Resin sheet for forming insulation layer of semiconductor package substrate

Abstract

To provide a resin sheet from which a cured product that has low dielectric characteristics, low roughness of a resin surface after desmear, and excellent adhesion between a conductor and itself, blister resistance and smear removability can be obtained.SOLUTION: A resin sheet for forming an insulation layer of a semiconductor package substrate has a support, and a resin composition layer provided on the support, wherein the resin composition layer contains (A) a radical polymerizable group-containing compound having a carbodiimide structure, (B) a radical polymerizable group-containing active ester-based curing agent, and (C) an inorganic filler.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin sheet for forming an insulating layer of a semiconductor package substrate, and further to a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition. [Background technology]

[0002] A known manufacturing technique for printed wiring boards is a build-up method in which insulating layers and conductor layers are alternately stacked. In build-up manufacturing methods, the insulating layer is generally formed by curing a resin composition. For example, Patent Document 1 discloses a resin composition containing an epoxy resin, an active ester compound, and an inorganic filler. Patent Document 2 also discloses a technique for forming an insulating layer by curing a resin composition containing a carbodiimide compound. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2023-10409 [Patent Document 2] International Publication No. 2023 / 027013 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, there has been a demand for finer wiring due to improved functionality of electronic components. To achieve even finer wiring, resin compositions that provide insulating layers with low dielectric loss tangent and dielectric constant (relative permittivity) are needed. Furthermore, to reduce transmission loss, resin compositions that provide insulating layers with low surface roughness (roughness) of the resin surface after desmearing, excellent adhesion to the conductor layer, blister resistance, and smear removability are also needed. However, at this stage, it is not yet possible to satisfy all of these requirements. Here, the property of an insulating layer that can suppress the phenomenon of swelling of the conductor layer during reflow is referred to as blister resistance, and the dielectric loss tangent and relative permittivity are sometimes collectively referred to as dielectric properties.

[0005] An object of the present invention is to provide a resin sheet which can give a cured product having low dielectric properties, low resin surface roughness after desmearing, and excellent adhesion to a conductor layer, blister resistance, and smear removability. [Means for solving the problem]

[0006] As a result of intensive investigations conducted by the present inventors in order to achieve the objects of the present invention, they have found that by using a resin composition layer containing (A) a radically polymerizable group-containing compound having a carbodiimide structure, (B) a radically polymerizable group-containing active ester curing agent, and (C) an inorganic filler, it is possible to obtain a cured product that has low dielectric properties, low resin surface roughness after desmearing, and excellent adhesion to a conductor layer, blister resistance, and smear removability, and they have completed the present invention.

[0007] That is, the present invention includes the following. [1] A film having a support and a resin composition layer provided on the support, The resin composition layer comprises: (A) a radical polymerizable group-containing compound having a carbodiimide structure; A resin sheet for forming an insulating layer of a semiconductor package substrate, comprising: (B) a radical-polymerizable group-containing active ester curing agent; and (C) an inorganic filler. [2] The resin sheet for forming an insulating layer of a semiconductor package substrate according to [1], further comprising (D) an epoxy resin. [3] A resin sheet for forming an insulating layer of a semiconductor package substrate according to [1] or [2], wherein the content of component (A) is 0.1% by mass or more and 10% by mass or less, when the resin component of the resin composition layer is 100% by mass. [4] A resin sheet for forming an insulating layer of a semiconductor package substrate according to any one of [1] to [3], wherein the content of component (B) is 10% by mass or more and 55% by mass or less, when the resin component of the resin composition layer is 100% by mass. [5] The resin sheet for forming an insulating layer of a semiconductor package substrate according to any one of [1] to [4], wherein the content of component (C) is 60% by mass or more and 90% by mass or less, when the non-volatile components of the resin composition layer are 100% by mass. [6] A semiconductor chip package substrate comprising an insulating layer made of a cured product of the resin composition layer of the resin sheet for forming an insulating layer of a semiconductor package substrate according to any one of [1] to [5]. [7] A semiconductor device comprising the semiconductor chip package substrate according to [6]. [Effects of the Invention]

[0008] According to the present invention, it is possible to obtain a resin sheet which can give a cured product having low dielectric properties, low resin surface roughness after desmearing, and excellent adhesion to a conductor layer, blister resistance, and smear removability. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described in detail below with reference to preferred embodiments thereof. However, the present invention is not limited to the following embodiments and examples, and can be implemented with any modifications within the scope of the claims of the present invention and their equivalents.

[0010] [Resin sheet for forming insulating layers on semiconductor package substrates] The resin sheet for forming an insulating layer of a semiconductor package substrate of the present invention has a support and a resin composition layer provided on the support, the resin composition layer containing (A) a radical-polymerizable-group-containing compound having a carbodiimide structure, (B) a radical-polymerizable-group-containing active ester curing agent, and (C) an inorganic filler. Such a resin sheet makes it possible to obtain a cured product that has a low dielectric tangent, low resin surface roughness after desmearing, and excellent adhesion to a conductor layer, blister resistance, and smear removability.

[0011] The resin sheet for forming an insulating layer of a semiconductor chip package substrate of the present invention is useful for use as an insulating layer in semiconductor package substrates. Examples of semiconductor package substrates include FC-CSP, MIS-BGA package, ETS-BGA package, fan-out type WLP (Wafer Level Package), fan-in type WLP, fan-out type PLP (Panel Level Package), and fan-in type PLP. Hereinafter, the "resin sheet for forming an insulating layer of a semiconductor package substrate" may be simply referred to as the "resin sheet."

[0012] <Support> The resin sheet has a support, and the support is bonded to one surface of the resin composition layer. Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferred.

[0013] When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, with inexpensive polyethylene terephthalate being particularly preferred.

[0014] When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0015] The surface of the support that is to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0016] The support may also be a support with a release layer, which has a release layer on the surface that bonds to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available products may also be used as the support with a release layer, including, for example, "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Uni-Peel" manufactured by Unitika Limited, which are PET films having a release layer primarily composed of an alkyd resin-based release agent.

[0017] The thickness of the support is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, even more preferably 10 μm or more, and is preferably 75 μm or less, more preferably 60 μm or less, even more preferably 50 μm or less. When a support with a release layer is used, it is preferable that the thickness of the entire support with a release layer is within the above range.

[0018] <Resin composition layer> The resin sheet has a resin composition layer and is provided on a support. The insulating layer can be formed by thermally curing the resin composition layer. Typically, the insulating layer contains a cured product of the resin composition layer, and preferably contains only the cured product of the resin composition layer. The resin composition layer contains (A) a radical-polymerizable group-containing compound having a carbodiimide structure, (B) a radical-polymerizable group-containing active ester-based curing agent, and (C) an inorganic filler. If necessary, the resin composition layer may further contain optional components such as (D) an epoxy resin, (E) a radical-polymerizable group-containing compound not having a carbodiimide structure, (F) a curing agent, (G) a curing accelerator, (H) other additives, and (I) a solvent.

[0019] In the present invention, unless otherwise specified, the content of each component in the resin composition layer is a value when the nonvolatile components in the resin composition layer are 100 mass %, and the nonvolatile components refer to all nonvolatile components in the resin composition layer excluding the solvent. Furthermore, in the present invention, the resin components in the resin composition layer refer to the nonvolatile components of the resin composition layer excluding the inorganic filler (C).

[0020] -(A) Radical polymerizable group-containing compound having a carbodiimide structure- The resin composition layer contains, as component (A), a radically polymerizable group-containing compound having a carbodiimide structure. By including component (A) in the resin composition layer, adhesion between the resin composition layer and the conductor layer can be improved, and the occurrence of blisters can be suppressed.

[0021] The (A) radically polymerizable group-containing compound having a carbodiimide structure is a compound having one or more carbodiimide structures (-N=C=N-) and one or more radically polymerizable groups in one molecule. The (A) component may further have one or more urethane bonds (-O-CO-NH-) in one molecule. Two or more carbodiimide structures, two or more radically polymerizable groups, and two or more urethane bonds may be present in one molecule. When an epoxy resin is included as the (C) thermosetting resin described below, the (A) component may react with the epoxy resin to cure it. The (A) component may be used alone or in combination of two or more.

[0022] The radical polymerizable group is a group having a radically polymerizable ethylenically unsaturated bond. Examples of the radical polymerizable group include unsaturated hydrocarbon groups such as vinyl, allyl, 1-propenyl, 3-cyclohexenyl, 3-cyclopentenyl, 2-vinylphenyl, 3-vinylphenyl, and 4-vinylphenyl; and α,β-unsaturated carbonyl groups such as acryloyl, methacryloyl, and maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl). The radical polymerizable group is preferably present at the terminal of component (A).

[0023] The component (A) preferably contains a structural unit represented by the following formula (A-1) in addition to the radical polymerizable group. [ka] In formula (A-1), Y represents a divalent hydrocarbon group which may have a substituent.

[0024] In formula (A-1), Y represents a divalent hydrocarbon group which may have a substituent. The divalent hydrocarbon group represented by Y usually has 1 or more carbon atoms, preferably 2 or more carbon atoms, and usually 30 or less carbon atoms. The divalent hydrocarbon group may be a divalent saturated hydrocarbon group or a divalent unsaturated hydrocarbon group. Unless otherwise specified, a divalent unsaturated hydrocarbon group represents a hydrocarbon group having at least one carbon-carbon double bond, carbon-carbon triple bond, or aromatic hydrocarbon ring, and includes linear, branched, and cyclic groups.

[0025] Preferred divalent hydrocarbon groups for Y include, for example, alkylene groups, cycloalkylene groups, arylene groups, and groups formed by combining these groups.

[0026] The number of carbon atoms in the alkylene group for Y is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6, even more preferably 1 to 4, and still more preferably 1 to 3. The number of carbon atoms does not include the number of carbon atoms of the substituent. Suitable examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group.

[0027] The number of carbon atoms in the cycloalkylene group for Y is preferably 3 to 20, more preferably 3 to 12, and even more preferably 3 to 6. The number of carbon atoms in the substituent is not included in this number of carbon atoms. Suitable examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.

[0028] The arylene group for Y represents a group obtained by removing two hydrogen atoms on an aromatic ring from an aromatic hydrocarbon. The number of carbon atoms in the arylene group is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, and still more preferably 6 to 10. The number of carbon atoms does not include the number of carbon atoms of substituents. Suitable examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.

[0029] The substituent for Y is not particularly limited, and examples thereof include a halogen atom, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an alkyl-oxy-carbonyl group, an alkenyl-oxy-carbonyl group, an aryl-oxy-carbonyl group, an alkyl-carbonyl-oxy group, an alkenyl-carbonyl-oxy group, an aryl-carbonyl-oxy group, etc. Among these, it is preferable that the divalent hydrocarbon group for Y has no substituent.

[0030] More preferably, Y represents a divalent saturated hydrocarbon group of 2 to 30 carbon atoms which may have a substituent, or a divalent unsaturated hydrocarbon group of 2 to 30 carbon atoms which may have a substituent. Even more preferably, Y represents a divalent saturated hydrocarbon group of 2 to 30 carbon atoms which may have a substituent and has a ring structure (for example, a ring structure selected from a cycloalkane ring, a benzene ring, and a naphthalene ring), or a divalent unsaturated hydrocarbon group of 2 to 30 carbon atoms which may have a substituent and has a ring structure (for example, a ring structure selected from a cycloalkane ring, a benzene ring, and a naphthalene ring).

[0031] Y in formula (A-1) preferably represents a divalent group represented by the following formula (A-2). [ka] In formula (A-2), Y a , Y b and Y c are each independently a single bond or C(R y )2;R y each independently represents a hydrogen atom or a methyl group; ring Y 1 and ring Y 2 each independently represents an optionally substituted cycloalkane ring having 4 to 10 carbon atoms, an optionally substituted benzene ring, or an optionally substituted naphthalene ring; y represents 0 or 1; * represents a binding site.

[0032] In formula (A-2), Ya , Y b and Y c are each independently a single bond or C(R y )2. Preferably, Y a and Y c is a single bond and Y b is C(R y )2. R y are each independently a hydrogen atom or a methyl group, and are preferably a hydrogen atom.

[0033] In formula (A-2), ring Y 1 and ring Y 2 each independently represents a cycloalkane ring having 4 to 10 carbon atoms which may have a substituent, a benzene ring which may have a substituent, or a naphthalene ring which may have a substituent. 1 and ring Y 2 each independently represents a cycloalkane ring having 4 to 10 carbon atoms, which may have a substituent. Examples of the cycloalkane ring having 4 to 10 carbon atoms include monocyclic saturated hydrocarbon rings such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, and a cyclodecane ring; bicyclic saturated hydrocarbon rings such as a bicyclo[2.2.1]heptane ring (norbornane ring), a bicyclo[4.4.0]decane ring (decalin ring), a bicyclo[5.3.0]decane ring, a bicyclo[4.3.0]nonane ring (hydrindane ring), a bicyclo[3.3.0]octane ring, and a bicyclo[3.3.1]nonane ring; 2,6 ] Decane ring (tetrahydrodicyclopentadiene ring), tricyclo[3.3.1.1 3,7 ] A tricyclic saturated hydrocarbon ring such as a decane ring (adamantane ring) is preferred. 1 and ring Y 2each independently represents a cyclohexane ring which may have a substituent. The substituents on the cycloalkane ring, benzene ring and naphthalene ring are not particularly limited, and examples thereof include a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group (an alkyl group substituted with an aryl group), an alkyl-aryl group (an aryl group substituted with an alkyl group), an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an alkyl-oxy-carbonyl group, an alkenyl-oxy-carbonyl group, an aryl-oxy-carbonyl group, an alkyl-carbonyl-oxy group, an alkenyl-carbonyl-oxy group, and an aryl-carbonyl-oxy group. Among these, the ring Y 1 and ring Y 2 is particularly preferably an unsubstituted cyclohexane ring.

[0034] Specific examples of Y include divalent groups represented by formulae (Y1) to (Y14), and the divalent group represented by formula (Y1) is particularly preferred. In formulae (Y1) to (Y14), * indicates a bonding site. [ka]

[0035] In a preferred example, the proportion of the structural unit represented by formula (A-1) contained in component (A) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, and may even be 90% by mass or more, relative to 100% by mass of the total molecular mass of component (A).

[0036] The component (A) is preferably a compound represented by formula (A-3). [ka] In formula (A-3), each R independently represents a hydrogen atom or a methyl group; 1 each independently represents a carbonyl group, a methylene group, a phenylene group, or a phenylene-methylene group; X 2each independently represent a divalent saturated hydrocarbon group having 2 to 4 carbon atoms; each Z independently represent a divalent saturated hydrocarbon group having 2 to 300 carbon atoms which may have a substituent, or a divalent unsaturated hydrocarbon group having 2 to 300 carbon atoms which may have a substituent; each a independently represent 0 or an integer of 1 or more; each b independently represent b≦1; each c independently represent c≦1; d independently represent 0 or d≦1; and each Y independently represent the above-mentioned group. The a units, b units, c units, and d units may be the same or different for each unit.

[0037] In formula (A-3), each R independently represents a hydrogen atom or a methyl group.

[0038] In formula (A-3), X 1 are each independently a carbonyl group, a methylene group, a phenylene group, or a phenylene-methylene group (the bonding direction is not particularly limited, but it is preferable that the phenylene side is bonded to C in "RC"). Preferably, X 1 are each independently a methylene group or a carbonyl group. The phenylene-methylene group includes a 1,2-phenylene-methylene group, a 1,3-phenylene-methylene group, and a 1,4-phenylene-methylene group.

[0039] In formula (A-3), X 2 are each independently a divalent saturated hydrocarbon group having 2 to 4 carbon atoms. The divalent saturated hydrocarbon group may be linear, branched, or cyclic. Specific examples of the divalent saturated hydrocarbon group having 2 to 4 carbon atoms include linear alkylene groups having 2 to 4 carbon atoms, such as an ethylene group, a trimethylene group, and a tetramethylene group; and branched alkylene groups having 2 to 4 carbon atoms, such as an ethylidene group, a propylidene group, an isopropylidene group, and an ethylmethylmethylene group. X 2 In one embodiment, each independently represents preferably a divalent saturated hydrocarbon group having 2 or 3 carbon atoms, and more preferably an ethylene group (—CH 2 —CH 2 —).

[0040] In formula (A-3), each Z independently represents a divalent saturated hydrocarbon group of 2 to 300 carbon atoms, which may have a substituent, or a divalent unsaturated hydrocarbon group of 2 to 300 carbon atoms, which may have a substituent. Preferably, each Z independently represents a divalent saturated hydrocarbon group of 2 to 300 carbon atoms, or a divalent unsaturated hydrocarbon group of 2 to 300 carbon atoms. More preferably, each Z independently represents a divalent hydrocarbon group of 300 or less carbon atoms, which has a structural unit selected from the group consisting of formulae (Z1) to (Z8) below. Even more preferably, each Z independently represents a divalent hydrocarbon group of 300 or less carbon atoms, which is composed of a structural unit selected from the group consisting of formulae (Z1) to (Z8). [ka]

[0041] It is more preferable that Z each independently represent a divalent hydrocarbon group having 300 or less carbon atoms and having a structural unit represented by formula (Z1); it is even more preferable that Z represent a divalent hydrocarbon group having 300 or less carbon atoms and consisting of a structural unit selected from formulas (Z1) to (Z8) and having at least a structural unit represented by formula (Z1). Of these, it is particularly preferable that Z represent a divalent hydrocarbon group having 300 or less carbon atoms and represented by the following formula (Z-1). [ka] (In formula (Z-1), n z indicates an integer of 1 or more; * indicates a binding site.)

[0042] In formula (A-3), each a independently represents 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 10, and more preferably 0 or 1.

[0043] In formula (A-3), b represents the average degree of polymerization of the carbodiimide group. Each b independently represents b≦1, and is preferably an integer of 1 or more, more preferably 1 to 100, and even more preferably an integer of 1 to 100, 1 to 10, or an integer of 1 to 10.

[0044] In formula (A-3), c represents the average degree of polymerization of the divalent saturated hydrocarbon group of 2 to 300 carbon atoms which may have a substituent and which is represented by Z. Each c independently represents c≦1, and is preferably an integer of 1 or more, more preferably 1 to 100, and even more preferably an integer of 1 to 100, 1 to 10, an integer of 1 to 10, or 1.

[0045] In formula (A-3), d represents the average degree of polymerization of the group represented by Z with the polycarbodiimide. Each d is independently 0 or d≦1, preferably 0 or an integer of 1 to 100, more preferably 0 or an integer of 1 to 100, and even more preferably 0 or an integer of 1 to 10.

[0046] Due to its manufacturing method, component (A) may contain isocyanate groups (-N=C=O) in the molecule. The content of isocyanate groups in component (A) (also referred to as the "NCO content") is preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, still more preferably 2% by mass or less, and particularly preferably 1% by mass or less or 0.5% by mass or less.

[0047] Specific examples of the component (A) include compounds represented by the following formulas (S1) to (S5). However, the component (A) is not limited to these specific examples. In the formulas, b' is the same as b in formula (A-3), d' is the same as d in formula (A-3), and e' is the same as c in formula (A-3). Note that in formula (S3), only 1,2-addition structural units are shown as e' units, but 1,4-addition structural units (cis, trans) are also included. [ka]

[0048] Component (A) can be prepared by a conventionally known method. One known method involves, for example, mixing and stirring a diisocyanate compound such as dicyclohexylmethane-4,4'-diisocyanate with a carbodiimidization catalyst such as 3-methyl-1-phenyl-2-phospholene-1-oxide to carry out a carbodiimidization reaction to obtain an isocyanate-terminated polycarbodiimide. The resulting isocyanate-terminated polycarbodiimide is then reacted with a compound having a radical polymerizable group such as a (meth)acryloyl group, and, if necessary, with other polymerizable compounds such as polybutadiene having hydroxyl groups at both ends. The reaction temperature, reaction time, and other parameters can be appropriately determined by those skilled in the art.

[0049] The weight average molecular weight of component (A) is preferably 500 or more, more preferably 600 or more, even more preferably 700 or more, even more preferably 800 or more, even more preferably 900 or more, and even more preferably 1000 or more, and is preferably 10,000 or less, more preferably 8,000 or less, even more preferably 7,000 or less, and even more preferably 6,000 or less. The weight average molecular weight of component (A) can be measured by gel permeation chromatography (GPC) (polystyrene equivalent).

[0050] The content of component (A) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, when the non-volatile components in the resin composition layer are taken as 100% by mass, and is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0051] The content of component (A), when the resin component in the resin composition layer is taken as 100% by mass, is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, 3% by mass or more, and is preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, 10% by mass or less.

[0052] -(B) Radical polymerizable group-containing active ester curing agent- The resin composition contains a radically polymerizable group-containing active ester curing agent (B) as component (B). This component (B) does not include the aforementioned component (A). By incorporating component (B) in combination with component (A) into the resin composition, excellent adhesion to the conductor layer, blister resistance, and smear removability are achieved. One type of component (B) may be used alone, or two or more types may be used in combination.

[0053] The (B) radically polymerizable group-containing active ester curing agent refers to an ester compound that contains one or more radically polymerizable groups in one molecule and is capable of undergoing an addition reaction with the epoxy group of the (D) epoxy resin, which will be described later. The radically polymerizable groups that the (B) component may have are as described above. The (B) component contains one or more radically polymerizable groups in one molecule, preferably two or more. There is no particular upper limit, but it can be 10 or less, 5 or less, etc. The radically polymerizable groups are preferably present as substituents on the aromatic ester skeleton, which will be described later.

[0054] Component (B) preferably has an aromatic ester skeleton. The aromatic ester skeleton refers to a skeleton having an ester bond and an aromatic ring bonded to one or both ends of the ester bond. Among these, those having aromatic rings at both ends of the ester bond are preferred. Examples of groups having such a skeleton include an arylcarbonyloxy group, an aryloxycarbonyl group, an arylenecarbonyloxy group, an aryleneoxycarbonyl group, an arylcarbonyloxyarylene group, an aryloxycarbonylarylene group, an arylenecarbonyloxyarylene group, and an aryleneoxycarbonylarylene group. The number of carbon atoms in such groups having a skeleton is preferably 7 to 20, more preferably 7 to 15, and even more preferably 7 to 11. The aromatic hydrocarbon groups such as aryl groups and arylene groups may have a substituent.

[0055] The aryl group in the arylcarbonyloxy group or the like is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms. Examples of such aryl groups include those in which one hydrogen atom has been removed from a monocyclic aromatic compound such as a phenyl group, a furanyl group, a pyrrolyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a pyridinyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, or a triazinyl group; and those in which one hydrogen atom has been removed from a fused-ring aromatic compound such as a naphthyl group, an anthracenyl group, a phenalenyl group, a phenanthrenyl group, a quinolinyl group, an isoquinolinyl group, a quinazolyl group, a phthalazinyl group, a pteridinyl group, a coumarinyl group, an indole group, a benzimidazolyl group, a benzofuranyl group, or an acridinyl group.

[0056] The arylene group in the arylenecarbonyloxyarylene group or the like is preferably an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 25 carbon atoms, and even more preferably an arylene group having 6 to 20 carbon atoms. Examples of such arylene groups include a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group (—C6H4—C6H4—), a benzylnaphthylene group, and the like.

[0057] Component (B) may have any of an aromatic hydrocarbon group, an aliphatic hydrocarbon group, an oxygen atom, a sulfur atom, and a group consisting of a combination thereof. The term "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring, and the aromatic ring may be monocyclic, polycyclic, or heterocyclic.

[0058] The aromatic hydrocarbon group is preferably a divalent aromatic hydrocarbon group, more preferably an arylene group or an aralkylene group, and even more preferably an arylene group. The arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms, and even more preferably an arylene group having 6 to 10 carbon atoms. Examples of such arylene groups include a phenylene group, a naphthylene group, an anthracenylene group, and a biphenylene group. The aralkylene group is preferably an aralkylene group having 7 to 30 carbon atoms, more preferably an aralkylene group having 7 to 20 carbon atoms, and even more preferably an aralkylene group having 7 to 15 carbon atoms. Among these, a phenylene group and a naphthylene group are preferred.

[0059] The aliphatic hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, more preferably a divalent saturated aliphatic hydrocarbon group, and even more preferably an alkylene group or a cycloalkylene group. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, and a hexylene group.

[0060] The cycloalkylene group is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 3 to 15 carbon atoms, and even more preferably a cycloalkylene group having 5 to 10 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclopentylene group, a cycloheptylene group, and cycloalkylene groups represented by the following formulas (a) to (d). In formulas (a) to (d), "*" represents a bond. [ka]

[0061] The aromatic ester skeleton, aromatic hydrocarbon group, and aliphatic hydrocarbon group may have a substituent, or may have a radically polymerizable group as a substituent. Examples of the substituent include unsaturated hydrocarbon groups such as radically polymerizable groups, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, halogen atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms. The substituent may be contained alone or in combination of two or more. When the aromatic ester skeleton, aromatic hydrocarbon group, and aliphatic hydrocarbon group have a radically polymerizable group as a substituent, the aromatic ester skeleton, aromatic hydrocarbon group, and aliphatic hydrocarbon group may be bonded to the radically polymerizable group via at least one of a divalent aromatic hydrocarbon group and a divalent aliphatic hydrocarbon group. The divalent aromatic hydrocarbon group and the divalent aliphatic hydrocarbon group are as described above.

[0062] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an isohexyl group, an n-nonyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclononyl group.

[0063] The alkoxy group having 1 to 10 carbon atoms is not particularly limited, but examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group.

[0064] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0065] Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0066] Examples of aralkyl groups having 7 to 20 carbon atoms include benzyl, phenethyl, hydrocinnamyl, α-methylbenzyl, α-cumyl, 1-naphthylmethyl, and 2-naphthylmethyl groups, with benzyl being preferred. Here, the term "aralkyl group" refers to an alkyl group substituted with one or more (preferably one) aryl groups.

[0067] The above-mentioned substituents may further have a substituent (hereinafter, sometimes referred to as a "secondary substituent"). The unsaturated hydrocarbon group is as described above. Unless otherwise specified, the same secondary substituents as those described above may be used.

[0068] The component (B) is preferably either a compound represented by the following general formula (B-1) or a compound represented by the following general formula (B-2), and more preferably a compound represented by the general formula (B-1). [ka] In formula (B-1), Ar 11 each independently represents a monovalent aromatic hydrocarbon group which may have a substituent, and Ar 12 each independently represents a divalent aromatic hydrocarbon group which may have a substituent, Ar 13 each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof. m and n each independently represent an integer from 0 to 10. In formula (B-2), Ar 11 each independently represents a monovalent aromatic hydrocarbon group which may have a substituent, and Ar 12 each independently represents a divalent aromatic hydrocarbon group which may have a substituent, Ar 13each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof. mb and nb each independently represent 0 or greater.

[0069] In formula (B-1) and formula (B-2), Ar 11 Each independently represents a monovalent aromatic hydrocarbon group which may have a substituent. Examples of the monovalent aromatic hydrocarbon group include monocyclic aromatic compounds such as phenyl, furanyl, pyrrolyl, thiophene, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, and triazinyl groups, from which one hydrogen atom has been removed; and condensed ring aromatic compounds such as naphthyl, anthracenyl, phenalenyl, phenanthrenyl, quinolinyl, isoquinolinyl, quinazolyl, phthalazinyl, pteridinyl, coumarinyl, indole, benzimidazolyl, benzofuranyl, and acridinyl groups, from which one hydrogen atom has been removed; and among these, phenyl and naphthyl groups are preferred from the viewpoint of achieving the remarkable effects of the present invention. Ar 11 The monovalent aromatic hydrocarbon group represented by may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton may have. Among them, Ar 11 When has a substituent, the substituent is preferably a radical polymerizable group.

[0070] In formula (B-1) and formula (B-2), Ar 12each independently represents a divalent aromatic hydrocarbon group which may have a substituent. Examples of the divalent aromatic hydrocarbon group include an arylene group and an aralkylene group, with an arylene group being preferred. As the arylene group, an arylene group having 6 to 30 carbon atoms is preferred, an arylene group having 6 to 20 carbon atoms is more preferred, and an arylene group having 6 to 10 carbon atoms is even more preferred. Examples of such an arylene group include a phenylene group, a naphthylene group, an anthracenylene group, and a biphenylene group. As the aralkylene group, an aralkylene group having 7 to 30 carbon atoms is preferred, an aralkylene group having 7 to 20 carbon atoms is more preferred, and an aralkylene group having 7 to 15 carbon atoms is even more preferred. Among these, Ar in formula (B-1) 12 are each independently preferably a phenylene group or a naphthylene group, more preferably a phenylene group. 12 are each independently preferably a phenylene group or a naphthylene group, more preferably a naphthylene group.

[0071] Ar 12 The divalent aromatic hydrocarbon group represented by may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton may have. Among them, Ar 12 has preferably an aralkyl group as a substituent, and more preferably a benzyl group as a substituent.

[0072] In the general formula (B-1) and the formula (B-2), Ar 13 each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof, and a divalent group consisting of a combination thereof is preferred. 12 The same applies to the divalent aromatic hydrocarbon group represented by the formula (I).

[0073] As the divalent aliphatic hydrocarbon group, a divalent saturated aliphatic hydrocarbon group is more preferred, an alkylene group or a cycloalkylene group is preferred, and a cycloalkylene group is more preferred.

[0074] The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, and a hexylene group.

[0075] The cycloalkylene group is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 3 to 15 carbon atoms, and even more preferably a cycloalkylene group having 5 to 10 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclopentylene group, a cycloheptylene group, and cycloalkylene groups represented by the above formulas (a) to (d), with a cycloalkylene group represented by formula (c) being preferred.

[0076] Divalent groups formed from these combinations are preferably divalent groups formed by combining an optionally substituted divalent aromatic hydrocarbon group and an optionally substituted divalent aliphatic hydrocarbon group, and more preferably divalent groups formed by alternating multiple optionally substituted divalent aromatic hydrocarbon groups and multiple optionally substituted divalent aliphatic hydrocarbon groups. Specific examples of the divalent groups include the divalent groups (B1) to (B13) below. In the formulae, a1 to a9 represent integers of 0 to 10, preferably integers of 0 to 6, and more preferably integers of 0 to 5. "*" represents a bond, and the wavy line represents a structure obtained by reaction of an aromatic compound, an acid halide of an aromatic compound, or an ester of an aromatic compound used in synthesizing component (B). [ka] [ka]

[0077] Ar 13 The divalent aromatic hydrocarbon group and the divalent aliphatic hydrocarbon group represented by may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton may have.

[0078] In general formula (B-1), m represents 0 to 10, preferably 0 to 5, more preferably 0 to 3, and particularly preferably 0. When the compound represented by general formula (B-1) is an oligomer or polymer, m represents its average value.

[0079] In general formula (B-1), n ​​represents 0 to 10, preferably 0 to 5, and more preferably 0 to 3. When the compound represented by general formula (B-1) is an oligomer or polymer, n represents its average value.

[0080] In formula (B-2), mb and nb each independently represent 0 or more, and preferably represent an integer of 0 to 20, more preferably 0 to 15, and even more preferably 0 to 10.

[0081] Specific examples of the component (B) include the following compounds (Bi) to (B-iv). Specific examples of the component (B) include the compounds described in paragraphs 0068 to 0071 of WO 2018 / 235424 and paragraphs 0113 to 0115 of WO 2018 / 235425. However, the component (B) is not limited to these specific examples. In the formula, a represents an integer of 0 to 6, s represents 0 or 1 or more, and r represents 1 to 10. n and m are 0 or more. [ka]

[0082] The component (B) may be synthesized by a known method. The component (B) can be synthesized, for example, by the method described in WO 2018 / 235424 or WO 2018 / 235425.

[0083] Component (B) can be a commercially available product, such as "PC1300-02-65MA" manufactured by Air Water Inc.

[0084] The weight average molecular weight of component (B) is preferably 150 or more, more preferably 200 or more, and even more preferably 250 or more, and is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1500 or less. The weight average molecular weight of component (B) is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0085] The unsaturated bond equivalent (radical polymerizable group equivalent) of component (B) is preferably 50 g / eq or more, more preferably 100 g / eq or more, even more preferably 150 g / eq, and is preferably 2000 g / eq or less, more preferably 1000 g / eq or less, even more preferably 500 g / eq or less. The unsaturated bond equivalent is the mass of component (B) containing one equivalent of unsaturated bonds.

[0086] The content of component (B) is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, and is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, when the non-volatile components of the resin composition layer are taken as 100% by mass.

[0087] The content of component (B) is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, or 15% by mass or more, when the resin component of the resin composition layer is 100% by mass, and is preferably 55% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less.

[0088] The total content of the (A) component and the (B) component is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, and is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, when the non-volatile components of the resin composition layer are taken as 100% by mass.

[0089] When the content of the (A) component is a1 and the content of the (B) component is b1, assuming that the nonvolatile components of the resin composition layer constitute 100% by mass, (a1 / b1) × 100 is preferably at least 1, more preferably at least 3, and even more preferably at least 5, and is preferably at most 50, more preferably at most 30, and even more preferably at most 20, and at most 15. By adjusting the amounts of the (A) component and the (B) component so that a1 / b1 falls within this range, it is possible to obtain a cured product that has a low dielectric tangent and excellent adhesion to the conductor layer, blister resistance, and smear removability.

[0090] -(C)Inorganic filler- The resin composition layer contains an inorganic filler (C) as the component (C). By using a resin composition layer containing the component (C), a cured product with low dielectric properties can be obtained. The inorganic filler (C) may be used alone or in combination of two or more types in any ratio.

[0091] The (C) inorganic filler is contained in the resin composition layer in the form of particles. An inorganic compound is used as the (C) inorganic filler. Examples of the (C) inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Spherical silica is preferred.

[0092] (C) inorganic fillers can be classified into hollow inorganic fillers having internal voids and solid inorganic fillers having no internal voids. (C) inorganic filler preferably contains either a hollow inorganic filler or a solid inorganic filler, and more preferably contains a solid inorganic filler from the viewpoint of obtaining a cured product with low dielectric properties.

[0093] The hollow inorganic filler may be a single hollow particle having only one void inside the particle, a multi-hollow particle having two or more voids inside the particle, or a combination of a single hollow particle and other hollow particles.

[0094] Since hollow inorganic fillers have pores, they usually have a porosity of more than 0% by volume. The porosity of the hollow inorganic filler is preferably 10% by volume or more, more preferably 15% by volume or more, and particularly preferably 20% by volume or more. In addition, from the viewpoint of the mechanical strength of the cured resin composition layer, the porosity of the hollow inorganic filler is preferably 80% by volume or less, more preferably 75% by volume or less, and particularly preferably 70% by volume or less.

[0095] The porosity P (vol %) of an inorganic filler is defined as the volume-based ratio of the total volume of one or more voids present inside the particle to the total volume of the particle based on the outer surface of the particle (total volume of voids / volume of particle). For example, the actual density measurement value D of the inorganic filler M (g / cm 3 ), and the theoretical value of the material density D of the material forming the inorganic filler T (g / cm 3 ) is used to calculate the following formula (1):

number

[0096] Hollow inorganic fillers generally have voids formed within the particles and an outer shell formed of an inorganic material surrounding the voids. Usually, the voids are separated from the outside of the particle by the outer shell. In this case, it is preferable that the voids do not communicate with the outside of the particle. Therefore, it is preferable that the outer shell is a non-porous shell that does not have holes that communicate the voids with the outside of the particle. The fact that the outer shell is non-porous can be confirmed by observation with a transmission electron microscope (TEM).

[0097] The hollow inorganic filler has an average particle size of preferably 0.01 μm or more, more preferably 0.1 μm or more, particularly preferably 0.3 μm or more, and preferably 5 μm or less, more preferably 4 μm or less, particularly preferably 3 μm or less.

[0098] The average particle size can be measured using a laser diffraction / scattering method based on Mie scattering theory. Specifically, a particle size distribution based on volume is created using a laser diffraction / scattering particle size distribution analyzer, and the median diameter is used as the average particle size. A measurement sample of inorganic filler can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing the mixture ultrasonically for 10 minutes. The measurement sample is measured using a laser diffraction particle size distribution analyzer with blue and red light source wavelengths using a flow cell system to measure the volumetric particle size distribution of the inorganic filler, and the average particle size can be calculated as the median diameter from the particle size distribution obtained. Examples of laser diffraction particle size distribution analyzers include the LA-960 manufactured by Horiba, Ltd.

[0099] The BET specific surface area of ​​the hollow inorganic filler is preferably 1 m 2 / g or more, more preferably 2m 2 / g or more, particularly preferably 5m 2 / g or more, preferably 100m 2 / g or less, more preferably 50m 2 / g or less, particularly preferably 30m 2 The BET specific surface area of ​​the particles can be measured in accordance with the BET method by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) and calculating the specific surface area using the BET multipoint method.

[0100] Commercially available hollow inorganic fillers may be used, such as "LHP-208" manufactured by Ube Exsymo Co., Ltd., and "MG-005," "MGH-005," "BA-1," and "CellSpheres" manufactured by Taiheiyo Cement Corporation.

[0101] Furthermore, the hollow inorganic filler may be produced by, for example, the method described in Japanese Patent No. 5940188 or a method equivalent thereto. Specifically, hollow silica particles, which are an example of a hollow inorganic filler, can be produced by a method including the steps of: preparing an aqueous solution containing a substance capable of forming pores and a basic compound; mixing the aqueous solution with an alkoxysilane and stirring to precipitate silica particles; removing the substance capable of forming pores from the silica particles to obtain hollow silica precursors; and calcining the hollow silica precursors.

[0102] Furthermore, hollow inorganic fillers may be produced by, for example, the method described in Japanese Patent No. 5864299 or a method equivalent thereto. Specifically, hollow silica particles, which are an example of hollow inorganic fillers, can be produced by a method including: (a) a step of preparing an aqueous solution containing a substance capable of forming hollow spaces and a basic compound; (b) a step of adding an alkoxysilane to the aqueous solution and stirring the mixture at 0°C to 100°C to precipitate silica particles; (c) a step of removing the substance capable of forming hollow spaces from the silica particles obtained in step (b) to obtain hollow silica precursors; and (c) a step of calcining the hollow silica precursor obtained in step (c) at a temperature exceeding 900°C to obtain hollow silica.

[0103] The hollow inorganic filler may be treated with a surface treatment agent to improve moisture resistance and dispersibility. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. One type of surface treatment agent may be used alone, or two or more types may be used in any combination.

[0104] Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy-type silane coupling agent), and Shin-Etsu Chemical Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane).

[0105] From the viewpoint of improving dispersibility, the degree of surface treatment with the surface treatment agent preferably falls within a specific range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% to 8% by mass of the surface treatment agent, more preferably with 0.2% to 5% by mass of the surface treatment agent, and even more preferably with 0.3% to 3% by mass of the surface treatment agent.

[0106] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2 On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition layer, it is more preferable that the amount of the resin composition layer is 1.0 mg / m 2 Less than 0.8 mg / m is preferred 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0107] The carbon amount per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the carbon amount per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. The carbon analyzer that can be used is the "EMIA-320V" manufactured by Horiba, Ltd.

[0108] The specific gravity of the hollow inorganic filler is preferably 3.50 g / cm 3 or less, more preferably 3.00 g / cm 3 or less, more preferably 2.50 g / cm 3 or less, preferably 0.05 g / cm 3 More preferably, 0.5 g / cm 3 More preferably, 1.0 g / cm 3 That's all.

[0109] The content (mass %) of the hollow inorganic filler may be 0 mass % or more than 0 mass %, and is preferably 1 mass % or more, more preferably 5 mass % or more, even more preferably 10 mass % or more, and is preferably 30 mass % or less, more preferably 20 mass % or less, even more preferably 15 mass % or less, when the non-volatile components in the resin composition layer are 100 mass %.

[0110] The content (vol %) of the hollow inorganic filler may be 0 vol % or more, and is preferably 5 vol % or more, more preferably 10 vol % or more, and even more preferably 20 vol % or more, and is preferably 50 vol % or less, more preferably 40 vol % or less, and even more preferably 30 vol % or less, assuming that the non-volatile components in the resin composition layer are 100 vol %.

[0111] A solid inorganic filler refers to an inorganic filler that is substantially free of voids or holes, including cases where voids are inevitably mixed in during the production of the solid inorganic filler. The porosity of the solid inorganic filler is less than 0.5% by volume, and the actual porosity is 0% by volume. Commercially available solid inorganic fillers may be used. Commercially available solid inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C," "YA050C," "YA050C-MJE," "YA010C," "SC2500SQ," "SO-C4," "SO-C2," and "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30," "DAW-03," and "FB-105FD" manufactured by Denka Co., Ltd.; "Silfil NSS-3N," "Silfil NSS-4N," and "Silfil NSS-5N" manufactured by Tokuyama Corporation; and "Sferique" manufactured by JGC Catalysts and Chemicals Co., Ltd.

[0112] The average particle size of the solid inorganic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more, even more preferably 0.3 μm or more, and is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 3 μm or less. The average particle size of the solid inorganic filler can be measured in the same manner as the average particle size of the hollow inorganic filler.

[0113] The BET specific surface area of ​​the solid inorganic filler is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, preferably 100m 2 / g or less, more preferably 70m 2 / g or less, more preferably 40m 2 The BET specific surface area of ​​the solid inorganic filler can be measured in the same manner as the BET specific surface area of ​​the hollow inorganic filler.

[0114] The solid inorganic filler may be treated with a surface treatment agent, similar to the hollow inorganic filler. The surface treatment agent, the degree of surface treatment, the amount of carbon, etc. are as described above.

[0115] The content (mass %) of the solid inorganic filler is preferably 50 mass % or more, more preferably 60 mass % or more, even more preferably 65 mass % or more, or 70 mass % or more, and is preferably 100 mass %, more preferably 100 mass % or less, even more preferably 90 mass % or less, 85 mass % or less, or 80 mass % or less, assuming that the non-volatile components in the resin composition layer are 100 mass %.

[0116] The content (vol %) of the solid inorganic filler may be 0 vol % or more, and is preferably 5 vol % or more, more preferably 10 vol % or more, and even more preferably 20 vol % or more, and is preferably 50 vol % or less, more preferably 40 vol % or less, and even more preferably 30 vol % or less, assuming that the non-volatile components in the resin composition layer are 100 vol %.

[0117] The proportion of voids contained in the entire (C) inorganic filler, including both hollow and solid inorganic fillers, is determined as the porosity (volume %) of the (C) inorganic filler. The porosity (volume %) of the (C) inorganic filler is a representative value that represents the proportion of voids in the volume of the (C) inorganic filler on a volume basis, and is expressed as "total volume of voids / total volume of the (C) inorganic filler." The specific range of the porosity of the (C) inorganic filler is preferably 10% by volume or more, more preferably 15% by volume or more, and even more preferably 20% by volume or more, and is preferably 80% by volume or less, more preferably 70% by volume or less, and even more preferably 60% by volume or less.

[0118] The average particle size of the entire (C) inorganic filler, including both hollow inorganic fillers and solid inorganic fillers, is preferably 0.01 μm or more, more preferably 0.1 μm or more, even more preferably 0.3 μm or more, and is preferably 5 μm or less, more preferably 4 μm or less, even more preferably 3 μm or less.

[0119] The BET specific surface area of ​​the entire inorganic filler (B), including both the hollow inorganic filler and the solid inorganic filler, is preferably 1 m 2 / g or more, more preferably 2m 2 / g or more, more preferably 5m2 / g or more, preferably 100m 2 / g or less, more preferably 50m 2 / g or less, more preferably 30m 2 / g or less.

[0120] The content (mass %) of (C) inorganic filler is preferably 60 mass % or more, more preferably 65 mass % or more, even more preferably 70 mass % or more, and is preferably 90 mass % or less, more preferably 85 mass % or less, even more preferably 80 mass % or less, when the non-volatile components in the resin composition layer are taken as 100 mass %.

[0121] The content (vol %) of (C) inorganic filler is preferably 20% by volume or more, more preferably 30% by volume or more, and even more preferably 40% by volume or more, and is preferably 80% by volume or less, more preferably 75% by volume or less, and particularly preferably 70% by volume or less, assuming that the non-volatile components in the resin composition layer are 100% by volume.

[0122] -(D) Epoxy resin- The resin composition layer may contain a (D) epoxy resin as the (D) component. The (D) epoxy resin as the (B) component does not include those corresponding to the (A) to (C) components. By including the (D) epoxy resin in the resin composition layer, a cured product exhibiting good mechanical strength and insulation reliability can be obtained. One type of (D) epoxy resin may be used alone, or two or more types may be used in combination.

[0123] (D) Epoxy resins include, for example, bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, and glycidyl ester type Examples of epoxy resins include epoxy resins, glycidyl cyclohexane-type epoxy resins, alkyl diglycidyl ether-type epoxy resins, cresol novolac-type epoxy resins, biphenyl-type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane-type epoxy resins, cyclohexane dimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylethane-type epoxy resins, and phenolphthalimidine-type epoxy resins.

[0124] The resin composition layer preferably contains, as component (D), an epoxy resin having two or more epoxy groups per molecule. The proportion of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the epoxy resin (D) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0125] Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition layer may contain, as component (D), only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin.

[0126] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0127] Preferred liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure, glycidyl cyclohexane type epoxy resins, phenolphthalimidine type epoxy resins, and alkyl diglycidyl ether type epoxy resins, with bisphenol A type epoxy resins and bisphenol F type epoxy resins being more preferred.

[0128] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "Epikote 828EL" (bisphenol A type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" and "630LSD" (glycidyl amine type epoxy resins) manufactured by Mitsubishi Chemical Corporation; and "ZX1" manufactured by Nippon Steel Chemical & Material Co., Ltd. Examples of epoxy resins that can be used include "EX-721" (a glycidyl ester epoxy resin) manufactured by Nagase ChemteX Corporation, "Celloxide 2021P" (an alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation, "PB-3600" (an epoxy resin having a butadiene structure) manufactured by Daicel Corporation, "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane epoxy resins) manufactured by Nippon Steel Chemical & Material Co., Ltd., and "YED216D" (an alkyl diglycidyl ether epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used alone or in combination of two or more.

[0129] As the solid epoxy resin, a solid epoxy resin having two or more epoxy groups in one molecule is preferred, a solid epoxy resin having three or more epoxy groups in one molecule is more preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is even more preferred.

[0130] Preferred solid epoxy resins include bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins, with naphthalene-type epoxy resins and biphenyl-type epoxy resins being more preferred.

[0131] Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphthylene ether type epoxy resin), manufactured by DIC Corporation; "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L" manufactured by Nippon Kayaku Co., Ltd.; Examples include "NC3100" (biphenyl-type epoxy resin); "ESN475V" (naphthalene-type epoxy resin) and "ESN485" (naphthol novolac-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YL6121" (biphenyl-type epoxy resin), "YX4000HK" (bixylenol-type epoxy resin), and "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF-type epoxy resin), "YL7800" (fluorene-type epoxy resin), "jER1010" (solid bisphenol A-type epoxy resin), and "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "WHR-991S" (phenolphthalimidine-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These may be used alone or in combination of two or more.

[0132] When a liquid epoxy resin and a solid epoxy resin are used in combination as component (D), the ratio by mass of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin:solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.15 to 1:10, and particularly preferably 1:0.2 to 1:5. When the ratio by mass of the liquid epoxy resin to the solid epoxy resin is within this range, the desired effects of the present invention can be significantly achieved.

[0133] The epoxy equivalent of component (D) is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., even more preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. By ensuring that the epoxy equivalent is within this range, a cured product with sufficient crosslink density can be obtained. The epoxy equivalent is the mass of an epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0134] The weight average molecular weight (Mw) of component (D) is preferably 100 to 5000, more preferably 150 to 3000, and even more preferably 200 to 1500. The weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0135] The content of component (D) is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition layer, and the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0136] The content of component (D) is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, based on 100% by mass of the resin component in the resin composition layer, and the upper limit is preferably 60% by mass or less, more preferably 55% by mass or less, even more preferably 50% by mass or less, 45% by mass or less, or 40% by mass or less.

[0137] The total content of components (A), (B), and (D), when the non-volatile components in the resin composition layer are taken as 100% by mass, is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and is preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less.

[0138] -(E) Radical polymerizable group-containing compound having no carbodiimide structure- The resin composition layer may contain, as component (E), a (E) radical polymerizable group-containing compound that does not have a carbodiimide structure. The (E) radical polymerizable group-containing compound that does not have a carbodiimide structure as component (E) does not include compounds that fall under the above-mentioned components (A) to (D). The (E) radical polymerizable group-containing compound that does not have a carbodiimide structure is a compound that contains one or more radical polymerizable groups in one molecule but does not have a carbodiimide structure (-N=C=N-). One type of (E) component may be used alone, or two or more types may be used in combination. From the viewpoint of improving the dielectric loss tangent, the resin composition may contain component (E).

[0139] The component (E) may have two or more radically polymerizable groups in one molecule. The radically polymerizable groups are as described above.

[0140] In the first embodiment, the component (E) preferably contains a thermoplastic resin having two or more radically polymerizable groups (for example, a number average molecular weight of 800 or more). The thermoplastic resin is not particularly limited, but examples include phenoxy resin, polyvinyl acetal resin, polystyrene resin, polyethylene resin, polypropylene resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polyetheretherketone resin, and polyester resin. In this embodiment, the component (E) contains a modified resin of these resins having two or more radically polymerizable groups.

[0141] In the first embodiment, the component (E) more preferably includes a resin selected from a modified polyphenylene ether resin having two or more radically polymerizable groups and a modified polystyrene resin having two or more radically polymerizable groups, even more preferably includes a modified polyphenylene ether resin having two or more radically polymerizable groups, and more preferably includes a resin represented by formula (E-1). [ka] In formula (E-1), R b each independently represents a hydrogen atom or a methyl group; X b are each independently a carbonyl group, a methylene group, a phenylene group, or a phenylene-methylene group (the bonding direction is not particularly limited, but the phenylene side is "R b -C"); R 11 and R 12 each independently represents an alkyl group; R 13 , R 14 , R 21 , R 22 , R 23 and R 24 each independently represents a hydrogen atom or an alkyl group; A represents a single bond, -C(R c )2-, -O-, -CO-, -S-, -SO-, or -SO2-; R c each independently represents a hydrogen atom or an alkyl group; p represents 0 or 1; and q and r each independently represent an integer of 1 or greater. The q units and r units may be the same or different for each unit.

[0142] R b X each independently represents a hydrogen atom or a methyl group. b are each independently a carbonyl group, a methylene group, a phenylene group, or a phenylene-methylene group (the bonding direction is not particularly limited, but the phenylene side is "R bIt is preferably bonded to C in "-C"), and is preferably a carbonyl group or a phenylene-methylene group.

[0143] R 11 and R 12 R each independently represents an alkyl group, preferably a methyl group. 13 and R 14 R each independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom. 21 and R 22 R each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and more preferably a methyl group. 23 and R 24 each independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom or a methyl group.

[0144] A is a single bond, -C(R c )2-, -O-, -CO-, -S-, -SO-, or -SO2-, and preferably represents a single bond, -C(R c )2- or -O-. c each independently represents a hydrogen atom or an alkyl group, and preferably a hydrogen atom or a methyl group. p represents 0 or 1, and preferably 1. q and r each independently represent an integer of 1 or more, and preferably an integer of 1 to 200, and more preferably an integer of 1 to 100.

[0145] The radical polymerizable group equivalent of the component (E) in the first embodiment is preferably 300 g / eq. to 2500 g / eq., and more preferably 400 g / eq. to 2000 g / eq. The radical polymerizable group equivalent represents the mass of the resin (compound) per equivalent of the radical polymerizable group.

[0146] The number average molecular weight of the component (E) in the first embodiment is preferably 800 to 10000, and more preferably 900 to 5000. The number average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0147] Examples of commercially available products of the component (E) in the first embodiment include "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Company, Inc.; and "SA9000" and "SA9000-111" (methacrylic-modified polyphenylene ether resins) manufactured by SABIC.

[0148] In the second embodiment, the component (E) contains a low-molecular-weight compound (e.g., a molecular weight of less than 800) having two or more radically polymerizable groups. Examples of such compounds include polyfunctional (meth)acryloyl group-containing compounds having a molecular weight of less than 800, polyfunctional vinylaryl group-containing compounds having a molecular weight of less than 800, and polyfunctional allyl group-containing compounds having a molecular weight of less than 800.

[0149] A polyfunctional (meth)acryloyl group-containing compound having a molecular weight of less than 800 is a compound having two or more (meth)acryloyl groups. Examples of polyfunctional (meth)acryloyl group-containing compounds having a molecular weight of less than 800 include aliphatic (meth)acrylic acid ester compounds such as cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; dioxane Examples of the ether-containing (meth)acrylic acid ester compounds include ricol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, 3,6,9-trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, and propoxylated bisphenol A di(meth)acrylate; and isocyanurate-containing (meth)acrylic acid ester compounds such as tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and ethoxylated isocyanuric acid tri(meth)acrylate.Examples of commercially available polyfunctional (meth)acryloyl group-containing compounds having a molecular weight of less than 800 include "A-DOG" (dioxane glycol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" (tricyclodecane dimethanol diacrylate) and "DCP" (tricyclodecane dimethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., and "KAYARAD R-684" (tricyclodecane dimethanol diacrylate) and "KAYARAD R-604" (dioxane glycol diacrylate) manufactured by Nippon Kayaku Co., Ltd.

[0150] A polyfunctional vinylaryl group-containing compound having a molecular weight of less than 800 is a compound having two or more vinylaryl groups. Examples of polyfunctional vinylaryl group-containing compounds having a molecular weight of less than 800 include 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl)ether.

[0151] A polyfunctional allyl group-containing compound having a molecular weight of less than 800 is a compound having two or more allyl groups. Examples of polyfunctional allyl group-containing compounds having a molecular weight of less than 800 include aromatic carboxylic acid allyl ester compounds such as diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, and diallyl 2,3-naphthalenecarboxylate; isocyanuric acid allyl ester compounds such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; epoxy-containing aromatic allyl compounds such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; benzoxazine-containing aromatic allyl compounds such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane; ether-containing aromatic allyl compounds such as 1,3,5-triallyl ether benzene; and allyl silane compounds such as diallyldiphenylsilane. Commercially available polyfunctional allyl group-containing compounds with a molecular weight of less than 800 include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Chemical Industry Co., Ltd., "DAD" (diallyl diphenate) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., "TRIAM-705" (triallyl trimellitate) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., "DAND" (2,3-diallyl naphthalenecarboxylate) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) manufactured by Shikoku Chemical Industry Co., Ltd., "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane) manufactured by Nippon Kayaku Co., Ltd., and "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Chemical Industry Co., Ltd.

[0152] The radical polymerizable group equivalent of the component (E) in the second embodiment is preferably 30 g / eq. to 400 g / eq., more preferably 50 g / eq. to 300 g / eq., and even more preferably 75 g / eq. to 200 g / eq.

[0153] The molecular weight of the component (E) in the second embodiment is preferably 100-700, more preferably 200-400, and even more preferably 250-500.

[0154] In the third embodiment, the component (E) preferably includes a maleimide compound having a partial structure represented by formula (E-2). The maleimide compound refers to a compound containing at least one maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group) in one molecule. In the third embodiment, the number of maleimide groups in one molecule of the maleimide compound is preferably two or more, and particularly preferably two. [ka] In the formula, ring E represents a monocycloalkane ring which may have a substituent, or a monocycloalkene ring which may have a substituent; i and j each independently represent an integer of 0 or 1 or greater, and the sum of i and j is 6 or greater; and * represents a bonding site.

[0155] The monocycloalkane ring refers to a monocyclic aliphatic saturated hydrocarbon ring. The monocycloalkane ring is preferably a monocycloalkane ring having 4 to 14 carbon atoms, more preferably a monocycloalkane ring having 4 to 10 carbon atoms, and particularly preferably a monocycloalkane ring having 5 or 6 carbon atoms. Examples of the monocycloalkane ring include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring. The monocycloalkene ring refers to a monocyclic aliphatic unsaturated hydrocarbon ring having at least one carbon-carbon double bond. The monocycloalkene ring is preferably a monocycloalkene ring having 4 to 14 carbon atoms, more preferably a monocycloalkene ring having 4 to 10 carbon atoms, and particularly preferably a monocycloalkene ring having 5 or 6 carbon atoms. Examples of the monocycloalkene ring include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, a cyclopentadiene ring, and a cyclohexadiene ring.

[0156] Examples of the substituents on the monocycloalkane ring and the monocycloalkene ring include the same as the substituents that may be carried on Y in formula (A-1).

[0157] Ring E represents a monocycloalkane ring which may have a substituent, or a monocycloalkene ring which may have a substituent. Ring E is preferably a monocycloalkane ring which may have a substituent selected from an alkyl group and an alkenyl group; or a monocycloalkene ring which may have a substituent selected from an alkyl group and an alkenyl group. Ring E is more preferably a monocycloalkane ring which may have a substituent selected from an alkyl group having 1 to 14 carbon atoms and an alkenyl group having 2 to 14 carbon atoms; or a monocycloalkene ring which may have a substituent selected from an alkyl group having 1 to 14 carbon atoms and an alkenyl group having 2 to 14 carbon atoms.

[0158] i and j each independently represent an integer of 0 or 1 or more, and the sum of i and j is 6 or more (preferably 8 or more, more preferably 10 or more). i and j are preferably each independently an integer of 0 to 20, and the sum of i and j is 6 or more (preferably 8 or more, more preferably 10 or more). i and j are more preferably each independently an integer of 1 to 20, and the sum of i and j is 6 or more (preferably 8 or more, more preferably 10 or more). i and j are further preferably each independently an integer of 5 to 10. i and j are particularly preferably 8.

[0159] In the third embodiment, the component (E) particularly preferably includes a maleimide compound represented by formula (E-3). [ka] In the formula, R 1 each independently represents a substituent; each ring F independently represents an aromatic ring which may have a substituent; D 1 and D 2 are each independently a single bond, -C(R x)2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-; R x each independently represents a hydrogen atom or an alkyl group; each e independently represents 0 or 1; each f independently represents an integer of 0 or 1 or greater; each g independently represents 0, 1, or 2; and m independently represents an integer of 0 or 1 or greater; and other symbols are as defined above. The f units, g units, and m units may be the same or different for each unit.

[0160] The aromatic ring refers to a ring that conforms to Hückel's rule, in which the number of electrons contained in the π-electron system on the ring is 4p+2 (p is a natural number). The aromatic ring may be an aromatic carbocyclic ring containing only carbon atoms as ring-constituting atoms, or an aromatic heterocyclic ring containing heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms in addition to carbon atoms as ring-constituting atoms. In one embodiment, the aromatic ring is preferably an aromatic carbocyclic ring. In one embodiment, the aromatic ring is preferably a 5- to 14-membered aromatic ring, more preferably a 6- to 14-membered aromatic ring, and even more preferably a 6- to 10-membered aromatic ring. Specific examples of suitable aromatic rings include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. A benzene ring or a naphthalene ring is more preferred, and a benzene ring is particularly preferred.

[0161] R 1 The substituents in and the aromatic ring are the same as the substituents that Y in formula (A-1) may have.

[0162] Each ring F independently represents an aromatic ring which may have a substituent, and is preferably a benzene ring which may have a substituent selected from alkyl groups. 1 and D 2 are each independently a single bond, -C(R x )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-, and preferably represents a single bond, -C(R x )2- or -O-. xare each independently a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group. e are each independently 0 or 1, preferably 0. f are each independently an integer of 0 or 1 or more, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2. g are each independently 0, 1 or 2, preferably 0. m are each independently an integer of 0 or 1 or more, preferably 0.

[0163] The partial structure represented by formula (E-4) contained in formula (E-3) is not particularly limited, and examples thereof include partial structures represented by formulas (Ea) to (Ec). [ka] In the formula, * represents a binding site, and other symbols are the same as above. [ka] In the formula, * represents a binding site.

[0164] The radical polymerizable group equivalent of the component (E) in the third embodiment is preferably 200 g / eq. to 2500 g / eq., more preferably 250 g / eq. to 2000 g / eq., and even more preferably 300 g / eq. to 1500 g / eq. The radical polymerizable group equivalent of the component (E) represents the mass of the resin per equivalent of the radical polymerizable group.

[0165] The weight average molecular weight of the component (E) in the third embodiment is preferably 400 to 100,000, more preferably 500 to 7,000, and particularly preferably 600 to 5,000.

[0166] Examples of commercially available products of the component (E) in the third embodiment include "BMI-689," "BMI-1500," "BMI-1700," and "BMI-3000J" manufactured by Designer Molecules Inc., and "SLK-6895-T90" and "SLK-1500-M70" manufactured by Shin-Etsu Chemical Co., Ltd.

[0167] In the fourth embodiment, the component (E) preferably includes a maleimide compound represented by formula (E-5). [ka] In the formula, R 2 each independently represents a hydrogen atom or an alkyl group; ring L, ring M, and ring N each independently represents an aromatic ring which may have a substituent; Z 1 are each independently a single bond, -C(R z )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-; R z each independently represents a hydrogen atom or an alkyl group; s represents an integer of 1 or greater; each independently represents 0 or 1; and each independently represents 0, 1, 2, or 3. The s units and u units may be the same or different for each unit.

[0168] R 2 are each independently a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0169] Ring L, ring M, and ring N each independently represent an aromatic ring which may have a substituent, preferably a benzene ring which may have a substituent, more preferably a benzene ring which may be substituted with a group selected from an alkyl group and an aryl group, and particularly preferably an (unsubstituted) benzene ring.

[0170] Z 1 are each independently a single bond, -C(R z )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-, and preferably a single bond, -C(R z )2- or -O-, and more preferably a single bond or -C(R z )2-, and particularly preferably a single bond. zeach independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom or a methyl group.

[0171] s represents an integer of 1 or more, preferably an integer of 1 to 10. Each t independently represents 0 or 1, preferably 1. Each u independently represents 0, 1, 2, or 3, preferably 0, 1, or 2, more preferably 0 or 1, and particularly preferably 1.

[0172] The radical polymerizable group equivalent of the component (E) in the fourth embodiment is preferably 150 g / eq. to 1000 g / eq., and more preferably 200 g / eq. to 500 g / eq.

[0173] The weight average molecular weight of the component (E) in the fourth embodiment is preferably 100 to 10,000, more preferably 150 to 5,000, and particularly preferably 200 to 3,000.

[0174] Commercially available products of the component (E) in the fourth embodiment include, for example, "MIR-3000-70MT" and "MIR-5000-60T" manufactured by Nippon Kayaku Co., Ltd.

[0175] The component (E) may contain any one of the preferred compounds in the first embodiment, the preferred compounds in the second embodiment, the preferred maleimide compounds in the third embodiment, and the preferred maleimide compounds in the fourth embodiment, alone, or may contain a combination of two or more of these compounds in any ratio.

[0176] The radical polymerizable group equivalent of the component (E) is preferably 30 g / eq. to 2500 g / eq., and particularly preferably 75 g / eq. to 2000 g / eq.

[0177] The content of component (E) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, when the non-volatile components in the resin composition layer are taken as 100% by mass.

[0178] The content of component (E) is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, when the resin component in the resin composition layer is taken as 100% by mass, and is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, or 15% by mass or less.

[0179] -(F) Hardener- The resin composition layer may contain a (F) curing agent as the (F) component. The (F) curing agent as the (F) component excludes those corresponding to the above-mentioned (A) to (E) components. The (F) component usually has the function of curing the resin composition layer by reacting with the (D) component. The (F) component may be used alone or in a combination of two or more types in any ratio.

[0180] As the component (F), a compound capable of reacting with the component (D) to cure the resin composition can be used, and examples thereof include phenolic curing agents, carbodiimide curing agents (excluding those corresponding to the component (A)), active ester curing agents having no radical polymerizable groups (excluding those corresponding to the component (B)), benzoxazine curing agents, acid anhydride curing agents, amine curing agents, cyanate ester curing agents, etc. Among these, the component (F) preferably contains any of an active ester curing agent having no radical polymerizable groups, a phenolic curing agent, and a carbodiimide curing agent, and from the viewpoint of adhesion to the substrate, it is more preferable that the component (F) contains a phenolic curing agent.

[0181] Examples of phenolic curing agents include curing agents having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring (such as a benzene ring or a naphthalene ring) per molecule. Among these, compounds having a hydroxyl group bonded to a benzene ring are preferred. Furthermore, from the viewpoint of heat resistance and water resistance, phenolic curing agents having a novolac structure are preferred. Furthermore, from the viewpoint of adhesion, nitrogen-containing phenolic curing agents are preferred, and triazine skeleton-containing phenolic curing agents are more preferred. In particular, from the viewpoint of achieving high levels of heat resistance, water resistance, and adhesion, triazine skeleton-containing phenolic novolac curing agents are preferred.

[0182] Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700," "MEH-7810," and "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd.; "NHN," "CBN," and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN-170," "SN-180," "SN-190," "SN-475," "SN-495," "SN-495V," "SN-375," and "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd.; Examples include "TD-2090," "TD-2090-60M," "LA-7052," "LA-7054," "LA-1356," "LA-3018," "LA-3018-50P," "EXB-9500," "HPC-9500," "KA-1160," "KA-1163," and "KA-1165" manufactured by DIC Corporation; and "GDP-6115L," "GDP-6115H," and "ELPC75" manufactured by Gun-ei Chemical Co., Ltd.

[0183] As the carbodiimide curing agent (excluding those corresponding to component (A)), a compound having one or more, preferably two or more, carbodiimide structures in one molecule and having no radical polymerizable group can be used.

[0184] Specific examples of carbodiimide-based curing agents include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane bis(methylene-t-butylcarbodiimide); aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide); poly(phenylenecarbodiimide), poly( Examples of polycarbodiimides include aromatic polycarbodiimides such as poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide].

[0185] Commercially available carbodiimide curing agents include, for example, "Carbodilite V-02B," "Carbodilite V-03," "Carbodilite V-04K," "Carbodilite V-07," and "Carbodilite V-09" manufactured by Nisshinbo Chemical Inc.; and "Stavaxol P," "Stavaxol P100," "Stavaxol P400," and "Hykasil 510" manufactured by Lanxess AG.

[0186] As the active ester curing agent having no radical polymerizable group (excluding those corresponding to component (B)), a compound having no radical polymerizable group but one or more active ester groups per molecule can be used. Among them, as the active ester curing agent having no radical polymerizable group, a compound having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, is preferred. The active ester curing agent having no radical polymerizable group is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent having no radical polymerizable group obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent having no radical polymerizable group obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred.

[0187] Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0188] Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalene, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolak. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one dicyclopentadiene molecule with two phenol molecules.

[0189] Preferred specific examples of active ester-based curing agents that do not have a radical polymerizable group include active ester-based curing agents containing a dicyclopentadiene-type diphenol structure, active ester-based curing agents containing a naphthalene structure, active ester-based curing agents containing an acetylated product of phenol novolac, and active ester-based curing agents containing a benzoylated product of phenol novolac. Among these, active ester-based curing agents containing a naphthalene structure and active ester-based curing agents containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structure consisting of phenylene-dicyclopentylene-phenylene.

[0190] Commercially available active ester curing agents without radical polymerizable groups include "EXB9451," "EXB9460," "EXB9460S," "HPC-8000," "HPC-8000H," "HPC-8000-65T," "HPC-8000H-65TM," "EXB-8000L," and "EXB-8000L-65TM" (manufactured by DIC Corporation) as active ester curing agents containing a dicyclopentadiene-type diphenol structure; and "HPC-8150-60T," "HPC-8150-62T," "EXB-8150-65T," "EXB-8100L-65T," "EXB-8150L-65T," and "E Examples of such curing agents include "XB9416-70BK" and "EXB-8151-62T" (manufactured by DIC Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent containing an acetylated phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent containing a benzoylated phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent which is an acetylated phenol novolac; and "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester curing agents which are benzoylated phenol novolac.

[0191] Specific examples of benzoxazine curing agents include "ODA-BOZ" manufactured by JFE Chemical Corporation, "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemicals Corporation.

[0192] Examples of acid anhydride curing agents include curing agents having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone. Examples of suitable curing agents include tetracarboxylic dianhydrides, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymeric acid anhydrides such as styrene-maleic acid resins (copolymers of styrene and maleic acid). Commercially available acid anhydride curing agents are also available, such as "MH-700" manufactured by New Japan Chemical Co., Ltd.

[0193] Examples of the amine curing agent include curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. Among these, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxybenzoyl). Examples of suitable amine curing agents include 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, and bis(4-(3-aminophenoxy)phenyl)sulfone. Commercially available amine curing agents may be used, such as "KAYABOND C-200S," "KAYABOND C-100," "KAYAHARD AA," "KAYAHARD AB," and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

[0194] Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac, cresol novolac, etc.; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate ester curing agents include "PT30" and "PT60" manufactured by Lonza (both of which are phenol novolac-type multifunctional cyanate ester resins); "ULL-950S" (multifunctional cyanate ester resin); "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been triazine-converted to form a trimer); and the like.

[0195] When the number of epoxy groups in component (D) is taken as 1, the number of active groups in the (F) curing agent is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. Here, "the number of epoxy groups in component (D)" refers to the total value obtained by dividing the mass of the non-volatile components of component (D) present in the resin composition layer by the epoxy equivalent. Furthermore, "the number of active groups in the (F) curing agent" refers to the total value obtained by dividing the mass of the non-volatile components of the (F) curing agent present in the resin composition layer by the active group equivalent.

[0196] The content of the (F) curing agent is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, based on 100% by mass of the non-volatile components in the resin composition layer, and is preferably 8% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0197] The content of the (F) curing agent is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less, when the resin component in the resin composition layer is taken as 100% by mass.

[0198] -(G) Curing accelerator- The resin composition layer may contain a (G) curing accelerator as component (G). This (G) curing accelerator as component (G) does not include those corresponding to the above-mentioned components (A) to (F). The (G) curing accelerator functions as a curing catalyst that accelerates the curing of the (D) epoxy resin.

[0199] As the (G) curing accelerator, a compound that accelerates the curing of the (D) epoxy resin can be used. Examples of such (G) curing accelerators include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. One type of (G) curing accelerator may be used alone, or two or more types may be used in combination.

[0200] Examples of the phosphorus-based curing accelerator include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrogenhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butyldimethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, and tetraphenylphosphonium tetra-p-tolylborate. aromatic phosphonium salts such as tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone adducts such as triphenylphosphine-p-benzoquinone adduct; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine;Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine aromatic phosphines such as benzene, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether;

[0201] Examples of the urea-based curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. aromatic dimethylureas such as toluene bis(dimethylurea), 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea].

[0202] Examples of guanidine curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide.

[0203] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-methylimidazole. Phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct Examples of imidazole compounds include 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds with epoxy resins. Commercially available imidazole curing accelerators include "1B2PZ," "2E4MZ," "2MZA-PW," "2MZ-OK," "2MA-OK," "2MA-OK-PW," "2PHZ," "2PHZ-PW," "Cl1Z," "Cl1Z-CN," "Cl1Z-CNS," and "C11Z-A" manufactured by Shikoku Chemicals Corporation; and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0204] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organic copper complexes such as copper(II) acetylacetonate, organic zinc complexes such as zinc(II) acetylacetonate, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0205] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc. Commercially available amine curing accelerators may be used, such as "MY-25" manufactured by Ajinomoto Fine-Techno Co., Inc.

[0206] The content of the (G) curing accelerator is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, or 0.05% by mass or more, and is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less, based on 100% by mass of the non-volatile components in the resin composition layer.

[0207] The content of the (G) curing accelerator is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.3% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less, when the resin component in the resin composition layer is taken as 100% by mass.

[0208] -(H) Other additives- The resin composition layer may contain (H) other additives as an optional non-volatile component. Examples of (H) other additives include thermoplastic resins (excluding those corresponding to components (A) to (G)); elastomers (excluding those corresponding to components (A) to (G)); polymerization initiators; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentone and montmorillonite; antifoaming agents such as silicone-based antifoaming agents, acrylic-based antifoaming agents, fluorine-based antifoaming agents, and vinyl resin-based antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; and urea silica. Examples of the additives include adhesion improvers such as oran; adhesion promoters such as triazole-based adhesion promoters, tetrazole-based adhesion promoters, and triazine-based adhesion promoters; antioxidants such as hindered phenol-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers; photopolymerization initiator aids such as tertiary amines; photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones, and thioxanthones; and antioxidants. (H) Other additives may be used alone or in combination of two or more.

[0209] -(I) Solvent- The resin composition layer may further contain (I) a solvent as an optional volatile component in addition to the nonvolatile components (A) to (H) described above. The (I) solvent is typically an organic solvent. Examples of organic solvents include ketone-based solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol-based solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methoxypropion. Examples of suitable solvents include ether ester solvents such as methyl lactate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (I) The solvents may be used singly or in combination of two or more.

[0210] The amount of (I) solvent is not particularly limited, but may be, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or even 0% by mass, relative to 100% by mass of all components of the resin composition layer.

[0211] The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 55 μm or less, from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product with excellent insulating properties even when the cured product of the resin composition layer is thin. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more, 10 μm or more, etc.

[0212] <Protective film> The resin sheet may optionally include a protective film conforming to the support as another layer. The protective film is provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite the support). By laminating the protective film on the resin sheet, adhesion of dust and the like to the surface of the resin composition layer and scratches can be suppressed.

[0213] Examples of the protective film include films made of plastic materials, metal foils, and release papers, with films made of plastic materials and metal foils being preferred.

[0214] When a film made of a plastic material is used as the protective film, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, with inexpensive polyethylene terephthalate being particularly preferred.

[0215] When a metal foil is used as the protective film, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0216] The surface of the protective film that is to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0217] The protective film may also be a protective film with a release layer, which has a release layer on the surface that bonds to the resin composition layer. Examples of the release agent used in the release layer of the protective film with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available protective films with a release layer may be used, including, for example, "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation, "Lumirror T60," "Lumirror R80," and "Lumirror" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Uni-Peel" manufactured by Unitika Limited, which are PET films having a release layer primarily composed of an alkyd resin-based release agent.

[0218] The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. When the protective film has a multi-layer structure such as a protective film with a release layer, it is preferable that the thickness of the entire protective film is in this range.

[0219] <Method of manufacturing resin sheet> The resin sheet can be produced, for example, by preparing a resin varnish by dissolving the components contained in the resin composition layer in a solvent, applying this resin varnish to a support using a die coater or the like, and then drying it to form a resin composition layer.

[0220] The solvent may be the same as the solvent explained as a component of the resin composition layer, and one type of solvent may be used alone, or two or more types may be used in combination.

[0221] Drying may be carried out by heating, blowing hot air, or the like. Drying conditions are not particularly limited, but drying is usually carried out so that the solvent content in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although this varies depending on the boiling point of the solvent in the resin composition layer, for example, when a resin composition containing 30% by mass to 60% by mass of solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0222] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can usually be used by peeling off the protective film.

[0223] <Physical properties of resin sheet> Since the resin composition layer in the resin sheet of the present invention contains a combination of components (A) to (C), the cured product of the resin composition layer exhibits the characteristic of a low dielectric loss tangent. This results in an insulating layer with a low dielectric loss tangent. The dielectric loss tangent of the cured product heat-cured at 190°C for 90 minutes is preferably 0.0050 or less, more preferably 0.0045 or less, even more preferably 0.004 or less, and particularly preferably 0.003 or less. There is no particular restriction on the lower limit, and it can be, for example, 0.0010 or more. The dielectric loss tangent can be measured by the method described in the Examples below.

[0224] Since the resin composition layer in the resin sheet of the present invention contains a combination of components (A) to (C), the cured resin composition layer exhibits the characteristic of a low dielectric constant (relative permittivity). This results in an insulating layer with a low relative permittivity. The relative permittivity of the cured product is preferably 3.6 or less, more preferably 3.5 or less, and even more preferably 3.4 or less. There is no particular lower limit, and it can be, for example, 0.1 or more. The relative permittivity can be measured by the method described in the Examples below.

[0225] The cured product obtained by curing the resin composition layer at 130°C for 30 minutes and then at 170°C for 30 minutes exhibits the property that smears generated during via hole formation are easily removed (excellent smear removability). That is, an insulating layer with good smear removability is obtained. Because of the excellent smear removability, the maximum smear length measured from the wall surface side of the bottom of the via hole is preferably less than 5 μm. The lower limit is not particularly limited, but can be 0.01 μm or more. The smear removability can be measured by the method described in the examples below.

[0226] The cured product obtained by curing the resin composition layer at 180°C for 30 minutes exhibits excellent blister resistance. This results in an insulating layer with excellent blister resistance. Specifically, a resin composition layer containing a resin composition is formed on an inner layer substrate. The resin composition layer is then heated and cured at 180°C for 30 minutes to obtain an insulating layer formed from the cured product. The surface of this insulating layer is subjected to a roughening treatment, including immersion in a swelling solution at 60°C for 5 minutes, immersion in a roughening solution at 80°C for 15 minutes, and immersion in a neutralizing solution at 40°C for 5 minutes. A plated conductor layer is then formed on the surface of the insulating layer using a semi-additive process to obtain an evaluation substrate. This evaluation substrate is then subjected to a test in which it is passed five times through a reflow device ("HAS-6116" manufactured by Nippon Antom Co., Ltd.) that reproduces a solder reflow temperature with a peak temperature of 260°C (the reflow temperature profile conforms to IPC / JEDEC J-STD-020C). This test demonstrates that swelling of the conductor layer is suppressed. For example, when the above test is carried out on five insulating layer samples, the number of samples in which blisters occur can be reduced to preferably two or less, and more preferably zero.

[0227] A cured product obtained by curing a resin composition layer at 130°C for 30 minutes and then at 170°C for 30 minutes exhibits excellent adhesion to the plated conductor layer. This results in an insulating layer with excellent adhesion to the plated conductor layer. The peel strength of the cured product is preferably 0.30 kgf / cm or more, more preferably 0.35 kgf / cm or more, and even more preferably 0.40 kgf / cm or more. There is no particular upper limit, and it can be, for example, 10 kgf / cm or less. The adhesion to the plated conductor layer can be measured by the method described in the Examples below.

[0228] The resin composition is thermally cured at 130°C for 30 minutes, then at 170°C for 30 minutes, and then at 190°C for 90 minutes to produce a cured product that exhibits excellent adhesion to metals such as copper foil (substrate adhesion). This results in an insulating layer with excellent substrate adhesion. The substrate adhesion is preferably 0.5 kgf / cm or more, more preferably 0.6 kgf / cm or more, and even more preferably 0.7 kgf / cm or more. There is no particular upper limit, and it can be, for example, 10 kgf / cm or less. The substrate adhesion can be measured by the method described in the Examples below.

[0229] The resin composition is thermally cured at 130°C for 30 minutes, followed by 30 minutes at 170°C, and the surface of the cured product is then roughened. The roughened surface exhibits a low arithmetic mean roughness (Ra). Therefore, the cured product provides an insulating layer with a low arithmetic mean roughness. The arithmetic mean roughness is preferably 100 nm or less, more preferably 90 nm or less, and even more preferably 80 nm or less. The lower limit of the arithmetic mean roughness is not particularly limited, and may be 1 nm or more. The arithmetic mean roughness (Ra) can be measured by the method described in the Examples below.

[0230] [Semiconductor package substrate and its manufacturing method] The semiconductor chip package of the present invention includes a circuit board and a semiconductor chip mounted on the circuit board, and the circuit board includes an insulating layer formed from a cured product of the resin composition layer in the resin sheet of the present invention. This semiconductor chip package can be produced by bonding the semiconductor chip to the circuit board. The circuit board will be described later.

[0231] The bonding conditions are not particularly limited as long as the terminal electrodes of the semiconductor chip are conductively connected to the circuit wiring of the circuit board, and known conditions used in flip-chip mounting of semiconductor chips may be used. Alternatively, the semiconductor chip and the circuit board may be bonded via an insulating adhesive.

[0232] In a preferred embodiment, the semiconductor chip is pressure-bonded to the circuit board under pressure conditions such as a pressure-bonding temperature in the range of 120°C to 240°C (preferably 130°C to 200°C, more preferably 140°C to 180°C) and a pressure-bonding time in the range of 1 second to 60 seconds (preferably 5 seconds to 30 seconds).

[0233] In another preferred embodiment, the semiconductor chip is bonded to the circuit board by reflow. The reflow conditions can be, for example, in the range of 120°C to 300°C.

[0234] After bonding the semiconductor chip to the circuit board, it is also possible to obtain a semiconductor chip package by, for example, filling the semiconductor chip with a mold underfill material. The method of filling with a mold underfill material can be carried out by a known method.

[0235] The circuit board includes an insulating layer formed from a cured product of the resin composition layer in the resin sheet of the present invention. This circuit board can be produced, for example, by a production method including the following steps (I) and (II). (I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) A step of curing the resin composition layer to form an insulating layer.

[0236] The "inner layer substrate" used in step (I) is a member that will become the substrate of a circuit board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The substrate may have a conductor layer on one or both sides, and this conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit board." Furthermore, intermediate products on which an insulating layer and / or a conductor layer is to be further formed during the production of a circuit board are also included in the aforementioned "inner layer substrate." When the circuit board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0237] The inner layer substrate and the resin sheet can be laminated, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as a "thermocompression bonding member") include a heated metal plate (such as a SUS plate) or a metal roll (such as a SUS roll). Note that rather than pressing the thermocompression bonding member directly onto the resin sheet, it is preferable to press it via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently conform to the surface irregularities of the inner layer substrate.

[0238] The lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure conditions of 26.7hPa or less.

[0239] The lamination can be performed using a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch vacuum pressure laminator.

[0240] After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression conditions for lamination. The smoothing treatment may be performed using a commercially available laminator. Note that lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0241] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0242] In step (II), the resin composition layer is cured to form an insulating layer made of a cured product of the resin composition layer. The resin composition layer is usually cured by thermal curing. Specific curing conditions for the resin composition layer may be those typically used when forming an insulating layer for a printed wiring board.

[0243] For example, the thermal curing conditions for the resin composition layer vary depending on the types of components contained in the resin composition layer, but in one embodiment, the curing temperature is preferably 120° C. to 240° C., more preferably 150° C. to 220° C., and even more preferably 170° C. to 210° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0244] Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C to 150°C, preferably 60°C to 140°C, more preferably 70°C to 130°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0245] When manufacturing a circuit board, the following steps may be further performed: (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer. These steps (III) to (V) may be performed according to various methods known to those skilled in the art and used in manufacturing circuit boards. When the support is removed after step (II), the removal of the support may be performed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). Furthermore, if necessary, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated to form a multilayer wiring board.

[0246] Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be determined appropriately depending on the design of the printed wiring board.

[0247] Step (IV) is a step of roughening the insulating layer. Typically, smear removal is also performed in this step (IV). The roughening treatment procedure and conditions are not particularly limited, and known procedures and conditions commonly used in forming insulating layers for printed wiring boards can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

[0248] Examples of swelling liquids used in the roughening treatment include alkaline solutions and surfactant solutions, with alkaline solutions being preferred. Examples of the alkaline solution include sodium hydroxide solution and potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. Swelling treatment using a swelling liquid can be performed by immersing the insulating layer in the swelling liquid at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in the swelling liquid at 40°C to 80°C for 5 to 15 minutes.

[0249] Examples of oxidizing agents used in the roughening treatment include alkaline permanganate solutions prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. Roughening treatment using an oxidizing agent such as alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigance P" manufactured by Atotech Japan.

[0250] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and a commercially available product such as "Reduction Solution Securigant P" manufactured by Atotech Japan can be cited. Treatment with a neutralizing solution can be carried out by immersing the surface that has been roughened with an oxidizing agent in a neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From the standpoint of workability, a preferred method is to immerse the object that has been roughened with an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0251] In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. There is no particular limitation on the lower limit and it can be, for example, 1 nm or more, 2 nm or more, etc. Furthermore, the root mean square roughness (Rq) of the insulating layer surface after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. There is no particular limitation on the lower limit and it can be, for example, 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

[0252] Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer. Examples of alloy layers include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among these, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

[0253] The conductor layer may have a single layer structure, or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of a nickel-chromium alloy.

[0254] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0255] In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using a conventionally known technique such as a semi-additive method or a full-additive method. From the viewpoint of ease of production, the semi-additive method is preferred. An example of forming a conductor layer using a semi-additive method will be described below.

[0256] First, a plating seed layer is formed on the surface of an insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer, exposing a portion of the plating seed layer corresponding to the desired wiring pattern. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, unnecessary plating seed layer is removed by etching or the like, thereby forming a conductor layer having the desired wiring pattern.

[0257] In another embodiment, the conductor layer may be formed using a metal foil. When a metal foil is used to form the conductor layer, step (V) is preferably performed between steps (I) and (II). For example, after step (I), the support is removed, and a metal foil is laminated on the exposed surface of the resin composition layer. The resin composition layer and the metal foil may be laminated by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Thereafter, a conductor layer having a desired wiring pattern can be formed using the metal foil on the insulating layer by a conventionally known technique such as a subtractive method or a modified semi-additive method.

[0258] The metal foil can be produced by a known method such as an electrolytic method, a rolling method, etc. Examples of commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Smelting Co., Ltd., and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd.

[0259] [Semiconductor Devices] Semiconductor devices that can be equipped with the semiconductor chip package of the present invention include various semiconductor devices used in electrical appliances (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft). [Example]

[0260] The present invention will be described in more detail below with reference to examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Unless otherwise specified, the temperature conditions are room temperature (23°C), and unless otherwise specified, the pressure conditions are atmospheric pressure (1 atm).

[0261] <Synthesis Example 1: Synthesis of polycarbodiimide compound> 100 parts by mass of dicyclohexylmethane-4,4'-diisocyanate (HMDI) and 0.5 parts by mass of 3-methyl-1-phenyl-2-phospholene-1-oxide as a carbodiimidization catalyst were placed in a reaction vessel equipped with a reflux condenser and a stirrer, and the mixture was stirred and mixed under a nitrogen stream at 185°C for 24 hours to carry out a carbodiimidization reaction, yielding an isocyanate-terminated polycarbodiimide. IR spectroscopy of the obtained isocyanate-terminated polycarbodiimide revealed a peak at a wavelength of 2150cm. -1 Absorption peaks due to carbodiimide groups were confirmed before and after the measurement. The terminal NCO content was 8.19 mass %, and the average degree of polymerization of the carbodiimide groups determined by the above measurement method was 3.5.

[0262] Next, 8.8 parts by mass of ethylene glycol monoacrylate was added to the isocyanate-terminated polycarbodiimide at 150°C under a nitrogen stream, and the mixture was heated to 180°C and stirred for 2 hours to react. -1After confirming that the absorption peak of the isocyanate group had disappeared, the reaction product was taken out of the reaction vessel and cooled to room temperature to obtain a pale yellow, transparent, solid polycarbodiimide compound (a radically polymerizable group-containing compound having a carbodiimide structure; the main component is the compound of formula (S1); b' means the average degree of polymerization of the carbodiimide group). [ka]

[0263] <Synthesis Example 2: Synthesis of polycarbodiimide compound> A solid polycarbodiimide compound (a radically polymerizable group-containing compound having a carbodiimide structure; the main component is a compound of formula (S2); b' is the same as above) was obtained in the same manner as in Synthesis Example 1, except that ethylene glycol monoallyl ether was used instead of ethylene glycol monoacrylate. [ka]

[0264] <Synthesis Example 3: Synthesis of polycarbodiimide compound> To the isocyanate-terminated polycarbodiimide obtained in the same manner as in Synthesis Example 1, 8.8 parts by mass of ethylene glycol monoacrylate and 4 parts by mass of polybutadiene having hydroxyl groups at both ends ("G-1000" manufactured by Nippon Soda Co., Ltd., number average molecular weight 1400, 1,2-addition structural unit 85% or more, trans-1,4-addition structural unit 15% or less) were added, and the mixture was heated to 180°C and stirred for 2 hours to react. IR spectroscopy showed a wavelength of 2200 to 2300 cm. -1After confirming that the absorption peak of the isocyanate group in the above had disappeared, the reaction product was removed from the reaction vessel and cooled to room temperature to obtain a pale yellow, transparent, solid polycarbodiimide compound (a radically polymerizable group-containing compound having a carbodiimide structure; the main component is a compound of formula (S3); b' is the same as above. d' means the average degree of polymerization of combined units of polybutadiene and polycarbodiimide. e' means the average degree of polymerization of butadiene units corresponding to the above number average molecular weight. Although only 1,2-addition structural units are shown as e' units, 1,4-addition structural units (cis, trans) are also included). [ka]

[0265] <Synthesis Example 4: Synthesis of Active Ester Resin A> A reaction vessel was charged with 89 parts by mass of ortho-allylphenol, 110 parts by mass of dicyclopentadiene-phenol copolymer resin (softening point 85°C, hydroxyl group equivalent weight approximately 165 g / eq.), and 1,000 parts by mass of toluene. The contents were dissolved under reduced pressure and nitrogen substitution. Subsequently, 135 parts by mass of isophthalic acid chloride was added and dissolved. Next, 0.5 g of tetrabutylammonium bromide was added, and 309 g of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while purging the vessel with nitrogen. The temperature in the system was controlled below 60°C. The mixture was then stirred for 1 hour. After the reaction was complete, the reaction mixture was separated and the aqueous layer was removed. This procedure was repeated until the pH of the aqueous layer reached 7. The toluene and other components were distilled off under heating and reduced pressure, yielding activated ester resin A. The unsaturated bond equivalent of the resulting activated ester resin A was calculated to be 428 g / eq. based on the charge ratio. Active ester resin A is represented by the following formula (Bi), where s is an integer of 0 or 1 or more, and the average value of r calculated from the charge ratio is 1. The wavy line represents a structure obtained by reaction of isophthalic acid chloride with a phenol polyaddition reaction resin and / or ortho-allylphenol. [ka]

[0266] <Synthesis Example 5: Synthesis of maleimide compound A> An MEK solution (62% by mass of non-volatile components) of a maleimide compound synthesized by the method described in Synthesis Example 1 of the Japan Institute of Invention and Innovation's Technical Journal Publication No. 2020-500211 was prepared. This maleimide compound has a structure represented by the following formula (1). [ka]

[0267] <Synthesis Example 6: Synthesis of vinyl resin A> According to Example 1 of WO 2017 / 115813, 3.0 moles (390.6 g) of divinylbenzene, 1.8 moles (229.4 g) of ethylvinylbenzene, 10.2 moles (1066.3 g) of styrene, and 15.0 moles (1532.0 g) of n-propyl acetate were charged into a 5.0 L reactor, and 600 mmol of boron trifluoride diethyl ether complex was added at 70 °C. The reaction was allowed to proceed for 4 hours. After the polymerization solution was terminated with aqueous sodium bicarbonate, the oil layer was washed three times with pure water, and the mixture was devolatilized under reduced pressure at 60 °C to recover the polymer. The resulting product was weighed, confirming that 896.7 g of vinyl resin A was obtained. The Mw of vinyl resin A was 41,300.

[0268] <Production of resin varnish> Each component was weighed out in the number of parts by mass shown in the table below, and then mixed with 10 parts of MEK and 10 parts of cyclohexanone. The mixture was uniformly dispersed using a high-speed rotating mixer to obtain a resin varnish. [Table 1] [Table 2] *1: Indicates the content when the non-volatile components in the resin composition layer are taken as 100% by mass.

[0269] Details of each component listed in the table are as follows: Component (A) Synthesis Example 1: Polycarbodiimide compound synthesized in Synthesis Example 1 Synthesis Example 2: Polycarbodiimide compound synthesized in Synthesis Example 2 Synthesis Example 3: Polycarbodiimide compound synthesized in Synthesis Example 3 (B) Component Active ester resin A: Active ester resin A synthesized in Synthesis Example 4 PC1300-02-65MA: an active ester-based curing agent represented by the following formula (B-ii) (functional group equivalent weight 200 g / eq., toluene solution with nonvolatile content of 62 mass%, manufactured by Air Water Inc.; in the formula, a represents an integer of 1 to 6, and r represents 1 to 10). [ka] Active ester resin B: Active ester resin (m, n≧0) shown in the following structure. Toluene solution with 70% nonvolatile content, functional group equivalent: 250 g / eq. [ka] (C) Component SO-C2: Spherical silica surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0.5 μm, specific surface area 5.8 m 2 / g, manufactured by Admatechs Co., Ltd. Hollow silica A: Spherical silica surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), with an average particle size of 2.6 μm, a porosity of 25% by volume, and a specific gravity of 1.7 g / cm 3 UFP-30: Spherical silica surface-treated with an amine-based alkoxysilane compound (Shin-Etsu Chemical Co., Ltd.'s "KBM573"), with an average particle size of 0.3 μm and a specific surface area of ​​5.8 m 2 / g, manufactured by Denka (D) Component NC-3000-L: Biphenyl type epoxy resin, functional group equivalent weight 269g / eq., manufactured by Nippon Kayaku Co., Ltd. HP-4032-SS: Naphthalene-type epoxy resin, functional group equivalent weight 144g / eq., manufactured by DIC Corporation ZX-1059: 1:1 mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, functional group equivalent weight 169g / eq., manufactured by Nippon Steel Chemical & Material Co., Ltd. (E) Component MIR-3000-70MT: Biphenylaralkyl-type multifunctional maleimide resin, functional group equivalent weight 393g / eq., MEK / toluene mixed solution with non-volatile content of 70%, manufactured by Nippon Kayaku Co., Ltd. SLK-1500-M70: Aliphatic maleimide resin, functional group equivalent weight 752g / eq., toluene solution with 70% non-volatile content, manufactured by Shin-Etsu Chemical Co., Ltd. Maleimide compound A: The maleimide compound synthesized in Synthesis Example 5 OPE-2St: Styrene-modified polyphenylene ether resin, toluene solution with 65% non-volatile content, manufactured by Mitsubishi Gas Chemical Co., Ltd. Vinyl resin A: Vinyl resin synthesized in Synthesis Example 6 (F) Component LA-3018-50P: Phenolic curing agent, functional group equivalent weight 151g / eq, non-volatile content 50% by mass, 1-methoxy-2-propanol solution, manufactured by DIC Corporation V-03: Carbodiimide curing agent, functional group equivalent weight 216g / eq., toluene solution with non-volatile content of 50% by mass, manufactured by Nisshinbo Chemical Inc. HPC-8000-65T: Active ester curing agent containing dicyclopentadiene-type diphenol structure, functional group equivalent weight 223 g / eq., toluene solution with 65% non-volatile content, manufactured by DIC Corporation (G) Component 1B2PZ: Shikoku Chemicals Corporation

[0270] <Preparation of Resin Sheet A Having a Resin Composition Layer Thickness of 40 μm> A polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness 38 μm) with a release layer was prepared as a support. The resin varnishes obtained in the Examples and Comparative Examples were uniformly applied onto the release layer of this support so that the thickness of the resin composition layer after drying would be 40 μm. Thereafter, the resin composition layer was dried at 80°C to 100°C (average 90°C) for 2 minutes to obtain a resin sheet including the support and the resin composition layer.

[0271] <Measurement of dielectric constant and dielectric loss tangent> (1) Preparation of the cured product Resin sheet A was cured for 90 minutes in an oven at 190° C. The resin sheet was taken out of the oven and the support was peeled off to obtain a cured resin composition layer.

[0272] (2) Measurement of dielectric constant and dielectric loss tangent The cured product was cut into a piece of 80 mm long and 2 mm wide, and the dielectric constant and dielectric loss tangent (Dk and Df values) were measured using an Agilent Technologies HP8362B by the cavity resonance perturbation method at a measurement frequency of 5.8 GHz and measurement temperatures of 23°C and 90°C. Measurements were performed on two test pieces, and the average was calculated.

[0273] <Evaluation of smear removal> (1) Surface preparation for interior substrates A glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness: 18 μm, substrate thickness: 0.8 mm, Panasonic "R1515A") was prepared as the inner layer substrate. The copper foil on the surface of this inner layer substrate was roughened by etching using a microetching agent (MEC "CZ8101") to remove 1 μm of copper. The substrate was then dried at 190°C for 30 minutes.

[0274] (2) Lamination and curing of resin sheet A Resin sheet A was laminated onto both sides of the inner layer substrate using a batch-type vacuum pressure laminator (a two-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) so that the resin composition layer was bonded to the inner layer substrate. This lamination was performed by reducing the pressure for 30 seconds to 13 hPa or less, and then pressing at a temperature of 100°C and a pressure of 0.74 MPa for 30 seconds.

[0275] The laminated resin sheet was then heat-pressed at atmospheric pressure at 100°C under a pressure of 0.5 MPa for 60 seconds to smooth it, and then placed in a 130°C oven and heated for 30 minutes, and then transferred to a 170°C oven and heated for 30 minutes.

[0276] (3) Formation of via holes Using a CO2 laser processing machine (LK-2K212 / 2C) manufactured by Via Mechanics, the insulating layer was processed under the conditions of a frequency of 2000 Hz, a pulse width of 3 μs, an output of 0.95 W, and a shot count of 3, to form via holes with a top diameter of 50 μm on the insulating layer surface and a diameter of 40 μm on the insulating layer bottom surface. After that, the support was peeled off.

[0277] (4) Roughening treatment The inner layer substrate was immersed in a swelling solution, Swelling Dip Securiganth P (manufactured by Atotech Japan), at 60°C for 10 minutes. Next, it was immersed in a roughening solution, Concentrate Compact P (aqueous solution of KMnO4: 60 g / L, NaOH: 40 g / L) (manufactured by Atotech Japan), at 80°C for 20 minutes. Finally, it was immersed in a neutralizing solution, Reduction Solution Securiganth P (manufactured by Atotech Japan), at 40°C for 5 minutes. The resulting substrate was designated evaluation substrate A.

[0278] (5) Evaluation of residue at the bottom of via holes The periphery of the bottom of the via hole was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the bottom of the via hole was measured from the obtained image and evaluated according to the following criteria. ○: Maximum smear length is less than 3 μm △: Maximum smear length is 3 μm or more and less than 5 μm ×: Maximum smear length is 5 μm or more

[0279] <Evaluation of peel strength> (1) Preparation of inner layer board Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic "R1515A") with an inner layer circuit formed on it were etched 1 μm deep with a microetching agent (MEC "CZ8101") to roughen the copper surface.

[0280] (2) Lamination of resin sheet A Using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., two-stage build-up laminator "CVP700"), resin sheet A was laminated onto both sides of the inner layer substrate so that the resin composition layer was in contact with the inner layer substrate. Lamination was performed by reducing the pressure for 30 seconds to 13 hPa or less, followed by pressure bonding at 120°C and a pressure of 0.74 MPa for 30 seconds. Next, a heat press was performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

[0281] (3) Thermal curing of the resin composition layer The inner layer substrate laminated with resin sheet A was then placed in an oven at 130°C and heated for 30 minutes, and then transferred to an oven at 170°C and heated for 30 minutes to thermally cure the resin composition layer and form an insulating layer. The support was then peeled off to obtain cured substrate A having the insulating layer, inner layer substrate, and insulating layer in this order.

[0282] (4) Roughening treatment A desmear treatment as a roughening treatment was performed on the cured substrate A. The desmear treatment was the following wet desmear treatment.

[0283] Cured substrate A was immersed in a swelling solution (Atotech Japan's "Swelling Dip Securigant P," an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, then in an oxidizing solution (Atotech Japan's "Concentrate Compact CP," an aqueous solution of approximately 6% potassium permanganate and 4% sodium hydroxide) at 80°C for 15 minutes, and then in a neutralizing solution (Atotech Japan's "Reduction Solution Securigant P," an aqueous sulfuric acid solution) at 40°C for 5 minutes, followed by drying at 80°C for 15 minutes. The resulting substrate is referred to as "Evaluation Substrate A."

[0284] (5) Formation of the conductor layer A conductor layer was formed on the roughened surface of the insulating layer using a semi-additive process. Specifically, the roughened substrate was immersed in an electroless plating solution containing PdCl2 at 40°C for 5 minutes, and then in an electroless copper plating solution at 25°C for 20 minutes. Next, the substrate was heated at 150°C for 30 minutes for annealing, after which an etching resist was formed and a pattern was formed by etching. Copper sulfate electroplating was then performed to form a 30 μm-thick conductor layer, which was then annealed at 200°C for 60 minutes. The resulting substrate is referred to as "Evaluation Substrate B."

[0285] (6) Measurement of peel strength of plated conductor layer The peel strength between the insulating layer and the plated conductor layer was measured in accordance with the Japanese Industrial Standard (JIS C6481). Specifically, a 10 mm wide, 100 mm long cut was made in the conductor layer of evaluation board B, one end of the cut was peeled off and gripped with a gripper. The peel strength was determined by measuring the load (kgf / cm) when 35 mm was peeled off vertically at a rate of 50 mm / min at room temperature. A tensile tester (TSE "AC-50C-SL") was used for the measurement.

[0286] <Measurement of substrate adhesion> Resin sheet A was laminated on a copper foil (Mitsui Mining & Smelting Co., Ltd., 3EC-III, thickness 35 μm) whose glossy side had been surface-treated (CZ8401 and AP3006 manufactured by MEC Co., Ltd., and alkali-treated) using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., two-stage build-up laminator "CVP700") so that the resin composition layer was in contact with the copper foil. After peeling off the PET, the laminate was laminated using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., two-stage build-up laminator CVP700) onto a glass cloth-based epoxy resin double-sided copper-clad laminate with an inner layer circuit (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic Corporation, R1515A, both sides of which had been etched 1 μm with a micro-etching agent (Mec Corporation, CZ8101) to roughen the copper surface), and then heated in an oven at 130°C for 30 minutes, then at 170°C for 30 minutes, and finally at 190°C for 90 minutes to prepare a sample.

[0287] The prepared sample was cut into small pieces measuring 150 x 30 mm. A cutter was used to make a 10 mm wide and 100 mm long cut in the copper foil portion of the small piece, and one end of the copper foil was peeled off and gripped with a gripper (TSE AC-50C-SL). The load [kgf / cm] when 35 mm was peeled off vertically at room temperature at a rate of 50 mm / min was measured using an Instron universal testing machine in accordance with JIS C6481.

[0288] <Evaluation of blister resistance> (1) Lamination of resin sheet A Resin sheet A was laminated using a batch-type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Co., Ltd.) so that the resin composition layer was in contact with both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate ("R5715ES" manufactured by Panasonic Corporation, 0.7 mm thick, 255 mm square). This lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, and then pressing for 30 seconds at 100°C and a pressure of 0.74 MPa.

[0289] (2) Curing of the resin composition layer The support was peeled off from the laminated resin sheet A. The resin composition layer was then thermally cured at 180°C for 30 minutes to form an insulating layer. This resulted in a "laminated substrate A" having an insulating layer, a laminate, and another insulating layer in this order.

[0290] (3) Roughening treatment The surface of the insulating layer of the prepared laminated substrate A was immersed in a swelling solution (Swelling Dip Securigand P containing diethylene glycol monobutyl ether, manufactured by Atotech Japan) at 60°C for 5 minutes, then in a roughening solution (Concentrate Compact P (aqueous solution of KMnO4: 60 g / L, NaOH: 40 g / L) manufactured by Atotech Japan) at 80°C for 15 minutes, and then in a neutralizing solution (Reduction Showreusin Securigand P manufactured by Atotech Japan) at 40°C for 5 minutes to obtain "roughened substrate B."

[0291] (4) Semi-additive plating To form a circuit on the surface of the insulating layer, the roughened substrate B was immersed in an electroless plating solution containing PdCl2, and then in an electroless copper plating solution. After annealing by heating at 150°C for 30 minutes, an etching resist was formed, and a pattern was formed by etching. Copper sulfate electroplating was then performed to form a conductor layer with a thickness of 30±5 μm. Next, annealing was performed at 180°C for 60 minutes. This resulted in "Evaluation Substrate C," a circuit board with a conductor layer on an insulating layer.

[0292] (5) Evaluation of blisters during the reflow process Evaluation board C was cut into small pieces measuring 100 mm x 50 mm. These small pieces were then subjected to a test in which they were passed five times through a reflow device ("HAS-6116" manufactured by Nippon Antom Co., Ltd.) that reproduces a solder reflow temperature of 260°C peak temperature (the reflow temperature profile conforms to IPC / JEDECJ-STD-020C). The above test was performed on five small pieces, and the small pieces were visually observed after the test. The results of the visual observation were evaluated according to the following criteria. ○: No abnormalities at all in any of the pieces. △: One or two small pieces with abnormalities such as swelling in the conductive layer. ×: Three or more small pieces have abnormalities such as swelling in the conductor layer.

[0293] <Measurement of arithmetic mean roughness (Ra)> The arithmetic mean roughness Ra of the surface of the insulating layer of evaluation substrate A prepared in the above <Evaluation of peel strength> was measured. Measurements were made using a non-contact surface roughness meter (WYKO NT3300 manufactured by Veeco Instruments) in VSI mode with a 50x lens, with a measurement range of 121 μm × 92 μm. This measurement was made at 10 measurement points, and the average values ​​are shown in the table below.

[0294] [Table 3] [Table 4]

Claims

1. A support and a resin composition layer provided on the support, The resin composition layer comprises: (A) a radical polymerizable group-containing compound having a carbodiimide structure; A resin sheet for forming an insulating layer of a semiconductor package substrate, comprising (B) a radical polymerizable group-containing active ester curing agent, and (C) an inorganic filler.

2. The resin sheet for forming an insulating layer of a semiconductor package substrate according to claim 1 , further comprising (D) an epoxy resin.

3. 2. The resin sheet for forming an insulating layer of a semiconductor package substrate according to claim 1, wherein the content of the component (A) is 0.1% by mass or more and 10% by mass or less, when the resin component of the resin composition layer is 100% by mass.

4. 2. The resin sheet for forming an insulating layer of a semiconductor package substrate according to claim 1, wherein the content of the component (B) is 10% by mass or more and 55% by mass or less, when the resin component of the resin composition layer is 100% by mass.

5. 2. The resin sheet for forming an insulating layer of a semiconductor package substrate according to claim 1, wherein the content of the component (C) is 60% by mass or more and 90% by mass or less, when the non-volatile components of the resin composition layer are 100% by mass.

6. A semiconductor chip package substrate comprising an insulating layer made of a cured product of the resin composition layer of the resin sheet for forming an insulating layer of a semiconductor package substrate according to any one of claims 1 to 5.

7. A semiconductor device comprising the semiconductor chip package substrate according to claim 6.

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