Method for manufacturing resin sheet and printed wiring board

Abstract

To provide a resin sheet which has a resin composition layer from which a cured product that maintains or improves dielectric characteristics and is excellent in conductor adhesion and mechanical characteristics is given, and a method for manufacturing a printed wiring board.SOLUTION: A resin sheet has a support, and a resin composition layer provided on the support, wherein the resin composition layer contains (A) a benzocyclobutene resin, (B) an inorganic filler and (C) a radical polymerizable resin, the resin composition layer has an oxygen transmission rate α measured when cured under the conditions of 220°C and 90 minutes of 70 cc / m2 day or less, the resin sheet has an oxygen transmission rate β measured when cured under the conditions of 220°C and 90 minutes of 40 cc / m2 day or less, and the oxygen transmission rate α and the oxygen transmission rate β are measurement values measured according to JIS K 7126-2:2006 (equal pressure method) under the atmosphere of 23°C and 0%RH.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a resin sheet and a printed wiring board, and further to a printed wiring board and a semiconductor device obtained by using a resin composition layer of the resin sheet. [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. As an insulating material for printed wiring boards used for such insulating layers, for example, a resin composition disclosed in Patent Document 1 is known. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2005-220270 A Summary of the Invention [Problem to be solved by the invention]

[0004] Resins having benzocyclobutene groups (hereinafter simply referred to as "benzocyclobutene resins") are known as curable resins used in insulating materials. Since the benzocyclobutene group is a reactive functional group with low polarity, the cured product of the benzocyclobutene resin generally has excellent dielectric properties.

[0005] However, the inventors have found through their investigations that a cured resin composition layer containing a benzocyclobutene resin may have poor adhesion to a conductor material (e.g., copper) (hereinafter also referred to as "conductor adhesion") and mechanical properties.

[0006] An object of the present invention is to provide a method for producing a resin sheet and a printed wiring board having a resin composition layer which provides a cured product having excellent dielectric properties, adhesion to a conductor, and mechanical properties. [Means for solving the problem]

[0007] Means for Solving the Problems The present inventors have conducted intensive research to solve the above problems, and as a result have found that the above problems can be solved by a resin sheet comprising a support and a resin composition layer, in which the resin composition layer contains (A) a benzocyclobutene resin in combination with (B) an inorganic filler and (C) a radically polymerizable resin, and by adjusting the oxygen permeability of the resin composition layer or the resin sheet after curing to a specific numerical value or less, thereby completing the present invention.

[0008] That is, the present invention includes the following. [1] A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition layer containing (A) a benzocyclobutene resin, (B) an inorganic filler, and (C) a radical polymerizable resin, the resin composition layer having an oxygen permeability α of 70 cc / m when cured at 220°C for 90 minutes. 2 ·day or less, and the resin sheet has an oxygen permeability β of 40 cc / m2 or less when cured at 220°C for 90 minutes. 2 ·day or less, where the oxygen permeability α and the oxygen permeability β are values ​​measured in an atmosphere of 23°C and 0% RH in accordance with JIS K7126-2:2006 (isobaric method). [2] The resin sheet according to [1], wherein the content of the (B) component is 30% by mass or more and 80% by mass or less, when the total amount of non-volatile components in the resin composition is 100% by mass. [3] The resin sheet according to [1] or [2], wherein the content of the component (A) is 3% by mass or more and 40% by mass or less, when the total amount of non-volatile components in the resin composition is 100% by mass. [4] The resin sheet according to any one of [1] to [3], wherein the component (A) contains a compound having two or more benzocyclobutene groups in the molecule, and the component (A) has a number average molecular weight (Mn) of 2000 or less. [5] The resin sheet according to any one of [1] to [4], wherein the component (C) is at least one resin selected from the group consisting of a maleimide resin, a (meth)acrylic resin, and a styryl resin. [6] The resin sheet according to any one of [1] to [5], wherein the support is selected from a single-layer resin film, a multi-layer resin film, a metal foil, a release paper, and a composite film containing a supporting substrate and a metal foil. [7] The resin sheet according to any one of [1] to [6], wherein the component (A) has a siloxane skeleton. [8] The resin sheet according to any one of [1] to [7], wherein the component (A) contains a compound represented by the following formula (A-2): [ka] (In formula (A-2), R 1 represents a divalent aliphatic group having an unsaturated bond, R 2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an arylalkyl group, or an aryl group; R A1 represents an alkyl group, a cyano group, or a halogen atom, R A2 represents an alkyl group, a trialkylsilyl group, an alkoxy group, or a halogen atom, nA1 represents an integer of 0 to 2, nA2 represents an integer of 0 to 3, nA4 represents an integer of 1 to 10. 1 , R 2 , R A1 and R A2 Each of R may independently have a substituent. 1 may be the same or different, and there may be multiple R 2 may be the same or different, R A1 When there are multiple, they may be the same or different, and R A2 If there are multiple, they may be the same or different.) [9] The resin sheet according to any one of [1] to [8], wherein the component (A) contains a compound represented by the following formula: [ka]

[10] The resin sheet according to any one of [1] to [9], wherein the resin composition layer has a dielectric constant of 3.0 or less after curing.

[11] The resin sheet according to any one of [1] to

[10] , wherein the cured product of the resin composition layer has a dielectric tangent value of 0.0030 or less.

[12] The resin sheet according to any one of [1] to

[11] , wherein one surface of the cured product of the resin composition layer is exposed when the oxygen permeability β is measured.

[13] The resin sheet according to any one of [1] to

[12] , which is for use as an insulating layer in a printed wiring board.

[14] A method for manufacturing a printed wiring board, comprising: The following process: (1) a step of preparing a resin sheet including a support and a resin composition layer provided on the support, one side of the resin composition layer being exposed; (2) laminating the resin sheet on a substrate of the printed wiring board such that the resin composition layer is laminated on the substrate; and (3) A step of curing the resin sheet laminated on the substrate in a state in which the support is not peeled off from the resin composition layer. Including, the resin composition layer contains (A) a benzocyclobutene resin, (B) an inorganic filler, and (C) a radical polymerizable resin, The resin composition layer is When cured at 220℃ for 90 minutes, the oxygen permeability α is 70cc / m 2 ·day or less, The resin sheet in which one surface of the resin composition layer is exposed is When cured at 220℃ for 90 minutes, the oxygen permeability β is 40cc / m 2 ·day or less, Here, the oxygen permeability α and the oxygen permeability β are measured in accordance with JIS K7126-2:2006 (isobaric method) under an atmosphere of 23°C and 0% RH. A method for manufacturing a printed wiring board. Effect of the Invention

[0009] According to the present invention, it is possible to provide a method for producing a resin sheet and a printed wiring board having a resin composition layer which provides a cured product having excellent dielectric properties, adhesion to a conductor, and mechanical properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] <Terminology explanation> As used herein, the term "optionally substituted" in reference to a compound or group means both the case where none of the hydrogen atoms of the compound or group are substituted with a substituent, and the case where some or all of the hydrogen atoms of the compound or group are substituted with a substituent.

[0011] In this specification, unless otherwise specified, the term "substituent" means a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a monovalent heterocyclic group, an alkylidene group, an amino group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, and an oxo group.

[0012] Examples of the halogen atom used as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0013] The alkyl group used as a substituent may be either linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 14, still more preferably 1 to 12, still more preferably 1 to 6, and particularly preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

[0014] The number of carbon atoms in the cycloalkyl group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and further preferably 3 to 6. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0015] The alkoxy group used as a substituent may be either linear or branched. The number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, and a decyloxy group.

[0016] The number of carbon atoms in the cycloalkyloxy group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and further preferably 3 to 6. Examples of the cycloalkyloxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

[0017] The aryl group used as a substituent is a group in which one hydrogen atom on an aromatic ring has been removed from an aromatic hydrocarbon. The number of carbon atoms in the aryl group used as a substituent is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.

[0018] The number of carbon atoms in the aryloxy group used as a substituent is preferably 6 to 24, more preferably 6 to 18, further preferably 6 to 14, and further more preferably 6 to 10. Examples of the aryloxy group used as a substituent include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group.

[0019] The number of carbon atoms in the arylalkyl group used as a substituent is preferably 7 to 25, more preferably 7 to 19, further preferably 7 to 15, and further preferably 7 to 11. Examples of the arylalkyl group include phenyl-C1 to C4 12 Alkyl groups, naphthyl-C1-C 12 Alkyl groups and anthracenyl-C1-C 12 Examples of such groups include alkyl groups.

[0020] The number of carbon atoms in the arylalkoxy group used as a substituent is preferably 7 to 25, more preferably 7 to 19, further preferably 7 to 15, and further preferably 7 to 11. Examples of the arylalkoxy group include phenyl-C1-C 12 Alkoxy groups and naphthyl-C1-C 12 Examples of the alkyl group include alkoxy groups.

[0021] The monovalent heterocyclic group used as a substituent refers to a group in which one hydrogen atom has been removed from a heterocyclic ring of a heterocyclic compound. The number of carbon atoms in the monovalent heterocyclic group is preferably 3 to 21, more preferably 3 to 15, and even more preferably 3 to 9. The monovalent heterocyclic group also includes a monovalent aromatic heterocyclic group (heteroaryl group). Examples of the monovalent heterocyclic ring include a thienyl group, a pyrrolyl group, a furanyl group, a furyl group, a pyridyl group, a pyridazinyl group, a pyrimidyl group, a pyrazinyl group, a triazinyl group, a pyrrolidyl group, a piperidyl group, a quinolyl group, and an isoquinolyl group.

[0022] The alkylidene group used as a substituent refers to a group in which two hydrogen atoms have been removed from the same carbon atom of an alkane. The number of carbon atoms in the alkylidene group is preferably 1 to 20, more preferably 1 to 14, even more preferably 1 to 12, still more preferably 1 to 6, and particularly preferably 1 to 3. Examples of the alkylidene group include a methylidene group, an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, a sec-butylidene group, an isobutylidene group, a tert-butylidene group, a pentylidene group, a hexylidene group, a heptylidene group, an octylidene group, a nonylidene group, and a decylidene group.

[0023] The acyl group used as a substituent refers to a group represented by the formula: -C(=O)-R (wherein R is an alkyl group or an aryl group). The alkyl group represented by R may be either linear or branched. Examples of the aryl group represented by R include a phenyl group, a naphthyl group, and an anthracenyl group. The number of carbon atoms in the acyl group is preferably 2 to 20, more preferably 2 to 13, and even more preferably 2 to 7. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, and a benzoyl group.

[0024] The acyloxy group used as a substituent refers to a group represented by the formula: -OC(=O)-R (wherein R is an alkyl group or an aryl group). The alkyl group represented by R may be either linear or branched. Examples of the aryl group represented by R include a phenyl group, a naphthyl group, and an anthracenyl group. The number of carbon atoms in the acyloxy group is preferably 2 to 20, more preferably 2 to 13, and even more preferably 2 to 7. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, and a benzoyloxy group.

[0025] The above-mentioned substituents may further have a substituent (hereinafter, sometimes referred to as a "secondary substituent"). Unless otherwise specified, the secondary substituent may be the same as the above-mentioned substituent.

[0026] In this specification, the term "aromatic ring" refers to a ring that follows the Huckel rule, in which the number of electrons in the π-electron system of the ring is 4n+2 (n is a natural number), and includes a monocyclic aromatic ring and a fused aromatic ring in which two or more monocyclic aromatic rings are fused together. The aromatic ring may be a carbocyclic ring or a heterocyclic ring. Examples of the aromatic ring include monocyclic aromatic rings such as a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring; fused rings in which two or more monocyclic aromatic rings are fused, such as a naphthalene ring, an anthracene ring, a benzofuran ring, an isobenzofuran ring, an indole ring, an isoindole ring, a benzothiophene ring, a benzimidazole ring, an indazole ring, a benzoxazole ring, a benzisoxazole ring, a benzothiazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, an acridine ring, a quinazoline ring, a cinnoline ring, and a phthalazine ring; and fused rings in which one or more monocyclic aromatic rings are fused to one or more monocyclic non-aromatic rings, such as an indane ring, a fluorene ring, and a tetralin ring.

[0027] In the present specification, the term "non-aromatic ring" means a ring other than an aromatic ring, and includes a monocyclic non-aromatic ring and a fused non-aromatic ring in which two or more monocyclic non-aromatic rings are fused. The non-aromatic ring may be a carbocyclic ring or a heterocyclic ring. The non-aromatic ring may be a saturated ring or an unsaturated ring. Examples of the non-aromatic ring include a cycloalkane ring; a cycloalkene ring; a monocyclic non-aromatic heterocyclic ring (preferably 3 to 10 members) such as a pyrrolidine ring, a tetrahydrofuran ring, a dioxane ring, or a tetrahydropyran ring; and a bicyclic or higher fused non-aromatic carbocyclic ring (preferably 8 to 15 members) such as a norbornane ring, a decalin ring, an adamantane ring, or a tetrahydrodicyclopentadiene ring.

[0028] The present invention will be described in detail below with reference to preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be modified and implemented as desired without departing from the scope of the claims of the present invention and their equivalents.

[0029] [Resin sheet] The resin sheet of the present invention comprises a support and a resin composition layer provided on the support, the resin composition layer containing (A) a benzocyclobutene resin, (B) an inorganic filler, and (C) a radical polymerizable resin. The resin composition layer in the resin sheet of the present invention has an oxygen permeability α of 70 cc / m when cured at 220° C. for 90 minutes. 2 ·day or less, and the resin sheet has an oxygen permeability β of 40cc / m2 when cured at 220°C for 90 minutes. 2 ·day or less. Here, the oxygen permeability α and the oxygen permeability β are values ​​measured in an atmosphere of 23°C and 0% RH in accordance with JIS K7126-2:2006 (constant pressure method).

[0030] Benzocyclobutene resin generates an isomeric diene (orthoquinodimethane) by heating, and this diene can be cured by undergoing a Diels-Alder type cycloaddition reaction. Since functional groups with high polarity such as hydroxyl groups are not generated by the curing reaction, benzocyclobutene resin is expected to produce a cured product with excellent dielectric properties. However, according to the study by the present inventors, when a cured product (insulating layer) is formed from a resin composition containing such a benzocyclobutene resin, it was found that the conductor adhesion and mechanical properties may be poor. Regarding the above reaction of benzocyclobutene resin, in addition to requiring high temperatures, its reactivity is poor in the presence of oxygen, so that it is presumed that the thermal history and the difficulty in obtaining the desired crosslinking or crosslinking degree are influenced by the above. In contrast, according to the resin sheet of the present invention, which contains benzocyclobutene resin in combination with an inorganic filler and a radical polymerizable resin, and has an oxygen permeability as a resin composition layer and an oxygen permeability as a resin sheet in a specific range after curing, a cured product with excellent conductor adhesion and mechanical properties can be produced. Moreover, the resin sheet of the present invention, which satisfies the above-mentioned specific composition and oxygen permeability conditions, can provide a cured product with improved dielectric properties such as dielectric constant and dielectric loss tangent. Furthermore, the present inventors have found that the resin sheet of the present invention also improves insulation. Thus, the present invention maintains or even improves the inherent advantage of excellent dielectric properties of benzocyclobutene resin, and realizes a cured product with good conductor adhesion, mechanical properties, and insulation properties, which significantly contributes to the recent demand for high-speed transmission.

[0031] As described above, the resin sheet of the present invention comprises a support and a resin composition layer provided on the support, and is characterized in that the resin composition layer contains a combination of (A) a benzocyclobutene resin, (B) an inorganic filler, and (C) a radically polymerizable resin, and that after curing, the oxygen permeability α of the resin composition layer and the oxygen permeability β of the resin sheet are within specific ranges.

[0032] The support and the resin composition layer will be described in detail later, but first, the oxygen permeabilities α and β will be described.

[0033] -Oxygen permeability α- The oxygen permeability α relates to the oxygen permeability of the resin composition layer after curing. The resin composition layer in the resin sheet of the present invention has an oxygen permeability α of 70 cc / m when cured at 220° C. for 90 minutes. 2 ·day or less.

[0034] From the viewpoint of providing a cured product having excellent dielectric properties, conductor adhesion and mechanical properties, the oxygen permeability α is preferably 68 cc / m 2 ·day or less, preferably 66cc / m 2 ·day or less or 65cc / m 2 ·day or less. The lower limit of the oxygen permeability α is not particularly limited, but is usually 1 cc / m 2 ·day or more, 5cc / m 2 ·day or more, 10cc / m 2 It can be more than one day, etc.

[0035] The oxygen permeability α can be measured according to the procedure described in the <Oxygen Permeability Measurement> section below, and is measured on the resin composition layer with both main surfaces exposed after curing under conditions of 220°C for 90 minutes. Therefore, when measuring the oxygen permeability α, both surfaces of the cured resin composition layer are exposed. The oxygen permeability α can be adjusted by changing the composition, thickness, etc. of the resin composition layer. It is preferable to cure the resin composition layer together with the support.

[0036] -Oxygen permeability β- The oxygen permeability β relates to the oxygen permeability of the resin sheet after curing. The resin sheet of the present invention has an oxygen permeability β of 40 cc / m when cured at 220° C. for 90 minutes. 2 ·day or less.

[0037] From the viewpoint of providing a cured product having excellent dielectric properties, conductor adhesion and mechanical properties, the oxygen permeability β is preferably 38 cc / m 2 ·day or less, preferably 36cc / m 2·day or less, 35cc / m 2 ·day or less, 35cc / m 2 ·day or less, 34cc / m 2 ·day or less, 32cc / m 2 ·day or less or 30cc / m 2 ·day or less. The lower limit of the oxygen permeability β is not particularly limited, and is 0 cc / m 2 ·day may be used.

[0038] The oxygen permeability β can be measured according to the procedure described in the <Oxygen Permeability Measurement> section below, and is measured on the resin sheet after curing at 220°C for 90 minutes. When measuring the oxygen permeability β on a resin sheet with a protective film, the protective film is peeled off to measure the resin sheet having a resin composition layer (cured product) with one side exposed. Therefore, when measuring the oxygen permeability β, one side of the cured product of the resin composition layer is exposed. The oxygen permeability β can be adjusted by changing the composition and thickness of the resin composition layer, the composition, type and thickness of the support, etc.

[0039] From the viewpoint of obtaining a cured product having excellent dielectric properties, conductor adhesion, and mechanical properties, it is important that both the oxygen permeabilities α and β satisfy the above conditions. If only one of the oxygen permeabilities α and β satisfies the above conditions, the effect of the present invention cannot be obtained.

[0040] The support, resin composition layer, and the like used in the resin sheet of the present invention will be described below.

[0041] <Support> The support is not particularly limited as long as the above-mentioned condition of oxygen permeability β is achieved in combination with the resin composition layer described later. The support is preferably selected from, for example, a single-layer resin film, a multi-layer resin film, a metal foil, a release paper, and a composite film containing a support substrate and a metal foil.

[0042] The single-layer resin film may be a single-layer film made of a plastic material, such as polyesters, such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate (PC), acrylics, such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide.

[0043] The multi-layer resin film may be a multi-layer film obtained by integrally stacking one or more types selected from the above-mentioned examples of single-layer resin films. The multi-layer resin film may have other materials interposed between the two mutually overlapping single-layer resin films. Examples of the other materials interposed include inorganic fillers, acid scavengers, desiccants, ultraviolet absorbers, etc.

[0044] Examples of the metal foil include copper foil, aluminum foil, etc. As the copper foil, a foil made of a single metal, copper, or a foil made of an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0045] In a composite film including a supporting substrate and a metal foil, the supporting substrate is not particularly limited as long as it can support the metal foil, and examples thereof include a resin film, a metal film, and the like. Examples of the resin film used as the supporting substrate include the above-mentioned single-layer or multi-layer resin film, and examples of the metal film used as the supporting substrate include films made of metals such as copper, aluminum, stainless steel, titanium, and copper alloys. In addition, in the composite film, the material of the metal foil is preferably, for example, copper foil or copper alloy foil. The composite film may include a release layer between the supporting substrate and the metal foil. The release layer is not particularly limited as long as it can peel the metal foil from the supporting substrate, and examples thereof include an alloy layer of an element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, and P; an organic coating, and the like. In the resin sheet of the present invention, when a composite film is used as a support, the resin composition layer may be provided on the metal foil or on the supporting substrate. When the resin composition layer is provided on the metal foil, it is beneficial because the conductor layer can be formed using the metal foil. In the composite film, the exposed surface of the metal foil is preferably subjected to a roughening treatment, which allows for good fixation of the cured resin composition layer formed on the upper surface.

[0046] The support may be subjected to a matte treatment, corona treatment, or antistatic treatment on one or both surfaces thereof. Such a treated surface is usually formed on the surface that will be bonded to the resin composition layer.

[0047] The support may also have a release layer on one or both sides. The release agent used in the release layer may be, for example, one or more selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. The support with the release layer may be a commercially available product, such as "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, "Purex" manufactured by Teijin Limited, and "Unipeel" manufactured by Unitika Limited, which are PET films having a release layer mainly composed of an alkyd resin-based release agent.

[0048] The thickness of the support is not particularly limited as long as the above-mentioned oxygen permeability β condition is achieved in combination with the resin composition layer described later. The suitable thickness varies depending on the type of support, but is preferably 5 μm or more, more preferably 8 μm or more, 10 μm or more, 12 μm or more, 14 μm or more, or 15 μm or more, and even more preferably 20 μm or more, 25 μm or more, 30 μm or more, or 35 μm or more, and the upper limit is preferably 150 μm or less, more preferably 140 μm or less, 120 μm or less, 100 μm or less, or 80 μm or less. In addition, when using a support with a release layer, it is preferable that the thickness of the entire support with a release layer is within the above range.

[0049] <Resin composition layer> In the resin sheet of the present invention, the resin composition layer contains (A) a benzocyclobutene resin, (B) an inorganic filler, and (C) a radical polymerizable resin.

[0050] As described above, the resin sheet of the present invention has a resin composition layer that contains a combination of (A) a benzocyclobutene resin, (B) an inorganic filler, and (C) a radically polymerizable resin, and satisfies both of the conditions for oxygen permeability α and β described above, thereby making it possible to realize a cured product that exhibits excellent dielectric properties, as well as excellent adhesion to a conductor and mechanical properties.

[0051] The resin composition constituting the resin composition layer will be described below.

[0052] The resin composition constituting the resin composition layer contains (A) a benzocyclobutene resin, (B) an inorganic filler, and (C) a radical polymerizable resin. The resin composition may further contain one or more components selected from (D) a thermoplastic resin, (E) a curing accelerator, an epoxy resin, an epoxy resin curing agent, other additives, and an organic solvent.

[0053] -(A) Benzocyclobutene resin- In the present invention, the resin composition contains a benzocyclobutene resin as component (A). This makes it possible to obtain a cured product (insulating layer) with excellent dielectric properties. The component (A) may be used alone or in combination of two or more kinds.

[0054] The structure of the (A) component is not particularly limited as long as it contains a benzocyclobutene group that can generate an isomeric diene by heating. In order to provide a cured product having excellent dielectric properties, conductor adhesion, and mechanical properties in combination with the (B) and (C) components described below, it is preferable that the (A) component contains a compound having two or more benzocyclobutene groups in the molecule. In order to provide a cured product having excellent dielectric properties, conductor adhesion, and mechanical properties in combination with the (B) and (C) components described below, it is preferable that the (A) component has an unsaturated group in addition to the benzocyclobutene group.

[0055] In one embodiment, the component (A) includes a compound represented by the following formula (A-1):

[0056] [ka]

[0057] In formula (A-1), R 1 represents a divalent aliphatic group having an unsaturated bond, L represents a single bond or a divalent linking group; R A1 represents an alkyl group, a cyano group, or a halogen atom, R A2 represents an alkyl group, a trialkylsilyl group, an alkoxy group, or a halogen atom, nA1 represents an integer of 0 to 2, nA2 represents an integer of 0 to 3, nA3 represents 0 or 1. 1 , R A1 and R A2 Each of R may independently have a substituent. 1 may be the same or different, RA1 When there are multiple, they may be the same or different, and R A2 When there are a plurality of nA1's, they may be the same or different. A plurality of nA1's may be the same or different. A plurality of nA2's may be the same or different.

[0058] R 1 The divalent group represented by the formula (I) preferably has 1 to 3 unsaturated bonds, more preferably 1 or 2 unsaturated bonds, and even more preferably 1 unsaturated bond. The unsaturated bond may be a double bond or a triple bond, but is preferably a double bond. 1 The divalent group represented by R is preferably an alkenylene group or an alkynylene group. 1 The number of carbon atoms in the divalent group represented by the following formula is preferably 2 to 10, and more preferably 2 to 6 or 2 to 4. The above number of carbon atoms does not include the number of carbon atoms of the substituent.

[0059] The divalent linking group represented by L is not particularly limited as long as it is a divalent group consisting of one or more (e.g., 1 to 3000, 1 to 1000, 1 to 100, 1 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms, and may be, for example, a divalent group consisting of one or more (e.g., 1 to 3000, 1 to 1000, 1 to 100, 1 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms, or a siloxane skeleton. Among these, L is preferably a siloxane skeleton. Therefore, in one embodiment, the component (A) has a siloxane skeleton.

[0060] R A1 The number of carbon atoms in the alkyl group represented by the formula (I) is preferably 1 to 10, and more preferably 1 to 6, 1 to 4, or 1 to 3. The number of carbon atoms does not include the number of carbon atoms in the substituent. A1 The halogen atom represented by the formula (I) is preferably a chlorine atom or a bromine atom.

[0061] R A2 The number of carbon atoms in the alkyl group and alkoxy group represented by R is preferably 1 to 10, and more preferably 1 to 6, 1 to 4, or 1 to 3. A2The number of carbon atoms in the alkyl portion of the trialkylsilyl group represented by the formula (I) is preferably 1 to 3, and more preferably 1 or 2. The number of carbon atoms does not include the number of carbon atoms of the substituent. A2 The halogen atom represented by the formula (I) is preferably a chlorine atom or a bromine atom.

[0062] In combination with the components (B) and (C) described below, from the viewpoint of providing a cured product in which the dielectric properties are maintained or further improved, and from the viewpoint of providing a cured product having better adhesion to a conductor and better mechanical properties, in formula (A-1), nA3 is preferably 1, and L is preferably a siloxane skeleton.

[0063] In a preferred embodiment, the component (A) includes a compound represented by the following formula (A-2):

[0064] [ka]

[0065] In formula (A-2), R 1 , R A1 , R A2 , nA1 and nA2 are as described in formula (A-1), R 2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an arylalkyl group, or an aryl group; nA4 represents an integer of 1 to 10. 2 may have a substituent. 2 may be the same or different.

[0066] R 2 The number of carbon atoms in the alkyl group represented by the formula (I) is preferably 1 to 10, and more preferably 1 to 6, 1 to 4, or 1 to 3. 2 The number of carbon atoms in the cycloalkyl group represented by the formula (I) is preferably 3 to 10, and more preferably 4 to 6. 2The number of carbon atoms in the arylalkyl group represented by the following formula is preferably 7 to 20, and more preferably 7 to 15 or 7 to 12. The aryl portion in the arylalkyl group is preferably a phenyl group. 2 The number of carbon atoms in the aryl group represented by the following formula is preferably 6 to 14, and more preferably 6 to 10. The aryl group is preferably a phenyl group. The number of carbon atoms in the above formula does not include the number of carbon atoms of the substituent.

[0067] R 1 , R A1 , R A2 , nA1 and nA2 are as described in formula (A-1), among which R 1 is an alkenylene group having 2 to 4 carbon atoms, and nA1 and nA2 are preferably 0.

[0068] In a particularly preferred embodiment, the component (A) comprises a compound represented by the following formula (A-3):

[0069] [ka]

[0070] In formula (A-3), R 2 and nA4 is as explained in formula (A-2).

[0071] The component (A) can be prepared according to the procedures described in, for example, U.S. Pat. No. 4,812,588 and U.S. Pat. No. 5,138,081. The component (A) may be a commercially available product, and examples of the compound represented by formula (A-3) include the CYCLOTENE (registered trademark) series manufactured by The Dow Chemical Company. From the viewpoint of keeping the oxygen transmission rate after curing at or below the specific value described above, it is preferable to use the dry etch type 3000 series of the CYCLOTENE (registered trademark) series. The non-volatile component contained in "CYCLOTENE (registered trademark) 3022" manufactured by The Dow Chemical Company is represented by the following formula.

[0072] [ka]

[0073] As mentioned above, the benzocyclobutene group produces an isomeric diene and undergoes a Diels-Alder type cycloaddition reaction. Therefore, the component (A) may be a compound (monomer) represented by the above formulas (A-1) to (A-3), a dimer or polymer produced by an addition reaction of such a compound, or a mixture of these.

[0074] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the component (A) are not particularly limited as long as the effects of the present invention are achieved in combination with the components (B) and (C) described below. In one embodiment, Mn is preferably 2000 or less, more preferably 1800 or less, and even more preferably 1600 or less, 1500 or less, 1400 or less, 1200 or less, or 1000 or less. In one embodiment, Mw is also within the above-mentioned preferred range. The lower limit of the molecular weight is not particularly limited, and may be, for example, 250 or more, 300 or more, or 350 or more. The Mw and Mn of the component (A) can be measured as values ​​converted into polystyrene by gel permeation chromatography (GPC). Thus, in a preferred embodiment, the component (A) contains a compound having two or more benzocyclobutene groups in the molecule, and the number average molecular weight (Mn) of the component (A) is 2000 or less.

[0075] The content of the (A) component in the resin composition is preferably 3% by mass or more, 4% by mass or more, 5% by mass or more, or 7% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass, from the viewpoint of realizing a cured product with maintained or improved dielectric properties. The upper limit of the content of the (A) component is not particularly limited, but from the viewpoint of providing a cured product with an oxygen permeability satisfying the above-mentioned range, preferably the above-mentioned preferred range, it is preferably 40% by mass or less, 35% by mass or less, 30% by mass or less, or 25% by mass or less. Therefore, in a preferred embodiment, the content of the (A) component is 3% by mass or more and 40% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass.

[0076] The content of the (A) component in the resin composition is preferably 6% by mass or more, 8% by mass or more, 10% by mass or more, or 14% by mass or more, when the resin component in the resin composition is taken as 100% by mass, from the viewpoint of realizing a cured product with maintained or improved dielectric properties. The resin component in the resin composition refers to the non-volatile components in the resin composition excluding the (B) inorganic filler. The upper limit of the content of the (A) component is not particularly limited, but is, for example, 90% by mass or less, and from the viewpoint of producing a cured product with low oxygen permeability, it is preferably 80% by mass or less or 70% by mass or less. Therefore, in a preferred embodiment, the content of the (A) component is 6% by mass or more and 80% by mass or less, when the resin component in the resin composition is taken as 100% by mass.

[0077] -(B) Inorganic filler- In the present invention, the resin composition contains an inorganic filler as component (B).

[0078] The present invention has realized that a cured product having excellent dielectric properties, conductor adhesion, and mechanical properties can be obtained by using a resin composition containing the above-mentioned component (A) in combination with the above-mentioned component (B) and the below-described component (C), and by making the resin composition layer or resin sheet satisfy both of the above-mentioned conditions of oxygen permeability α and β as described above. In addition, by including the component (B) in the resin composition, a cured product having excellent thermal properties (for example, linear thermal expansion coefficient) can be obtained.

[0079] Examples of the (B) component 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 zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, spherical silica is preferred as the silica. The (B) component may be used alone or in combination of two or more.

[0080] Examples of commercially available products of component (B) include "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs; "UFP-30" manufactured by Denka Company; "Silfill NSS-3N", "Silfill NSS-4N", and "Silfill NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs; and "DAW-03" and "FB-105FD" manufactured by Denka Company.

[0081] The average particle size of component (B) is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 3 μm or less, 2 μm or less, 1 μm or less, or 0.7 μm or less. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.07 μm or more, 0.1 μm or more, or 0.2 μm or more. The average particle size of component (B) can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction / scattering type particle size distribution measuring device, and the median diameter is taken as the average particle size. The measurement sample can be prepared by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing the mixture by ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction type particle size distribution measuring device with blue and red light source wavelengths, and the particle size distribution of the inorganic filler on a volume basis was measured using a flow cell method, and the average particle size was calculated as the median diameter from the particle size distribution obtained. An example of a laser diffraction type particle size distribution measuring device is the "LA-960" manufactured by Horiba, Ltd.

[0082] The specific surface area of ​​component (B) is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, 3m 2 / g or more or 5m 2 The upper limit of the specific surface area is not particularly limited, but is preferably 100 m 2 / g or less, more preferably 80m 2 / g or less, more preferably 60m 2 / g or less, 50m 2 / g or less or 40m 2 The specific surface area of ​​component (B) is obtained 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.) according to the BET method, and calculating the specific surface area using the BET multipoint method.

[0083] The (B) component is preferably surface-treated with a suitable surface treatment agent. By performing the surface treatment, the moisture resistance and dispersibility of the (B) component can be improved. Examples of the surface treatment agent include silane coupling agents such as vinyl-based silane coupling agents, epoxy-based silane coupling agents, styryl-based silane coupling agents, (meth)acrylic-based silane coupling agents, amino-based silane coupling agents, isocyanurate-based silane coupling agents, ureido-based silane coupling agents, mercapto-based silane coupling agents, isocyanate-based silane coupling agents, and acid anhydride-based silane coupling agents; non-silane coupling-alkoxysilane compounds such as methyltrimethoxysilane and phenyltrimethoxysilane; and silazane compounds. The surface treatment agent may be used alone or in combination of two or more.

[0084] Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd.

[0085] The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, it is preferable that 100% by mass of the inorganic filler is surface-treated with 0.2 to 5% by mass of the surface treatment agent.

[0086] 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 more2 On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in the form of a sheet, it is more preferable that the melt viscosity 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 more preferable. The carbon amount per unit surface area of ​​component (B) 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. As the carbon analyzer, an "EMIA-320V" manufactured by Horiba, Ltd., or the like can be used.

[0087] The content of the (B) component in the resin composition is preferably 30% by mass or more, more preferably 35% by mass or more, based on 100% by mass of the non-volatile components in the resin composition, from the viewpoint of obtaining a cured product having excellent dielectric properties, conductor adhesion, and mechanical properties. The upper limit of the content of the (B) component is not particularly limited, but is preferably 80% by mass or less, more preferably 75% by mass or less. Therefore, in a preferred embodiment, the content of the (B) component is 30% by mass or more and 80% by mass or less, based on 100% by mass of the non-volatile components in the resin composition.

[0088] From the viewpoint of obtaining the effects of the present invention more significantly, the blending ratio of the (B) component to the (A) component, i.e., the mass ratio of the (B) component / the (A) component, calculated on a non-volatile component basis, is preferably at least 1, more preferably at least 1.5, and even more preferably at least 2.0. The upper limit of the mass ratio is not particularly limited, but may be, for example, 50 or less, 40 or less, or 30 or less.

[0089] In order to obtain the effects of the present invention more significantly, the blending ratio of the (B) component to the (A) and (C) components, i.e., the mass ratio of the (B) component / {(A) component+(C) component}, calculated as non-volatile components, is preferably 0.5 or more. The upper limit of the mass ratio is not particularly limited, but may be, for example, 25 or less.

[0090] -(C) Radical polymerizable resin- In the present invention, the resin composition contains a radical polymerizable resin as component (C). However, component (C) does not have a benzocyclobutene group and is different from component (A). In other words, component (C) does not correspond to component (A).

[0091] The present invention has realized that a cured product having excellent dielectric properties, adhesion to a conductor, and mechanical properties can be obtained by using a combination of the above-mentioned component (C) and the above-mentioned component (B) in addition to the above-mentioned component (A) in a resin composition, and by making the resin composition layer or resin sheet satisfy both of the above-mentioned conditions for oxygen permeability α and β as described above.

[0092] The component (C) has a radically polymerizable unsaturated group in the molecule. The component (C) may be used alone or in combination of two or more types.

[0093] The component (C) is not particularly limited as long as it has a radically polymerizable unsaturated group in the molecule; however, from the viewpoint of providing a cured product that is exceptionally excellent in dielectric properties, conductor adhesion, and mechanical properties in combination with the components (A) and (B), the component (C) preferably contains a compound having, as a radically polymerizable unsaturated group, one or more selected from a vinyl group, an allyl group, a styryl group, a vinylphenyl group, an acryloyl group, a methacryloyl group, a maleimide group, a fumaroyl group, and a maleoyl group, and more preferably contains a compound containing one or more selected from an allyl group, a styryl group, a vinylphenyl group, an acryloyl group, and a methacryloyl group.

[0094] Therefore, the component (C) is preferably at least one selected from a maleimide resin, a styryl resin, a (meth)acrylic resin, an allyl resin, and a butadiene resin, more preferably at least one selected from a maleimide resin, a (meth)acrylic resin, and a styryl resin, and more preferably either a maleimide resin or a styryl resin.

[0095] The component (C) more preferably contains a compound having two or more radically polymerizable unsaturated groups in the molecule. There is no particular upper limit, but it may be 10 or less.

[0096] The maleimide resin contains a maleimide group represented by the following formula (C-1) in the molecule. [ka] (C-1)

[0097] From the viewpoint of significantly obtaining the intended effects of the present invention, the number of maleimide groups per molecule of the maleimide resin is preferably 2 or more, more preferably 3 or more, and is preferably 10 or less, more preferably 6 or less, and even more preferably 3 or less.

[0098] From the viewpoint of significantly achieving the intended effects of the present invention, the maleimide resin preferably has either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably has an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

[0099] The aliphatic hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, more preferably a divalent saturated aliphatic hydrocarbon group, and further preferably an alkylene 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, further preferably an alkylene group having 1 to 3 carbon atoms, and particularly preferably a methylene group.

[0100] As the aromatic hydrocarbon group, monovalent and divalent aromatic hydrocarbon groups are preferred, and aryl and arylene groups are more 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, an aralkyl group, a biphenylene group, and a biphenylaralkyl group, and among these, a phenylene group, an aralkyl group, a biphenylene group, and a biphenylaralkyl group are preferred, and a phenylene group, an aralkyl group, and a biphenylene group are even more preferred. As the aryl group, an aryl group having 6 to 30 carbon atoms is preferred, an aryl group having 6 to 20 carbon atoms is more preferred, an aryl group having 6 to 10 carbon atoms is even more preferred, and a phenyl group is particularly preferred.

[0101] In the maleimide resin, from the viewpoint of significantly achieving the intended effect of the present invention, the nitrogen atom of the maleimide group is preferably directly bonded to a monovalent or divalent aromatic hydrocarbon group, where "directly" means that there is no other group between the nitrogen atom of the maleimide group and the aromatic hydrocarbon group.

[0102] The maleimide resin preferably contains, for example, a compound represented by the following formula (C-2).

[0103] [ka] (C-2) In formula (C-2), R 31 and R 36 represents a maleimide group, and R 32 , R 33 , R 34 and R 35 each independently represents a hydrogen atom, an alkyl group, or an aryl group, and each D independently represents a divalent aromatic group. m1 and m2 each independently represent an integer of 1 to 10, and a represents an integer of 1 to 100.

[0104] R in formula (C-2) 32 , R33 , R 34 and R 35 each independently represents a hydrogen atom, an alkyl group, or an aryl group, and a hydrogen atom is preferred.

[0105] As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 3 carbon atoms is even more preferred. The alkyl group may be linear, branched, or cyclic. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, and the like.

[0106] As the aryl group, an aryl group having 6 to 20 carbon atoms is preferred, an aryl group having 6 to 15 carbon atoms is more preferred, and an aryl group having 6 to 10 carbon atoms is even more preferred. The aryl group may be a monocyclic ring or a condensed ring. Examples of such an aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and the like.

[0107] The alkyl group and the aryl group may have a substituent. The substituent is not particularly limited and may be the same as those described above. For example, a halogen atom, -OH, -O-C 1-6 alkyl group, -N(C 1-10 alkyl group)2, C 1-10 alkyl group, C 6-10 aryl group, -NH2, -CN, -C(O)O-C 1-10 alkyl group, -COOH, -C(O)H, -NO2, etc. are mentioned. Here, the term "C p-q " (p and q are positive integers and satisfy p < q) represents that the number of carbon atoms of the organic group described immediately after this term is p to q. For example, the expression "C 1-10 alkyl group" indicates an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure includes a spiro ring and a condensed ring.

[0108] D in formula (C-2) represents a divalent aromatic group. Examples of the divalent aromatic group include a phenylene group, a naphthylene group, an anthracenylene group, an aralkyl group, a biphenylene group, and a biphenylaralkyl group. Among them, a biphenylene group and a biphenylaralkyl group are preferable, and a biphenylene group is more preferable. The divalent aromatic group may have a substituent. As the substituent, R in formula (C-2) may be used. 32 The substituents are the same as those that the alkyl group represented by the formula (I) may have.

[0109] m1 and m2 each independently represent an integer of 1 to 10, preferably 1 to 6, more preferably 1 to 3, even more preferably 1 or 2, and still more preferably 1.

[0110] "a" represents an integer of 1 to 100, preferably 1 to 50, more preferably 1 to 20, and further preferably 1 to 5.

[0111] The maleimide resin preferably contains a compound represented by formula (C-3). [ka] (C-3) In formula (C-3), R 37 and R 38 represents a maleimide group. a1 represents an integer of 1 to 100.

[0112] a1 is the same as a in formula (C-2), and the preferred range is also the same.

[0113] As the maleimide resin, a commercially available product can be used, for example, "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.

[0114] The maleimide resin preferably contains a compound containing at least one of an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms.

[0115] The number of carbon atoms of the alkyl group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. The alkyl group may be linear, branched, or cyclic, and linear is preferable. Examples of such an alkyl group include a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. The alkyl group having 5 or more carbon atoms may be a substituent of an alkylene group having 5 or more carbon atoms. The alkyl group having 5 or more carbon atoms may be a part of an alkenyl group or an alkapolyenyl group (the number of double bonds is preferably 2).

[0116] The number of carbon atoms of the alkylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. The alkylene group may be linear, branched, or cyclic, and linear is preferred. Here, the cyclic alkylene group is a concept that includes the case where it is composed of only a cyclic alkylene group and the case where it contains both a linear alkylene group and a cyclic alkylene group. Examples of such alkylene groups include pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, heptadecylene, hexatriacontylene, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure. An alkylene group having 5 or more carbon atoms may be a part of an alkenylene group or an alkapolyenylene group (the number of double bonds is preferably 2).

[0117] From the viewpoint of significantly obtaining the intended effects of the present invention, it is also preferable that the maleimide resin contains a compound containing both an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms.

[0118] The alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring. Examples of the ring formed by bonding to each other include a cyclohexane ring.

[0119] The alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms preferably have no substituent, but may have a substituent. As the substituent, as described above, suitable examples include an unsaturated hydrocarbon group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, etc. The substituent may be contained alone or in combination of two or more kinds.

[0120] The maleimide resin preferably contains a compound in which the above-mentioned alkyl group having 5 or more carbon atoms and alkylene group having 5 or more carbon atoms are directly bonded to the nitrogen atom of the maleimide group.

[0121] In one embodiment, the maleimide resin includes a compound represented by the following general formula (C-4): [ka] (C-4) In formula (C-4), M represents a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms which may have a substituent, and L represents a single bond or a divalent linking group.

[0122] M represents a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms which may have a substituent. Preferably, M represents an alkylene group, alkenylene group, or alkapolyenylene group having 5 or more carbon atoms which may have a substituent (more preferably, the number of double bonds is 2). The alkylene group of M is the same as the alkylene group having 5 or more carbon atoms described above. The substituent of M is the same as the substituent that may be possessed by the alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms described above, and the substituent is preferably an alkyl group having 5 or more carbon atoms.

[0123] L represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -C(=O)-, -C(=O)-O-, -NR 0 -(R 0 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom, or C(=O)NR 0 -, a divalent group derived from phthalimide, a divalent group derived from pyromellitic diimide, and a group consisting of a combination of two or more of these divalent groups. The alkylene group, alkenylene group, alkynylene group, arylene group, divalent group derived from phthalimide, divalent group derived from pyromellitic diimide, and a group consisting of a combination of two or more of these divalent groups may have an alkyl group having 5 or more carbon atoms as a substituent. The divalent group derived from phthalimide represents a divalent group derived from phthalimide, specifically a group represented by general formula (C-5). The divalent group derived from pyromellitic diimide represents a divalent group derived from pyromellitic diimide, specifically a group represented by general formula (C-6). In the formula, "*" represents a bond.

[0124] [ka] (C-5)

[0125] [ka] (C-6)

[0126] The alkylene group as the divalent linking group in L is preferably an alkylene group having 1 to 50 carbon atoms, more preferably an alkylene group having 1 to 45 carbon atoms, and particularly preferably an alkylene group having 1 to 40 carbon atoms. This alkylene group may be linear, branched, or cyclic. Examples of such alkylene groups include a methylethylene group, a cyclohexylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecylene group, a hexatriacontylene group, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure.

[0127] The alkenylene group as the divalent linking group in L is preferably an alkenylene group having 2 to 20 carbon atoms, more preferably an alkenylene group having 2 to 15 carbon atoms, and particularly preferably an alkenylene group having 2 to 10 carbon atoms. This alkenylene group may be linear, branched, or cyclic. Examples of such alkenylene groups include a methylethylenylene group, a cyclohexenylene group, a pentenylene group, a hexenylene group, a heptenylene group, and an octenylene group.

[0128] The alkynylene group as the divalent linking group in L is preferably an alkynylene group having 2 to 20 carbon atoms, more preferably an alkynylene group having 2 to 15 carbon atoms, and particularly preferably an alkynylene group having 2 to 10 carbon atoms. This alkynylene group may be linear, branched, or cyclic. Examples of such alkynylene groups include a methylethynylene group, a cyclohexynylene group, a pentynylene group, a hexynylene group, a heptynylene group, and an octynylene group.

[0129] The arylene group as the divalent linking group in L is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, still more preferably an arylene group having 6 to 14 carbon atoms, and even more preferably an arylene group having 6 to 10 carbon atoms. Examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.

[0130] The alkylene group, alkenylene group, alkynylene group, and arylene group, which are the divalent linking groups in L, may have a substituent. The substituent is the same as the substituent that may be possessed by the above-mentioned alkyl group having 5 or more carbon atoms and alkylene group having 5 or more carbon atoms, and is preferably an alkyl group having 5 or more carbon atoms.

[0131] Examples of the group consisting of a combination of two or more divalent groups in L include a divalent group consisting of a combination of an alkylene group, a divalent group derived from phthalimide, and an oxygen atom; a divalent group consisting of a combination of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a divalent group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; and the like. The group consisting of a combination of two or more divalent groups may form a ring such as a condensed ring by the combination of the respective groups. In addition, the group consisting of a combination of two or more divalent groups may be a repeating unit having a repeating unit number of 1 to 10.

[0132] Among them, L in the general formula (C-4) is preferably an oxygen atom, an arylene group having 6 to 24 carbon atoms which may have a substituent, an alkylene group having 1 to 50 carbon atoms which may have a substituent, an alkyl group having 5 or more carbon atoms, a divalent group derived from phthalimide, a divalent group derived from pyromellitic diimide, or a divalent group consisting of a combination of two or more of these groups. Among them, L is more preferably an alkylene group; a divalent group having a structure of an alkylene group-a divalent group derived from phthalimide-oxygen atom-a divalent group derived from phthalimide; a divalent group having a structure of an alkylene group-a divalent group derived from phthalimide-oxygen atom-arylene group-alkylene group-arylene group-oxygen atom-a divalent group derived from phthalimide; or a divalent group having a structure of an alkylene-a divalent group derived from pyromellitic diimide.

[0133] The compound represented by general formula (C-4) preferably includes a compound represented by general formula (C-7). [ka] (C-7) In general formula (C-7), M 1 each independently represents a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms which may have a substituent, each Z independently represents an alkylene group having 5 or more carbon atoms which may have a substituent or a divalent group having an aromatic ring which may have a substituent, and t represents an integer of 1 to 10.

[0134] M 1 each independently represents a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms which may have a substituent. 1 each independently represents an alkylene group, an alkenylene group, or an alkapolyenylene group (more preferably having two double bonds) having 5 or more carbon atoms which may have a substituent. 1 is more preferably the same as M in general formula (C-4).

[0135] Each Z independently represents an alkylene group having 5 or more carbon atoms which may have a substituent, or a divalent group having an aromatic ring which may have a substituent. The alkylene group in Z may be any of linear, branched, and cyclic, and among them, a cyclic alkylene group having 5 or more carbon atoms which may have a substituent is preferred. The number of carbon atoms of the alkylene group is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. Examples of such alkylene groups include a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure.

[0136] The aromatic ring in the divalent group having an aromatic ring represented by Z may be as described above, but examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic diimide ring, and an aromatic heterocycle, and the like. A benzene ring, a phthalimide ring, and a pyromellitic diimide ring are preferred. That is, examples of the divalent group having an aromatic ring include a divalent group having a benzene ring which may have a substituent, a divalent group having a phthalimide ring which may have a substituent, and a divalent group having a pyromellitic diimide ring which may have a substituent. Examples of the divalent group having an aromatic ring include a group consisting of a combination of a divalent group derived from phthalimide and an oxygen atom; a group consisting of a combination of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; a divalent group derived from pyromellitic diimide; a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group; and the like. The arylene group and alkylene group are the same as the arylene group and alkylene group in the divalent linking group represented by L in general formula (C-4).

[0137] The alkylene group and the divalent group having an aromatic ring represented by Z may have a substituent. The substituent is the same as the substituent that may be possessed by the above-mentioned alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms.

[0138] Specific examples of the group represented by Z include the following groups: In the formula, "*" represents a bond.

[0139] [ka]

[0140] [ka]

[0141] The compound represented by general formula (C-4) is preferably any one of a compound represented by general formula (C-8) and a compound represented by general formula (C-9).

[0142] [ka] (C-8) In general formula (C-8), M 2 and M 3 each independently represents a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms which may have a substituent; R 40 each independently represents an oxygen atom, an arylene group, an alkylene group, or a divalent group consisting of a combination of two or more of these groups. t1 represents an integer of 1 to 10.

[0143] [ka] (C-9) In general formula (C-9), M 4 , M 6 and M 7 each independently represents a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms which may have a substituent; M5 each independently represents a divalent group having an aromatic ring which may have a substituent; R 41 and R 42 each independently represents an alkyl group having 5 or more carbon atoms. t2 represents an integer of 0 to 10, and u1 and u2 each independently represent an integer of 0 to 4.

[0144] M 2 and M 3 each independently represents a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms which may have a substituent. 2 and M 3 each independently represents an alkylene group, an alkenylene group, or an alkapolyenylene group (more preferably having two double bonds) having 5 or more carbon atoms which may have a substituent. 2 and M 3 is more preferably the same as the alkylene group having 5 or more carbon atoms represented by M in the general formula (C-4), and a hexatriacontylene group is preferred.

[0145] R 40 R each independently represents an oxygen atom, an arylene group, an alkylene group, or a group consisting of a combination of two or more of these divalent groups. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (C-4). 40 is preferably an oxygen atom or a group formed from a combination of two or more divalent groups.

[0146] R 40 In the formula, examples of the group consisting of a combination of two or more divalent groups include a combination of an oxygen atom, an arylene group, and an alkylene group. Specific examples of the group consisting of a combination of two or more divalent groups include the following groups. In the formula, "*" represents a bond. [ka]

[0147] M 4 , M6 and M 7 each independently represents a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms which may have a substituent. 4 , M 6 and M 7 each independently represents an alkylene group, an alkenylene group, or an alkapolyenylene group (more preferably having two double bonds) having 5 or more carbon atoms which may have a substituent. 4 , M 6 and M 7 is the same as the alkylene group having 5 or more carbon atoms which may have a substituent represented by M in general formula (C-4), and is preferably a hexylene group, a heptylene group, an octylene group, a nonylene group or a decylene group, more preferably an octylene group.

[0148] M 5 Each of M independently represents a divalent group having an aromatic ring which may have a substituent. 5 is the same as the divalent group having an aromatic ring which may have a substituent represented by Z in general formula (C-7), and is preferably a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group, and more preferably a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide. The arylene group and alkylene group are the same as the arylene group and alkylene group in the divalent linking group represented by L in general formula (C-4).

[0149] M 5 Specific examples of the group represented by the formula include the following groups: In the formula, "*" represents a bond. [ka]

[0150] R 41 and R 42 R each independently represents an alkyl group having 5 or more carbon atoms. 41 and R 42is the same as the above-mentioned alkyl group having 5 or more carbon atoms, and is preferably a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group, and more preferably a hexyl group or an octyl group.

[0151] Each of u1 and u2 independently represents an integer of 1 to 15, and an integer of 1 to 10 is preferable.

[0152] Specific examples of the maleimide resin include the following compounds (C1) to (C3). However, the maleimide resin is not limited to these specific examples. In the formula, n represents an integer of 1 to 10.

[0153] [ka] (C1)

[0154] [ka] (C2)

[0155] [ka] (C3)

[0156] Specific examples of maleimide resins include "BMI1500" (compound of formula (C1)), "BMI1700" (compound of formula (C2)), and "BMI689" (compound of formula (C3)), all manufactured by Designer Molecules.

[0157] From the viewpoint of significantly obtaining the intended effects of the present invention, the maleimide group equivalent of the maleimide resin is preferably 50 g / eq. to 2000 g / eq., more preferably 100 g / eq. to 1000 g / eq., and further preferably 150 g / eq. to 500 g / eq. The maleimide group equivalent is the mass of a compound containing one equivalent of a maleimide group.

[0158] The styryl resin has one or more groups selected from a styryl group and a vinylphenyl group in the molecule, and preferably has a vinylphenyl group. The vinylphenyl group is a group having the structure shown below. [ka] (* represents a bond.)

[0159] From the viewpoint of obtaining a cured product with a low dielectric tangent, the styryl resin more preferably has two or more vinylphenyl groups.

[0160] The styryl resin preferably has a cyclic structure from the viewpoint of obtaining a cured product with a low dielectric tangent. The cyclic structure is preferably a divalent cyclic group. The divalent cyclic group may be any of a cyclic group containing a non-aromatic ring, such as an alicyclic structure, and a cyclic group containing an aromatic ring structure. In addition, the styryl resin may have a plurality of divalent cyclic groups.

[0161] From the viewpoint of significantly obtaining the intended effect of the present invention, the divalent cyclic group is preferably a 3-membered or more ring, more preferably a 4-membered or more ring, and even more preferably a 5-membered or more ring, and is preferably a 20-membered or less ring, more preferably a 15-membered or less ring, and even more preferably a 10-membered or less ring. In addition, the divalent cyclic group may be a monocyclic structure or a polycyclic structure.

[0162] The ring in the divalent cyclic group may have a ring skeleton constituted by a heteroatom other than carbon atoms. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom, and an oxygen atom is preferred. The ring may have one or more heteroatoms.

[0163] Specific examples of the divalent cyclic group include the following divalent groups (xii) and (xiii). [ka] (In the divalent groups (xii) and (xiii), R 51 , R 52 , R55 , R 56 , R 57 , R 61 , and R 62 each independently represents a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group; R 53 , R 54 , R 58 , R 59 , and R 60 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.

[0164] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Examples of alkyl groups having 6 or less carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups, with methyl being preferred. 51 , R 52 , R 55 , R 56 , R 57 , R 61 , and R 62 R preferably represents a methyl group. 53 , R 54 , R 58 , R 59 , and R 60 is preferably a hydrogen atom or a methyl group.

[0165] In addition, the divalent cyclic group may be a combination of a plurality of divalent cyclic groups. Specific examples of the combination of divalent cyclic groups include the divalent cyclic group represented by the following formula (C4) (divalent group (a)). [ka] (C4) (In formula (C4), R 71 , R 72 , R 75 , R 76 , R 77 , R 81 , R 82 , R 85 and R 86each independently represents a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group; R 73 , R 74 , R 78 , R 79 , R 80 , R 83 and R 84 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. d1 and d2 each represent an integer of 0 to 300, except for the case where one of d1 and d2 is 0.

[0166] R 71 , R 72 , R 85 and R 86 R in formula (xii) 51 is the same as R 73 , R 74 , R 83 and R 84 R in formula (xii) 53 is the same as R 75 , R 76 , R 77 , R 81 , and R 82 R in formula (xiii) 55 is the same as R 78 , R 79 , and R 80 R in formula (xiii) 58 is the same as:

[0167] d1 and d2 represent an integer of 0 to 300, except when one of d1 and d2 is 0. d1 and d2 preferably represent an integer of 1 to 100, more preferably an integer of 1 to 50, and even more preferably an integer of 1 to 10. d1 and d2 may be the same or different.

[0168] The divalent cyclic group may have a substituent, such as a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, or an oxo group, and an alkyl group is preferred.

[0169] The vinylphenyl group may be directly bonded to the divalent cyclic group, or may be bonded via a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, and the like, and may be a group in which a plurality of these are combined. 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 5 carbon atoms or an alkylene group having 1 to 4 carbon atoms. The alkylene group may be linear, branched, or cyclic. Examples of such alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, and 1,1-dimethylethylene groups, and are preferably methylene, ethylene, or 1,1-dimethylethylene. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferred, an alkenylene group having 2 to 6 carbon atoms is more preferred, and an alkenylene group having 2 to 5 carbon atoms is even more preferred. As the arylene group or heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferred, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferred. As the divalent linking group, an alkylene group is preferred, and among them, a methylene group is preferred.

[0170] The styryl resin preferably contains a compound represented by the following formula (C-10). [ka] (C-10) (In formula (C-10), R91 and R 92 each independently represents a divalent linking group. Ring B1 represents a divalent cyclic group.

[0171] R 91 and R 92 each independently represents a divalent linking group. The divalent linking group is the same as the divalent linking group described above.

[0172] Ring B1 represents a divalent cyclic group. Ring B is the same as the above divalent cyclic group.

[0173] Ring B1 may have a substituent. The substituent is the same as the substituent that the above divalent cyclic group may have.

[0174] Specific examples of the styryl resin are shown below, but the present invention is not limited thereto. [ka] (q1 is the same as d1 in formula (C4), and q2 is the same as d2 in formula (C4).)

[0175] The styryl resin may be a commercially available product, such as "OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Inc. The styryl resin may be used alone or in combination of two or more kinds.

[0176] From the viewpoint of significantly obtaining the intended effects of the present invention, the number average molecular weight of the styryl resin is preferably 3000 or less, more preferably 2500 or less, even more preferably 2000 or less, or 1500 or less. The lower limit is preferably 100 or more, more preferably 300 or more, even more preferably 500 or more, or 1000 or more. The number average molecular weight is the number average molecular weight in terms of polystyrene measured using gel permeation chromatography (GPC).

[0177] The (meth)acrylic resin includes a compound having an acryloyl group or a methacryloyl group in the molecule. From the viewpoint of significantly obtaining the intended effect of the present invention, the (meth)acrylic resin preferably includes a compound having two or more (meth)acryloyl groups per molecule. The term "(meth)acryloyl group" is a general term for an acryloyl group and a methacryloyl group.

[0178] The (meth)acrylic resin preferably has a cyclic structure from the viewpoint of significantly achieving the desired effects of the present invention. The cyclic structure is preferably a divalent cyclic group. The divalent cyclic group may be any of a cyclic group containing a non-aromatic ring, for example, an alicyclic structure, and a cyclic group containing an aromatic ring structure. Among them, from the viewpoint of significantly achieving the desired effects of the present invention, a cyclic group containing an alicyclic structure is preferable.

[0179] From the viewpoint of significantly obtaining the intended effect of the present invention, the divalent cyclic group is preferably a 3-membered or more ring, more preferably a 4-membered or more ring, and even more preferably a 5-membered or more ring, and is preferably a 20-membered or less ring, more preferably a 15-membered or less ring, and even more preferably a 10-membered or less ring. In addition, the divalent cyclic group may be a monocyclic structure or a polycyclic structure.

[0180] The ring in the divalent cyclic group may have a ring skeleton constituted by a heteroatom other than carbon atoms. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom, and an oxygen atom is preferred. The ring may have one or more heteroatoms.

[0181] Specific examples of the divalent cyclic group include the following divalent groups (i) to (xi). Among them, the divalent cyclic group is preferably (x) or (xi). [ka]

[0182] The divalent cyclic group may have a substituent, such as a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, or an oxo group, and an alkyl group is preferred.

[0183] The (meth)acryloyl group may be directly bonded to the divalent cyclic group, or may be bonded via a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, and the like, and may be a group in which a plurality of these are combined. 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 5 carbon atoms or an alkylene group having 1 to 4 carbon atoms. The alkylene group may be linear, branched, or cyclic. Examples of such alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, and 1,1-dimethylethylene groups, and are preferably methylene, ethylene, or 1,1-dimethylethylene. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferred, an alkenylene group having 2 to 6 carbon atoms is more preferred, and an alkenylene group having 2 to 5 carbon atoms is even more preferred. As the arylene group or heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferred, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferred. As the divalent linking group, an alkylene group is preferred, and among them, a methylene group or a 1,1-dimethylethylene group is preferred.

[0184] The (meth)acrylic resin preferably contains a compound represented by the following formula (C-11). [ka] (C-11) (In formula (C-11), R 101 and R 104 each independently represents an acryloyl group or a methacryloyl group, R 102 and R 103 each independently represents a divalent linking group. Ring B2 represents a divalent cyclic group.

[0185] R 101 and R 104 each independently represents an acryloyl group or a methacryloyl group, and an acryloyl group is preferred.

[0186] R 102 and R 103 each independently represents a divalent linking group. The divalent linking group is the same as the divalent linking group which may have a (meth)acryloyl group bonded thereto.

[0187] Ring B2 represents a divalent cyclic group. Ring B2 is the same as the divalent cyclic group. Ring B2 may have a substituent. The substituent is the same as the substituent that the divalent cyclic group may have.

[0188] Specific examples of the (meth)acrylic resin include the following, but the present invention is not limited thereto. [ka]

[0189] As the (meth)acrylic resin, commercially available products may be used, and examples thereof include "A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" manufactured by Kyoeisha Chemical Co., Ltd., "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", and "DPHA" manufactured by Nippon Kayaku Co., Ltd., and "NK Ester DCP" manufactured by Shin-Nakamura Chemical Co., Ltd.

[0190] From the viewpoint of significantly obtaining the intended effects of the present invention, the (meth)acryloyl group equivalent of the (meth)acrylic resin is preferably 30 g / eq. to 400 g / eq., more preferably 50 g / eq. to 300 g / eq., and further preferably 75 g / eq. to 200 g / eq. The (meth)acryloyl group equivalent is the mass of a compound containing one equivalent of a (meth)acryloyl group.

[0191] The allyl resin has at least one allyl group in the molecule. The allyl resin more preferably has two or more allyl groups in one molecule. The upper limit is not particularly limited, but is preferably 10 or less, more preferably 5 or less.

[0192] In order to remarkably obtain the intended effects of the present invention, the allyl resin preferably has, in addition to the allyl group, any one of a benzoxazine ring, a phenol ring, an isocyanuric ring, an epoxy group, and a carboxylic acid derivative having a cyclic structure.

[0193] The allyl resin having a benzoxazine ring is preferably bonded to either the nitrogen atom of the benzoxazine ring or the benzene ring, and more preferably bonded to the nitrogen atom.

[0194] Examples of allyl resins having a phenol ring include cresol resins containing an allyl group, novolac-type phenol resins containing an allyl group, and cresol novolac resins containing an allyl group.

[0195] In the allyl resin having an isocyanuric structure, a nitrogen atom of the isocyanuric structure and an allyl group are preferably directly bonded to each other. Examples of the allyl resin having an isocyanuric structure include allyl isocyanurate, diallyl isocyanurate, and triallyl isocyanurate.

[0196] The allyl resin having an epoxy group preferably contains two or more epoxy groups in one molecule. The allyl resin having an epoxy group preferably has an aromatic structure, and when two or more allyl resins having an epoxy group are used, it is more preferable that at least one of them has an aromatic structure. The aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatic rings and aromatic heterocycles. The allyl resin having an epoxy group preferably has a bisphenol structure, and examples of the bisphenol structure include bisphenol A type, bisphenol F type, and bisphenol AF type.

[0197] As the allyl resin having a carboxylic acid derivative having a cyclic structure, an allyl carboxylate having a cyclic structure is preferred. The cyclic structure may be any of a non-aromatic ring, for example, a cyclic group containing an alicyclic structure and a cyclic group containing an aromatic ring structure. In addition, the cyclic group may have a ring skeleton formed by heteroatoms other than carbon atoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, and nitrogen atoms, and nitrogen atoms are preferred. The ring may have one or more heteroatoms.

[0198] Examples of carboxylic acids having a cyclic structure include isocyanuric acid, diphenic acid, phthalic acid, cyclohexanedicarboxylic acid, etc. Examples of allyl resins having a carboxylic acid derivative having a cyclic structure include allyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate, diallyl diphenate, allyl diphenate, ortho-diallyl phthalate, meth-diallyl phthalate, para-diallyl phthalate, allyl cyclohexanedicarboxylate, diallyl cyclohexanedicarboxylate, etc.

[0199] The allyl resin may be a commercially available product. Examples of commercially available products include "MEH-8000H" and "MEH-8005" (allyl resin having a phenol ring) manufactured by Meiwa Kasei Co., Ltd.; "RE-810NM" (allyl resin having an epoxy group) manufactured by Nippon Kayaku Co., Ltd.; "ALP-d" (allyl resin having a benzoxazine ring) manufactured by Shikoku Kasei Kogyo Co., Ltd.; "L-DAIC" (allyl resin having an isocyanuric ring) manufactured by Shikoku Kasei Kogyo Co., Ltd.; "TAIC" (allyl resin having an isocyanuric ring (triallyl isocyanurate) manufactured by Nippon Kasei Co., Ltd.; "MDAC" (allyl resin having a cyclohexanedicarboxylic acid derivative) manufactured by Osaka Soda Co., Ltd.; "DAD" (diallyl diphenate) manufactured by Nissho Techno Fine Chemical Co., Ltd.; and "Daiso DAP Monomer" (ortho-diallyl phthalate) manufactured by Osaka Soda Co., Ltd.

[0200] From the viewpoint of significantly obtaining the intended effects of the present invention, the allyl group equivalent of the allyl resin is preferably 20 g / eq. to 1000 g / eq., more preferably 50 g / eq. to 500 g / eq., and further preferably 100 g / eq. to 300 g / eq. The allyl group equivalent is the mass of a compound containing one equivalent of an allyl group.

[0201] The butadiene resin has a butadiene skeleton. The polybutadiene structure may be included in the main chain or in the side chain. The polybutadiene structure may be partially or entirely hydrogenated. As the butadiene resin, one or more resins selected from the group consisting of hydrogenated polybutadiene skeleton-containing resin, hydroxyl group-containing butadiene resin, phenolic hydroxyl group-containing butadiene resin, carboxyl group-containing butadiene resin, acid anhydride group-containing butadiene resin, epoxy group-containing butadiene resin, isocyanate group-containing butadiene resin, and urethane group-containing butadiene resin are more preferable.

[0202] Specific examples of butadiene resins include "JP-100" manufactured by Nippon Soda Co., Ltd., and "Ricon100", "Ricon150", "Ricon130MA8", "Ricon130MA13", "Ricon130MA20", "Ricon131MA5", "Ricon131MA10", "Ricon131MA17", "Ricon131MA20", and "Ricon 184MA6" manufactured by CRAY VALLEY Corporation.

[0203] From the viewpoint of enhancing the intended effects of the present invention, the content of component (C) is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more, and is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on 100% by mass of non-volatile components in the resin composition.

[0204] From the viewpoint of enhancing the intended effects of the present invention, the content of the (C) component, relative to 100 mass% of the resin component in the resin composition, is preferably 2 mass% or more, more preferably 10 mass% or more, even more preferably 16 mass% or more, and is preferably 90 mass% or less, more preferably 87 mass% or less, even more preferably 85 mass% or less.

[0205] The resin sheet of the present invention, which is provided with a resin composition layer containing a combination of the (A), (B) and (C) components and satisfies both the above-mentioned conditions for oxygen permeability α and β, can realize a cured product excellent in conductor adhesion and mechanical properties while maintaining or improving the advantage of the excellent dielectric properties inherent to the (A) component. The above-mentioned effect cannot be obtained with a resin composition layer in which the (A) component is combined with only the (B) component or only the (C) component, even if both the above-mentioned conditions for oxygen permeability α and β are satisfied, but it has been confirmed that a specific effect can be obtained when the (A) component is combined with the (B) component and the (C) component and both the above-mentioned conditions for oxygen permeability α and β are satisfied.

[0206] -(D)Thermoplastic resin- In the present invention, the resin composition may further contain a thermoplastic resin as component (D).

[0207] Examples of the (D) component include, for example, phenoxy resins, polyimide resins, polycarbonate resins, polyvinyl acetal resins, polyolefin resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyetheretherketone resins, polystyrene resins, polyester resins, etc. Among these, from the viewpoint of obtaining a cured product having excellent dielectric properties, the (D) component is preferably one or more selected from phenoxy resins, polyimide resins, and polycarbonate resins, and from the viewpoint of obtaining a cured product having even more excellent mechanical properties, such as elongation at break, it is more preferable to use a polyimide resin.

[0208] Examples of the phenoxy resin include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

[0209] Commercially available phenoxy resins include, for example, "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both of which are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", and "YL7482" manufactured by Mitsubishi Chemical Corporation.

[0210] The polyimide resin may be a resin having an imide structure. The polyimide resin may generally be obtained by an imidization reaction between a diamine compound and an acid anhydride. The polyimide resin may be a commercially available product, such as "Rikacoat SN20" and "Rikacoat PN20" manufactured by New Japan Chemical Co., Ltd. In addition, the thermoplastic resin d in the solution prepared in <Synthesis Example 1> (synthesis of solution of thermoplastic resin d) described later or a modified product thereof may be used as the polyimide resin.

[0211] Polycarbonate resins are resins having a carbonate structure. Examples of such resins include carbonate resins having no reactive group, hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, urethane group-containing carbonate resins, and epoxy group-containing carbonate resins. The reactive group here refers to a functional group that can react with other components, such as a hydroxyl group, a phenolic hydroxyl group, a carboxyl group, an acid anhydride group, an isocyanate group, a urethane group, and an epoxy group.

[0212] Commercially available polycarbonate resins can be used, including "FPC0220" and "FPC2136" manufactured by Mitsubishi Gas Chemical Co., "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Chemicals Corporation, and "C-1090", "C-2090", and "C-3090" (polycarbonate diols) manufactured by Kuraray Co., Ltd.

[0213] From the viewpoint of obtaining a cured product having even more excellent mechanical properties, such as elongation at break, the weight average molecular weight (Mw) of component (D) is preferably 5000 or more, more preferably 8000 or more, and even more preferably 10000 or more. There are no particular limitations on the upper limit of Mw, but it is preferably 100000 or less, more preferably 80000 or less, and even more preferably 50000 or less. The Mw of component (D) can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0214] When the resin composition contains the (D) component, the content of the (D) component in the resin composition is not particularly limited as long as it does not excessively inhibit the effects of the present invention, but may be 0.1% by mass or more, 0.3% by mass or more, or 0.5% by mass or more, assuming that the non-volatile components in the resin composition are 100% by mass. The lower limit of the content of the (D) component is preferably 0.7% by mass or more, 0.8% by mass or more, or 1.0% by mass or more, from the viewpoint of obtaining a cured product having better mechanical properties, such as breaking elongation. The upper limit of the content of the (D) component is not particularly limited, but is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less.

[0215] -(E) Curing accelerator- In the present invention, the resin composition may further contain a curing accelerator as component (E). A typical example of the curing accelerator as component (E) is a peroxide curing accelerator.

[0216] Examples of component (E) include peroxides such as t-butylcumyl peroxide, t-butyl peroxyacetate, α,α'-di(t-butylperoxy)diisopropylbenzene, t-butyl peroxylaurate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, and t-butyl peroxybenzoate.

[0217] Commercially available products of component (E) include, for example, NOF Corporation's “Perbutyl (registered trademark) C”, “Perbutyl (registered trademark) A”, “Perbutyl (registered trademark) P”, “Perbutyl (registered trademark) L”, “Perbutyl (registered trademark) O”, “Perbutyl (registered trademark) ND”, “Perbutyl (registered trademark) Z”, “Perhexyl (registered trademark) D”, “Percumyl (registered trademark) P”, and “Percumyl (registered trademark) D”.

[0218] When the resin composition contains the (E) component, the content of the (E) component, relative to 100 mass% of the non-volatile components in the resin composition, is preferably 0.01 mass% or more, more preferably 0.03 mass% or more, even more preferably 0.05 mass% or more, and is preferably 1 mass% or less, more preferably 0.5 mass% or less, even more preferably 0.3 mass% or less.

[0219] -Other ingredients- In the present invention, the resin composition may further contain an epoxy resin and an epoxy resin curing agent.

[0220] Examples of epoxy resins include 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, glycidyl ester 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, etc. The epoxy resins may be used alone or in combination of two or more.

[0221] Epoxy resins include epoxy resins that are liquid at a temperature of 20° C. (hereinafter referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20° C. (hereinafter referred to as "solid epoxy resins"). The resin composition for a resin sheet of the present invention may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin.

[0222] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "Epicoat 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; and "630" and "630LSD" (glycidylamine type epoxy resins) manufactured by Mitsubishi Chemical Corporation. ); "ZX1059" manufactured by Nippon Steel Chemical & Material Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase ChemteX Corporation (glycidyl ester type epoxy resin); "Celloxide 2021P" manufactured by Daicel Corporation (alicyclic epoxy resin with an ester skeleton); "PB-3600" manufactured by Daicel Corporation (epoxy resin with a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.

[0223] Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC Corporation; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200HH", "HP-7200H", and "HP-7200" (dicyclopentadiene epoxy resins) manufactured by DIC Corporation. ene type epoxy resins); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", and "HP6000" (naphthylene ether type epoxy resins) manufactured by DIC; "EPPN-502H" (trisphenol type epoxy resins) manufactured by Nippon Kayaku; "NC7000L" (naphthol novolac type epoxy resins) manufactured by Nippon Kayaku; "NC3000H", "NC3000", and "NC3000L" manufactured by Nippon Kayaku ","NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; " Examples of epoxy resins include "YX8800" (anthracene type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; and "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical.

[0224] The epoxy equivalent of the epoxy resin 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. The epoxy equivalent is the mass of a compound containing one equivalent of an epoxy group. This epoxy equivalent can be measured according to JIS K7236.

[0225] The weight average molecular weight (Mw) of the epoxy resin is preferably from 100 to 5000, more preferably from 250 to 3000, and further preferably from 400 to 1500. The Mw of the epoxy resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0226] When the resin composition contains an epoxy resin, the content of the epoxy resin in the resin composition, relative to 100 mass% of non-volatile components in the resin composition, is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, even more preferably 0.5 mass% or more, 1 mass% or more, or 1.5 mass% or more, and is preferably 10 mass% or less, more preferably 5 mass% or less, or 3 mass% or less.

[0227] Examples of epoxy resin curing agents include active ester curing agents, phenolic curing agents, naphthol curing agents, benzoxazine curing agents, cyanate ester curing agents, carbodiimide curing agents, amine curing agents, acid anhydride curing agents, etc. These may be used alone or in combination of two or more.

[0228] The content of the epoxy resin curing agent is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, and even more preferably 0.5 mass% or more, and is preferably 10 mass% or less, more preferably 5 mass% or less, based on 100 mass% of the non-volatile components in the resin composition.

[0229] The resin composition may further contain any additive. Examples of such additives include curing accelerators other than the above-mentioned peroxide-based curing accelerators, such as phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators; organic fillers such as rubber particles; 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; defoamers such as silicone-based defoamers, acrylic defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; antioxidants such as hindered phenol antioxidants and hindered amine antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; and stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers. These additives may be used alone or in combination of two or more. The content of each additive can be appropriately determined by those skilled in the art.

[0230] The resin composition may further contain an arbitrary organic solvent as a volatile component in addition to the non-volatile components described above. As the organic solvent, a known one can be appropriately used, and the type is not particularly limited. Examples of the organic solvent include ketone-based solvents such as acetone, methyl ethyl ketone, 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, and diphenyl ether; 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 methyl methoxypropionate. Examples of the organic solvent include ether ester 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. The organic solvent may be used alone or in combination of two or more.

[0231] In the present invention, the resin composition can be produced, for example, by adding and mixing the components (A), (B), and (C), and if necessary, the components (D) and (E), epoxy resin, epoxy resin curing agent, other additives, and organic solvent in any preparation vessel in any order and / or all or part of them at the same time. In the process of adding and mixing each component, the temperature can be appropriately set, and heating and / or cooling may be performed temporarily or throughout. In the process of adding and mixing or thereafter, the resin composition may be stirred or shaken using a stirring device or shaking device such as a mixer to disperse the resin composition uniformly. In addition, degassing may be performed under low pressure conditions such as under vacuum at the same time as stirring or shaking.

[0232] The resin sheet of the present invention can be produced, for example, by preparing the above-mentioned resin composition, preparing a resin varnish by dissolving the liquid resin composition in an organic solvent, applying the resin varnish to a support using a die coater or the like, and then drying the support to form a resin composition layer. When preparing the resin varnish, the organic solvent may be one described above.

[0233] Drying may be performed by a known method such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer becomes 10 mass% or less, preferably 5 mass% or less. Although it varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when a resin composition or resin varnish containing 15 mass% to 60 mass% of the organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 1 minute to 10 minutes.

[0234] In the resin sheet of the present invention, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, from the viewpoint of thinning the printed wiring board. 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.

[0235] <any layer> The resin sheet of the present invention may include an optional layer. Examples of the optional layer include a protective film, a barrier film, and a metal foil. The material of the protective film, the barrier film, and the metal foil is preferably selected from the group of materials of the support listed above. The optional layer is preferably provided so as to be peelable from the resin sheet. The optional layer is preferably provided on the surface of the resin sheet that is not bonded to the support of the resin composition layer (i.e., the surface opposite to the support), thereby making it possible to suppress adhesion of dirt and the like to the surface of the resin composition layer and scratches. The thickness of the optional layer is not particularly limited, but is, for example, 1 μm to 100 μm.

[0236] The resin sheet can be stored in a rolled form. When the resin sheet has an optional layer such as a protective film, a barrier film, or a metal foil, the resin sheet can be used by peeling off the optional layer.

[0237] The resin sheet of the present invention can be suitably used to form an insulating layer of a printed wiring board (for the insulating layer of a printed wiring board), and can be more suitably used to form an interlayer insulating layer of a printed wiring board (for the interlayer insulating layer of a printed wiring board). The resin sheet of the present invention can also be suitably used when the printed wiring board is a circuit board with built-in components, since it provides an insulating layer with good component embedding properties. The resin sheet of the present invention can also be suitably used to form an insulating layer on which a conductor layer (including a rewiring layer) is provided (for the insulating layer for forming a conductor layer). The resin sheet of the present invention can also be used in a wide range of applications, such as solder resist, underfill material, die bonding material, semiconductor encapsulation material, hole filling resin, and component embedding resin.

[0238] In one embodiment, the cured product formed using the resin sheet of the present invention is characterized by a low dielectric constant (Dk). For example, when measured at 5.8 GHz and 23°C as described in the <Evaluation of Dielectric Properties> section below, the dielectric constant (Dk) of the cured product of the resin composition layer for the resin sheet of the present invention can be preferably 3.0 or less or 2.9 or less.

[0239] In one embodiment, the cured product formed using the resin sheet of the present invention is characterized by a low dielectric loss tangent (Df). For example, when measured at 5.8 GHz and 23° C. as described in the <Evaluation of Dielectric Properties> section below, the dielectric loss tangent (Df) of the cured product of the resin composition layer for the resin sheet of the present invention can be preferably 0.0030 or less, 0.0029 or less, or 0.0028 or less.

[0240] In one embodiment, the cured product formed using the resin sheet of the present invention is characterized by excellent adhesion to a conductor. For example, the adhesion strength to a conductor measured by the method described in the <Evaluation of Adhesion to a Conductor> section below can be preferably 0.50 kgf / cm or more, 0.52 kgf / cm or more, or 0.54 kgf / cm or more.

[0241] In one embodiment, the cured product formed using the resin sheet of the present invention is characterized by excellent mechanical properties. For example, the maximum stress measured by the method described in the section <Evaluation of mechanical properties (maximum stress and breaking elongation)> below can be preferably 100 MPa or more, 101 MPa or more, 102 MPa or more, or 105 MPa or more. In addition, the breaking elongation can be preferably 1.4% or more, or 1.5% or more.

[0242] In one embodiment, the cured product formed using the resin sheet of the present invention tends to exhibit excellent insulation reliability. For example, when the HAST test is performed under conditions of 130°C and 85% RH according to the method described in the <Evaluation of insulation reliability> section below, the insulation resistance value after 300 hours is preferably more than 50% of the initial insulation resistance value, more preferably 51% or more, or 52% or more.

[0243] [Printed wiring board] A printed wiring board can be produced using the resin sheet of the present invention. In this case, the printed wiring board includes an insulating layer made of a cured product of the resin composition layer in the resin sheet of the present invention.

[0244] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet, by a method including the following steps (I) and (II). (I) A step of laminating a resin sheet on an inner layer substrate such that a resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) A step of curing (e.g., heat curing) the resin composition layer to form an insulating layer.

[0245] The "inner layer substrate" used in step (I) is a member that becomes the substrate of the printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. The substrate may have a conductor layer on one or both sides, and the conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be called an "inner layer circuit substrate". In addition, an intermediate product on which an insulating layer and / or a conductor layer is to be formed during the manufacture of a printed wiring board is also included in the "inner layer substrate" of the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0246] The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as the "thermocompression bonding member") include a heated metal plate (such as a SUS plate) or a metal roll (SUS roll). The thermocompression bonding member may be pressed directly onto the resin sheet, or may be pressed via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface irregularities of the inner layer substrate.

[0247] The lamination of the inner layer substrate and the resin sheet may be performed 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 in the range of 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination may be performed under reduced pressure conditions, preferably at a pressure of 26.7hPa or less.

[0248] The lamination can be performed by 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 type vacuum pressure laminator.

[0249] After lamination, the laminated resin sheet 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 the lamination. The smoothing treatment may be performed using a commercially available laminator. The lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0250] The support may be removed between step (I) and step (II), but is preferably removed or peeled off after step (II).

[0251] A preferred embodiment of the method for producing a printed wiring board is as follows. A method for manufacturing a printed wiring board, comprising the steps of: The following process: (1) a step of preparing a resin sheet including a support and a resin composition layer provided on the support, one side of the resin composition layer being exposed; (2) laminating the resin sheet on a substrate of the printed wiring board such that the resin composition layer is laminated on the substrate; and (3) A step of curing the resin sheet laminated on the substrate in a state in which the support is not peeled off from the resin composition layer. Including, the resin composition layer contains (A) a benzocyclobutene resin, (B) an inorganic filler, and (C) a radical polymerizable resin, The resin composition layer is When cured at 220℃ for 90 minutes, the oxygen permeability α is 70cc / m 2 ·day or less, The resin sheet in which one surface of the resin composition layer is exposed is When cured at 220℃ for 90 minutes, the oxygen permeability β is 40cc / m 2 ·day or less, Here, the oxygen permeability α and the oxygen permeability β are measured in accordance with JIS K7126-2:2006 (isobaric method) under an atmosphere of 23°C and 0% RH. A method for manufacturing a printed wiring board.

[0252] When a metal foil is used as the support, the conductor layer may be formed using the metal foil without peeling off the support. When a metal foil with a support substrate is used as the support, the support substrate (and the peel layer) may be peeled off. Then, the conductor layer can be formed using the metal foil.

[0253] In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of a cured product of the resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions that are usually adopted when forming an insulating layer for a printed wiring board may be used.

[0254] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, etc., but in one embodiment, the curing temperature is preferably 120° C. to 250° C., more preferably 150° C. to 240° C., and even more preferably 180° C. to 230° C. The curing time can be preferably 5 minutes to 240 minutes, more preferably 10 minutes to 150 minutes, and even more preferably 15 minutes to 120 minutes.

[0255] Before the resin composition layer is thermally cured, 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 120° C., preferably 60° C. to 115° C., more preferably 70° C. to 110° 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.

[0256] In manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in manufacturing printed wiring boards. When the support is removed after step (II), the removal of the support may be carried out between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). In addition, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated to form a multilayer wiring board, as necessary.

[0257] Step (III) is a step of drilling holes in the insulating layer, which allows holes such as via holes and through holes to be formed in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined depending on the design of the printed wiring board.

[0258] Step (IV) is a step of roughening the insulating layer. Usually, smears are also removed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by carrying out 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.

[0259] The swelling liquid used in the roughening treatment is not particularly limited, but includes an alkaline solution, a surfactant solution, etc., and is preferably an alkaline solution, and more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment using the swelling liquid is not particularly limited, but can be performed by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 to 20 minutes, for example. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 to 15 minutes.

[0260] The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Atotech Japan.

[0261] 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 mentioned.

[0262] The treatment with the 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 viewpoint of workability, etc., a method in which the object that has been roughened with an oxidizing agent is immersed in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferred.

[0263] 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, and examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among these, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, and the like, 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.

[0264] The conductor layer may be a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds 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.

[0265] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, and preferably 5 μm to 30 μm.

[0266] 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 by a conventionally known technique such as a semi-additive method or a full-additive method, and from the viewpoint of ease of production, it is preferable to form the conductor layer by the semi-additive method. An example of forming the conductor layer by the semi-additive method will be described below.

[0267] 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 to expose a part of the plating seed layer corresponding to a 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 to form a conductor layer having a desired wiring pattern.

[0268] In another embodiment, the conductor layer may be formed using a metal foil. When the conductor layer is formed using a metal foil, it is preferable to carry out step (V) 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 lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is carried out to form an insulating layer. Thereafter, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method or a modified semi-additive method, using the metal foil on the insulating layer.

[0269] The metal foil can be produced by a known method such as an electrolytic method, a rolling method, etc. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd.

[0270] Alternatively, when a metal foil or a metal foil with a supporting substrate is used as the support for the resin sheet, the conductor layer may be formed using the metal foil, as described above.

[0271] In addition, the resin composition layer for a resin sheet of the present invention can be suitably used as a resin composition layer for forming an insulating layer for forming a rewiring layer (resin composition layer for forming a rewiring layer) and a resin composition layer for sealing a semiconductor chip (resin composition layer for sealing a semiconductor chip) when manufacturing a semiconductor chip package. Techniques for manufacturing a semiconductor chip package using a resin composition layer (resin sheet) are widely known in the art, and the resin sheet or its resin composition layer of the present invention can be applied to any method or technique.

[0272] [Semiconductor Devices] A semiconductor device can be manufactured to include an insulating layer made of a cured product of the resin composition layer for a resin sheet of the present invention. Such a semiconductor device can be manufactured using the above-mentioned printed wiring board or semiconductor package.

[0273] Examples of the semiconductor device include various semiconductor devices used in electric appliances (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircraft). EXAMPLES

[0274] The present invention will be specifically described 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 and pressure conditions are room temperature (25°C) and atmospheric pressure (1 atm).

[0275] First, various measurement and evaluation methods will be explained.

[0276] [Preparation of samples for measurement and evaluation] 1. Preparation of cured materials for evaluation The protective film was peeled off from the resin sheet A with the protective film produced in the examples and comparative examples to expose one side of the resin composition layer. Then, the resin composition layer was quickly heat-cured under a nitrogen atmosphere at 220°C for 90 minutes. This resulted in a resin sheet B consisting of a support and a cured product provided on the support. Furthermore, a portion of the resin sheet B was cut out and the support was peeled off to expose both sides of the resin composition layer, thereby obtaining a film-like cured product C made of the cured product of the resin composition layer.

[0277] 2. Preparation of the first evaluation board (1) Copper foil preparation The shiny surface of "3EC-III" (electrolytic copper foil, 35μm) manufactured by Mitsui Mining & Smelting Co., Ltd. was immersed in MEC Etch Bond "CZ-8201" manufactured by MEC Corporation to roughen the copper surface to a Ra value of 0.5μm. Then, it was subjected to anti-rust treatment (CL8300) and further to heat treatment in an oven at 130°C for 30 minutes. As a result, a copper foil with a low surface roughness (hereinafter referred to as "CZ copper foil") was obtained.

[0278] (2) Preparation of the substrate The protective film was peeled off from the resin sheet A with the protective film produced in the examples and comparative examples to expose one side of the resin composition layer. Then, using a batch-type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Co., Ltd.), the resin sheet from which the protective film had been peeled off was laminated on both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, manufactured by Panasonic Corporation "R1515A") on which an inner layer circuit was formed, so that the exposed side of the resin composition layer was bonded to the laminate. The lamination was performed by reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less, and then pressing at 100°C and a pressure of 0.74 MPa for 30 seconds. After the lamination, the support was peeled off from the resin sheet. Then, the treated side of the CZ copper foil was laminated on the exposed side of the resin composition layer under the same conditions as above. After the lamination treatment, the resin composition layer was thermally cured at 220° C. for 90 minutes to form a cured product (insulating layer). In this manner, a substrate D having CZ copper foils laminated on both sides was produced.

[0279] 3. Preparation of the second evaluation board An imide film having a comb-shaped electrode (line / space: 15 μm / 15 μm) formed on one side was prepared. The protective film was peeled off from the resin sheet A with the protective film to expose one side of the resin composition layer. Then, using a batch-type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.), the exposed surface of the resin composition layer was laminated so as to be joined to the circuit formation surface (electrode formation surface) of the imide film. The lamination was performed by reducing the pressure for 30 seconds to 13 hPa or less, and then pressing at 100°C and a pressure of 0.74 MPa for 30 seconds. Thereafter, the resin composition layer was cured by heating at 100°C for 30 minutes, followed by heating at 220°C for 90 minutes in a nitrogen atmosphere. In this way, a substrate E including an imide film and a cured product of the resin composition layer provided on the imide film was produced.

[0280] <Oxygen permeability measurement> The oxygen permeability was measured for resin sheet B and cured product C. Using an oxygen permeability measuring device ("OX-TRAN2 / 21" manufactured by MOCON), measurements were performed in accordance with JIS K7126-2:2006 (constant pressure method) in an atmosphere of 23°C and 0% RH. The oxygen permeability of resin sheet B is designated as "oxygen permeability β" and the oxygen permeability of cured product C is designated as "oxygen permeability α". Further, the oxygen permeability was measured in the same manner as above for the support used in producing the protective film-attached resin sheet A. The oxygen permeability of each support used in the examples and comparative examples is shown below. Oxygen permeability of support A: 40cc / m 2 ·day Oxygen permeability of support B: 0.1cc / m 2 ·day Oxygen permeability of support C: 0.1cc / m 2 ·day

[0281] <Evaluation of dielectric properties> The dielectric properties of the cured product C were evaluated. Specifically, the cured product C was cut into a piece 2 mm wide and 80 mm long to obtain a test piece. The dielectric constant (Dk value) and dielectric loss tangent (Df value) of the obtained test piece were measured by a cavity resonance perturbation method using an Agilent Technologies "HP8362B" at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Measurements were performed on three test pieces (n=3), and the average value was calculated. The dielectric properties of the cured product C were evaluated according to the following evaluation criteria.

[0282] Dielectric property evaluation criteria: ○: The average dielectric constant is 3.0 or less, and the average dielectric tangent is 0.0030 or less (excellent dielectric properties) ×: Either or both of the average value of the dielectric constant and the average value of the dielectric tangent do not satisfy the above criteria (poor dielectric properties)

[0283] <Evaluation of Conductor Adhesion> Using evaluation substrate D, conductor adhesion was evaluated. In detail, the evaluation board D was cut into small pieces of 150×30 mm. A cutter was used to make a 10 mm wide and 100 mm long cut in the copper foil part of the small piece. Then, one end of the copper foil was peeled off and held with a gripper attached to the tensile tester described below, and the load [kgf / cm] was measured when peeling 35 mm in the vertical direction at a speed of 50 mm / min at room temperature (normal temperature). A tensile tester (Autocom Universal Tester "AC-50C-SL" manufactured by TSE Corporation) was used for the measurement. The measurement was performed in accordance with the Japanese Industrial Standard JIS C6481. The load value obtained as a result of the measurement is hereinafter referred to as "conductor adhesion strength". The conductor adhesion was evaluated according to the following evaluation criteria.

[0284] Conductor adhesion evaluation criteria: ○: Conductor adhesion strength is 0.50kgf / cm or more (excellent conductor adhesion) ×: Conductor adhesion strength is less than 0.50 kgf / cm (poor conductor adhesion)

[0285] <Evaluation of mechanical properties (maximum stress and breaking elongation)> The mechanical properties of the cured product C were evaluated. Specifically, the cured product C was cut into a dumbbell-shaped No. 1 test piece to obtain it. The obtained test piece was subjected to tensile strength measurement at a test speed of 5 mm / min using an Orientec tensile tester "RTC-1250A", and the breaking elongation and maximum stress at 23°C were measured. The measurement was carried out in accordance with JIS K7127. The measurement was carried out five times (n=5), and the average of the top three points was calculated. The mechanical properties of the cured product were evaluated according to the following evaluation criteria.

[0286] Mechanical property evaluation criteria: ○: The average breaking elongation is 1.4% or more, and the average maximum point stress is 100 MPa or more (excellent mechanical properties) ×: Either or both of the average value of the maximum stress and the average value of the breaking elongation do not meet the above criteria (inferior mechanical properties)

[0287] <Evaluation of insulation reliability> Using the substrate E, the insulation reliability was evaluated. In detail, first, the initial insulation resistance value of the substrate E was measured. Then, the substrate E was placed in a high-temperature and high-humidity chamber in an atmosphere of 130°C and 85% humidity, and a voltage of 3.3 V was charged. The HAST test was performed in the chamber for 300 hours under the conditions of 130°C and 85% RH. After 300 hours, the insulation resistance value of the substrate F was measured and evaluated according to the following criteria.

[0288] Insulation reliability evaluation criteria: 〇: Insulation resistance after 300 hours is more than 50% of the initial insulation resistance (excellent insulation reliability) ×: Insulation resistance after 300 hours is 50% or less of the initial insulation resistance (poor insulation reliability)

[0289] <Synthesis Example 1> (Synthesis of solution of thermoplastic resin d) A 500 mL separable flask equipped with a water content receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer was prepared. 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 29.6 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane were added to this flask, and the mixture was stirred at 45°C for 2 hours under a nitrogen stream to carry out a reaction. Next, the reaction solution was heated and maintained at about 160°C, while the condensed water was azeotropically removed together with toluene under a nitrogen stream. It was confirmed that a predetermined amount of water had accumulated in the water content receiver, and that no water was flowing out. After confirmation, the reaction solution was further heated and stirred at 200°C for 1 hour. The mixture was then cooled to obtain a solution (20% by mass of non-volatile components) containing a thermoplastic resin having a 1,1,3-trimethylindane skeleton (hereinafter also referred to as "thermoplastic resin d"). The obtained thermoplastic resin d was a polyimide compound having a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). The weight average molecular weight of the thermoplastic resin d was 12,000.

[0290] [ka]

[0291] [ka]

[0292] -Examples 1 to 6, Comparative Examples 1 to 5- Examples and comparative examples are illustrated below with respect to embodiments of a resin sheet including a support and a resin composition layer including a component selected from the group consisting of the components (A), (B), and (C).

[0293] [Example 1] (1) Preparation of Resin Composition Constituting Resin Composition Layer 28.6 parts (20 parts as non-volatile components) of radical polymerizable resin c1 ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.; MEK / toluene mixed solution with 70% by mass of non-volatile components) as component (C) and 28.6 parts (10 parts as non-volatile components) of benzocyclobutene resin a ("CYCLOTEN (registered trademark) 3022" manufactured by Dow Chemical Co.; number average molecular weight: 390, mesitylene solution with 35% by mass of non-volatile components) as component (A) were dissolved in 10 parts of methyl ethyl ketone (MEK) by heating with stirring. This gave a solution.

[0294] The non-volatile component contained in the radical polymerizable resin c1 ("MIR-3000-70MT") is represented by the following structural formula: In the formula, e1 is an integer of 1-100.

[0295] [ka]

[0296] The resulting solution was cooled to room temperature. Then, 13.8 parts (9 parts as non-volatile components) of a radical polymerizable resin c2 ("OPE-2St" (oligophenylene ether-styrene resin) manufactured by Mitsubishi Gas Chemical Co., Ltd.; number average molecular weight: 1200, toluene solution containing 65% by mass of non-volatile components) as component (C), inorganic filler b (spherical silica "SO-C2" manufactured by Admatechs Co., Ltd., surface-treated with an amine-based silane coupling agent "KBM573" manufactured by Shin-Etsu Chemical Co., Ltd. (average particle size: 0.5 μm, specific surface area: 5.8 m) as component (B) were added to the solution. 2 The mixture was mixed and dispersed uniformly in a high-speed rotating mixer. This resulted in a dispersion. As a result, a resin varnish (non-volatile content: 69% by mass) of the resin composition containing the (A) to (E) components was prepared.

[0297] (2) Preparation of resin sheet with protective film A PET film ("Lumirror R80" manufactured by Toray Industries, Inc.; thickness 38 μm, softening point 130° C.) whose one main surface was release-treated with an alkyd resin-based release agent ("AL-5" manufactured by Lintec Corporation) was prepared as the support A. The overall thickness (total thickness) of the support A was 38 μm.

[0298] The resin varnish of the resin composition prepared in (1) above was uniformly applied onto the release-treated surface of the support A using a die coater so that the thickness of the resin composition layer after drying was 40 μm, and then dried for 3 minutes at 90° C. In this way, a resin sheet including the support A and the resin composition layer provided on the support A was obtained.

[0299] Next, the support A as a protective film was laminated on the exposed surface of the resin composition layer (the surface not bonded to the support A) so that its release-treated surface was bonded to the resin composition layer. This resulted in a resin sheet including the support, the resin composition layer provided on the support, and the protective film provided on the resin composition layer. The resin sheet thus obtained is also collectively referred to as "resin sheet A with protective film".

[0300] [Example 2] A resin varnish was prepared in the same manner as in Example 1, except that 1) the amount of benzocyclobutene resin a was changed from 28.6 parts to 38.5 parts (25 parts as non-volatile components), 2) the amount of radical polymerizable resin c1 was changed from 28.6 parts to 0 parts (i.e., no resin was added), and the amount of radical polymerizable resin c2 was changed from 13.8 parts to 21.5 parts (14 parts as non-volatile components). A resin varnish was prepared and a resin sheet was produced using support A.

[0301] [Example 3] A resin varnish was prepared in the same manner as in Example 1, except that 1) the amount of inorganic filler b was changed from 60 parts to 40 parts, 2) the amount of radical polymerizable resin c1 was changed from 28.6 parts to 42.9 parts (19 parts as non-volatile components), and the amount of radical polymerizable resin c2 was changed from 13.8 parts to 29.2 parts (14 parts as non-volatile components). A resin varnish was prepared and a resin sheet was produced using support A.

[0302] [Example 4] A resin varnish was prepared in the same manner as in Example 3, except that the support A was changed to the support B, and a resin sheet was produced using the support B. As the support B, a PET film ("Lumirror R80" manufactured by Toray Industries, Inc.; thickness 38 μm) was used, which had an alkyd-based release treatment ("AL-5" manufactured by Lintec Corporation) on one main surface of the film, and a PET film ("Techbarrier (registered trademark) HX" manufactured by Mitsubishi Chemical Corporation; thickness 12 μm) on which a 300 nm silica deposition layer was formed on the other main surface via an adhesive layer (thickness 3 μm). The thickness (total thickness) of the entire support B was 53 μm.

[0303] [Example 5] A resin varnish was prepared in the same manner as in Example 3, except that the support A was changed to the support C, and a resin sheet was produced using the support C. The support C was prepared as follows. First, a metal-film-attached film (layer structure: 38 μm thick PET film / 2 μm thick water-soluble resin layer / 1000 nm thick copper layer) was prepared, which was the same as the metal-film-attached film described in Example 1 of Japanese Patent No. 5500074. Next, an alkyd-based release treatment ("AL-5" manufactured by Lintec Corporation) was applied to the exposed surface of the PET film of this metal-film-attached film. The thickness (total thickness) of the entire support C obtained in this manner was 41 μm.

[0304] [Example 6] A resin varnish was prepared in the same manner as in Example 1, except that 1) the amount of inorganic filler b was changed from 60 parts to 50 parts, 2) the amount of radical polymerizable resin c1 was changed from 28.6 parts to 0 parts (i.e., no filler), and the amount of radical reactive resin c2 was changed from 13.8 parts to 15.4 parts (10 parts as non-volatile components), 3) the amount of thermoplastic resin d was changed from 5 parts to 150 parts (30 parts as non-volatile components), and 4) support A was changed to support B. A resin varnish was prepared in the same manner as in Example 1, and a resin sheet was produced using support B.

[0305] [Comparative Example 1] A resin varnish was prepared in the same manner as in Example 1, except that 1) the amount of radically polymerizable resin c1 was changed from 28.6 parts to 0 parts (i.e., no blend) and the amount of radically polymerizable resin c2 was changed from 13.8 parts to 0 parts (i.e., no blend) (i.e., component (C) was not used), and 3) the amount of thermoplastic resin d was changed from 5 parts to 150 parts (30 parts as non-volatile components). A resin varnish was prepared and a resin sheet was produced using support A.

[0306] [Comparative Example 2] A resin varnish was prepared in the same manner as in Example 1, except that 1) the amount of inorganic filler b was changed from 60 parts to 40 parts, 2) the amount of radical polymerizable resin c1 was changed from 28.6 parts to 0 parts (i.e., no filler), and the amount of radical polymerizable resin c2 was changed from 13.8 parts to 15.4 parts (10 parts as non-volatile components), and 3) the amount of thermoplastic resin d was changed from 5 parts to 200 parts (40 parts as non-volatile components). A resin varnish was prepared and a resin sheet was produced using support A.

[0307] [Comparative Example 3] A resin varnish was prepared in the same manner as in Comparative Example 2, except that 1) the amount of benzocyclobutene resin a was changed from 28.6 parts to 85.7 parts (30 parts as non-volatile components) and 2) the amount of inorganic filler b was changed from 40 parts to 20 parts. A resin sheet was produced using support A.

[0308] [Comparative Example 4] A resin varnish was prepared in the same manner as in Comparative Example 3, except that support A was changed to support B, and a resin sheet was produced using support B.

[0309] [Comparative Example 5] A resin varnish was prepared in the same manner as in Example 6, except that support B was changed to support A, and a resin sheet was produced using support A.

[0310] The results of Examples 1 to 6 and Comparative Examples 1 to 5 are shown in Tables 1 and 2.

[0311] [Table 1]

[0312]

Table 2

Claims

1. A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition layer comprises (A) a compound having two or more benzocyclobutene groups in the molecule, (B) an inorganic filler, and (C) a resin having a radical polymerizable unsaturated group in the molecule, The number average molecular weight (Mn) of component (A) is 2000 or less, The resin composition layer is When cured at 220°C for 90 minutes, the oxygen permeability α is 70cc / m ２ ・day or less, The resin sheet is When cured at 220°C for 90 minutes, the oxygen permeability β is 40 cc / m ２ ・day or less, Here, the oxygen permeability α and the oxygen permeability β are measured in accordance with JIS K7126-2:2006 (isobaric method) under an atmosphere of 23°C and 0% RH. Resin sheet.

2. The resin sheet according to claim 1 , wherein the content of the component (B) is 30% by mass or more and 80% by mass or less, based on 100% by mass of non-volatile components in the resin composition.

3. The resin sheet according to claim 1 or 2, wherein the content of the component (A) is 3% by mass or more and 40% by mass or less, based on 100% by mass of non-volatile components in the resin composition.

4. The resin sheet according to any one of claims 1 to 3, wherein the component (C) is at least one selected from a resin having a maleimide group, a resin having an acryloyl group, a resin having a methacryloyl group, and a resin having a styryl group.

5. The support is selected from a single-layer resin film, a multi-layer resin film, a metal foil, a release paper, and a composite film containing a supporting substrate and a metal foil. The resin sheet according to any one of claims 1 to 4.

6. The resin sheet according to any one of claims 1 to 5, wherein the component (A) has a siloxane skeleton.

7. The resin sheet according to any one of claims 1 to 6, wherein the component (A) includes a compound represented by the following formula (A-2): 【Chemistry 1】 (In formula (A-2), R １ represents a divalent aliphatic group having an unsaturated bond, R ２ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an arylalkyl group, or an aryl group; R Ａ１ represents an alkyl group, a cyano group, or a halogen atom, R Ａ２ represents an alkyl group, a trialkylsilyl group, an alkoxy group, or a halogen atom, nA1 represents an integer of 0 to 2; nA2 represents an integer of 0 to 3; nA4 represents an integer of 1 to 10. １ , R ２ , R Ａ１ and R Ａ２ Each of R may independently have a substituent. １ may be the same or different, and there are multiple R ２ may be the same or different, R Ａ１ When there are a plurality of R Ａ２ If there are multiple, they may be the same or different.)

8. The resin sheet according to any one of claims 1 to 7, wherein the component (A) comprises a compound represented by the following formula: 【Chemistry 2】

9. The resin sheet according to any one of claims 1 to 8, wherein the cured product of the resin composition layer has a dielectric constant of 3.0 or less.

10. The resin sheet according to any one of claims 1 to 9, wherein the cured product of the resin composition layer has a dielectric tangent value of 0.0030 or less.

11. The resin sheet according to any one of claims 1 to 10, wherein one surface of the cured product of the resin composition layer is exposed when the oxygen permeability β is measured.

12. The resin sheet according to any one of claims 1 to 11, which is for use as an insulating layer in a printed wiring board.

13. A method for manufacturing a printed wiring board, comprising the steps of: The following steps: (1) A step of preparing a resin sheet including a support and a resin composition layer provided on the support, one side of the resin composition layer being exposed; (2) laminating the resin sheet on a substrate of the printed wiring board such that the resin composition layer is laminated on the substrate; and (3) A step of curing the resin sheet laminated on the substrate in a state in which the support is not peeled off from the resin composition layer. Including, the resin composition layer comprises (A) a compound having two or more benzocyclobutene groups in the molecule, (B) an inorganic filler, and (C) a resin having a radical polymerizable unsaturated group in the molecule, The number average molecular weight (Mn) of component (A) is 2000 or less, The resin composition layer is When cured at 220°C for 90 minutes, the oxygen permeability α is 70cc / m ２ ・day or less, The resin sheet in which one surface of the resin composition layer is exposed is When cured at 220°C for 90 minutes, the oxygen permeability β is 40 cc / m ２ ・day or less, Here, the oxygen permeability α and the oxygen permeability β are measured in accordance with JIS K7126-2:2006 (isobaric method) under an atmosphere of 23°C and 0% RH. A method for manufacturing a printed wiring board.

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