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

Abstract

The present invention provides a resin composition, a hardened product, a resin sheet, a prepreg, a laminate, a wiring board, a material, an adhesive, and a semiconductor device, which can achieve low dielectric properties, high heat resistance, low elastic modulus, and low water absorption, and have good adhesion to a substrate in terms of the properties of the hardened product. A thermally curable resin composition, comprising: a bismaleimide compound (A) comprising a structural unit represented by the following formula (1) and a maleimide group at both ends of a molecular chain; a thermally curable resin or compound (B); a polymerization initiator (C); and / or a hardening accelerator (D).

Description

Technical Field

[0001] This invention relates to a thermosetting resin composition. More specifically, this invention relates to a thermosetting resin composition that can be used as a sealing material for laminates such as printed circuit boards and electronic components such as semiconductor devices. 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] Previously, cyanate ester resins were widely known as thermosetting resins with excellent heat resistance, low dielectric constant, and low dielectric loss. For example, Patent Document 1 discloses a phenolic varnish-type cyanate ester resin as a resin with excellent heat resistance and storage stability. However, while the cured product obtained using the phenolic varnish-type cyanate ester resin described in Patent Document 1 has excellent resistance to thermal expansion, it has a high water absorption rate and deterioration in dielectric properties.

[0004] Patent Document 2 discloses a resin composition comprising polyamide-imide resin, diphenyl ethane bismaleimide, and allylphenol resin, as a resin composition that can produce a cured product with excellent mechanical strength, adhesion strength to the substrate, film-forming properties, heat resistance, and pressure resistance. However, the resin composition described in Patent Document 2 uses a thermoplastic high-molecular-weight polyamide-imide resin, resulting in poor low-temperature melting properties. Furthermore, the polyamide-imide resin has poor compatibility with maleimide compounds. Therefore, phase separation sometimes occurs during film curing, making it difficult to obtain a uniform coating. Additionally, because a high-boiling-point solvent such as N-methyl pyrrolidone (NMP) is used, residual solvent may remain in stage B.

[0005] Furthermore, Patent Document 3 discloses an epoxy resin composition for semiconductor sealing, comprising an epoxy resin, an imidazole compound, and a maleimide compound, as a resin composition for forming a cured product with good adhesion and excellent moisture resistance. However, the resin composition described in Patent Document 3 sometimes exhibits cracking or other defects in the cured product under stress from large temperature changes, such as temperature cycling tests, and its heat resistance may not be sufficient.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 11-124433

[0009] Patent Document 2: Japanese Patent Application Publication No. 2004-168894

[0010] Patent Document 3: Japanese Patent Publication No. 2014-521754 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] The present invention was made in view of the problems of the prior art, and its object is to provide a thermosetting resin composition, which is a low viscosity thermosetting resin composition, and in terms of the properties of the cured product, it can achieve low dielectric properties, high heat resistance, low elastic modulus and low water absorption, and has good adhesion to the substrate.

[0013] Technical means to solve the problem

[0014] The inventors and others have conducted research to solve the above-mentioned problems, and have found that the problems can be solved by the following invention.

[0015] That is, the present invention provides the following invention.

[0016] [1] A thermosetting resin composition comprising: a bismaleimide compound (A) comprising a structural unit represented by the following formula (1) and having maleimide groups at both ends of the molecular chain; a thermosetting resin or compound other than the bismaleimide compound (A) (B); a polymerization initiator (C) and / or a curing accelerator (D).

[0017] [Chemistry 1]

[0018]

[0019] (In equation (1), Q) 1 This refers to 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. Q 2 This refers to 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. Q 3 Each can independently represent 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.

[0020] Q 4Each of these can independently represent 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. 1 Each represents an integer from 1 to 4 independently. m 1 Each of them independently represents an integer from 1 to 4.

[0021] [2] The thermosetting resin composition according to [1], wherein the thermosetting resin or compound (B) further comprises one or more of the group consisting of maleimide compounds other than the bismaleimide compounds according to [1], cyanate ester compounds, phenolic resins, epoxy resins, oxadiene resins, benzoxazine compounds, carbodiimide compounds, and compounds having an ethylene unsaturated group.

[0022] [3] The thermosetting resin composition according to [1] or [2], wherein the polymerization initiator (C) comprises a thermal free radical polymerization initiator.

[0023] [4] The thermosetting resin composition according to any one of [1] to [3], wherein the curing accelerator (D) comprises at least one compound selected from the group consisting of phosphine compounds, compounds having phosphonium salts and imidazole compounds.

[0024] [5] The thermosetting resin composition according to any one of [1] to [4], wherein, when the total amount of the bismaleimide compound (A) and the thermosetting resin or compound (B) is set to 100 parts by mass, the content of the bismaleimide compound (A) is 1 part by mass to 99 parts by mass.

[0025] [6] The thermosetting resin composition according to any one of [1] to [5], wherein it further comprises a filler.

[0026] [7] A hardener comprising a thermosetting resin composition according to any one of [1] to [6].

[0027] [8] A resin sheet comprising: a support; and a resin layer disposed on one or both sides of the support, the resin layer comprising a thermosetting resin composition according to any one of [1] to [6].

[0028] [9] A prepreg comprising: a substrate; and a thermosetting resin composition according to any one of [1] to [6], impregnated or coated on the substrate.

[0029]

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

[0030]

[11] A multilayer printed wiring board having: an insulating layer; and a conductor layer formed on one or both sides of the insulating layer, the insulating layer comprising a thermosetting resin composition according to any one of [1] to [6].

[0031]

[12] A sealing material comprising a thermosetting resin composition according to any one of [1] to [6].

[0032]

[13] A fiber-reinforced composite material comprising a thermosetting resin composition according to any one of [1] to [6], and reinforcing fibers.

[0033]

[14] An adhesive comprising a thermosetting resin composition according to any one of [1] to [6].

[0034]

[15] A semiconductor device having a thermosetting resin composition according to any one of [1] to [6].

[0035] The effects of the invention

[0036] According to the present invention, a thermosetting resin composition is provided, which is a low-viscosity thermosetting resin composition, and in terms of the properties of the cured product, it can achieve low dielectric properties, high heat resistance, low elastic modulus, and low water absorption. By using the thermosetting resin composition of the present invention, which has the above-mentioned effects, as a sealing material, the properties of laminates such as printed circuit boards and electronic components such as semiconductor devices can be significantly improved. Detailed Implementation

[0037] The present invention will now be described in detail according to its suitable embodiments.

[0038] [Bismaleimide compound (A)]

[0039] The resin composition of this embodiment contains the bismaleimide compound (A) of this embodiment (also referred to as component (A)), which contains the structural unit represented by formula (1) and contains maleimide groups at both ends of the molecular chain.

[0040] [Chemistry 2]

[0041]

[0042] (In equation (1), Q)1 This refers to 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. Q 2 This refers to 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. Q 3 Each can independently represent 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. Q 4 Each of these can independently represent 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. 1 Each represents an integer from 1 to 4 independently. m 1 Each of them independently represents an integer from 1 to 4.

[0043] The bismaleimide compound (A) of this embodiment exhibits excellent permeability and heat resistance due to its inclusion of the structural unit represented by formula (1). Furthermore, because it possesses a maleimide group with free radical polymerization reactivity at the end, during the curing process, the maleimide group readily reacts with the polymerizable functional groups in the thermosetting resin or compound (B) described later, namely citrileimide, vinyl, maleimide, (meth)acryloyl, and allyl groups. Therefore, the crosslinking density of the obtained cured product is increased, but because the main skeleton is a soft skeleton, the adhesion is excellent, and consequently, the heat resistance (glass transition temperature) is improved. Moreover, the resin composition of this embodiment, by including the thermosetting resin or compound (B), the curing accelerator (D), and the bismaleimide compound (A) of this embodiment, as described above, exhibits low dielectric properties and excellent adhesion to the substrate.

[0044] Thus, the resin composition of this embodiment, due to its excellent balance of dielectric properties, adhesion, tack, permeability, and heat resistance, is suitable for use as an underfill material, and is even more suitable for use as a pre-applied underfill material. Furthermore, for example, in resins containing epoxy groups, water-absorbing polar groups are generated after the reaction, but in the case of the bismaleimide compound (A) of this embodiment, water-absorbing polar groups are not generated. Therefore, a cured material with low water absorption (wetness) and high insulation reliability can be obtained.

[0045] The bismaleimide compound (A) is not particularly limited as long as it achieves the effects of the present invention. In terms of obtaining suitable viscosity and suppressing the increase of varnish viscosity, the mass-average molecular weight of the bismaleimide compound (A) is preferably 100 to 6000, more preferably 300 to 5000. Furthermore, in this embodiment, "mass-average molecular weight" refers to the mass-average molecular weight obtained by gel permeation chromatography (GPC) converted from polystyrene standards.

[0046] The structure of the bismaleimide compound (A) is then described.

[0047] In the above equation (1), Q 1 This refers to 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. As Q 1 In terms of obtaining suitable viscosity and controlling the increase of varnish viscosity, linear or branched alkylene compounds are preferred, and linear alkylene compounds are more preferred.

[0048] 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.

[0049] 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, octadecylene, neopentylene, dimethylbutylene, methylhexylene, ethylhexylene, dimethylhexylene, trimethylhexylene, methylheptylene, dimethylheptylene, trimethylheptylene, tetramethylheptylene, ethylheptylene, methyloctylene, methylnonylene, methyldecylene, methyl dodecylene, methyl undecylene, methyl tridecylene, methyl tetradecylene, methyl decadecylene, and methyl hexadecylene.

[0050] 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.

[0051] 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.

[0052] In the above equation (1), Q 2This refers to 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. As Q 2 In terms of obtaining suitable viscosity and controlling the increase of varnish viscosity, linear or branched alkylene compounds are preferred, and linear alkylene compounds are more preferred.

[0053] 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.

[0054] As a linear or branched alkylene group, refer to Q. 2 .

[0055] 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.

[0056] As a linear or branched subalkenyl group, refer to the Q described above. 2 .

[0057] In equation (1), Q 1 With Q 2 They can be the same or different, but in terms of making it easier to synthesize the bismaleimide compound (A), they are preferred to be the same.

[0058] In the above equation (1), Q 3 Each can independently represent 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. Regarding obtaining suitable viscosity and controlling the increase in varnish viscosity, Q... 3 Preferably, each of the atoms is a hydrogen atom or a straight-chain or branched alkyl group having 1 to 16 carbon atoms; more preferably, it is Q. 3 One to five bases (Q) 3 ) is a straight-chain or branched alkyl group having 1 to 16 carbon atoms, with the remaining groups (Q) 3 Q is a hydrogen atom, and therefore preferably a hydrogen atom. 3 One to three bases (Q) 3 ) is a straight-chain or branched alkyl group having 1 to 16 carbon atoms, with the remaining groups (Q) 3 ) represents a hydrogen atom.

[0059] 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 alkyl group is preferably 2 to 14, and more preferably 4 to 12.

[0060] Examples of linear or branched alkyl groups include: methyl, ethyl, n-propyl, isopropyl, 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, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, and 2-methylpentan-3-yl.

[0061] 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.

[0062] Examples of alkenyl groups that are linear or branched include vinyl, allyl, 4-pentenyl, isopropenyl, and isopentenyl.

[0063] In the above equation (1), Q 4 Each of these can be independently represented by 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. Regarding dielectric properties, Q... 4 Preferably, it is a straight-chain or branched alkyl group with hydrogen atoms and 1 to 6 carbon atoms.

[0064] 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.

[0065] Examples of linear or branched alkyl groups include: methyl, ethyl, n-propyl, and isopropyl.

[0066] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0067] 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.

[0068] Examples of linear or branched alkoxy groups include: methyl, ethyl, n-propyl, and isopropyl.

[0069] In equation (1), n 1 Each represents an integer from 1 to 2 independently. m 1 Each can independently represent an integer from 1 to 4.

[0070] 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, when the structural unit represented by formula (1) is located at the end of the molecular chain of the bismaleimide compound (A), it means that the maleimide group is present at Q. 1The maleimide group is located at the end of the molecular chain, or at the N atom of the maleimide ring, or at both ends. Bismaleimide compounds (A) may also have maleimide groups in addition to the two ends of the molecular chain.

[0071] In this embodiment, the maleimide group is represented by the following formula (2), and the N atom is bonded to the molecular chain of the formula (1). In addition, the maleimide groups bonded to the formula (1) may be all the same or different, but the maleimide groups at both ends of the molecular chain are preferably the same.

[0072] [Chemistry 3]

[0073]

[0074] In equation (2), Q 5 Each can independently represent a hydrogen atom, or a straight-chain or branched alkyl group having 1 to 4 carbon atoms. For suitability in hardening, Q 5 Preferably, both are hydrogen atoms.

[0075] The number of carbon atoms in the alkyl group is preferably 1 to 3, more preferably 1 to 2, in terms of suitability for hardening.

[0076] As a linear or branched alkyl group, refer to Q. 3 .

[0077] As such a bismaleimide compound (A), for example, maleimide compounds represented by formula (3) can be listed.

[0078] [Chemistry 4]

[0079]

[0080] In the formula (3), 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.

[0081] In the resin composition of this embodiment, the content of the bismaleimide compound (A) is not particularly limited. From the viewpoint of obtaining a cured product with the bismaleimide compound as the main component, further improving curability, and obtaining lower porosity, the total amount of the bismaleimide compound (A) and the free radical polymerizable resin or compound (B) described later is preferably 1 to 99 parts by mass, more preferably 3 to 95 parts by mass, even more preferably 5 to 90 parts by mass, even more preferably 10 to 85 parts by mass, and even more preferably 15 to 85 parts by mass.

[0082] Bismaleimide compound (A) can also be used alone or in appropriate combinations of two or more.

[0083] (Method for manufacturing bismaleimide compound (A))

[0084] The bismaleimide compound (A) of this embodiment 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 are subjected to an addition polymerization reaction typically for 0.5 hours to 50 hours, preferably 1 hour to 20 hours, at a temperature typically of 80°C to 250°C, preferably 100°C to 200°C, to obtain an addition polymer. Then, the addition polymer is subjected to an imidization reaction, i.e., a dehydration and ring-closing reaction, typically for 0.1 hours to 2 hours, preferably 0.1 hours to 0.5 hours, at a temperature typically of 60°C to 120°C, preferably 80°C to 100°C, thereby obtaining the bismaleimide compound (A).

[0085] 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. These include eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), and nisinic acid.

[0086] 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.

[0087] 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 ...

[0088] When performing addition polymerization and imidization reactions, various known solvents can be used. There are no particular limitations on the solvent; examples 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 solvents with 1 to 10 carbon atoms such as methanol, ethanol, and propanol. Alcohols; phenols 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; cyclic 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.

[0089] Furthermore, a catalyst is preferably used in the imidization reaction. The catalyst is not particularly limited; for example, tertiary amines and dehydration catalysts can be used. As a tertiary amine, heterocyclic tertiary amines are preferred, such as pyridine, picolin, quinoline, isoquinoline, etc. The dehydration catalyst is not particularly limited; examples include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, trifluoroacetic anhydride, etc.

[0090] There is no particular limitation on the amount of catalyst added. For example, it is preferable that the imidizing agent is in a molar ratio of 0.5 to 5.0 times the molar equivalent of the amide group, and the dehydration catalyst is in a molar ratio of 0.5 to 10.0 times the molar equivalent of the amide group.

[0091] 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. There are no particular limitations on the poor solvent; examples include: water, methanol, ethanol, 2-propanol, ethylene glycol, triethylene glycol, 2-butanol, 2-pentanol, 2-hexanol, cyclopentanol, cyclohexanol, phenol, and tert-butanol.

[0092] [Resin Composition]

[0093] The resin composition of this embodiment contains the bismaleimide compound (A) of this embodiment. Due to this configuration, the resin composition of this embodiment exhibits excellent adhesion to chips and substrates. In this embodiment, from the viewpoint of obtaining even better adhesion to chips and substrates, the content of the maleimide compound (A) of this embodiment is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of the resin composition of this embodiment. The content of the bismaleimide compound (A) of this embodiment is not particularly limited, for example, it is 90 parts by mass or less.

[0094] [Thermosetting resin or compound (B)]

[0095] The resin composition of this embodiment may further comprise one or more of the following groups as a thermosetting resin or compound (B): maleimide compounds other than the bismaleimide compound (A) of this embodiment (hereinafter also referred to as "other maleimide compounds"), cyanate ester compounds, phenolic resins, epoxy resins, oxadiene resins, benzoxazine compounds, carbodiimide compounds, and compounds having vinyl unsaturated groups. The components will be described below.

[0096] (Other maleimide compounds)

[0097] There are no particular limitations on other maleimide compounds, as long as they are compounds having one or more maleimide groups in their molecules, other than the bismaleimide compound (A) of this embodiment. Specific examples include: N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, 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, Phenylacetyl maleimide, 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, 1,6-bismaleimide hexane, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 1,8-bismaleimide Amine-3,6-dioxaoctane, 1,11-bismaleimide-3,6,9-trioxaundecanane, 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 bisciconimide, 2,2-bis[4-(4-ciconimidephenoxy)phenyl]propane, bis(3,5-dimethyl-4-ciconimidephenyl)methane, bis(3-ethyl-5-methyl-4-ciconimidephenyl) The following are maleimide compounds represented by formula (4): methane, bis(3,5-diethyl-4-citronimide-phenyl)methane, polyphenylmethane maleimide, etc.; maleimide compounds represented by formula (5): the following; maleimide compounds represented by formula (6): the following; maleimide compounds represented by formula (7): the following; maleimide compounds represented by formula (8): the following; maleimide compounds represented by formula (9): the following; maleimide compounds represented by formula (10): the following; maleimide compounds represented by formula (11): the following; maleimide compounds represented by formula (12): the following; 1,6-bismaleimide-(2,2,4-Trimethyl)hexane (maleimide compounds represented by formula (13) below), maleimide compounds represented by formula (14) below, and fluorescein-5-maleimide, as well as prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds, etc. These other maleimide compounds can also be used alone or in appropriate combinations of two or more.

[0098] [Chemistry 5]

[0099]

[0100] In formula (4), each of the plurality of R1s independently represents a hydrogen atom or a methyl group. n2 represents an integer greater than or equal to 1, preferably an integer from 1 to 10, and more preferably an integer from 1 to 5.

[0101] [Chemistry 6]

[0102]

[0103] In the formula (5), R2 independently represents a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a phenyl group, l independently represents an integer from 1 to 3, and n3 represents an integer from 1 to 10.

[0104] 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.

[0105] [Chemistry 7]

[0106]

[0107] In formula (6), R3 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 n4 represents an integer from 1 to 10.

[0108] 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.

[0109] [Chemistry 8]

[0110]

[0111] In the formula (7), n5 (average) is 1 or more, preferably 1 to 21, and more preferably 1 to 16 from the viewpoint of exhibiting excellent light curing properties.

[0112] [Chemistry 9]

[0113]

[0114] In the above formula (8), the number of x is 10 to 35.

[0115] In the above formula (8), the quantity of y is 10 to 35.

[0116] [Chemistry 10]

[0117]

[0118] In equation (9), R a 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 1 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.

[0119] The number of carbon atoms in the alkyl group is preferably 1 to 16, and more preferably 4 to 12 in terms of exhibiting excellent light curing properties.

[0120] The number of carbon atoms in the alkenyl group is preferably 1 to 16, and more preferably 4 to 12 in terms of exhibiting excellent photocurability.

[0121] As a linear or branched alkyl group, refer to Q in formula (1). 3 The records state that, in terms of exhibiting excellent photocurability, n-heptyl, n-octyl, and n-nonyl are preferred, with n-octyl being more preferred.

[0122] In equation (9), 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 1 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.

[0123] The number of carbon atoms in the alkyl group is preferably 1 to 16, and more preferably 4 to 12 in terms of exhibiting excellent light curing properties.

[0124] The number of carbon atoms in the alkenyl group is preferably 1 to 16, and more preferably 4 to 12 in terms of exhibiting excellent photocurability.

[0125] As a specific example of an alkyl group, refer to the R described above. a Alkyl groups in the form of n-heptyl, n-octyl, or n-nonyl are preferred in terms of exhibiting excellent photocurability, with n-octyl being more preferred.

[0126] As a specific example of an alkenyl group, see the R described above. 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.

[0127] In equation (9), 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.

[0128] In equation (9), n b The quantity is 1 or more, preferably 2 to 16, and more preferably 3 to 14 from the viewpoint of exhibiting excellent photocurability.

[0129] n a With n b The quantities can be the same or different.

[0130] [Chemistry 11]

[0131]

[0132] In the above formula (10), n6 represents an integer from 1 to 10, and m2 represents an integer from 8 to 40.

[0133] [Chemistry 12]

[0134]

[0135] In the above formula (11), n7 represents an integer from 1 to 10, and m3 represents an integer from 8 to 40.

[0136] [Chemistry 13]

[0137]

[0138] In the formula (12), n8 represents an integer greater than or equal to 1, and is preferably an integer from 1 to 10.

[0139] [Chemistry 14]

[0140]

[0141] [Chemistry 15]

[0142]

[0143] (In formula (14), R4 independently represents a hydrogen atom, a methyl group, or an ethyl group, and R5 independently represents a hydrogen atom or a methyl group.)

[0144] Other maleimide compounds can also be used from commercially available products.

[0145] As an example of the maleimide compound represented by formula (4), BMI-2300 (trade name) manufactured by Daiwa Chemical Industries, Ltd. can be cited.

[0146] As an example of the maleimide compound represented by the formula (5), MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd. can be cited.

[0147] As an example of the maleimide compound represented by the formula (6), MIR-5000 (trade name) manufactured by Nippon Kayaku Co., Ltd. can be cited.

[0148] Examples of maleimide compounds represented by formula (7) include BMI-1000P (trade name, n5 = 13.6 (average) in formula (7)) manufactured by KI Chemical Co., Ltd., BMI-650P (trade name, n5 = 8.8 (average) in formula (7)) manufactured by KI Chemical Co., Ltd., BMI-250P (trade name, n5 = 3 to 8 (average) in formula (7)) manufactured by KI Chemical Co., Ltd., and CUA-4 (trade name, n5 = 1 in formula (7)) manufactured by KI Chemical Co., Ltd.

[0149] Examples of maleimide compounds represented by formula (8) include BMI-6100 (trade name, x=18, y=18 in formula (11)) manufactured by DesignerMolecules Inc.

[0150] Examples of maleimide compounds represented by formula (9) include BMI-689 (trade name, formula (15) below, functional group equivalent: 346 g / eq.) manufactured by DesignerMolecules Inc.

[0151] [Chemistry 16]

[0152]

[0153] Examples of maleimide compounds represented by formula (10) include BMI-1500 (trade name, n6 = 1.3 in formula (10), functional group equivalent: 754 g / eq.) manufactured by Designer Molecules Inc.

[0154] As the maleimide compound represented by formula (11), commercially available products can also be used, such as BMI-1700 (trade name) manufactured by Designer Molecules Inc. (DMI).

[0155] As the maleimide compound represented by formula (12), commercially available products may also be used, such as 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).

[0156] As the maleimide compound represented by formula (13), commercially available products can also be used, such as BMI-TMH (trade name) manufactured by Yamato Chemical Industries, Ltd.

[0157] As the maleimide compound represented by formula (14), commercially available products can also be used, such as BMI-70 (trade name) manufactured by KI Chemical Co., Ltd.

[0158] The other maleimide compounds can also be used alone or in appropriate combinations of two or more.

[0159] In the resin composition of this embodiment, the total content of maleimide compounds other than the bismaleimide compound (A) of this embodiment is not particularly limited. From the viewpoint of obtaining better adhesion to chips, substrates, etc., the content of the resin solids in the resin composition of this embodiment is preferably 0.01 parts to 95 parts by mass, more preferably 1 part to 90 parts by mass, relative to 100 parts by mass of resin solids.

[0160] (Cyanate ester compounds)

[0161] The cyanate compound is not particularly limited as long as it is a resin having an aromatic moiety substituted with at least one cyanooxy group (cyanate group) within the molecule.

[0162] For example, the following can be represented by equation (16).

[0163] [Chemistry 17]

[0164]

[0165] In formula (16), 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. Ra independently represents a hydrogen atom, an alkyl group with 1-6 carbon atoms, an alkenyl group with 1-6 carbon atoms, an aryl group with 6-12 carbon atoms, an alkoxy group with 1-4 carbon atoms, or an alkyl group with 1-6 carbon atoms bonded to an aryl group with 6-12 carbon atoms. The aromatic ring in Ra may have substituents, and the substituents in Ar1 and Ra can be in any position. p represents the number of cyanoxy groups bonded to Ar1, and each is an independent integer from 1 to 3. 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 two benzene rings bonded together by a single bond. t represents the average number of repetitions, and is an integer from 0 to 50; the cyanate ester compound may be a mixture of compounds with different t values. In the presence of multiple X groups, each can independently be a single bond, a divalent organic group with 1 to 50 carbon atoms (hydrogen atoms may be replaced by heteroatoms), a divalent organic group with 1 to 10 nitrogen atoms (e.g., -NRN- (where R represents an organic group)), 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.

[0166] The alkyl group in Ra of formula (16) may have either a straight or branched chain structure or a cyclic structure (e.g., cycloalkyl).

[0167] In addition, the hydrogen atoms in the alkyl group in formula (16) and the aryl group in Ra can also be substituted by halogen atoms such as fluorine atoms and chlorine atoms; alkoxy groups such as methoxy and phenoxy; or cyano groups.

[0168] 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.

[0169] 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.

[0170] 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.

[0171] Examples of alkoxy groups include: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy.

[0172] Specific examples of divalent organic groups with 1 to 50 carbon atoms in X of formula (16) include: methylene, ethylene, trimethylene, cyclopentylene, cyclohexylene, trimethylcyclohexylene, biphenylmethylene, dimethylmethylene-phenylene-dimethylmethylene, fluorenediyl, and phthalolidediyl, etc. The hydrogen atom in the divalent organic group may be substituted with halogen atoms such as fluorine or chlorine; alkoxy groups such as methoxy or phenoxy; or cyano, etc.

[0173] Examples of divalent organic groups with nitrogen number 1 to 10 in X of formula (16) include imino and polyimide groups.

[0174] In addition, the organic group of X in formula (16) can be, for example, an organic group with the structure represented by formula (17) or formula (18) below.

[0175] [Chemistry 18]

[0176]

[0177] In formula (17), Ar2 represents phenyldiyl, naphthyl, or biphenyldiyl. When u is 2 or more, 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.

[0178] [Chemistry 19]

[0179]

[0180] In formula (18), Ar3 represents phenyldiyl, naphthyldiyl, or biphenyldiyl. When v is 2 or more, Ar3 can 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 can also be a mixture of compounds with different v values.

[0181] Furthermore, as X in equation (16), the divalent bases represented by the following equations can be listed.

[0182] [Chemistry 20]

[0183]

[0184] 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.

[0185] Specific examples of Ar2 in formula (17) and Ar3 in formula (18) include: phenyldiyl groups with two carbon atoms in formula (17) or two oxygen atoms in formula (18) bonded at the 1,4 or 1,3 positions; biphenyldiyl groups with the 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 the 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.

[0186] The alkyl and aryl groups in Rb, Rc, Rd, Re, Rf and Rg of formula (17) and Ri and Rj of formula (18) have the same meaning as the alkyl and aryl groups in formula (16).

[0187] Specific examples of cyanooxy-substituted aromatic compounds represented by formula (16) 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 bis(N-3-cyanooxy-4-methylphenyl)-4,4'-oxophthalimide, bis(N-4-cyanooxy-2-methylphenyl)-4,4'-oxophthalimide, bis(N-4-cyanooxyphenyl)-4,4'-oxophthalimide, bis(N-4-cyanooxy-2-methylphenyl)-4,4'-(hexafluoroisopropylidene)diphthalimide, tris(3,5-dimethyl-4-cyanooxybenzyl) Isocyanurate, 2-phenyl-3,3-bis(4-cyanoxyphenyl)benzylcarboxamide, 2-(4-methylphenyl)-3,3-bis(4-cyanoxyphenyl)benzylcarboxamide, 2-phenyl-3,3-bis(4-cyanoxy-3-methylphenyl)benzylcarboxamide, 1-methyl-3,3-bis(4-cyanoxyphenyl)indololin-2-one, and 2-phenyl-3,3-bis(4-cyanoxyphenyl)indololin-2-one.

[0188] These cyanate compounds can also be used alone or in appropriate combinations of two or more.

[0189] As another specific example of the cyanate ester compound represented by formula (16), examples include phenolic resins prepared by cyanate esterification using the same method as described above, and their prepolymers, etc.: phenolic varnish resins and cresol 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 varnish resins (prepared by reacting hydroxybenzaldehyde with phenol in the presence of an acidic catalyst), fluorene 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 esters using known methods). These include compounds formed by reacting with an acidic catalyst or without a catalyst; compounds formed by reacting bis(alkoxymethyl) compounds, such as Ar4-(CH2OR)2 (R represents alkyl), with phenolic compounds in the presence of an acidic catalyst; compounds formed by reacting bis(hydroxymethyl) compounds, such as Ar4-(CH2OH)2, with phenolic compounds in the presence of an acidic catalyst; or compounds formed by the condensation polymerization of aromatic aldehyde compounds with aralkyl compounds and phenolic compounds; phenol-modified xylene-formaldehyde resin (formed by reacting xylene-formaldehyde 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). There are no particular limitations on these. These cyanate compounds can also be used alone or in appropriate combinations of two or more.

[0190] 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.

[0191] Resin curing products using these cyanate compounds have excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion.

[0192] In the resin composition of this embodiment, the total content of cyanate ester compounds is not particularly limited, and in 100 parts by weight of resin solids in the resin composition of this embodiment, it is preferably 0.01 parts by weight to 60 parts by weight.

[0193] (Phenolic resin)

[0194] As the phenolic resin mentioned, any phenolic resin having two or more hydroxyl groups in one molecule may be used, and generally known phenolic resins may be used. Examples include bisphenol A type phenolic resin, bisphenol E type phenolic resin, bisphenol F type phenolic resin, bisphenol S type phenolic resin, phenolic varnish resin, bisphenol A phenolic varnish type phenolic resin, glycidyl ester type phenolic resin, aralkyl phenolic varnish type phenolic resin, biphenyl aralkyl type phenolic resin, cresol phenolic varnish type phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol phenolic varnish resin, polyfunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified phenolic varnish type phenolic resin, phenolic aralkyl type phenolic resin, naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin, alicyclic phenolic resin, polyol type phenolic resin, phosphorus-containing phenolic resin, phenolic resin containing polymerizable unsaturated hydrocarbon groups, and silicone resins containing hydroxyl groups, etc., but there are no particular limitations. These phenolic resins can also be used alone or in appropriate combinations of two or more.

[0195] In the resin composition of this embodiment, the total content of phenolic resin is not particularly limited, but the resin solid component in the resin composition of this embodiment is preferably 0.01 to 60 parts by weight out of 100 parts by weight.

[0196] (Epoxy resin)

[0197] There are no particular limitations on the epoxy resin used; any commonly known epoxy resin 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 epoxy resin, biphenyl type epoxy resin, phenolic varnish epoxy resin, cresol phenolic varnish epoxy resin, xylene phenolic varnish epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified phenolic varnish 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.

[0198] In the resin composition of this embodiment, the total content of epoxy resin is not particularly limited, but the amount of solid resin component in the resin composition of this embodiment is preferably 0.01 to 60 parts by weight out of 100 parts by weight.

[0199] (Oxycyclic butane resin)

[0200] As the oxetane resin, generally known oxetane resins can be used. Examples include oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane and other alkyloxetanes, 3-methyl-3-methoxymethyloxetane, 3,3-di(trifluoromethyl)perfluorooxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane, OXT-101 (manufactured by Dong-A Synthetic Co., Ltd., trade name), and OXT-121 (manufactured by Dong-A Synthetic Co., Ltd., trade name), etc., but there are no particular limitations. These oxetane resins can also be used alone or in appropriate mixtures of two or more.

[0201] In the resin composition of this embodiment, the total content of oxetane resin is not particularly limited, and the resin solids in the resin composition of this embodiment are preferably 0.01 to 40 parts by weight per 100 parts by weight.

[0202] (Benzoxazine compounds)

[0203] As the benzoxazine compound, any known benzoxazine compound may be used as long as it has two or more dihydrobenzoxazine rings in one molecule. Examples include bisphenol A type benzoxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), bisphenol F type benzoxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), bisphenol S type benzoxazine BS-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), phenolphthalein type benzoxazine, etc., but there are no particular limitations. These benzoxazine compounds can also be used alone or in appropriate combinations of two or more.

[0204] In the resin composition of this embodiment, the total content of benzoxazine compounds is not particularly limited, and the resin solids in the resin composition of this embodiment are preferably 0.01 to 40 parts by weight per 100 parts by weight.

[0205] (Carbodiimide compound)

[0206] As a carbodiimide compound, there are no particular limitations as long as it has at least one carbodiimide group in the molecule, and generally known carbodiimide compounds can be used. Examples include: 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 carbodiimides, polycarbodiimides such as Carbodilite (registered trademark: manufactured by Nisshinbo Chemical Co., Ltd.) and Stabaxol (registered trademark: manufactured by LANXESS Deutschland GmbH). These carbodiimide compounds can also be used alone or in appropriate combinations of two or more.

[0207] In the resin composition of this embodiment, the total content of carbodiimide compounds is not particularly limited, and in 100 parts by weight of resin solids in the resin composition of this embodiment, it is preferably 0.01 parts by weight to 40 parts by weight.

[0208] (Compounds containing vinyl unsaturated groups)

[0209] As for the compound having an ethylene unsaturated group, there is no particular limitation as long as it has one or more ethylene unsaturated groups in one molecule, and generally known compounds having ethylene unsaturated groups can be used. For example, compounds having (meth)acryloyl and vinyl groups can be listed.

[0210] 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.

[0211] 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.

[0212] 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 hexamethylene diisocyanate, and their isocyanurates, biuret reactants, and other polyisocyanates to form urethane (meth)acrylates.

[0213] 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.

[0214] 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-valerol 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-valerol to 1 mole of dipentaerythritol; or mono(meth)acrylates or poly(meth)acrylates of polyols such as triols, tetraols, pentaols, or hexaols.

[0215] 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 the aforementioned diol components, polybasic acids and their anhydrides, as well as cyclic lactones such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone modified polyester diols.

[0216] 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.

[0217] Examples of vinyl compounds include: ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, and other vinyl ethers. Examples of styrene compounds include: styrene, methylstyrene, ethylstyrene, divinylbenzene, etc. Examples of other vinyl compounds include: triallyl isocyanurate, trimethylallyl isocyanurate, dielyl thiamethoxam, etc.

[0218] These compounds with ethylene unsaturated groups can also be used alone or in appropriate combinations of two or more.

[0219] In the resin composition of this embodiment, the total content of compounds having vinyl unsaturated groups is not particularly limited, and in 100 parts by weight of resin solids in the resin composition of this embodiment, it is preferably 0.01 parts by weight to 40 parts by weight.

[0220] (C) Polymerization initiator)

[0221] As the (C) polymerization initiator, a thermal free radical polymerization initiator is preferred, and organic peroxide or azo compounds used previously may be appropriately used.

[0222] Examples of organic peroxide-based polymerization initiators include: methyl ethyl ketone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis(tert-butyl peroxide)3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexyl peroxide)cyclohexane, 1,1-bis(tert-hexyl peroxide)3,3,5-trimethylcyclohexane, 1,1-bis(tert-butyl peroxide)cyclohexane, 2,2-bis(4,4-di-tert-butylperoxide)propane, 1,1-bis(tert-butyl peroxide)cyclododecane, n-butyl 4,4-bis(tert-butyl peroxide)valerate, 2,2-(tert-butyl peroxide)butane, 1,1-bis(tert-butyl peroxide)-2-methylcyclohexane, tert-butyl... Hydrogen peroxide, p-menthane hydrogen peroxide, 1,1,3,3-tetramethylbutyl hydrogen peroxide, tert-hexyl hydrogen peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyl peroxide)hexane, α,α'-bis(tert-butyl peroxide)diisopropylbenzene, tert-butylcumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyl peroxide)hexyn-3, isobutyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, cinnamic acid peroxide, m-toluyl peroxide, benzoyl peroxide, diisopropyl peroxide, bis(4-tert-butylcyclohexyl) peroxide, di-3-methoxybutyl peroxide Dicarbonyl peroxide, di-2-ethylhexyl peroxide, di-sec-butyl peroxide, di(3-methyl-3-methoxybutyl) peroxide, di(4-tert-butylcyclohexyl) peroxide, α,α'-bis(neodecanyl peroxide)diisopropylbenzene, cumyl peroxide neodecanoate, 1,1,3,3-tetramethylbutyl peroxide neodecanoate, 1-cyclohexyl-1-methylethyl peroxide neodecanoate, tert-hexyl peroxide neodecanoate, tert-butyl peroxide neodecanoate, tert-hexyl peroxide trimethyl acetate, tert-butyl peroxide trimethyl acetate, 2,5-dimethyl-2,5-bis(2-ethylhexanoyl peroxide)hexane, 1,1,3,3-tetramethylperoxide butyl-2-ethylhexanoate 1-Cyclohexyl-1-peroxymethylethyl-2-ethylhexanoate, tert-hexyl-2-ethylhexanoate, tert-butyl-2-ethylhexanoate, tert-butyl isobutyrate, tert-butyl maleic acid, tert-butyl laurate, tert-butyl-3,5,5-trimethylhexanoate, tert-butyl isopropyl monocarbonate, tert-butyl-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis(benzoyl peroxide)hexane, tert-butyl acetate, tert-hexyl benzoate, tert-butyl-m-toluyl benzoate, tert-butyl benzoate, bis(tert-butyl peroxide) isophthalate, tert-butyl allyl monocarbonate, 3,3',4,4'-Tetra(tert-butyl peroxide)benzophenone, etc.

[0223] In addition, examples of azo polymerization initiators include: 2-phenylazo-4-methoxy-2,4-dimethylpentanonitrile, 1-[(1-cyano-1-methylethyl)azo]formamide, 1,1'-azobis(cyclohexane-1-carboxylonitrile), 2,2'-azobis(2-methylbutanonitrile), 2,2'-azobisisobutanonitrile, 2,2'-azobis(2,4-dimethylpentanonitrile), 2,2'-azobis(2-methylpropionidium) dihydrochloride, 2,2'-azobis(2-methyl-N-phenylpropionidium) dihydrochloride, 2,2'-azobis[N-(4-chlorophenyl)-2-methyl] [2,2'-Azobis[N-(4-hydroxyphenyl)-2-methylpropane] dihydrochloride, 2,2'-Azobis[2-methyl-N-(phenylmethyl)propane] dihydrochloride, 2,2'-Azobis[2-methyl-N-(2-propenyl)propane] dihydrochloride, 2,2'-Azobis[N-(2-hydroxyethyl)-2-methylpropane] dihydrochloride, 2,2'-Azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-Azobis [2-(4,5,6,7-tetrahydro-1H-1,3-diazacycloheptatrien-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-methyl-N-[ [1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide, 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(2-methylpropionamide), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), dimethyl-2,2-azobis(2-methylpropionate), 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis[2-(hydroxymethyl)propionitrile], etc.

[0224] The thermal polymerization initiator can be used alone or in combination of two or more.

[0225] (C) The content of the polymerization initiator is not particularly limited, but is preferably 0.1 to 10 parts by mass relative to the total amount of bismaleimide compound (A) and compound (B) of 100 parts by mass, more preferably 0.5 to 5 parts by mass.

[0226] (D) Hardening accelerator)

[0227] The curing accelerator (D) is not particularly limited, and examples include phosphine compounds, compounds containing phosphonium salts, imidazole compounds, etc., and one or more of these can be used. Among them, imidazole compounds are preferred. Imidazole compounds have particularly excellent function as catalysts, and therefore can more effectively promote the polymerization reaction of bismaleimide compound (A).

[0228] The imidazole compounds are not particularly limited, and examples include: 2-ethyl-4-methylimidazolium, 2-methylimidazolium, 2-ethylimidazolium, 2,4-dimethylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 1-vinyl-2-methylimidazolium, 1-propyl-2-methylimidazolium, 2-isopropylimidazolium, 1-cyanomethyl-2-methylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyanoethyl-2-phenylimidazolium, etc. Among these, 2-methylimidazolium, 2-phenylimidazolium, 2-undecylimidazolium, and 2-ethyl-4-methylimidazolium are preferred. Using these compounds can further promote the reaction between the bismaleimide compound (A) and the thermosetting resin or compound (B), resulting in improved heat resistance of the cured product. These compounds can be used alone or in combination of two or more.

[0229] Phosphine compounds are not particularly limited, but examples include: primary phosphines such as alkylphosphine (e.g., ethylphosphine, propylphosphine), and phenylphosphine; secondary phosphines such as dialkylphosphine (e.g., dimethylphosphine, diethylphosphine), diphenylphosphine, methylphenylphosphine, and ethylphenylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, alkyldiphenylphosphine, dialkylphenylphosphine, tribenzylphosphine, trimethylstyrylphosphine, tris(2,6-dimethoxyphenyl)phosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine, and tri-2-cyanoethylphosphine. Tertiary phosphines are preferred. These can be used alone or in combination of two or more.

[0230] Examples of compounds containing phosphonium salts include those containing tetraphenylphosphonium salts, alkyltriphenylphosphonium salts, tetraalkylphosphonium, etc. More specifically, examples include tetraphenylphosphonium-thiocyanate, tetraphenylphosphonium-tetra-p-methylphenylboronic acid ester, butyltriphenylphosphonium-thiocyanate, tetraphenylphosphonium-phthalic acid, tetrabutylphosphonium-1,2-cyclohexyldicarboxylic acid, etc.

[0231] (D) The content of the curing accelerator is not particularly limited, but is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the total amount of bismaleimide compound (A) and thermosetting resin or compound (B), and more preferably 0.5 to 5 parts by mass.

[0232] The thermosetting resin composition of this embodiment may contain either one of a polymerization initiator (C) and a curing accelerator (D), or both. When both a polymerization initiator (C) and a curing accelerator (D) are included, the total content of these components is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total amount of the bismaleimide compound (A) and the thermosetting resin or compound (B).

[0233] In the thermosetting resin composition of this embodiment, inorganic fillers, release agents, flame retardants, ion traps, antioxidants, adhesion promoters, stress reducers, colorants, and coupling agents may be incorporated as (E) components other than the essential components, within a range that does not impair the effects of the present invention.

[0234] (filler material)

[0235] In the resin composition of this embodiment, a filler may also be included to improve various properties such as coating properties and heat resistance. As a filler, it is preferable to have insulating properties and not to impede the transmission of wavelengths up to 405 nm (h-rays). There are no particular limitations on the filler materials, but examples include: silica (e.g., natural silica, fused silica, synthetic silica, hollow silica, etc.), aluminum compounds (e.g., borosilicate, aluminum hydroxide, aluminum oxide, aluminum nitride, etc.), boron compounds (e.g., boron nitride, etc.), magnesium compounds (e.g., magnesium oxide, magnesium hydroxide, etc.), calcium compounds (e.g., calcium carbonate, etc.), molybdenum compounds (e.g., molybdenum oxide, zinc molybdate, etc.), barium compounds (e.g., barium sulfate, barium silicate, etc.), talc (e.g., natural talc, calcined talc, etc.), mica, glass (e.g., short glass fibers, spherical glass, glass micropowders (e.g., E glass, T glass, D glass, etc.)), silicone powder, fluoropolymer fillers, urethane resin fillers, (meth)acrylic resin fillers, polyethylene fillers, styrene-butadiene rubber, and silicone rubber, etc. These fillers can also be used alone or in appropriate combinations of two or more.

[0236] Among these, preferably one or more are selected from the group consisting of silica, boehmite, barium sulfate, silicone powder, fluoropolymer fillers, urethane resin fillers, (meth)acrylic resin fillers, polyethylene fillers, styrene-butadiene rubber, and silicone rubber.

[0237] These fillers can also be surface-treated using silane coupling agents, etc., as described later.

[0238] From the viewpoint of improving the heat resistance of the cured product obtained by curing the resin composition of this embodiment and obtaining good coating properties, silica is preferred, and fused silica is more preferred. Specific examples of silica include: SFP-130MC manufactured by Denka Ltd., and SC2050-MB, SC1050-MLE, YA010C-MFN, and YA050C-MJA manufactured by Admatechs Ltd.

[0239] The particle size of the filler is not particularly limited, but is usually 0.005μm to 100μm, preferably 0.01μm to 50μm.

[0240] In the resin composition of this embodiment, the content of filler is not particularly limited. From the viewpoint of ensuring good heat resistance of the cured product, it is preferably set to 1000 parts by weight or less, more preferably 500 parts by weight or less, and most preferably 300 parts by weight or less, relative to 100 parts by weight of the resin solids in the resin composition. Furthermore, when filler is included, the lower limit value is not particularly limited. From the viewpoint of obtaining the effect of improving various properties such as coating properties and heat resistance, it is generally 1 part by weight relative to 100 parts by weight of the resin solids in the resin composition.

[0241] <Silane Coupling Agents and Wetting / Dispersing Agents>

[0242] 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 also be used.

[0243] As for these silane coupling agents, there are no particular limitations as long as they are silane coupling agents generally used for the surface treatment of inorganic materials. Specific examples include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, N-(2-aminoethyl)-3-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 aminosilanes such as [3-(N,N-dimethylamino)-propyl]trimethoxysilane; 3-glycidyl etheroxypropyltrimethoxysilane, 3-glycidyl etheroxypropyltriethoxysilane, 3-glycidyl etheroxypropyldimethoxymethylsilane, 3-glycidyl etheroxypropyldiethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and epoxysilanes such as [8-(glycidyloxy)-n-octyl]trimethoxysilane; vinyltris(2-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, tri... Vinyl silanes such as methoxy(7-octen-1-yl)silane and trimethoxy(4-vinylphenyl)silane; methacryloylsilanes such as 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyldimethoxymethylsilane, and 3-methacryloyloxypropyldiethoxymethylsilane; acryloylsilanes such as 3-acryloyloxypropyltrimethoxysilane and 3-acryloyloxypropyltriethoxysilane; isocyanate silanes such as 3-isocyanate propyltrimethoxysilane and 3-isocyanate propyltriethoxysilane; tri-(trimethoxysilylpropyl)isocyanurate, etc. Cyanoureate silanes; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyldimethoxymethylsilane; ureosilanes such as 3-ureopropyltriethoxysilane; styrylsilanes such as p-styryltrimethoxysilane; cationic silanes such as N-[2-(N-vinylbenzylamino)ethyl]-3-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.

[0244] In the resin composition of this embodiment, the content of the silane coupling agent is not particularly limited, and is generally 0.1 to 10 parts by mass relative to 100 parts by mass of the resin solids in the resin composition.

[0245] 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 Co., Ltd. These wetting and dispersing agents can be used alone or in appropriate combinations of two or more.

[0246] In the resin composition of this embodiment, the content of the wetting and dispersing agent is not particularly limited, and is generally 0.1 to 10 parts by mass relative to 100 parts by mass of the resin solids in the resin composition.

[0247] <Organic Solvents>

[0248] 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. Specific examples are not particularly limited, but 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 toluene, xylene, and anisole.

[0249] These organic solvents can also be used alone or in appropriate combinations of two or more.

[0250] <Other Ingredients>

[0251] 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, which are not listed herein; and additives. These are not particularly limited for general users. For example, flame-retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine, as well as phosphoric acid esters, aromatic condensed phosphates, and halogenated condensed phosphates. Additives include: ultraviolet absorbers, antioxidants, fluorescent whitening agents, photosensitizers, dyes, pigments, tackifiers, lubricants, defoamers, surface conditioners, gloss agents, polymerization inhibitors, and curing accelerators. These components can also be used alone or in appropriate combinations of two or more.

[0252] In the resin composition of this embodiment, the content of other components is not particularly limited, and is generally 0.1 parts by mass to 10 parts by mass relative to 100 parts by mass of the resin solids in the resin composition.

[0253] <Method for manufacturing resin composition>

[0254] The resin composition of this embodiment is prepared by appropriately mixing the maleimide compound of this embodiment with a resin or compound as needed, a photocuring initiator, fillers, other components, and additives. The resin composition of this embodiment can be suitably used as a varnish when manufacturing the resin sheets of this embodiment described later.

[0255] The method for manufacturing the resin composition in this embodiment is not particularly limited. For example, a method in which the above-mentioned components are sequentially added to a solvent and stirred thoroughly can be listed.

[0256] When manufacturing the resin composition, known treatments (stirring, mixing, kneading, etc.) for uniformly dissolving or dispersing the components can be performed as needed. Specifically, by using a stirring tank equipped with a stirrer having appropriate stirring capacity, the dispersibility of the filler relative to the resin composition can be improved. The 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, or rotating or self-rotating mixing devices, etc. Furthermore, organic solvents can be used as needed when preparing the resin composition of this embodiment. 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.

[0257] <Uses>

[0258] The resin composition of this embodiment can be used for applications requiring insulation, and while not particularly limited, 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 sealing materials, hole-filling resins, component embedding resins, fiber-reinforced composite materials, and so on. Among these, the resin composition of this embodiment exhibits superior adhesion to chips and substrates, as well as excellent heat resistance and thermal stability, making it suitable for use as an insulating layer in multilayer printed circuit boards or as a solder resist.

[0259] [Hardened material]

[0260] The cured product of this embodiment is obtained by curing the resin composition of this embodiment. While not particularly limited, the cured product can be obtained, for example, by melting or dissolving the resin composition in a solvent, flowing it into a mold, and then curing it under normal conditions using heat or light. In the case of thermosetting, the curing temperature is not particularly limited, but from the viewpoint of efficiently curing and preventing the resulting cured product from deteriorating, a range of 120°C to 300°C is preferred. In the case of photosetting, the wavelength region of the light is not particularly limited, but curing is preferably carried out in the range of 100 nm to 500 nm, which is efficient for curing by photopolymerization initiators, etc.

[0261] [Resin Sheets]

[0262] 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 comprises the resin composition of this embodiment. The resin sheet can be manufactured by coating the resin composition onto the support and drying it. The resin layer in the resin sheet of this embodiment has excellent adhesion to chips and substrates, and also has excellent heat resistance and thermal stability.

[0263] The support can be any known support, and while there are no particular limitations, 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.

[0264] To facilitate peeling from the resin layer, a resin film coated with a release agent can be suitably used. 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; if the thickness exceeds 100 μm, the resolution tends to decrease when exposing from the support.

[0265] In addition, to reduce light scattering during exposure, the resin film is preferably a film with excellent transparency.

[0266] Furthermore, in the resin sheet of this embodiment, the resin layer can also be protected by a protective film.

[0267] 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 not particularly limited, but is preferably in the range of 1 μm to 50 μm, more preferably in the range of 5 μm to 40 μm. A thickness less than 1 μm tends to reduce the operability of the protective film, while a thickness exceeding 50 μm tends to decrease its cost-effectiveness. 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.

[0268] The method for manufacturing the resin sheet in this embodiment is not particularly limited. For example, the following methods can be used: 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.

[0269] Regarding the coating method, it can be carried out by known methods such as using a roller coater, comma coater, gravure coater, die coater, bar coater, lip coater, doctor blade coater, and extrusion coater. The drying can be carried out, for example, by heating in a dryer at 60°C to 200°C for 1 to 60 minutes.

[0270] 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.

[0271] The resin sheet of this embodiment can be used for manufacturing the insulating layer of a multilayer printed circuit board.

[0272] [Prepreg]

[0273] The prepreg of this embodiment comprises a substrate and a resin composition impregnated or coated onto the substrate. The method for manufacturing the prepreg of this embodiment is not particularly limited as long as it involves combining the resin composition of this embodiment with the substrate. For example, after impregnating or coating the resin composition of this embodiment onto the substrate, the prepreg is semi-cured (stage B) by drying in a dryer at 120°C to 220°C for approximately 2 to 15 minutes, thereby manufacturing the prepreg of this embodiment. At this time, the amount of resin composition adhering to the substrate, i.e., the content of the resin composition relative to 100 parts by weight of the semi-cured prepreg (including fillers), is preferably in the range of 20 parts by weight to 99 parts by weight.

[0274] As the substrate used in manufacturing the prepreg of this embodiment, various known substrates used in printed circuit board materials can be used. The substrate is not particularly limited, and examples include: inorganic fibers other than glass such as glass fiber and quartz; organic fibers such as polyimide, polyamide, and polyester; and woven fabrics such as liquid crystal polyester. As for the shape of the substrate, woven fabric, non-woven fabric, roving, chopped strand mat, and surfacing mat are known, and any of these can be used. One substrate can be used alone, or two or more can be used in combination. In woven fabrics, from the viewpoint of dimensional stability, fabrics that have undergone super-opening treatment or pore-clogging treatment are particularly suitable. From the perspective of electrical properties, liquid crystal polyester fabric is preferred. The thickness of the substrate is not particularly limited, but if it is for laminate applications, it is preferably in the range of 0.01 mm to 0.2 mm.

[0275] [Metal Foil-Clad Laminate]

[0276] The metal foil laminate of this embodiment comprises: a layer containing at least one selected from the group consisting of resin sheets and prepregs of this embodiment; and a metal foil disposed on one or both sides of the layer, the layer containing a cured form of the resin composition of this embodiment. When using a prepreg, for example, it can be manufactured by laminating a metal foil such as copper or aluminum on one or both sides of a single prepreg or by stacking multiple prepregs. The metal foil used here is not particularly limited as long as it is a metal foil used for printed circuit board materials, but rolled copper foil and electrolytic copper foil are preferred. The thickness of the metal foil is not particularly limited, but is preferably 2 μm to 70 μm, more preferably 3 μm to 35 μm. As forming conditions, methods commonly used in the manufacture of printed circuit board laminates and multilayer boards can be employed. For example, multi-stage presses, multi-stage vacuum presses, continuous forming machines, or autoclave forming machines can be used to achieve a temperature of 180℃~350℃, a heating time of 100 minutes~300 minutes, and a surface pressure of 20kg / cm².2 ~100kg / cm 2 The metal-clad laminate of this embodiment is manufactured by laminating the prepreg under the specified conditions. Alternatively, a multilayer board can be manufactured by combining the prepreg with a separately manufactured inner layer wiring board and then laminating them. As a method for manufacturing a multilayer board, for example, 35μm copper foil is disposed on both sides of a prepreg, and after lamination under the specified conditions, an inner layer circuit is formed. The circuit is then blackened to form an inner layer circuit board. Furthermore, one inner layer circuit board and one prepreg are alternately arranged, and copper foil is disposed on the outermost layer, and lamination is performed under the specified conditions, preferably in a vacuum. In this way, a multilayer board can be manufactured.

[0277] The metal foil laminate of this embodiment, through further patterning, can be suitably used as a printed wiring board. The printed wiring board can be manufactured using conventional methods, and the manufacturing method is not particularly limited. An example of a method for manufacturing a printed wiring board is shown below.

[0278] First, the metal foil laminate is prepared. Next, the surface of the metal foil laminate is etched to form inner layer circuits, thereby fabricating an inner layer substrate. On the surface of the inner layer circuits on the inner layer substrate, a surface treatment to improve adhesion strength is applied as needed. Then, the required number of prepreg sheets are stacked on the surface of the inner layer circuits. Next, metal foils for outer layer circuits are stacked on the outside, and the layers are heated and pressurized to integrally form the laminate. In this way, a multilayer laminate is manufactured with an insulating layer consisting of a substrate and a thermosetting resin composition formed between the metal foils for the inner and outer layer circuits. Next, through-hole or via-hole drilling is performed on the multilayer laminate, and a plated metal film is formed on the wall of the hole to conduct the metal foils for the inner and outer layer circuits. Then, the metal foils for the outer layer circuits are etched to form outer layer circuits, thereby manufacturing a printed circuit board.

[0279] The printed wiring board obtained in the manufacturing example is configured to have an insulating layer and a conductor layer formed on one or both sides of the insulating layer, and the insulating layer contains the resin composition of this embodiment. For example, the prepreg (substrate and the resin composition of this embodiment impregnated or coated therein) of this embodiment and the resin composition layer of the metal foil laminate of this embodiment (layer containing the resin composition of this embodiment) may be configured as an insulating layer containing the resin composition of this embodiment.

[0280] Multilayer printed wiring board

[0281] 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 contains the resin composition of this embodiment. For example, the insulating layer can also be obtained by overlapping and curing one or more resin sheets. The prepreg of this embodiment can also be used instead of the resin sheet of this embodiment. The multilayer printed circuit board of this embodiment can be manufactured according to conventional methods, and the manufacturing method is not particularly limited. Hereinafter, an example of a manufacturing method of the multilayer printed circuit board is shown.

[0282] First, the metal foil laminate is prepared. Next, the surface of the metal foil laminate is etched to form inner layer circuits, thereby fabricating an inner layer substrate. On the surface of the inner layer circuits on the inner layer substrate, a surface treatment is applied as needed to improve adhesion strength. Then, the required number of prepreg sheets are stacked on the surface of the inner layer circuits. Next, metal foils for outer layer circuits are stacked on the outer side, and the layers are heated and pressurized to integrally form the laminate. In this way, a multilayer laminate is manufactured with an insulating layer consisting of a hardened material comprising a substrate and a resin composition formed between the metal foils for the inner and outer layer circuits. Next, the multilayer laminate is perforated or through-holeed, and a plated metal film is formed on the wall of the hole to conduct electricity between the metal foils for the inner and outer layer circuits. Then, the metal foils for the outer layer circuits are etched to form outer layer circuits, thereby manufacturing a multilayer printed circuit board.

[0283] The printed wiring board obtained in the manufacturing example is configured to have an insulating layer and a conductor layer formed on one or both sides of the insulating layer, and the insulating layer contains the resin composition of this embodiment. For example, the prepreg (substrate and the resin composition of this embodiment impregnated or coated therein) of this embodiment and the resin composition layer of the metal foil laminate of this embodiment (layer containing the resin composition of this embodiment) may be configured as an insulating layer containing the resin composition of this embodiment.

[0284] [Sealing materials]

[0285] 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.

[0286] [Fiber-reinforced composite materials]

[0287] 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.

[0288] 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.

[0289] [Adhesive]

[0290] 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.

[0291] [Semiconductor Devices]

[0292] The semiconductor device of this embodiment includes the resin composition of this embodiment. Specifically, it can be manufactured by the following method. The semiconductor device can be manufactured by mounting a semiconductor chip to a conductive portion of a multilayer printed circuit board of this embodiment. Here, the conductive portion refers to a portion in the multilayer printed circuit board that transmits electrical signals, and the location 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.

[0293] As long as the semiconductor chip functions effectively, there is no particular limitation on the mounting method of the semiconductor chip when manufacturing the semiconductor device of this embodiment. 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).

[0294] Alternatively, a semiconductor device can be manufactured by forming an insulating layer comprising the resin composition of this embodiment 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 the multilayer printed circuit board.

[0295] [Example]

[0296] The present invention will now be described in more detail based on embodiments and comparative examples, but the present invention is not limited to the following embodiments.

[0297] The conditions for determining molecular weight are as follows.

[0298] Model: GPC Tosoh HLC-8220GPC

[0299] Column: Super HZM-N

[0300] Eluent: Tetrahydrofuran (THF); 0.35 ml / min, 40 °C

[0301] Detector: Differential refractometer (RI)

[0302] Molecular weight standard: Polystyrene

[0303] <Synthesis of bismaleimide compound (A)>

[0304] [Synthesis example 1]

[0305] 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 44-(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).

[0306] [Comparative Synthesis Example 1]

[0307] 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).

[0308] [Examples 1 to 3 and Comparative Examples 1 to 3]

[0309] <Preparation of Thermosetting Resin Compositions and Resin Films>

[0310] The thermosetting resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were prepared by mixing the components shown in Table 1 with the compositions listed below. Using a coater, the thermosetting resin compositions were coated onto a 12 μm ultra-low roughness electrolytic copper foil (CF-T4X-SV (trade name), manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) on a hot plate heated to 60°C. The foil was then subjected to a heat treatment at 120°C for 30 minutes in an oven to produce a resin film of 100 μm thickness in the B-stage state. Furthermore, in Table 1, the amounts of components (A) to (D) represent parts by mass. In addition, in preparing the thermosetting resin compositions, the compound obtained in Synthesis Example 1 was used in Examples 1, 2, and 3, and the compound obtained in Comparative Synthesis Example 1 was used in Comparative Example 3.

[0311] <(A) Bismaleimide Compound>

[0312] (A-1) A bismaleimide compound containing the structural unit represented by general formula (1) and maleimide groups at both ends of the molecular chain.

[0313] The bismaleimide compound A-1 of Synthetic Example 1 (the compound represented by formula (3) below, which is a high-viscosity liquid at 25°C)

[0314] [Chemistry 21]

[0315]

[0316] In equation (3), 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.

[0317] <(A') Bismaleimide compounds that do not satisfy general formula (1)>

[0318] (A'-1)BMI-2300 (polyphenylmethane maleimide, a compound represented by the following formula (19), manufactured by Yamato Chemical Co., Ltd., solid at 25°C)

[0319] (A'-2)BMI-3000 (the compound represented by formula (12) below, manufactured by Designnermollectles Inc., is a solid at 25°C)

[0320] (A'-3) Comparative Synthesis Example 1 (the compound represented by formula (20) below is liquid at 25°C)

[0321] [Chemistry 22]

[0322]

[0323] In equation (19), all of the plurality of R1s represent hydrogen atoms. n9 represents an integer greater than or equal to 1, preferably an integer from 1 to 10, and more preferably an integer from 1 to 5.

[0324] [Chemistry 23]

[0325]

[0326] In the formula (12), n8 represents an integer greater than or equal to 1, and is preferably an integer from 1 to 10.

[0327] [Chemistry 24]

[0328]

[0329] In equation (20), n 10 It represents an integer greater than or equal to 1, preferably an integer from 1 to 6.

[0330] <(B) Thermosetting resins or compounds>

[0331] (B-1)BMI-689 (the compound represented by formula (15) below, manufactured by Designer Molecules Inc., is liquid at 25°C)

[0332] (B-2)MIR-5000 (the compound represented by formula (21) below, manufactured by Nippon Kayaku Co., Ltd., is a solid at 25°C)

[0333] [Chemistry 25]

[0334]

[0335] [Chemistry 26]

[0336]

[0337] In the above equation (21), n 11 It represents an integer greater than or equal to 1, preferably an integer from 1 to 10.

[0338] <(C) Polymerization Initiator>

[0339] (C-1) Percumyl D (Dicumyl Peroxide, manufactured by Nippon Oil & Fat Co., Ltd.)

[0340] <(D) Hardening Accelerator>

[0341] (D-1)2-Ethyl-4-methylimidazolium (manufactured by Shikoku Chemical Co., Ltd.)

[0342] <Fabrication of Copper Foil Laminates>

[0343] The resin film stripped by etching is laminated with two copper foils (CF-T4X-SV (trade name), manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) with the mirror surface of the copper foil facing the resin film. The laminate is then hot-pressed at 220°C, 1.0 MPa and 2 hours to obtain a laminate formed by sequentially stacking copper foil, resin film and copper foil.

[0344] <Characteristic Evaluation>

[0345] The following properties were measured for the prepared thermosetting resin composition and copper foil laminate. The results are shown in Table 1.

[0346] [Compatibility]

[0347] Compatibility refers to the visual state of a mixture after stirring a compound containing bismaleimide (A), a thermosetting resin or compound (B), a polymerization initiator (C), and a curing accelerator (D). Good compatibility means that the mixture can be coated onto a substrate without exudates, while poor compatibility means that the mixture contains exudates, making it difficult to coat onto a substrate.

[0348] (Evaluation Criteria)

[0349] ○: No precipitates

[0350] ×: There is precipitate

[0351] [Dielectric Properties]

[0352] 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 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.

[0353] [Tension elastic modulus]

[0354] 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 6cm × 5mm test piece. The tensile modulus and elongation were measured on the obtained test piece using a tensile testing machine (trade name "RTG-1201" manufactured by A&D Corporation) at 25°C and a speed of 5mm / min.

[0355] [Heat resistance]

[0356] 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 into 4mm squares. 1.0mg to 5.0mg of each square was weighed into a measuring pan, and the 5% weight loss (Td5) was measured under conditions of an air flow rate of 100mL / sec and a heating rate of 10°C / min. The measuring apparatus used was a thermogravimetric analysis / differential scanning calorimeter (TGA / DSC)¹ (manufactured by Mettler Toledo).

[0357] Glass transition temperature

[0358] 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.

[0359] Water absorption rate

[0360] 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.

[0361] [High Accelerated Stress Test (HAST) Tolerance]

[0362] 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.

[0363] ○··100 hours or more

[0364] △··20 hours~100 hours

[0365] ×·· Less than 20 hours

[0366] [Table 1]

[0367]

[0368] As clearly demonstrated by the results shown in Table 1, the thermosetting resin compositions of Examples 1 to 3 exhibit good adhesion to the substrate and, in terms of the characteristics of their cured products, possess low dielectric properties, low elastic modulus, high heat resistance, and low water absorption. Therefore, the thermosetting resin compositions of the present invention can be used for applications such as photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit boards (for laminates, multilayer printed circuit boards, etc.), solder resists, underfill materials, die bonders, semiconductor sealants, hole-filling resins, component embedding resins, and fiber-reinforced composite materials. This can significantly improve the characteristics of laminates such as printed circuit boards and electronic components such as semiconductor devices.

Claims

1. A thermosetting resin composition comprising: a bismaleimide compound (A) comprising a structural unit represented by the following formula (1) and comprising a maleimide group at both ends of a molecular chain; a thermosetting resin or compound (B); and a polymerization initiator (C) and / or a hardening accelerator (D), In formula (1), Q 1 represents a linear or branched alkylene group having 1 to 16 carbons, or a linear or branched alkenylene group having 2 to 16 carbons; Q 2 represents a linear or branched alkylene group having 1 to 16 carbons, or a linear or branched alkenylene group having 2 to 16 carbons; Q 3 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbons, or a linear or branched alkenyl group having 2 to 16 carbons; Q 4 each independently represents a hydrogen atom, a linear or branched alkyl group having a carbon number of 1 to 6, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having a carbon number of 1 to 6; n 1 each independently represents an integer of 1 to 4; m 1 each independently represents an integer of 1 to 4, wherein, the thermosetting resin or compound (B) comprises a maleimide compound represented by the following formula (6) or a maleimide compound represented by the following formula (9), in formula (6), R3 each independently represents a hydrogen atom, an alkyl group having a carbon number of 1 to 5, or a phenyl group, l2 each independently represents an integer of 1 to 3, and n4 represents an integer of 1 to 10, In formula (9), R a represents a linear or branched alkyl group having 1 to 16 carbons, or a linear or branched alkenyl group having 1 to 16 carbons, R b represents a linear or branched alkyl group having 1 to 16 carbons, or a linear or branched alkenyl group having 1 to 16 carbons, n a represents an integer of 2 to 16, n b represents an integer of 2 to 16, n a may be the same or different. b may be the same or different.

2. The thermosetting resin composition according to claim 1, wherein the polymerization initiator (C) comprises a thermal radical polymerization initiator.

3. The thermosetting resin composition according to claim 1 or 2, wherein, the hardening accelerator (D) comprises at least one compound selected from the group consisting of a phosphine compound, a compound having a phosphonium salt, and an imidazole-based compound.

4. The thermosetting resin composition according to claim 1 or 2, wherein, a content of the bismaleimide compound (A) is 1 mass part to 99 mass parts in a case where a total amount of the bismaleimide compound (A) and the thermosetting resin or compound (B) is set to 100 mass parts.

5. The thermosetting resin composition according to claim 1 or 2, wherein, a filler is further included.

6. A hardened product comprising the thermosetting resin composition according to any one of claims 1 to 5.

7. A resin sheet having: a support; and a resin layer disposed on one face or both faces of the support, the resin layer comprising the thermosetting resin composition according to any one of claims 1 to 5.

8. A prepreg comprising: a base material; and the thermosetting resin composition according to any one of claims 1 to 5 impregnated or coated on the base material.

9. A metal-clad laminate having: a layer comprising at least one selected from the group consisting of the resin sheet according to claim 7 and the prepreg according to claim 8; and a metal foil disposed on one face or both faces of the layer, the layer comprising a hardened product of the thermosetting resin composition.

10. A multilayer printed wiring board having: an insulating layer; and a conductor layer formed on one face or both faces of the insulating layer, the insulating layer comprising the thermosetting resin composition according to any one of claims 1 to 5.

11. A sealing material comprising the thermosetting resin composition according to any one of claims 1 to 5.

12. A fiber-reinforced composite material comprising the thermosetting resin composition according to any one of claims 1 to 5 and a reinforcing fiber.

13. An adhesive comprising the thermosetting resin composition according to any one of claims 1 to 5.

14. A semiconductor device having the thermosetting resin composition according to any one of claims 1 to 5. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​

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