Resin composition, hardened product, resin sheet, prepreg, laminate, wiring board, material, adhesive, and semiconductor device

Abstract

This invention provides a resin composition, a cured product, a resin sheet, a prepreg, a laminate, a wiring board, a material, an adhesive, and a semiconductor device. The resin composition of this invention comprises a bismaleimide compound (A), a resin or compound (B), and a photocuring initiator (C), wherein the bismaleimide compound (A) comprises a structural unit represented by formula (1) and contains maleimide groups at both ends of the molecular chain, and the resin or compound (B) is at least one selected from the group consisting of maleimide compounds other than bismaleimide compound (A), cyanate ester compounds, benzoxazine compounds, epoxy resins, carbodiimide compounds, and compounds having vinyl unsaturated groups.

Description

Technical Field

[0001] This invention relates to a resin composition, a cured material, a resin sheet, a prepreg, a metal foil-coated laminate, a multilayer printed circuit board, a sealing material, a fiber-reinforced composite material, an adhesive, and a semiconductor device. Background Technology

[0002] In recent years, especially with advancements in cutting-edge materials, there has been a growing demand for higher-performance materials. For example, materials suitable for high-capacity communication devices, antenna modules for smartphones, and cable systems for notebook computers; materials suitable for millimeter-wave radar; and related equipment for automatic braking systems in automobiles require increasingly superior dielectric properties, heat resistance, low stress, water resistance, and adhesion of electronic circuit boards.

[0003] Due to the miniaturization and high density of multilayer printed circuit boards (PCBs), research on thinning the laminates used in PCBs has become prevalent. With this thinning trend, the insulation layer also requires thinner profiles, necessitating resin sheets that do not contain glass cloth. The resin compositions used as insulation layers are primarily thermosetting resins, and the openings used to create conductivity between insulation layers are generally achieved through laser processing.

[0004] On the other hand, laser processing of openings has the problem that the processing time increases with the number of holes in high-density substrates. Therefore, in recent years, there has been a search for a resin sheet that can perform batch opening processing in the exposure and development processes by using a resin composition in which the exposed portion hardens due to irradiation by light or the like (exposure process) and the unexposed portion can be removed (development process).

[0005] As an exposure method, a mercury lamp is used as the light source, and exposure is performed through a photomask. The aim is to find a material that can be appropriately exposed using the mercury lamp light source. The mercury lamp exposure method uses a mixed g-ray (gamma rays wavelength 436 nm, h-ray wavelength 405 nm, i-ray wavelength 365 nm) to allow for the selection of a general photocuring initiator. In recent years, the direct-drawing exposure method has also been promoted. This method involves drawing directly on a photosensitive resin composition layer based on digital pattern data without the need for a photomask. Compared to exposure methods with a photomask, the direct-drawing exposure method offers better alignment accuracy and can obtain highly detailed patterns. Therefore, its adoption is particularly encouraged in substrates requiring high-density wiring. The light source uses monochromatic light such as lasers. In devices using Digital Micromirror Devices (DMDs) capable of forming highly detailed resist patterns, a light source with a wavelength of 405 nm (h-rays) is used.

[0006] In the photosensitive resin composition used for the laminate or resin sheet, compounds with vinyl unsaturated groups, such as (meth)acrylate, are used in order to enable rapid curing during the exposure process.

[0007] For example, Patent Document 1 describes a photosensitive thermosetting resin composition comprising a carboxyl-modified epoxy (meth)acrylate resin, a biphenyl-type epoxy resin, a photocuring initiator, and a diluent, wherein the carboxyl-modified epoxy (meth)acrylate resin is obtained by reacting a bisphenol-type epoxy resin with (meth)acrylic acid followed by a reaction with an anhydride.

[0008] In addition, Patent Document 2 describes a resin composition comprising: a photocurable adhesive polymer, a photopolymerizable compound having ethylene unsaturated bonds, a photopolymerization (curing) initiator, a sensitizer, and a dielyl thiamide compound and a bismaleimide compound as thermocuring agents.

[0009] Patent Document 3 describes a resin composition comprising a bismaleimide compound (curing resin) and a photoradical polymerization initiator (curing agent) as a photosensitive resin composition for laminates or resin sheets.

[0010] Existing technical documents

[0011] Patent documents

[0012] Patent Document 1: Japanese Patent Application Publication No. 2005-62450

[0013] Patent Document 2: Japanese Patent Application Publication No. 2010-204298

[0014] Patent Document 3: WO2018 / 56466A1 Summary of the Invention

[0015] The problem that the invention aims to solve

[0016] However, cured products using existing (meth)acrylate resins cannot achieve sufficient physical properties and have limitations in forming excellent protective films and interlayer insulation layers.

[0017] Among the cured products obtained from the resin composition described in Patent Document 1, there are records of products that have excellent flexibility, folding resistance, and heat resistance as solder resists. However, no specific value is shown for the heat resistance, and there is a problem of deterioration in heat resistance and thermal stability when used as an interlayer insulation layer.

[0018] Patent document 2 describes the use of a bismaleimide compound, but it is described as a thermosetting agent; the photopolymerizable compound used is (meth)acrylate. Therefore, when used as an interlayer insulation layer, there are problems with deterioration in heat resistance and thermal stability.

[0019] In Patent Document 3, a bismaleimide compound is used as the curing resin. However, maleimide compounds typically have poor light transmittance. Therefore, if a maleimide compound is included, light will not sufficiently reach the photocuring initiator, making it difficult for the photocuring initiator to generate free radicals, resulting in very low reactivity. Thus, in Patent Document 3, the maleimide compound is cured by additional heating before development. However, due to the accompanying heating, a highly detailed resist pattern cannot be obtained. Furthermore, Patent Document 3 does not describe its use as a light source capable of irradiating active energy lines containing wavelengths of 405 nm (h-rays).

[0020] Therefore, the present invention has been made in view of the aforementioned problems, and provides a resin composition, a resin sheet using the resin composition, a multilayer printed circuit board, and a semiconductor device, wherein the resin composition, when used in a multilayer printed circuit board, has excellent photocurability and can produce a cured product with excellent balanced heat resistance, thermal stability, and insulation reliability.

[0021] Technical means to solve the problem

[0022] The inventors discovered that the aforementioned problem can be solved by using a resin composition comprising a specific bismaleimide compound (A), a specific resin or compound (B), and a photocuring initiator (C), thereby completing the present invention.

[0023] That is, the present invention includes the following.

[0024] [1] A resin composition comprising:

[0025] Bismaleimide compound (A) comprises the structural unit represented by the following formula (1), and contains maleimide groups at both ends of the molecular chain;

[0026] The resin or compound (B) is at least one selected from the group consisting of maleimide compounds other than the bismaleimide compound (A), cyanate ester compounds, benzoxazine compounds, epoxy resins, carbodiimide compounds, and compounds having an vinyl unsaturated group; and

[0027] Photocuring initiator (C).

[0028] [Chemistry 1]

[0029]

[0030] (In formula (1), R1 represents a straight-chain or branched alkylene group having 1 to 16 carbon atoms, or a straight-chain or branched alkenyl 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 alkenyl 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. R4 each independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms. n1 each independently represents an integer from 1 to 4. n2 each independently represents an integer from 1 to 4.)

[0031] [2] According to the resin composition of [1], wherein the photocuring initiator (C) comprises a compound represented by the following formula (2).

[0032] [Chemistry 2]

[0033]

[0034] (In formula (2), R4 independently represents the substituent or phenyl group represented by formula (3) below.)

[0035] [Chemistry 3]

[0036]

[0037] (In formula (3), -* represents a bond, and R5 independently represents a hydrogen atom or a methyl group.)

[0038] [3] The resin composition according to any one of [1] or [2], wherein, when the total amount of the bismaleimide compound (A), the resin or compound (B) and the photocuring initiator (C) is set to 100 parts by mass, the content of the bismaleimide resin represented by the general formula (1) is 5 parts by mass to 99.4 parts by mass.

[0039] [4] The resin composition according to any one of [1] to [3] further comprises a filler.

[0040] [5] A hardened material comprising a resin composition according to any one of [1] to [3].

[0041] [6] A resin sheet comprising: a support; and a resin layer disposed on one or both sides of the support, the resin layer comprising a resin composition according to any one of [1] to [3].

[0042] [7] The resin sheet according to [6], wherein the thickness of the resin layer is 1 μm to 50 μm.

[0043] [8] A prepreg comprising: a substrate; and a resin composition according to any one of [1] to [4], impregnated or coated on the substrate.

[0044] [9] A metal foil laminate comprising: a layer comprising at least one selected from the group consisting of a resin sheet according to [7] and a prepreg according to [8]; and a metal foil disposed on one or both sides of the layer, the layer comprising a cured form of the resin composition.

[0045]

[10] A multilayer printed circuit board, comprising: an insulating layer; and a conductor layer formed on one or both sides of the insulating layer.

[0046] The insulating layer comprises a resin composition according to any one of [1] to [4].

[0047]

[11] A sealing material comprising a resin composition according to any one of [1] to [4].

[0048]

[12] A fiber-reinforced composite material comprising a resin composition according to any one of [1] to [4] and reinforcing fibers.

[0049]

[13] An adhesive comprising a resin composition according to any one of [1] to [4].

[0050]

[14] A semiconductor device having a resin composition according to any one of [1] to [4].

[0051] The effects of the invention

[0052] According to the present invention, a resin composition, a resin sheet using the resin composition, a multilayer printed circuit board, and a semiconductor device may be provided, wherein the resin composition, when used in a multilayer printed circuit board, has excellent photocurability and can produce a cured product with excellent balanced heat resistance, thermal stability, and insulation reliability. Detailed Implementation

[0053] Hereinafter, a detailed description will be given of a method for carrying out the present invention (hereinafter referred to as "this embodiment"). This embodiment is merely an example for illustrating the present invention and is not intended to limit the invention to the following. The present invention can be implemented with appropriate modifications within the scope of its gist.

[0054] Furthermore, in this specification, "(meth)acryloyloxy" refers to both "acryloyloxy" and its corresponding "methacryloyloxy", "(meth)acrylate" refers to both "acrylate" and its corresponding "methacrylate", and "(meth)acrylic acid" refers to both "acrylic acid" and its corresponding "methacrylic acid".

[0055] [Resin Composition]

[0056] The resin composition of this embodiment comprises: a specific bismaleimide compound (A) (also referred to as "component (A)"); at least one resin or compound (B) selected from the group consisting of maleimide compounds other than bismaleimide compound (A), cyanate ester compounds, benzoxazine compounds, epoxy resins, carbodiimide compounds, and compounds having vinyl unsaturated groups (also referred to as "component (B)" or "resin or compound (B)"); and a photocuring initiator (C) (also referred to as "component (C)"). Each component will be described below.

[0057] [Bismaleimide compound (A)]

[0058] The resin composition contains a bismaleimide compound (A) (also referred to as component (A)). The bismaleimide compound (A) contains the structural unit represented by formula (1) and contains maleimide groups at both ends of the molecular chain.

[0059] [Chemistry 4]

[0060]

[0061] In formula (1), R1 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenyl 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 alkenyl group having 2 to 16 carbon atoms. R3 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 independently represents an integer from 1 to 4. n2 independently represents an integer from 1 to 4.

[0062] Typically, maleimide compounds have poor light transmittance. Therefore, if a maleimide compound is included, light will not sufficiently reach the photocuring initiator dispersed in the resin composition, making it difficult for the photocuring initiator to generate free radicals. Consequently, photoradical reactions of maleimide compounds are generally difficult to occur, and even when free radical polymerization or dimerization of maleimide monomers is performed, the reactivity is very low. However, bismaleimide compound (A) contains the structural unit represented by formula (1), thus exhibiting excellent light transmittance. Therefore, light sufficiently reaches the photocuring initiator, thereby efficiently inducing the photoradical reaction of maleimide. Bismaleimide compound (A) can be used with the resin or compound (B) and photocuring initiator (C) described later for photocuring using various active energy lines.

[0063] In this embodiment, when a chloroform solution containing 1% by mass of bismaleimide compound (A) is prepared, and the transmittance of the chloroform solution containing 1% by mass of bismaleimide compound (A) is measured using an active energy line containing a wavelength of 365 nm (i-rays), the transmittance is 5% or more, exhibiting very excellent light transmittance. Furthermore, when the transmittance of the chloroform solution containing 1% by mass of bismaleimide compound (A) is measured using an active energy line (light) containing a wavelength of 405 nm (h-rays), the transmittance is 5% or more, exhibiting very excellent light transmittance. Therefore, for example, when manufacturing a printed wiring board with high-density and high-fineness wiring formation (pattern) using the direct drawing exposure method, even when using an active energy line containing a wavelength of 405 nm (h-rays), the photoradical reaction of maleimide is efficiently induced. Regarding exhibiting even better light transmittance, the transmittance at a wavelength of 365 nm (i-rays) is preferably 8% or more, more preferably 10% or more. In terms of manufacturing printed wiring boards with higher density and finer wiring patterns, the transmittance at a wavelength of 405 nm (h-rays) is preferably 8% or more, more preferably 10% or more. The upper limit of the transmittance at a wavelength of 365 nm (i-rays) and the transmittance at a wavelength of 405 nm (h-rays) is, for example, 99.9% or less.

[0064] Generally, photocuring initiators tend to have reduced absorbance when using long-wavelength light. For example, when using an active energy line containing a wavelength of 405 nm (h-rays), this wavelength is relatively long and is therefore not absorbed by conventional photocuring initiators. Without a photocuring initiator that can appropriately absorb this light to generate free radicals, polymerization will not proceed. Therefore, as the photocuring initiator (C) described later, it is preferable to use a photocuring initiator that exhibits very excellent absorbance, with an absorbance of 0.1 or more relative to light at a wavelength of 405 nm (h-rays), when the absorbance of a chloroform solution containing 0.01% by mass of the photocuring initiator (C) is measured.

[0065] Because the bismaleimide compound (A) has excellent light transmittance as described above, for example, when using an active energy line containing a wavelength of 365 nm or a wavelength of 405 nm, light sufficiently reaches the photocuring initiator, and a free radical reaction using free radicals generated by the photocuring initiator occurs. Photocuring can also occur in compositions containing a large amount of bismaleimide compound (A). Therefore, the resin composition of this embodiment exhibits excellent photocurability.

[0066] On the other hand, even after photocuring, the bismaleimide compound (A) retains a rigid imide ring, thus exhibiting high heat resistance and thermal stability. However, when the cured product obtained by photocuring the bismaleimide compound is further cured by heating in a post-baking process after the exposure or development process, wrinkles will occur. Therefore, the cured product obtained by homopolymerizing the bismaleimide compound (A) is not suitable for use in multilayer printed circuit boards. However, by blending the bismaleimide compound (A) with the resin or compound (B) described later and the photocuring initiator (C), excellent photocurability and insulation reliability are achieved, along with higher heat resistance and thermal stability. Therefore, the cured product obtained from the resin composition of this embodiment exhibits excellent heat resistance, thermal stability, and insulation reliability. According to this embodiment, protective films and insulating layers in multilayer printed circuit boards and semiconductor devices can be suitably formed.

[0067] In terms of obtaining a suitable viscosity and suppressing the increase of varnish viscosity, the mass-average molecular weight of the maleimide compound (A) is preferably 100 to 6000, more preferably 300 to 5500. Furthermore, "mass-average molecular weight" refers to the mass-average molecular weight converted from polystyrene standard by gel permeation chromatography (GPC).

[0068] The structure of the bismaleimide compound (A) is then described.

[0069] In 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 alkenyl group having 2 to 16 carbon atoms. As R1, a linear or branched alkylene group is preferred in terms of obtaining suitable viscosity and controlling the increase in varnish viscosity, and a linear alkylene group is more preferred.

[0070] In terms of obtaining a more suitable viscosity and better controlling the increase in varnish viscosity, the number of carbon atoms in the alkylene group is preferably 2 to 14, and more preferably 4 to 12.

[0071] Examples of linear or branched alkylene compounds include: methylene, ethylene, propylene, 2,2-dimethylpropylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, undecylene, tridecylene, tetradecylene, decadecylene, hexadecylene, neopentylene, dimethylbutylene, methylhexylene, ethylhexylene, dimethylhexylene, trimethylhexylene, methylheptylene, dimethylheptylene, trimethylheptylene, tetramethylheptylene, ethylheptylene, methyloctylene, methylnonylene, methyldecylene, methyl dodecylene, methyl undecylene, methyl tridecylene, methyl tetradecylene, and methyl decadecylene.

[0072] In terms of obtaining a more suitable viscosity and being able to better control the increase in varnish viscosity, the number of carbon atoms in the alkenyl group is preferably 2 to 14, and more preferably 4 to 12.

[0073] Examples of straight-chain or branched alkenyl groups include: vinylene, 1-methylvinylene, allenepropylene, propenylene, isopropenylene, 1-butenylene, 2-butenylene, 1-pentenylene, 2-pentenylene, isopentenylene, cyclopentenylene, cyclohexenylene, and dicyclopentadienylene.

[0074] In formula (1), R2 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. As R2, a linear or branched alkylene group is preferred in terms of obtaining suitable viscosity and controlling the increase in varnish viscosity, and a linear alkylene group is more preferred.

[0075] In terms of obtaining a more suitable viscosity and better controlling the increase in varnish viscosity, the number of carbon atoms in the alkylene group is preferably 2 to 14, and more preferably 4 to 12.

[0076] For linear or branched alkylene groups, see R1.

[0077] In terms of obtaining a more suitable viscosity and better controlling the increase in varnish viscosity, the number of carbon atoms in the alkenyl group is preferably 2 to 14, and more preferably 4 to 12.

[0078] For linear or branched alkenyl groups, refer to R1.

[0079] In the formula (1), R1 and R2 may be the same or different, but they are preferably the same in order to make it easier to synthesize the bismaleimide compound (A).

[0080] In formula (1), each of R3 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. For obtaining suitable viscosity and controlling the increase in varnish viscosity, R3 is preferably a hydrogen atom or a straight-chain or branched alkyl group having 1 to 16 carbon atoms, more preferably one to four of the R3 groups (R3) are straight-chain or branched alkyl groups having 1 to 16 carbon atoms, and the remaining groups (R3) are hydrogen atoms, and even more preferably one to three of the R3 groups (R3) are straight-chain or branched alkyl groups having 1 to 16 carbon atoms, and the remaining groups (R3) are hydrogen atoms.

[0081] In terms of obtaining a more suitable viscosity and better controlling the increase in varnish viscosity, the number of carbon atoms in the alkyl group is preferably 2 to 14, and more preferably 4 to 12.

[0082] Examples of linear or branched alkyl groups include: methyl, ethyl, n-propyl, isopropyl, 1-ethylpropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-hexyl, 3-hexyl, n-heptyl, n-octyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylpentan-3-yl, and n-nonyl.

[0083] In terms of obtaining a more suitable viscosity and better controlling the increase in varnish viscosity, the number of carbon atoms in the alkenyl group is preferably 2 to 14, and more preferably 4 to 12.

[0084] Examples of alkenyl groups that are linear or branched include vinyl, allyl, 4-pentenyl, isopropenyl, isopentenyl, 2-heptenyl, 2-octenyl, and 2-nonenyl.

[0085] In formula (1), R4 independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms. In terms of dielectric properties, R4 is preferably a hydrogen atom or a straight-chain or branched alkyl group having 1 to 6 carbon atoms.

[0086] The number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 to 3, in order to obtain a more suitable viscosity.

[0087] Examples of linear or branched alkyl groups include: methyl, ethyl, n-propyl, and isopropyl.

[0088] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0089] Regarding the number of carbon atoms in the alkoxy group, 1 to 6 is preferred, and more preferably 1 to 3, in order to obtain a more suitable viscosity.

[0090] Examples of linear or branched alkoxy groups include: methyl, ethyl, n-propyl, and isopropyl.

[0091] In equation (1), n1 independently represents an integer from 1 to 4. n2 independently represents an integer from 1 to 4.

[0092] The bismaleimide compound (A) has maleimide groups at both ends of its molecular chain. In this embodiment, "both ends" refers to the two ends of the molecular chain of the bismaleimide compound (A). For example, in the case where the structural unit represented by formula (1) is located at the end of the molecular chain of the bismaleimide compound (A), it means that the maleimide group is present at the end of the molecular chain of R1, or at the end of the molecular chain at the N atom of the maleimide ring, or at both ends. The bismaleimide compound (A) may also have maleimide groups other than at the two ends of the molecular chain.

[0093] In this embodiment, the maleimide group is represented by formula (4), and the N atom is bonded to the molecular chain of formula (1). In addition, the maleimide groups bonded to formula (1) may be all the same or different, but the maleimide groups at both ends of the molecular chain are preferably the same.

[0094] [Chemistry 5]

[0095]

[0096] In formula (4), R6 independently represents either a hydrogen atom or a straight-chain or branched alkyl group having 1 to 4 carbon atoms. For the purpose of suitable photocuring, R6 is preferably both hydrogen atoms.

[0097] The number of carbon atoms in the alkyl group is preferably 1 to 3, more preferably 1 to 2, in terms of suitability for photocuring.

[0098] For linear or branched alkyl groups, see R3.

[0099] As the bismaleimide compound (A), for example, bismaleimide compounds represented by formula (5) can be listed. These can also be used alone or in appropriate combinations of two or more.

[0100] [Chemistry 6]

[0101]

[0102] In equation (5), a represents an integer from 1 to 10. In terms of obtaining a more suitable viscosity and being able to better control the increase in varnish viscosity, a is preferably an integer from 1 to 6.

[0103] In the resin composition of this embodiment, regarding the content of the bismaleimide compound (A), from the viewpoint that a cured product with the bismaleimide compound as the main component can be obtained, and that the photocurability, heat resistance and dielectric properties can be improved in a balanced manner, the content of the bismaleimide compound (A), the resin or compound (B) described later and the photocuring initiator (C) described later is preferably 5 parts by mass to 99.4 parts by mass, more preferably 8 parts by mass to 98 parts by mass, and even more preferably 13 parts by mass to 93 parts by mass, relative to a total of 100 parts by mass of the bismaleimide compound (A), the resin or compound (B) described later and the photocuring initiator (C) described later.

[0104] The bismaleimide compound (A) can also be used alone or in appropriate combinations of two or more.

[0105] (Method for manufacturing bismaleimide compound (A))

[0106] The bismaleimide compound (A) can be manufactured by known methods. For example, 4-(2,5-dioxatetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, a monomer comprising a diamine including a dimer diamine, and a maleimide compound such as maleimide anhydride are subjected to an addition polymerization reaction at a temperature typically around 80°C to 250°C, preferably around 100°C to 200°C, for typically 0.5 hours to 50 hours, preferably 1 hour to 20 hours, to obtain an addition polymer. Then, the addition polymer is subjected to an imidization reaction, i.e., a dehydration and ring-closing reaction, typically around 0.1 hours to 2 hours, preferably around 0.1 hours to 0.5 hours, at a temperature typically around 60°C to 120°C, preferably around 80°C to 100°C, thereby obtaining the bismaleimide compound (A).

[0107] Dimeric diamines are obtained, for example, through the reductive amination reaction of dimer acids. The amination reaction can be carried out by known methods, such as reduction using ammonia and a catalyst (e.g., the method described in Japanese Patent Application Publication No. 9-12712). A dimer acid refers to a dicarboxylic acid obtained by dimerizing unsaturated fatty acids through intermolecular polymerization reactions. While depending on the synthesis and purification conditions, it typically contains small amounts of monomeric acids or trimer acids in addition to dimer acids. After the reaction, double bonds remain within the obtained molecule; however, in this embodiment, saturated dicarboxylic acids are also included in the dimer acid, where double bonds present in the molecule are reduced through hydrogenation. Dimer acids are obtained, for example, by polymerizing unsaturated fatty acids using Lewis acids and Bronsted acids as catalysts. Dimer acids can be manufactured by known methods (e.g., the method described in Japanese Patent Application Publication No. 9-12712). Examples of unsaturated fatty acids include: crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, transoleic acid, vaccenic acid, gadooleic acid, eicosenoic acid, erucic acid, nervonic acid, linolenic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, bosseopentaenoic acid, osbond acid, and clupatonic acid. Unsaturated fatty acids typically have 4 to 24 carbon atoms, preferably 14 to 20.

[0108] In the manufacture of the bismaleimide compound (A), the monomer containing the diamine is preferably dissolved or dispersed in an organic solvent in an inert environment such as argon or nitrogen beforehand to prepare a monomer solution containing the diamine. Furthermore, 4-(2,5-dioxatetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride 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.

[0109] By adjusting the molar number of 4-(2,5-dioxatetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride and the total molar number of 4-(2,5-dioxatetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, as well as the total molar number of 4-(2,5-dioxatetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, and ...

[0110] Various known solvents can be used for addition polymerization and imidization reactions. Examples of solvents 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 with 1 to 10 carbon atoms such as methanol, ethanol, and propanol. Phenolic compounds containing aromatic groups, such as phenol and cresol; alcohols containing aromatic groups, such as benzyl alcohol; diols, such as ethylene glycol and propylene glycol, or diol ethers of these diols with methanol, ethanol, butanol, hexanol, octanol, benzyl alcohol, phenol, and cresol, or esters of these monoethers; ethers, such as dioxane and tetrahydrofuran; cyclic carbonates, such as ethylene carbonate and propylene carbonate; aliphatic hydrocarbons and aromatic hydrocarbons, such as toluene and xylene; and aprotic polar solvents, such as dimethyl sulfoxide. These solvents may be used alone or in combination of two or more, as needed.

[0111] Furthermore, a catalyst is preferably used in the imidization reaction. Examples of catalysts include tertiary amines and dehydration catalysts. Heterocyclic tertiary amines are preferred, such as pyridine, picolin, quinoline, and isoquinoline. Examples of dehydration catalysts include acetic anhydride, propionic anhydride, butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride.

[0112] The amount of catalyst added is preferably such that the imidizing agent is about 0.5 to 5.0 molar equivalents relative to the amide group, and the dehydration catalyst is about 0.5 to 10.0 molar equivalents relative to the amide group.

[0113] After the imidization reaction is complete, the solution can be used as a solution of bismaleimide compound (A), or a poor solvent can be added to the reaction solvent to prepare bismaleimide compound (A) into a solid form. Examples of poor solvents include: water, methanol, ethanol, 2-propanol, ethylene glycol, triethylene glycol, 2-butanol, 2-pentanol, 2-hexanol, cyclopentanol, cyclohexanol, phenol, tert-butanol, etc.

[0114] [Resin or compound (B)]

[0115] The resin composition of this embodiment includes at least one resin or compound (B) (also referred to as component (B)) selected from the group consisting of maleimide compounds other than bismaleimide compound (A), cyanate ester compounds, benzoxazine compounds, epoxy resins, carbodiimide compounds, and compounds having vinyl unsaturated groups. These resins or compounds (B) can be used alone or in appropriate combinations of two or more, depending on the properties and intended use of the cured product.

[0116] In this embodiment, when the resin or compound (B) is used in conjunction with the bismaleimide compound (A) and the photocuring initiator described later, excellent photocurability, heat resistance, and thermal stability are achieved. The reason for this is not definitively determined, but the inventors infer that it is because the photocurability and insulating reliability of the bismaleimide compound (A) can coexist with the heat resistance and thermal stability of the resin or compound (B). Furthermore, the obtained cured product can be endowed with various physical properties possessed by both the bismaleimide compound (A) and the resin or compound (B). The bismaleimide compound (A) has excellent light transmittance; therefore, even when using the resin or compound (B), light sufficiently reaches the photocuring initiator, thereby efficiently inducing the photoradical reaction of maleimide, allowing for photocuring using various active energy lines. Therefore, for example, even when using an active energy line containing a wavelength of 365 nm or an active energy line containing a wavelength of 405 nm, the light reaches the photocuring initiator sufficiently, and a free radical reaction using free radicals generated by the photocuring initiator is carried out, and photocuring can be performed in a composition incorporating a resin or compound (B).

[0117] Various active energy lines can be used to photo-cure resins or compounds (B) together with bismaleimide compounds (A) and photocuring initiators (C) to obtain cured products.

[0118] In this embodiment, when preparing an N-methylpyrrolidone solution containing 1% by mass of resin or compound (B) and measuring the transmittance of an N-methylpyrrolidone solution containing one or more carboxyl groups at 1% by mass using an active energy line containing a wavelength of 365 nm (i-rays), the transmittance is preferably 5% or more. The resin or compound (B) exhibits very excellent light transmittance. Furthermore, when measuring the transmittance of an N-methylpyrrolidone solution containing 1% by mass of resin or compound (B) using an active energy line containing a wavelength of 405 nm (h-rays), the transmittance is preferably 5% or more, which also exhibits very excellent light transmittance. When using the resin or compound (B), for example, when manufacturing a printed wiring board with high-density and high-fine wiring formation (pattern) using a direct-draw exposure method, even when using an active energy line containing a wavelength of 405 nm (h-rays), a photoradical reaction of maleimide is efficiently induced. Furthermore, for obtaining a resin composition with superior photocurability, the transmittance at a wavelength of 365 nm (i-rays) is more preferably 8% or more, and even more preferably 10% or more. For obtaining a resin composition with superior photocurability, the transmittance at a wavelength of 405 nm (h-rays) is more preferably 8% or more, and even more preferably 10% or more. Furthermore, the upper limit for both the transmittance at a wavelength of 365 nm (i-rays) and the transmittance at a wavelength of 405 nm (h-rays) is, for example, 99.9% or less.

[0119] From the viewpoint of suppressing the increase in varnish viscosity, the molecular weight of the resin or compound (B) is preferably between 100 and 5,000. Furthermore, while there are no particular limitations as long as the effects of the present invention are achieved, from the viewpoint of suppressing the increase in varnish viscosity, the mass-average molecular weight of the resin or compound (B) is preferably between 100 and 50,000. Moreover, in this embodiment, the term "mass-average molecular weight" refers to the mass-average molecular weight converted from polystyrene standards by gel permeation chromatography (GPC).

[0120] From the viewpoint that the total content of the resin or compound (B) in the resin composition can obtain a cured product with bismaleimide compound as the main component and improve photocurability, the total content of the resin or compound (B) and the photocuring initiator (C) described later is preferably 0.5 parts to 85 parts by mass, more preferably 1 part to 84 parts by mass, and even more preferably 5 parts to 80 parts by mass, relative to 100 parts by mass of the total content of bismaleimide compound (A), resin or compound (B) and photocuring initiator (C) described later.

[0121] (maleimide compounds other than bismaleimide compound (A))

[0122] In the resin composition, a maleimide compound (B1) other than bismaleimide compound (A) may be used (also referred to as component (B1)). The maleimide compound (B1) is described below.

[0123] The term "maleimide compound (B-1)" is not particularly limited to any compound other than maleimide compound (A) that has one or more maleimide groups in its molecule. Specific examples include: N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-anilinephenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, 6-maleimide hexanoic acid, 4-maleimide butyric acid, bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, 4,4-diphenylmethane bismaleimide, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4-maleimidephenyl) Methane, bis(3,5-diethyl-4-maleimidephenyl)methane, phenylmethanemaleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene bisciconimide, m-phenylene bisciconimide, p-phenylene bisciconimide, 2,2-bis(4-(4-maleimidephenoxy)-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 Maleimide 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(maleimidemethyl)cyclohexane, 1,4-bis(maleimidemethyl)cyclohexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy) Benzene, 4,4-diphenylmethane bis(citconimide), 2,2-bis[4-(4-citconimide phenoxy)phenyl]propane, bis(3,5-dimethyl-4-citconimide phenyl)methane, bis(3-ethyl-5-methyl-4-citconimide phenyl)methane, bis(3,5-diethyl-4-citconimide phenyl)methane, polyphenylmethane maleimide, and other maleimide compounds represented by formula (6) below, maleimide compounds represented by formula (7) below, fluorescein-5-maleimide, and prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds, etc. These maleimide compounds (B-1) can also be used alone or in appropriate mixtures of two or more.

[0124] As the maleimide compound represented by formula (6) below, commercially available products can also be used, such as BMI-2300 (trade name) manufactured by Daiwa Chemical Industries, Ltd. As the maleimide compound represented by formula (7) below, commercially available products can also be used, such as MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd. As the maleimide compound represented by formula (8) below, commercially available products can also be used, such as MIR-5000 (trade name) manufactured by Nippon Kayaku Co., Ltd.

[0125] [Chemistry 7]

[0126]

[0127] In formula (6), R7 independently represents a hydrogen atom or a methyl group. n3 represents an integer of 1 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5.

[0128] [Chemistry 8]

[0129]

[0130] In formula (7), R8 independently represents a hydrogen atom or a methyl group. n4 represents an integer greater than or equal to 1, preferably an integer from 1 to 5.

[0131] [Chemistry 9]

[0132]

[0133] In the formula (8), R9 independently represents a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a phenyl group, l2 independently represents an integer from 1 to 3, and n5 represents an integer from 1 to 10.

[0134] Examples of alkyl groups having 1 to 5 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and neopentyl.

[0135] In this embodiment, in order to efficiently induce the photoradical reaction of the bismaleimide compound (A), when preparing a chloroform solution containing 1% by mass of the maleimide compound (B1) and measuring the transmittance of the chloroform solution using an active energy line containing a wavelength of 365 nm (i-rays), it is preferable to show a light transmittance of 5% or more. More preferably, the transmittance is 8% or more, and even more preferably 10% or more.

[0136] Furthermore, in order to efficiently induce the photoradical reaction of the bismaleimide compound (A), when preparing a chloroform solution containing 1% by mass of the maleimide compound (B1) and measuring the transmittance of the chloroform solution using an active energy line containing a wavelength of 405 nm (h-rays), it is preferable to show a light transmittance of 5% or more. When using the maleimide compound (B1), for example, when manufacturing a printed wiring board with high-density and high-fine wiring formation (pattern) using a direct-drawing exposure method, the photoradical reaction of the maleimide is efficiently induced even when using an active energy line containing a wavelength of 405 nm (h-rays). For obtaining a resin composition with superior photocurability, a light transmittance of 8% or more is more preferable, and even more preferably 10% or more.

[0137] Examples of the maleimide compound (B-1) include, for example, the maleimide compound represented by formula (9), the maleimide compound represented by formula (10), the maleimide compound represented by formula (17), the maleimide compound represented by formula (11), the maleimide compound represented by formula (12), the maleimide compound represented by formula (13), the maleimide compound represented by formula (14), 1,6-bismaleimide-(2,2,4-trimethyl)hexane (the maleimide compound represented by formula (14)), the maleimide compound represented by formula (16), and fluorescein-5-maleimide.

[0138] [Chemistry 10]

[0139]

[0140] In the formula (9), n6 (average) is 1 or more, preferably 1 to 21, and more preferably 1 to 16 from the viewpoint of exhibiting excellent light curing properties.

[0141] [Chemistry 11]

[0142]

[0143] In the above formula (10), the number of x is 10 to 35.

[0144] In the above formula (10), the quantity of y is 10 to 35.

[0145] [Chemistry 12]

[0146]

[0147] In equation (11), R aThis refers to 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. As R a Preferably, it is a linear or branched alkyl group, and more preferably a linear alkyl group in terms of exhibiting excellent photocurability.

[0148] The number of carbon atoms in the alkyl group is preferably 4 to 12, which exhibits excellent light curing properties.

[0149] The number of carbon atoms in the alkenyl group is preferably 4 to 12, which exhibits excellent photocurability.

[0150] As a straight-chain or branched alkyl group, refer to R3 in bismaleimide compound (A). Among these, n-heptyl, n-octyl, and n-nonyl are preferred in terms of exhibiting excellent photocurability, with n-octyl being more preferred.

[0151] As a linear or branched alkenyl group, refer to R3 in bismaleimide compound (A). Among these, 2-heptenyl, 2-octenyl, and 2-nonenyl are preferred in terms of exhibiting excellent photocurability, and 2-octenyl is more preferred.

[0152] In equation (11), R b This refers to 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. As R b Preferably, it is a linear or branched alkyl group, and more preferably a linear alkyl group in terms of exhibiting excellent photocurability.

[0153] The number of carbon atoms in the alkyl group is preferably 4 to 12, which exhibits excellent light curing properties.

[0154] The number of carbon atoms in the alkenyl group is preferably 4 to 12, which exhibits excellent photocurability.

[0155] For a specific example of an alkyl group, see R. a Alkyl groups in the form of n-heptyl, n-octyl, or n-nonyl are preferred for exhibiting excellent photocurability, with n-octyl being more preferred.

[0156] For a specific example of an alkenyl group, see R. a The alkenyl group in the compound. Among them, 2-heptenyl, 2-octenyl, and 2-nonenyl are preferred in terms of exhibiting excellent photocurability, and 2-octenyl is more preferred.

[0157] In equation (11), n a The quantity is 1 or more, preferably 2 to 16, and more preferably 3 to 14 from the viewpoint of exhibiting excellent photocurability.

[0158] In equation (11), nb The quantity is 1 or more, preferably 2 to 16, and more preferably 3 to 14 from the viewpoint of exhibiting excellent photocurability.

[0159] n a With n b The quantities can be the same or different.

[0160] [Chemistry 13]

[0161]

[0162] In the formula (12), n7 (average) is 0.5 or more, preferably 0.8 to 10, and more preferably 1 to 8 from the viewpoint of exhibiting excellent photocurability.

[0163] [Chemistry 14]

[0164]

[0165] In the formula (13), n8 represents an integer greater than or equal to 1, and is preferably an integer from 1 to 10.

[0166] [Chemistry 15]

[0167]

[0168] In the formula (14), n9 represents an integer greater than or equal to 1, and is preferably an integer from 1 to 10.

[0169] [Chemistry 16]

[0170]

[0171] [Chemistry 17]

[0172]

[0173] In equation (16), R 10 Each can independently represent a hydrogen atom, a methyl group, or an ethyl group; R 11 Each can be used independently to represent a hydrogen atom or a methyl group.

[0174] Maleimide compound (B-1) is also available in commercially available products.

[0175] Examples of maleimide compounds represented by formula (9) include BMI-1000P (trade name, n6 = 13.6 (average) in formula (9)) manufactured by KI Chemical Co., Ltd., BMI-650P (trade name, n6 = 8.8 (average) in formula (9)) manufactured by KI Chemical Co., Ltd., BMI-250P (trade name, n6 = 3 to 8 (average) in formula (9)) manufactured by KI Chemical Co., Ltd., and CUA-4 (trade name, n6 = 1 in formula (9)) manufactured by KI Chemical Co., Ltd.

[0176] Examples of maleimide compounds represented by formula (10) include BMI-6100 (trade name, x=18, y=18 in formula (10)) manufactured by Designer Molecules Inc.

[0177] Examples of maleimide compounds represented by formula (11) include BMI-689 (trade name, formula (17) below, functional group equivalent: 346 g / eq.) manufactured by Designer Molecules Inc.

[0178] [Chemistry 18]

[0179]

[0180] Examples of maleimide compounds represented by formula (12) include BMI-1500 (trade name, n7 = 1.3 in formula (12), functional group equivalent: 754 g / eq.) manufactured by Designer Molecules Inc.

[0181] As the maleimide compound represented by formula (13), commercially available products can also be used, such as BMI-1700 (trade name) manufactured by Designer Molecules Inc. (DMI).

[0182] As the maleimide compound represented by formula (14), commercially available products may also be used, for example, BMI-3000 (trade name) manufactured by Artificial Molecular Corporation (DMI), BMI-5000 (trade name) manufactured by Artificial Molecular Corporation (DMI), and BMI-9000 (trade name) manufactured by Artificial Molecular Corporation (DMI).

[0183] As the maleimide compound represented by formula (15), commercially available products can also be used, such as BMI-TMH (trade name) manufactured by Yamato Chemical Industries, Ltd.

[0184] As the maleimide compound represented by the formula (16), commercially available products can also be used, such as BMI-70 (trade name) manufactured by KI Chemical (stock).

[0185] These maleimide compounds (B1) can also be used alone or in appropriate combinations of two or more.

[0186] In the resin composition, the preferred amount of maleimide compound (B1) is 0.5 to 85 parts by mass relative to the total amount of bismaleimide compound (A), maleimide compound (B-1) and photocuring initiator (C).

[0187] (Cyanate ester compounds)

[0188] In the resin composition, cyanate ester compound (B-2) (also known as component (B-2)) may be used. Cyanate ester compound (B-2) is described below.

[0189] As a cyanate compound, there are no particular limitations as long as it is a resin having an aromatic moiety that is substituted with at least one cyanooxy group (cyanate group) within the molecule.

[0190] For example, cyanate compounds represented by the following formula (18) can be listed.

[0191] [Chemistry 19]

[0192]

[0193] In formula (18), Ar1 represents a benzene ring, a naphthalene ring, or two benzene rings bonded together by a single bond. Ar1 may be the same or different in multiple cases. Ar1 is preferably a naphthalene ring. 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, or a group formed by the bonding of an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms. Ra is preferably a hydrogen atom. The aromatic ring in Ra may have substituents, and the substituents in Ar1 and Ra can be chosen in any position. p represents the number of cyanoxy groups bonded to Ar1, and each is an independent integer from 1 to 3, preferably 1. q represents the number of Ra groups bonded to Ar1, and is 4-p when Ar1 is a benzene ring, 6-p when Ar1 is a naphthalene ring, and 8-p when Ar1 is formed by the bonding of two benzene rings by a single bond. t represents the average number of repetitions and is an integer from 0 to 50, preferably an integer from 1 to 30, and more preferably an integer from 1 to 10. The cyanate compound may be a mixture of compounds with different t values. When multiple X are present, each X is independently a single bond, a divalent organogroup with 1 to 50 carbon atoms (hydrogen atoms may be replaced by heteroatoms), a divalent organogroup with 1 to 10 nitrogen atoms (e.g., -NRN- (where R represents an organogroup)), a carbonyl group (-CO-), a carboxyl group (-C(=O)O-), a carbonyl dioxide (-OC(=O)O-), a sulfonyl group (-SO2-), a divalent sulfur atom, or a divalent oxygen atom.

[0194] The alkyl group in Ra of formula (18) may have either a straight or branched chain structure or a cyclic structure (e.g., cycloalkyl).

[0195] In addition, the hydrogen atoms in the alkyl group and the aryl group in the formula (18) can also be substituted by halogen atoms such as fluorine atoms and chlorine atoms; alkoxy groups such as methoxy and phenoxy; or cyano groups.

[0196] Specific examples of alkyl groups include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2,2-dimethylpropyl, cyclopentyl, hexyl, cyclohexyl, and trifluoromethyl, etc.

[0197] Specific examples of alkenyl groups include: vinyl, (methyl)allyl, isopropenyl, 1-propenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 2-methyl-2-propenyl, 2-pentenyl, and 2-hexenyl.

[0198] Specific examples of aryl groups include: phenyl, xylyl, mesitylene, naphthyl, phenoxyphenyl, ethylphenyl, o-fluorophenyl, m-fluorophenyl or p-fluorophenyl, dichlorophenyl, dicyanophenyl, trifluorophenyl, methoxyphenyl, and o-tolyl, m-tolyl or p-tolyl, etc. Furthermore, examples of alkoxy groups include: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy, etc.

[0199] Specific examples of divalent organic groups with 1 to 50 carbon atoms in X of formula (18) include: methylene, ethylene, trimethylene, cyclopentylene, cyclohexylene, trimethylcyclohexylene, biphenylmethylene, dimethylmethylene-phenyl-dimethylmethylene, methylene-phenyl-methylene, fluorenediyl, and phthalolidediyl, etc. Among these, methylene-phenyl-methylene is preferred. The hydrogen atom in the divalent organic group may be substituted by halogen atoms such as fluorine or chlorine; alkoxy groups such as methoxy or phenoxy; or cyano, etc.

[0200] Examples of divalent organic groups with nitrogen number 1 to 10 in X of formula (18) include imino and polyimide groups.

[0201] In addition, the organic group of X in the above formula (18) can be, for example, an organic group with the structure represented by the following formula (19) or the following formula (20).

[0202] [Chemistry 20]

[0203]

[0204] In formula (19), Ar2 represents phenyldiyl, naphthyl, or biphenyldiyl. When u is an integer greater than or equal to 2, Ar2 can be the same or different from each other. 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 select from 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.

[0205] [Chemistry 21]

[0206]

[0207] In formula (20), Ar3 represents phenyldiyl, naphthyl, or biphenyldiyl. When v is an integer greater than or equal to 2, Ar3 may be the same or different from each other. Ri and Rj each independently represent at least one substituted aryl group selected from hydrogen atom, alkyl group with 1 to 6 carbon atoms, aryl group with 6 to 12 carbon atoms, benzyl group, alkoxy group with 1 to 4 carbon atoms, hydroxyl group, trifluoromethyl group, or cyanoxy group. v represents an integer from 0 to 5, but may also be a mixture of compounds with different v values.

[0208] Furthermore, as X in the above equation (18), the divalent base represented by the following equation can be listed.

[0209] [Chemistry 22]

[0210]

[0211] Here, in the formula, z represents an integer from 4 to 7. Rk each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0212] Specific examples of Ar2 in formula (19) and Ar3 in formula (20) include: phenyldiyl groups with two carbon atoms in formula (19) or two oxygen atoms in formula (20) bonded at the 1,4 or 1,3 positions; biphenyldiyl groups with two carbon atoms or two oxygen atoms bonded at the 4,4', 2,4', 2,2', 2,3', 3,3', or 3,4' positions; and naphthyl groups with two carbon atoms or two oxygen atoms bonded at the 2,6, 1,5, 1,6, 1,8, 1,3, 1,4, or 2,7 positions.

[0213] The alkyl and aryl groups in Rb, Rc, Rd, Re, Rf and Rg of formula (19) and Ri and Rj of formula (20) have the same meaning as the alkyl and aryl groups in formula (18).

[0214] Specific examples of cyanooxy-substituted aromatic compounds represented by formula (18) include: cyanooxybenzene, 1-cyanooxy-2-methylbenzene, 1-cyanooxy-3-methylbenzene, or 1-cyanooxy-4-methylbenzene, 1-cyanooxy-2-methoxybenzene, 1-cyanooxy-3-methoxybenzene, or 1-cyanooxy-4-methoxybenzene, 1-cyanooxy-2,3-dimethylbenzene, 1-cyanooxy-2,4-dimethylbenzene, 1-cyanooxy-2,5-dimethylbenzene, 1-cyanooxy-2,6-dimethylbenzene, 1-cyanooxy-3,4-dimethylbenzene, or 1-cyanooxy-3,5-dimethylbenzene, cyanooxy-ethylbenzene, cyanooxy-butylbenzene, cyanooxy-octylbenzene, cyanooxy-nonylbenzene, 2-(4-cyanophenyl)-2-phenylpropanoid Alkane (cyanate ester of 4-α-cumylphenol), 1-cyanooxy-4-cyclohexylbenzene, 1-cyanooxy-4-vinylbenzene, 1-cyanooxy-2-chlorobenzene or 1-cyanooxy-3-chlorobenzene, 1-cyanooxy-2,6-dichlorobenzene, 1-cyanooxy-2-methyl-3-chlorobenzene, cyanooxynitrobenzene, 1-cyanooxy-4-nitro-2-ethylbenzene, 1-cyanooxy-2-methoxy-4-allylbenzene (cyanate ester of eugenol), methyl (4-cyanooxyphenyl) sulfide, 1-cyanooxy-3-trifluoromethylbenzene, 4-cyanooxybiphenyl, 1-cyanooxy-2-acetylbenzene or 1-cyanooxy-4-acetylbenzene, 4-cyanooxybenzaldehyde, methyl 4-cyanooxybenzoate, phenyl 4-cyanooxybenzoate, 1-cyanooxy-4-ethylbenzene Amide-based benzene, 4-cyanoxybenzophenone, 1-cyanoxy-2,6-di-tert-butylbenzene, 1,2-dicyanoxybenzene, 1,3-dicyanoxybenzene, 1,4-dicyanoxybenzene, 1,4-dicyanoxy-2-tert-butylbenzene, 1,4-dicyanoxy-2,4-dimethylbenzene, 1,4-dicyanoxy-2,3,4-dimethylbenzene, 1,3-dicyanoxy-2,4,6-trimethylbenzene, 1,3-dicyanoxy-5-methylbenzene, 1-cyanoxynaphthalene or 2-cyanoxynaphthalene, 1-cyanoxy-4-methoxynaphthalene, 2-cyanoxy-6-methoxynaphthalene, 2-cyanoxy-7-methoxynaphthalene, 2,2'-dicyanoxy-1,1'-binaphthylene, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 2, 3-, 2,6- or 2,7-dicyanoxynaphthalene, 2,2'- or 4,4'-dicyanoxybiphenyl, 4,4'-dicyanoxyoctafluorobiphenyl, 2,4'- or 4,4'-dicyanoxydiphenylmethane, bis(4-cyanoxy-3,5-dimethylphenyl)methane, 1,1-bis(4-cyanoxyphenyl)ethane, 1,1-bis(4-cyanoxyphenyl)propane, 2,2-bis(4-cyanoxyphenyl)propane, 2,2-bis(4-cyanoxy-3-methylphenyl)propane, 2,2-bis(2-cyanoxy-5-biphenyl)propane, 2,2-bis(4-cyanoxyphenyl)hexafluoropropane, 2,2-bis(4-cyanoxy-3,5-dimethylphenyl)propane, 1,1-bis(4-cyanoxyphenyl)butane, 1,1-Bis(4-cyanoxyphenyl)isobutane, 1,1-bis(4-cyanoxyphenyl)pentane, 1,1-bis(4-cyanoxyphenyl)-3-methylbutane, 1,1-bis(4-cyanoxyphenyl)-2-methylbutane, 1,1-bis(4-cyanoxyphenyl)-2,2-dimethylpropane, 2,2-bis(4-cyanoxyphenyl)butane, 2,2-bis(4-cyanoxyphenyl)pentane, 2,2-bis(4-cyanoxyphenyl)hexane, 2,2-bis(4-cyanoxyphenyl)-3-methylbutane, 2,2-bis(4-cyanoxyphenyl)-4-methylpentane, 2,2-bis(4-cyanoxyphenyl)-3,3-dimethylbutane, 3,3-bis(4-cyanoxyphenyl)hexane, 3,3- bis(4-cyanoxyphenyl)heptane, 3,3-bis(4-cyanoxyphenyl)octane, 3,3-bis(4-cyanoxyphenyl)-2-methylpentane, 3,3-bis(4-cyanoxyphenyl)-2-methylhexane, 3,3-bis(4-cyanoxyphenyl)-2,2-dimethylpentane, 4,4-bis(4-cyanoxyphenyl)-3-methylheptane, 3,3-bis(4-cyanoxyphenyl)-2-methylheptane, 3,3-bis(4-cyanoxyphenyl)-2,2-dimethylhexane, 3,3-bis(4-cyanoxyphenyl)-2,4-dimethylhexane, 3,3-bis(4-cyanoxyphenyl)-2,2,4-trimethylpentane, 2,2-bis(4-cyanoxyphenyl)-1,1,1,3 3,3-Hexafluoropropane, bis(4-cyanoxyphenyl)phenylmethane, 1,1-bis(4-cyanoxyphenyl)-1-phenylethane, bis(4-cyanoxyphenyl)biphenylmethane, 1,1-bis(4-cyanoxyphenyl)cyclopentane, 1,1-bis(4-cyanoxyphenyl)cyclohexane, 2,2-bis(4-cyanoxy-3-isopropylphenyl)propane, 1,1-bis(3-cyclohexyl-4-cyanoxyphenyl)cyclohexane, bis(4-cyanoxyphenyl)diphenylmethane, bis(4-cyanoxyphenyl)-2,2-dichloroethylene, 1,3-bis[2-(4-cyanoxyphenyl)-2-propyl]benzene, 1,4-bis[2-(4-cyanoxyphenyl)-2-propyl]benzene, 1,1-bis(4-cyanoxyphenyl) 3,3,5-Trimethylcyclohexane, 4-[bis(4-cyanoxyphenyl)methyl]biphenyl, 4,4-dicyanoxybenzophenone, 1,3-bis(4-cyanoxyphenyl)-2-propen-1-one, bis(4-cyanoxyphenyl) ether, bis(4-cyanoxyphenyl) sulfide, bis(4-cyanoxyphenyl) sulfone, 4-cyanoxybenzoic acid-4-cyanoxyphenyl ester (4-cyanoxyphenyl-4-cyanoxybenzoate), bis-(4-cyanoxyphenyl) carbonate, 1,3-bis(4-cyanoxyphenyl)adamantane, 1,3-bis(4-cyanoxyphenyl)-5,7-dimethyladamantane, 3,3-bis(4-cyanoxyphenyl)isobenzofuran-1(3H)-one (cyanate ester of phenolphthalein), 3,3-Bis(4-cyanoxy-3-methylphenyl)isobenzofuran-1(3H)-one (cyanate ester of o-cresolphenolphthalein), 9,9'-bis(4-cyanoxyphenyl)fluorene, 9,9-bis(4-cyanoxy-3-methylphenyl)fluorene, 9,9-bis(2-cyanoxy-5-biphenyl)fluorene, tris(4-cyanoxyphenyl)methane, 1,1,1-tris(4-cyanoxyphenyl)ethane, 1,1,3-tris(4-cyanoxyphenyl)propane α,α,α'-tris(4-cyanoxyphenyl)-1-ethyl-4-isopropylbenzene, 1,1,2,2-tetra(4-cyanoxyphenyl)ethane, tetra(4-cyanoxyphenyl)methane, 2,4,6-tris(N-methyl-4-cyanoxyanilino)-1,3,5-triazine, 2,4-bis(N-methyl-4-cyanoxyanilino)-6-(N-methylanilino)-1,3,5-triazine, bis(N-4-cyanoxy-2- 4,4'-Oxyphthalimide, bis(N-3-cyanooxy-4-methylphenyl)-4,4'-Oxyphthalimide, bis(N-4-cyanooxyphenyl)-4,4'-Oxyphthalimide, bis(N-4-cyanooxy-2-methylphenyl)-4,4'-(hexafluoroisopropylidene)diphthalimide, tris(3,5-dimethyl-4-cyanooxybenzyl)isocyanurate, 2-phenyl -3,3-bis(4-cyanoxyphenyl)benzylformamide, 2-(4-methylphenyl)-3,3-bis(4-cyanoxyphenyl)benzylformamide, 2-phenyl-3,3-bis(4-cyanoxy-3-methylphenyl)benzylformamide, 1-methyl-3,3-bis(4-cyanoxyphenyl)indololin-2-one, 2-phenyl-3,3-bis(4-cyanoxyphenyl)indololin-2-one, and α-naphthol aralkyl cyanate resins. Among these, for the sake of improved heat resistance of the cured product, α-naphthol aralkyl cyanate resins represented by the following formula (28) are preferred (including n in formula (28) described below). 18 (It is an α-naphthol aralkyl cyanate resin of 1 to 4).

[0215] These cyanate compounds can also be used alone or in appropriate combinations of two or more.

[0216] As another specific example of the cyanate ester compound represented by formula (18), examples include phenolic resins prepared by cyanate esterification using the same method as described above, and their prepolymers, etc.: phenolic phenolic varnish resins and cresol phenolic varnish resins (prepared by reacting phenol, alkyl-substituted phenol, or halogen-substituted phenol with formaldehyde compounds such as formaldehyde, paraformaldehyde, etc., in an acidic solution using known methods), triphenolic phenolic varnish resins (prepared by reacting hydroxybenzaldehyde with phenol in the presence of an acidic catalyst), fluorene phenolic varnish resins (prepared by reacting fluorene ketone compounds 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 (prepared by reacting dihalomethyl compounds such as Ar4-(CH2Y)2 (Ar4 represents phenyl, Y represents a halogen atom. The same applies in the following paragraphs) with phenolic phenolic esters using known methods). These cyanate esters are formed by reacting compounds under acidic catalysts or without catalysts; by reacting bis(alkoxymethyl) compounds, such as Ar4-(CH2OR)2 (R represents alkyl), with phenolic compounds in the presence of an acidic catalyst; by reacting bis(hydroxymethyl) compounds, such as Ar4-(CH2OH)2, with phenolic compounds in the presence of an acidic catalyst; or by condensing aromatic aldehyde compounds with aralkyl compounds and phenolic compounds; phenol-modified xyleneformaldehyde resin (formed by reacting xyleneformaldehyde resin with phenolic compounds in the presence of an acidic catalyst using known methods); modified naphthaldehyde resin (formed by reacting naphthaldehyde resin with hydroxyl-substituted aromatic compounds in the presence of an acidic catalyst using known methods); phenol-modified dicyclopentadiene resin; and phenolic resins with a polynatrimethylene ether structure (formed by dehydration condensation of polyhydroxynaphthalene compounds having two or more phenolic hydroxyl groups in one molecule in the presence of an alkaline catalyst using known methods). These cyanate ester compounds can also be used alone or in appropriate mixtures of two or more.

[0217] There are no particular limitations on the methods for manufacturing these cyanate compounds, and known methods can be used. Examples of such methods include obtaining or synthesizing a hydroxyl-containing compound with the desired skeleton, and then cyanate-esterifying it by modifying the hydroxyl groups using known techniques. Examples of methods for cyanate-esterifying the hydroxyl groups include those described in Ian Hamerton, *Chemistry and Technology of Cyanate Ester Resins*, Blackie Academic & Professional.

[0218] Cured products using these cyanate compounds exhibit excellent properties such as glass transition temperature, low thermal expansion, and good adhesion.

[0219] In the resin composition, the content of the cyanate compound is preferably 0.5 to 85 parts by mass relative to a total of 100 parts by mass of the bismaleimide compound (A), the cyanate compound (B-2), and the photocuring initiator (C).

[0220] (Benzoxazine compounds)

[0221] In the resin composition, benzoxazine compound (B-3) (also known as component (B-3)) may be used. Benzoxazine compound (B-3) is described below.

[0222] As for benzoxazine compounds (B-3), any known benzoxazine compound can be used as long as it has an oxazine ring as its basic skeleton. Benzoxazine compounds also include compounds with a polycyclic oxazine skeleton, such as naphthoxazine compounds.

[0223] As for benzoxazine compounds (B-3), the compounds represented by formula (21) and the compounds represented by formula (22) are preferred in terms of obtaining good photocurability.

[0224] [Chemistry 23]

[0225]

[0226] In the above equation (21), R 12 Each can independently represent a hydrogen atom, aryl, aralkyl, alkenyl, alkyl, or cycloalkyl group. 10 Each can independently represent an integer from 1 to 4. R 13 Each can independently represent a hydrogen atom, aryl, aralkyl, alkenyl, alkyl, or cycloalkyl group. 11 Each represents an integer from 1 to 4 independently. T 1 The radical represents an alkylene group, a radical represented by formula (22), a radical represented by formula "-SO2-", a radical represented by "-CO-", an oxygen atom, or a single bond.

[0227] R 12 and R 13 The aryl group is preferably an aryl group having 6 to 18 carbon atoms. Examples of such aryl groups include phenyl, naphthyl, indene, biphenyl, and anthracene. Phenyl is more preferred. These aryl groups may have one or more, preferably one to three, lower alkyl groups having 1 to 4 carbon atoms. Examples of aryl groups having such lower alkyl groups include tolyl, xylyl, and methylnaphthyl.

[0228] R 12 and R13 The aryl groups are preferably benzyl and phenethyl. These may have one or more, preferably one to three, lower alkyl groups having 1 to 4 carbon atoms on their phenyl groups.

[0229] R 12 and R 13 Examples of alkenyl groups include vinyl, (methyl)allyl, propenyl, butenyl, and hexenyl. Among these, vinyl, allyl, and propenyl are preferred, and allyl is more preferred.

[0230] R 12 and R 13 The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. The alkyl group having 3 or more carbon atoms can be straight-chain or branched. Examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, tert-hexyl, n-heptyl, n-octyl, n-ethylhexyl, n-nonyl, and n-decyl.

[0231] R 12 and R 13 Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and cycloheptyl. Cyclohexyl is preferred.

[0232] As T 1 The alkylene group in the form of a linear or branched alkylene group is preferred. Examples of linear alkylene groups include: methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, nonylene, decylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene. Examples of branched alkylene groups include: alkylmethylene groups of -C(CH3)2-, -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups of -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-.

[0233] [Chemistry 24]

[0234]

[0235] In the above equation (22), R 14 Each can independently represent a hydrogen atom, aryl, aralkyl, alkenyl, alkyl, or cycloalkyl group. 12 Each can independently represent an integer from 1 to 3. R 15Each can independently represent a hydrogen atom, aryl, aralkyl, alkenyl, alkyl, or cycloalkyl group. 13 Each can be an integer from 1 to 5. T2 represents an alkylene group, a group represented by formula (22), a group represented by formula "-SO2-", a group represented by "-CO-", an oxygen atom, or a single bond.

[0236] Regarding R 14 and R 15 The aryl, aralkyl, alkenyl, alkyl, and cycloalkyl groups are as described above. The alkylene groups in T2 are as described above.

[0237] [Chemistry 25]

[0238]

[0239] In formula (23), Z is an alkylene group or a hydrocarbon group having an aromatic ring with 6 or more but less than 30 carbon atoms. 14 n represents an integer greater than 0 and less than 5. 14 Preferably, it is an integer greater than or equal to 1 and less than or equal to 3, more preferably 1 or 2.

[0240] Regarding the alkylene group in Z, as described above.

[0241] As a hydrocarbon group having 6 or more but less than 30 carbon atoms in an aromatic ring, examples include divalent groups obtained by removing two hydrogen atoms from the nucleus of aromatic compounds such as benzene, biphenyl, naphthalene, anthracene, fluorene, phenanthrene, indacene, terphenyl, acenaphthene, and phenaene.

[0242] As a benzoxazine compound (B-3), commercially available products can be used, such as: Pd type benzoxazine (manufactured by Shikoku Chemical Industry Co., Ltd., 3,3'-(methylene-1,4-diphenylene)bis(3,4-dihydro-2H-1,3-benzoxazine), the compound represented by formula (20), Fa type benzoxazine (manufactured by Shikoku Chemical Industry Co., Ltd., 2,2-bis(3,4-dihydro-2H-3-phenyl-1,3-benzoxazinyl)methane, the compound represented by formula (21), bisphenol A type benzoxazine BA-BXZ (manufactured by Konishi Chemical Industry Co., Ltd., trade name), bisphenol F type benzoxazine BF-BXZ (manufactured by Konishi Chemical Industry Co., Ltd., trade name), bisphenol S type benzoxazine BS-BXZ (manufactured by Konishi Chemical Industry Co., Ltd., trade name), and phenolphthalein type benzoxazine, etc.

[0243] These benzoxazine compounds (B-3) can also be used alone or in appropriate combinations of two or more.

[0244] For the sake of good heat resistance, the benzoxazine compound is preferably the compound represented by formula (20) and the compound represented by formula (21), more preferably 3,3'-(methylene-1,4-diphenylene)bis(3,4-dihydro-2H-1,3-benzoxazine).

[0245] In the resin composition, the content of the benzoxazine compound is preferably 0.5 to 85 parts by mass relative to a total of 100 parts by mass of the bismaleimide compound (A), the benzoxazine compound (B-3), and the photocuring initiator (C).

[0246] (Epoxy resin)

[0247] In the resin composition, epoxy resin (B-4) (also referred to as component (B-4)) may be used. Epoxy resin (B-4) is described below.

[0248] As the epoxy resin (B-4), commonly known epoxy resins can be used. Examples include: bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A phenolic varnish type epoxy resin, biphenyl type epoxy resin, phenolic varnish type epoxy resin, cresol phenolic varnish type epoxy resin, xylene phenolic varnish type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified phenolic varnish type epoxy resin, naphthylene ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, and triglycidyl isocyanuric acid. Ester, glycidyl ester type epoxy resin, alicyclic epoxy resin, dicyclopentadiene phenolic varnish type epoxy resin, biphenyl phenolic varnish type epoxy resin, phenol aralkyl phenolic varnish type epoxy resin, naphthol aralkyl phenolic varnish type epoxy resin, aralkyl phenolic varnish type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, glycidylamine, compounds obtained by epoxidation of the double bonds of butadiene, compounds obtained by the reaction of hydroxyl-containing silicone resins with epichlorohydrin, and halides thereof. These epoxy resins can also be used alone or in appropriate mixtures of two or more.

[0249] Commercially available epoxy resins can also be used. For example, an epoxy resin represented by the formula (24) below (NC-3000FH (trade name) manufactured by Nippon Kayaku Co., Ltd., where n in formula (24) below... 15 3 to 5, approximately 4), and the naphthalene-type epoxy resin represented by the following formula (25) (HP-4710 (trade name) manufactured by DIC (stock)).

[0250] [Chemistry 26]

[0251]

[0252] [Chemistry 27]

[0253]

[0254] These epoxy resins can also be used alone or in appropriate combinations of two or more.

[0255] For the reason that the cured material has excellent heat resistance, the epoxy resin is preferably the epoxy resin represented by formula (23) and the epoxy resin represented by formula (24), and more preferably the epoxy resin represented by formula (23).

[0256] In the resin composition, the content of epoxy resin is preferably 0.5 to 85 parts by weight relative to a total of 100 parts by weight of bismaleimide compound (A), epoxy resin (B4) and photocuring initiator (C).

[0257] (Carbodiimide compound)

[0258] In the resin composition, a carbodiimide compound (B-5) (also known as component (B-5)) may be used. The carbodiimide compound (B-5) is described below.

[0259] As a carbodiimide compound (B-5), any generally known carbodiimide compound can be used as long as it has at least one carbodiimide group in the molecule. Examples include: N,N'-dicyclohexylcarbodiimide, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, tert-butylisopropylcarbodiimide, diphenylcarbodiimide, di-tert-butylcarbodiimide, di-β-naphthylcarbodiimide, N,N'-di-2,6-diisopropylphenylcarbodiimide, 2,6,2',6'-tetraisopropyldiphenylcarbodiimide, cyclic carbodiimide, Carbodilite (registered trademark) B-01 (manufactured by Nisshinbo Chemical Co., Ltd.), and Stabaxol (registered trademark: manufactured by Rhein Chemie), etc., which are polycarbodiimides.

[0260] These carbodiimide compounds (B-5) can also be used alone or in appropriate combinations of two or more.

[0261] For the reasons that it has good heat resistance and good adhesion to the conductor layer when used as an insulation layer in printed wiring boards, the carbodiimide compound is preferably Carbodilite (registered trademark) B-01, V-03, V05 (trade names, manufactured by Nisshinbo Chemical Co., Ltd.), and more preferably Carbodilite (registered trademark) B-01 (trade name, manufactured by Nisshinbo Chemical Co., Ltd.).

[0262] In the resin composition, the content of the carbodiimide compound is preferably 0.5 to 85 parts by mass relative to 100 parts by mass of the resin solids in the resin composition.

[0263] (Compounds containing vinyl unsaturated groups)

[0264] In the resin composition, a compound (B-6) having an vinyl unsaturated group (also referred to as component (B-6)) may be used. The compound (B-6) having an vinyl unsaturated group is described below.

[0265] As a compound having an ethylene unsaturated group (B-6), any compound having one or more ethylene unsaturated groups in one molecule can be used; generally known compounds having ethylene unsaturated groups can be used. Examples include compounds having (meth)acryloyl and vinyl groups.

[0266] Examples of compounds containing a (meth)acryloyl group include: methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, polyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate monomethyl ether, phenyl ethyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, tetrahydrofurfuryl methacrylate, dibutyl methacrylate, hexanediol dimethacrylate, neopentyl methacrylate, nonanediol dimethacrylate, di(meth)acrylate, diethylene dimethacrylate, polyethylene glycol di(meth)acrylate, tri(meth)acryloyloxyethyl isocyanurate, and polypropylene glycol. Di(meth)acrylate, adipic acid epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide (meth)acrylate, bisphenol di(meth)acrylate, ε-caprolactone modified hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, ε-caprolactone modified dipentaerythritol hexa(meth)acrylate, ε-caprolactone modified dipentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylolpropane tri(meth)acrylate, and their ethylene oxide adducts; pentaerythritol tri(meth)acrylate and its ethylene oxide adducts; pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate and its ethylene oxide adducts.

[0267] In addition, examples include urethane (meth)acrylates that have both (meth)acryloyl and urethane bonds in the same molecule; polyester (meth)acrylates that have both (meth)acryloyl and ester bonds in the same molecule; epoxy (meth)acrylates derived from epoxy resins that also have (meth)acryloyl groups; and reactive oligomers that use these bonds in combination.

[0268] The so-called urethane (meth)acrylates can be categorized as: hydroxyl-containing (meth)acrylates reacted with polyisocyanates, and other alcohols used as needed. Examples include: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, and other hydroxyalkyl methacrylates; glycerol mono(meth)acrylate, glycerol di(meth)acrylate, and other glycerol (meth)acrylates; and sugar alcohol (meth)acrylates such as toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexane methylene diisocyanate, and their isocyanurates, biuret reactants, and other polyisocyanates to form urethane (meth)acrylates.

[0269] Examples of polyester (meth)acrylates include: monofunctional (poly)acrylate (meth)acrylates such as caprolactone-modified 2-hydroxyethyl methacrylate, ethylene oxide and / or propylene oxide-modified phthalic acid acrylate, ethylene oxide-modified succinate (meth)acrylate, and caprolactone-modified tetrahydrofurfuryl methacrylate; di(poly)acrylate (meth)acrylates such as neopentyl glycol di(meth)acrylate, caprolactone-modified neopentyl glycol di(meth)acrylate, and epichlorohydrin-modified di(meth)acrylate; and mono, di, or tri(meth)acrylates of triols obtained by adding more than 1 mole of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, and δ-valerol to 1 mole of trimethylolpropane or glycerol.

[0270] Examples include: mono-, di-, tri-, or tetra-(meth)acrylates of triols obtained by adding more than 1 mole of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone to 1 mole of pentaerythritol, dimethylolpropane, trimethylolpropane, or tetramethylolpropane; mono-(meth)acrylates of triols obtained by adding more than 1 mole of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone to 1 mole of dipentaerythritol; or mono-(meth)acrylates or poly(meth)acrylates of polyols such as triols, tetraols, pentaols, or hexaols.

[0271] Furthermore, examples include: (meth)acrylates of polyester polyols containing diol components such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, (poly)butane glycol, 3-methyl-1,5-pentanediol, and hexanediol, and reacting with polybasic acids such as maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, sodium 5-isophthalate sulfonate, and their anhydrides; and (meth)acrylates of polyfunctional (poly)acrylates containing diol components, polybasic acids, their anhydrides, and cyclic lactones such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone modified polyester diols.

[0272] The term "epoxy (meth)acrylate" refers to compounds containing epoxy groups and carboxylic acid esters of (meth)acrylic acid. Examples include: phenolic varnish-type epoxy (meth)acrylates, cresolic varnish-type epoxy (meth)acrylates, trihydroxyphenylmethane-type epoxy (meth)acrylates, dicyclopentadiene-phenol-type epoxy (meth)acrylates, bisphenol F-type epoxy (meth)acrylates, bisphenol-type epoxy (meth)acrylates, bisphenol A-type varnish-type epoxy (meth)acrylates, epoxy (meth)acrylates containing a naphthalene skeleton, glyoxal-type epoxy (meth)acrylates, heterocyclic epoxy (meth)acrylates, and their anhydride-modified epoxy (meth)acrylates.

[0273] Examples of vinyl compounds include: vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether; and styrene compounds such as styrene, methylstyrene, ethylstyrene, and divinylbenzene. Other vinyl compounds include: triallyl isocyanurate, trimethylallyl isocyanurate, and diallyl thiamethoxam.

[0274] As a compound having an ethylene unsaturated group, commercially available products can be used, for example: dicyclopentadiene phenolic epoxy acrylate (KAYARAD (registered trademark) ZXA-101H (trade name) manufactured by Nippon Kayaku Co., Ltd.) as the compound represented by formula (26), acid-modified dicyclopentadiene phenolic epoxy acrylate (KAYARAD (registered trademark) ZXA-1807H (trade name), KAYARAD (registered trademark) ZXR-1810H (trade name), KAYARAD (registered trademark) ZXR-1816H (trade name), and KAYARAD (registered trademark) ZXR-1889H (trade name) as the compound represented by formula (27) below.

[0275] [Chemistry 28]

[0276]

[0277] In equation (26), n 16 Represents an integer from 0 to 10. In terms of obtaining a more suitable viscosity and better controlling the rise in varnish viscosity, n... 16 Preferably, it is an integer from 0 to 5.

[0278] [Chemistry 29]

[0279]

[0280] In equation (27), n 17 Represents an integer from 0 to 10. In terms of obtaining a more suitable viscosity and better controlling the rise in varnish viscosity, n... 17 Preferably, it is an integer from 0 to 5.

[0281] These compounds (B-6) with ethylene unsaturated groups can also be used alone or in appropriate combinations of two or more.

[0282] As a compound having an ethylene unsaturated group, propylene glycol monomethyl ether acetate is preferred for its good thermal stability.

[0283] In the resin composition, the content of the compound having an ethylene unsaturated group is preferably 0.5 to 85 parts by mass relative to a total of 100 parts by mass of the bismaleimide compound (A), the benzoxazine compound (B-3), and the photocuring initiator (C).

[0284] [Photocuring initiator (C)]

[0285] The resin composition of this embodiment contains a photocuring initiator (C) (also referred to as component (C)). The photocuring initiator (C) may be a photocuring initiator known in the field of photocurable resin compositions. The photocuring initiator (C) may be used to photocur with a bismaleimide compound (A) and a resin or compound (B) using various active energy lines.

[0286] Examples of photocuring initiators (C) include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether, etc.; organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, and di-tert-butyl phthalate dipperoxide; phosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 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-methoxyacetophenone, etc. Acetophenones such as linyl-propane-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1; anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, and 2-pentylanthraquinone; thioxanones such as 2,4-diethylthioxanone, 2-isopropylthioxanone, and 2-chlorothioxanone; ketals such as acetophenone dimethyl ketal and benzoyl dimethyl ketal; diphenylmethyl... Benzophenones such as 4-benzoyl-4'-methyldiphenyl sulfide and 4,4'-dimethylaminobenzophenone; oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-acetone-1-(O-acetyl oxime), etc., are free radical photocuring initiators.

[0287] Alternatively, diazonium salts of Lewis acids such as p-methoxyphenyl diazonium salt of fluorophosphonic acid and N,N-diethylaminophenyl diazonium salt of hexafluorophosphonic acid; monium salts of Lewis acids such as diphenyl monium salt of hexafluorophosphonic acid and diphenyl monium salt of hexafluoroantimony; sulfonium salts of Lewis acids such as triphenyl sulfonium salt of hexafluorophosphonic acid and triphenyl sulfonium salt of hexafluoroantimony; phosphonium salts of Lewis acids such as triphenyl phosphonium salt of hexafluoroantimony; other halides; triazine initiators; borate initiators; other cationic photocuring initiators such as photoacid generators.

[0288] Commercially available products can also be used as photocuring initiators (C). Examples of commercially available products include: Omnirad (registered trademark) 369 (trade name) manufactured by IGM Resins, Omnirad (registered trademark) 819 (trade name) manufactured by IGM Resins, Omnirad (registered trademark) 819DW (trade name) manufactured by IGM Resins, Omnirad (registered trademark) 907 (trade name) manufactured by IGM Resins, Omnirad (registered trademark) TPO (trade name) manufactured by IGM Resins, Omnirad (registered trademark) TPO-L (trade name) manufactured by IGM Resins, and others. The following products are manufactured by Resins: Omnirad (registered trademark) 784 (trade name); Irgacure (registered trademark) OXE01 (trade name); Irgacure (registered trademark) OXE02 (trade name); Irgacure (registered trademark) OXE03 (trade name); and Irgacure (registered trademark) OXE04 (trade name).

[0289] These photocuring initiators (C) can also be used alone or in appropriate combinations of two or more.

[0290] In this embodiment, when the photocuring initiator (C) is prepared as a chloroform solution containing 0.01% by mass of the photocuring initiator (C) and the absorbance of the chloroform solution containing 0.01% by mass of the photocuring initiator (C) is measured using an active energy line containing a wavelength of 365 nm (i-rays), the absorbance is preferably 0.1 or higher, indicating that the photocuring initiator (C) exhibits very excellent absorbance. Furthermore, when the absorbance of the chloroform solution containing 0.01% by mass of the photocuring initiator (C) is measured using an active energy line containing a wavelength of 405 nm (h-rays), the absorbance is preferably 0.1 or higher, also indicating very excellent absorbance. When the photocuring initiator (C) is used, for example, when manufacturing a printed wiring board with high-density and high-fine wiring formation (pattern) using a direct drawing exposure method, even when using an active energy line containing a wavelength of 405 nm (h-rays), the photoradical reaction of maleimide is efficiently induced. Furthermore, for obtaining a resin composition with superior photocurability, the absorbance at a wavelength of 365 nm (i-rays) is more preferably 0.15 or higher. For obtaining a resin composition with superior photocurability, the absorbance at a wavelength of 405 nm (h-rays) is more preferably 0.15 or higher. Furthermore, the upper limit for both the absorbance at 365 nm (i-rays) and the absorbance at 405 nm (h-rays) is, for example, 99.9 or lower.

[0291] The photocuring initiator (C) is preferably a compound represented by the following formula (2).

[0292] [Chemistry 30]

[0293]

[0294] In formula (2), R4 each independently represents a substituent or phenyl group represented by formula (3) below.

[0295] [Chemistry 31]

[0296]

[0297] In formula (3), R5 independently represents either a hydrogen atom or a methyl group. In formula (3), -* represents a bond with the phosphorus atom (P) in formula (2).

[0298] The compound represented by formula (2), when prepared as a chloroform solution containing 0.01% by mass and the absorbance of the chloroform solution measured using an active energy line containing a wavelength of 365 nm (i-rays), exhibits an absorbance of 0.1 or higher and shows very excellent absorption relative to light at a wavelength of 365 nm (i-rays). Therefore, the compound suitably generates free radicals relative to light at a wavelength of 365 nm (i-rays). The absorbance is preferably 0.15 or higher. The upper limit is, for example, 5.0 or lower, and may also be 10.0 or lower.

[0299] Furthermore, when the compound represented by formula (2) is used to prepare a chloroform solution containing 0.01% by mass and the absorbance of the chloroform solution is measured using an active energy line containing a wavelength of 405 nm (h-rays), the absorbance is 0.1 or higher, exhibiting very excellent absorption relative to light at a wavelength of 405 nm (h-rays). Therefore, the compound suitably generates free radicals relative to light at a wavelength of 405 nm (h-rays). The absorbance is preferably 0.15 or higher. The upper limit is, for example, 5.0 or lower, and may also be 10.0 or lower.

[0300] In formula (2), each of R4 independently represents a substituent or phenyl group represented by formula (3). Preferably, one or more of R4 are substituents represented by formula (3).

[0301] In formula (3), each of R5 independently represents a hydrogen atom or a methyl group. Preferably, one or more of R5 are methyl groups, and more preferably all of them are methyl groups.

[0302] Examples of compounds represented by formula (2) include phosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Among these, phenylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide are preferred in terms of excellent light transmittance. These compounds can also be used alone or in appropriate mixtures of two or more.

[0303] Acylphosphine oxides exhibit excellent absorption relative to active energy lines containing wavelengths of 405 nm (h-rays). For example, bismaleimide compounds (A) that allow for free radical polymerization with transmittance of 5% or more at 405 nm (h-rays) can be suitably manufactured. Therefore, resin compositions, resin sheets, multilayer printed circuit boards using these compounds, and semiconductor devices can be suitably manufactured, particularly when used in multilayer printed circuit boards, exhibiting excellent photocurability, heat resistance, thermal stability, and insulation reliability in a balanced manner.

[0304] Regarding the content of photocuring initiator (C) in the resin composition, from the viewpoint of obtaining better heat resistance and thermal stability by fully photocuring the bismaleimide compound (A) and the resin or compound (B), it is preferably 0.1 to 10 parts by mass relative to a total of 100 parts by mass of the bismaleimide compound (A), the resin or compound (B) and the photocuring initiator (C), more preferably 1 to 8 parts by mass, and even more preferably 2 to 7 parts by mass.

[0305] [Filling material]

[0306] In the resin composition of this embodiment, a filler (D) (also referred to as component (D)) may be included to improve various properties such as coating properties and heat resistance. As filler (D), it is preferable to have insulating properties and not to impede the transmission of various active energy lines used in photocuring, and more preferably not to impede the transmission of active energy lines containing wavelengths of 365 nm (i-rays) and / or 405 nm (h-rays).

[0307] Examples of fillers (D) include: silica (e.g., natural silica, fused silica, synthetic silica, and hollow silica), aluminum compounds (e.g., borosilicate, 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 glass fibers, spherical glass, glass micropowder, E glass, T glass, and D glass), silicone powder, fluoropolymer fillers, urethane resin fillers, (meth)acrylic resin fillers, polyethylene fillers, styrene-butadiene rubber, and silicone rubber. These fillers (D) can also be used alone or in appropriate combinations of two or more.

[0308] Among these, silica, boehmite, barium sulfate, silicone powder, fluoropolymer filler, urethane resin filler, (meth)acrylic resin filler, polyethylene filler, styrene-butadiene rubber, and silicone rubber are preferred.

[0309] These fillers (D) can also be surface treated using silane coupling agents, etc., as described later.

[0310] From the viewpoint of improving the heat resistance of the cured material and obtaining good coating properties, silica is preferred, and fused silica is more preferred. Specific examples of silica include: SFP-130MC (trade name) manufactured by Denka Ltd., SC2050-MB (trade name), SC1050-MLE (trade name), YA010C-MFN (trade name), and YA050C-MJA (trade name) manufactured by Admatechs Ltd.

[0311] From the viewpoint of the ultraviolet light transmittance of the resin composition, the particle size of the filler (D) is generally 0.005 μm to 10 μm, preferably 0.01 μm to 1.0 μm.

[0312] In the resin composition of this embodiment, regarding the content of filler (D), from the viewpoint of improving the light transmittance and heat resistance of the cured resin composition, it is preferably set to 300 parts by mass or less, more preferably 200 parts by mass or less, and even more preferably 100 parts by mass or less, relative to a total of 100 parts by mass of bismaleimide compound (A), resin or compound (B), and photocuring initiator (C). The upper limit can be 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less. Furthermore, when filler (D) is included, from the viewpoint of obtaining the effect of improving various properties such as coating properties and heat resistance, the lower limit is generally 1 part by mass relative to a total of 100 parts by mass of bismaleimide compound (A), resin or compound (B), and photocuring initiator (C).

[0313] [Silane coupling agents and wetting and dispersing agents]

[0314] In the resin composition of this embodiment, in order to improve the dispersibility of the filler and the adhesion strength between the polymer and / or the resin and the filler, a silane coupling agent and / or a wetting and dispersing agent may be used.

[0315] As for these silane coupling agents, there is no limitation as long as they are silane coupling agents generally used for the surface treatment of inorganic materials. Specific 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-dimethylamino)-propyl]trimethoxysilane and other aminosilanes; γ-glycidyl etheroxypropyltrimethoxysilane, 3-glycidyl etheroxypropyltriethoxysilane, 3-glycidyl etheroxypropyldimethoxymethylsilane, 3-glycidyl etheroxypropyldiethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and [8-(glycidyloxy)-n-octyl]trimethoxysilane and other epoxysilanes; vinyltris(2-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trimethoxy... Vinylsilanes such as methyl(7-octen-1-yl)silane and trimethoxy(4-vinylphenyl)silane; methacryloylsilanes such as 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyldimethoxymethylsilane, and 3-methacryloyloxypropyldiethoxymethylsilane; (meth)acryloylsilanes such as γ-acryloyloxypropyltrimethoxysilane and 3-acryloyloxypropyltriethoxysilane; isocyanate silanes such as 3-isocyanate propyltrimethoxysilane and 3-isocyanate propyltriethoxysilane; tri-(trimethoxysilylpropyl)isocyanurate The silane coupling agents include isocyanurate silanes; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyldimethoxymethylsilane; ureosilanes such as 3-ureopropyltriethoxysilane; styrylsilanes such as p-styryltrimethoxysilane; cationic silanes such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride; anhydride systems such as [3-(trimethoxysilyl)propyl]succinic anhydride; phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, and p-tolyltrimethoxysilane; and arylsilanes such as trimethoxy(1-naphthyl)silane. These silane coupling agents can also be used alone or in appropriate combinations of two or more.

[0316] In the resin composition of this embodiment, the content of silane coupling agent is typically 0.1 to 10 parts by mass relative to a total of 100 parts by mass of maleimide compound (A), resin or compound (B) and photocuring initiator (C).

[0317] As a wetting and dispersing agent, there are no particular limitations as long as it is a dispersing stabilizer used in coating applications. Specific examples include wetting and dispersing agents such as DISPERBYK (registered trademark)-110, 111, 118, 180, 161, W996, W9010, and W903 manufactured by BYK Chemie Japan (stock). These wetting and dispersing agents can be used alone or in appropriate combinations of two or more.

[0318] In the resin composition of this embodiment, the content of wetting and dispersing agent is typically 0.1 to 10 parts by mass relative to a total of 100 parts by mass of maleimide compound (A), resin or compound (B) and photocuring initiator (C).

[0319] [Hardening Accelerator]

[0320] In the resin composition of this embodiment, a curing accelerator is preferably included to appropriately adjust the curing speed as needed. As a curing accelerator, compounds commonly used as curing accelerators, such as cyanate ester compounds, can be used. Examples of curing accelerators include: organometallic salts such as zinc octanoate, zinc naphthenate, cobalt naphthenate, copper naphthenate, acetylacetone iron, nickel octanoate, and manganese octanoate; phenolic compounds such as phenol, xylenol, cresol, resorcinol, catechol, octylphenol, and nonylphenol; alcohols such as 1-butanol and 2-ethylhexanol; imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole, and these imidazoles. Derivatives such as adducts of carboxylic acids or their anhydrides; amines such as dicyandiamine, benzyldimethylamine, and 4-methyl-N,N-dimethylbenzylamine; phosphorus compounds such as phosphine compounds, phosphine oxide compounds, phosphonium salt compounds, and diphosphine compounds; epoxy-imidazolium adduct compounds; peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, di-tert-butyl peroxide, diisopropyl peroxide, and di-2-ethylhexyl peroxide; and azo compounds such as 2,2'-azobisisobutyronitrile (hereinafter also known as "AIBN"). These curing accelerators can also be used alone or in appropriate combinations of two or more.

[0321] In the resin composition of this embodiment, the content of the curing accelerator is typically 0.1 to 20 parts by mass relative to a total of 100 parts by mass of the bismaleimide compound (A), the resin or compound (B), and the photocuring initiator (C).

[0322] [Organic solvents]

[0323] In the resin composition of this embodiment, an organic solvent may be included as needed. If an organic solvent is used, the viscosity of the resin composition during preparation can be adjusted. There are no particular limitations on the type of organic solvent, as long as it can dissolve part or all of the resin in the resin composition. Examples of organic solvents include: ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alicyclic ketones such as cyclopentanone and cyclohexanone; cellosol solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, methyl methoxypropionate, methyl hydroxyisobutyrate, and γ-butyrolactone; polar solvents such as amides such as dimethylacetamide and dimethylformamide; and non-polar solvents such as aromatic hydrocarbons such as toluene, xylene, and anisole.

[0324] These organic solvents can also be used alone or in appropriate combinations of two or more.

[0325] [Other ingredients]

[0326] In the resin composition of this embodiment, various polymeric compounds, such as thermosetting resins, thermoplastic resins, their oligomers, and elastomers, which are not listed herein, can also be used without impairing the characteristics of this embodiment; flame-retardant compounds not listed herein; additives, etc. These are not particularly limited for general users. For example, flame-retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine, compounds containing oxazine rings, phosphate esters of phosphorus compounds, aromatic condensed phosphate esters, halogenated condensed phosphate esters, etc. Additives include: ultraviolet absorbers, antioxidants, fluorescent whitening agents, photosensitizers, dyes, pigments, tackifiers, lubricants, defoamers, surface conditioners, gloss agents, polymerization inhibitors, thermosetting accelerators, etc. These components can also be used alone or in appropriate combinations of two or more.

[0327] In the resin composition of this embodiment, the contents of other components are typically 0.1 to 10 parts by mass relative to a total of 100 parts by mass of bismaleimide compound (A), resin or compound (B) and photocuring initiator (C).

[0328] [Method for manufacturing resin composition]

[0329] The resin composition of this embodiment is prepared by appropriately mixing a bismaleimide compound (A), a resin or compound (B), a photocuring initiator (C), a filler (D) as needed, other resins, other compounds, and additives. The resin composition can be suitably used as a varnish in the manufacture of the resin sheets of this embodiment described later. Furthermore, the organic solvent used in the preparation of the varnish is not particularly limited, and specific examples are as described above.

[0330] One method for manufacturing the resin composition is, for example, to sequentially add the above-mentioned components to a solvent and stir thoroughly. The resin composition exhibits excellent photocurability, and the cured product obtained from the resin composition demonstrates excellent heat resistance, thermal stability, and insulation reliability.

[0331] When manufacturing the resin composition, known treatments (stirring, mixing, kneading, etc.) for uniformly dissolving or dispersing the components can be performed as needed. Specifically, stirring and dispersing treatments using a stirring tank equipped with a mixer having appropriate stirring capacity can improve the dispersibility of the components in the resin composition. Stirring, mixing, and kneading treatments can be performed using, for example, stirring devices for dispersion purposes such as ultrasonic homogenizers, mixing devices for mixing purposes such as three-roll mills, ball mills, bead mills, and sand mills, and other known devices such as rotating or self-rotating mixing devices. In addition, organic solvents can be used as needed when preparing the resin composition. There are no particular limitations on the type of organic solvent, as long as it can dissolve the resin in the resin composition; specific examples are as described above.

[0332] The resin composition can be suitably used as a varnish when manufacturing the resin sheet of the embodiment described later. The varnish can be obtained by known methods. For example, the varnish can be obtained by adding 10 to 900 parts by mass of an organic solvent to 100 parts by mass of the components other than the organic solvent in the resin composition of this embodiment, and performing the known mixing treatment (stirring, kneading, etc.).

[0333] [use]

[0334] The resin composition is preferably used in applications requiring reliable insulation. Examples of applications include photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit boards (for laminates, multilayer printed circuit boards, etc.), solder resists, underfill materials, die bond materials, semiconductor sealants, hole-filling resins, and component embedding resins. Among these, the resin composition is suitable for use as an insulating layer in multilayer printed circuit boards or as a solder resist due to its excellent photocurability, heat resistance, and thermal stability.

[0335] [Hardened material]

[0336] The cured product is obtained by curing the resin composition of this embodiment. For example, the cured product can be obtained by melting or dissolving the resin composition in a solvent, flowing it into a mold, and then curing it under normal conditions using light. Regarding the wavelength range of the light, it is preferable to cure it in the range of 100 nm to 500 nm, which is where curing is most efficient by photopolymerization initiators or the like.

[0337] [Resin Sheets]

[0338] The resin sheet of this embodiment is a resin sheet with a support, and a resin layer disposed on one or both sides of the support, wherein the resin layer contains a resin composition. The resin sheet can be manufactured by coating the resin composition onto the support and drying it. The resin layer in the resin sheet has excellent heat resistance, thermal stability, and insulation reliability.

[0339] The support can be any known support, but a resin film is preferred. Examples of resin films include: polyimide films, polyamide films, polyester films, polyethylene terephthalate (PET) films, polybutylene terephthalate (PBT) films, polypropylene (PP) films, polyethylene (PE) films, polyethylene naphthalate (PET) films, polyvinyl alcohol (PVA) films, and triacetyl acetate (TAA) films. Among these, PET films are preferred.

[0340] To facilitate peeling from the resin layer, the resin film is preferably coated with a release agent. The thickness of the resin film is preferably in the range of 5 μm to 100 μm, more preferably in the range of 10 μm to 50 μm. If the thickness is less than 5 μm, the support is prone to breakage during support peeling before development; if the thickness exceeds 100 μm, the resolution tends to decrease when exposed from the support.

[0341] In addition, to reduce light scattering during exposure, the resin film is preferably a film with excellent transparency.

[0342] Furthermore, in the resin sheet of this embodiment, the resin layer can also be protected by a protective film.

[0343] By using a protective film to protect the resin layer, dust and other contaminants can be prevented from adhering to the resin layer surface, thus preventing damage. The protective film can be made of the same material as the resin film. The thickness of the protective film is preferably in the range of 1 μm to 50 μm, more preferably in the range of 5 μm to 40 μm. When the thickness is less than 1 μm, the operability of the protective film tends to decrease; if it exceeds 50 μm, its cost-effectiveness tends to deteriorate. Furthermore, the protective film preferably has a lower adhesion between the resin layer and the protective film compared to the adhesion between the resin layer and the support.

[0344] The method for manufacturing the resin sheet according to this embodiment can be exemplified by the following: coating the resin composition of this embodiment onto a support such as a PET film, removing the organic solvent by drying, thereby manufacturing the resin sheet.

[0345] Regarding the coating method, it can be carried out using known methods such as roller coaters, comma coaters, gravure coaters, die coaters, bar coaters, lip coaters, doctor blade coaters, and extrusion coaters. Drying can be carried out, for example, by heating in a dryer at 60°C to 200°C for 1 to 60 minutes.

[0346] Regarding the amount of residual organic solvent in the resin layer, from the viewpoint of preventing the diffusion of organic solvent in subsequent processes, it is preferably set to 5% by mass or less relative to the total mass of the resin layer. From the viewpoint of improving operability, the thickness of the resin layer is preferably set to 1 μm to 50 μm.

[0347] Resin sheets are preferably used for manufacturing insulating layers for multilayer printed circuit boards.

[0348] Multilayer printed wiring board

[0349] The multilayer printed circuit board of this embodiment has an insulating layer and a conductor layer formed on one or both sides of the insulating layer, and the insulating layer comprises a resin composition. For example, the insulating layer can also be obtained by overlapping and curing one or more resin sheets. The number of layers of the insulating layer and the conductor layer is not particularly limited, and the number of layers 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, such as copper and aluminum foil. As copper foil, rolled copper foil and electrolytic copper foil are examples. The thickness of the conductor layer is usually 1 μm to 100 μm. Specifically, it can be manufactured by the following method.

[0350] (Lamination process)

[0351] In the lamination process, a vacuum laminator is used to laminate the resin layer of a resin sheet onto one or both sides of a circuit board. Examples of circuit boards include: glass epoxy boards, metal substrates, ceramic substrates, silicon substrates, semiconductor sealing resin substrates, polyester substrates, polyimide substrates, bismaleimide triazine (BT) resin substrates, and thermosetting polyphenylene ether substrates. Furthermore, a circuit board refers to a substrate on one or both sides of which a patterned conductor layer (circuit) is formed. Additionally, in multilayer printed circuit boards (PCBs) formed by alternating layers of conductors and insulating layers, the outermost layer of the PCB, on one or both sides, is also included within the category of circuit boards. Furthermore, the insulating layer laminated on the multilayer printed circuit board can be an insulating layer obtained by overlapping one or more resin sheets of this embodiment and then curing them, or it can be an insulating layer obtained by overlapping one or more known resin sheets different from the resin sheets of this embodiment. Furthermore, the method of overlapping the resin sheets of this embodiment with known resin sheets different from the resin sheets of this embodiment is not particularly limited. The surface of the conductor layer can also be pre-roughened by blackening treatment and / or copper etching. In the lamination process, if the resin sheet has a protective film, after peeling off the protective film, the resin sheet and the circuit board are preheated as needed, and the resin layer of the resin sheet is pressed onto the circuit board while being pressurized and heated. In this embodiment, a method of laminating the resin layer of the resin sheet onto the circuit board under reduced pressure using vacuum lamination can be suitably used.

[0352] Regarding the conditions for the lamination process, for example, it is preferable to set the pressing temperature (lamination temperature) to 50℃~140℃ and the pressing pressure to 1kgf / cm. 2 ~15kgf / cm 2 Lamination is performed under reduced pressure, with the pressing time set to 5 to 300 seconds and the air pressure set to below 20 mmHg. The lamination process can be batch or continuous using rollers. Vacuum lamination can be performed using commercially available vacuum laminators. Examples of commercially available vacuum laminators include the 2-stage build-up laminator (trade name) manufactured by Nikko Materials Co., Ltd.

[0353] (Exposure process)

[0354] In the exposure process, after a resin layer is deposited on the circuit board through a lamination process, an active energy line, which serves as a light source, is irradiated onto a designated portion of the resin layer to harden the resin layer in the irradiated portion.

[0355] Irradiation can be achieved through a mask pattern or by direct irradiation. Examples of active energy lines include ultraviolet light, visible light, electron beams, and X-rays. The wavelength of an active energy line is typically in the range of 200 nm to 600 nm. When using ultraviolet light, the irradiation dose is approximately 10 mJ / cm². 2 ~1000mJ / cm 2 Furthermore, when manufacturing printed wiring boards with high-density and high-precision wiring patterns using a stepper exposure method, it is preferable to use active energy lines containing a wavelength of 365 nm (i-rays) as the active energy lines. When using active energy lines containing a wavelength of 365 nm (i-rays), the irradiation dose is approximately 10 mJ / cm². 2 ~10,000mJ / cm 2 When manufacturing printed wiring boards with high-density and high-precision wiring patterns using the direct-draw exposure method, active energy lines containing wavelengths of 405 nm (h-rays) are preferably used as the active energy lines. When using active energy lines containing wavelengths of 405 nm (h-rays), the irradiation dose is approximately 10 mJ / cm². 2 ~10,000mJ / cm 2 .

[0356] Exposure methods using mask patterns include contact exposure, where the mask pattern is in close contact with the multilayer printed circuit board, and non-contact exposure, where the mask pattern is not in close contact and parallel light is used for exposure; either method can be used. Additionally, if a support is present on the resin layer, exposure can be performed from the support or after the support has been peeled off.

[0357] (Developing process)

[0358] In this embodiment, a developing step may also be included if necessary.

[0359] That is, when there is no support on the resin layer, after the exposure process, the uncured portion (unexposed portion) is removed by wet development, thereby forming the pattern of the insulating layer. Alternatively, when there is a support on the resin layer, after the exposure process, the support is removed, and the uncured portion (unexposed portion) is removed by wet development, thereby forming the pattern of the insulating layer.

[0360] In the case of wet development, there are no particular limitations on the developer used, as long as it selectively dissolves the unexposed portions. For example, organic solvents such as cyclohexanone, cyclopentanone, and γ-butyrolactone can be used; alkaline 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 also be used alone or in appropriate mixtures of two or more of these developers.

[0361] In addition, known methods such as immersion, coating, spraying, agitation immersion, brushing, and scraping can be used as development methods. These development methods can also be used concurrently in pattern formation as needed. Furthermore, high-pressure spraying is suitable as it further improves resolution. The spray pressure when using a spraying method is preferably 0.02 MPa to 0.5 MPa.

[0362] (Post-baking process)

[0363] After the exposure or development process, a post-baking process is performed to form an insulating layer (hardened material). Examples of post-baking processes include ultraviolet irradiation using a high-pressure mercury lamp and heating in a cleanroom oven; these processes can also be combined. When irradiating with ultraviolet light, the irradiation dose can be adjusted as needed, for example, to 50 mJ / cm². 2 ~10,000mJ / cm 2 Irradiation is performed at approximately the same intensity. The heating conditions can be selected as needed, but are preferably within the range of 150°C to 220°C for 20 to 180 minutes, and more preferably within the range of 160°C to 200°C for 30 to 150 minutes.

[0364] (Conductor layer formation process)

[0365] After the insulating layer (hardened material) is formed, a conductor layer is formed on the surface of the insulating layer by dry plating. Known methods such as vapor deposition, sputtering, and ion plating can be used for dry plating. Vacuum deposition, for example, involves placing a multilayer printed circuit board in a vacuum chamber and heating and evaporating the metal, thereby forming a metal film on the insulating layer. Sputtering, for example, also involves placing a multilayer printed circuit board in a vacuum chamber, introducing an inert gas such as argon, and applying a DC voltage, causing the ionized inert gas to collide with the target metal, and using the knocked-out metal to form a metal film on the insulating layer.

[0366] Subsequently, a conductor layer is formed by electroless plating or electrolytic plating. Methods for subsequent pattern formation include, for example, subtractive methods and semi-additive methods.

[0367] [Sealing materials]

[0368] The sealing material of this embodiment comprises the resin composition of this embodiment. As a method for manufacturing the sealing material, generally known methods may be appropriately applied, and there are no particular limitations. For example, the sealing material can be manufactured by mixing the resin composition of this embodiment with various known additives or solvents generally used in sealing material applications using a known mixer. Furthermore, during mixing, the methods for adding the maleimide compound, various additives, and solvents of this embodiment may be appropriately applied, and there are no particular limitations.

[0369] [Fiber-reinforced composite materials]

[0370] The fiber-reinforced composite material of this embodiment includes the resin composition of this embodiment and reinforcing fibers. Commonly known reinforcing fibers can be used as the reinforcing fibers, and there are no particular limitations. Examples include: glass fibers such as E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, and spherical glass; carbon fibers; polyaramid fibers; boron fibers; poly-p-phenylene benzobisoxazole (PBO) fibers; high-strength polyethylene fibers; alumina fibers; and silicon carbide fibers. There are no particular limitations on the form and arrangement of the reinforcing fibers, and they can be appropriately selected from fabrics, non-woven fabrics, felts, knitted fabrics, ribbons, unidirectional yarns, rovings, and chopped strands. Furthermore, as the form of the reinforcing fibers, preforms (those formed by layering fabric base fabrics containing reinforcing fibers or by sewing them together with thread, or fiber structures such as three-dimensional fabrics or braids) can also be used.

[0371] As a method for manufacturing these fiber-reinforced composite materials, generally known methods can be appropriately applied without particular limitation. Examples include liquid composite molding, resin film infusion, filament winding, hand lay-up, and pultrusion. Among these, resin transfer molding, as one of the liquid composite molding methods, allows raw materials other than preforms such as metal sheets, foam cores, and honeycomb cores to be pre-set in the molding die, thus enabling it to handle various applications. Therefore, it is preferably used for situations where relatively complex composite materials need to be mass-produced in a short time.

[0372] [Adhesive]

[0373] The adhesive of this embodiment comprises the resin composition of this embodiment. As for the method of manufacturing the adhesive, generally known methods can be appropriately applied, and there is no particular limitation. For example, the adhesive can be manufactured by mixing the resin composition of this embodiment with various known additives or solvents generally used in adhesive applications using a known mixer. Furthermore, during mixing, the method of adding the maleimide compound, various additives, and solvents of this embodiment can be appropriately applied, and there is no particular limitation.

[0374] [Semiconductor Devices]

[0375] The semiconductor device of this embodiment comprises a resin composition. 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 a portion in the multilayer printed circuit board that transmits electrical signals; this portion can be a surface or an embedded portion. Furthermore, the semiconductor chip is not particularly limited as long as it is an electrical circuit element made of semiconductor material.

[0376] As long as the semiconductor chip functions effectively, there are no particular limitations on the mounting method of the semiconductor chip during the manufacture of the semiconductor device. Specifically, examples include wire bonding mounting method, flip chip mounting method, mounting method using bumpless build-up layer (BBUL), mounting method using anisotropic conductive film (ACF), and mounting method using non-conductive film (NCF), etc.

[0377] Alternatively, a semiconductor device 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 shape of a wafer or a panel. After forming the insulating layer, it can be manufactured using the same method as a multilayer printed circuit board.

[0378] Example

[0379] The present embodiment will be described in more detail below using examples and comparative examples. The present embodiment is not limited in any way by the following examples.

[0380] The conditions for determining molecular weight are as follows.

[0381] Model: GPC Tosoh HLC-8220GPC

[0382] Column: Super HZM-N

[0383] Eluent: Tetrahydrofuran (THF); 0.35 ml / min, 40 °C

[0384] Detector: Differential refractometer (RI)

[0385] Molecular weight standard: Polystyrene

[0386] <Synthesis of bismaleimide compounds>

[0387] [Synthesis example 1]

[0388] In a 500 ml round-bottom flask equipped with a fluoropolymer-coated stir bar, 100 g of toluene and 33 g of N-methylpyrrolidone were added. Next, 80.2 g (0.16 mol) of PRIAMINE 1075 (manufactured by Croda Japan) was added, followed by the slow addition of 14.4 g (0.16 mol) of anhydrous methanesulfonic acid to form a salt. The mixture was stirred for approximately 10 minutes to combine, and then 22.5 g (0.08 mol) of 4-(2,5-dioxatetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride was slowly added to the stirred mixture. A Dean-Stark trap and condenser were installed in the flask. The mixture was heated under reflux for 6 hours to form an amine-terminated diimide. At this point, the theoretical amount of water produced from the condensation was obtained. The reaction mixture was cooled to below room temperature, and 17.6 g (0.19 mol) of maleic anhydride was added to the flask. The mixture was further refluxed for 8 hours to obtain the desired amount of water produced. After cooling to room temperature, 200 mL of toluene was added to the flask. The diluted organic layer was then washed with water (100 mL × three times) to remove salts and unreacted starting materials. The solvent was then removed under vacuum to obtain 104 g (93% yield, Mw = 3,700) of a dark amber liquid bismaleimide compound (A-1).

[0389] [Comparative Synthesis Example 1]

[0390] In a 500 ml round-bottom flask equipped with a fluoropolymer-coated stir bar, 110 g of toluene and 36 g of N-methylpyrrolidone were added. Next, 90.5 g (0.17 mol) of PRIAMINE 1075 (manufactured by Croda Japan) was added, followed by the slow addition of 16.3 g (0.17 mol) of anhydrous methanesulfonic acid to form a salt. The mixture was stirred for approximately 10 minutes to combine, and then 18.9 g (0.08 mol) of 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride was slowly added to the stirred mixture. A Dean-Stark trap and condenser were installed in the flask. The mixture was heated under reflux for 6 hours to form an amine-terminated diimide. At this point, the theoretical amount of water produced from the condensation was obtained. The reaction mixture was cooled to below room temperature, and 19.9 g (0.20 mol) of maleic anhydride was added to the flask. The mixture was refluxed for another 8 hours to obtain the desired amount of water. After cooling to room temperature, 200 ml of toluene was added to the flask. The diluted organic layer was then washed with water (100 ml three times) to remove salts and unreacted starting materials. The solvent was then removed under vacuum to obtain 110 g of an amber-colored, waxy bismaleimide compound (yield 93%, Mw = 3,000) (A'-3).

[0391] <Synthesis of Cyanate Compounds>

[0392] [Synthesis example 2]

[0393] Dissolve 0.47 mol (OH group conversion) of α-naphthol aralkyl phenolic resin (including SN495V (trade name) manufactured by Nippon Steel Chemical Co., Ltd., with an OH group equivalent of 236 g / eq. and an α-naphthol aralkyl repeating unit n of 1 to 5) in 500 mL of chloroform, and add 0.7 mol of triethylamine (solution 1) to the solution.

[0394] While maintaining the temperature at -10℃, solution 1 was added dropwise to 300g of a 0.93mol cyanogen chloride chloroform solution over a period of 1.5 hours. After the addition was completed, the mixture was stirred for 30 minutes.

[0395] Then, a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was added dropwise to the reactor, and the reaction was stirred for 30 minutes to complete the reaction. After separating the by-product triethylamine hydrochloride from the reaction solution by filtration, the filtrate was washed with 500 mL of 0.1 N hydrochloric acid, and then washed four times with 500 mL of water. After drying with sodium sulfate, it was evaporated at 75 °C, and then degassed under reduced pressure at 90 °C to obtain a brown solid α-naphthol aralkyl cyanate resin (containing SNCN, formula (28), n 18(B-2) is an α-naphthol aralkyl cyanate resin with a composition of 1–4. The obtained α-naphthol aralkyl cyanate resin was analyzed using infrared absorption spectroscopy, and the results confirmed a concentration up to 2264 cm⁻¹. -1 Absorption of nearby cyanate groups.

[0396] [Chemistry 32]

[0397]

[0398] <Synthesis of Compounds with Ethylene Unsaturated Groups>

[0399] [Synthesis example 3]

[0400] 225g of XD-1000 (manufactured by Nippon Kayaku Co., Ltd., softening point 74.8℃, epoxy equivalent 255g / eq.), 72.1g of acrylic acid, 3g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent to make the solid content 80% were added to a flask equipped with a thermometer, cooling pipe, and stirrer. The mixture was reacted at 100℃ for 24 hours to obtain an epoxy carboxylic acid ester compound solution as a reaction intermediate.

[0401] Subsequently, 140 g of 1,2,3,6-tetrahydrophthalic anhydride (THPA) (trade name: Rikacid TH, manufactured by Shin Nippon Rikka Co., Ltd.) as a polyacid anhydride and propylene glycol monomethyl ether monoacetate as a solvent to achieve a solids content of 65% were added to the obtained reactive epoxy carboxylic acid ester compound solution. The reaction was carried out at 100°C for 6 hours to obtain a compound (B-6) with an vinyl unsaturated group. The solids acid value (AV: mgKOH / g) of the obtained compound (B-6) with an vinyl unsaturated group was 110.

[0402] The materials used in this embodiment are shown.

[0403] <(A) Bismaleimide Compound>

[0404] (A-1) A bismaleimide resin containing the structural unit represented by general formula (1) and maleimide groups at both ends of the molecular chain.

[0405] The bismaleimide resin A-1 of Synthetic Example 1 (the compound represented by formula (3) below, which is a high-viscosity liquid at 25°C)

[0406] [Chemistry 33]

[0407]

[0408] In equation (5), a represents an integer from 1 to 10. In terms of obtaining a more suitable viscosity and being able to better control the increase in varnish viscosity, a is preferably an integer from 1 to 6.

[0409] <(A') Bismaleimide compounds that do not satisfy general formula (1)>

[0410] (A'-1)BMI-2300 (polyphenylmethane maleimide, a compound represented by the following formula (29), manufactured by Yamato Chemical Co., Ltd., solid at 25°C)

[0411] (A'-2)BMI-3000 (the compound represented by formula (14) below, manufactured by DESIGNERMOLECULES Inc., is a solid at 25°C)

[0412] (A'-3) Comparative Synthesis Example 1 (the compound represented by formula (30) below is liquid at 25°C)

[0413] [Chemistry 34]

[0414]

[0415] In equation (29), n 19 The integer represents an integer greater than or equal to 1, preferably an integer representing 1 to 10, and more preferably an integer representing 1 to 5.

[0416] [Chemistry 35]

[0417]

[0418] In the formula (14), n9 represents an integer greater than or equal to 1, and is preferably an integer from 1 to 10.

[0419] [Chemistry 36]

[0420]

[0421] In equation (30), n 20 It represents an integer greater than or equal to 1, preferably an integer from 1 to 6.

[0422] <(B) Resin or compound>

[0423] (B-1) MIR-5000 as a bismaleimide resin (the compound represented by formula (31) below, manufactured by Nippon Kayaku Co., Ltd., is solid at 25°C)

[0424] (B-2) The α-naphthol aralkyl cyanate resin (SNCN, cyanate resin) obtained in Synthesis Example 2

[0425] (B-3) Pd-type benzoxazine compounds (manufactured by Shikoku Chemical Industry Co., Ltd., 3,3'-(methylene-1,4-diphenylene)bis(3,4-dihydro-2H-1,3-benzoxazine), benzoxazine compounds)

[0426] (B-4) Biphenylaryl type epoxy resin (NC-3000H (trade name) manufactured by Nippon Kayaku Co., Ltd., epoxy resin)

[0427] (B-5) Carbodiimide compound (Carbodilite B-01 (trade name) manufactured by Nisshinbo Chemical Co., Ltd.)

[0428] (B-6) The acid-modified dicyclopentadiene phenolic epoxy acrylate compound obtained in Synthesis Example 3 (KAYARAD (registered trademark) ZXR-1889H (trade name) manufactured by Nippon Kayaku Co., Ltd., a compound having an ethylene unsaturated group)

[0429] [Chemistry 37]

[0430]

[0431] In the above equation (31), n 21 Represents integers from 1 to 10.

[0432] <(C) Photopolymerization Initiator>

[0433] (C-1) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Omnirad 819 (trade name) manufactured by IGM Resins, Inc.)

[0434] (C-2)2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (Omnirad 369 (trade name) manufactured by IGM Resins)

[0435] (C-3)2-Methyl-1-[4-(Methylthio)phenyl]-2-morpholinylpropane-1-one (Omnirad 907, manufactured by IGM Resins, Inc., a registered trademark)

[0436] <Evaluation of Resin Compositions>

[0437] The resin compositions of Examples 1 to 8 and Comparative Examples 1 to 3 were evaluated as shown below. The results are summarized in Table 1.

[0438] [Sensitivity]

[0439] The photosensitive resin compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 3 were applied onto a copper-clad laminate (Sumitomo Bakelite (Group) Co., Ltd. ELC4762) using an applicator, and heated at 80°C for 30 minutes to form a coating with a thickness of 20 μm. Subsequently, an ultra-high pressure mercury lamp (USH-500BY1, trade name) manufactured by Ushio (Group) Co., Ltd.) capable of irradiating active energy lines containing wavelengths of 405 nm (h-rays) was used, and exposure was performed using a projection exposure machine with an exposure level of 7 levels of residual exposure after development using a 21-step exposure meter.

[0440] The sensitivity was evaluated according to the following criteria, and the evaluation results are shown in Table 1.

[0441] [Evaluation Criteria]

[0442] ◎: Exposure less than 500mJ / cm 2 And still retains level 7

[0443] ○: Exposure is 500mJ / cm 2 Above and below 1000 mJ / cm 2 And still retains level 7

[0444] △: Exposure is 1000mJ / cm 2 Above and below 3000 mJ / cm 2 And still retains level 7

[0445] ×: Even if the exposure is 3000mJ / cm 2 The above has not hardened.

[0446] [Tension elastic modulus]

[0447] First, the photosensitive resin compositions obtained in each example and comparative example were coated onto an ultra-low roughness electrolytic copper foil (CF-T4X-SV (trade name), manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) with a thickness of 12 μm using a coating applicator. The foil was then dried at 80°C for 30 minutes to form a film-like photosensitive resin composition on the copper foil. The coating thickness of the photosensitive resin composition was adjusted so that the film thickness of the dried film-like photosensitive resin composition was 20 μm. A light source capable of irradiating active energy lines containing wavelengths of 405 nm (h-rays) (Ushio (stock) 500W MultiLight (trade name) ultra-high pressure mercury lamp) was used with an exposure dose of 3000 mJ / cm². 2 The film-like photosensitive resin composition is exposed to light, then heated at 180°C for 60 minutes to harden it, and finally the copper foil is removed by etching to obtain a hardened film.

[0448] Subsequently, the obtained hardened film was cut into 6cm×5mm test pieces, and the tensile modulus (MPa) and elongation at break (%) were determined by a tensile testing machine (trade name "RTG-1201" manufactured by A&D Corporation) at 25°C and a speed of 5mm / min.

[0449] [Dielectric Properties]

[0450] The copper foil in the copper foil laminate was removed by etching. After drying at 130°C for 30 minutes, the hardened resin film was cut to prepare a 10cm × 5cm test piece. The relative permittivity and dielectric loss tangent at 10GHz were measured on the obtained test piece using a cavity resonator method dielectric constant measuring device (manufactured by AET Corporation). After the measurement, the test piece was immersed in water to absorb water for 24 hours, then removed from the water and wiped dry. After being placed in an environment of 25°C and 30% for one day, the relative permittivity and dielectric loss tangent at 10GHz were measured again.

[0451] Glass transition temperature

[0452] The copper foil on both sides of the copper foil laminate was removed by etching. After drying at 130°C for 30 minutes, the hardened resin film was cut to prepare a 5cm × 5mm test piece. The obtained test piece was tested using a dynamic viscoelasticity testing machine (dynamic mechanical analyzer (DMA): trade name "RSA-G2", manufactured by TA Instruments), and the temperature at which tanδ reaches its maximum value was determined as the glass transition temperature.

[0453] Water absorption rate

[0454] The copper foil on both sides of the copper foil laminate was removed by etching. After drying at 130°C for 30 minutes, the hardened resin film was cut to prepare a 10cm × 5cm test piece. The obtained test piece was immersed in water to absorb water for 24 hours. After being removed from the water and wiped dry, the weight gain rate of the test piece was taken as the water absorption rate.

[0455] [High Accelerated Stress Test (HAST) Tolerance]

[0456] Each composition was coated to a thickness of 25 μm onto an ESPANEX M series substrate (manufactured by Nippon Steel Chemicals: base imide thickness 25 μm, Cu thickness 18 μm) with a comb pattern of L / S = 100 μm / 100 μm, using a screen printing method. The coating was dried for 60 minutes using a hot air dryer at 80°C. Subsequently, AFREX (Grade: 25N NT) (manufactured by AGC Corporation) was coated onto the resin surface, and the substrate was heated at 220°C for 2 hours to obtain a test substrate for HAST evaluation. The electrode portions of the obtained substrate were wired together using solder, and the substrate was placed in an environment of 130°C and 85% RH with a voltage of 100V applied, and the resistance was measured until it reached 1 × 10⁻⁶. 8 The time below Ω.

[0457] ○··300 hours or more

[0458] △··30 hours~300 hours

[0459] ×·· Less than 30 hours

[0460] [Table 1]

[0461]

[0462] *1: Even at 3000mJ / cm 2 No hardening film was obtained even under exposure.

[0463] *2: No determination was made because a hardened film could not be obtained.

[0464] As can be seen from Table 1, according to this embodiment, when exposed to any light source containing active energy lines with wavelengths from 200 nm to 600 nm, photocuring can be performed effectively by light exposure.

[0465] Furthermore, it can be confirmed that the resin compositions of Examples 1 to 8, in terms of the characteristics of their cured products, have low dielectric properties and little change in dielectric properties after water absorption. They are characterized by low elasticity, high elongation, high heat resistance, and low water absorption, and have excellent insulation reliability.

[0466] Industrial availability

[0467] The resin composition of this embodiment has excellent photocurability and alkali developability, so it can be effectively used in industry. For example, it can be used for photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit boards (for laminates, multilayer printed circuit boards, etc.), solder resists, underfill materials, die bond materials, semiconductor sealants, hole-filling resins, component embedding resins, fiber-reinforced composite materials, etc.

Claims

1. A resin composition comprising: Bismaleimide compound (A) comprises the structural unit represented by the following formula (1), and contains maleimide groups at both ends of the molecular chain; The resin or compound (B) is selected from at least one of the group consisting of bismaleimide compounds, cyanate compounds, benzoxazine compounds, epoxy resins, and carbodiimide compounds represented by formula (31); and The photocuring initiator (C) represented by the following formula (2) In formula (1), R1 represents a straight-chain or branched alkylene group having 1 to 16 carbon atoms, or a straight-chain or branched alkenyl 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 alkenyl group having 2 to 16 carbon atoms; R3 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; R4 independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms; n1 independently represents an integer from 1 to 4; n2 independently represents an integer from 1 to 4. In formula (31), n 21 represents an integer of 1 to 10, In formula (2), R4 independently represents the substituent or phenyl group represented by formula (3) below; In formula (3), -* represents a bond, and R5 independently represents a hydrogen atom or a methyl group. in, Relative to a total of 100 parts by mass of the bismaleimide compound (A), the resin or compound (B), and the photocuring initiator (C), the content of the bismaleimide compound (A) is 13 to 85 parts by mass, the content of the resin or compound (B) is 0.5 to 10 parts by mass, and the content of the photocuring initiator (C) is 2 to 5 parts by mass.

2. The resin composition according to claim 1, further comprising a filler.

3. A cured compound comprising the resin composition as described in claim 1 or 2.

4. A resin sheet, comprising: Support; and A resin layer is disposed on one or both sides of the support. The resin layer comprises the resin composition as described in claim 1 or 2.

5. The resin sheet according to claim 4, wherein, The thickness of the resin layer is 1 μm to 50 μm.

6. A prepreg comprising: Substrate; and The resin composition as described in claim 1 or 2 is impregnated or coated onto the substrate.

7. A metal foil-coated laminate, comprising: The layer comprises at least one selected from the group consisting of the resin sheet as described in claim 5 and the prepreg as described in claim 6; and A metal foil disposed on one or both sides of the layer, the layer comprising a cured form of the resin composition.

8. A multilayer printed circuit board, comprising: Insulating layer; and A conductor layer is formed on one or both sides of the insulating layer. The insulating layer comprises the resin composition as described in claim 1 or 2.

9. A sealing material comprising the resin composition as described in claim 1 or 2.

10. A fiber-reinforced composite material comprising the resin composition as described in claim 1 or 2, and reinforcing fibers.

11. An adhesive comprising the resin composition as described in claim 1 or 2.

12. A semiconductor device having the resin composition as described in claim 1 or 2.

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