Resin composition, resin sheet, prepreg, metal foil-clad laminate, and printed wiring board

Abstract

To provide a resin composition that allows obtaining a cured product in which brittleness is more effectively improved and which is excellent in thermal conductivity and heat resistance.SOLUTION: A resin composition comprises a cyanate ester compound (A) represented by the following formula (1) and an epoxy compound (B) represented by the following formula (2), wherein the epoxy compound (B) contains 85 mol% or more of an epoxy compound represented by the following formula (2a).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition, and to a single-layer resin sheet, a laminated resin sheet, a prepreg, a cured product, a metal foil-clad laminate, a printed wiring board, a semiconductor package, and a semiconductor device using the same. [Background technology]

[0002] In recent years, the integration and miniaturization of semiconductors, which are widely used in electronic devices, communication devices, personal computers, etc., have been accelerating. Accordingly, the properties required of printed wiring boards used in semiconductor packages and semiconductor devices have become increasingly stringent. Examples of required properties include low water absorption, moisture absorption heat resistance, flame retardancy, low dielectric constant, low dielectric dissipation factor, low thermal expansion coefficient, heat resistance, chemical resistance, and high plating peel strength.

[0003] Cyanate ester compounds have long been known as resins for printed wiring boards that have excellent heat resistance and electrical properties, and in recent years, resin compositions containing cyanate ester compounds in combination with epoxy resins, bismaleimide compounds, etc. have been widely used as materials for high-performance printed wiring boards for semiconductor packages, etc. For example, Patent Document 1 describes that a resin composition comprising a cyanate ester compound of a specific structure and other components has excellent properties such as low water absorption and a low coefficient of thermal expansion. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2012 / 105547 Summary of the Invention [Problem to be solved by the invention]

[0005] Although the resin composition described in Patent Document 1 can be said to have favorable physical properties such as low water absorption and low thermal expansion coefficient, there is still room for improvement in terms of thermal conductivity. For example, when used as an insulating material for printed wiring boards or other resin sheets, if the thermal conductivity is insufficient, it is difficult to apply the composition to applications requiring heat dissipation. Furthermore, further improvement in brittleness and better heat resistance are also required.

[0006] The present invention has been made in view of the above-mentioned problems, and aims to provide a resin composition that can further improve brittleness and give a cured product with excellent thermal conductivity and heat resistance. [Means for solving the problem]

[0007] Means for Solving the Problems of the Invention The present inventors conducted extensive research to achieve the objects of the present invention and found that the above-mentioned problems can be solved by using a cyanate ester compound having a specific structure in combination with an epoxy compound having a specific structure, thereby completing the present invention.

[0008] That is, the present invention is as follows. [1] A composition comprising a cyanate ester compound (A) represented by the following formula (1) and an epoxy compound (B) represented by the following formula (2), The resin composition, wherein the epoxy compound (B) contains 85 mol % or more of an epoxy compound represented by the following formula (2a):

[0009] [ka]

[0010] [In formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom; R9 each independently represents an alkyl group having 1 to 6 carbon atoms or a halogen atom; a represents an integer of 0 to 6, and a double line consisting of two solid lines and a dashed line represents one single bond and the other a double bond.

[0011] [ka]

[0012] [In formula (2), R a , R b , R c , R d , R e , R f , R g , and R h each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]

[0013] [ka]

[0014] [2] The resin composition according to [1] above, wherein the cyanate ester compound (A) comprises at least one selected from the group consisting of cyanate ester compounds represented by the following formula (1a) and cyanate ester compounds represented by the following formula (1b):

[0015] [ka]

[0016] [3] The resin composition according to [1] or [2] above, wherein the content of the cyanate ester compound (A) is 50 parts by mass or more and 99 parts by mass or less, relative to 100 parts by mass of the total of the cyanate ester compound (A) and the epoxy compound (B). [4] The resin composition according to any one of the above [1] to [3], further comprising a filler having a thermal conductivity of 3 W / (m·K) or more. [5] The resin composition according to any one of the above [1] to [4], which is for use in a sheet-shaped molded product. [6] A single-layer resin sheet formed from the resin composition according to any one of the above [1] to [4]. [7] A laminated resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of [1] to [4] above, provided on one or both sides of the support. [8] A prepreg comprising a substrate and the resin composition according to any one of [1] to [4] above, which is impregnated into or applied to the substrate. [9] A cured product formed by curing the resin composition according to any one of the above [1] to [4].

[10] A metal foil-clad laminate having a cured layer containing a cured product formed by curing the resin composition according to any one of [1] to [4] above, and a metal foil provided on one or both sides of the cured layer.

[11] A printed wiring board comprising an insulating layer containing a cured product formed by curing the resin composition according to any one of the above [1] to [4].

[12] A semiconductor package comprising the printed wiring board according to

[11] above and a semiconductor element.

[13] A semiconductor device having the printed wiring board according to

[11] above. [Effects of the Invention]

[0017] According to the resin composition of the present invention, brittleness can be further improved, and a cured product having excellent thermal conductivity and heat resistance can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be implemented with any modifications within the scope of the claims of the present invention and their equivalents.

[0019] In this specification, the resin solid content refers to components excluding fillers and solvents, and is intended to include the cyanate ester compound (A), the epoxy compound (B), and other components that are blended as necessary, as well as resin additive components (additives such as flame retardants, etc.).

[0020] [Resin composition] The resin composition of this embodiment contains a cyanate ester compound (A) represented by formula (1) and an epoxy compound (B) represented by formula (2). In this embodiment, the epoxy compound (B) contains 85 mol % or more of an epoxy compound represented by formula (2a). The resin composition of this embodiment can further improve brittleness and can provide a cured product with excellent thermal conductivity and heat resistance.

[0021] [Cyanate ester compound (A)] The resin composition of the present embodiment contains a cyanate ester compound (A) represented by the following formula (1).

[0022] [ka]

[0023] [In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom; R 9 each independently represents an alkyl group having 1 to 6 carbon atoms or a halogen atom; a represents an integer of 0 to 6, and a double line consisting of two solid lines and a dashed line represents one single bond and the other a double bond.

[0024] The alkyl group refers to a linear, branched, and / or cyclic monovalent aliphatic saturated hydrocarbon group. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclopentyl group, and a cyclohexyl group. The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0025] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom, and in one embodiment, is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or a methyl group, and from the viewpoint of further improving liquid crystallinity, is particularly preferably a hydrogen atom. a represents an integer of 0 to 6, and in one embodiment, is particularly preferably 0.

[0026] The cyanate ester compound (A) is a compound selected from the group consisting of cyanate ester compounds represented by the following formula (1-1) and cyanate ester compounds represented by the following formula (1-2).

[0027] [ka]

[0028] [In the formula, the definitions of each symbol are the same as in formula (1)]

[0029] In one embodiment, from the viewpoint of further improving liquid crystal properties, the cyanate ester compound (A) particularly preferably contains at least one of a cyanate ester compound represented by the following formula (1a) (i.e., 1,4-bis(4-cyanatophenyl)-1-cyclohexene) and a cyanate ester compound represented by the following formula (1b) (i.e., 1,4-bis(4-cyanatophenyl)-2-cyclohexene).

[0030] [ka]

[0031] The cyanate ester compound (A) can be produced by cyanating a phenol compound represented by the following formula (1') using a known method or a method equivalent thereto. Known methods for cyanating a phenol compound include those described in U.S. Pat. No. 3,553,244, Japanese Patent No. 3,319,061, Japanese Patent No. 3,905,559, Japanese Patent No. 4,055,210, Japanese Patent No. 2,991,054, and Japanese Patent No. 5,026,727.

[0032] [ka]

[0033] [In the formula, the definitions of each symbol are the same as in formula (1)]

[0034] From the viewpoint of ease of handling, the melting point of the cyanate ester compound (A) is preferably 200°C or less, more preferably 170°C or less, even more preferably 150°C or less, and particularly preferably 130°C or less. When the melting point of the cyanate ester compound (A) is within the above range, the handleability is further improved, and the compatibility of the filler with the cyanate ester compound (A) at low temperatures is further improved. The lower limit of the melting point of the cyanate ester compound (A) is not particularly limited, but may be -50°C or 0°C, since the cyanate ester compound (A) may be in a liquid state at room temperature.

[0035] The content of the cyanate ester compound (A) relative to 100 parts by mass of the resin solid content in the resin composition is not particularly limited, but in one embodiment, from the viewpoint of further improving brittleness, it is preferably 99 parts by mass or less, more preferably 97 parts by mass or less, even more preferably 95 parts by mass or less, even more preferably 93 parts by mass or less, and particularly preferably 92 parts by mass or less, and from the viewpoint of further improving heat resistance, the lower limit is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 40 parts by mass or more, and particularly preferably 50 parts by mass or more.

[0036] The content of the cyanate ester compound (A) relative to 100 parts by mass in total of the cyanate ester compound (A) and the epoxy compound (B) described below is not particularly limited, but in one embodiment, from the viewpoint of further improving heat resistance, it is preferably 99 parts by mass or less, more preferably 97 parts by mass or less, even more preferably 95 parts by mass or less, even more preferably 93 parts by mass or less, and particularly preferably 92 parts by mass or less; and from the viewpoint of further improving brittleness, the lower limit is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 40 parts by mass or more, and particularly preferably 50 parts by mass or more.

[0037] [Epoxy compound (B)] The resin composition of the present embodiment contains an epoxy compound (B) represented by the following formula (2).

[0038] [ka]

[0039] [In the formula, R a , R b , R c , R d , R e , R f , R g , and R h each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]

[0040] R a , R b , R c , R d , R e , R f , R g , and R h each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; in one embodiment, R a , R b , R e , and R f are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R c , R d , R g , and R h is preferably a hydrogen atom; R a , R b , R e , and R f are each independently a hydrogen atom or a methyl group, and R c , R d , R g , and R h is more preferably a hydrogen atom; R a , R b , R c , R d , R e , R f , R g , and R h is particularly preferably a hydrogen atom.

[0041] The epoxy compound (B) contains 85 mol % or more of an epoxy compound represented by the following formula (2a) (i.e., 4,4'-bis(glycidyloxy)-1,1'-biphenyl), and in one embodiment, from the viewpoint of further improving liquid crystallinity and thermal conductivity, it preferably contains 90 mol % or more of an epoxy compound represented by the following formula (2a).

[0042] [ka]

[0043] The content of the epoxy compound (B) relative to 100 parts by mass of the resin solid content in the resin composition is not particularly limited, but in one embodiment, from the viewpoint of further improving heat resistance, it is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, and particularly preferably 50 parts by mass or less, and the lower limit, from the viewpoint of further improving brittleness, is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, even more preferably 7 parts by mass or more, and particularly preferably 8 parts by mass or more.

[0044] [Filling material] The resin composition of this embodiment may further contain a filler. From the viewpoint of thermal conductivity, the filler preferably contains a filler having a thermal conductivity of 3 W / (m·K) or more. The filler preferably contains a filler having a thermal conductivity of 5 W / (m·K) or more, even more preferably a filler having a thermal conductivity of 10 W / (m·K) or more, even more preferably a filler having a thermal conductivity of 15 W / (m·K) or more, even more preferably a filler having a thermal conductivity of 20 W / (m·K) or more, even more preferably a filler having a thermal conductivity of 25 W / (m·K) or more, and particularly preferably a filler having a thermal conductivity of 30 W / (m·K) or more. The thermal conductivity of the filler can be confirmed by referring to the "Thermal Properties Handbook" compiled by the Japan Society of Thermophysical Properties, etc., and a known value can be used as the thermal conductivity of the filler. It is preferable that 50 mass% or more of the filler in the resin composition has a thermal conductivity of 3 W / (m·K) or more, and more preferably 75 mass% or more of the filler has a thermal conductivity of 3 W / (m·K) or more, based on the total amount of filler contained in the resin composition.

[0045] As the filler, fillers generally used in laminated plate applications can be suitably used. Specific examples include silicas such as natural silica, crystalline silica, synthetic silica, amorphous silica, aerosil, and hollow silica; oxides such as white carbon, titanium white, zinc oxide, magnesium oxide, and zirconium oxide; boron nitride, agglomerated boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide, heat-treated aluminum hydroxide (aluminum hydroxide that has been heat-treated to remove some of the water of crystallization); boehmite; metal hydrates such as magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, short glass fibers (including glass fine powders such as E-glass, T-glass, D-glass, S-glass, and Q-glass), hollow glass, and spherical glass. Among these, from the viewpoint of excellent thermal conductivity, at least one selected from the group consisting of silicas, boron nitride, aggregated boron nitride, silicon nitride, aluminum nitride, boehmite, and alumina is preferred, and at least one selected from the group consisting of alumina, aluminum nitride, boron nitride, and aggregated boron nitride is particularly preferred. In addition to the inorganic filler, the resin composition of this embodiment may contain organic fillers such as styrene-type, butadiene-type, and acrylic-type rubber powders, core-shell-type rubber powders, silicone resin powders, silicone rubber powders, and silicone composite powders.

[0046] The amount of filler to be filled is not particularly limited, but from the viewpoint of providing better thermal conductivity, it is preferably 40% by volume or more, more preferably 50% by volume or more, even more preferably 60% by volume or more, and even more preferably 70% by volume or more, relative to the volume of the total solid content (including the filler) in the resin composition, while from the viewpoint of moldability, it is preferably 90% by volume or less, more preferably 85% by volume or less.

[0047] When the filler is contained in the resin composition, a silane coupling agent or a wetting and dispersing agent may be used in combination. As the silane coupling agent, those generally used for the surface treatment of inorganic materials can be suitably used, and the type thereof is not particularly limited. Specific examples of the silane coupling agent include, but are not limited to, 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, Amino-based silane coupling agents such as N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, [3-(6-aminohexylamino)propyl]trimethoxysilane, and [3-(N,N-dimethylamino)propyl]trimethoxysilane; epoxy-based silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldiethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and [8-(glycidyloxy)-n-octyl]trimethoxysilane; vinyltris(2-methoxyethoxy) Vinyl silane coupling agents such as silane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trimethoxy(7-octen-1-yl)silane, and trimethoxy(4-vinylphenyl)silane; methacrylic silane coupling agents such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, and 3-methacryloxypropyldiethoxymethylsilane; acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane; and 3-isocyanatepropyltrimethoxysilane.Isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane, isocyanurate-based silane coupling agents such as tris-(trimethoxysilylpropyl)isocyanurate, mercapto-based silane coupling agents such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyldimethoxymethylsilane, ureido-based silane coupling agents such as 3-ureidopropyltriethoxysilane, styryl-based silane coupling agents such as p-styryltrimethoxysilane, N-[2-(N-biphenyl)-2-(methylphenyl)-2-(phenyl ... Examples of suitable silane coupling agents include cationic silane coupling agents such as [3-(trimethoxysilyl)propyl]succinic anhydride silane coupling agents, phenyl silane coupling agents such as phenyl trimethoxysilane, phenyl triethoxysilane, dimethoxymethyl phenyl silane, diethoxymethyl phenyl silane, and p-tolyl trimethoxysilane, and aryl silane coupling agents such as trimethoxy(1-naphthyl)silane. These silane coupling agents can be used alone or in combination of two or more. Suitable wetting and dispersing agents are those commonly used in paints, and the type is not particularly limited. A copolymer-based wetting and dispersing agent is preferably used, and commercially available products may also be used. Specific examples of commercially available products include, but are not limited to, Disperbyk-110, 111, 161, 180, BYK-W996, BYK-W9010, BYK-W903, and BYK-W940 manufactured by BYK-Chemie Japan Co., Ltd. One type of wetting and dispersing agent can be used alone, or two or more types can be used in combination.

[0048] [Curing accelerator] The resin composition of this embodiment may further contain a curing accelerator. As the curing accelerator, those generally used as curing accelerators for cyanate ester compounds, epoxy resins, etc. can be suitably used, and the type thereof is not particularly limited. Specific examples of the curing accelerator include organic metal salts such as zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetonate, nickel octylate, and manganese octylate; phenolic compounds such as phenol, xylenol, cresol, resorcinol, catechol, octylphenol, and nonylphenol; alcohols such as 1-butanol and 2-ethylhexanol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole. Examples of the curing accelerator include imidazoles such as 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole, derivatives of these imidazoles such as adducts of carboxylic acids or their acid anhydrides, amines such as dicyandiamide, benzyldimethylamine and 4-methyl-N,N-dimethylbenzylamine, phosphine compounds, phosphine oxide compounds, phosphonium salt compounds such as tetraphenylphosphonium tetra-p-tolylborate, phosphorus compounds such as diphosphine compounds, and epoxy-imidazole adduct compounds. One type of curing accelerator can be used alone, or two or more types can be used in combination.

[0049] The content of the curing accelerator is not particularly limited, but in one embodiment, when the resin solid content in the resin composition is 100 parts by mass, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 2 parts by mass or less, and the lower limit is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 1 part by mass or more.

[0050] [Other thermosetting compounds] The resin composition of this embodiment may contain a thermosetting compound (other thermosetting compound) other than the cyanate ester compound (A) represented by formula (1) and the epoxy compound (B) represented by formula (2). Examples of such other thermosetting compounds include, but are not limited to, cyanate ester compounds other than the cyanate ester compound (A) represented by formula (1), epoxy compounds other than the epoxy compound (B) represented by formula (2), maleimide compounds, phenolic compounds, oxetane compounds, benzoxazine compounds, and radically polymerizable group-containing compounds. The other thermosetting compounds may be used alone or in combination of two or more.

[0051] When the resin composition of the present embodiment contains another thermosetting compound, the content thereof is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and may be 10 parts by mass or more or 20 parts by mass or more, based on 100 parts by mass of the resin solid content in the resin composition, depending on the application, etc. The upper limit of the content is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less.

[0052] When the resin composition of the present embodiment contains other thermosetting compounds, the total content of the cyanate ester compound (A) represented by formula (1) and the epoxy compound (B) represented by formula (2) relative to 100 parts by mass of the resin solid content in the resin composition is, from the viewpoint of the effects of the present invention, preferably 50 parts by mass or more, more preferably 70 parts by mass or more, even more preferably 80 parts by mass or more, and even more preferably 90 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition, and may be 95 parts by mass or more or 99 parts by mass or more depending on the application, etc.

[0053] [Cyanate ester compounds other than cyanate ester compound (A)] The resin composition of the present embodiment may further contain a cyanate ester compound other than the cyanate ester compound (A). Examples of cyanate ester compounds other than the cyanate ester compound (A) include benzene compounds substituted with two or three cyanato groups (e.g., 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, etc.), naphthalene compounds substituted with two or three cyanato groups (e.g., 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricinatonaphthalene, etc.), biphenyl compounds substituted with two or three cyanato groups (e.g., 4,4'-dicyanatobiphenyl, etc.), novolak-type cyanate esters, aralkyl-type cyanate esters (e.g., phenol aralkyl-type cyanate esters, naphthol aralkyl-type cyanate esters, etc.), and the like. Examples of suitable cyanate esters include, but are not limited to, bisphenol cyanate esters (e.g., bisphenol A cyanate esters, bisphenol E cyanate esters, bisphenol F cyanate esters, bisphenol AD ​​cyanate esters, bisphenol B cyanate esters, bisphenol AP cyanate esters, bisphenol S cyanate esters, bisphenol Z cyanate esters, and bisphenol TMC cyanate esters), and diallyl bisphenol cyanate esters (e.g., diallyl bisphenol A cyanate esters, diallyl bisphenol F cyanate esters, diallyl bisphenol E cyanate esters, and diallyl bisphenol S cyanate esters), and prepolymers of these cyanate esters. These cyanate ester compounds can be used alone or in combination of two or more.

[0054] [Epoxy compounds other than epoxy compound (B)] The resin composition of the present embodiment may further contain an epoxy compound other than the epoxy compound (B). Examples of epoxy compounds other than the epoxy compound (B) include bisphenol A type epoxy resins, bisphenol E type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD ​​type epoxy resins, phenol novolac type epoxy resins, bisphenol A novolac type epoxy resins, aralkyl novolac type epoxy resins, biphenyl aralkyl type epoxy resins, biphenyl novolac type epoxy resins, naphthylene ether type epoxy resins, cresol novolac type epoxy resins, polyfunctional phenol type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, dihydroanthracene ... Examples of epoxy compounds include, but are not limited to, talc skeleton-modified novolac epoxy resins, phenol aralkyl epoxy resins, naphthol aralkyl epoxy resins, dicyclopentadiene epoxy resins, triphenylmethane epoxy resins, tetraphenylethane epoxy resins, isocyanuric acid epoxy resins, fluorene epoxy resins, xanthene epoxy resins, alicyclic epoxy resins, polyol epoxy resins, phosphorus-containing epoxy resins, glycidylamine epoxy resins, glycidyl ester epoxy resins, compounds in which the double bond of butadiene or the like has been epoxidized, and compounds obtained by reacting hydroxyl group-containing silicone resins with epichlorohydrin. These epoxy compounds can be used alone or in combination of two or more.

[0055] [Maleimide Compound] The resin composition of the present embodiment may further contain a maleimide compound. Examples of the maleimide compound include monofunctional maleimide compounds having one maleimide group per molecule (e.g., N-phenylmaleimide, N-hydroxyphenylmaleimide, etc.), bifunctional maleimide compounds having two maleimide groups per molecule (e.g., bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane), m-phenylmaleimide, bis(4-maleimidophenyl)methane ... Examples of suitable maleimide compounds include, but are not limited to, phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, maleimide compounds having a carbon skeleton derived from dimer acid, maleimide compounds having an indane ring skeleton, dicyclopentadiene maleimide compounds, novolac maleimide compounds, aralkyl maleimide compounds (e.g., biphenylaralkyl maleimide compounds), and prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds. These maleimide compounds can be used alone or in combination of two or more.

[0056] [Phenol compounds] The resin composition of this embodiment may further contain a phenolic compound. Examples of the phenolic compound include bisphenol A phenolic resins, bisphenol E phenolic resins, bisphenol F phenolic resins, bisphenol S phenolic resins, phenol novolac resins, bisphenol A novolac phenolic resins, glycidyl ester phenolic resins, aralkyl novolac phenolic resins, biphenyl aralkyl phenolic resins, cresol novolac phenolic resins, multifunctional phenolic resins, naphthol resins, naphthol novolac resins, multifunctional naphthol resins, anthracene phenolic resins, naphthalene skeleton-modified novolac phenolic resins, phenol aralkyl phenolic resins, naphthol aralkyl phenolic resins, dicyclopentadiene phenolic resins, biphenyl phenolic resins, alicyclic phenolic resins, polyol phenolic resins, phosphorus-containing phenolic resins, and hydroxyl group-containing silicone resins, but are not particularly limited thereto. These phenolic compounds may be used alone or in combination of two or more.

[0057] [Oxetane Compounds] The resin composition of this embodiment may further contain an oxetane compound. Examples of the oxetane compound include alkyl oxetanes such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3-di(trifluoromethyl)perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl oxetane, 3-ethyl-3-hydroxymethyloxetane, and xylylene bisoxetane, but are not particularly limited thereto. These oxetane compounds can be used alone or in combination.

[0058] [Benzoxazine Compounds] The resin composition of this embodiment may further contain a benzoxazine compound. Examples of the benzoxazine compound include, but are not limited to, bisphenol A benzoxazine, bisphenol F benzoxazine, bisphenol S benzoxazine, Pd benzoxazine, and Fa benzoxazine. These benzoxazine compounds can be used alone or in combination of two or more.

[0059] [Radically polymerizable group-containing compound] The resin composition of this embodiment may further contain a radically polymerizable group-containing compound. Examples of radically polymerizable group-containing compounds include, but are not limited to, vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; (meth)acrylates of monohydric or polyhydric alcohols such as methyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; epoxy(meth)acrylates such as bisphenol A-type epoxy(meth)acrylate and bisphenol F-type epoxy(meth)acrylate; and benzocyclobutene resins. These radically polymerizable group-containing compounds may be used alone or in combination. The term "(meth)acrylate" encompasses acrylate and methacrylate.

[0060] [Other additives] The resin composition of this embodiment may further contain other thermosetting resins, epoxy resin curing agents, various polymeric compounds such as thermoplastic resins and their oligomers, elastomers, flame-retardant compounds, and various additives, provided that the desired properties are not impaired. These may be any commonly used compounds, but are not limited to these. Examples of epoxy resin curing agents include active ester compounds, carbodiimide compounds, amine compounds, and acid anhydrides. Specific examples of flame-retardant compounds include, but are not limited to, bromine compounds such as 4,4'-dibromobiphenyl, nitrogen compounds such as phosphate esters, melamine phosphate, melamine, and benzoguanamine, oxazine ring-containing compounds, and silicone compounds. Examples of various additives include, but are not limited to, ultraviolet absorbers, antioxidants, radical polymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, flow control agents, lubricants, antifoaming agents, dispersants, leveling agents, gloss agents, and polymerization inhibitors. These may be used alone or in combination as desired.

[0061] 〔solvent〕 The resin composition of this embodiment may contain a solvent. The resin composition of this embodiment can be used in a form (solution or varnish) in which at least a portion, preferably all, of the various resin components described above are dissolved or compatible in the solvent. Any known solvent can be used as long as it can dissolve or compatible at least a portion, preferably all, of the various resin components described above. The type of solvent is not particularly limited. Specific examples of solvents include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alicyclic ketones such as cyclopentanone and cyclohexanone; cellosolve-based solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ester-based solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, and methyl hydroxyisobutyrate; polar solvents such as amides such as dimethylacetamide and dimethylformamide; and nonpolar solvents such as aromatic hydrocarbons such as toluene and xylene. The solvents can be used alone or in combination of two or more.

[0062] [Method for producing resin composition] The resin composition of this embodiment can be prepared according to a conventional method, and the preparation method is not particularly limited as long as it is a method that can obtain a resin composition uniformly containing the cyanate ester compound (A), the epoxy compound (B), and, as necessary, the other optional components described above. For example, the resin composition of this embodiment can be easily prepared by sequentially blending the cyanate ester compound (A), the epoxy compound (B), and the other optional components described above in a solvent and thoroughly stirring the mixture.

[0063] When preparing the resin composition, known processes (such as stirring, mixing, and kneading) can be performed to uniformly dissolve or disperse each component. For example, when a filler is used, the filler's dispersibility in the resin composition can be improved by performing a stirring and dispersion process using a stirring tank equipped with a stirrer having appropriate stirring capabilities to uniformly disperse the filler. The stirring, mixing, and kneading processes can be appropriately performed using, for example, a mixing device such as a ball mill or a bead mill, or a known device such as a revolution / rotation type mixer.

[0064] [Uses of resin composition] The resin composition of this embodiment has excellent thermal conductivity, particularly in the cured product, and is therefore particularly preferred for use in sheet-like molded articles such as single-layer resin sheets, laminated resin sheets, and prepregs. The resin composition of this embodiment is also suitable for use in the production of printed wiring boards. Therefore, the resin composition of this embodiment can be suitably used as a resin composition for forming an insulating layer of a printed wiring board. The resin composition of this embodiment can also be used in a wide range of applications, such as metal foil-clad laminates, solder resist materials, underfill materials, die bonding materials, and semiconductor encapsulants.

[0065] For example, a build-up film or dry film solder resist can be obtained by using a peelable plastic film as a support, dissolving the resin composition of this embodiment in a solvent, applying the solution to the plastic film, and drying the solution. The solvent can be removed by drying at a temperature of 20°C to 150°C for 1 to 90 minutes. The resin composition of this embodiment can be used in an uncured state from which the solvent has been removed, or, if necessary, in a semi-cured state (B-stage).

[0066] [Cured product of resin composition] The cured product of this embodiment is formed by curing the resin composition of this embodiment. The method for producing the cured product is not particularly limited, but for example, the resin composition can be melted or dissolved in a solvent, poured into a mold, and cured under normal conditions using heat, light, or the like. In the case of heat curing, the curing temperature is not particularly limited, but is preferably within the range of 120°C to 300°C from the viewpoint of efficient curing and preventing deterioration of the resulting cured product. In the case of photocuring, the wavelength range of light is not particularly limited, but is preferably within the range of 100 nm to 500 nm, at which curing proceeds efficiently using a photopolymerization initiator, etc.

[0067] The cured product of this embodiment has excellent thermal conductivity. Therefore, in certain embodiments, the thermal conductivity of the cured product of this embodiment can be, for example, preferably 0.20 W / (m·K) or more, more preferably 0.25 W / (m·K) or more, even more preferably 0.30 W / (m·K) or more, and even more preferably 0.32 W / (m·K) or more. The thermal conductivity of the cured product of this embodiment can be calculated based on the thermal diffusion coefficient of the cured product of this embodiment, the specific heat of the cured product of this embodiment, and the density of the cured product of this embodiment, according to the following formula (X). More specifically, the thermal conductivity can be calculated using, for example, the method described in Reference Test Example 1. Formula (X): λ = α·Cp·ρ [λ: Thermal conductivity (W / (m K)), α: Thermal diffusion coefficient (m 2 / s), Cp: Specific heat (J / g K), ρ: Density (kg / m 3 )

[0068] The cured product of this embodiment has excellent heat resistance. Therefore, in a specific embodiment, the glass transition temperature of the cured product of this embodiment can be, for example, preferably 200°C or higher, more preferably 230°C or higher, even more preferably 250°C or higher, and particularly preferably 260°C or higher. More specifically, the glass transition temperature can be calculated using the method described in Test Example 2, for example.

[0069] The cured product of this embodiment has improved brittleness. Therefore, for example, in a specific embodiment, when the loss factor tan δ at 25°C of a cured product obtained by independently curing only the corresponding cyanate ester compound (A) without using the corresponding epoxy compound (B) is taken as the reference (=1.0), the relative value of the loss factor tan δ of the cured product of this embodiment may be preferably 1.1 or more.

[0070] [Laminated resin sheet] The laminated resin sheet includes a support and a resin composition layer formed from the resin composition of the present embodiment and provided on one or both sides of the support. The method for producing the laminated resin sheet can be performed according to a conventional method and is not particularly limited. For example, the laminated resin sheet can be obtained by applying a solvent-containing varnish-like resin composition of the present embodiment to the support and drying it.

[0071] The support used here is not particularly limited, but examples include polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylene tetrafluoroethylene copolymer film, and release films obtained by applying a release agent to the surface of these films, organic film substrates such as polyimide film, conductive foils such as copper foil and aluminum foil, glass plate, SUS plate, FRP, and other plate-shaped materials.

[0072] Examples of the application method include a method in which the resin composition of this embodiment in the form of a varnish containing a solvent is applied onto a support using a bar coater, a die coater, a doctor blade, a baker applicator, or the like.

[0073] In producing a laminated resin sheet, the drying conditions for removing the solvent are not particularly limited, but a low temperature makes it easy for the solvent to remain in the resin composition layer, and a high temperature causes the resin composition layer to harden too quickly. Therefore, a temperature of 20 to 170°C for 1 to 90 minutes is preferred.

[0074] The thickness of the resin composition layer in the laminated resin sheet can be adjusted by the varnish concentration and coating thickness of the resin composition of the present embodiment, and is not particularly limited. However, since a thicker coating thickness generally makes it more likely that the solvent will remain when dried, a thickness of 0.1 to 500 μm is preferred.

[0075] The laminated resin sheet can be used in a state where the solvent has been removed from the resin composition layer (uncured state), or the resin composition layer can be used in a semi-cured (B-stage) state, but it is preferable to use it in a semi-cured state.

[0076] [Single-layer resin sheet] The single-layer resin sheet is formed from the resin composition of the present embodiment (for example, by molding it into a sheet). The method for manufacturing the single-layer resin sheet can be carried out according to a conventional method and is not particularly limited. For example, in the method for manufacturing the laminated resin sheet, a method can be mentioned in which the resin composition of the present embodiment in the form of a varnish containing a solvent is applied to a support and dried, and then the support is peeled off or etched from the laminated resin sheet. Note that a single-layer resin sheet can also be obtained without using a support by supplying the resin composition of the present embodiment in the form of a varnish containing a solvent into a mold having a sheet-shaped cavity and drying it to mold it into a sheet.

[0077] In producing a single-layer resin sheet, the drying conditions for removing the solvent are not particularly limited, but a low temperature makes it easy for the solvent to remain in the resin composition, and a high temperature causes the resin composition to harden excessively, so a temperature of 20 to 170°C for 1 to 90 minutes is preferred.

[0078] The thickness of the single-layer resin sheet can be adjusted by the concentration and coating thickness of the varnish of the resin composition of this embodiment, and is not particularly limited. However, a thicker coating thickness generally makes it more likely that the solvent will remain when dried, so a thickness of 0.1 to 500 μm is preferred.

[0079] [Prepreg] The prepreg includes a substrate and the resin composition of this embodiment impregnated into or coated on the substrate. The method for producing the prepreg is not particularly limited, as long as it is a method for producing a prepreg by combining the resin composition of this embodiment with a substrate. Specifically, the prepreg of this embodiment can be produced by impregnating or coating the substrate with the resin composition of this embodiment and then semi-curing it by, for example, drying it in a dryer at 120 to 220°C for about 2 to 15 minutes. In this case, the amount of the resin composition attached to the substrate, i.e., the content of the resin composition (including filler) relative to the total amount of the semi-cured prepreg, is preferably in the range of 20 to 99% by mass.

[0080] The substrate used in producing the prepreg may be a known material used in various printed wiring board materials. Examples of such substrates include, but are not limited to, 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. Known substrate shapes include woven fabrics, nonwoven fabrics, roving, chopped strand mats, and surfacing mats, and any of these may be used. The substrate may be used alone or in combination with two or more suitable types. Among woven fabrics, woven fabrics that have undergone ultra-opening or clogging treatments are particularly suitable from the viewpoint of dimensional stability. Furthermore, liquid crystal polyester woven fabrics are preferred from the viewpoint of electrical properties. Furthermore, the thickness of the substrate is not particularly limited, but is preferably in the range of 0.01 to 0.2 mm for laminate applications.

[0081] [Metal foil-clad laminate] The metal foil-clad laminate has a cured layer containing a cured product formed by curing the resin composition of this embodiment, and a metal foil provided on one or both sides of the cured layer. The metal foil-clad laminate can be manufactured using, for example, the single-layer resin sheet, laminated resin sheet, and prepreg described above. A specific example of using a prepreg is by laminating a metal foil such as copper or aluminum on one or both sides of a single prepreg or a stack of multiple prepregs. The metal foil used here is not particularly limited as long as it is used as a printed wiring board material, but copper foil such as rolled copper foil and electrolytic copper foil is preferred. The thickness of the metal foil is not particularly limited, but is preferably 2 to 70 μm, more preferably 3 to 35 μm. The molding conditions can be the same as those used in the manufacture of conventional laminates and multilayer boards for printed wiring boards. For example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like is used, and the temperature is 180 to 350°C, the heating time is 100 to 300 minutes, and the surface pressure is 20 to 100 kg / cm. 2 The metal foil-clad laminate of this embodiment can be produced by laminating and molding under the above conditions. A multilayer board can also be produced by combining the above prepreg with a separately prepared inner layer wiring board and laminating and molding it. A multilayer board can be produced, for example, by placing 35 μm copper foil on both sides of one of the above prepregs, laminating them under the above conditions, forming an inner layer circuit, and then blackening the circuit to form an inner layer circuit board. Furthermore, these inner layer circuit boards and the above prepregs are alternately arranged one by one, and copper foil is placed on the outermost layer, followed by laminating and molding under the above conditions, preferably in a vacuum. In this way, a multilayer board can be produced.

[0082] [Printed wiring board] The printed wiring board includes an insulating layer containing a cured product formed by curing the resin composition of this embodiment. The printed wiring board has an insulating layer and a conductor layer formed on the surface of the insulating layer. The printed wiring board can be formed, for example, by etching the metal foil of a metal foil-clad laminate into a predetermined wiring pattern to form a conductor layer. The printed wiring board may be a printed wiring board including an insulating layer formed of one or more materials selected from the group consisting of the above-mentioned prepreg and single-layer resin sheet, and a conductor layer formed on the surface of the insulating layer.

[0083] Specifically, a printed wiring board can be manufactured, for example, by the following method. First, a metal foil-clad laminate is prepared. The metal foil of the metal foil-clad laminate is etched into a predetermined wiring pattern to create an inner layer substrate having a conductor layer (inner layer circuit). Next, a predetermined number of prepregs and / or single-layer resin sheets serving as insulating layers and metal foil for the outer layer circuit are laminated in this order on the surface of the conductor layer (interior circuit) of the inner layer substrate, and the laminate is integrally molded (laminate molding) by heating and pressurizing to obtain a laminate. The laminate molding method and molding conditions are the same as those for the above-mentioned metal foil-clad laminate. Next, the laminate is drilled for through holes and via holes, and a plated metal film is formed on the wall surfaces of the holes to electrically connect the conductor layer (interior circuit) and the metal foil for the outer layer circuit. Next, the metal foil for the outer layer circuit is etched into a predetermined wiring pattern to create an outer layer substrate having a conductor layer (external layer circuit). In this manner, a printed wiring board is manufactured.

[0084] In addition, when a metal foil-clad laminate is not used, a printed wiring board may be produced by forming a conductor layer that will become a circuit on the insulating layer. In this case, the conductor layer may be formed by electroless plating.

[0085] [Semiconductor Package] A semiconductor package is a semiconductor package that includes a printed wiring board and a semiconductor element. A semiconductor package can be manufactured, for example, by mounting a semiconductor element such as a semiconductor chip or memory at a specific position on a printed wiring board.

[0086] [Semiconductor Device] The printed wiring board can be used to manufacture semiconductor devices having the printed wiring board, such as personal computers, smartphones, smartwatches, digital cameras, televisions, car navigation systems, printers, liquid crystal displays, electronic dictionaries, game consoles, automobiles, ships, trains, and aircraft. [Example]

[0087] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Unless otherwise specified, the temperature conditions are room temperature (25°C), and unless otherwise specified, the pressure conditions are atmospheric pressure (1 atm).

[0088] (Synthesis Example 1: Synthesis of cyanate ester compound A (1,4-bis(4-cyanatophenyl)-1-cyclohexene))

[0089] [ka]

[0090] A 2 L four-neck flask equipped with an argon inlet and a thermometer was charged with 40.0 g (0.15 mol) of 1,4-bis(4-hydroxyphenyl)-1-cyclohexene (synthesized by a method similar to that described in WO 2019 / 031178) and 800 mL of tetrahydrofuran under argon flow. After adding 44.5 g (0.42 mol) of cyanogen bromide, the internal temperature was adjusted to -10 °C in a dry ice / acetone bath. 45.5 g (0.45 mol) of triethylamine was added dropwise over 20 minutes so that the internal temperature did not exceed -5 °C, and the mixture was stirred at -5 °C for 2 hours. An additional 400 mL of tetrahydrofuran was added during the reaction. After warming to room temperature, the reaction solution was filtered. The filtrate was concentrated under reduced pressure, and the resulting solid was dissolved in 800 mL of chloroform. The chloroform solution was washed three times with 400 mL of 2.5% saline and once with 400 mL of water, and then concentrated under reduced pressure to obtain a solid. 600 mL of hexane was added to the obtained solid, and the mixture was suspended and stirred. The solid was then collected by filtration and dried to obtain 45.4 g of the target cyanate ester compound A (1,4-bis(4-cyanatophenyl)-1-cyclohexene).

[0091] (Synthesis Example 2: Synthesis of cyanate ester compound B (1-(4-cyanato-3-methylphenyl)-4-(4-cyanatophenyl)-1-cyclohexene))

[0092] [ka]

[0093] Cyanate ester compound B (1-(4-cyanato-3-methylphenyl)-4-(4-cyanatophenyl)-1-cyclohexene) was synthesized by a method similar to that described in WO 2019 / 031178.

[0094] (Comparative Synthesis Example 1: Synthesis of cyanate ester compound C (4,4''-dicyanato-3-methyl-p-terphenyl))

[0095] [ka]

[0096] Cyanate ester compound C (4,4″-dicyanato-3-methyl-p-terphenyl) was synthesized by a method similar to that described in WO 2019 / 031178.

[0097] Reference Example 1: Preparation of a cured resin product from cyanate ester compound A of Synthesis Example 1 A curable resin composition was obtained by heating and melting 100.0 parts by mass of the cyanate ester compound A obtained in Synthesis Example 1 and 0.05 parts by mass of zinc octylate (Nihon Kagaku Sangyo Co., Ltd., trade name Nikka Octix Zinc, metal content 18%). The obtained curable resin composition was filled into a 1 mm thick mold and vacuum hot pressed (220°C, 90 minutes, press pressure 10 MPa) to produce a cured resin (not filled with alumina).

[0098] Reference Example 2: Preparation of a cured resin from cyanate ester compound B of Synthesis Example 2 A cured resin (not filled with alumina) was prepared in the same manner as in Reference Example 1, except that 100.0 parts by mass of cyanate ester compound B obtained in Synthesis Example 2 was used instead of 100.0 parts by mass of cyanate ester compound A.

[0099] Comparative Reference Example 1: Preparation of a cured resin product from cyanate ester compound C of Synthesis Example 3 A cured resin (not filled with alumina) was prepared in the same manner as in Reference Example 1, except that 100.0 parts by mass of cyanate ester compound C obtained in Comparative Synthesis Example 1 was used instead of 100.0 parts by mass of cyanate ester compound A.

[0100] (Comparative Reference Example 2: Preparation of a cured resin from commercially available 2,2-bis(4-cyanatophenyl)propane) A cured resin (not filled with alumina) was prepared in the same manner as in Reference Example 1, except that 100.0 parts by mass of commercially available 2,2-bis(4-cyanatophenyl)propane (manufactured by Mitsubishi Gas Chemical Company, Inc.) was used instead of 100.0 parts by mass of cyanate ester compound A.

[0101] Reference Example 3: Preparation of an alumina-filled cured product of cyanate ester compound A of Synthesis Example 1 A varnish was prepared by mixing 100.0 parts by mass of the cyanate ester compound A obtained in Synthesis Example 1, 0.05 parts by mass of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd., trademark Nikka Octix Zinc, metal content 18%), 190.7 parts by mass of alumina particles (manufactured by Micron Company, Nippon Steel & Sumikin Materials Co., Ltd., AZ35-75), 190.7 parts by mass of alumina particles (manufactured by Micron Company, Nippon Steel & Sumikin Materials Co., Ltd., AZ10-75), 95.3 parts by mass of alumina particles (manufactured by Sumitomo Chemical Co., Ltd., AA-03), and 4.8 parts by mass of 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., LS-2940). The mixture was diluted with methyl ethyl ketone (Wako Pure Chemical Industries, Ltd., special grade reagent). The prepared varnish was applied to the rough surface of copper foil (Mitsui Mining & Smelting Co., Ltd., 3EC-VLP, thickness 18 μm) using an applicator and dried at 130°C for 10 minutes to obtain copper foil with a B-stage resin composition. The B-stage resin composition was peeled from the copper foil and pulverized in a mortar. The obtained resin composition powder was filled into a 1 mm thick mold and vacuum hot pressed (220°C, 90 minutes, press pressure 10 MPa) to obtain an alumina-filled cured product (alumina content 60% by volume).

[0102] Reference Example 4: Preparation of an alumina-filled cured product of cyanate ester compound B of Synthesis Example 2 An alumina-filled cured product (containing 60% by volume of alumina) was prepared in the same manner as in Reference Example 3, except that 100.0 parts by mass of cyanate ester compound B obtained in Synthesis Example 2 was used instead of 100.0 parts by mass of cyanate ester compound A.

[0103] (Reference Test Example 1: Calculation of thermal conductivity of cyanate ester compound alone (without alumina)) Thermal diffusion coefficient: The cured resin products of Reference Examples 1 and 2 and Comparative Reference Examples 1 and 2 were cut into 1 cm square pieces and placed in a sample holder in a xenon flash thermal diffusivity measuring device (NETZSCH, LFA447 NanoFlash), and measurements were performed at 25°C in the atmosphere to determine the thermal diffusion coefficient. Specific heat: Measured using a DSC (Seiko Instruments Inc., EXSTAR6000 DSC6220) in accordance with JIS K7123 (method for measuring specific heat capacity of plastics). Density: Measured by the underwater displacement method using a density measuring instrument (MS-DNY-43, manufactured by Mettler-Toledo K.K.). Thermal conductivity: From the calculated thermal diffusion coefficient, specific heat, and density, the thermal conductivity of the cured resin products (Synthesis Examples 1 and 2, Comparative Synthesis Example 1, and the cured products of the commercially available cyanate ester compound alone) was calculated using the following formula. Formula (X): λ = α·Cp·ρ [λ: Thermal conductivity (W / (m K)), α: Thermal diffusion coefficient (m 2 / s), Cp: Specific heat (J / g K), ρ: Density (kg / m 3 )

[0104] (Reference Test Example 2: Calculation of the thermal conductivity of a cyanate ester compound alone cured product (thermal conductivity of the resin portion when filled with alumina)) The thermal conductivity of the resin portion of the filler-containing cured product (single-cured product of the cyanate ester compound of Synthesis Examples 1 and 2) was calculated from the thermal conductivity of the filler-containing cured product obtained in Reference Examples 3 and 4, which was calculated in the same manner as in Reference Test Example 1, using the following formula (Y): Formula (Y): 1-φ=[(λc-λf) / (λm-λf)]×(λm / λc) 1 / 3 [φ: filler volume fraction (vol %), λc: thermal conductivity of the cured product containing the filler (W / (m K)), λf: thermal conductivity of alumina (30 W / (m K)), λm: thermal conductivity of the resin portion of the cured product containing the filler (W / (m K))]

[0105] (Reference Test Example 3: Measurement of Melting Point of Cyanate Ester Compound (Monomer)) The melting points of the cyanate ester compounds A to C of Synthesis Examples 1 to 3 and the commercially available 2,2-bis(4-cyanatophenyl)propane (manufactured by Mitsubishi Gas Chemical Company, Inc.) were determined using a DSC (manufactured by Seiko Instruments Inc., EXSTAR6000 DSC6220) under the following conditions in accordance with JIS K7121 (measurement method for transition temperature of plastics). Sample weight: 5 to 10 mg Temperature range: -30 to 300°C Heating rate: 5℃ / min Measurement atmosphere: N2 flow (50 mL / min)

[0106] The calculation results or measurement results of Reference Test Examples 1 to 3 are summarized in Table 1 below.

[0107] [Table 1]

[0108] Conventional commercially available 2,2-bis(4-cyanatophenyl)propane has a low melting point and is excellent in filler compatibility at low temperatures, but has low thermal conductivity. Furthermore, cyanate ester compound C of Comparative Synthesis Example 1 has superior thermal conductivity compared to conventional cyanate ester compounds, but has a high melting point and is not sufficient in filler compatibility at low temperatures. On the other hand, cyanate ester compounds A and B of Synthesis Examples 1 and 2 have significantly superior thermal conductivity, low melting points, and excellent in filler compatibility at low temperatures, even compared to cyanate ester compound C of Comparative Synthesis Example 1.

[0109] Example 1 30.13 g of the cyanate ester compound A synthesized in Synthesis Example 1 was placed in a 1000 mL beaker, and 600 mL of chloroform was added to dissolve it. After stirring for 5 minutes, the mixture was subjected to suction filtration. The solvent in the filtrate was evaporated in an evaporator, and then the filtrate was dried in a vacuum thermostatic oven at 100°C for 2 hours. As a result, 28.28 g of purified cyanate ester compound A was obtained as a pale yellow powder.

[0110] Separately, 50.0 g of biphenyl-type epoxy (YL6121HA (Mitsubishi Chemical Corporation) (epoxy compound of the following formula (2a): epoxy compound of the following formula (2b) = 5:5 (molar ratio))), 50 mL of MEK (methyl ethyl ketone), and 150 mL of MIBK (methyl isobutyl ketone) were added to a 500 mL separable flask and dissolved. The mixture was then stirred at 110 °C for 1 hour and cooled to room temperature for 12 hours. Finally, the mixture was suction filtered and dried in a vacuum high-temperature oven at 80 °C for 3 hours. The resulting product was dissolved in 35 mL of MEK and 105 mL of MIBK and recrystallized twice. 19.9 g of white powder of biphenyl-type epoxy DGEBP (epoxy compound of the following formula (2a): epoxy compound of the following formula (2b) = 9:1 (molar ratio)) was obtained.

[0111] [ka]

[0112] 1.82 g of the purified cyanate ester compound A, 0.18 g of the DGEBP obtained above, and 0.04 g of TTP-TTB (tetraphenylphosphonium tetra-p-tolylborate) were added to a mortar and mixed for 10 minutes, then dried in a vacuum thermostatic chamber at 60°C for 2 hours. The dried sample was heated on a hot plate at 140°C for 4 minutes to completely melt it, and then degassed under reduced pressure for 8 minutes. It was then heat-cured in a thermostatic chamber at 170°C for 1 hour, 190°C for 1 hour, 210°C for 0.5 hours, and 230°C for 0.5 hours, and then slowly cooled to room temperature. This cured product was then post-cured under the same heating conditions as above at 250°C for 1 hour to obtain a cured resin.

[0113] Example 2 A cured resin was obtained in the same manner as in Example 1, except that the amount of purified cyanate ester compound A used was changed from 1.82 g to 1.36 g, the amount of DGEBP used was changed from 0.18 g to 0.64 g, and post-curing was not performed.

[0114] Example 3 A cured resin was obtained in the same manner as in Example 1, except that the amount of purified cyanate ester compound A used was changed from 1.82 g to 1.02 g, the amount of DGEBP used was changed from 0.18 g to 0.98 g, and post-curing was not performed.

[0115] (Comparative Example 1) A cured resin was obtained in the same manner as in Example 1, except that the amount of purified cyanate ester compound A used was changed from 1.82 g to 2.00 g, DGEBP was not used, the temperature of the reduced pressure thermostatic bath was changed from 60°C to 80°C, and post-curing was not performed.

[0116] (Test Example 1: Measurement of thermal conductivity) The thermal conductivities of the cured resin products obtained in Examples 1 to 3 and Comparative Example 1 were calculated in the same manner as in Reference Test Example 1.

[0117] (Test Example 2: Calculation of brittleness improvement index (crack resistance index) and glass transition temperature) Dynamic viscoelasticity measurements were carried out using a DMA (Seiko Instruments Inc., EXSTAR6000 DMS6100) in accordance with JIS K7244 4 "Plastics - Test methods for dynamic mechanical properties - Part 4: Tensile vibration non-resonance curve method."

[0118] Regarding the brittleness improvement index, the value of the loss factor tan δ at 25°C (loss factor tan δ = loss modulus (G'') / storage modulus (G')) was read from the temperature dependence data of the elastic modulus obtained by DMA measurement, and the value calculated as the relative value of tan δ obtained by DMA measurement of each sample (value of [tan δ obtained by DMA measurement of each sample] / [tan δ obtained by DMA measurement of Comparative Example 1]) was used as the brittleness improvement index, with the tan δ obtained in Comparative Example 1 being used as the reference (=1.0).

[0119] Regarding the glass transition point, the peak position of the loss factor tan δ in the DMA measurement was taken as the glass transition temperature (Tg, ° C.).

[0120] The calculation or measurement results of Test Examples 1 and 2 are summarized in Table 2 below.

[0121] [Table 2]

[0122] Comparative Example 1, which does not use an epoxy resin, is excellent in thermal conductivity and heat resistance but has insufficient improvement in brittleness.On the other hand, Examples 1 to 3, which contain a cyanate ester compound (A) represented by formula (1) and an epoxy compound (B) represented by formula (2), and in which the epoxy compound (B) contains 85 mol % or more of an epoxy compound represented by formula (2a), are excellent in thermal conductivity and heat resistance and also have sufficient improvement in brittleness.

Claims

1. The composition contains a cyanate ester compound (A) represented by the following formula (1) and an epoxy compound (B) represented by the following formula (2), The resin composition, wherein the epoxy compound (B) contains 85 mol % or more of an epoxy compound represented by the following formula (2a): 【Chemistry 1】 [In formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom; R 9 each independently represents an alkyl group having 1 to 6 carbon atoms or a halogen atom; a represents an integer from 0 to 6; and a double line consisting of two solid lines and a dashed line represents one single bond and the other a double bond. 【Chemistry 2】 [In formula (2), R a , R b , R c , R d , R e , R f , R g , and R h each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 【Transformation 3】

2. The resin composition according to claim 1, wherein the cyanate ester compound (A) includes at least one of a cyanate ester compound represented by the following formula (1a) and a cyanate ester compound represented by the following formula (1b): 【Chemistry 4】

3. 2. The resin composition according to claim 1, wherein the content of the cyanate ester compound (A) is 50 parts by mass or more and 99 parts by mass or less, relative to 100 parts by mass of the total of the cyanate ester compound (A) and the epoxy compound (B).

4. The resin composition according to claim 1, further comprising a filler having a thermal conductivity of 3 W / (m·K) or more.

5. The resin composition according to any one of claims 1 to 4, which is for use in a sheet-like molded product.

6. A single-layer resin sheet formed from the resin composition according to any one of claims 1 to 4.

7. A laminated resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 4 provided on one or both sides of the support.

8. A prepreg comprising a substrate and the resin composition according to any one of claims 1 to 4 impregnated into or coated on the substrate.

9. A cured product formed by curing the resin composition according to any one of claims 1 to 4.

10. A metal foil-clad laminate having a cured layer containing a cured product formed by curing the resin composition according to any one of claims 1 to 4, and a metal foil provided on one or both sides of the cured layer.

11. A printed wiring board comprising an insulating layer containing a cured product formed by curing the resin composition according to any one of claims 1 to 4.

12. A semiconductor package comprising the printed wiring board according to claim 11 and a semiconductor element.

13. A semiconductor device comprising the printed wiring board according to claim 11.

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