 parts by mass as nonvolatile content) of a MEK (methyl ethyl ketone) solution (nonvolatile content 60.5%) of 3SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 300 nm) and 5.0 parts by mass of NIKALAC (registered trademark) MW-100LM (trade name, compound represented by formula (a)) manufactured by Sanwa Chemical Co., Ltd. as a crosslinking agent. 42 parts by mass of MEK was added to the mixture. The mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) in the varnish (resin composition) was 1.

[0461] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0462] [Example 7]

[0463] 40 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1889H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), and BASF Japan Ltd., 1.0 parts by mass of Irgacure (registered trademark) OXE03 (trade name, oxime esters), 16.3 parts by mass of NE-X-9470S (trade name, compound represented by formula (6)) (non-volatile content 61.0%) manufactured by DIC Corporation as the maleimide compound (D) (10 parts by mass as converted to non-volatile content), 15.3 parts by mass of OPE (registered trademark)-2St1200 (trade name, modified polyphenylene ether compound having a structure represented by formula (24)) (non-volatile content 65.0%) manufactured by Mitsubishi Gas Chemical Co., Ltd. as the resin or compound (E), and Admatechs Co., Ltd. as the filler (F). A varnish (resin composition) was prepared by adding 41.3 parts by mass (25 parts by mass as nonvolatile content) of a MEK (methyl ethyl ketone) solution (nonvolatile content 60.5%) of 3SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 300 nm) and 5.0 parts by mass of NIKALAC (registered trademark) MW-100LM (trade name, compound represented by formula (a)) manufactured by Sanwa Chemical Co., Ltd. as a crosslinking agent. To this was added 39 parts by mass of MEK to obtain the varnish (resin composition). The mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) in the varnish (resin composition) was 1.

[0464] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0465] [Example 8]

[0466] 40 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1889H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), and BASF Japan Ltd., 10 parts by mass of Irgacure (registered trademark) OXE03 (trade name, oxime esters), 16.3 parts by mass of NE-X-9470S (trade name, compound represented by formula (6)) (non-volatile content 61.0%) manufactured by DIC Corporation as the maleimide compound (D) (10 parts by mass as converted to non-volatile content), 15.3 parts by mass of OPE (registered trademark)-2St1200 (trade name, modified polyphenylene ether compound having a structure represented by formula (24)) (non-volatile content 65.0%) manufactured by Mitsubishi Gas Chemical Co., Ltd. as the resin or compound (E) (10 parts by mass as converted to non-volatile content), and Admatechs Co., Ltd. as the filler (F). A varnish (resin composition) was prepared by adding 41.3 parts by mass (25 parts by mass as nonvolatile content) of a MEK (methyl ethyl ketone) solution (nonvolatile content 60.5%) of 3SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 300 nm) and 5.0 parts by mass of NIKALAC (registered trademark) MW-100LM (trade name, compound represented by formula (a)) manufactured by Sanwa Chemical Co., Ltd. as a crosslinking agent. To this was added 46 parts by mass of MEK to obtain the varnish (resin composition). The mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) in the varnish (resin composition) was 1.

[0467] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0468] [Example 9]

[0469] 25 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 68.2 parts by mass (45 parts by mass in terms of non-volatile content) of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. (non-volatile content 66.0%) as an epoxy (meth)acrylate (B), and BASF Japan Ltd.) 5 parts by mass of Irgacure (registered trademark) OXE03 (trade name, oxime esters), 16.3 parts by mass of NE-X-9470S (trade name, compound represented by formula (6)) (non-volatile content 61.0%) manufactured by DIC Corporation as a maleimide compound (D) (10 parts by mass in terms of non-volatile content), and OPE (registered trademark)-2St1200 (trade name, having a structure represented by formula (24)) manufactured by Mitsubishi Gas Chemical Co., Ltd. as a resin or compound (E). A varnish (resin composition) was prepared by adding 15.3 parts by mass (10 parts by mass as nonvolatile content) of a modified polyphenylene ether compound (nonvolatile content 65.0%), 41.3 parts by mass (25 parts by mass as nonvolatile content) of a MEK (methyl ethyl ketone) solution (nonvolatile content 60.5%) of Admatechs 3SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 300 nm) manufactured by Admatechs Co., Ltd., as a filler (F), and 5.0 parts by mass of NIKALAC (registered trademark) MW-100LM (trade name, compound represented by formula (a)) manufactured by Sanwa Chemical Co., Ltd. as a crosslinking agent. 40 parts by mass of MEK were added to obtain the varnish (resin composition). The mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) in the varnish (resin composition) was 0.56.

[0470] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0471] [Example 10]

[0472] 40 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 60.6 parts by mass (40 parts by mass in terms of non-volatile content) of ZXR-1889H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile content 66.0%), and BASF Japan Ltd.) 5.0 parts by mass of Irgacure (registered trademark) OXE03 (trade name, oxime esters), 16.3 parts by mass of NE-X-9470S (trade name, compound represented by formula (6)) (non-volatile matter 61.0%) manufactured by DIC Corporation as a maleimide compound (D) (10 parts by mass in terms of non-volatile matter), and OPE (registered trademark)-2St1200 (trade name, compound represented by formula (24)) manufactured by Mitsubishi Gas Chemical Co., Ltd. as a resin or compound (E). 15.3 parts by mass (10 parts by mass as non-volatile content) of a modified polyphenylene ether compound having a structure shown in FIG. 1 (non-volatile content 65.0%), 41.3 parts by mass (25 parts by mass as non-volatile content) of a MEK (methyl ethyl ketone) solution (non-volatile content 60.5%) of Admatechs 3SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 300 nm) manufactured by Admatechs Co., Ltd. as a filler (F), and 5.0 parts by mass of NIKALAC (registered trademark) MW-100LM (trade name, compound represented by formula (a)) manufactured by Sanwa Chemical Co., Ltd. as a crosslinking agent were added to 42 parts by mass of MEK to obtain a varnish (resin composition). In the varnish (resin composition), the mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) was 1.

[0473] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0474] [Example 11]

[0475] 40 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1889H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), and BASF Japan Ltd.) 5.0 parts by mass of Irgacure (registered trademark) OXE03 (trade name, oxime esters), 15.3 parts by mass of OPE (registered trademark)-2St1200 (trade name, modified polyphenylene ether compound having a structure represented by formula (24)) (non-volatile content 65.0%) manufactured by Mitsubishi Gas Chemical Co., Ltd. as the resin or compound (E) (10 parts by mass as non-volatile content), 41.3 parts by mass of a MEK (methyl ethyl ketone) solution of Admatechs Co., Ltd. 3SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 300 nm) (non-volatile content 60.5%) as the filler (F), and 25 parts by mass of SANWA CHEMICAL Co., Ltd. as the crosslinking agent. 5.0 parts by mass of NIKALAC (registered trademark) MW-100LM (trade name, compound represented by formula (a)) manufactured by CO., LTD. and 40 parts by mass of MEK were added to obtain a varnish (resin composition).

[0476] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0477] [Example 12]

[0478] 40 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1889H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), and BASF Japan Ltd.) 5.0 parts by mass of Irgacure (registered trademark) OXE03 (trade name, oxime esters), 16.3 parts by mass of DIC Corporation's NE-X-9470S (trade name, compound represented by formula (6)) (non-volatile content 61.0%) as a maleimide compound (D) (10 parts by mass as non-volatile content conversion), 41.3 parts by mass of Admatechs Corporation's 3SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 300 nm) in MEK (methyl ethyl ketone) (non-volatile content 60.5%) as a filler (F) (25 parts by mass as non-volatile content conversion), and 5.0 parts by mass of SANWA CHEMICAL CO., LTD.'s NIKALAC (registered trademark) MW-100LM (trade name, compound represented by formula (a)) as a crosslinking agent were added. In the varnish (resin composition), the mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) was 1.

[0479] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0480] [Example 13]

[0481] 40 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1889H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), and BASF Japan Ltd., 5.0 parts by mass of Irgacure (registered trademark) OXE03 (trade name, oxime esters), 16.3 parts by mass of NE-X-9470S (trade name, compound represented by formula (6)) (non-volatile content 61.0%) manufactured by DIC Corporation as the maleimide compound (D) (10 parts by mass as converted to non-volatile content), 15.3 parts by mass of OPE (registered trademark)-2St1200 (trade name, modified polyphenylene ether compound having a structure represented by formula (24)) (non-volatile content 65.0%) manufactured by Mitsubishi Gas Chemical Co., Ltd. as the resin or compound (E), and Admatechs Co., Ltd. as the filler (F). To 41.3 parts by mass (25 parts by mass, calculated as nonvolatile content) of a MEK (methyl ethyl ketone) solution (60.5%) of 3SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 300 nm) was added 42 parts by mass of MEK to obtain a varnish (resin composition). The mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) in the varnish (resin composition) was 1.

[0482] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0483] [Example 14]

[0484] 40 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1889H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), and BASF Japan Ltd., 5.0 parts by mass of Irgacure (registered trademark) OXE03 (trade name, oxime esters), 16.3 parts by mass of NE-X-9470S (trade name, compound represented by formula (6)) (non-volatile content 61.0%) manufactured by DIC Corporation as the maleimide compound (D) (10 parts by mass as converted to non-volatile content), 15.3 parts by mass of OPE (registered trademark)-2St1200 (trade name, modified polyphenylene ether compound having a structure represented by formula (24)) (non-volatile content 65.0%) manufactured by Mitsubishi Gas Chemical Co., Ltd. as the resin or compound (E), and Admatechs Co., Ltd. as the filler (F). To 82.6 parts by mass (50 parts by mass, calculated as 50 parts by mass, of a methyl ethyl ketone (MEK) solution (non-volatile content 60.5%) of 3SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 300 nm) was added 20 parts by mass of MEK to obtain a varnish (resin composition). The mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) in the varnish (resin composition) was 1.

[0485] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0486] [Example 15]

[0487] 40 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1889H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), and BASF Japan Ltd., 5.0 parts by mass of Irgacure (registered trademark) OXE03 (trade name, oxime esters), 16.3 parts by mass of NE-X-9470S (trade name, compound represented by formula (6)) (non-volatile content 61.0%) manufactured by DIC Corporation as the maleimide compound (D) (10 parts by mass as converted to non-volatile content), 15.3 parts by mass of OPE (registered trademark)-2St1200 (trade name, modified polyphenylene ether compound having a structure represented by formula (24)) (non-volatile content 65.0%) manufactured by Mitsubishi Gas Chemical Co., Ltd. as the resin or compound (E), and Admatechs Co., Ltd. as the filler (F). To 50 parts by mass (25 parts by mass as nonvolatile content) of a MEK (methyl ethyl ketone) solution (50.1%) of K180SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 180 nm) was added 42 parts by mass of MEK to obtain a varnish (resin composition). The mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) in the varnish (resin composition) was 1.

[0488] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0489] [Example 16]

[0490] 40 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1889H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), and BASF Japan Ltd., 5.0 parts by mass of Irgacure (registered trademark) OXE03 (trade name, oxime esters), 16.3 parts by mass of NE-X-9470S (trade name, compound represented by formula (6)) (non-volatile content 61.0%) manufactured by DIC Corporation as the maleimide compound (D) (10 parts by mass as converted to non-volatile content), 15.3 parts by mass of OPE (registered trademark)-2St1200 (trade name, modified polyphenylene ether compound having a structure represented by formula (24)) (non-volatile content 65.0%) manufactured by Mitsubishi Gas Chemical Co., Ltd. as the resin or compound (E), and Admatechs Co., Ltd. as the filler (F). A varnish (resin composition) was prepared by adding 41.3 parts by mass (25 parts by mass as nonvolatile content) of a MEK (methyl ethyl ketone) solution (60.5% nonvolatile content) of 3SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 300 nm) and 5.0 parts by mass of TAIC (registered trademark) (triallyl isocyanurate) from Mitsubishi Chemical Corporation as a crosslinking agent. To this was added 42 parts by mass of MEK. The varnish (resin composition) had a mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) of 1.

[0491] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0492] [Example 17]

[0493] 40 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1889H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), and BASF Japan Ltd., 5.0 parts by mass of Irgacure (registered trademark) OXE03 (trade name, oxime esters), 16.3 parts by mass of NE-X-9470S (trade name, compound represented by formula (6)) (non-volatile content 61.0%) manufactured by DIC Corporation as the maleimide compound (D) (10 parts by mass as converted to non-volatile content), 15.3 parts by mass of OPE (registered trademark)-2St1200 (trade name, modified polyphenylene ether compound having a structure represented by formula (24)) (non-volatile content 65.0%) manufactured by Mitsubishi Gas Chemical Co., Ltd. as the resin or compound (E), and Admatechs Co., Ltd. as the filler (F). A varnish (resin composition) was prepared by adding 41.3 parts by mass (25 parts by mass as nonvolatile content) of a MEK (methyl ethyl ketone) solution (60.5% nonvolatile content) of 3SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 300 nm), 4.0 parts by mass of TAIC (registered trademark) (triallyl isocyanurate) from Mitsubishi Chemical Corporation as a crosslinking agent, and 0.50 parts by mass of CUREZOL (registered trademark) 2P4MZ (trade name, 2-phenyl-4-methylimidazole) from Shikoku Chemical Industry Co., Ltd. 42 parts by mass of MEK. The varnish (resin composition) had a mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) of 1.

[0494] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0495] [Example 18]

[0496] 40 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1889H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), and BASF Japan Ltd., 5.0 parts by mass of Irgacure (registered trademark) OXE03 (trade name, oxime esters), 16.3 parts by mass of NE-X-9470S (trade name, compound represented by formula (6)) (non-volatile content 61.0%) manufactured by DIC Corporation as the maleimide compound (D) (10 parts by mass as converted to non-volatile content), 15.3 parts by mass of OPE (registered trademark)-2St1200 (trade name, modified polyphenylene ether compound having a structure represented by formula (24)) (non-volatile content 65.0%) manufactured by Mitsubishi Gas Chemical Co., Ltd. as the resin or compound (E), and Admatechs Co., Ltd. as the filler (F). A varnish (resin composition) was prepared by adding 41.3 parts by mass (25 parts by mass as nonvolatile content) of a MEK (methyl ethyl ketone) solution (60.5% nonvolatile content) of 3SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 300 nm), 5.0 parts by mass of TAIC (registered trademark) (triallyl isocyanurate) from Mitsubishi Chemical Corporation as a crosslinking agent, and 0.50 parts by mass of CUREZOL (registered trademark) 2P4MZ (trade name, 2-phenyl-4-methylimidazole) from Shikoku Chemical Industry Co., Ltd., to 42 parts by mass of MEK. The varnish (resin composition) had a mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) of 1.

[0497] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0498] [Example 19]

[0499] 40 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1889H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), and BASF Japan Ltd. Irgacure (registered trademark) OXE01 (trade name, 1,2-octanedione-1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)]) 5.0 parts by mass, DIC Corporation NE-X-9470S (trade name, compound represented by formula (6)) (non-volatile content 61.0%) as the maleimide compound (D) 16.3 parts by mass (10 parts by mass as non-volatile content conversion) of DIC Corporation NE-X-9470S, Mitsubishi Gas Chemical Co., Ltd. OPE (registered trademark)-2St1200 (trade name, modified polyphenylene ether compound having a structure represented by formula (24)) (non-volatile content 65.0%) as the resin or compound (E), Admatechs Co., Ltd. as the filler (F) A varnish (resin composition) was prepared by adding 41.3 parts by mass (25 parts by mass as nonvolatile content) of a MEK (methyl ethyl ketone) solution (60.5% nonvolatile content) of 3SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 300 nm), 5.0 parts by mass of TAIC (registered trademark) (triallyl isocyanurate) from Mitsubishi Chemical Corporation as a crosslinking agent, and 0.50 parts by mass of CUREZOL (registered trademark) (2P4MZ) (trade name, 2-phenyl-4-methylimidazole) from Shikoku Chemical Industry Co., Ltd., to 42 parts by mass of MEK. The varnish (resin composition) had a mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) of 1.

[0500] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0501] [Example 20]

[0502] 40 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1889H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), 30.3 parts by mass (20 parts by mass as non-volatile matter) of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile matter 66.0%), and BASF Japan Ltd. Irgacure (registered trademark) OXE01 (trade name, 1,2-octanedione-1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)]) 2.5 parts by mass, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM Resins) as a photocuring initiator (C) 4.0 parts by mass of Omnirad (registered trademark) 819 (trade name) manufactured by BV Co., Ltd., 16.3 parts by mass of NE-X-9470S (trade name, compound represented by formula (6)) (non-volatile content 61.0%) manufactured by DIC Corporation as a maleimide compound (D) (10 parts by mass as converted to non-volatile content), 15.3 parts by mass of OPE (registered trademark)-2St1200 (trade name, modified polyphenylene ether compound having a structure represented by formula (24)) (non-volatile content 65.0%) manufactured by Mitsubishi Gas Chemical Co., Ltd. as a resin or compound (E), and 10 parts by mass of Admatechs Co., Ltd. as a filler (F). A varnish (resin composition) was prepared by adding 41.3 parts by mass (25 parts by mass as nonvolatile content) of a MEK (methyl ethyl ketone) solution (60.5% nonvolatile content) of 3SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 300 nm), 5.0 parts by mass of TAIC (registered trademark) (triallyl isocyanurate) from Mitsubishi Chemical Corporation as a crosslinking agent, and 0.50 parts by mass of CUREZOL (registered trademark) (2P4MZ) (trade name, 2-phenyl-4-methylimidazole) from Shikoku Chemical Industry Co., Ltd., to 42 parts by mass of MEK. The varnish (resin composition) had a mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) of 1.

[0503] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0504] [Comparative Example 1]

[0505] 60 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A) and BASF Japan Ltd., 5.0 parts by mass of Irgacure (registered trademark) OXE03 (trade name, oxime esters), 16.3 parts by mass of NE-X-9470S (trade name, compound represented by formula (6)) (non-volatile content 61.0%) manufactured by DIC Corporation as the maleimide compound (D) (10 parts by mass as converted to non-volatile content), 15.3 parts by mass of OPE (registered trademark)-2St1200 (trade name, modified polyphenylene ether compound having a structure represented by formula (24)) (non-volatile content 65.0%) manufactured by Mitsubishi Gas Chemical Co., Ltd. as the resin or compound (E), and Admatechs Co., Ltd. as the filler (F). To 41.3 parts by mass (25 parts by mass as nonvolatile matter) of a MEK (methyl ethyl ketone) solution (nonvolatile matter 60.5%) of 3SE-CM1 (trade name, slurry (fused) silica surface-treated with epoxy silane, average particle size: 300 nm) and 5.0 parts by mass of NIKALAC (registered trademark) MW-100LM (trade name, compound represented by formula (a)) manufactured by SANWA CHEMICAL CO., LTD. as a crosslinking agent were added 36 parts by mass of MEK to obtain a varnish (resin composition).

[0506] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0507] [Comparative Example 2]

[0508] 90.9 parts by mass (60 parts by mass in terms of non-volatile content) of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as epoxy (meth)acrylate (B) and 60 parts by mass of ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as a photocuring initiator (C) were mixed. Ltd., 5.0 parts by mass of Irgacure (registered trademark) OXE03 (trade name, oxime esters), 16.3 parts by mass of NE-X-9470S (trade name, compound represented by formula (6)) (non-volatile content 61.0%) manufactured by DIC Corporation as the maleimide compound (D) (10 parts by mass as converted to non-volatile content), 15.3 parts by mass of OPE (registered trademark)-2St1200 (trade name, modified polyphenylene ether compound having a structure represented by formula (24)) (non-volatile content 65.0%) manufactured by Mitsubishi Gas Chemical Co., Ltd. as the resin or compound (E), and Admatechs Co., Ltd. as the filler (F). To 41.3 parts by mass (25 parts by mass as nonvolatile matter) of a MEK (methyl ethyl ketone) solution (nonvolatile matter 60.5%) of 3SE-CM1 (trade name, slurry (fused) silica surface-treated with epoxy silane, average particle size: 300 nm) and 5.0 parts by mass of NIKALAC (registered trademark) MW-100LM (trade name, compound represented by formula (a)) manufactured by SANWA CHEMICAL CO., LTD. as a crosslinking agent were added 36 parts by mass of MEK to obtain a varnish (resin composition).

[0509] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0510] [Comparative Example 3]

[0511] 40 parts by mass of MIZ-001 (trade name, mass average molecular weight (Mw): 3000, a mixture containing a maleimide compound of formula (3), wherein a in formula (3) is 1 to 6 (integer)) manufactured by Nippon Kayaku Co., Ltd. as a bismaleimide compound (A), 30.3 parts by mass (20 parts by mass in terms of non-volatile content) of ZXR-1889H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) (non-volatile content 66.0%), and ZXR-1807H (trade name, compound represented by formula (36)) manufactured by Nippon Kayaku Co., Ltd. as an epoxy (meth)acrylate (B) were mixed. 66.0%)) 30.3 parts by mass (20 parts by mass as non-volatile components), NE-X-9470S (trade name, compound represented by formula (6)) manufactured by DIC Corporation as a maleimide compound (D) (non-volatile components 61.0%) 16.3 parts by mass (10 parts by mass as non-volatile components), OPE (registered trademark)-2St1200 (trade name, modified polyphenylene ether compound having a structure represented by formula (24)) (non-volatile components 65.0%) manufactured by Mitsubishi Gas Chemical Co., Ltd. as a resin or compound (E), Admatechs Co., Ltd. as a filler (F) A varnish (resin composition) was prepared by adding 41.3 parts by mass (25 parts by mass as nonvolatile content) of a MEK (methyl ethyl ketone) solution (nonvolatile content 60.5%) of 3SE-CM1 (trade name, epoxysilane-surface-treated slurry (fused) silica, average particle size: 300 nm) and 5.0 parts by mass of NIKALAC (registered trademark) MW-100LM (trade name, compound represented by formula (a)) manufactured by Sanwa Chemical Co., Ltd. as a crosslinking agent. 42 parts by mass of MEK was added to the mixture. The mass ratio ((A) / (B)) of the bismaleimide compound (A) to the epoxy (meth)acrylate (B) in the varnish (resin composition) was 1.

[0512] A resin sheet, a laminate for evaluation, and a laminated resin sheet for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.

[0513] 〔evaluate〕

[0514] The resin sheet, the evaluation laminate, and the evaluation laminated resin sheet were measured and evaluated by the following methods. The results are shown in Tables 2 to 4.

[0515] (1) Photocuring (200-600nm)

[0516] Using a Photo-DSC (DSC-2500 (trade name) manufactured by TA Instruments Japan Co., Ltd.) equipped with a light source capable of irradiating active energy rays having a wavelength of 200 to 600 nm (Omnicure (registered trademark) S2000 (trade name) manufactured by Uvix Co., Ltd.), the obtained resin sheet was irradiated with active energy rays having a wavelength of 200 to 600 nm at an illumination of 30 mW and an exposure time of 3.5 minutes to obtain a graph with time (seconds) on the horizontal axis and heat flow (mW) on the vertical axis.

[0517] In the obtained graph, the peak area when a line was drawn horizontally from the end point of the graph was defined as enthalpy (J / g). The curability was evaluated based on the following criteria.

[0518] "AA": enthalpy is 1 (J / g) or more.

[0519] "CC": enthalpy is less than 1 (J / g).

[0520] In addition, the enthalpy of 1 (J / g) or more means that curing of the resin proceeds sufficiently by exposure at a predetermined wavelength.

[0521] (2) Photocuring (365nm)

[0522] Using a Photo-DSC (DSC-2500 (trade name) manufactured by TA Instruments Japan Co., Ltd.) equipped with a light source capable of irradiating active energy rays having a wavelength of 200 to 600 nm (Omnicure (registered trademark) S2000 (trade name) manufactured by Uvix Co., Ltd.) and an optical filter (manufactured by Lumen Dynamics Group Inc., extraction wavelength 360 nm to 385 nm), the obtained resin sheet was irradiated with active energy rays having a wavelength of 365 nm at an illumination of 14 mW and an exposure time of 3.5 minutes. A graph was obtained with time (seconds) on the horizontal axis and heat flow (mW) on the vertical axis.

[0523] In the obtained graph, the peak area when a line was drawn horizontally from the end point of the graph was defined as enthalpy (J / g). The curability was evaluated based on the following criteria.

[0524] "AA": enthalpy is 1 (J / g) or more.

[0525] "CC": enthalpy is less than 1 (J / g).

[0526] In addition, the enthalpy of 1 (J / g) or more means that curing of the resin proceeds sufficiently by exposure at a predetermined wavelength.

[0527] (3) Alkali developability

[0528] Using a light source capable of irradiating active energy rays having a wavelength of 200 to 600 nm (MA-20 (trade name) manufactured by MIKASACO., LTD.) and an optical filter (manufactured by MIKASACO., LTD., extraction wavelength 346 nm to 384 nm), a chromium mask having a through-hole pattern (through-hole diameter: 30 μm) was used to illuminate the support (PET film) of the obtained evaluation laminate at an illumination intensity of 5 mW and an irradiation dose of 20 mJ / cm 2 The cured product was irradiated with active energy rays having a wavelength of 365 nm, and the support was peeled off from the cured product, and the peeled cured product was shaken in a 1% sodium carbonate aqueous solution at 33° C. for 180 seconds.

[0529] Then, the through-hole pattern was observed using an optical microscope, and the alkali developability was evaluated based on the following criteria.

[0530] "AA": After development, it can form The following through-holes.

[0531] "CC": After development, no The following through-holes.

[0532] (4) Relative dielectric constant (Dk) and dielectric loss tangent (Df)

[0533] A light source capable of irradiating active energy rays having a wavelength of 200 to 600 nm (MA-20 (trade name) manufactured by MIKASACO., LTD.) and an optical filter (manufactured by MIKASACO., LTD., extraction wavelength 346 nm to 384 nm) were used. The substrate (PET film) in the obtained evaluation laminated resin sheet was illuminated at an illumination intensity of 5 mW and an irradiation dose of 50 mJ / cm 2 The cured product was irradiated with active energy rays having a wavelength of 365 nm, and then the support was peeled off from the cured product to obtain a sample for evaluation.

[0534] The relative dielectric constant (Dk) and dielectric loss tangent (Df) of the evaluation samples were measured at 10 GHz using a network analyzer (Agilent (registered trademark) 8722ES (trade name), manufactured by Agilent Technologies Co., Ltd.) The relative dielectric constant (Dk) and dielectric loss tangent (Df) were measured under a temperature of 23°C ± 1°C and a humidity of 50% RH ± 5% RH.

[0535] The relative dielectric constant (Dk) and dielectric loss tangent (Df) were evaluated according to the following criteria.

[0536] Relative dielectric constant (Dk)

[0537] "AA": relative dielectric constant is 2.6 or less.

[0538] "BB": relative dielectric constant exceeds 2.6 and is 2.7 or less.

[0539] "CC": Relative dielectric constant exceeds 2.7.

[0540] When the relative dielectric constant is 2.7 or less, a cured product (insulating layer) having a low relative dielectric constant tends to be obtained.

[0541] Dielectric loss tangent (Df)

[0542] "AA": Dielectric loss tangent is 0.007 or less.

[0543] “BB”: The dielectric loss tangent exceeds 0.007 and is 0.008 or less.

[0544] "CC": Dielectric loss tangent exceeds 0.008.

[0545] In addition, when the dielectric loss tangent is 0.008 or less, there is a tendency that a cured product (insulating layer) having a low dielectric loss tangent is obtained.

[0546] [Table 2]

[0547]

[0548] [Table 3]

[0549]

[0550] [Table 4]

[0551]

[0552] As shown in Tables 2 to 4, according to the present embodiment, when various active energy rays, especially active energy rays comprising a wavelength of 365nm (i-rays) are used for exposure, it is possible to photosensitively and photocuring. Furthermore, according to the present embodiment, a cured product with excellent alkali developability can be obtained. Furthermore, according to the present embodiment, a cured product with low relative dielectric constant and dielectric loss tangent can be obtained. Therefore, by using the resin composition of the present embodiment, a high-density printed circuit board and a semiconductor device with a high-precision insulating layer and a high-precision resist pattern having a low relative dielectric constant and dielectric loss tangent can be obtained.

[0553] This application claims priority based on Japanese Patent Application No. 2023-012019 filed with the Japan Patent Office on January 30, 2023, the contents of which are incorporated herein by reference.

[0554] Industrial applicability

[0555] The resin combination of present embodiment, when making multilayer printed circuit board (PCB), in exposure process, has excellent photocurability for various active energy rays, particularly wavelength 365nm (i rays), and in developing process, can give excellent alkali developability.In addition, by using the resin combination of present embodiment, can obtain the low cured product of relative dielectric constant and dielectric loss tangent.Therefore, industrially useful, for example, can be used for photosensitive film, with the photosensitive film of support, prepreg, resin sheet, circuit substrate (laminate purposes, multilayer printed circuit board (PCB) purposes etc.), solder resist, bottom filling material, chip bonding material, semiconductor sealing material, hole-filling resin and parts embedding resin etc.Wherein, resin combination can obtain the lower cured product of relative dielectric constant and dielectric loss tangent, and photocurability and alkali developability are excellent, therefore can be suitable for the insulating layer of multilayer printed circuit board (PCB) with or solder resist with.

Claims

1. A resin composition comprising: A bismaleimide compound A comprising a structural unit represented by the following formula (1) and maleimide groups located at both ends of the molecular chain; Dicyclopentadienol-type epoxy (meth)acrylate B containing one or more carboxyl groups; and Photocuring initiator C, In formula (1), R1 represents a straight-chain or branched alkylene group having 1 to 16 carbon atoms, or a straight-chain or branched alkenylene group having 2 to 16 carbon atoms; R2 represents a straight-chain or branched alkylene group having 1 to 16 carbon atoms, or a straight-chain or branched alkenylene group having 2 to 16 carbon atoms; R3 each independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 16 carbon atoms, or a straight-chain or branched alkenyl group having 2 to 16 carbon atoms; and n1 each independently represents an integer from 1 to 10.

2. The resin composition according to claim 1, wherein The content of the bismaleimide compound A is 5.0 to 90 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. The content of the epoxy (meth)acrylate B is 5.0 to 90 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. The content of the photocuring initiator C is 0.1 to 50 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

3. The resin composition according to claim 1, further comprising a maleimide compound D other than the bismaleimide compound A, The content of the maleimide compound D is 1.0 to 25 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

4. The resin composition according to claim 1, further comprising one or more resins or compounds E selected from the group consisting of modified polyphenylene ether compounds, cyanate compounds, phenolic resins, oxetane resins, benzoxazine compounds, and epoxy resins, The total content of the resin or compound E is 1.0 to 25 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

5. The resin composition according to claim 1, further comprising a filler F, The content of the filler F is 5.0 to 100 parts by mass based on 100 parts by mass of the total resin solid content in the resin composition.

6. A resin sheet comprising a support and a resin layer disposed on one or both surfaces of the support, The resin layer comprises the resin composition according to claim 1 .

7. The resin sheet according to claim 6, wherein The thickness of the resin layer is 1 to 50 μm.

8. A multilayer printed circuit board comprising an insulating layer and a conductor layer formed on one or both sides of the insulating layer, The insulating layer comprises the resin composition according to claim 1 . 9 . A semiconductor device comprising the resin composition according to claim 1 .

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