WO2019203292A1 - Composition de durcissement thermique, préimprégné, stratifié, stratifié plaqué de feuille métallique, carte de circuit imprimé, et carte de circuit imprimé multicouche - Google Patents

Composition de durcissement thermique, préimprégné, stratifié, stratifié plaqué de feuille métallique, carte de circuit imprimé, et carte de circuit imprimé multicouche Download PDF

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Publication number
WO2019203292A1
WO2019203292A1 PCT/JP2019/016554 JP2019016554W WO2019203292A1 WO 2019203292 A1 WO2019203292 A1 WO 2019203292A1 JP 2019016554 W JP2019016554 W JP 2019016554W WO 2019203292 A1 WO2019203292 A1 WO 2019203292A1
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mass
parts
compound
thermosetting composition
group
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PCT/JP2019/016554
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English (en)
Japanese (ja)
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翔平 山口
弘晃 田所
克哉 富澤
典浩 志田
英利 河合
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三菱瓦斯化学株式会社
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Priority to JP2020514430A priority Critical patent/JP7307896B2/ja
Publication of WO2019203292A1 publication Critical patent/WO2019203292A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits

Definitions

  • the present invention relates to a thermosetting composition, a prepreg, a laminate, a metal foil-clad laminate, a printed wiring board, and a multilayer printed wiring board.
  • Patent Document 1 combines an epoxy resin, a polyfunctional phenol resin, a curing accelerator, and a reducing agent for the purpose of imparting excellent electrical insulation characteristics when applied to a printed wiring board material.
  • An epoxy resin composition is disclosed. This document discloses that when a phenol-based reducing agent is used as the reducing agent, the electrical insulation characteristics can be improved without lowering other physical properties such as drill workability.
  • Patent Document 2 when a printed wiring board is used, it has excellent low moisture absorption, heat resistance, high temperature characteristics, electric corrosion resistance, and heat discoloration resistance, a high glass transition temperature, and occurrence of metal migration.
  • Epoxy resin composition for printed wiring boards that combines a specific epoxy resin, a condensate of bisphenol A and formaldehyde, a flame retardant, a curing accelerator, and a phenolic antioxidant for the purpose of suppressing high electrical insulation Is disclosed. This document also discloses that the use of a phenolic antioxidant can improve the electrical insulation characteristics without deteriorating other characteristics such as drill workability.
  • Patent Document 3 discloses an imidazole compound, an epoxy compound, and a phenol having a specific structure for the purpose of simultaneously satisfying low thermal expansion, high glass transition temperature, flame retardancy, and high degree of cure even when cured at low temperature.
  • a resin composition containing a compound and a maleimide compound is disclosed.
  • a copper foil laminate formed using a prepreg obtained by impregnating and applying the above resin composition to E glass woven fabric has an excellent low thermal expansion coefficient, high glass transition temperature, It is disclosed to have flame retardancy, high degree of cure, high moisture absorption heat resistance, and high peel strength.
  • JP-A-3-43413 Japanese Patent Application Laid-Open No. 10-279979 JP 2014-37485 A
  • Patent Documents 1 and 2 have not been studied for suppressing package warpage.
  • Patent Document 3 in order to solve the above-mentioned problem, normally, as in Patent Document 3, by reducing the thermal expansion coefficient in the surface direction of the printed wiring board, the printed wiring board and the semiconductor element mounted on the printed wiring board It is conceivable to reduce the difference in thermal expansion coefficient. However, even with the above-described method, it is required to further reduce package warpage.
  • the present inventors have made extensive studies in order to suppress the above-described package warpage, and as a result, a material having a high elastic modulus in a normal state and a strong viscous behavior (that is, easy to plastically deform) in a heating process. Found that the residual stress can be reduced in the mounting process and is effective in suppressing package warpage.
  • a material usually has a high melt viscosity, resulting in molding defects in, for example, a step of laminating a prepreg. Such a problem is a remarkable problem in a thin printed wiring board.
  • an object of the present invention is to provide a thermosetting composition, a prepreg, a laminate, a metal foil-clad laminate, which has excellent moldability and can reduce warpage (package warpage) when manufacturing an electronic component (package).
  • An object is to provide a printed wiring board and a multilayer printed wiring board.
  • the present inventors have included a predetermined amount of a hindered phenol compound having a specific structure in a thermosetting composition containing a phenol compound and an epoxy compound. The present inventors have found that the above problems can be solved and have completed the present invention.
  • thermosetting compound containing a phenolic compound and an epoxy compound includes a hindered phenol compound having a structure represented by the following formula (1) or a structure represented by the following formula (2),
  • the thermosetting composition whose content of the said hindered phenol compound in the said phenol compound is 35 mass% or more.
  • R 1 and R 2 are monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 1 and R 2 may be the same or different from each other.
  • R 3 is a monovalent or divalent hydrocarbon group having 1 to 12 carbon atoms, and the two R 3 may be the same or different from each other.
  • R 4 is a divalent hydrocarbon group having 1 to 12 carbon atoms
  • R 5 is a monovalent or divalent hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom
  • two R 5 are Each may be the same or different.
  • [2] The thermosetting composition according to [1], wherein the content of the hindered phenol compound is 10 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the thermosetting composition solid content.
  • [3] The thermosetting composition according to the above [1] or [2], wherein the content of the hindered phenol compound is more than 20 parts by mass and less than 60 parts by mass with respect to 100 parts by mass of the epoxy compound.
  • thermosetting composition according to any one of [1] to [3], wherein the hindered phenol compound has a structure represented by the following formula (3) or a structure represented by the formula (2).
  • L represents a linking group
  • n represents an integer of 2 or more
  • R 1 and R 2 each have the same meanings as R 1 and R 2 of formula (1).
  • the hindered phenol compound has a phenol equivalent of 140 g / eq.
  • the thermosetting composition according to any one of [1] to [4].
  • R 1 and R 2 are each one group selected from the group consisting of a methyl group, a tert-butyl group, a cyclohexyl group, and a phenyl group, [1] to [5]
  • the thermosetting composition of any of. [7] The thermosetting composition according to any one of [1] to [6], wherein the content of the phenol compound is 30 to 40 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • thermosetting compound contains a bifunctional bifunctional thermosetting compound and a trifunctional or higher polyfunctional thermosetting compound, The content of the bifunctional thermosetting compound is 40 to 90 parts by mass with respect to 100 parts by mass of the thermosetting composition solid content,
  • thermosetting composition according to any one of [1] to [7], wherein the content of the polyfunctional thermosetting compound is 10 to 60 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • the epoxy compound contains a bifunctional epoxy compound and a polyfunctional epoxy compound having three or more functions,
  • the content of the bifunctional epoxy compound is 20 to 70 parts by mass with respect to 100 parts by mass of the thermosetting composition solid content
  • the thermosetting composition according to any one of [1] to [8], wherein the content of the polyfunctional epoxy compound is 10 to 50 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • the phenolic compound comprises a bifunctional phenolic compound;
  • the thermosetting composition according to any one of [1] to [9], wherein the content of the bifunctional phenol compound is 20 to 60 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • thermosetting composition according to any one of [1] to [10], wherein the content of the filler is 40 parts by mass or more and 700 parts by mass or less with respect to 100 parts by mass of the thermosetting composition solid content.
  • the filler includes one or more inorganic fillers selected from the group consisting of silica, boehmite, and alumina.
  • the thermosetting composition according to any one of [1] to [12] which is used for a printed wiring board.
  • thermosetting composition according to any one of [1] to [12], which is for a multilayer printed wiring board.
  • a prepreg comprising a substrate and the thermosetting composition according to any one of [1] to [15] impregnated or coated on the substrate.
  • the substrate is made of one or more glass fibers selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass.
  • prepreg. [18] A laminate comprising the prepreg according to [16] or [17]. [19] [16] or [17] prepreg; A metal foil disposed on one or both sides of the prepreg; A metal foil-clad laminate.
  • a printed wiring board having an insulating layer formed of the prepreg according to [16] or [17] and a conductor layer formed on a surface of the insulating layer.
  • a plurality of insulating layers comprising a first insulating layer and one or more second insulating layers laminated on one side of the first insulating layer;
  • a plurality of conductor layers comprising a first conductor layer disposed between each of the plurality of insulating layers and a second conductor layer disposed on a surface of the outermost layer of the plurality of insulating layers;
  • the multilayer printed wiring board in which the first insulating layer and the second insulating layer each have a cured product of the prepreg of [16] or [17].
  • thermosetting composition a prepreg, a laminate, a metal foil-clad laminate, and a printed wiring that are excellent in moldability and can reduce warpage (package warpage) when manufacturing an electronic component (package). Boards and multilayer printed wiring boards can be provided.
  • FIG. 9 is a process flow diagram showing an example of a procedure for manufacturing a panel of a multilayer coreless substrate (however, the method of manufacturing the multilayer coreless substrate is not limited to this, and the same applies to FIGS. 2 to 8 below). It is a process flow figure which shows an example of the procedure which produces the panel of a multilayer coreless board
  • thermosetting composition solids refers to the components excluding the solvent and filler in the thermosetting composition of the present embodiment, unless otherwise specified.
  • the solid content of 100 parts by mass means that the total of components excluding the solvent and filler in the thermosetting composition is 100 parts by mass.
  • thermosetting composition includes a thermosetting compound containing a phenol compound and an epoxy compound, and the phenol compound is represented by the structure represented by the following formula (1) or the following formula (2).
  • the content of the hindered phenol compound in the phenol compound is 35% by mass or more, including a hindered phenol compound having a structure (hereinafter also referred to as “specific hindered phenol compound”).
  • R 1 and R 2 are monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 1 and R 2 may be the same or different from each other.
  • R 3 is a monovalent or divalent hydrocarbon group having 1 to 12 carbon atoms, and the two R 3 may be the same or different from each other.
  • R 4 is a divalent hydrocarbon group having 1 to 12 carbon atoms,
  • R 5 is a monovalent or divalent hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, and two R 5 are Each may be the same or different.
  • thermosetting composition of the present embodiment is excellent in moldability by having the above-described configuration, and can reduce warpage (package warpage) when manufacturing an electronic component (package). This factor is considered as follows. In addition, although consideration is included in the following description, this invention is not limited at all by this consideration.
  • the thermosetting composition of this embodiment can lower the Tg of the cured product and can strongly develop the viscous behavior at high temperature mainly due to the combination of the phenol compound and the epoxy compound. As a result, the thermosetting composition of the present embodiment is excellent in stress relaxation during a mounting process for mounting a semiconductor chip on a printed wiring board (particularly a multilayer coreless substrate), and is used for manufacturing an electronic component (package). Warpage (package warpage) can be reduced.
  • the curing temperature of phenolic compounds and epoxy compounds generally tends to be low, and when a composition in which a phenolic compound and an epoxy compound are combined is melted, the melt viscosity increases. As a result, there is a problem in formability.
  • the thermosetting composition of this embodiment can reduce the melt viscosity without excessively hindering the effect of reducing package warpage by including a predetermined amount of a hindered phenol compound having a specific structure, Excellent formability.
  • the curing temperature of the hindered phenol compound having a specific structure is that the phenol compound not having the structure has a structure in which a predetermined substituent is bonded to the two ortho positions of the aromatic ring with respect to the phenolic hydroxyl group. It tends to be higher than the curing temperature. Thereby, it is considered that the curing reaction of the composition combining the phenol compound and the epoxy compound is delayed, and as a result, the melt viscosity can be reduced.
  • thermosetting compound refers to a compound that can be cured by heating.
  • a functional group also referred to as “thermosetting functional group” capable of proceeding a polymerization reaction or a crosslinking reaction between the same functional groups or different functional groups by heating is also included in the molecule.
  • the compound which has at least 1 or more is mentioned.
  • the thermosetting functional group is not particularly limited. For example, phenolic hydroxyl group, epoxy group, cyanate group (—O—C ⁇ N), allyl group, maleimide group, hydroxyl group, amino group, isocyanate group, and other polymerizable groups. And unsaturated groups.
  • thermosetting compound of this embodiment contains a phenol compound and an epoxy compound.
  • the thermosetting compound can reduce warpage of a metal foil-clad laminate, a printed wiring board, and a multilayer printed wiring board (especially a multilayer coreless board), and further an electronic component (package). ) Can be reduced (package warpage).
  • the phenol compound includes at least a specific hindered phenol compound and may include other phenol compounds (phenol compounds excluding the specific hindered phenol compound).
  • the phenol compound can reduce the melt viscosity without excessively inhibiting the effect of reducing warpage (particularly package warpage), and is excellent in moldability.
  • the content of the specific hindered phenol compound in the phenol compound is 35% by mass or more (for example, 35% by mass or more and 100% by mass or less). When the content is 35% by mass or more, the melt viscosity can be reduced and the moldability is excellent. From the same viewpoint, the content is preferably 37.5% by mass or more.
  • the content of the specific hindered phenol compound in the phenol compound is preferably 80% by mass or less and more preferably 60% by mass or less from the viewpoint of further enhancing the effect of reducing warpage (particularly package warpage). More preferably, it is more preferably 50% by mass or less.
  • the specific hindered phenol compound has a structure represented by the following formula (1) (also referred to as “structure (1)”) or a structure represented by the following formula (2) (“structure (2)”). Also called).
  • R 1 and R 2 are monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 1 and R 2 may be the same or different from each other, * Represents a bond.
  • R 1 and R 2 are each independently a monovalent hydrocarbon group having 1 to 12 carbon atoms.
  • the monovalent hydrocarbon group includes a linear or branched alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group, etc.), cycloalkyl group (For example, cyclopentyl group, cyclohexyl group, etc.), aryl group which may have a substituent (for example, phenyl group; alkylphenyl group such as methylphenyl (tolyl) group, dimethylphenyl (xylyl) group), naphthyl group, biphenyl Group) and aralkyl groups (for example, benzyl group, phenethyl group, etc.).
  • alkyl group for example, methyl group, ethyl group, propyl group, isopropyl group,
  • R 1 and R 2 are each independently a straight chain having 1 to 4 carbon atoms from the viewpoint of further reducing the melt viscosity without excessively inhibiting the effect of reducing warpage (particularly package warpage). It is preferably one group selected from the group consisting of linear or branched alkyl groups, cyclohexyl groups, and phenyl groups, and is selected from the group consisting of methyl groups, tert-butyl groups, cyclohexyl groups, and phenyl groups. One kind of group is more preferable.
  • a substituent may be further bonded to the benzene ring in the formula (1) as long as the effects of the present invention are not inhibited. It does not specifically limit as a substituent, For example, said hydrocarbon group is mentioned.
  • the specific hindered phenol compound has one structure (1) (the number of the structures (1) is one), the specific hindered phenol compound has a structure represented by the following formula (1a) .
  • M represents a hydrogen atom, a halogen atom or a monovalent organic group
  • R 1 and R 2 each have the same meanings as R 1 and R 2 in the formula (1).
  • the monovalent organic group is not particularly limited, and for example, a hydrocarbon group (for example, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, etc.), a substituted amino group (for example, the above-mentioned N-mono or N, N-disubstituted amino group substituted with a hydrocarbon group, etc.), aromatic ring-containing groups (for example, benzene ring-containing groups, mesitylene ring-containing groups, etc.), heterocycle-containing groups (for example, , Isocyanurate ring-containing groups, spirodioxane ring-containing groups, and the like.
  • a hydrocarbon group for example, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, etc
  • the monovalent organic group is an n-valent group corresponding to the above-exemplified monovalent group (that is, a group from which n hydrogen atoms are eliminated), or the above-exemplified monovalent group,
  • One or more structures in which an n-valent group corresponding to the above-exemplified monovalent group is bonded via a linking group may be included.
  • Specific examples of the specific hindered phenol compound having one structure represented by the formula (1) are 2, 4 , 6-tri-tert-butylphenol, 4-[[4,6-bis (octylthio) -1,3,5-triazin-2-yl] amino] -2,6-di-tert-butylphenol, 3- ( Stearyl 3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,5-di-tert-butyl Diethyl 4-hydroxybenzylphosphonate, 2,6-di-tertbutyl-4-dimethylaminomethylphenol, 3- (3,5-di-tert-butyl-4-hydroxy Eniru) include stearyl propionate.
  • R 3 is a monovalent or divalent hydrocarbon group having 1 to 12 carbon atoms, and the two R 3 may be the same or different from each other.
  • 4 is a divalent hydrocarbon group having 1 to 12 carbon atoms
  • R 5 is a monovalent or divalent hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, and two R 5 are May be the same or different.
  • a substituent may be further bonded to the benzene ring in the formula (2) as long as the effects of the present invention are not inhibited. It does not specifically limit as a substituent, For example, said hydrocarbon group is mentioned.
  • each R 3 is independently a monovalent or divalent hydrocarbon group having 1 to 12 carbon atoms
  • R 5 is each independently a monovalent having 1 to 12 carbon atoms.
  • the monovalent hydrocarbon group include the hydrocarbon groups exemplified as R 1 and R 2 in Formula (1).
  • the divalent hydrocarbon group one hydrogen atom is eliminated from the hydrocarbon group. Divalent groups.
  • each R 3 is independently a straight chain or branched chain having 1 to 4 carbon atoms.
  • each R 5 is independently a straight chain having 1 to 4 carbon atoms.
  • R 4 is a divalent hydrocarbon group having 1 to 12 carbon atoms.
  • the divalent hydrocarbon group include a linear or branched alkylene group (for example, a methylene group, an ethylene group, an ethylidene group, a trimethylene group, a propylidene group, an isopropylidene group, etc.).
  • R 4 is preferably a linear or branched alkylene group having 1 to 12 carbon atoms, and is a straight chain having 1 to 6 carbon atoms, from the viewpoint of more effectively and reliably achieving the effects of the present invention.
  • a chain or branched alkylene group is more preferable, and a linear or branched alkylene group having 1 to 3 carbon atoms is more preferable.
  • R 3 is each independently a methyl group, a tert-butyl group or the like from the viewpoint of more effectively and reliably achieving the effects of the present invention.
  • a cyclohexyl group, and a phenyl group is a linear or branched alkylene group having 1 to 3 carbon atoms
  • R 5 is independently selected from the group consisting of And a group selected from the group consisting of a methyl group, a tert-butyl group, a cyclohexyl group, a phenyl group and a hydrogen atom.
  • hindered phenol compound having the structure represented by the formula (2) examples include 2,2′-methylenebis [6- (1 methylcyclohexyl) -p-cresol], 2,2′-ethylidenebis (4 , 6-di-tert-butylphenol), 2,2′-butylidenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (6-tert-butyl-4-methylphenol), 2,2 ′ -Methylenebis (6-tert-butyl-4-ethylphenol).
  • the specific hindered phenol compound preferably has a structure represented by the following formula (3) or a structure represented by the above formula (2).
  • L represents a linking group
  • n represents an integer of 2 or more
  • R 1 and R 2 each have the same meanings as R 1 and R 2 of formula (1).
  • n represents an integer of 2 or more, and is, for example, 2 to 10, preferably 2 to 6 from the viewpoint of more effectively and reliably achieving the effects of the present invention. It is more preferable that
  • L represents an n-valent linking group.
  • the linking group include an n-valent organic group, and examples of the organic group include a group obtained by eliminating n-1 hydrogen atoms from the groups exemplified as the monovalent organic group described above.
  • Specific examples of the specific hindered phenol compound in which n is 2 in the formula (3) include 3,9-bis ⁇ 2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) Propionyloxy] -1,1, -dimethylethyl ⁇ -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4′-methylenebis (2,6-di-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6- Hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) prepionate], 4,4′-thiobis (6-tert-butyl- -Cresol), bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid
  • Specific examples of the specific hindered phenol compound in which n is 3 in the formula (3) include 1,3,5-tris [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [2- [3- (3,5-di-tert-butyl -4-hydroxyphenyl) propanoyloxy] ethyl] hexahydro-1,3,5-triazine 2,4,6-trione, 2,4,6-tris (3 ', 5'-di-tert-butyl-4 '-Hydroxybenzyl) mesitylene, 1,3,5-tris [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoyloxy] ethyl] hexahydro-1,3-5 Triazine-2,
  • Specific examples of the specific hindered phenol compound in which n is 4 in the formula (3) include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like. It is done.
  • a commercially available product may be used, or a preparation prepared by a known method may be used.
  • Commercially available products include “ADK STAB AO-20”, “ADK STAB AO-50”, “ADK STAB AO-50F”, “ADK STAB AO-60”, “ADK STAB AO-60G” and “ADK STAB AO-80”. , “Adeka Stub AO-330”, Sumitomo Chemical Co., Ltd.
  • the phenol equivalent of a specific hindered phenol compound is 140 g / eq. It is preferable that it is above (for example, 140 g / eq. Or more and 500 g / eq. Or less). Phenol equivalent is 140 g / eq. By being the above, the volatility at the time of heat curing can be further reduced, it can sufficiently act as a curing agent, the melt viscosity can be further reduced, and the moldability tends to be further improved. From the same viewpoint, the phenol equivalent is 150 g / eq. Or more, preferably 170 g / eq. More preferably.
  • the molecular weight of the specific hindered phenol compound is not particularly limited, and is, for example, 500 or less, and is preferably 450 or less and 400 or less from the viewpoint of further reducing the melt viscosity and further improving the moldability. Is more preferable.
  • the content of the specific hindered phenol compound in the thermosetting composition is preferably 10 to 40 parts by mass with respect to 100 parts by mass of the thermosetting composition solid content.
  • the melt viscosity can be further reduced without excessively inhibiting the effect of reducing warpage (particularly package warpage), and as a result, the moldability tends to be further improved.
  • the lower limit of the content is preferably 10 parts by mass or more, more preferably 12 parts by mass or more, and further preferably 13 parts by mass or more.
  • the upper limit is preferably 40 parts by mass or less, more preferably 38 parts by mass or less, and further preferably 35 parts by mass or less.
  • content of the specific hindered phenol compound in a thermosetting composition is 20 to 60 mass parts with respect to 100 mass parts of epoxy compounds.
  • content is in the above range, the melt viscosity can be further reduced without excessively inhibiting the effect of reducing warpage (particularly package warpage), and as a result, the moldability tends to be further improved.
  • the lower limit of the content is preferably 20 parts by mass or more from the viewpoint of melt viscosity, more preferably more than 20 parts by mass, still more preferably 23 parts by mass or more, and the upper limit of the content is From the viewpoint of improving the effect of reducing package warpage, it is preferably 60 parts by mass or less, more preferably 57 parts by mass or less, and further preferably 55 parts by mass or less.
  • the other phenolic compound is not particularly limited as long as it is a phenolic compound other than the specific hindered phenolic compound described above, but is preferably a compound having two or more phenolic hydroxyl groups in one molecule and in the form of a resin. There may be.
  • examples of other phenol compounds include phenols having two or more phenolic hydroxyl groups in one molecule, bisphenol type phenol resins (for example, bisphenol A type resin, bisphenol M type resin, bisphenol E type resin, bisphenol F type resin).
  • Bisphenol S resin etc.
  • phenol novolak resins eg, phenol novolak resin, naphthol novolak resin, cresol novolac resin, etc.
  • naphthalene type phenol resin anthracene type phenol resin
  • dicyclopentadiene type phenol resin biphenyl type phenol resin
  • Polyol-type phenol resin aralkyl-type phenol resin, phenol-modified aromatic hydrocarbon formaldehyde resin, and the like.
  • phenolic compounds are preferably bifunctional phenolic compounds from the viewpoint of improving the effect of reducing melt viscosity and package warpage in a more balanced manner.
  • the “bifunctional phenol compound” referred to in the present specification refers to a compound having two phenolic hydroxyl groups in one molecule (the number of phenolic hydroxyl groups in one molecule is 2).
  • the content of the bifunctional phenol compound is preferably 20 to 60 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition from the viewpoint of improving the effect of reducing the melt viscosity and the package warpage in a more balanced manner.
  • the amount is more preferably 20 to 50 parts by mass, and further preferably 20 to 40 parts by mass.
  • Bifunctional phenol compounds include bisphenol, biscresol, bisphenols having a fluorene skeleton (eg, bisphenol having a fluorene skeleton, biscresol having a fluorene skeleton, etc.), diallyl bisphenol (eg, diallyl bisphenol A), biphenol (eg, , P, p′-biphenol, etc.), dihydroxy diphenyl ether (eg, 4,4′-dihydroxy diphenyl ether, etc.), dihydroxy diphenyl ketone (eg, 4,4′-dihydroxy diphenyl ether, etc.), dihydroxy diphenyl sulfide (eg, 4,4 '-Dihydroxydiphenyl sulfide and the like) and dihydroxyarene (eg, hydroquinone and the like).
  • diallyl bisphenol eg, diallyl bisphenol A
  • biphenol eg, , P, p′-biphenol, etc.
  • bifunctional phenol compounds are used singly or in combination of two or more.
  • the bifunctional phenol compound is preferably a bisphenol having a bisphenol, a biscresol, or a fluorene skeleton from the viewpoint of further improving the effect of reducing the melt viscosity and the package warpage in a balanced manner.
  • bisphenol examples include bisphenol A, bisphenol M, bisphenol E, bisphenol F, bisphenol AD, bisphenol P, bisphenol AP, bisphenol S, bisphenol Z, and bisphenol TMC. These bisphenols are used alone or in combination of two or more. Among these, bisphenol is preferably bisphenol A or bisphenol M from the viewpoint of improving the effect of reducing melt viscosity and package warpage in a more balanced manner.
  • the phenol equivalent of other phenolic compounds is 400 g / eq. From the viewpoint of further improving the heat resistance, moisture absorption heat resistance, chemical resistance, melt viscosity and package warpage reduction effect in a more balanced manner. Or less, preferably 380 g / eq. Or less, more preferably 350 g / eq. More preferably, it is as follows.
  • the content of the phenolic compound in the thermosetting composition is 30 to 40 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition from the viewpoint of further improving the effect of reducing the melt viscosity and the package warpage.
  • the lower limit of the content is preferably 30 parts by mass or more, more preferably 32 parts by mass or more
  • the upper limit of the content is preferably 40 parts by mass or less, More preferably, it is 38 parts by mass or less.
  • the epoxy compound is not particularly limited, but is preferably a compound having two or more epoxy groups in one molecule, and may be in the form of a resin.
  • the epoxy compound include bisphenol type epoxy resins (for example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin), and phenol novolac type epoxy resins (for example, phenol novolak type epoxy).
  • Resin bisphenol A novolac type epoxy resin, cresol novolac type epoxy resin), aralkyl type epoxy resin, biphenyl type epoxy resin containing biphenyl skeleton, naphthalene type epoxy resin containing naphthalene skeleton, anthracene type epoxy resin containing anthracene skeleton , Glycidyl ester type epoxy resin, polyol type epoxy resin, isocyanurate ring-containing epoxy resin, dicyclopentadiene type epoxy resin, Scan phenol A-type structural unit with the epoxy resin consisting of a hydrocarbon-based structural units, these halogen compounds. These epoxy compounds are used individually by 1 type or in combination of 2 or more types.
  • aralkyl type epoxy resin naphthalene type epoxy resin, dicyclopentadiene type It is preferably at least one selected from the group consisting of epoxy resins and epoxy resins consisting of bisphenol A structural units and hydrocarbon-based structural units, and selected from the group consisting of naphthalene type epoxy resins and dicyclopentadiene type epoxy resins. More preferably, it is a naphthalene type epoxy resin.
  • aralkyl type epoxy resin As an aralkyl type epoxy resin, the compound represented by a following formula (3a) is mentioned, for example.
  • each Ar 3 independently represents a benzene ring or a naphthalene ring
  • each Ar 4 represents a benzene ring, a naphthalene ring, or a biphenyl ring
  • each R 3a independently represents a hydrogen atom.
  • it represents a methyl group
  • k represents an integer of 1 to 50
  • each ring may have a substituent other than a glycidyloxy group (for example, an alkyl group having 1 to 5 carbon atoms or a phenyl group).
  • k represents an integer of 1 to 50, and preferably represents an integer of 1 to 10 from the viewpoint of more effectively and reliably achieving the effects of the present invention. It is preferable to represent an integer of 1 to 3.
  • the aralkyl type epoxy resin when the aralkyl type epoxy resin includes the compound represented by the formula (3a), it may include a plurality of types of compounds having the same k, or may include a plurality of types of compounds having different k. When the aralkyl type epoxy resin includes a plurality of types of compounds having different k, it is preferable to include a compound in which k is 1 to 3 in the formula (3a).
  • the compound represented by the formula (3a) is a compound in which, in the formula (3a), Ar 3 is a naphthalene ring and Ar 4 is a benzene ring from the viewpoint of further reducing warpage (particularly package warpage).
  • “Naphthalene aralkyl type epoxy resin”) and Ar 3 are preferably benzene rings, and Ar 4 is preferably a biphenyl ring compound (also referred to as “biphenyl aralkyl type epoxy resin”). More preferably, it is an aralkyl type epoxy resin.
  • the biphenyl aralkyl type epoxy resin is preferably a compound represented by the following formula (3b) from the viewpoint of further improving the heat resistance and low water absorption of the resulting cured product and the effect of reducing warpage (particularly package warpage). .
  • ka represents an integer of 1 or more, preferably represents an integer of 1 to 6, and more preferably represents an integer of 1 to 3.
  • aralkyl type epoxy resin may be a compound represented by the following formula (3-a) or the following formula (3-b).
  • ky represents an integer of 1 to 10.
  • kz represents an integer of 1 to 10.
  • aralkyl epoxy resin a commercially available product may be used, or a preparation prepared by a known method may be used.
  • examples of commercially available naphthalene aralkyl epoxy resins include “Epototo (registered trademark) ESN-155”, “Epototo (registered trademark) ESN-355”, “Epototo (registered trademark) ESN-” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • Naphthalene type epoxy resin Although it does not specifically limit as a naphthalene type epoxy resin, for example, it is an epoxy resin except said naphthalene aralkyl type epoxy resin, Comprising: The epoxy resin which has a naphthalene skeleton is mentioned.
  • Specific examples of the naphthalene type epoxy resin include, for example, an epoxy resin represented by the following formula (3c-1), a naphthylene ether type epoxy resin, and the like, and the resulting cured product has heat resistance, low water absorption and low heat.
  • a naphthylene ether type epoxy resin is preferable from the viewpoint of further improving the expansion and the effect of reducing warpage (particularly package warpage).
  • epoxy resin represented by the above formula (3c-1) a commercially available product may be used, or a preparation prepared by a known method may be used. Examples of commercially available products include “HP-4710” manufactured by DIC Corporation.
  • Naphthylene ether type epoxy resin As a naphthylene ether type epoxy resin, the compound represented by a following formula (3c) is mentioned, for example.
  • each R 3b independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aralkyl group, a naphthyl group or a naphthyl group containing a glycidyloxy group, and k1 represents 0 to 10 Represents an integer.
  • Examples of the compound represented by the formula (3c) include a compound represented by the formula (3c-2).
  • naphthylene ether type epoxy resin a commercially available product may be used, or a preparation prepared by a known method may be used.
  • commercial products of naphthylene ether type epoxy resins for example, “HP-4032”, “HP-6000”, “EXA-7300”, “EXA-7310”, “EXA-731”, “DIC” manufactured by DIC Corporation EXA-7311L ”,“ EXA7311-G3 ”and the like.
  • k1 represents an integer of 0 to 10, and preferably represents an integer of 0 to 6, and more preferably represents an integer of 0 to 4, from the viewpoint of more effectively and reliably achieving the effects of the present invention. More preferably, it is more preferably 2 to 3.
  • each R 3b independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aralkyl group, or a naphthyl group from the viewpoint of more effectively and reliably achieving the effects of the present invention. It is preferable.
  • the number of glycidyloxy groups containing an epoxy group in the molecule is preferably 2 to 6, and more preferably 2 to 4.
  • the naphthylene ether type epoxy resin when the naphthylene ether type epoxy resin includes the compound represented by the formula (3c), it may include a plurality of types of compounds having the same k1 or may include a plurality of types of compounds having different k1.
  • the naphthylene ether type epoxy resin when the naphthylene ether type epoxy resin includes a plurality of types of compounds having different k1, in the formula (3c), it preferably includes a compound in which k1 is 0 to 4, and more preferably includes a compound in which 2-3 is present. preferable.
  • dicyclopentadiene type epoxy resin As a dicyclopentadiene type epoxy resin, the compound represented by a following formula (3d) is mentioned, for example.
  • R 3c each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and k2 represents an integer of 0 to 10.
  • k2 represents an integer of 0 to 10, and preferably represents an integer of 0 to 6, and preferably an integer of 0 to 2 (preferably from the viewpoint of more effectively and reliably achieving the effects of the present invention. Preferably represents 0 or 1).
  • the dicyclopentadiene type epoxy resin when the dicyclopentadiene type epoxy resin includes the compound represented by the formula (3d), it may include a plurality of types of compounds having the same k2 or may include a plurality of types of compounds having different k2.
  • the dicyclopentadiene type epoxy resin when the dicyclopentadiene type epoxy resin includes a plurality of types of compounds having different k 2, it is preferable to include a compound in which k 2 is 0 to 2 in the formula (3d).
  • dicyclopentadiene type epoxy resin a commercially available product may be used, or a preparation prepared by a known method may be used.
  • examples of commercially available dicyclopentadiene type epoxy resins include “EPICLON HP-7200L”, “EPICLON HP-7200”, “EPICLON HP-7200H”, “EPICLON HP-7000HH” and the like manufactured by DIC Corporation.
  • Epoxy resin consisting of bisphenol A structural unit and hydrocarbon-based structural unit An epoxy resin composed of a bisphenol A-type structural unit and a hydrocarbon-based structural unit (also referred to as “specific epoxy resin”) includes one or more bisphenol A-type structural units and one or more hydrocarbon-based molecules in the molecule. Has a structural unit.
  • specific epoxy resin the compound represented by a following formula (3e) is mentioned, for example.
  • R 1x and R 2x each independently represent a hydrogen atom or a methyl group
  • R 3x to R 6x each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom
  • X represents an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a propyleneoxypropyl group, a di (propyleneoxy) propyl group, a tri (propyleneoxy) propyl group, or carbon Represents an alkylene group of 2 to 15, and k3 represents an integer.
  • k3 represents an integer, and is preferably an integer of 1 to 10, more preferably an integer of 1 to 6, from the viewpoint of more effectively and reliably achieving the effects of the present invention.
  • An integer of 1 to 2 is more preferable, and 1 is particularly preferable.
  • X is preferably an ethylene group from the viewpoint of more effectively and reliably achieving the effects of the present invention.
  • specific epoxy resin a commercial product may be used, or a preparation prepared by a known method may be used.
  • specific epoxy resins include “EPICLON EXA-4850-150” and “EPICLON EXA-4816” manufactured by DIC Corporation.
  • the epoxy equivalent of the epoxy compound is 100 to 500 g / eq. From the viewpoint of improving the effect of reducing melt viscosity and warpage (particularly package warpage) in a more balanced manner. Or less, preferably 450 g / eq. Or less, more preferably 350 g / eq. More preferably, it is as follows.
  • the content of the epoxy compound in the thermosetting composition is from 50 to 100 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition from the viewpoint of improving the effect of reducing melt viscosity and warpage (particularly package warpage) in a more balanced manner. It is preferable that it is 70 mass parts. From the same viewpoint, the lower limit value of the content is preferably 50 parts by mass or more, more preferably 55 parts by mass or more, and the upper limit value of the content is preferably 70 parts by mass or less. More preferably, it is 65 parts by mass or less.
  • the epoxy compound preferably contains a bifunctional epoxy compound and a polyfunctional epoxy compound from the viewpoint of improving the effect of reducing warpage (particularly package warpage).
  • the term “bifunctional epoxy compound” as used herein refers to a compound having two epoxy groups in one molecule (the number of epoxy groups in one molecule is 2). A compound having three or more epoxy groups in one molecule (the number of epoxy groups in one molecule is 3 or more).
  • the epoxy compound as the bifunctional epoxy compound and the polyfunctional epoxy compound examples include those corresponding to the bifunctional epoxy compound and the polyfunctional epoxy compound among the above-described epoxy compounds. Whether the epoxy compound is used alone or in combination of two or more, the epoxy compound includes a bifunctional epoxy compound and a polyfunctional epoxy compound from the viewpoint of effectively and reliably achieving the effects of the present invention. preferable.
  • the bifunctional epoxy compound is preferably a bisphenol type epoxy resin from the viewpoint of further improving the heat resistance of the obtained cured product.
  • polyfunctional epoxy compounds are aralkyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, and bisphenol A type structural units and hydrocarbons from the viewpoint of further improving the heat resistance of the resulting cured product. It is preferably at least one selected from the group consisting of epoxy resins composed of structural units, and more preferably naphthalene type epoxy resins.
  • the epoxy compound is a naphthalene type epoxy resin containing a naphthalene skeleton containing 3 or more epoxy groups in one molecule (preferably as a polyfunctional epoxy compound from the viewpoint of more effectively and reliably achieving the effects of the present invention (preferably A naphthylene ether type epoxy resin having 3 or more epoxy groups in one molecule) and / or a naphthalene aralkyl type epoxy resin having 3 or more epoxy groups and a naphthalene ring in one molecule, and a bifunctional epoxy compound (preferably Preferably contains a bisphenol type epoxy resin).
  • the content of the bifunctional epoxy compound is preferably 20 to 70 parts by weight with respect to 100 parts by weight of the solid content of the thermosetting composition from the viewpoint of improving the effect of reducing warpage (particularly package warpage).
  • the amount is more preferably 60 parts by mass, still more preferably 20 to 50 parts by mass, and particularly preferably 20 to 40 parts by mass.
  • the content of the polyfunctional epoxy compound is preferably 10 to 50 parts by mass and more preferably 20 to 40 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • the total content of the phenolic compound and the epoxy compound in the thermosetting composition is 100 mass parts of the thermosetting composition solid content from the viewpoint of improving the effect of reducing melt viscosity and warpage (particularly package warpage) in a more balanced manner.
  • it is preferably 60 parts by mass or more and 100 parts by mass or less.
  • the lower limit of the total content is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, still more preferably 80 parts by mass or more, and the upper limit of the total content
  • the value is preferably 100 parts by mass or less, and more preferably 95 parts by mass or less.
  • the ratio of the phenol equivalent of the phenol compound to the epoxy equivalent of the epoxy compound is 0.5 or more and 1. from the viewpoint of further improving the effect of reducing the melt viscosity and warpage (particularly package warpage). 5 or less is preferable.
  • the lower limit value of the ratio is preferably 0.5 or more, more preferably 0.6 or more, still more preferably 0.7 or more, and the upper limit value of the ratio is 1 0.5 or less is preferable, 1.4 or less is more preferable, and 1.3 or less is still more preferable.
  • thermosetting composition contains a phenol compound and / or a cyanate ester compound and an epoxy compound
  • the thermosetting composition with respect to the amount of epoxy groups (containing part by mass / epoxy equivalent) in the thermosetting composition is preferably 0.5 to 1.5.
  • thermosetting composition contains both a phenol compound and a cyanate ester compound
  • said ratio is the ratio of the total amount of the said phenol group amount with respect to the said epoxy group amount, and the said cyanate group amount.
  • the storage elastic modulus at the time of heating tends to be a value suitable for suppressing warpage.
  • the lower limit of the ratio is preferably 0.5 or more, more preferably 0.6 or more, further preferably 0.7 or more, and 0.9 or more.
  • the upper limit of the ratio is preferably 1.5 or less, more preferably 1.4 or less, further preferably 1.3 or less, and 1.2 or less. Particularly preferred.
  • the above-mentioned phenol group amount means the total value of the phenol group amounts of each phenol compound, and when there are a plurality of types of cyanate ester compounds, the above-mentioned cyanate.
  • group amount refers to the total value of the cyanate group amount of each cyanate ester compound.
  • group amount refers to the total value of the epoxy group amount of each epoxy compound.
  • thermosetting compound of this embodiment may further contain a cyanate ester compound.
  • cyanate ester compound refers to a compound having one or more cyanato groups (cyanate ester groups) in one molecule, and may be in the form of a resin.
  • the cyanate ester compound examples include an aromatic hydrocarbon compound containing two or more cyanato groups in one molecule, a compound in which two aromatic rings containing two or more cyanato groups are bonded by a linking group, and a novolak Type cyanate ester, bisphenol type cyanate ester, diallyl bisphenol type cyanate ester (for example, diallyl bisphenol A type cyanate ester, diallyl bisphenol E type cyanate ester, diallyl bisphenol F type cyanate ester, diallyl bisphenol S type cyanate Esters), aralkyl cyanate esters, and prepolymers of these cyanate esters.
  • a cyanate ester compound is used individually by 1 type or in combination of 2 or more types.
  • p is preferably an integer of 2 to 6, more preferably an integer of 2 to 3, and still more preferably an integer of 2.
  • the compound in which p is 2 is not particularly limited.
  • the compound in which two aromatic rings containing two or more cyanato groups are bonded by a linking group is not particularly limited.
  • bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone and the like are examples.
  • Examples of the novolak-type cyanate ester include compounds represented by the following formula (1x).
  • R 1a each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R 1b each independently represents a hydrogen atom or a methyl group (preferably a hydrogen atom).
  • N represents an integer of 1 to 10.
  • n is an integer of 1 to 10, and is preferably an integer of 1 to 6 from the viewpoint of more effectively and reliably achieving the effects of the present invention.
  • the novolac-type cyanate ester when the novolac-type cyanate ester includes the compound represented by the formula (1x), it may include a plurality of types of compounds in which n is the same, or may include a plurality of types of compounds in which n is different.
  • the compound represented by the formula (1x) is not particularly limited, and examples thereof include bis (3,5-dimethyl4-cyanatophenyl) methane, bis (4-sinaatphenyl) methane, and 2,2′-bis ( 4-Cyanatophenyl) propane and the like.
  • the bisphenol-type cyanate ester is not particularly limited, and examples thereof include compounds in which the hydrogen atom of the phenolic hydroxyl group of bisphenol exemplified in the section of the phenol compound is substituted with a cyan group (—C ⁇ N).
  • a cyan group —C ⁇ N
  • bisphenol A type cyanate ester, bisphenol E type cyanate ester, bisphenol F type cyanate ester, bisphenol AD type cyanate ester, Bisnophenol B type cyanate ester, bisphenol AP type cyanate ester bisphenol Examples thereof include S-type cyanate ester, bisphenol Z-type cyanate ester, and bisphenol TMC-type cyanate ester.
  • the bisphenol-type cyanate ester a commercially available product may be used, or a preparation prepared by a known method may be used.
  • a commercial item of bisphenol-type cyanate ester "CA210" etc. of Mitsubishi Gas Chemical Co., Ltd. product are mentioned, for example.
  • the aralkyl cyanate ester is not particularly limited, and examples thereof include naphthol aralkyl cyanate ester and biphenyl aralkyl cyanate ester.
  • naphthol aralkyl type cyanate ester examples include a compound represented by the following formula (1a).
  • R 1d each independently represents a hydrogen atom or a methyl group (preferably a hydrogen atom), and n1 represents an integer of 1 to 10.
  • n1 is an integer of 1 to 10, and is preferably an integer of 1 to 6 from the viewpoint of more effectively and reliably achieving the effects of the present invention.
  • the aralkyl type cyanate ester when the aralkyl type cyanate ester includes the compound represented by the formula (1a), it may include a plurality of types of compounds in which n1 is the same, or may include a plurality of types of compounds in which n1 is different.
  • biphenyl aralkyl type cyanate ester examples include compounds represented by the following formula (1b).
  • R 1e each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R 1f each independently represents a hydrogen atom or a methyl group (preferably a hydrogen atom)
  • n2 represents an integer of 1 to 10.
  • n2 represents an integer of 1 to 10, and preferably represents an integer of 1 to 6 from the viewpoint of more effectively and reliably achieving the effects of the present invention.
  • the biphenylaralkyl type cyanate ester when the biphenylaralkyl type cyanate ester includes the compound represented by the formula (1b), it may include a plurality of types of compounds in which n2 is the same, or may include a plurality of types of compounds in which n2 is different.
  • aralkyl cyanate ester a commercially available product may be used, or a product synthesized by a known method may be used.
  • a method for synthesizing an aralkyl cyanate ester for example, a phenol resin corresponding to the target aralkyl cyanate ester (hereinafter also referred to as “corresponding phenol resin”), cyanogen halide, basic compound, And a method in which a salt formed by reacting a corresponding phenol resin and a basic compound in an aqueous solution with cyanogen halide is subjected to a two-phase interfacial reaction.
  • an aralkyl cyanate ester can be obtained by cyanating the hydrogen atom of the phenolic hydroxyl group of the corresponding phenol resin. More specifically, for example, the methods described in the examples are used.
  • the content of the cyanate ester compound may be, for example, 0 to 45 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition, from the viewpoint of more effectively and reliably achieving the effects of the present invention. 35 parts by mass or less, more preferably 25 parts by mass or less, still more preferably 15 parts by mass or less, and particularly preferably 5 parts by mass or less.
  • the thermosetting compound of this embodiment may further contain a maleimide compound.
  • the “maleimide compound” refers to a compound having one or more maleimide groups in one molecule, and may be in the form of a resin.
  • the maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule.
  • a monomaleimide compound having one maleimide group in one molecule for example, N-phenylmaleimide, N -Hydroxyphenylmaleimide and the like
  • polymaleimide compounds having two or more maleimide groups in one molecule for example, bis (4-maleimidophenyl) methane, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis ( 3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) methane), prepolymers of these maleimide compounds and amine compounds, and the like.
  • These maleimide compounds are used alone or in combination of two or more.
  • polymaleimide compound examples include a compound in which a plurality of maleimide groups are bonded to a benzene ring (for example, phenylene bismaleimide such as m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide), linear or A compound having a maleimide group bonded to both ends of a branched alkyl chain (for example, 1,6-bismaleimide- (2,2,4-trimethyl) hexane), bisphenol A diphenyl ether bismaleimide, represented by the following formula (4a) The compound which is made is mentioned.
  • phenylene bismaleimide such as m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide
  • linear or A compound having a maleimide group bonded to both ends of a branched alkyl chain for example, 1,6-bismaleimide- (2,2,4-trimethyl) hexane
  • R 4a and R 5a each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom.
  • R 4b each independently represents a hydrogen atom or a methyl group, and preferably represents a hydrogen atom from the viewpoint of more effectively and reliably achieving the effects of the present invention.
  • s represents an integer of 1 or more.
  • s represents an integer of 1 or more, and preferably represents an integer of 1 to 6 from the viewpoint of more effectively and reliably achieving the effects of the present invention. Is more preferable, and an integer of 1 to 2 is more preferable, and 1 is particularly preferable.
  • Specific examples of the compound represented by the formula (4a) include bis (4-maleimidophenyl) methane, 2,2-bis ⁇ 4- (4-maleimidophenoxy) -phenyl ⁇ propane, bis (3-ethyl-5 -Methyl-4-maleimidophenyl) methane.
  • the polymaleimide compound contains the maleimide compound represented by the formula (4a)
  • the thermal expansion coefficient of the obtained cured product is further lowered, and the heat resistance and the glass transition temperature (Tg) tend to be further improved.
  • a maleimide compound may be used individually by 1 type, and may use 2 or more types together.
  • maleimide compound a commercially available product may be used, or a preparation prepared by a known method may be used.
  • Commercially available maleimide compounds include “BMI-70” and “BMI-80” manufactured by KAI Kasei Co., Ltd., “BMI-2300”, “BMI-1000P” and “BMI” manufactured by Daiwa Kasei Kogyo Co., Ltd. -3000 ",” BMI-4000 “,” BMI-5100 ",” BMI-7000 "and the like.
  • the content of the maleimide compound may be, for example, 0 to 45 parts by mass relative to 100 parts by mass of the solid content of the thermosetting composition. From the viewpoint of more effectively and reliably achieving the effects of the present invention, 35 It is preferably no greater than part by mass, more preferably no greater than 25 parts by mass, even more preferably no greater than 15 parts by mass, and particularly preferably no greater than 5 parts by mass.
  • the thermosetting compound of this embodiment may further contain an alkenyl-substituted nadiimide compound.
  • the “alkenyl-substituted nadiimide compound” refers to a compound having one or more alkenyl-substituted nadiimide groups in the molecule.
  • Examples of the alkenyl-substituted nadiimide compound include a compound represented by the following formula (5a).
  • each R 6a independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R 6b represents an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, or a naphthylene.
  • R 6c represents a methylene group, an isopropylidene group, or a substituent represented by CO, O, S, or SO 2 .
  • each R 6d independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.
  • examples of the alkenyl-substituted nadiimide compound also include compounds represented by the following formula (12) and / or (13).
  • alkenyl-substituted nadiimide compound a commercially available product may be used, or a preparation prepared by a known method may be used.
  • the commercial product of the alkenyl-substituted nadiimide compound is not particularly limited, and examples thereof include “BANI-M” and “BANI-X” manufactured by Maruzen Petrochemical Co., Ltd.
  • the content of the alkenyl-substituted nadiimide compound may be, for example, from 0 to 45 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition. From the viewpoint of more effectively and reliably achieving the effects of the present invention. 35 parts by mass or less, more preferably 25 parts by mass or less, still more preferably 15 parts by mass or less, and particularly preferably 5 parts by mass or less.
  • thermosetting compound of this embodiment preferably contains a bifunctional thermosetting compound and a polyfunctional thermosetting compound.
  • bifunctional thermosetting compound refers to a compound having two thermosetting functional groups in one molecule (the number of thermosetting functional groups in one molecule is two).
  • polyfunctional thermosetting compound refers to a compound having three or more thermosetting functional groups in one molecule (the number of thermosetting functional groups in one molecule is three or more).
  • the content of the bifunctional thermosetting compound is set to 100 parts by mass of the solid content of the thermosetting composition from the viewpoint of improving the effect of reducing melt viscosity and warpage (particularly package warpage) in a more balanced manner.
  • the lower limit of the content is preferably 40 parts by mass or more, more preferably 44 parts by mass or more
  • the upper limit of the content is preferably 90 parts by mass or less, More preferably, it is 85 mass parts or less, More preferably, it is 80 mass parts or less, More preferably, it is 70 mass parts or less.
  • the content of the polyfunctional thermosetting compound is 10 parts by mass or more and 60 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition from the viewpoint of improving the effect of reducing melt viscosity and warpage (particularly package warpage) in a more balanced manner. It is preferable that it is below mass parts.
  • the lower limit of the content is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 30 parts by mass or more.
  • the upper limit of the content is preferably 60 parts by mass or less, and more preferably 50 parts by mass or less.
  • thermosetting composition of the present embodiment may contain other resins shown below as long as the effects of the present invention are not impaired.
  • other resins include compounds having polymerizable unsaturated groups, oxetane resins, and benzoxazine compounds.
  • Examples of the compound having a polymerizable unsaturated group include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, divinylbiphenyl; methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Monovalents such as (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate Or (meth) acrylates of polyhydric alcohols; epoxy (meth) acrylates such as bisphenol A type epoxy (meth) acrylate and bisphenol F type epoxy (meth) acrylate ; Benzocyclobutene resins.
  • vinyl compounds such as ethylene, prop
  • oxetane resin examples include alkyl oxetanes such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3 '-Di (trifluoromethyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl-type oxetane, “OXT-101” and “OXT-121” manufactured by Toagosei Co., Ltd. Etc.
  • alkyl oxetanes such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, 3-methyl-3
  • the benzoxazine compound may be any compound having two or more dihydrobenzoxazine rings in one molecule.
  • “Bisphenol F-type benzoxazine BF-BXZ” “Bisphenol S-type benzoxazine” manufactured by Konishi Chemical Co., Ltd. BS-BXZ ”and the like.
  • thermosetting composition of this embodiment may further contain a filler.
  • the filler include an inorganic filler and / or an organic filler.
  • the inorganic filler is not particularly limited, and examples thereof include silicas, silicon compounds (for example, white carbon), metal oxides (for example, alumina, titanium white, zinc oxide, magnesium oxide, zirconium oxide, etc.), metal nitriding.
  • Products for example, boron nitride, agglomerated boron nitride, silicon nitride, aluminum nitride, etc.
  • metal sulfates for example, barium sulfate, etc.
  • metal hydroxides for example, aluminum hydroxide, aluminum hydroxide heat treated products (for example, Heat treated aluminum hydroxide and reduced part of crystal water), boehmite, magnesium hydroxide, etc.
  • molybdenum compounds eg, molybdenum oxide, zinc molybdate, etc.
  • zinc compounds eg, zinc borate, Zinc stannate, etc.
  • the filler is composed of silica, metal hydroxide, and metal oxide from the viewpoint of further excellent low thermal expansion, dimensional stability, flame retardancy, rigidity, and reduction of warpage (particularly package warpage). It is preferably at least one selected from the group, more preferably at least one selected from the group consisting of silica, boehmite, and alumina, and more preferably silica.
  • silicas examples include natural silica, fused silica, synthetic silica, amorphous silica, aerosil, and hollow silica.
  • fused silica is preferable from the viewpoint of further excellent low thermal expansion, rigidity, and reduction of warpage (particularly package warpage).
  • the organic filler is not particularly limited, and examples thereof include rubber powders such as styrene type powder, butadiene type powder and acrylic type powder; core shell type rubber powder; silicone type powder and the like. These organic fillers are used alone or in combination of two or more. Among these, a silicone type powder is preferable from the viewpoint of further excellent low thermal expansion, flexibility, and reduction of warpage (particularly package warpage).
  • silicone type powder examples include silicone resin powder, silicone rubber powder, and silicone composite powder.
  • silicone composite powder is preferable from the viewpoint of further excellent low thermal expansion, flexibility, and reduction of warpage (particularly package warpage).
  • the filler of this embodiment preferably contains an inorganic filler and an organic filler from the viewpoint of further excellent low thermal expansion, dimensional stability, flexibility, rigidity, and reduction of warpage (particularly package warpage).
  • content of an inorganic filler is 30 to 700 mass parts with respect to 100 mass parts of thermosetting composition solid content.
  • the lower limit of the content is preferably 30 parts by mass or more, more preferably 35 parts by mass or more, further preferably 40 parts by mass or more, and 50 parts by mass or more. It may be 100 mass parts or more.
  • the upper limit of the content is preferably 700 parts by mass or less, more preferably 600 parts by mass or less, further preferably 500 parts by mass or less, and 250 parts by mass or less. Is particularly preferable, and may be 200 parts by mass or less.
  • the content of the organic filler is low thermal expansion, flexibility, and warpage (particularly package warpage) with respect to 100 parts by mass of the thermosetting composition solid content. From the viewpoint of more excellent reduction, it is preferably 1 part by mass or more and 50 parts by mass or less. From the same viewpoint, the lower limit of the content 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, and the upper limit of the content is 50 parts by mass. Part or less, preferably 40 parts by weight or less, and more preferably 30 parts by weight or less.
  • the content of the filler is 40 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition, from the viewpoint of further being excellent in low thermal expansion, dimensional stability, flexibility, rigidity, and warpage (particularly package warpage).
  • the amount is preferably 700 parts by mass or less.
  • the lower limit of the content is preferably 40 parts by mass or more, more preferably 45 parts by mass or more, and may be 50 parts by mass or more.
  • the upper limit of the content is 700 parts by mass. Part or less, preferably 600 parts by weight or less, more preferably 500 parts by weight or less, and particularly preferably 250 parts by weight or less.
  • thermosetting composition of this embodiment may further contain a silane coupling agent.
  • the thermosetting composition of the present embodiment contains a silane coupling agent, so that the dispersibility of the filler is further improved, the components of the thermosetting composition of the present embodiment, a base material to be described later, There exists a tendency for the adhesive strength of to improve further.
  • the silane coupling agent is not particularly limited, and examples thereof include silane coupling agents generally used for inorganic surface treatment, and aminosilane compounds (for example, ⁇ -aminopropyltriethoxysilane, N- ⁇ - (aminoethyl)) - ⁇ -aminopropyltrimethoxysilane, etc.), epoxy silane compounds (eg, ⁇ -glycidoxypropyltrimethoxysilane, etc.), acrylic silane compounds (eg, ⁇ -acryloxypropyltrimethoxysilane, etc.), cationic Examples include silane compounds (for example, N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane hydrochloride), phenylsilane compounds, and the like.
  • aminosilane compounds for example, ⁇ -aminopropyltriethoxysilane, N- ⁇ - (aminoethyl)
  • a silane coupling agent is used individually by 1 type or in combination of 2 or more types.
  • the silane coupling agent is preferably an epoxysilane compound.
  • the epoxy silane compound include “KBM-403”, “KBM-303”, “KBM-402”, “KBE-403” and the like manufactured by Shin-Etsu Chemical Co., Ltd.
  • the content of the silane coupling agent is not particularly limited, but may be 0.1 to 10.0 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • thermosetting composition of this embodiment may further contain a wetting and dispersing agent.
  • the thermosetting composition of the present embodiment tends to further improve the dispersibility of the filler by containing a wetting dispersant.
  • any known dispersing agent used for dispersing the filler may be used.
  • DISPER BYK-110, 111, 118, 180 manufactured by Big Chemie Japan Co., Ltd. 161, BYK-W996, W9010, W903, and the like.
  • the content of the wetting and dispersing agent is not particularly limited, but is preferably 0.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the thermosetting composition solid content.
  • the lower limit of the content is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, and further preferably 1.5 parts by mass or more.
  • thermosetting composition of this embodiment may further contain a curing accelerator.
  • the curing accelerator is not particularly limited, and examples thereof include imidazoles (for example, triphenylimidazole), organic peroxides (for example, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, dialkyl).
  • azo compounds eg, azobisnitrile, etc.
  • tertiary amines eg, N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N- Dimethyltoluidine, N, N-dimethylpyridine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine Etc.
  • organometallic salts e.g., Lead phthalate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, acetylacetone iron, etc.
  • organic metal salts with hydroxyl-containing compounds
  • the curing accelerator is preferably triphenylimidazole from the viewpoint of promoting the curing reaction and further improving the glass transition temperature (Tg) of the obtained cured product.
  • thermosetting composition of this embodiment may further contain a solvent.
  • the viscosity at the time of preparation of the thermosetting composition is lowered, handling property (handling property) is further improved, and impregnation property to a substrate is further improved. It tends to improve.
  • the solvent is not particularly limited as long as it can dissolve a part or all of the organic resin in the thermosetting composition.
  • ketones acetone, methyl ethyl ketone, etc.
  • aromatic hydrocarbons for example, Toluene, xylene and the like
  • amides for example, dimethylformaldehyde and the like
  • propylene glycol monomethyl ether and acetate thereof and the like.
  • thermosetting composition of the present embodiment is not particularly limited, and examples thereof include a method in which each component is mixed in a solvent in a batch or sequentially and stirred. At this time, in order to uniformly dissolve or disperse each component, known processes such as stirring, mixing, and kneading can be used.
  • thermosetting composition of the present embodiment is a cured product obtained by curing a prepreg obtained by impregnating or coating a substrate (hereinafter, also simply referred to as “cured product” or “cured product of prepreg”). It is preferable to satisfy the conditions (i) and (ii).
  • a, b, and c represent the storage elastic modulus (unit: GPa) of the cured product at 30 ° C., 100 ° C., and 260 ° C., respectively.
  • the prepreg may be a prepreg obtained by a known method. Specifically, the prepreg is impregnated or coated with the thermosetting composition of the present embodiment on a substrate, and then heat-dried at 100 to 200 ° C. to be semi-cured (B-stage). Is obtained.
  • a base material here is not specifically limited, For example, what is necessary is just a well-known base material used for the material of various printed wiring boards. Further, the impregnation or coating method is not particularly limited, and a known method may be used.
  • the cured product refers to a cured product obtained by thermally curing the prepreg under the conditions of a heating temperature of 200 to 230 ° C. and a heating time of 60 to 180 minutes.
  • the pressure conditions for curing are not particularly limited as long as the effects of the present invention are not impaired.
  • suitable conditions for curing the prepreg can be used, and heating means for curing the prepreg
  • a normal heating means for example, a dryer
  • b / a ratio of storage elastic modulus at 100 ° C. to storage elastic modulus at 30 ° C.
  • the glass transition temperature of the prepreg can be sufficiently improved.
  • sufficient rigidity can be ensured even when the temperature is raised, so that the handling property (handleability) in the manufacturing process of a printed wiring board (particularly a thin substrate such as a multilayer coreless substrate) tends to be improved.
  • b / a is preferably 0.85 or more, more preferably 0.90 or more, and further preferably 0.94 or more.
  • a printed wiring board may be a semiconductor chip. It is possible to develop viscous behavior during the reflow processing step for mounting the substrate, and as a result, it is possible to reduce warpage (package warpage) when manufacturing an electronic component (package).
  • the lower limit value of c / a is preferably 0.08 or more, and more preferably 0.10 or more.
  • the upper limit value of c / a is preferably 0.25 or less, more preferably 0.23 or less, and further preferably 0.21 or less.
  • thermosetting composition of this embodiment further satisfies the relationship represented by the following formula (iii). 15 ⁇ a ⁇ 30 (iii)
  • a storage elastic modulus at 40 ° C.
  • the rigidity tends to be sufficiently secured.
  • a is more preferably 16 GPa or more, and further preferably 18 GPa or more.
  • a is 30 GPa or less, it is possible to further reduce warpage (package warpage) in manufacturing electronic components (packages), and to reduce metal foil-clad laminates, printed wiring boards (and multilayer printed wiring boards (especially multilayer coreless)).
  • a is preferably 25 GPa or less, and more preferably 23 GPa or less.
  • thermosetting composition of this embodiment further satisfies the relationship represented by the following formula (iv) and / or the following formula (v). 0.10 ⁇ d / a ⁇ 0.65 (iv) 0.05 ⁇ e / a ⁇ 0.25 (v)
  • d and e are storage elastic moduli (units at 200 ° C. and 330 ° C.) of a cured product obtained by curing a prepreg obtained by impregnating or applying the thermosetting composition of the present embodiment to a substrate, respectively. : GPa).
  • d / a ratio of storage elastic modulus at 200 ° C. to storage elastic modulus at 30 ° C.
  • a process including heat treatment for example, a press molding process, an annealing process
  • warpage package warpage
  • the lower limit value of d / a is more preferably 0.14 or more, further preferably 0.16 or more
  • the upper limit value of d / a is 0.40 or less. Is more preferable, and it is still more preferable that it is 0.30 or less.
  • the lower limit value of e / a is more preferably 0.08 or more, still more preferably 0.10 or more, and the upper limit value of e / a is 0.22 or less. Is more preferably 0.20 or less.
  • thermosetting composition of this embodiment further satisfies the relationship represented by the following formula (x). 100 ⁇ Tg ⁇ 220 (x)
  • Tg represents a glass transition temperature (unit: ° C.) of a cured product obtained by curing a prepreg obtained by impregnating or applying the thermosetting composition of the present embodiment to a substrate.
  • thermosetting composition of the present embodiment satisfies the relationship represented by the formula (x), sufficient rigidity can be ensured even when the temperature is increased, so that a printed wiring board (particularly a multilayer coreless substrate or the like) is thin.
  • the handling property (handling property) in the manufacturing process of the substrate) tends to be further improved.
  • the lower limit value of the glass transition temperature of the cured product is more preferably 120 ° C. or more, further preferably 130 ° C. or more, and the upper limit value of the glass transition temperature of the cured product is 215 ° C. or less. It is more preferable that it is 210 degrees C or less.
  • thermosetting composition of this embodiment further satisfies the relationship represented by the following formula (y). D ⁇ 0.1 (y)
  • D represents a loss tangent of elastic modulus at a glass transition temperature of a cured product obtained by curing a prepreg obtained by impregnating or applying the thermosetting composition of the present embodiment to a substrate.
  • D when D is a specific value or more, warpage (package warpage) in manufacturing an electronic component (package) can be further reduced, and a metal foil-clad laminate, a printed wiring board (and multilayer print)
  • D is more preferably 0.11 or more (for example, 0.11 to 0.30), and the warp of the wiring board (particularly the multilayer coreless substrate) tends to be further reduced. More preferably, it is 13 or more.
  • the storage elastic modulus, glass transition temperature, and loss tangent of the cured product can be measured by the DMA method (Dynamic Mechanical Analysis method) based on JIS C6481.
  • DMA method Dynamic Mechanical Analysis method
  • 100 Laminate molding (thermosetting) for a minute is performed to obtain a copper foil clad laminate having a predetermined thickness.
  • the obtained copper foil-clad laminate is cut into a size of 5.0 mm ⁇ 20 mm with a dicing saw, and then the copper foil on the surface is removed by etching to obtain a measurement sample.
  • the storage elastic modulus, glass transition temperature and loss tangent of the obtained measurement sample are measured using a dynamic viscoelasticity analyzer (TA instrument product). The measured value is obtained, for example, as an arithmetic average value of three measured values.
  • thermosetting composition of the present embodiment can sufficiently reduce the warpage of a metal foil-clad laminate, a printed wiring board, and a multilayer printed wiring board (particularly a multilayer coreless board), and can sufficiently reduce package warping. It can be reduced and has excellent moldability. For this reason, the thermosetting composition of this embodiment is used for a metal foil-clad laminate, a printed wiring board, and a multilayer printed wiring board. In particular, since the problem of warpage is remarkable in a multilayer coreless substrate, the thermosetting composition of this embodiment is suitably used for a multilayer coreless substrate. In addition, the thermosetting composition of this embodiment is used suitably also as a prepreg, an insulating layer, and a laminated board.
  • the prepreg of this embodiment includes a base material and the thermosetting composition of this embodiment impregnated or coated on the base material.
  • the prepreg may be a prepreg obtained by a known method. Specifically, after impregnating or applying the thermosetting composition of the present embodiment to a substrate, the prepreg is heated to 100 to 200 ° C. It is obtained by semi-curing (B-stage) by heating and drying under conditions.
  • the prepreg of the present embodiment includes a cured product obtained by thermally curing a semi-cured prepreg at a heating temperature of 200 to 230 ° C. and a heating time of 60 to 180 minutes.
  • the content of the thermosetting composition in the prepreg is preferably 30 to 90% by volume, more preferably 35 to 85% by volume, and still more preferably 40% in terms of solid content with respect to the total amount of the prepreg. ⁇ 80% by volume.
  • the solid content of the prepreg is a component obtained by removing the solvent from the prepreg.
  • the filler is included in the solid content of the prepreg.
  • Base material It does not specifically limit as a base material,
  • the well-known base material used for the material of various printed wiring boards is mentioned.
  • Specific examples of the substrate include glass substrates, inorganic substrates other than glass (for example, inorganic substrates composed of inorganic fibers other than glass such as quartz), organic substrates (for example, wholly aromatic polyamides, polyesters). , Organic base materials composed of organic fibers such as polyparaphenylene benzoxazole and polyimide). These base materials are used individually by 1 type or in combination of 2 or more types.
  • a glass substrate is preferable from the viewpoint of further improving the rigidity and further improving the heat dimensional stability.
  • the fibers constituting the glass substrate include E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass.
  • the fiber which comprises a glass base material consists of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass from a viewpoint which is further excellent in intensity
  • One or more fibers selected from the group are preferred.
  • the form of the substrate is not particularly limited, and examples thereof include woven cloth, non-woven cloth, roving, chopped strand mat, and surfacing mat.
  • the weaving method of the woven fabric is not particularly limited, and for example, plain weave, Nanako weave, twill weave and the like are known, and can be appropriately selected from these known ones depending on the intended use and performance. .
  • the thing which spread-processed these, and the glass woven fabric surface-treated with the silane coupling agent etc. are used suitably.
  • the thickness and mass of the substrate are not particularly limited, those having a thickness of about 0.01 to 0.1 mm are preferably used.
  • the laminated board of this embodiment has the prepreg of this embodiment.
  • the laminated board of this embodiment includes one or a plurality of prepregs, and in the case where a plurality of prepregs are included, has a form in which prepregs are stacked.
  • the laminated board of this embodiment can sufficiently reduce the warpage of a metal foil-clad laminated board, a printed wiring board, and a multilayer printed wiring board (particularly a multilayer coreless board), and package warpage. Can be sufficiently reduced, and the moldability is excellent.
  • the metal foil tension laminate sheet of this embodiment has the prepreg of this embodiment and the metal foil arranged on one side or both sides of the prepreg.
  • the metal foil-clad laminate of this embodiment includes one or more prepregs. When the number of prepregs is one, the metal foil-clad laminate has a form in which metal foil is disposed on one side or both sides of the prepreg. When the number of prepregs is plural, the metal foil-clad laminate has a form in which metal foil is disposed on one side or both sides of a laminated prepreg (a prepreg laminate).
  • the metal foil-clad laminate of this embodiment can sufficiently reduce the warpage of the metal foil-clad laminate, the printed wiring board, and the multilayer printed wiring board (particularly the multilayer coreless board) by having the prepreg of this embodiment.
  • the package warpage can be sufficiently reduced and the moldability is excellent.
  • the metal foil may be any metal foil used for various printed wiring board materials.
  • the metal foil include copper and aluminum foils.
  • the copper metal foil include rolled copper foil and electrolytic copper. Copper foil, such as foil, is mentioned.
  • the thickness of the conductor layer is, for example, 1 to 70 ⁇ m, preferably 1.5 to 35 ⁇ m.
  • the forming method and forming conditions of the laminate and the metal foil-clad laminate are not particularly limited, and general techniques and conditions of a laminate for a printed wiring board and a multilayer board can be applied.
  • a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine, etc. can be used at the time of shaping
  • the temperature is generally 100 to 300 ° C.
  • the pressure is 2 to 100 kgf / cm 2
  • the heating time is generally 0.05 to 5 hours. It is.
  • post-curing can be performed at a temperature of 150 to 300 ° C., if necessary.
  • a temperature of 200 ° C. to 250 ° C., a pressure of 10 to 40 kgf / cm 2 , and a heating time of 80 minutes to 130 minutes are preferable, and a temperature of 215 ° C. More preferably, the temperature is 235 ° C., the pressure is 25 to 35 kgf / cm 2 , and the heating time is 90 to 120 minutes.
  • a multilayer board can be formed by laminating and combining the above-described prepreg and a separately prepared wiring board for an inner layer.
  • the printed wiring board of the present embodiment has an insulating layer formed by the prepreg of the present embodiment and a conductor layer formed on the surface of the insulating layer.
  • the printed wiring board of this embodiment can be formed, for example, by etching the metal foil of the metal foil-clad laminate of this embodiment into a predetermined wiring pattern to form a conductor layer.
  • the printed wiring board of the present embodiment has the prepreg of the present embodiment, so that the warp of the metal foil-clad laminate, the printed wiring board, and the multilayer printed wiring board (particularly the multilayer coreless board) can be sufficiently reduced, and the package Warpage can be sufficiently reduced, and formability is excellent.
  • the printed wiring board of the present embodiment can be manufactured by the following method, for example.
  • a metal foil-clad laminate of this embodiment is prepared.
  • the metal foil of the metal foil-clad laminate is etched into a predetermined wiring pattern to produce an inner layer substrate having a conductor layer (inner layer circuit).
  • a predetermined number of prepregs and a metal foil for the outer layer circuit are laminated in this order on the surface of the conductor layer (inner circuit) of the inner layer substrate, and the layers are laminated by heating and pressurizing and integrally forming (laminating). Get the body.
  • the method of lamination molding and its molding conditions are the same as the method of lamination molding and the molding conditions in the above-mentioned laminate and metal foil-clad laminate.
  • the laminated body is subjected to drilling for through holes and via holes, and a plated metal film for electrically connecting the conductor layer (inner circuit) and the metal foil for the outer layer circuit to the wall surface of the hole formed thereby Form.
  • an outer layer substrate having a conductor layer (outer layer circuit) is prepared by etching a metal foil for an outer layer circuit into a predetermined wiring pattern. In this way, a printed wiring board is manufactured.
  • a printed wiring board may be produced by forming a conductor layer serving as a circuit on the prepreg. At this time, a method of electroless plating can be used for forming the conductor layer.
  • the multilayer printed wiring board of the present embodiment includes a plurality of insulating layers including a first insulating layer and one or more second insulating layers stacked on one side of the first insulating layer, A plurality of conductor layers comprising a first conductor layer disposed between each of the plurality of insulating layers and a second conductor layer disposed on a surface of the outermost layer of the plurality of insulating layers; Each of the first insulating layer and the second insulating layer has a cured product of the prepreg of the present embodiment.
  • the multilayer printed wiring board shown in FIG. 9 includes a first conductor layer (3) disposed between each of the plurality of insulating layers (1, 2), and the plurality of insulating layers (1, 2). ) Of the second conductor layer (3) disposed in the outermost layer.
  • the multilayer printed wiring board of this embodiment is, for example, a so-called coreless type multilayer printed wiring board (multilayer coreless substrate) in which the second insulating layer is laminated only in one direction of the first insulating layer.
  • the multilayer coreless substrate since another insulating layer formed of another prepreg is usually laminated only in one direction of the insulating layer formed of the prepreg, the problem of warping of the substrate is remarkable.
  • the multilayer printed wiring board of this embodiment has the prepreg of this embodiment to sufficiently reduce the warpage of the metal foil-clad laminate, the printed wiring board, and the multilayer printed wiring board (particularly the multilayer coreless board). It is possible, and the package warp can be sufficiently reduced, and the moldability is excellent. For this reason, the thermosetting composition of the present embodiment can be effectively used as a multilayer coreless substrate for a semiconductor package because warpage can be sufficiently reduced (low warpage is achieved) in a multilayer coreless substrate.
  • the method described in Examples of the present application can be referred to.
  • Example 1 25 parts by mass of bisphenol A (manufactured by Tokyo Chemical Industry Co., Ltd.), 15 parts by mass of a phenol compound having a hindered phenol structure (“ADEKA STAB AO-20” manufactured by ADEKA Corporation), naphthylene ether type epoxy compound (DIC Corporation) 50 parts by weight of the product “EPICLON HP-6000”), 10 parts by weight of a naphthalene type epoxy compound (“EPICLON HP-4710” by DIC Corporation), slurry silica X (SC2050-MB, average particle size 0.7 ⁇ m, ad Matex Co., Ltd.) 140 parts by mass, Slurry Silica Y (SC5050-MOB, average particle size 1.5 ⁇ m, Admatechs Co., Ltd.) 60 parts by mass, Wetting Dispersant X (DISPERBYK-161, Big Chemie Japan Co., Ltd.) 1) parts by weight, wet dispersing agent Y (DISPER) YK-111, manufactured by Big Che
  • thermosetting composition 1 part by mass, silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts by mass, 2,4,5-triphenylimidazole (Tokyo Chemical Industry ( Co., Ltd.) 0.5 parts by mass was blended (mixed), and then diluted with methyl ethyl ketone to obtain a varnish (thermosetting composition).
  • the content of the bifunctional epoxy compound is 22.8 parts by mass with respect to 100 parts by mass of the thermosetting composition solid content
  • the content of the polyfunctional epoxy compound is the thermosetting composition solid content.
  • thermosetting composition It is 33.0 parts by mass with respect to 100 parts by mass, and the content of the bifunctional phenol compound is 23.3 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • the amount is 14.0 parts by mass with respect to 100 parts by mass of the thermosetting composition solid content, and the content of the bifunctional thermosetting compound is 46. with respect to 100 parts by mass of the thermosetting composition solid content.
  • This varnish (thermosetting composition) was impregnated and applied to E glass woven fabric (IPC # 1280) and dried by heating at 150 ° C. for 4 minutes to obtain a prepreg having a thickness of about 80 ⁇ m. Content of the composition (solid content) in the obtained prepreg was 73 volume%.
  • the ratio of the bifunctional thermosetting compound and the polyfunctional thermosetting compound of each compound was determined by gel permeation chromatography (GPC) under the following conditions. That is, a RID-10A detector was connected to an LC-20AD pump manufactured by Shimadzu Corporation, and a column was connected to Shodex GPC KF-801, KF-802, KF-803, KF-804 manufactured by Showa Denko KK, and a column temperature of 40 Used at ° C. As the mobile phase, tetrahydrofuran was used at a flow rate of 1.0 mL / min. Each compound was adjusted to a tetrahydrofuran solution of 5%, 20 ⁇ L of the solution was attached to a measuring machine, and the ratio of the bifunctional compound and the polyfunctional compound contained in each compound was determined from the peak area.
  • GPC gel permeation chromatography
  • Example 2 The blending amount of bisphenol A was changed to 25 parts by mass, 22 parts by mass, the blending amount of the naphthylene ether type epoxy compound was changed to 50 parts by mass, and 53 parts by mass, having a hindered phenol structure.
  • Example 1 except that 15 parts by mass of a phenol compound having a hindered phenol structure (“ADEKA STAB AO-80” manufactured by ADEKA Corporation) was blended in place of 15 parts by mass of the phenol compound (“ADK STAB AO-20”). In the same manner as above, a prepreg having a thickness of about 80 ⁇ m was obtained.
  • ADEKA STAB AO-80 manufactured by ADEKA Corporation
  • the content of the bifunctional epoxy compound is 24.2 parts by mass with respect to 100 parts by mass of the thermosetting composition solid content
  • the content of the polyfunctional epoxy compound is the thermosetting composition solid content. It is 34.4 parts by mass with respect to 100 parts by mass
  • the content of the bifunctional phenol compound is 20.5 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • the amount is 14.0 parts by mass with respect to 100 parts by mass of the thermosetting composition solid content
  • the content of the bifunctional thermosetting compound is 44.100 parts by mass with respect to 100 parts by mass of the thermosetting composition solid content.
  • the content of the polyfunctional thermosetting compound was 48.4 parts by mass with respect to 100 parts by mass of the thermosetting composition solid content.
  • Content of the composition (solid content) in the obtained prepreg was 73 volume%.
  • Example 3 The amount of bisphenol A was changed to 20 parts by mass instead of 25 parts by mass, the amount of the naphthylene ether type epoxy compound was changed to 50 parts by mass, and 55 parts by mass, having a hindered phenol structure.
  • Example 1 except that 15 parts by mass of a phenol compound having a hindered phenol structure (“MDP-S” manufactured by Sumitomo Chemical Co., Ltd.) instead of 15 parts by mass of the phenol compound (“ADK STAB AO-20”) was used. In the same manner as above, a prepreg having a thickness of about 80 ⁇ m was obtained.
  • MDP-S phenol compound having a hindered phenol structure
  • ADK STAB AO-20 15 parts by mass of the phenol compound
  • the content of the bifunctional epoxy compound is 25.1 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition
  • the content of the polyfunctional epoxy compound is the solid content of the thermosetting composition. It is 35.4 parts by mass with respect to 100 parts by mass
  • the content of the bifunctional phenol compound is 32.6 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • the amount is 0 part by mass with respect to 100 parts by mass of the solid content of the thermosetting composition
  • the content of the bifunctional thermosetting compound is 57.6 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • the content of the polyfunctional thermosetting compound was 35.4 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • Content of the composition (solid content) in the obtained prepreg was 73 volume%.
  • Example 4 Instead of 15 parts by mass of a phenol compound having a hindered phenol structure (“ADK STAB AO-20”), 15 parts by mass of a phenol compound having a hindered phenol structure (“ADEKA STAB AO-60” manufactured by ADEKA Corporation) was blended. Except for the above, a prepreg having a thickness of about 80 ⁇ m was obtained in the same manner as in Example 1. In this example, the content of the bifunctional epoxy compound is 22.8 parts by mass with respect to 100 parts by mass of the thermosetting composition solid content, and the content of the polyfunctional epoxy compound is the thermosetting composition solid content.
  • thermosetting composition It is 33.0 parts by mass with respect to 100 parts by mass, and the content of the bifunctional phenol compound is 37.2 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • the amount is 0 parts by mass with respect to 100 parts by mass of the thermosetting composition solid content, and the content of the bifunctional thermosetting compound is 60.0 masses with respect to 100 parts by mass of the thermosetting composition solid content.
  • the content of the polyfunctional thermosetting compound was 33.0 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • Content of the composition (solid content) in the obtained prepreg was 73 volume%.
  • Example 5 Instead of 15 parts by mass of a phenol compound having a hindered phenol structure (“ADK STAB AO-20”), a phenol compound having a hindered phenol structure (2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane (Manufactured by Tokyo Chemical Industry Co., Ltd.) A prepreg having a thickness of about 80 ⁇ m was obtained in the same manner as in Example 3 except that 15 parts by mass was blended.
  • the content of the bifunctional epoxy compound is 25.1 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition
  • the content of the polyfunctional epoxy compound is the solid content of the thermosetting composition.
  • thermosetting composition It is 35.4 parts by mass with respect to 100 parts by mass, and the content of the bifunctional phenol compound is 32.6 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • the amount is 0 part by mass with respect to 100 parts by mass of the solid content of the thermosetting composition, and the content of the bifunctional thermosetting compound is 57.6 parts by mass with respect to 100 parts by mass of the thermosetting composition solid content.
  • the content of the polyfunctional thermosetting compound was 35.4 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • Content of the composition (solid content) in the obtained prepreg was 73 volume%.
  • Example 6 35 parts by mass of a phenol compound having a hindered phenol structure (2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, manufactured by Tokyo Chemical Industry Co., Ltd.), naphthylene ether type epoxy compound (product of DIC Corporation) "EPICLON HP-6000") 55 parts by mass, naphthalene type epoxy compound (DIC Corporation "EPICLON HP-4710") 10 parts by mass, slurry silica X (SC2050-MB, average particle size 0.7 ⁇ m, Admatechs) 140 parts by mass, slurry silica Y (SC5050-MOB, average particle size 1.5 ⁇ m, manufactured by Admatechs) 60 parts by mass, wetting and dispersing agent X (DISPERBYK-161, Big Chemie Japan) 1 part by mass, wet dispersing agent Y (DISPERBYK-111, Bi 1 part by mass (Ckemy Japan Co., Ltd.), 5 parts by mass of silane coupling agent (K
  • the content of the bifunctional epoxy compound is 25.1 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition
  • the content of the polyfunctional epoxy compound is the solid content of the thermosetting composition. It is 35.4 parts by mass with respect to 100 parts by mass
  • the content of the bifunctional phenol compound is 32.6 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • the amount is 0 part by mass with respect to 100 parts by mass of the solid content of the thermosetting composition
  • the content of the bifunctional thermosetting compound is 57.6 parts by mass with respect to 100 parts by mass of the thermosetting composition solid content.
  • the content of the polyfunctional thermosetting compound was 35.4 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • This varnish was impregnated and coated on E glass woven fabric (IPC # 1280) and dried by heating at 150 ° C. for 6 minutes to obtain a prepreg having a thickness of about 80 ⁇ m. Content of the composition (solid content) in the obtained prepreg was 73 volume%.
  • the content of the bifunctional epoxy compound is 26.0 parts by mass with respect to 100 parts by mass of the thermosetting composition solid content
  • the content of the polyfunctional epoxy compound is the thermosetting composition solid content. It is 36.3 parts by mass with respect to 100 parts by mass, and the content of the bifunctional phenol compound is 30.7 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • the amount is 0 part by mass with respect to 100 parts by mass of the thermosetting composition solid content, and the content of the bifunctional thermosetting compound is 56.7 parts by mass with respect to 100 parts by mass of the thermosetting composition solid content.
  • the content of the polyfunctional thermosetting compound was 36.3 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • This varnish was impregnated and applied to E glass woven fabric (IPC # 1280) and dried by heating at 150 ° C. for 4 minutes to obtain a prepreg having a thickness of about 80 ⁇ m. Content of the composition (solid content) in the obtained prepreg was 73 volume%.
  • the content of the bifunctional epoxy compound is 22.8 parts by mass with respect to 100 parts by mass of the thermosetting composition solid content
  • the content of the polyfunctional epoxy compound is the thermosetting composition solid content. It is 33.0 parts by mass with respect to 100 parts by mass
  • the content of the bifunctional phenol compound is 37.2 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • the amount is 0 parts by mass with respect to 100 parts by mass of the thermosetting composition solid content
  • the content of the bifunctional thermosetting compound is 60.0 masses with respect to 100 parts by mass of the thermosetting composition solid content.
  • the content of the polyfunctional thermosetting compound was 33.0 parts by mass with respect to 100 parts by mass of the solid content of the thermosetting composition.
  • This varnish was impregnated and applied to E glass woven fabric (IPC # 1280) and dried by heating at 150 ° C. for 4 minutes to obtain a prepreg having a thickness of about 80 ⁇ m. Content of the composition (solid content) in the obtained prepreg was 73 volume%.
  • Copper foil (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 12 ⁇ m) was placed on both upper and lower surfaces of one prepreg obtained in Examples 1 to 6 and Comparative Examples 1 and 2, and a pressure of 30 kgf / cm 2. Then, laminate molding (thermosetting) was performed at a temperature of 220 ° C. for 100 minutes to obtain a copper foil-clad laminate having an insulating layer formed of prepreg and a copper foil. The thickness of the insulating layer of this copper foil-clad laminate was about 80 ⁇ m.
  • the obtained copper foil-clad laminate was cut into a size of 5.0 mm ⁇ 20 mm with a dicing saw, and then the surface copper foil was removed by etching to obtain a measurement sample.
  • mechanical properties (30 ° C, 100 ° C, 200 ° C, 260 ° C, and 330 ° C storage) by a DMA method using a dynamic viscoelasticity analyzer (TA Instruments) in accordance with JIS C6481
  • Copper foil (3EC-VLP, thickness 12 ⁇ m) was placed on both upper and lower surfaces of one prepreg obtained in Examples 1 to 6 and Comparative Examples 1 and 2, and the pressure was 30 kgf / cm 2 and the temperature was 220 ° C. for 100 minutes.
  • Lamination molding (thermosetting) was performed to obtain a copper foil-clad laminate having an insulating layer formed of prepreg and a copper foil.
  • the thickness of the insulating layer of this copper foil-clad laminate was about 80 ⁇ m.
  • the surface was observed and the presence or absence of voids was evaluated. “A” indicates no void and “B” indicates no void.
  • the carrier copper foil surface of the ultrathin copper foil with carrier (b1) (MT18Ex, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 5 ⁇ m) is provided on both sides of the prepreg to be the support (a).
  • the prepreg (c1) obtained in Examples 1 to 6 and Comparative Examples 1 and 2 was further arranged thereon, and a copper foil (d) (3EC-VLP, thickness 12 ⁇ m) was further arranged thereon.
  • a copper foil (d) (3EC-VLP, thickness 12 ⁇ m) was further arranged thereon.
  • laminate molding was performed at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes to obtain a copper foil-clad laminate shown in FIG.
  • the copper foil (d) of the obtained copper foil-clad laminate shown in FIG. 2 was removed by etching to obtain a laminate shown in FIG.
  • the prepregs (c2) obtained in Examples 1 to 6 and Comparative Examples 1 and 2 are arranged on both surfaces of the laminate shown in FIG. (B2) (MT18Ex, thickness 5 ⁇ m) was placed, and laminate molding was performed at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 100 minutes to obtain a copper foil-clad laminate shown in FIG.
  • the carrier copper foil and the ultrathin copper foil of the carrier-attached ultrathin copper foil (b1) placed on the support (a) (cured support prepreg) are peeled off.
  • the two laminated plates are peeled off from the support (a), and the carrier copper foil is further peeled from the ultrathin copper foil with carrier (b2) on the upper portion of each laminated plate.
  • a multilayer coreless substrate panel (size: 500 mm ⁇ 400 mm) was obtained.
  • the copper foil was removed by etching from the obtained multilayer coreless substrate panel (copper foil-clad laminate in FIG. 7) to obtain a laminate.
  • the 20 mm x 200 mm strip-shaped board was cut out from the obtained laminated board.
  • a liquid underfill manufactured by ThreeBond Co., Ltd., 2274E
  • a semiconductor element size 10 mm ⁇ 10 mm, thickness 100 ⁇ m
  • the underfill was cured at 150 ° C. for 30 minutes. Then, it cut
  • Table 1 shows relative values (vs comparative example 1) of each example and comparative example when the measured value in comparative example 1 is 1.
  • Comparative Example 1 where no hindered phenol compound was used, it was found that the minimum melt viscosity was high and the moldability was difficult.
  • this application example for example, as is clear from the comparison between the application example 1 and the comparative example 1, by using a specific hindered phenol compound, the effect of reducing the package warpage is not excessively inhibited. It has been found that the minimum melt viscosity can be greatly reduced and the moldability can be improved. Furthermore, when compared with Example 1 and Comparative Example 2, it was found that the effect of greatly reducing the melt viscosity can be obtained by including a specific hindered phenol compound in the thermosetting resin composition. Moreover, when Example 5 and Example 6 are compared, when the content of the specific hindered phenol compound is increased, the result that the minimum melt viscosity is further reduced while the physical property parameter is within the predetermined range can be obtained. I understood.

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Abstract

L'invention concerne une composition de durcissement thermique comprenant un composé de durcissement thermique qui contient un composé phénol et un composé époxy, le composé phénol comprenant un composé phénol encombré ayant une structure spécifiée, et la teneur du composé phénol encombré dans le composé phénol est d'au moins 35 % en masse.
PCT/JP2019/016554 2018-04-20 2019-04-17 Composition de durcissement thermique, préimprégné, stratifié, stratifié plaqué de feuille métallique, carte de circuit imprimé, et carte de circuit imprimé multicouche WO2019203292A1 (fr)

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JPWO2021230002A1 (fr) * 2020-05-15 2021-11-18
WO2022131346A1 (fr) 2020-12-17 2022-06-23 株式会社Adeka Composé et composition

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JPH09104731A (ja) * 1995-10-11 1997-04-22 Nippon Kayaku Co Ltd ポリフェノール類、エポキシ樹脂、エポキシ樹脂組成物及びその硬化物
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Publication number Priority date Publication date Assignee Title
JPWO2021230002A1 (fr) * 2020-05-15 2021-11-18
WO2021230002A1 (fr) * 2020-05-15 2021-11-18 富士フイルム株式会社 Composition durcissable, matériau thermoconducteur, feuille thermoconductrice, dispositif à couche thermoconductrice, et composé
JP7440626B2 (ja) 2020-05-15 2024-02-28 富士フイルム株式会社 硬化性組成物、熱伝導材料、熱伝導シート、熱伝導層付きデバイス、化合物
WO2022131346A1 (fr) 2020-12-17 2022-06-23 株式会社Adeka Composé et composition
KR20230121723A (ko) 2020-12-17 2023-08-21 가부시키가이샤 아데카 화합물 및 조성물

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