resin sheets

Abstract

The objective of this invention is to provide a resin sheet or the like that exhibits good mechanical strength while also being expected to exhibit dielectric properties in a cured form. This objective can be achieved by using a resin sheet for forming an insulating layer, which is processed by vacuum pressure. The resin sheet includes a support and a resin composition layer disposed on the support. The support has a metal foil, and the resin composition layer contains (A) a free radical polymerizable compound.

Description

[Technical Field]

[0001] This invention relates to resin sheets, and more particularly to printed wiring boards, semiconductor devices, and methods for manufacturing printed wiring boards using the resin sheets. [Previous Technology]

[0002] In the manufacture of printed circuit boards, the insulating layer, for example as described in Patent Document 1, is formed on the circuit board by laminating a resin composition layer of resin sheets and then curing it using a vacuum lamination method. [Prior Art Documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2017-59779 [Summary of the Invention]

[0004] [The problem solved by the invention]

[0005] With the increasing speed of transmission, there is a growing expectation for lower dielectric constant and lower dielectric loss in insulating materials. Regarding improvements in these dielectric properties, free radical polymeric compounds, as curing compounds used in insulating materials, are anticipated. However, when using these free radical polymeric compounds to form cured materials (insulating layers), the mechanical strength of the resulting cured materials sometimes deteriorates, and the desired dielectric properties are sometimes not observed.

[0006] The object of the present invention is to provide a resin sheet that exhibits good mechanical strength while also being expected to exhibit dielectric properties; to provide a printed circuit board and a semiconductor device formed using the resin sheet; and a method for manufacturing the printed circuit board. [Means for Solving the Problem]

[0007] Based on a detailed review of the above-mentioned problems, the inventors found that by using a support containing a metal foil and a resin sheet containing a resin composition layer of a (A) free radical polymerizable compound disposed on the support, the above-mentioned problems can be solved by vacuum pressure treatment and forming an insulating layer, thereby completing the present invention.

[0008] That is, the present invention contains the following: [1] A resin sheet, which is a resin sheet for forming an insulating layer using vacuum pressure treatment, wherein it contains a support and a resin composition layer disposed on the support, the support having a metal foil, and the resin composition layer containing (A) a free radical polymerizable compound. [2] The resin sheet described in [1] containing a free radical polymerizable compound comprising maleimide groups (A) is a resin sheet. [3] The resin sheet described in [1] or [2] containing copper foil (A) is a resin sheet. [4] The resin composition layer, in a dynamic viscoelasticity test from 60°C to 200°C, has a maximum tanδ value of 2.0 or less at 100°C or higher (A) of any one of the resin sheets described in [1] to [3]. [5] The resin composition layer further contains (B) a resin sheet described in any one of the thermoplastic resins described in [1] to [4]. [6] The resin composition layer further contains any of the resin flakes described in [1] to [5] of the inorganic filler (C). [7] The content of component (C) is 50% by mass or more of the resin flakes described in [6] when the non-volatile component in the resin composition layer is taken as 100% by mass. [8] A printed wiring board containing an insulating layer formed by a hardened resin composition layer of resin flakes described in [1] to [7]. [9] A semiconductor device containing a printed wiring board described in [8].

[10] A method for manufacturing a printed wiring board, comprising (1) laminating resin flakes described in [1] to [7] on an inner substrate by vacuum pressure treatment, and (2) forming an insulating layer by thermosetting the resin composition layer. [Effects of the Invention]

[0009] According to the present invention, a resin sheet of a cured material exhibiting good mechanical strength and dielectric properties can be obtained; a printed wiring board, a semiconductor device formed using the resin sheet can also be provided; and a method for manufacturing a printed wiring board can also be provided.

Implementation Method

[0011] [Type of Invention Implementation]

[0012] The preferred embodiments of the present invention will be described in detail below. However, the present invention is not limited to the embodiments and examples described below, and can be implemented in any way without departing from the scope of the claims and their equivalents.

[0013] [Resin Sheet] The resin sheet of the present invention is a resin sheet for forming an insulating layer using vacuum pressure processing. The resin sheet comprises a support and a resin composition layer disposed on the support, the support having a metal foil, and the resin composition layer containing a (A) free radical polymerizable compound.

[0014] In improving dielectric properties, compounds with free radical polymerizable unsaturated groups having low polarity reactive functional groups (free radical polymerizable compounds) can be considered as curing compounds used in insulating materials. However, when a curing material (insulating layer) is formed using a free radical polymerizable compound, the mechanical strength of the resulting insulating layer deteriorates, and sometimes the desired dielectric properties are not exhibited. In contrast, the inventors have discovered that by using a resin sheet of the present invention containing a support comprising a metal foil and a resin composition layer containing a free radical polymerizable compound disposed on the support, an insulating layer (cured resin composition layer) is formed by vacuum pressure treatment. The resulting insulating layer exhibits good mechanical strength and excellent flexibility (MIT folding resistance), while also exhibiting the desired dielectric properties. Furthermore, when forming an insulating layer using resin sheets (resin composition layers), compared to the vacuum lamination method used in the past, the inventors have identified a new problem: during vacuum pressure processing, the pressure applied to the resin sheets (resin composition layers) during lamination is higher, leading to resin penetration and preventing the desired insulating layer thickness from being obtained. Regarding the deviation in the insulating layer thickness after vacuum pressure processing (difference from the target thickness), it has been confirmed that it is related to the amount of residual solvent in the resin composition layer, or the maximum value of tanδ in a specific temperature range of the dynamic viscoelasticity of the resin composition layer (where tanδ is the ratio of storage elastic modulus E' (GPa) to loss elastic modulus E' (Pa) E” / E'). Solutions based on these residual solvent amounts or the maximum value of tanδ are described below.

[0015] Hereinafter, each layer constituting the resin sheet will be described in detail.

[0016] <Support> For the resin sheet of the present invention, the support has a metal foil. Thereby, a conductor layer, described later, can be formed from the support.

[0017] As a metal foil, examples include copper foil and aluminum foil, with copper foil being preferred. As a copper foil, foil made of copper as a single metal can be used, or foil made of an alloy of copper with other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

[0018] The metal foil can be a single-layer structure or a multilayer structure consisting of two or more single metal layers or alloy layers made of different types of metals or alloys. Examples of multilayer metal foils include a metal foil containing a carrier metal foil and an extremely thin metal foil bonded to the carrier metal foil. Between the carrier metal foil and the extremely thin metal foil, the multilayer metal foil may contain a release layer that allows the extremely thin metal foil to be peeled off from the carrier metal foil. There are no particular limitations on the release layer; examples include alloy layers selected from elements in the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, and P; organic films, etc. Furthermore, when a multilayer metal foil is used as a support, a resin composition layer is disposed on the extremely thin metal foil.

[0019] There are no particular limitations on the manufacturing method of metal foil. For example, it can be manufactured by known methods such as electrolysis and rolling.

[0020] The support body may use commercially available products. Examples of commercially available products include "HLP foil" and "JXUT-III foil" manufactured by JX NIKKO NISEKI METAL CO., LTD., and "Microsin MT-Ex copper foil" and "TP-III foil" manufactured by Mitsui Mining & Smelting Co., Ltd.

[0021] From the viewpoint that significant effects of the present invention can be obtained, the thickness of the support is preferably 50 μm or less, more preferably 45 μm or less, even more preferably 40 μm or less, 35 μm or less, or 30 μm or less, preferably 1 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more. Furthermore, when the metal foil is a multilayer structure, it is preferable that the overall thickness of the metal foil is within this range, wherein the thickness of the extremely thin metal foil can, for example, be in the range of 0.1 μm or more and 10 μm or less.

[0022] <Resin Composition Layer> For the resin sheet of the present invention, the resin composition layer disposed on the support contains (A) a free radical polymerizable compound.

[0023] The resin composition layer may contain any components that are combined with component (A). Examples of such arbitrary components include (B) thermoplastic resin, (C) inorganic filler, (D) polymerization initiator, and (E) other additives. The components contained in the resin composition layer will be described in detail below.

[0024] -(A) Free radical polymerizable compound- Free radical polymerizable compound may be contained as component (A) in the resin composition layer. By using a support containing a metal foil and a resin composition layer containing component (A), a cured material with excellent dielectric properties can be obtained. Component (A) may be used alone or in combination with two or more.

[0025] As component (A), a compound that can be polymerized by generating free radicals through heat or light can be used, i.e., a compound having a free radical polymerizable unsaturated group can be used. Examples of free radical polymerizable unsaturated groups include groups with vinyl double bonds that exhibit hardening properties when irradiated by active energy lines. Examples of such free radical polymerizable unsaturated groups include vinyl, allyl, vinylphenyl, acrylonitrile, methacrylamide, maleimino, fumarate, and maleyl, preferably selected from at least one of maleimino, allyl, vinylphenyl, acrylonitrile, and methacrylamide.

[0026] As component (A), it is preferred to have one or more unsaturated groups with free radical polymerization properties, and it is even more preferred to have two or more. There is no particular limit to the upper limit, and it can be less than 10, etc.

[0027] As a compound having a free radical polymerizable unsaturated group, it is preferred to include at least one of the following: a free radical polymerizable compound containing a maleimide group (maleimide-based free radical polymerizable compound), a free radical polymerizable compound containing a vinylphenyl group (vinylphenyl-based free radical polymerizable compound), a free radical polymerizable compound containing a (meth)acrylic acid group ((meth)acrylic acid-based free radical polymerizable compound), a free radical polymerizable compound containing an allyl group (allyl-based free radical polymerizable compound), and a free radical polymerizable compound containing a butadiene skeleton (butadiene-based free radical polymerizable compound). It is more preferred to include at least any one of a maleimide-based free radical polymerizable compound, a vinylphenyl-based free radical polymerizable compound, an allyl-based free radical polymerizable compound, and a (meth)acrylic acid-based free radical polymerizable compound. It is even more preferred to include a maleimide-based free radical polymerizable compound.

[0028] Maliimines are free radical polymerizable compounds containing maleimide groups as shown in formula (A-1) in their molecules.

[0029] The maleimide-based free radical polymerizable compound is preferably one of the following (A1) to (A3). The resin composition layer is preferably containing at least one of the maleimide-based free radical polymerizable compounds (A1) to (A3), more preferably containing a plurality of (A1) to (A3), and even more preferably containing all (A1) to (A3). (A1) Solid maleimide-based free radical polymerizable compound. (A2) Liquid or semi-solid maleimide-based free radical polymerizable compound. (A3) Maleimide-based free radical polymerizable compound containing a backbone of aromatic rings and aliphatic hydrocarbon rings condensed together. However, the maleimide-based free radical polymers of (A1) and (A2) exclude those equivalent to the maleimide-based free radical polymers of (A3).

[0030] The determination of whether a substance is liquid, semi-solid, or solid can be made in accordance with the second part of the Ministry Ordinance on the testing and properties of hazardous materials (Ministry of Home Affairs Ordinance No. 1 of 1962), "Method for Confirmation of Liquid Form". The specific determination method is as follows.

[0031] (1) Thermostatic water bath: The bath should be equipped with a stirrer, heater, thermometer, and automatic temperature regulator (which can control the temperature within ±0.1℃) and have a depth of 150mm or more. In determining whether the water is liquid, semi-solid or solid, a combination of a low-temperature thermostatic water bath (model BU300) and an immersion thermostatic heater (model BF500) manufactured by Yamato Scientific Co., Ltd. is used. Approximately 22 liters of tap water are placed in the low-temperature thermostatic water bath (model BU300), the power supply of the heater (model BF500) installed therein is turned on, and the set temperature (20℃ or 60℃) is set. The water temperature can be finely adjusted to the set temperature ±0.1℃ by the heater (model BF500). However, the device can be adjusted to the same value, and any one of them can be used.

[0032] Test Tube: As shown in Figure 1, a flat-bottomed cylindrical transparent glass tube with an inner diameter of 30 mm and a height of 120 mm is used as the test tube. Markings 11A and 12B are made at heights of 55 mm and 85 mm from the bottom of the tube, respectively. A liquid judgment test tube 10a with a rubber plug 13a is sealed at the tube opening, and a rubber plug 13b with the same markings and a hole in the center for inserting and supporting a thermometer is sealed at the tube opening. The temperature measurement test tube 10b with a thermometer 14 is inserted into the rubber plug 13b. Hereinafter, the height mark at 55 mm from the bottom of the tube is referred to as "Line A", and the height mark at 85 mm from the bottom of the tube is referred to as "Line B". As for the thermometer 14, a glass thermometer for freezing point determination as specified in JIS B7410 (1982) "Glass Thermometers for Petroleum Testing" (SOP-58 scale range 0 to 100°C) is used. Any thermometer that can measure a temperature range of 0 to 100°C is acceptable.

[0033] (2) The test procedure is as follows: The test samples placed at atmospheric pressure of 60±5℃ for more than 24 hours are placed in the liquid determination test tube 10a shown in Figure 1(a) and the temperature measurement test tube 10b shown in Figure 1(b) up to line 11A. The two test tubes 10a and 10b are placed upright in a low-temperature constant temperature water bath with line 12B below the water surface. The thermometer is positioned so that the lower end is 30mm lower than line 11A. After the test sample temperature reaches the set temperature ±0.1℃, it is maintained in this state for 10 minutes. After 10 minutes, the liquid determination test tube 10a is removed from the low-temperature constant temperature water bath and immediately placed horizontally on a horizontal test platform. The time it takes for the tip of the liquid surface in the test tube to move from line 11A to line 12B is measured with a stopwatch and recorded.

[0034] Similarly, for samples placed at atmospheric pressure at a temperature of 20±5℃ for more than 24 hours, the same test as that conducted at atmospheric pressure at a temperature of 60±5℃ for more than 24 hours was performed. The time it took for the tip of the liquid level in the test tube to move from line 11A to line 12B was measured and recorded using a stopwatch.

[0035] For samples measured at 20°C for less than 90 seconds, they are classified as liquid. For samples measured at 20°C for more than 90 seconds, and for samples measured at 60°C for less than 90 seconds, they are classified as semi-solid. For samples measured at 60°C for more than 90 seconds, they are classified as solid.

[0036] The number of maleimide groups in each molecule of the solid maleimide-based free radical polymerizable compound is preferably one or more, more preferably two or more, more preferably three or more, preferably ten or less, more preferably six or less, and especially preferably three or less, from the viewpoint that the desired effect of the present invention can be obtained.

[0037] From the viewpoint that the solid maleimide-based free radical polymerizable compound can achieve the desired effect of the present invention, it is preferable to have either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and it is even more preferable to have both an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

[0038] As an aliphatic hydrocarbon group, a divalent aliphatic hydrocarbon group is preferred, a divalent saturated aliphatic hydrocarbon group is more preferred, and an alkyl group is even more preferred. As an 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, an alkyl group having 1 to 3 carbon atoms is even more preferred, and a methylene group is particularly preferred.

[0039] As an aromatic hydrocarbon group, monovalent and divalent aromatic hydrocarbon groups are preferred, and aryl and arylyl groups are even more preferred. As an arylyl group, arylyl groups with 6 to 30 carbon atoms are preferred, arylyl groups with 6 to 20 carbon atoms are even more preferred, and arylyl groups with 6 to 10 carbon atoms are even more preferred. Examples of such arylyl groups include phenyl, naphthyl, anthracene, aralkyl, diphenylene, and biphenylaralkyl, among which phenyl, aralkyl, diphenylene, and biphenylaralkyl are preferred, and phenyl, aralkyl, and diphenylene are even more preferred. As an aryl group, aryl groups with 6 to 30 carbon atoms are preferred, aryl groups with 6 to 20 carbon atoms are even more preferred, aryl groups with 6 to 10 carbon atoms are even more preferred, and phenyl is particularly preferred.

[0040] From the viewpoint that the desired effects of the present invention can be obtained significantly from solid maleimide-based free radical polymerizable compounds, it is preferable that the nitrogen atom of the maleimide group is directly bonded to a monovalent or divalent aromatic hydrocarbon group. Herein, "directly" means that there is no other group between the nitrogen atom of the maleimide group and the aromatic hydrocarbon group.

[0041] Solid maleimide is a free radical polymerizable compound, preferably having the structure represented by the following formula (A-2). In formula (A-2), R31 and R36 represent maleimide groups, R32, R33, R34 and R35 each independently represent a hydrogen atom, an alkyl group or an aryl group, and D each independently represent a divalent aromatic group. m1 and m2 each independently represent an integer from 1 to 10, and a represents an integer from 1 to 100.

[0042] In formula (A-2), R32, R33, R34 and R35 each independently represent a hydrogen atom, an alkyl group or an aryl group, with hydrogen atoms being preferred.

[0043] As an 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 can be linear, branched, or cyclic. Examples of such alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, and isopropyl.

[0044] The aryl group is preferably an aryl group with 6 to 20 carbon atoms, more preferably an aryl group with 6 to 15 carbon atoms, and even more preferably an aryl group with 6 to 10 carbon atoms. The aryl group can be a monocyclic ring or a condensed ring. Examples of such aryl groups include phenyl, naphthyl, and anthracene.

[0045] Alkyl and aryl groups may have substituents. There are no particular limitations on substituents; examples include halogen atoms, -OH, -O-C1-6 alkyl, -N(C1-10 alkyl)2, C1-20 alkyl, C2-30 alkenyl, C2-30 alkynyl, C6-10 aryl, -NH2, -CN, -C(O)O-C1-10 alkyl, -COOH, -C(O)H, -NO2, etc. The term "Cp-q" (where p and q are positive integers, satisfying p < q) indicates that the number of carbon atoms in the organic group described after the term is p to q. For example, "C1-10 alkyl" indicates an alkyl group with 1 to 10 carbon atoms. These substituents can bond together to form rings, and the ring structure may contain spirocyclic or condensed rings.

[0046] The above-mentioned substituent may further have substituents (hereinafter sometimes referred to as "secondary substituents"). As secondary substituents, unless otherwise specified, the same substituents as the above-mentioned substituents may be used.

[0047] In formula (A-2), D represents a divalent aromatic group. Examples of divalent aromatic groups include phenylene, naphthylene, anthracene, aralkyl, diphenylene, and biphenylaralkyl, with diphenylene and biphenylaralkyl being preferred, and diphenylene being even more preferred. The divalent aromatic group may have substituents. Substituents are the same as those represented by R32 in the general formula (A-2), which may have alkyl substituents.

[0048] m1 and m2 each independently represent integers from 1 to 10, preferably from 1 to 6, more preferably from 1 to 3, even more preferably from 1 to 2, with 1 being the most preferred.

[0049] a represents an integer from 1 to 100, preferably from 1 to 50, more preferably from 1 to 20, and even more preferably from 1 to 5.

[0050] As a solid maleimide-based free radical polymerizable compound, the resin shown in formula (A-3) is preferred. In formula (A-3), R37 and R38 represent maleimide groups. a1 represents an integer from 1 to 100.

[0051] a1 is the same as a in formula (A-2), and the preferred range is also the same.

[0052] Solid maleimide-based free radical polymerizable compounds can be commercially available. Examples of commercially available products include "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.

[0053] Liquid or semi-solid maleimide-based free radical polymerizable compounds are those having at least one maleimide group in the molecule, preferably containing an aliphatic group with 5 or more carbon atoms that can be substituents. Liquid or semi-solid maleimide-based free radical polymerizable compounds can be obtained, for example, by acetylation reaction of an aliphatic amine compound (such as a diamine compound having a dimer acid backbone), maleic anhydride, and a tetracarboxylic dianhydride as needed.

[0054] The aliphatic group having 5 or more carbon atoms can be monovalent, divalent, or trivalent or more. The aliphatic group having 5 or more carbon atoms can be saturated aliphatic group or unsaturated aliphatic group. Examples of aliphatic groups having 5 or more carbon atoms include alkyl, alkylene, and alkenyl groups. Liquid or semi-solid maleimide-based free radical polymerizable compounds are preferably maleimide compounds containing at least one hydrocarbon group selected from a group consisting of an alkyl group having 5 or more carbon atoms that can have substituents, an alkylene group having 5 or more carbon atoms that can have substituents, and an alkenyl group having 5 or more carbon atoms that can have substituents. For example, liquid or semi-solid maleimide-based free radical polymerizable compounds are preferably maleimide compounds containing at least one hydrocarbon group selected from a group consisting of an alkyl group having 5 or more carbon atoms that can have substituents and an alkylene group having 5 or more carbon atoms that can have substituents. Furthermore, the liquid or semi-solid maleimide-based free radical polymerizable compound is preferably a maleimide compound containing at least one hydrocarbon group selected from a group consisting of an alkyl group having 5 or more carbon atoms that may have substituents and an alkenyl group having 5 or more carbon atoms that may have substituents.

[0055] The aliphatic group typically has 5 or more carbon atoms. From the viewpoint that significant effects of the present invention can be obtained, it is preferable that the aliphatic group has 6 or more carbon atoms, more preferably 8 or more, more preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. In this specification, when a substituent contains a certain group, unless otherwise specified, the number of carbon atoms of that substituent is not included in the number of carbon atoms of the aforementioned group. Therefore, when a substituent containing an aliphatic group has 5 or more carbon atoms, unless otherwise specified, the number of carbon atoms of that substituent is not included in the number of carbon atoms of the aliphatic group with 5 or more carbon atoms.

[0056] The alkyl group having 5 or more carbon atoms preferably has 6 or more carbon atoms, more preferably 8 or more, more preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. The alkyl group can be straight-chain, branched-chain, or cyclic, with straight-chain being preferred. Examples of such alkyl groups include pentyl, hexyl, heptyl, octyl, nonyl, and decyl. The alkyl group having 5 or more carbon atoms can be a substituent for an alkyl group having 5 or more carbon atoms or an alkenyl group having 5 or more carbon atoms.

[0057] The carbon number of the alkyl group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, more preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. The alkyl group can be linear, branched, or cyclic, with linear being preferred. The term "cyclic alkyl group" is not only narrowly defined as consisting solely of cyclic alkyl groups, but also broadly encompasses both linear and cyclic alkyl groups. Examples of such alkyl groups include pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, heptadecanyl, hexadecyl, octyl, octyl-cyclohexyl-octyl, propyl-cyclohexyl-octyl, etc.

[0058] The number of carbon atoms in the alkenyl group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, more preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. This alkenyl group can be linear, branched, or cyclic, with linear being preferred. When a cyclic alkenyl group is formed solely from cyclic alkenyl groups, it also encompasses a broader concept including both linear and cyclic alkenyl groups. Examples of such alkenyl groups include pentyryneyl, hexynyl, heptyryneyl, octyryneyl, nonynyl, decynyl, undecaynyl, dodecaynyl, tridecaynyl, heptadecynyl, trihexaynyl, trihexaynyl, octylynyl, groups having an octylynyl-cyclohexynyl structure, groups having an octylynyl-cyclohexynyl-octylynyl structure, and groups having a propyne-cyclohexynyl-octylynyl structure.

[0059] For liquid or semi-solid maleimide-based free radical polymerizable compounds, it is preferable that the aliphatic group with 5 or more carbon atoms is directly bonded to the nitrogen atom of the maleimide group. Here, "directly" means that there are no other groups between the nitrogen atom of the maleimide group and the aliphatic group.

[0060] The liquid or semi-solid maleimide is a free radical polymerizable compound, and from the viewpoint that significant effects of the present invention can be obtained, it is preferable to contain 2 or more aliphatic groups with 5 or more carbon atoms.

[0061] Aliphatic groups with 5 or more carbon atoms can bond with each other to form rings, and the ring structure may contain spirocyclic or condensed rings. Examples of rings formed by mutual bonding include the cyclohexane ring.

[0062] Aliphatic groups having 5 or more carbon atoms may or may not have substituents. As substituents, they are the same as those represented by R32 in the general formula (A-2), which may have alkyl substituents.

[0063] Liquid or semi-solid maleimide-based free radical polymerizable compounds are preferably those containing an aromatic ring in the molecule. Therefore, liquid or semi-solid maleimide-based free radical polymerizable compounds are preferably maleimide compounds containing an aliphatic group with 5 or more carbon atoms that may have substituents and an aromatic ring. The aromatic ring may be a monocyclic aromatic ring or a condensed aromatic ring formed by the condensation of two or more monocyclic aromatic rings. Examples of such aromatic rings include monocyclic aromatic rings such as benzene rings and pyridine rings; and condensed aromatic rings such as indene rings, fluorene rings, and naphthalene rings. Among these aromatic rings, aromatic carbon rings are preferred. The number of carbon atoms in the aromatic carbon ring is preferably 6 or more but less than 10.

[0064] The number of maleimide groups in each molecule of the liquid or semi-solid maleimide-based free radical polymerizable compound may be one, but is preferably two or more and ten or less, more preferably six or less, and especially preferably three or less. The significant effects of the present invention can be obtained by using liquid or semi-solid maleimide-based free radical polymerizable compounds having two or more maleimide groups per molecule.

[0065] Liquid or semi-solid maleimide is a free radical polymerizable compound. From the viewpoint that significant effects of the present invention can be obtained, the maleimide compound shown in the following general formula (A-4) is preferred. In the general formula (A-4), R represents a divalent aliphatic group having 5 or more carbon atoms that may have substituents, and L represents a single bond or a divalent linker.

[0066] In the general formula (A-4), R represents a divalent aliphatic group having 5 or more carbon atoms that may have substituents. The number of carbon atoms in the divalent aliphatic group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, more preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. This divalent aliphatic group can be any of linear, branched, or cyclic, with linear being preferred. The term "cyclic divalent aliphatic group" refers to a case containing only cyclic aliphatic groups and a case containing both linear and cyclic aliphatic groups. Examples of divalent aliphatic groups include alkyl groups and alkenyl groups. The alkyl and alkenyl groups are as described above.

[0067] As a substituent of R, it is the same as that represented by R32 in general formula (A-2), which may have alkyl substituents.

[0068] In the general formula (A-4), L represents a single bond or a divalent linkage. Examples of divalent linkages include alkyl, alkenyl, alkynyl, aryl, -C(=O)-, -C(=O)-O-, -NR0- (R0 is a hydrogen atom and an alkyl group with 1 to 3 carbon atoms), oxygen atom, sulfur atom, C(=O)NR0-, divalent groups derived from phthalimide, divalent groups derived from diphenyltetracarboxylic acid diimide, and groups formed by combinations of two or more such divalent groups. Alkenyl, alkenyl, alkynyl, aryl, divalent groups derived from phthalimide, divalent groups derived from diphenyltetracarboxylic acid diimide, and groups formed by combinations of two or more such divalent groups may have an alkyl group having 5 or more carbon atoms as a substituent. The divalent group derived from phthalimide refers to a divalent group derived from phthalimide. A specific example is the group shown in general formula (A-5). The divalent group derived from benzoic acid diimide refers to a divalent group derived from benzoic acid diimide. A specific example is the group shown in general formula (A-6). In the formulas, "*" indicates the bond position.

[0069] The alkyl group that is the divalent linker in L of the general formula (A-4) is preferably an alkyl group with 1 to 50 carbon atoms, more preferably an alkyl group with 1 to 45 carbon atoms, and particularly preferably an alkyl group with 1 to 40 carbon atoms. This alkyl group can be linear, branched, or cyclic. Examples of such alkyl groups include methyl ethyl (2-propyl), cyclohexyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, heptadecanyl, hexadecyl, octyl, groups having an octyl-cyclohexyl structure, groups having an octyl-cyclohexyl-octyl structure, and groups having an propyl-cyclohexyl-octyl structure.

[0070] The alkenyl group, which is the divalent linker in L of the general formula (A-4), is preferably an alkenyl group with 2 to 50 carbon atoms, more preferably an alkenyl group with 2 to 45 carbon atoms, and particularly preferably an alkenyl group with 2 to 40 carbon atoms. This alkenyl group can be linear, branched, or cyclic. Examples of such alkenyl groups include methylalkenyl (2-alkenylene), cycloalkenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridedecenyl, pentadecenyl, hexadecenyl, octynyl, groups having an octyynyl-cyclohexynyl structure, groups having an octyynyl-cyclohexynyl-octyynyl structure, and groups having a propyne-cyclohexynyl-octyynyl structure.

[0071] The alynyl group, which is the divalent linker in L of the general formula (A-4), is preferably an alynyl group with 2 to 50 carbon atoms, more preferably an alynyl group with 2 to 45 carbon atoms, and particularly preferably an alynyl group with 2 to 40 carbon atoms. This alynyl group can be any of the following: straight-chain, branched-chain, or cyclic. Examples of such alynyl groups include 2-propynyl, cyclohexynyl, pentylyl, hexynyl, heptylyl, octylyl, nonynyl, decanynyl, undecanynyl, dodecanynyl, tridecanynyl, heptadecynyl, trihexadecynyl, octylynyl, groups having an octylynyl-cyclohexynyl structure, groups having an octylynyl-cyclohexynyl-octylynyl structure, and groups having a propynyl-cyclohexynyl-octylynyl structure.

[0072] The aryl group that forms the divalent linker in L of the general formula (A-4) is preferably an aryl group with 6 to 24 carbon atoms, more preferably an aryl group with 6 to 18 carbon atoms, even more preferably an aryl group with 6 to 14 carbon atoms, and even more preferably an aryl group with 6 to 10 carbon atoms. Examples of aryl groups include phenyl, naphthyl, and anthraceneyl groups.

[0073] The alkyl, alkenyl, ynyl, and aryl groups of the divalent linkage in L of the general formula (A-4) may have substituents. As substituents, they may be the same as those of the alkyl group represented by R32 in the general formula (A-2), and preferably alkyl groups having 5 or more carbon atoms.

[0074] Examples of groups formed by combining two or more divalent groups in L of the general formula (A-4) include: a divalent group formed by combining an alkyl group with a divalent group from phthalimide and an oxygen atom; a divalent group formed by combining a divalent group from phthalimide, an oxygen atom, an aryl group, and an alkyl group; a divalent group formed by combining an alkyl group and a divalent group from benzoyl diimide; a divalent group formed by combining an alkyne group, a divalent group from phthalimide, and an oxygen atom; a divalent group formed by combining a divalent group from phthalimide, an oxygen atom, an aryl group, and an alkyne group; and a divalent group formed by combining an alkyne group and a divalent group from benzoyl diimide. Groups formed by combining two or more divalent groups can form condensation rings or other rings through the combination of these groups. Furthermore, the number of repeating units of a base formed by a combination of two or more divalent bases can also be 1 to 10.

[0075] Wherein, L in the general formula (A-4) is preferably an oxygen atom, an aryl group having 6 to 24 carbon atoms that may have substituents, an alkyl group having 1 to 50 carbon atoms that may have substituents, an alkyne group having 1 to 50 carbon atoms that may have substituents, an enylene group having 1 to 50 carbon atoms that may have substituents, a divalent group from phthalimide, a divalent group from diphenyltetracarboxylic acid diimide, or a divalent group formed by a combination of 2 or more of these groups. Wherein, L is also an alkyl group; a divalent group having the structure of alkyl-divalent group from phthalimide-oxygen atom-divalent group from phthalimide; a divalent group having the structure of alkyl-divalent group from phthalimide-oxygen atom-aryl-alkyl-aryl-oxygen atom-divalent group from phthalimide; a divalent group having the structure of alkyl-divalent group from phthalic acid diimide; an enyl group; a divalent group having the structure of enyl-divalent group from phthalimide-oxygen atom-divalent group from phthalimide; an enyl group having the structure of enyl-divalent group from phthalimide-oxygen atom-divalent group from phthalimide; an enyl group having the structure of enyl-divalent group from phthalimide-oxygen atom-divalent group from phthalimide. A divalent group with the structure of divalent group - oxygen atom - aryl - aryl - aryl - oxygen atom - divalent group from phthalimide; a divalent group with the structure of aryl - aryl - divalent group from phthalic acid diimide; a divalent group with the structure of aryl - aryl - oxygen atom - divalent group from phthalimide; a divalent group with the structure of aryl - aryl - aryl - aryl - oxygen atom - divalent group from phthalimide; a divalent group with the structure of aryl - aryl - oxygen atom - aryl - aryl - oxygen atom - divalent group from phthalimide; a divalent group with the structure of aryl - aryl - divalent group from phthalic acid diimide is preferred.

[0076] Maleimine compounds of general formula (A-4) are preferably those of general formula (A-7). In general formula (A-7), R100 each independently represents a divalent aliphatic group having 5 or more carbon atoms that may have substituents, and A each independently represents a divalent aliphatic group having 5 or more carbon atoms that may have substituents, or a divalent group having an aromatic ring that may have substituents. n represents an integer from 1 to 10.

[0077] In general formula (A-7), each R100 independently represents a divalent aliphatic group having 5 or more carbon atoms that can have substituents. R1 is the same as R in general formula (A-4).

[0078] In the general formula (A-7), each A independently represents a divalent aliphatic group having 5 or more carbon atoms that may have substituents, or a divalent group having an aromatic ring that may have substituents. Examples of divalent aliphatic groups in A include alkyl groups and alkenyl groups. The divalent aliphatic group in A can be chain-like, branched chain-like, or cyclic, with cyclic divalent aliphatic groups having 5 or more carbon atoms that may have substituents being preferred.

[0079] The number of carbon atoms in the alkyl group is preferably 6 or more, more preferably 8 or more, more preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. Examples of such alkyl groups include those having an octyl-cyclohexyl structure, those having an octyl-cyclohexyl-octyl structure, and those having an propyl-cyclohexyl-octyl structure.

[0080] The number of carbon atoms in the alkenyl group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, more preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. This alkenyl group can be linear, branched, or cyclic, with linear being preferred. The term "cyclic alkenyl" encompasses both cases consisting solely of cyclic alkenyl groups and cases involving both linear and cyclic alkenyl groups. Examples of such alkenyl groups include alkenylpentynyl, alkenylhexynyl, alkenylheptyynyl, alkenyloctyynyl, alkenylnonenyl, alkenyldecynyl, alkenylundetyynyl, alkenyldodecynyl, alkenyldetaceynyl, alkenylheptadecynyl, alkenylheptadecynyl, alkenylhexadecosynyl, alkenyloctyynyl, groups having an octyynyl-cyclohexyynyl structure, groups having an octyynyl-cyclohexyynyl-octyynyl structure, and groups having a propyynyl-cyclohexyynyl-octyynyl structure.

[0081] Examples of aromatic rings among the divalent groups having aromatic rings shown in A include benzene rings, naphthalene rings, anthracene rings, phthalimide rings, benzoic acid diimide rings, and aromatic heterocycles, with benzene rings, phthalimide rings, and benzoic acid diimide rings being preferred. That is, as the divalent group having an aromatic ring, a benzene ring having a substituent, a phthalimide ring having a substituent, or a benzoic acid diimide ring having a substituent are preferred. Examples of divalent groups having an aromatic ring include groups formed by the combination of a divalent group from phthalimide and an oxygen atom; groups formed by the combination of a divalent group from phthalimide, an oxygen atom, an aryl group, and an alkyl group; groups formed by the combination of an alkyl group and a divalent group from benzoyl diimide; divalent groups from benzoyl diimide; and groups formed by the combination of a divalent group from phthalimide and an alkyl group. The aforementioned aryl groups are the same as the aryl groups in the divalent linked groups represented by L in general formula (2).

[0082] The divalent group represented by A in general formula (A-7), which has a divalent aliphatic group and an aromatic ring, may have substituents. As substituents, they are the same as the substituents represented by R32 in general formula (A-2), which may have alkyl groups.

[0083] Wherein, A in the general formula (A-7) may preferably represent a cyclic alkyl group having 5 or more carbon atoms that may have substituents; a divalent group having a benzene ring that may have substituents; a divalent group having an o-phthalimide ring that may have substituents; or a divalent group having a benzoic acid diimide ring that may have substituents.

[0084] As a specific example of the basis represented by A in the general formula (A-7), the following basis can be given. In the formula, "*" indicates the bond position.

[0085] The maleimine compound shown in general formula (A-4) is preferably either the maleimine compound shown in general formula (A-8) or the maleimine compound shown in general formula (A-9). In general formula (A-8), R2a and R3a each independently represent a divalent aliphatic group having 5 or more carbon atoms that may have substituents, and R10a each independently represent a divalent group formed by an oxygen atom, an aryl group, an alkyl group, an alkenyl group, or a combination of 2 or more of these groups. n1 represents an integer from 1 to 10. In general formula (A-9), R4a, R6a, and R7a each independently represent a divalent aliphatic group having 5 or more carbon atoms that may have substituents, R5a each independently represents a divalent aromatic ring having substituents, and R11a and R12a each independently represent an alkyl group having 5 or more carbon atoms. t2 represents an integer from 0 to 10, and m1 and m2 each independently represent an integer from 0 to 4.

[0086] In general formula (A-8), R2a and R3a each independently represent a divalent aliphatic group having 5 or more carbon atoms that may have substituents. R2a and R3a are the same as the divalent aliphatic group having 5 or more carbon atoms represented by R in general formula (A-4), and are preferably hexadecynyl or hexadecylalkyl.

[0087] In general formula (A-8), each R10a independently represents an oxygen atom, an aryl group, an alkyl group, an alkenyl group, or a combination of two or more divalent groups. The aryl group, alkyl group, and alkenyl group are the same as the aryl group, alkyl group, and alkenyl group represented by L in general formula (A-4). It is preferred that R10a is a group formed by a combination of two or more divalent groups or an oxygen atom.

[0088] As a group formed by a combination of two or more divalent groups in R10a of the general formula (A-8), combinations of oxygen atoms, aryl groups, and alkyl groups can be given. Specific examples of groups formed by a combination of two or more divalent groups include the following groups. In the formula, "*" indicates the bonding position.

[0089] In general formula (A-9), R4a, R6a, and R7a each independently represent a divalent aliphatic group having 5 or more carbon atoms that may have substituents. R4a, R6a, and R7a are the same divalent aliphatic groups having 5 or more carbon atoms that may have substituents represented by R in general formula (A-4), preferably hexyl, heptyl, octyl, nonyl, or decyl, with octyl being the most preferred.

[0090] In general formula (A-9), R5a independently represents a divalent group having an aromatic ring that can have substituents. R5a is the same as the divalent group having an aromatic ring having substituents represented by A in general formula (A-7), preferably a group formed by a combination of an alkyl group and a divalent group from diphenyltetracarboxylic acid diimide; a group formed by a combination of a divalent group from phthalimide and an alkyl group is preferred, and a group formed by a combination of an alkyl group and a divalent group from diphenyltetracarboxylic acid diimide is even more preferred. The alkyl group is the same as the aryl group and alkyl group in the divalent linkage group represented by L in general formula (A-4).

[0091] As a specific example of the basis represented by R5a in the general formula (A-9), the following basis can be given for example. In the formula, "*" indicates the bond position.

[0092] In general formula (A-9), R11a and R12a each independently represent an alkyl group having 5 or more carbon atoms. R11a and R12a are the same as the alkyl groups having 5 or more carbon atoms mentioned above, with hexyl, heptyl, octyl, nonyl, and decyl being preferred, and hexyl and octyl being even more preferred.

[0093] In the general formula (A-9), m1 and m2 each independently represent integers from 1 to 15, with integers from 1 to 10 being preferred.

[0094] Specific examples of maleimide-based free radical polymerizable compounds in liquid or semi-solid form include the following compounds (A-10) to (A-13). However, the liquid or semi-solid maleimide-based free radical polymerizable compounds are not limited to these specific examples. In the formula, a represents an integer from 1 to 10.

[0095] Liquid or semi-solid maleimide-based free radical polymerizable compounds may be commercially available. Specific examples of liquid or semi-solid maleimide-based free radical polymerizable compounds include "BMI1500" (compound of formula (A-10), "BMI1700" (compound of formula (A-11), "BMI3000J", "BMI3000" (compound of formula (A-12), and "BMI689" (compound of formula (A-13)) manufactured by Digigner Moleculars.

[0096] The aromatic ring and aliphatic hydrocarbon ring condensed skeleton of a maleimine-based free radical polymerizable compound (hereinafter sometimes referred to as "(3) component") can be exemplified by indane skeleton, trimethyl indane skeleton, tetrahydronaphthalene skeleton, benzocyclobutene skeleton, indane skeleton, etc. From the viewpoint of obtaining significant effects of the present invention, trimethyl indane skeleton is preferred. Therefore, maleimine compounds containing trimethyl indane skeleton are preferred for (3) component. The so-called trimethyl indane skeleton is represented by the skeleton shown in the following formula (A-14).

[0097] Substituents can be bonded to the benzene ring contained in the trimethylindene skeleton. Examples of substituents include alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, cycloalkyl, halogen atoms, hydroxyl, and mercapto. The alkyl group preferably has 1 to 10 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, n-butyl, and t-butyl. The alkyloxy group preferably has 1 to 10 carbon atoms. Examples of alkyloxy groups include methoxy, ethoxy, propoxy, and butoxy. The alkylthio group preferably has 1 to 10 carbon atoms. Examples of alkylthio groups include methylthio, ethylthio, propylthio, and butylthio. The aryl group preferably has 6 to 10 carbon atoms. Examples of aryl groups include phenyl and naphthyl. The aryloxy group preferably has 6 to 10 carbon atoms. Examples of aryloxy groups include phenyloxy and naphthyl. The aryl thio group preferably has 6 to 10 carbon atoms. Examples of aryl thio groups include phenyl thio and naphthio. The cycloalkyl group preferably has 3 to 10 carbon atoms. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and cycloheptyl. Examples of halogen atoms include fluorine, chlorine, and iodine.

[0098] Among the aforementioned substituents, the hydrogen atoms of alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio and cycloalkyl groups may be replaced by halogen atoms.

[0099] The number of substituents bonded to the benzene ring in the trimethylindane skeleton can be 1 or more. The number of substituents bonded to the benzene ring in the trimethylindane skeleton is usually 0 to 3. When the number of substituents is 2 or more, these 2 or more substituents can be the same or different. Preferably, the benzene ring in the trimethylindane skeleton does not contain any substituents.

[0100] The number of trimethylindene skeletons contained in one molecule of component (3) may be 1 or more. The upper limit may be, for example, 10 or less, 8 or less, 7 or less or 6 or less.

[0101] (3) In addition to the above-mentioned trimethylindane skeleton, the component preferably contains an aromatic ring skeleton. The number of ring-forming carbons in the aromatic ring skeleton is preferably 6 to 10. Examples of aromatic ring skeletons include benzene ring skeletons and naphthalene ring skeletons. (3) The number of the aforementioned aromatic ring skeletons contained in one molecule of the component is preferably 1 or more, more preferably 2 or more, more preferably 6 or less, more preferably 4 or less, and especially preferably 3 or less. (3) The component contains 2 or more aromatic ring skeletons, and these aromatic ring skeletons may be the same or different except for the trimethylindane skeleton.

[0102] Substituents can be bonded to the aforementioned aromatic ring containing an aromatic ring skeleton. Examples of substituents that can be bonded to the benzene ring contained in the trimethylindene skeleton include the aforementioned substituents and nitro groups. The number of substituents bonded to one aromatic ring can be one or more. The number of substituents bonded to the aromatic ring is generally 0 to 4. When the number of substituents is 2 or more, these 2 or more substituents can be the same or different.

[0103] (3) It is preferable that the component, in addition to the above-mentioned trimethylindane skeleton, further contains a divalent aliphatic hydrocarbon group. In particular, when component (3) contains an aromatic ring skeleton other than the benzene ring contained in the trimethylindane skeleton, it is preferable that component (3) contains a divalent aliphatic hydrocarbon group. In this case, it is preferable that the benzene ring contained in the divalent aliphatic hydrocarbon trimethylindane skeleton is linked to the aromatic ring skeleton. Furthermore, it is preferable that the divalent aliphatic hydrocarbon group is linked to the aromatic ring skeleton.

[0104] The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 or more, preferably 12 or less, more preferably 8 or less, and especially preferably 5 or less. As a divalent aliphatic hydrocarbon group, an alkyl group that is a saturated aliphatic hydrocarbon group is preferred. Examples of divalent aliphatic hydrocarbon groups include straight-chain alkyl groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; branched alkyl groups such as ethylene (-CH(CH3)-), propylene (-CH(CH2CH3)-), isopropylene (-C(CH3)2-), ethylmethylmethylene (-C(CH3)(CH2CH3)-), and diethylmethylene (-C(CH2CH3)2-). In maleimine compounds containing a (C-2b) trimethylindane skeleton, the divalent aliphatic hydrocarbon groups containing 2 or more carbon atoms can be the same or different, except when the compound contains a trimethylindane skeleton.

[0105] (3) The component is preferably one that contains the structure shown in the following formula (A-15). (3) The entire component may have the structure shown in formula (A-15), and (3) a part of the component may have the structure shown in formula (A-15).

[0106] (In the formula, Ara1 represents a divalent aromatic hydrocarbon group that may have substituents; each of Ra1 independently represents an alkyl group with 1 to 10 carbon atoms, an alkyloxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aryloxy group with 6 to 10 carbon atoms, an arylthio group with 6 to 10 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; each of Ra2 independently represents an alkyl group with 1 to 10 carbon atoms, an alkyloxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aryloxy group with 6 to 10 carbon atoms, or an arylthio group with 6 to 10 carbon atoms.) The alkyl group has 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; Ra3 independently represents a divalent aliphatic hydrocarbon group; na1 represents a positive integer; na2 independently represents an integer from 0 to 4; na3 independently represents an integer from 0 to 3. The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups in Ra1 can be substituted with halogen atoms. The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups in Ra2 can be substituted with halogen atoms. When na2 has 2 to 4 carbon atoms, Ra1 within the same ring can be the same or different. When na3 has 2 to 3 carbon atoms, Ra2 within the same ring can be the same or different.

[0107] For formula (A-15), Ara1 represents a divalent aromatic hydrocarbon group that may have substituents. The number of carbon atoms in this divalent aromatic hydrocarbon group is preferably 6 or more, preferably 20 or less, and preferably 16 or less. Examples of divalent aromatic hydrocarbon groups include phenyl and naphthyl. Examples of substituents that may be present in the divalent aromatic hydrocarbon group include alkyl groups with 1 to 10 carbon atoms, alkyloxy groups with 1 to 10 carbon atoms, alkylthio groups with 1 to 10 carbon atoms, aryl groups with 6 to 10 carbon atoms, aryloxy groups with 6 to 10 carbon atoms, arylthio groups with 6 to 10 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, halogen atoms, hydroxyl groups, and mercapto groups. The hydrogen atoms of each substituent may be further substituted with halogen atoms. Furthermore, as specific examples of such substituents, examples of substituents that can bond with the benzene ring contained in the trimethylindene skeleton can be given. When a divalent aromatic hydrocarbon group has substituents, the number of substituents is preferably 1 to 4. When a divalent aromatic hydrocarbon group has 2 or more substituents, these 2 or more substituents can be the same or different. Among them, Ara1 is preferred as a divalent aromatic hydrocarbon group without substituents.

[0108] In formula (A-15), each Ra1 independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group. The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted by halogen atoms. As a specific example of such a group, the same example of a substituent that can be bonded to the benzene ring contained in the trimethylindene skeleton can be given. Among them, Ra1 is preferably selected from one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 10 carbon atoms, and is particularly preferred to be an alkyl group having 1 to 4 carbon atoms.

[0109] For formula (A-15), Ra2 independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl atom, or a mercapto group. The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with halogen atoms. As a specific example of such a group, the same example of a substituent that can bond to the benzene ring contained in the trimethylindene skeleton can be given, for example. Among them, Ra2 is preferably selected from one or more types of groups grouped by alkyl groups having 1 to 4 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 10 carbon atoms.

[0110] For formula (A-15), Ra3 independently represents a divalent aliphatic hydrocarbon group. The preferred range of divalent aliphatic hydrocarbon groups is as shown above.

[0111] For formula (A-15), na1 represents a positive integer. na1 is preferably 1 or higher, preferably 10 or lower, and ideally 8 or lower.

[0112] For equation (A-15), each na2 independently represents an integer from 0 to 4. na2 is preferably 2 or 3, with 2 being more preferred. While complex numbers na2 can be different, they are preferred to be the same. When na2 is 2 or higher, complex numbers Ra1 within the same ring can be the same or different.

[0113] For equation (A-15), each of na3 independently represents an integer from 0 to 3. Although the complex numbers na3 can be different, it is preferable that they are the same. na3 is preferably 0.

[0114] (3) It is particularly preferred that the component contains the structure shown in the following formula (A-16). (3) The entire component may have the structure shown in formula (A-16), or a part of the component (3) may have the structure shown in formula (A-16). (In the formula, each of Rb1 independently represents an alkyl group with 1 to 10 carbon atoms, an alkyloxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aryloxy group with 6 to 10 carbon atoms, an arylthio group with 6 to 10 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group or a mercapto group; each of Rb2 independently represents an alkyl group with 1 to 10 carbon atoms, an alkyloxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aryloxy group with 6 to 10 carbon atoms, an arylthio group with 6 to 10 carbon atoms, an arylthio group with 3 to 10 carbon atoms, a cycloalkyl group with 1 ... ~10 cycloalkyl, halogen, hydroxyl, or mercapto groups; nb1 represents a positive integer; nb2 each independently represents an integer from 0 to 4; nb3 each independently represents an integer from 0 to 3. The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups in Rb1 can be substituted with halogen atoms. The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups in Rb2 can be substituted with halogen atoms. When nb2 is 2 to 4, Rb1 within the same ring can be the same or different. When nb3 is 2 to 3, Rb2 within the same ring can be the same or different.

[0115] In formula (A-16), Rb1, Rb2, nb1, nb2 and nb3 are the same as Ra1, Ra2, na1, na2 and na3 in formula (A-15).

[0116] (3) The component may further contain the structure shown in the following formula (A-17). In formula (A-17), Rc1, Rc2, nc2 and nc3 are the same as Ra1, Ra2, na2 and na3 in formula (A-15). Also, in formula (A-17), nc1 is the number of repeating units, representing an integer from 1 to 20. And in formula (A-17), * indicates the bonding position. For example, in formula (A-15), if na2 is 3 or less in component (3), and there are two or more unbonded Ra1s in the ortho and para positions of the maleimide group of the benzene ring bonded by the maleimide group, it may contain the structure shown in the aforementioned formula (A-17) combined with the structure shown in formula (A-15). Furthermore, for example, in formula (A-16), if nb2 is 3 or less, and if there are two or more unbonded Rb1 groups in the ortho and para positions of the maleimine group of the benzene ring bonded by the maleimine group, then the structure shown in formula (A-17) may be contained in combination with the structure shown in formula (A-16).

[0117] (3) The ingredients can be used alone or in combination of two or more in any ratio.

[0118] (3) There are no particular limitations on the manufacturing method of component (3). Component (3) can be manufactured, for example, by the method described in Patent Application Publication No. 2020-500211. According to the manufacturing method described in Patent Application Publication No. 2020-500211, a maleimide compound having a repeating unit distribution of a trimethylindene skeleton can be obtained. The maleimide compound obtained by this method contains the structure shown in formula (A-18). Therefore, component (3) can also contain a maleimide compound having the structure shown in formula (A-18). (In the formula, R1 independently represents an alkyl group with 1 to 10 carbon atoms, an alkyloxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aryloxy group with 6 to 10 carbon atoms, an arylthio group with 6 to 10 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; R2 independently represents an alkyl group with 1 to 10 carbon atoms, an alkyloxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aryloxy group with 6 to 10 carbon atoms, an arylthio group with 6 to 10 carbon atoms, or a cycloalkyl group with 3 to 10 carbon atoms.) Cycloalkyl, halogen, hydroxyl, or mercapto groups; n1 represents the average number of repeating units from 0.95 to 10.0; n2 each independently represents an integer from 0 to 4; n3 each independently represents an integer from 0 to 3. The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups in R1 can be substituted with halogen atoms. The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups in R2 can be substituted with halogen atoms. When n2 is 2 to 4, R1 within the same ring can be the same or different. When n3 is 2 to 3, R2 within the same ring can be the same or different.

[0119] In formula (A-18), R1, R2, n2 and n3 are the same as Ra1, Ra2, na2 and na3 in formula (A-15).

[0120] In formula (A-18), n1 represents the average number of repeating units, which ranges from 0.95 to 10.0. According to the manufacturing method described in Patent Application Publication No. 2020-500211 of the China Inventors Association, a group of maleimine compounds containing the structure shown in formula (A-18) can be obtained. Since the average number of repeating units n1 in formula (A-18) can be smaller than 1.00, it can be seen that the maleimine compound containing the structure shown in formula (A-18) obtained in this way can contain maleimine compounds with a repeating unit number of 0 for the trimethylindane skeleton. Therefore, by purifying and removing maleimine compounds with a repeating unit number of 0 for the trimethylindane skeleton from the maleimine compound containing the structure shown in formula (A-18), component (3) can be obtained, and only component (3) obtained can be contained in the resin composition layer. However, the effects of the present invention can still be obtained even when the maleimide compound with zero repeating units of the trimethylindane skeleton is contained in the resin composition layer. Furthermore, omitting purification can reduce costs. Therefore, it is preferable to contain a maleimide compound with the structure shown in formula (A-18) in the resin composition layer without removing the maleimide compound with zero repeating units of the trimethylindane skeleton.

[0121] For formula (A-18), the average number of repeating units n1 is preferably 0.95 or more, more preferably 0.98 or more, even more preferably 1.0 or more, particularly preferably 1.1 or more, preferably 10.0 or less, more preferably 8.0 or less, even more preferably 7.0 or less, and particularly preferably 6.0 or less. When the average number of repeating units n1 is within the aforementioned range, significant effects of the present invention can be obtained. In particular, it can effectively increase the glass transition temperature of the resin composition.

[0122] As an example of the structure shown in equation (A-18), the following can be cited.

[0123] Maleimine compounds containing the structure shown in formula (A-18) may further contain the structure shown in formula (A-17). For example, in formula (A-18), when n2 is 3 or less and there are two or more unbonded R1s in the ortho and para positions of the maleimine group of the benzene ring bonded to the maleimine group, the combination with the structure shown in formula (A-18) may contain the structure shown in formula (A-17).

[0124] The molecular weight distribution (Mw / Mn) of the maleimine compound containing the structure shown in formula (A-18) is preferably within a specific range when determined by gel permeation chromatography (GPC). The molecular weight distribution is the value calculated by dividing the weight-average molecular weight Mw by the number-average molecular weight Mn, and is expressed as "Mw / Mn". Specifically, the molecular weight distribution (Mw / Mn) of the maleimine compound containing the structure shown in formula (A-18) is preferably 1.0 to 4.0, more preferably 1.1 to 3.8, even more preferably 1.2 to 3.6, and particularly preferably 1.3 to 3.4. Significant effects of the present invention can be obtained when the molecular weight distribution (Mw / Mn) of the maleimine compound containing the structure shown in formula (A-18) is within the aforementioned range.

[0125] It is preferable that the amount of maleimide compounds containing the structure shown in formula (A-18) with a mean repeat number n1 of 0 is within a specific range. When performing the aforementioned GPC determination of maleimide compounds containing the structure shown in formula (A-18), the amount of maleimide compounds with a mean repeat number n1 of 0 can be expressed as area % based on the results of the GPC determination. Specifically, for the chromatogram obtained by the aforementioned GPC determination, the amount of maleimide compounds with a mean repeat number n1 of 0 can be expressed as the ratio (area %) of the total area of ​​the absorption peaks of maleimide compounds containing the structure shown in formula (A-18) to the area of ​​the absorption peaks of maleimide compounds with a mean repeat number n1 of 0. Specifically, the amount of maleimide compound containing the structure shown in formula (A-18) in 100% area percentage and with an average repeating unit number n1 of 0 is preferably 32% or less, more preferably 30% or less, and even more preferably 28% or less. When the amount of maleimide compound with an average repeating unit number n1 of 0 is within the aforementioned range, the significant effects of the present invention can be obtained.

[0126] The maleimide equivalent of the maleimide-based free radical polymerizable compound is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, even more preferably 120 g / eq. or more, 200 g / eq. or more, preferably 10000 g / eq. or less, even more preferably 9000 g / eq. or less, 8000 g / eq. or less, 2000 g / eq. or less, 1000 g / eq. or less, or 800 g / eq. or less. The maleimide equivalent is the mass of the maleimide-based free radical polymerizable compound containing 1 equivalent of maleimide groups.

[0127] The weight average molecular weight (Mw) of maleimide-based free radical polymerizable compounds is preferably 150 to 16,000, and more preferably 200 to 15,000.

[0128] From the viewpoint that the molecular weight of the maleimide-based free radical polymerizable compound can obtain significant effects of the present invention, it is preferably 200 or more, more preferably 300 or more, more preferably 400 or more, preferably 100,000 or less, more preferably 80,000 or less, and more preferably 60,000 or less.

[0129] Vinylphenyl-based free radical polymerizable compounds are free radical polymerizable compounds having a vinylphenyl group. Vinylphenyl-based free radical polymerizable compounds are preferably in liquid or semi-solid form. The determination of liquid or semi-solid form is as described above. A vinylphenyl group is a group having the structure shown below. (* indicates the bond position)

[0130] From the viewpoint that a hardened compound with excellent dielectric properties can be obtained, vinylphenyl free radical polymerizable compounds are preferably those with more than 2 vinylphenyl groups per molecule.

[0131] From the viewpoint of obtaining cured compounds with excellent dielectric properties, vinylphenyl-based free radical polymerizable compounds preferably have a cyclic structure. As a cyclic structure, a divalent cyclic group is preferred. The divalent cyclic group can be either a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. Furthermore, the divalent cyclic group can be present in multiples.

[0132] From the viewpoint that the divalent cyclic group can achieve the desired effect of the present invention, it is preferable to have 3 or more rings, more preferably 4 or more rings, even more preferably 5 or more rings, preferably 20 or fewer rings, more preferably 15 or fewer rings, and even more preferably 10 or fewer rings. Furthermore, the divalent cyclic group can be a monocyclic structure or a multicyclic structure.

[0133] In addition to carbon atoms, the ring in the divalent cyclic group can also be composed of heteroatoms to form the ring skeleton. Examples of heteroatoms include oxygen atoms, sulfur atoms, and nitrogen atoms, with oxygen atoms being preferred. There can be one or more heteroatoms in the aforementioned ring.

[0134] Specific examples of divalent cyclic groups include the following divalent groups (a) or (b). (In divalent groups (a) and (b), R51, R52, R55, R56, R57, R61 and R62 each independently represent a halogen atom, an alkyl group or phenyl group with 6 or fewer carbon atoms, and R53, R54, R58, R59 and R60 each independently represent a hydrogen atom, a halogen atom, an alkyl group or phenyl group with 6 or fewer carbon atoms.)

[0135] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Examples of alkyl groups with 6 or fewer carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl, with methyl being preferred. Examples of R51, R52, R55, R56, R57, R61, and R62 are preferably methyl. Examples of R53, R54, R58, R59, and R60 are preferably hydrogen atoms or methyl groups.

[0136] Furthermore, divalent cyclic groups can combine to form a complex number of divalent cyclic groups. A specific example of combining divalent cyclic groups is the divalent cyclic group shown in the following formula (A-19). (In the formula, R71, R72, R75, R76, R77, R81, R82, R85, and R86 each independently represent a halogen atom, an alkyl group with 6 or fewer carbon atoms, or a phenyl group; R73, R74, R78, R79, R80, R83, and R84 each independently represent a hydrogen atom, a halogen atom, an alkyl group with 6 or fewer carbon atoms, or a phenyl group. d1 and d2 represent integers from 0 to 300. However, this does not apply if either d1 or d2 is 0.)

[0137] R71, R72, R85 and R86 are the same as R510 in equation (a). R73, R74, R83 and R84 are the same as R530 in equation (a). R75, R76, R77, R81 and R82 are the same as R550 in equation (b). R78, R79 and R80 are the same as R580 in equation (b).

[0138] d1 and d2 represent integers from 0 to 300. However, this does not apply if either d1 or d2 is 0. It is preferable for d1 and d2 to represent integers from 1 to 100, even more preferable for d1 to 50, and even more preferable for d1 to 10. d1 and d2 may be the same or different.

[0139] The divalent cyclic group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, arylalkyl groups, silicone groups, acetyl groups, aceoxy groups, carboxyl groups, sulfonic acid groups, cyano groups, nitro groups, hydroxyl groups, mercapto groups, oxo groups, etc., with alkyl groups being preferred.

[0140] The vinylphenyl group can be directly bonded to a divalent cyclic group, or it can be bonded through a divalent linker. Examples of divalent linkers include alkyl, alkenyl, aryl, heteroaryl, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, etc., and complex combinations of these groups are also possible. As for the alkyl group, alkyl groups with 1 to 10 carbon atoms are preferred, alkyl groups with 1 to 6 carbon atoms are more preferred, and alkyl groups with 1 to 5 carbon atoms or alkyl groups with 1 to 4 carbon atoms are even more preferred. The alkyl group can be straight-chain, branched, or cyclic. Examples of such alkyl groups include methylene, ethyl, propyl, butyl, pentyl, hexyl, and 1,1-dimethylethyl, with methylene, ethyl, and 1,1-dimethylethyl being preferred. As an alkenyl group, an alkenyl group with 2 to 10 carbon atoms is preferred, an alkenyl group with 2 to 6 carbon atoms is more preferred, and an alkenyl group with 2 to 5 carbon atoms is even more preferred. As aryl or heteroaryl groups, aryl or heteroaryl groups with 6 to 20 carbon atoms are preferred, and aryl or heteroaryl groups with 6 to 10 carbon atoms are more preferred. As a divalent linked group, an alkyl group is preferred, with methylene being particularly preferred.

[0141] Vinylphenyl free radical polymerizable compounds are preferably those shown in the following formula (A-20). (In the formula, R91 and R92 each independently represent divalent linkages. Ring A1 represents a divalent cyclic group.)

[0142] R91 and R92 each independently represent a divalent linkage. As a divalent linkage, it is the same as the divalent linkage described above.

[0143] Ring A1 represents a divalent cyclic group. Ring B is the same as the divalent cyclic group described above.

[0144] Cyclone A1 may have substituents. As substituents, they are the same as those that may be present in the divalent cyclic group described above.

[0145] The following are specific examples of vinylphenyl-based free radical polymerizable compounds, but the present invention is not limited to these. (q1 is the same as d1 in formula (A-19), and q2 is the same as d2 in formula (A-19).)

[0146] Vinylphenyl free radical polymerizable compounds may be commercially available, such as "OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd. Vinylphenyl free radical polymerizable compounds may be used alone or in combination of two or more types.

[0147] The number average molecular weight of the vinylphenyl-based free radical polymerizable compound is preferably 3000 or less, more preferably 2500 or less, even more preferably 2000 or less, and 1500 or less, from the viewpoint that significant effects of the present invention can be obtained. The lower limit is preferably 100 or more, more preferably 300 or more, even more preferably 500 or more, and 1000 or more. The number average molecular weight is the number average molecular weight converted from polystyrene as determined by gel permeation chromatography (GPC).

[0148] (Meth)acrylic acid-based free radical polymerizable compounds include acrylonitrile and methacrylonitrile, as well as combinations thereof. From the viewpoint of obtaining significant desired effects of the present invention, it is preferable that each molecule has two or more (meth)acrylonitrile groups. The term "(meth)acrylonitrile" includes acrylonitrile and methacrylonitrile, as well as combinations thereof.

[0149] (Meth)acrylic acid is a free radical polymerizable compound, and from the viewpoint of obtaining significant effects desired by the present invention, it is preferably having a cyclic structure. As a cyclic structure, a divalent cyclic group is preferred. As a divalent cyclic group, it can be either a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. Among these, from the viewpoint of obtaining significant effects desired by the present invention, a cyclic group containing an alicyclic structure is preferred.

[0150] From the viewpoint that the divalent cyclic group can achieve the desired effect of the present invention, it is preferable to have 3 or more rings, more preferably 4 or more rings, even more preferably 5 or more rings, preferably 20 or fewer rings, more preferably 15 or fewer rings, and even more preferably 10 or fewer rings. Furthermore, the divalent cyclic group can be a monocyclic structure or a multicyclic structure.

[0151] In addition to carbon atoms, the rings in a divalent cyclic group can also form a ring framework through heteroatoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, and nitrogen atoms, with oxygen atoms being preferred. A heteroatom may have one or more of the aforementioned rings.

[0152] Specific examples of divalent cyclic groups can be given by the following divalent groups (i) to (xi). Among them, (x) or (xi) is preferred as a divalent cyclic group.

[0153] The divalent cyclic group may have substituents. Examples of such substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, arylalkyl groups, silicone groups, acetyl groups, aceoxy groups, carboxyl groups, sulfonic acid groups, cyano groups, nitro groups, hydroxyl groups, mercapto groups, oxo groups, etc., with alkyl groups being preferred.

[0154] (Meth)acrylyl can be directly bonded to a divalent cyclic group, or it can be bonded through a divalent linker. Examples of divalent linkers include alkyl, alkenyl, aryl, heteroaryl, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, etc., and multiple combinations of these groups are also possible. As for alkyl groups, alkyl groups with 1 to 10 carbon atoms are preferred, alkyl groups with 1 to 6 carbon atoms are more preferred, alkyl groups with 1 to 5 carbon atoms, or alkyl groups with 1 to 4 carbon atoms are even more preferred. alkyl groups can be straight-chain, branched, or cyclic. Examples of such alkyl groups include methylene, ethyl, propyl, butyl, pentyl, hexyl, and 1,1-dimethylethyl, with methylene, ethyl, and 1,1-dimethylethyl being preferred. As for the alkenyl group, alkenyl groups with 2 to 10 carbon atoms are preferred, alkenyl groups with 2 to 6 carbon atoms are more preferred, and alkenyl groups with 2 to 5 carbon atoms are even more preferred. As for the aryl and heteroaryl groups, aryl or heteroaryl groups with 6 to 20 carbon atoms are preferred, and aryl or heteroaryl groups with 6 to 10 carbon atoms are more preferred. As a divalent linked group, alkyl groups are preferred, with methylene and 1,1-dimethylethyl being particularly preferred.

[0155] (Meth)acrylic acid-based free radical polymerizable compounds are preferably those shown in the following formula (A-21). (In the formula, R101 and R104 each independently represent an acrylonitrile or a methacrylonitrile group, and R102 and R103 each independently represent a divalent linker group. Ring A2 represents a divalent cyclic group.)

[0156] R101 and R104 each independently represent acrylonitrile or methacrylonitrile, with acrylonitrile being preferred.

[0157] R102 and R103 each independently represent divalent linkages. As divalent linkages, they are the same as divalent linkages that can be bonded to (meth)acrylic acid.

[0158] Ring A2 represents a divalent cyclic group. Ring A2 is the same as the divalent cyclic group described above. Ring A2 may have substituents. Substituents are the same as those that may be present in the divalent cyclic group described above.

[0159] Specific examples of (meth)acrylic acid-based free radical polymerizable compounds include the following, but the present invention is not limited to these.

[0160] (Meth)acrylic acid free radical polymerizable compounds can be commercially available, such as "A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "DCP-A" manufactured by Kyoe Chemical Co., Ltd., "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", "DPHA" manufactured by Nippon Kayaku Co., Ltd., and "NK ester DCP" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

[0161] From the viewpoint that the desired effects of the present invention can be obtained significantly, the (meth)acrylic acid free radical polymerizable compound has a (meth)acrylic acid ester equivalent of 30 g / eq. to 400 g / eq., more preferably 50 g / eq. to 300 g / eq., and even more preferably 75 g / eq. to 200 g / eq. The (meth)acrylic acid ester equivalent is the mass of a (meth)acrylic acid free radical polymerizable compound containing 1 ester of (meth)acrylic acid ester.

[0162] An allyl-based free radical polymerizable compound is a compound having at least one allyl group in its molecule. Allyl-based free radical polymerizable compounds are preferably those having one or more allyl groups per molecule, and more preferably those having two or more allyl groups. While there is no particular lower limit, 10 or fewer allyl groups are preferred, and 5 or fewer are more desirable.

[0163] Furthermore, allyl is a free radical polymerizable compound, and from the viewpoint that the desired effects of the present invention can be obtained significantly, in addition to allyl, it is also preferred to be any one of carboxylic acid derivatives having a benzoxazine ring, a phenolic ring, an isocyanate ring, an epoxy group, and a cyclic structure.

[0164] The allyl radical polymerizable compound having a benzoxazine ring is preferably bonded to either the nitrogen atom of the benzoxazine ring or the benzene ring, and preferably bonded to the nitrogen atom.

[0165] Examples of allyl-based free radical polymerizable compounds containing phenolic rings include cresol resins containing allyl groups, phenolic varnish-type phenolic resins containing allyl groups, and cresol phenolic varnish resins containing allyl groups.

[0166] Allyl-based free radical polymerizable compounds having an isocyanuric acid structure are preferably those that directly bond the nitrogen atom of the isocyanuric acid structure to the allyl group. Examples of allyl-based free radical polymerizable compounds having an isocyanuric acid structure include allyl isocyanurate, diallyl isocyanurate, and triallyl isocyanurate.

[0167] Allyl-based free radical polymerizable compounds with epoxy groups are preferably those having two or more epoxy groups per molecule. Furthermore, allyl-based free radical polymerizable compounds with epoxy groups are preferably those with aromatic structures, and when two or more allyl-based free radical polymerizable compounds with epoxy groups are used, at least one with an aromatic structure is preferred. An aromatic structure is generally defined as an aromatic chemical structure, and also includes polycyclic aromatics and aromatic heterocycles. As an allyl-based free radical polymerizable compound with epoxy groups, a bisphenol structure is preferred; examples of bisphenol structures include bisphenol A, bisphenol F, and bisphenol AF.

[0168] As an allyl-based free radical polymerizable compound containing a carboxylic acid derivative with a cyclic structure, allyl carboxylic acid with a cyclic structure is preferred. The cyclic structure can be either a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. Furthermore, the cyclic group can be a ring skeleton constructed by heteroatoms in addition to carbon atoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, and nitrogen atoms, with nitrogen atoms being preferred. The heteroatom can have one or more of the aforementioned rings.

[0169] Examples of carboxylic acids having a cyclic structure include isocyanuric acid, biphenyl dicarboxylic acid, phthalic acid, and cyclohexanedicarboxylic acid. Examples of allyl-based free radical polymerizable compounds containing carboxylic acid derivatives having a cyclic structure include allyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate, diallyl biphenyl dicarboxylate, o-diallyl phthalate, m-diallyl phthalate, p-diallyl phthalate, allyl cyclohexanedicarboxylate, and diallyl cyclohexanedicarboxylate.

[0170] Allyl-based free radical polymerizable compounds can be commercially available. Examples of commercially available products include: "MEH-8000H" and "MEH-8005" (allyl-based free radical polymerizable compounds with phenolic rings) manufactured by Meiwa Chemical Co., Ltd.; "RE-810NM" (allyl-based free radical polymerizable compounds with epoxy groups) manufactured by Nippon Kayaku Co., Ltd.; "ALP-d" (allyl-based free radical polymerizable compounds with benzoxazine rings) manufactured by Shikoku Chemical Industry Co., Ltd.; "L-DAIC" (allyl-based free radical polymerizable compounds with isocyanuric acid rings) manufactured by Shikoku Chemical Industry Co., Ltd.; "TAIC" (allyl-based free radical polymerizable compounds with isocyanuric acid rings (trylyl isocyanurate)) manufactured by Nippon Kayaku Co., Ltd.; "MDAC" (allyl ester free radical polymerizable compounds with cyclohexane dicarboxylic acid derivatives) manufactured by Osaka Soda Co., Ltd.; Nikko Techno Fine Chemical Co., Ltd., Ltd. manufactures "DAD" (dallyl biphenyl); Osaka Soda Co., Ltd. manufactures "Daiso Dup Monomer" (o-diallyl phthalate), etc.

[0171] From the viewpoint of obtaining significant desired effects of the present invention, the allyl equivalent of the allyl-based free radical polymerizable compound is preferably 20 g / eq. to 1000 g / eq., more preferably 50 g / eq. to 500 g / eq., and even more preferably 100 g / eq. to 300 g / eq. The allyl equivalent is the mass of the allyl-based free radical polymerizable compound containing 1 allyl equivalent.

[0172] A butadiene-based free radical polymerizable compound is a compound having at least one butadiene skeleton in its molecule. The polybutadiene structure may be contained in the main chain or in the side chain. Furthermore, the polybutadiene structure may be partially or completely hydrogenated. As a butadiene-based free radical polymerizable compound, it is preferable to select one or more resins selected from the group consisting of resins containing hydrogenated polybutadiene skeletons, butadiene resins containing hydroxyl groups, butadiene resins containing phenolic hydroxyl groups, butadiene resins containing carboxyl groups, butadiene resins containing acid anhydride groups, butadiene resins containing epoxy groups, butadiene resins containing isocyanate groups, and butadiene resins containing carbamate groups.

[0173] Specific examples of butadiene-based free radical polymerizable compounds 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 Co., Ltd.

[0174] As for the content of component (A), from the viewpoint that a cured product with excellent dielectric properties can be obtained, when the non-volatile component in the resin composition layer is taken as 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, and more preferably 30% by mass or less.

[0175] -(B) Thermoplastic resin- In addition to component (A), the resin composition layer may further contain thermoplastic resin as component (B) as an arbitrary component. By including component (B) in the resin composition layer, a hardened material exhibiting quite good mechanical strength can be obtained. Component (B) may be used alone or in combination with two or more.

[0176] (B) From the viewpoint of obtaining a cured material with excellent dielectric properties, the weight average molecular weight (Mn) of the component is preferably 5000 or higher, preferably 8000 or higher, especially 10000 or higher, preferably 100000 or lower, preferably 80000 or lower, and especially 50000 or lower. (B) The weight average molecular weight of the component is the weight average molecular weight converted from polystyrene as determined by gel permeation chromatography (GPC).

[0177] As component (B), a high weight average molecular weight may be used. Examples of such components include thermoplastic resins such as polyimide resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polyamide-imide resins, polyether-imide resins, polyurethane resins, polyether ether ketone resins, and polyester resins; and elastomers. Among these, as component (B), from the viewpoint of obtaining a cured product with excellent dielectric properties, at least one selected from polyimide resins and elastomers is preferred.

[0178] Polyimide resins can be used in resins with amide bonds in repeating units. Polyimide resins generally contain those obtained by amide imidization reaction of diamine compounds and acid anhydrides.

[0179] The diamine compound to be used to formulate polyimide resin is not particularly limited, for example, aliphatic diamine compounds and aromatic diamine compounds can be cited.

[0180] Examples of aliphatic diamine compounds include linear aliphatic diamine compounds such as 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, 1,5-diaminopentane, and 1,10-diaminodecane; branched aliphatic diamine compounds such as 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butane, and 2-methyl-1,5-diaminopentane; alicyclic diamine compounds such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, and 4,4'-methylenebis(cyclohexylamine); and dimeric acid type diamines (hereinafter also referred to as "dimeric diamines"), among which dimeric acid type diamines are preferred.

[0181] The term "diamine of dimeric acid" refers to a diamine compound obtained by replacing the two terminal carboxylic acid groups (-COOH) of a dimeric acid with an aminomethyl group (-CH2-NH2) or an amino group (-NH2). Diamines are known compounds obtained by dimerizing unsaturated fatty acids (preferably those with 11 to 22 carbons, especially those with 18 carbons), and the industrial manufacturing process is almost standardized in the industry. Diamines are most easily obtained by dimerizing 36-carbon dimers obtained from 18-carbon unsaturated fatty acids such as oleic acid and linoleic acid, which are convenient and readily available. Furthermore, depending on the manufacturing method, purification level, etc., dimeric acids may sometimes contain arbitrary amounts of monomeric acids, trimeric acids, other polymeric fatty acids, etc. Although double bonds remain after the polymerization reaction of unsaturated fatty acids, in this specification, hydrides that further undergo hydrogenation to reduce the degree of unsaturation are also included in dimeric acids. Dimeric acid-type diamines can be commercially available, such as "PRIAMINE1073", "PRIAMINE1074", and "PRIAMINE1075" manufactured by Croda Japan; and "Versamine 551" and "Versamine 552" manufactured by Cognis Japan.

[0182] Examples of aromatic diamine compounds include phenylenediamine compounds, naphthylenediamine compounds, and diphenylamine compounds.

[0183] A phenylenediamine compound refers to a compound consisting of a benzene ring having two amino groups, which may further have 1 to 3 substituents. These substituents are the same as those represented by R32 in the general formula (A-2), which may have alkyl substituents. Examples of phenylenediamine compounds include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobiphenyl, and 2,4,5,6-tetrafluoro-1,3-phenylenediamine.

[0184] A naphthalene diamine compound refers to a compound consisting of a naphthalene ring having two amino groups, and the naphthalene ring may optionally have 1 to 3 substituents. The substituents are the same as those represented by R32 in the general formula (A-2) which have alkyl substituents. Examples of naphthalene diamine compounds include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, and 2,3-diaminonaphthalene.

[0185] A diphenylamine compound is defined as a compound containing two aniline structures within its molecule, wherein each of the two benzene rings in the two aniline structures may further have 1 to 3 substituents. The substituents are the same as those represented by R32 in the general formula (A-2), which may have alkyl substituents. The two aniline structures in a diphenylamine compound are bonded by direct bonding and / or by one or two linker structures having 1 to 100 skeletal atoms selected from carbon, oxygen, sulfur, and nitrogen atoms. Diphenylamine compounds may also contain compounds in which the two aniline structures are bonded by two bonds.

[0186] Specific examples of "linker structures" in diphenylamine compounds include -NHCO-, -CONH-, -OCO-, -COO-, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH(CH3)-, -C(CH3)2-, -C(CF3)2-, -CH=CH-, -O-, -S-, -CO-, -SO2-, -NH-, -Ph-, -Ph-Ph-, -C(CH3)2-Ph-C(CH3)2-, -O-Ph-O-, -O-Ph-Ph-O-, -O-Ph-SO2-Ph-O-, -O-Ph-C(CH3)2-Ph-O-, -Ph-CO-O-Ph-, -C(CH3)2-Ph-C(CH3)2-, the groups shown in formulas (I) and (II) below, and groups formed by combinations thereof. In this specification, "Ph" represents 1,4-epenylphenyl, 1,3-epenylphenyl, or 1,2-epenylphenyl.

[0187]

[0188] In one embodiment, as a diphenylamine compound, specific examples include 4,4'-diamino-2,2'-bis(trifluoromethyl)-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, and 4-aminophenyl-4-aminobenzoic acid. Ester, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropylidene)diphenylamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, α,α-bis[ [4-(4-aminophenoxy)phenyl]-1,3-diisopropylbenzene, α,α-bis[4-(4-aminophenoxy)phenyl]-1,4-diisopropylbenzene, 4,4'-(9-fluorene)diphenylamine, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-methyl-4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl-1,1'-biphenyl The preferred compounds are 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl)fluorene, 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindene, etc., with 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindene being the most preferred.

[0189] For other embodiments, diphenylamine compounds, for example, diamine compounds as shown in formula (B-1) below can be cited.

[0190] (In formula (B-1), R1 to R8 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X9-R9 or -X10-R10, at least one of R1 to R8 is -X10-R10, each of X9 independently represents a single bond, -NR9'-, -O-, -S-, -CO-, -SO2-, -NR9'CO-, -CONR9'-, -OCO- or -COO-, each of R9 independently represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, each of R9' independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, each of X10 independently represents a single bond, -(substituted or unsubstituted alkenyl)-, -NH-, -O-, -S-, -CO-, -SO2-, -NHCO-, -CONH-, -OCO- or -COO-, R10 each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0191] The alkyl group represented by R9 and R9' in formula (B-1) is a straight-chain, branched, or cyclic monovalent aliphatic saturated hydrocarbon group. Alkyl groups with 1 to 6 carbon atoms are preferred, and those with 1 to 3 carbon atoms are even more preferred. Examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, cyclopentyl, and cyclohexyl.

[0192] The alkenyl group represented by R9 and R9' in formula (B-1) is a straight-chain, branched, or cyclic monovalent unsaturated hydrocarbon group having at least one carbon-carbon double bond. Alkenyl groups with 2 to 6 carbon atoms are preferred, and those with 2 or 3 carbon atoms are even more preferred. Examples of such alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, and 2-cyclohexenyl. Substituents for the alkenyl group in "substituted or unsubstituted alkenyl group" are not particularly limited, and examples include halogen atoms, cyano groups, alkoxy groups, aryl groups, heteroaryl groups, amino groups, nitro groups, hydroxyl groups, carboxyl groups, sulfonic acid groups, etc. As for the number of substituents, 1 to 3 are preferred, and 1 is more preferred.

[0193] The substituents of the alkyl group in "substituted or unsubstituted alkyl" and the substituents of the alkenyl group in "substituted or unsubstituted alkenyl" are not particularly limited, and examples include halogen atoms, cyano groups, alkoxy groups, amino groups, nitro groups, hydroxyl groups, carboxyl groups, sulfonic acid groups, etc. As for the number of substituents, 1 to 3 are preferred, and 1 is more preferred.

[0194] An alkoxy group is a monovalent group (alkyl-O-) formed by bonding an alkyl group to an oxygen atom. Alkoxy groups with 1 to 6 carbon atoms are preferred, and those with 1 to 3 carbon atoms are even more preferred. Examples of such alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and pentoxy.

[0195] The alkyl group represented by X10 in formula (B-1) can be a straight-chain, branched, or cyclic divalent aliphatic saturated hydrocarbon group, preferably an alkyl group with 1 to 6 carbon atoms, and more preferably an alkyl group with 1 to 3 carbon atoms. Examples of alkyl groups include -CH2-, -CH2-CH2-, -CH(CH3)-, -CH2-CH2-CH2-, -CH2-CH(CH3)-, -CH(CH3)-CH2-, -C(CH3)2-, -CH2-CH2-CH2-CH2-, -CH2-CH2-CH(CH3)-, -CH2-CH(CH3)-CH2-, -CH(CH3)-CH2-CH2-, -CH2-C(CH3)2-, -C(CH3)2-CH2-, etc. The substituents of the alkyl group in "substituted or unsubstituted alkyl group" are not particularly limited, and examples include halogen atoms, cyano groups, alkoxy groups, aryl groups, heteroaryl groups, amino groups, nitro groups, hydroxyl groups, carboxyl groups, sulfonic acid groups, etc. As for the number of substituents, 1 to 3 are preferred, and 1 is more preferred.

[0196] The aryl group represented by R10 in formula (B-1) is preferably an aryl group with 6 to 14 carbon atoms, and more preferably an aryl group with 6 to 10 carbon atoms. Examples of such aryl groups include phenyl, 1-naphthyl, and 2-naphthyl, with phenyl being preferred. The substituents of the aryl group in "substituted or unsubstituted aryl group" are not particularly limited, and examples include halogen atoms, cyano, alkyl, alkoxy, aryl, heteroaryl, amino, nitro, hydroxyl, carboxyl, and sulfonic acid groups. The number of substituents is preferably 1 to 3, with 1 being more preferred.

[0197] The heteroaryl group represented by R10 in formula (B-1) is an aromatic heterocyclic group having 1 to 4 heteroatoms selected from oxygen, nitrogen and sulfur atoms. The heteroaryl group is preferably a monocyclic, bicyclic or tricyclic (preferably monocyclic) aromatic heterocyclic group with 5 to 12 members (preferably 5 or 6 members). Examples of such heteroaryl groups include furanyl, thiopheneyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, frazanyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, pyridinyl, pyridazinyl, pyrazinyl, and triazinyl. The substituents of the heteroaryl groups in "substituted or unsubstituted heteroaryl groups" are the same as the substituents of the aryl groups in "substituted or unsubstituted aryl groups".

[0198] R1 to R8 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X9-R9, or -X10-R10. R1 to R8 are preferably each independently represented by a hydrogen atom or -X10-R10.

[0199] At least one of R1 to R8 is -X10-R10. It is preferable that one or two of R1 to R8 are -X10-R10, more preferably that one or two of R5 to R8 are -X10-R10, and even more preferably that one or two of R5 and R7 are -X10-R10.

[0200] In one embodiment, it is preferable that one or two of R1 to R8 are -X10-R10, and the others of R1 to R8 are hydrogen atoms; it is even more preferable that one or two of R5 to R8 are -X10-R10, and the others of R1 to R8 are hydrogen atoms; and it is even more preferable that one or two of R5 and R7 are -X10-R10, and the others of R1 to R8 are hydrogen atoms.

[0201] X9 each independently represents a single bond, -NR9'-, -O-, -S-, -CO-, -SO2-, -NR9'CO-, -CONR9'-, -OCO-, or -COO-. R9 each independently represents a substituted or unsubstituted alkyl or substituted or unsubstituted alkenyl group. X9 is preferably a single bond.

[0202] R9' each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. R9 is preferably a substituted or unsubstituted alkyl group.

[0203] X10 can be individually represented as a single bond, -(substituted or unsubstituted alkyl)-, -NH-, -O-, -S-, -CO-, -SO2-, -NHCO-, -CONH-, -OCO-, or -COO-. X10 is preferably a single bond.

[0204] R10 each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R10 is preferably a substituted or unsubstituted aryl group.

[0205] In one embodiment, the diamine compound represented by formula (B-1) is preferably the compound represented by formula (B-2) below, and more preferably the compound represented by formula (B-3) below (4-aminobenzoic acid 5-amino-1,1'-biphenyl-2-yl). (In the formula, R1 to R6 and R8 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, and -X9-R9, and other symbols are the same as in formula (B-1).)

[0206] The diamine compound may be commercially available or synthesized by known methods. For example, the diamine compound shown in formula (B-1) may be synthesized by the synthesis method described in or according to Patent No. 6240798. A single diamine compound may be used alone or in combination of two or more.

[0207] The anhydride used to prepare the polyimide resin is not particularly limited, but in a preferred embodiment, it is an aromatic tetracarboxylic dianhydride. Examples of aromatic tetracarboxylic dianhydrides include phenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, anthracenetetracarboxylic dianhydride, and bisphthalic dianhydride, with bisphthalic dianhydride being preferred.

[0208] The term "benzenetetracarboxylic acid dianhydride" refers to a dianhydride of benzene having four carboxyl groups, wherein the benzene ring may have 1 to 3 substituents. Preferably, the substituents are selected from halogen atoms, cyano groups, and -X13-R13 (as defined in formula (B-4) below). Examples of benzenetetracarboxylic acid dianhydrides include benzoic acid dianhydride and 1,2,3,4-benzenetetracarboxylic acid dianhydride.

[0209] Naphthalenetetracarboxylic acid dianhydride refers to a dianhydride of naphthalene having four carboxyl groups, wherein the naphthalene ring may optionally have 1 to 3 substituents. Preferred substituents are halogen atoms, cyano groups, and -X13-R13 (as defined in formula (B-4) below). Specific examples of naphthalenetetracarboxylic acid dianhydrides include 1,4,5,8-naphthalenetetracarboxylic acid dianhydride and 2,3,6,7-naphthalenetetracarboxylic acid dianhydride.

[0210] The term "anthracite tetracarboxylic dianhydride" refers to an anthracene dianhydride having four carboxyl groups, wherein the anthracene ring may have 1 to 3 substituents. Preferably, the substituents are selected from halogen atoms, cyano groups, and -X13-R13 (as defined in formula (B-4) below). Examples of anthracene tetracarboxylic dianhydrides include 2,3,6,7-anthracite tetracarboxylic dianhydrides.

[0211] The term "bisphthalic dianhydride" refers to a compound containing two phthalic anhydrides within its molecule, wherein each of the two benzene rings in the two phthalic anhydrides may have 1 to 3 substituents. Preferably, the substituents are selected from halogen atoms, cyano groups, and -X13-R13 (as defined in formula (B-4) below). The two phthalic anhydrides in the bisphthalic dianhydride may be directly bonded, or they may be bonded through a linker structure having 1 to 100 skeletal atoms selected from carbon, oxygen, sulfur, and nitrogen atoms.

[0212] As a bisphthalic dianhydride, for example, the compound shown in formula (B-4) can be cited. (In the formula, R11 and R12 each independently represent a halogen atom, cyano, nitro or -X13-R13, X13 each independently represents a single bond, -NR13'-, -O-, -S-, -CO-, -SO2-, -NR13'CO-, -CONR13'-, -OCO- or -COO-, R13 each independently represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, R13' each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, Y represents a single bond, or a linker structure having 1 to 100 skeletal atoms selected from carbon, oxygen, sulfur and nitrogen atoms, and n1 and m1 each independently represent an integer from 0 to 3.)

[0213] Y preferably has a linkage structure having 1 to 100 skeletal atoms selected from carbon, oxygen, sulfur and nitrogen atoms. n1 and m1 are preferably 0.

[0214] The “linker structure” in Y has 1 to 100 skeletal atoms selected from carbon, oxygen, sulfur and nitrogen atoms. The “linker structure” is preferably a divalent group as shown in -[A-Ph]aA-[Ph-A]b- [where A independently represents a single bond, -(substituted or unsubstituted alkyl)-, -O-, -S-, -CO-, -SO2-, -CONH-, -NHCO-, -COO- or -OCO-, and a and b independently represent integers from 0 to 2 (preferably 0 or 1)].

[0215] The “connector structure” in Y can be specifically exemplified by -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH(CH3)-, -C(CH3)2-, -O-, -CO-, -SO2-, -Ph-, -O-Ph-O-, -O-Ph-SO2-Ph-O-, -O-Ph-C(CH3)2-Ph-O-, etc.

[0216] Specific examples of bis(phthalic acid) dianhydrides include 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl sulfonate tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride, 2,2',3,3'-biphenyl tetracarboxylic acid dianhydride, and 2,3,3',4'-biphenyl tetracarboxylic acid. Dihydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl tannic acid tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)tannic acid dianhydride, methylene-4,4'-bisphthalic acid dianhydride, 1,1-ethynlidene-4,4'-bisphthalic acid dianhydride Citric acid dianhydride, 2,2-propynyl-4,4'-diphthalic acid dianhydride, 1,2-epoxyethyl-4,4'-diphthalic acid dianhydride, 1,3-trimethylene-4,4'-diphthalic acid dianhydride, 1,4-tetramethylene-4,4'-diphthalic acid dianhydride, 1,5-pentamethylene-4,4'-diphthalic acid dianhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic acid dianhydride Anhydrides, 1,4-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic anhydride, etc.

[0217] Aromatic tetracarboxylic acid dianhydrides may be used from those that are sold or synthesized by known methods or methods thereof. Aromatic tetracarboxylic acid dianhydrides may be used alone or in combination of two or more.

[0218] In one embodiment, the anhydride used to manufacture the polyimide resin may contain other anhydrides besides aromatic tetracarboxylic acid dianhydrides.

[0219] Other acid anhydrides that can be specifically cited include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, and methylene-4,4 Aliphatic tetracarboxylic dianhydrides include '-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-epethyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, and sulfonylurea-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride.

[0220] The content of the aromatic tetracarboxylic acid dianhydride structure in the entire structure of the anhydride constituting the polyimide resin is preferably 10 mol% or more, preferably 30 mol% or more, even more preferably 50 mol% or more, even more preferably 70 mol% or more, even more preferably 90 mol% or more, and especially preferably 100 mol% or more.

[0221] The polyimide resin is preferably one having the structural unit shown in the following general formula (B). (In general formula (B), R51 represents a single bond or a residue from an acid anhydride, and R52 represents a single bond or a residue from a diamine compound.)

[0222] R51 indicates a single bond or a residue from an anhydride, preferably a residue from an anhydride. The residue from an anhydride represented by R51 indicates a divalent group obtained by removing two oxygen atoms from the anhydride. This is as described above for anhydrides.

[0223] R52 represents a single bond or a residue from a diamine compound, preferably a residue from a diamine compound. The residue from a diamine compound represented by R52 indicates a divalent group obtained by removing two amino groups from the diamine compound. This applies to diamine compounds as described above.

[0224] Polyimide resins can be prepared by methods known in the past. Examples of known methods include reacting a mixture of a diamine compound, an anhydride, and a solvent by heating. The amount of the diamine compound, for example, with respect to the anhydride, is typically 0.5 to 1.5 molar equivalents, preferably 0.9 to 1.1 molar equivalents.

[0225] Examples of solvents used in the preparation of polyimide resins include acetamine solvents such as N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone; ketone solvents such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; ester solvents such as γ-butyrolactone; and hydrocarbon solvents such as cyclohexane and methylcyclohexane. Furthermore, aceiminizing catalysts, azeotropic dehydrating solvents, and acid catalysts may also be used as necessary for the preparation of polyimide resins. Examples of aceiminizing catalysts include triethylamine, triisopropylamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, N,N-dimethyl-4-aminopyridine, and pyridine, which are tertiary amines. Examples of azeotropic dehydrating solvents include toluene, xylene, and ethylcyclohexane. Examples of acid catalysts include acetic anhydride. The amounts of amide catalysts, azeotropic dehydrating solvents, and acid catalysts used can be appropriately set by the manufacturer. The reaction temperature for adjusting polyamide resins is typically 100–250°C.

[0226] Examples of phenoxy resins include those having one or more skeletons selected from the group consisting of bisphenol A, bisphenol F, bisphenol S, bisphenol acetophenone, phenolic varnish, biphenyl, fluorene, dicyclopentadiene, norbornene, naphthalene, anthracene, adamantane, terpene, and trimethylcyclohexane skeletons. The terminal group of the phenoxy resin may be any functional group selected from phenolic hydroxyl, epoxy, etc. Phenoxy resins with a weight average molecular weight of 30,000 or higher are preferred.

[0227] Specific examples of phenoxy resins include Mitsubishi Chemical's "1256" and "4250" (both phenoxy resins containing a bisphenol A backbone); Mitsubishi Chemical's "YX8100" (phenoxy resin containing a bisphenol S backbone); Mitsubishi Chemical's "YX6954" (phenoxy resin containing a bisphenol acetophenone backbone); Nippon Steel Chemical & Materials Co., Ltd.'s "FX280" and "FX293"; and Mitsubishi Chemical's "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482", etc.

[0228] Polyamide-imide resin is a resin having an amide-imide structure. From the viewpoint of compatibility with other components in the resin composition layer, polyamide-imide resins with an alicyclic structure in the molecular structure, polyamide-imide resins with a siloxane structure as described in Japanese Patent Application Publication No. 05-112760, polyamide-imide resins with a high-volume branched structure, polyamide-imide resins using asymmetric monomers as raw materials, and polyamide-imide resins with a multi-branched structure are preferred.

[0229] Among them, polyamide-imide resins also have improved compatibility and dispersibility in resin coatings due to their isocyanate ring structure. This can be categorized as (i) polyamide-imide resins with an isocyanate ring structure in their molecular structure (i.e., polyamide-imide resins with an isocyanate ring structure and an imide backbone or an imide backbone) and (ii) polyamide-imide resins with an isocyanate ring structure and an alicyclic structure in their molecular structure. The polyamide-imide resin with the following structure (i.e., a polyamide-imide resin having an isocyanate ring structure, an alicyclic structure, and an imide skeleton or an amide skeleton), and (iii) a polyamide-imide resin containing repeating units of an isocyanate ring structure and an alicyclic structure (i.e., a polyamide-imide resin containing repeating units of an isocyanate ring structure, an alicyclic structure, and an imide skeleton or an amide skeleton) is preferred.

[0230] As a preferred embodiment of the polyamide imide resin described in (i) to (iii) above, examples include (1) a branched polyamide imide containing carboxylic acid groups obtained by reacting a polyisocyanate compound derived from an alicyclic diisocyanate with an anhydride of a polycarboxylic acid having three or more carboxyl groups (hereinafter sometimes referred to as "(compound B-b1)"), (2) a compound (B-b1) reacting with an anhydride of a polycarboxylic acid having one epoxy group and one or more self-carboxyl groups. The compound obtained by reacting a compound with a radical polymerizable unsaturated group is a branched polymerizable polyamide containing a carboxylic acid group (hereinafter sometimes referred to as "compound (B-b2)"). Or (3) the compound obtained by reacting a compound with a residual isocyanate group having one hydroxyl group and one or more radical polymerizable unsaturated groups during the synthesis of compound (B-b1) is a branched polymerizable polyamide containing a carboxylic acid group (hereinafter sometimes referred to as "compound (B-b3)").

[0231] As a compound (B-b1), the compound shown in the general formula (I) below can be specifically cited. Furthermore, the repeating unit in the compound shown in the general formula (I) is taken as the repeating unit (I-1). (In the formula, w represents 0 to 15.)

[0232] As a compound (B-b2), examples include compounds (II) having a structure (I-2) in which a carboxyl group and / or a terminal carboxyl group of any part of the repeating unit (I-1) in general formula (I) is added to GMA (glycidyl methacrylate). (In the formula, R40 represents a residue in formula (I).)

[0233] The proportion of GMA denaturation of the carboxyl groups is preferably 0.3 mol% or more, more preferably 0.5 mol% or more, more preferably 0.7 mol% or more, or 0.9 mol% or more, depending on the number of carboxyl groups in the compound (B-b1). The upper limit is preferably 50 mol% or less, more preferably 40 mol% or less, more preferably 30 mol% or less, or 20 mol% or less.

[0234] As compound (B-b3), examples include compounds (III) having a structure (I-3) in which any part of the repeating unit (I-1) in formula (I) above and / or the terminal amide group is an isocyanate residue, and which have a hydroxyl group that adds to pentaerythritol triacrylate. (In the formula, R' represents a residue in formula (I).)

[0235] The amount of pentaerythritol triacrylate added is preferably 40 mol% or less, more preferably 38 mol% or less, and even more preferably 35 mol% or less, relative to the number of isocyanate groups in the polyisocyanate at the time of loading. On the other hand, from the viewpoint that sufficient effect can be obtained by this addition, the amount of pentaerythritol triacrylate added is preferably 0.3 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, relative to the number of isocyanate groups in the polyisocyanate at the time of loading.

[0236] Polyamide-imide resins can be synthesized by various known methods. For example, the method for synthesizing polyamide-imide resins can be referred to paragraphs 0020 to 0030 of International Publication No. 2010 / 074197, the contents of which are incorporated herein by reference.

[0237] Polyamide-imide resins can be used in commercial products. Examples of commercial products include "UnidicV-8000" manufactured by DIC Corporation, "VylomaxHR11NN" and "VylomaxHR16NN" manufactured by Toyobo Corporation, and "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane backbone) manufactured by Hitachi Chemical Corporation.

[0238] From the viewpoint of compatibility with other components in the resin composition layer, polyester resins with a fluorene structure in their molecular structure are preferred. In addition to the fluorene structure, those with structural units derived from diols and structural units derived from dicarboxylic acids are also preferred.

[0239] As a specific example of polyester resin, one can cite "OKP4HT" manufactured by Osaka Gas Chemical Co., Ltd.

[0240] As specific examples of polyurethane resins, we can cite polyurethanes "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0241] Examples of polyethylene acetal resins include polyethylene formaldehyde resin and polyethylene butyral resin, with polyethylene butyral resin being preferred. Specific examples of polyethylene acetal resins include the S-LECBH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemicals Co., Ltd.

[0242] As a specific example of polyether resin, one can cite Sumitomo Chemical Co., Ltd.’s “PES5003P”, etc.

[0243] The elastomer in component (B) refers to a resin with softness, preferably a resin with rubber elasticity or a resin that exhibits rubber elasticity by polymerization with other components. For example, a resin that exhibits an elastic modulus of less than 1 GPa when subjected to a tensile test at 25°C and 40% RH according to Japanese Industrial Standard (JIS K7161) can be cited as an example. The elastomer is typically an amorphous resin component soluble in organic solvents. This elastomer (e) can be used alone or in any combination of two or more types.

[0244] For one embodiment, the elastic system is preferably a resin having one or more structures selected from polybutadiene, polysiloxane, poly(meth)acrylate, polyalkylene, polyalkoxy, polyisoprene, polyisobutylene, polycarbonate, and polystyrene within its molecules. "(meth)acrylate" refers to methacrylate and acrylate.

[0245] Furthermore, in another embodiment, the elastic system is preferably selected from one or more resins with a glass transition temperature (Tg) below 25°C and resins that are liquid at 25°C or below. The glass transition temperature of the resin with a glass transition temperature (Tg) below 25°C is preferably below 20°C, and more preferably below 15°C. While there is no particular limitation on the lower limit of the glass transition temperature, it can generally be set to -15°C or higher. Furthermore, as for the resin that is liquid at 25°C, a resin that is liquid at 20°C or below is preferred, and more preferably a resin that is liquid at 15°C or below. The glass transition temperature can be measured by DSC (differential scanning calorimetry).

[0246] Examples of elastomers include resins containing a polybutadiene structure. The polybutadiene structure may be contained in the main chain or in the side chains. Furthermore, part or all of the polybutadiene structure may be hydrogenated. Resins containing a polybutadiene structure are sometimes referred to as "polybutadiene resins". Specific examples of polybutadiene resins include Clay Valley's "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", and "Ricon 184MA6" (polybutadiene containing anhydride groups); Nippon Soda's "GQ-1000" (polybutadiene with introduced hydroxyl and carboxyl groups), "G-1000", "G-2000", "G-3000" (polybutadiene with two-terminated hydroxyl groups), "GI-1000", "GI-2000", and "GI-3000" (hydrogenated polybutadiene with two-terminated hydroxyl groups); and Nagase. Chemtex's "FCA-061L" (hydrogenated polybutadiene-backbone epoxy resin), etc. Specific examples of polybutadiene resins include linear polyimides (as described in Japanese Patent Application Publication No. 2006-37083 and International Publication No. 2008 / 153208) using hydroxyl-terminated polybutadiene, diisocyanate compounds, and tetrabasic anhydrides as raw materials, and butadiene containing phenolic hydroxyl groups. The butadiene content of this polyimide resin is preferably 60% to 95% by mass, and more preferably 75% to 85% by mass. For details on this polyimide resin, please refer to Japanese Patent Application Publication No. 2006-37083 and International Publication No. 2008 / 153208, the contents of which are incorporated herein by reference.

[0247] As an elastomer, examples include resins containing a poly(meth)acrylate structure. Sometimes, resins containing a poly(meth)acrylate structure are referred to as "poly(meth)acrylate resins". Specific examples of poly(meth)acrylate resins include Teisan resin manufactured by Nagase Chemtex, and "ME-2000", "W-116.3", "W-197C", "KG-25", and "KG-3000" manufactured by Negami Kogyo Co., Ltd.

[0248] Examples of elastomers include resins containing a polycarbonate structure. Resins containing a polycarbonate structure are sometimes referred to as "polycarbonate resins." Examples of such resins include carbonate resins without reactive groups, carbonate resins containing hydroxyl groups, carbonate resins containing phenolic hydroxyl groups, carbonate resins containing carboxyl groups, carbonate resins containing acid anhydride groups, carbonate resins containing isocyanate groups, carbonate resins containing urethane groups, and carbonate resins containing epoxy groups. Here, "reactive group" refers to a functional group obtained by reacting hydroxyl, phenolic hydroxyl, carboxyl, acid anhydride, isocyanate, urethane, and epoxy groups with other components. Specific examples of polycarbonate resins include "FPC0220" and "FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemical Co., Ltd., and "C-1090", "C-2090", and "C-3090" (polycarbonate diol) manufactured by Kurarai Co., Ltd. Furthermore, linear polyimides using hydroxyl-terminated polycarbonate, diisocyanate compounds, and tetracarboxylic anhydrides as raw materials can also be used. The carbonate structure content of this polyimide resin is preferably 60% to 95% by mass, and more preferably 75% to 85% by mass. For details on this polyimide resin, please refer to International Publication No. 2016 / 129541, which is incorporated herein by reference.

[0249] As an elastomer, resins containing a polysiloxane structure can be cited as an example. Sometimes, resins containing a polysiloxane structure are referred to as "siloxane resins". Specific examples of siloxane resins include "SMP-2006", "SMP-2003PGMEA", and "SMP-5005PGMEA" manufactured by Shin-Etsu Silicon Oxide Co., Ltd., as well as linear polyimides made from amine-terminated polysiloxanes and tetrabasic anhydrides (International Publication No. 2010 / 053185, Japanese Patent Application Publication No. 2002-12667, and Japanese Patent Application Publication No. 2000-319386, etc.).

[0250] Examples of elastomers include resins containing polyalkyl or polyalkoxy structures. Resins containing polyalkyl structures are sometimes referred to as "alkyl resins." Similarly, resins containing polyalkoxy structures are sometimes referred to as "alkoxy resins." The polyalkoxy structure is preferably a polyalkoxy structure with 2 to 15 carbon atoms, more preferably a polyalkoxy structure with 3 to 10 carbon atoms, and particularly preferably a polyalkoxy structure with 5 to 6 carbon atoms. Specific examples of alkyl and alkoxy resins include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Corporation.

[0251] As an elastomer, resins containing a polyisoprene structure can be cited as an example. Sometimes resins containing a polyisoprene structure are called "isoprene resins". Specific examples of isoprene resins include "KL-610" and "KL613" manufactured by Kuraray Co., Ltd.

[0252] As an elastomer, examples include resins containing a polyisobutylene structure. Sometimes, resins containing a polyisobutylene structure are called "isobutylene resins". Specific examples of isobutylene resins include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation.

[0253] Examples of elastomers include resins containing a polystyrene structure. Resins containing a polystyrene structure are sometimes referred to as "styrene resins." In styrene resins, the term "polystyrene resin" can refer to a copolymer composed of styrene units containing any repeating units different from the aforementioned styrene units, or it can be a hydrogenated polystyrene resin.

[0254] As any repeating unit, examples include repeating units having a structure obtained by polymerizing a conjugated diene (conjugated diene unit), repeating units having a structure obtained by hydrogenation of this (hydrogenated conjugated diene unit), etc. Examples of conjugated dienes include aliphatic conjugated dienes such as butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, and 1,3-hexadiene; and halogenated aliphatic conjugated dienes such as chloroprene. From the viewpoint of significantly obtaining the effects of the present invention, aliphatic conjugated dienes are preferred, and butadiene is more preferred. A single type of conjugated diene can be used alone, or two or more types can be used in combination. Furthermore, the polystyrene resin can be a random copolymer or a block copolymer.

[0255] Examples of styrene resins include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), styrene-ethylene-butene-styrene block copolymers (SEBS), styrene-ethylene-propylene-styrene block copolymers (SEPS), styrene-ethylene-butene-propyltrisyl-styrene block copolymers (SEEPS), styrene-butadiene-butene-styrene block copolymers (SBBS), styrene-butadiene diblock copolymers, hydrogenated styrene-butadiene block copolymers, hydrogenated styrene-isoprene block copolymers, hydrogenated styrene-butadiene random copolymers, and styrene-maleic anhydride copolymers. Specific examples of styrene resins include hydrogenated styrene thermoplastic elastomers "H1041", "Tough techH1043", "Tough techP2000", and "Tough techMP10" (manufactured by Asahi Kasei Corporation); epoxidized styrene-butadiene thermoplastic elastomers "EpofriendAT501" and "CT310" (manufactured by Daicel Chemical Industries, Ltd.); hydroxyl-containing modified styrene elastomer "SeptonHG252" (manufactured by Kuraray Corporation); carboxyl-containing modified styrene elastomers "Tough techN503M", amino-containing modified styrene elastomers "Tough techN501", and anhydride-containing modified styrene elastomers "Tough "techM1913" (manufactured by Asahi Kasei Chemicals); "SeptonS8104" (manufactured by Kuraray) - unmodified styrene-based elastomer; "FG1924" (manufactured by Kraton) and "EF-40" (manufactured by CRAY VALLEY) - styrene-ethylene / butadiene-styrene block copolymers.

[0256] The number average molecular weight (Mn) of the elastomer is preferably 1,000 or higher, more preferably 1,500 or higher, even more preferably 3,000 or higher, and especially preferably 5,000 or higher. It is preferably 1,000,000 or lower, and more preferably 900,000 or lower. The number average molecular weight (Mn) can be determined by conversion to polystyrene using GPC (gel permeation chromatography).

[0257] As for the content of component (B), from the viewpoint that a cured product with excellent dielectric properties can be obtained, when the non-volatile component in the resin composition layer is taken as 100% by mass, it is preferably 10% by mass or more, more preferably 15% by mass or more, more preferably 20% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, and more preferably 30% by mass or less.

[0258] -(C) Inorganic filler - In addition to the above-mentioned components, the resin composition layer may further contain an inorganic filler as component (C).

[0259] Inorganic compounds are used as inorganic fillers. Examples of inorganic fillers include silicon dioxide, alumina, glass, cordierite, silicates, 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 dioxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silicon dioxide is particularly preferred. Examples of silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. Furthermore, spherical silica is preferred as a silica material. (C) Inorganic fillers can be used alone or in combination of two or more types.

[0260] Products sold as component (C) include, for example, Denka's "UFP-30"; Nippon Steel & Sumitomo Metal Materials' "SP60-05" and "SP507-05"; Admatechs' "YC100C", "YA050C", "YA050C-MJE", and "YA010C"; Tokuyama's "SilfirNSS-3N", "SilfirNSS-4N", and "SilfirNSS-5N"; and Admatechs' "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1".

[0261] The specific surface area of ​​component (C) is preferably 1 m² / g or more, more preferably 2 m² / g or more, and especially preferably 3 m² / g or more. While there is no particular upper limit, it is preferably 60 m² / g or less, 50 m² / g or less, or 40 m² / g or less. The specific surface area is calculated using the BET method, by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mountech), and then using the BET multi-point method.

[0262] (C) The average particle size of the component is preferably 0.01 μm or more from the viewpoint that the desired effect of the present invention can be obtained significantly. It is more preferably 0.05 μm or more, especially preferably 0.1 μm or more, preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less.

[0263] The average particle size of component (C) can be determined by laser diffraction and scattering based on the Mie scattering theory. Specifically, using a laser diffraction and scattering particle size distribution measuring device, the particle size distribution of the inorganic filler is prepared according to a volume basis, and the median diameter is used as the average particle size. The test sample is prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone in a sample bottle and dispersing them by ultrasound for 10 minutes. The test sample is then tested using a laser diffraction and scattering particle size distribution measuring device, with the light source wavelength set to blue and red, and the volume basis particle size distribution of component (C) is measured in a flow cell manner. The average particle size, as the median diameter, is calculated from the obtained particle size distribution. Examples of laser diffraction and scattering particle size distribution measuring devices include the "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

[0264] (C) From the viewpoint of improving moisture resistance and dispersibility, the component treated with a surface treatment agent is preferred. Examples of surface treatment agents include vinyl silane coupling agents, (meth)acrylic acid coupling agents, fluorinated silane coupling agents, amino silane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. Among these, from the viewpoint of obtaining significant effects of the present invention, amino silane coupling agents are preferred. Furthermore, a single type of surface treatment agent can be used alone, or two or more types can be used in combination.

[0265] Commercially available products as surface treatment agents include, for example, Shin-Etsu Chemical Co., Ltd.'s "KBM1003" (vinyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM503" (3-methacryloxypropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-epoxypropoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), and Shin-Etsu Chemical Co., Ltd.'s "KBE903" (…). 3-Aminopropyltriethoxysilane), Shin-Etsu Chemical Industry Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Industry Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Industry Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Industry Co., Ltd.'s "KBM-4803" (long-chain epoxy silane coupling agent), Shin-Etsu Chemical Industry Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), etc.

[0266] From the viewpoint of improving the dispersibility of inorganic fillers, it is preferable to control the degree of surface treatment by the surface treatment agent within a predetermined range. Specifically, it is preferable to surface treat 100 parts by weight of inorganic filler with 0.2 to 5 parts by weight of surface treatment agent, 0.2 to 3 parts by weight of surface treatment agent, or 0.3 to 2 parts by weight of surface treatment agent.

[0267] The degree of surface treatment by the surface treatment agent can be evaluated by the carbon content per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m2 or more, preferably 0.1 mg / m2 or more, and even more preferably 0.2 mg / m2 or more. On the other hand, from the viewpoint of the melt viscosity of the resin coating and suppressing the increase of melt viscosity in sheet form, it is preferably 1 mg / m2 or less, preferably 0.8 mg / m2 or less, and even more preferably 0.5 mg / m2 or less.

[0268] The carbon content per unit surface area of ​​the inorganic filler can be determined by washing the surface-treated inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK is added to the surface-treated inorganic filler, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the clear liquid and drying the solid components, the carbon content per unit surface area of ​​the inorganic filler can be determined using a carbon analyzer. A carbon analyzer such as the "EMIA-320V" manufactured by Horiba Corporation can be used.

[0269] (C) From the viewpoint that the content of the component can achieve a low dielectric loss tangent and reduce the maximum value of tanδ, when the non-volatile component in the resin composition layer is taken as 100% by mass, it is preferably 50% by mass or more, more preferably 52% by mass or more or 54% by mass or more, even more preferably 55% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less.

[0270] -(D) Polymerization Initiator- The resin composition layer may contain a (D) polymerization initiator as an arbitrary component. By containing a (D) polymerization initiator, the curing of free radical polymerizable compounds can be carried out efficiently.

[0271] There is no particular limitation on the type of polymerization initiator, but examples include cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, diisopropylphenyl hydroperoxide, cumyl hydroperoxide, tert-butyl hydroperoxide, and 2,3-dimethyl-2,3-diphenylbutane, which are free radical generating agents. One or more of these can be used.

[0272] Commercially available polymerization initiators may be used. Examples of commercially available initiators include "Perhexin 25B" manufactured by Nippon Oil Company.

[0273] From the viewpoint that the non-volatile component in the resin composition layer can achieve significant effects of the present invention, the content of the polymerization initiator is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, more preferably 0.05% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.

[0274] -(E) Other Additives- In addition to the above-mentioned components, the resin composition layer may further contain other additives as optional components. Examples of such additives include tackifiers, defoamers, leveling agents, adhesion promoters, and other resin additives. These additives may be used alone or in combination of two or more types. The content of each can be appropriately set by the manufacturer.

[0275] The resin composition layer may further contain any solvent as a volatile component. By containing a solvent in the resin composition used to form the resin composition layer, the viscosity of the paint can be adjusted. Examples of solvents include organic solvents. However, it is preferable that the resin composition layer does not contain toluene, and when the total amount of the resin composition layer is 100% by mass, the toluene content is preferably 0.1% by mass or less, 0.01% by mass or less, 0.001% by mass or less, or 0.0001% by mass or less.

[0276] Examples of organic solvents include ketones such as methyl ethyl ketone (MEK) and cyclohexanone, aromatic hydrocarbons such as xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, ethyl diethylene glycol acetate, aliphatic hydrocarbons such as octane and decane, petroleum ethers, naphtha, hydrogenated naphtha, solvent naphtha, and other petroleum-based solvents. These can be used alone or in combination of two or more.

[0277] As previously stated, the inventors have confirmed that when forming an insulating layer using a resin sheet (resin composition layer), compared to the conventional vacuum lamination method, the pressure applied to the resin sheet (resin composition layer) during lamination is high during vacuum pressure treatment, causing resin leakage and preventing the desired insulating layer thickness from being achieved, which has become a new problem. It has been confirmed that the thickness deviation of the insulating layer after vacuum pressure treatment (difference from the target thickness) is related to the amount of residual solvent in the resin composition layer, or the maximum value of tanδ in a specific temperature range of the dynamic viscoelasticity of the resin composition layer (where tanδ represents the ratio of storage elastic modulus E' (GPa) to loss elastic modulus E' (Pa) E” / E'). Hereinafter, the approach to achieving the desired insulating layer thickness after vacuum hot pressing will be expressed from the perspective of the amount of residual solvent or the maximum value of tanδ.

[0278] From the viewpoint of achieving the desired insulation layer thickness after vacuum pressure treatment by adjusting the melt viscosity of the resin composition layer, the lower the amount of solvent in the resin composition layer, the better. The amount of solvent in the resin composition layer (residual solvent content) is preferably 3% by mass or less, more preferably 2.5% by mass or less, even more preferably 2% by mass or less, even more preferably 1.5% by mass or less, and particularly preferably 1% by mass or less. While there are no particular limitations on the lower limit, it can be 0.0001% by mass or more. The residual solvent content can be measured using the method described in the examples below.

[0279] From the viewpoint of achieving the desired insulation layer thickness after vacuum pressure treatment, in the dynamic viscoelasticity measurement of the resin composition layer from 60°C to 200°C, the maximum value of tanδ above 100°C is preferably 2.0 or less, more preferably 1.9 or less, and even more preferably 1.8 or less. From the viewpoint of achieving good circuit embedding performance, the lower limit of this maximum value can be 0.3 or more, 0.4 or more, 0.5 or more, etc. The maximum value of tanδ of dynamic viscoelasticity above 100°C can be measured according to the method described in the embodiments below.

[0280] From the viewpoint that the thickness of the resin composition layer can improve the thinness of the printed circuit board and that the cured resin composition can improve the insulation performance even if it is a thin film, it is preferable to have a thickness of 60 μm or less, more preferably 50 μm or less, and even more preferably 40 μm or less. Although there is no particular limitation on the lower limit of the thickness of the resin composition layer, it is usually 5 μm or more, 10 μm or more, etc.

[0281] <Other Layers> In one embodiment, the resin sheet may further include other layers as necessary. Examples of such other layers include, for instance, a protective film disposed on the surface not bonded to the support of the resin composition layer (i.e., the opposite side of the support). The thickness of the protective film is not particularly limited, but can be, for example, 1 μm to 40 μm. By laminating the protective film, the adhesion of debris or scratches to the surface of the resin composition layer can be suppressed.

[0282] <Method for manufacturing resin sheets> Resin sheets can be manufactured, for example, by preparing a resin coating in which the resin composition is dissolved in an organic solvent, applying the resin coating to a support using a mold coating or similar method, and then drying it to form a resin composition layer. The above-mentioned organic solvents can be used.

[0283] Drying can be carried out by known methods such as heating or blowing hot air. There are no particular limitations on the drying conditions, but the content of organic solvent in the resin composition layer should be less than 10% by mass, preferably less than 5% by mass. Although it varies depending on the boiling point of the organic solvent in the resin coating, for example, when using a resin coating containing 30% to 60% by mass of organic solvent, a resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0284] The resin sheet can be rolled into a cylinder for storage. When the resin sheet has a protective film, it can be used after peeling off the protective film.

[0285] <Properties and Uses of Resin Sheets> The resin sheet of the present invention is a resin sheet for forming an insulating layer using vacuum pressure processing. It comprises a support and a resin composition layer disposed on the support. The support has a metal foil, and the resin composition layer contains component (A). By using a resin composition layer containing component (A) along with a support containing a metal foil, and forming an insulating layer by vacuum pressure processing, an insulating layer exhibiting good mechanical strength and excellent MIT folding resistance can be achieved, while also exhibiting the desired dielectric properties.

[0286] A resin composition layer of a resin sheet processed by vacuum pressure is laminated to a circuit board. The resin composition layer is then heat-cured at 100°C for 30 minutes and then at 200°C for 120 minutes. The resulting cured resin composition layer exhibits a low dielectric loss tangent. Therefore, the aforementioned cured product can achieve an insulating layer with a low dielectric loss tangent. A dielectric loss tangent of less than 0.0031 is preferred, less than 0.0030 is more preferred, and less than 0.0026 or 0.0025 is even more preferred. The lower limit of the dielectric loss tangent can be 0.0001 or higher. The dielectric loss tangent can be measured according to the method described in the embodiments described later.

[0287] A resin composition layer of a resin sheet subjected to vacuum pressure treatment is laminated to a circuit board. The resin composition layer is then heat-cured at 100°C for 30 minutes and then at 200°C for 120 minutes. The resulting cured resin composition layer exhibits a low dielectric constant. Therefore, the aforementioned cured layer can achieve an insulating layer with a low dielectric constant. A dielectric constant of less than 2.95 is preferred, less than 2.9 is more preferred, and less than 2.9 is even more preferred. The lower limit of the dielectric constant can be 1 or higher. The dielectric constant can be measured according to the method described in the following examples.

[0288] A resin composition layer of a resin sheet subjected to vacuum pressure treatment is laminated to a circuit board. The resin composition layer is then heat-cured at 100°C for 30 minutes and then at 200°C for 120 minutes. The resulting cured resin composition layer exhibits excellent mechanical strength and flexibility (MIT folding endurance). Therefore, the aforementioned cured product can achieve an insulating layer with excellent mechanical strength and flexibility. The folding endurance test apparatus is preferably 400 times or more, more preferably 410 times or more, and even more preferably 420 times or more. The upper limit can be 1000 times or less. The MIT folding endurance can be measured according to the method described in the following examples.

[0289] Using the resin sheet of the present invention, by forming an insulating layer subjected to vacuum pressure treatment, it exhibits good mechanical strength and excellent MIT (Medium-to-Fold) resistance, while also achieving an insulating layer exhibiting the desired dielectric properties. Therefore, the resin sheet of the present invention can be used as a resin sheet for forming an insulating layer by vacuum pressure treatment (for forming an insulating layer by vacuum pressure treatment). The resin sheet of the present invention has a support containing a metal foil, which can be used to form a conductor layer. Therefore, the resin sheet of the present invention can be used in the manufacture of printed circuit boards as a resin sheet for forming a double layer of insulating and conductor layers by vacuum pressure treatment (for forming an insulating and conductor layer by vacuum pressure treatment). The resin sheet of the present invention can be applied to the insulating layer (and conductor layer) to be formed on a printed circuit board, preferably on the interlayer insulating layer (and conductor layer) to be formed on a printed circuit board. In the present invention, the term "printed circuit board" also includes a rewiring substrate for semiconductor packaging.

[0290] [Printed wiring board, method of manufacturing printed wiring board] The printed wiring board of the present invention contains an insulating layer formed by a hardened resin composition layer of the resin sheet of the present invention.

[0291] A printed wiring board, for example, can be manufactured using the above-mentioned resin sheet by a method comprising the steps (I) and (II) below. (I) A step of laminating the resin sheet onto an inner substrate by vacuum pressure treatment; (II) A step of forming an insulating layer by thermosetting the resin composition layer.

[0292] The term "inner layer substrate" used in step (I) refers to a component that serves as the substrate of a printed wiring board. Examples of such components include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. Furthermore, the substrate may have conductor layers on one or both sides, and these conductor layers may be patterned. An inner layer substrate with conductor layers (circuit loops) formed on one or both sides of the substrate is sometimes called an "inner layer circuit board." Intermediate products formed by insulating layers and / or conductor layers during the manufacture of a printed wiring board are also included in the "inner layer substrate" of this invention. When the printed wiring board is a component-embedded circuit board, an inner layer substrate with embedded components can be used.

[0293] The inner layer substrate and the resin sheet are laminated by vacuum pressure processing, which bonds the resin composition layer of the laminated resin sheet to the inner layer substrate. By laminating the inner layer substrate and the resin composition layer through vacuum pressure processing, the dielectric properties, mechanical strength and electrical properties can be improved.

[0294] First, to bond the resin composition layer of the resin sheet to the inner substrate, the inner substrate and the resin sheet are placed in a vacuum pressure device. Next, under reduced pressure, the inner substrate and the resin composition layer are subjected to a vacuum pressure treatment involving heating and pressing. The vacuum pressure treatment is preferably a heated vacuum hot pressing treatment (vacuum hot pressing treatment).

[0295] It is preferable that the inner layer substrate and resin sheet are mounted on a vacuum pressure device by means of metal plates such as padding paper, stainless steel plates (SUS plates), or release films.

[0296] Vacuum pressure processing can be performed by using a conventional vacuum pressure device that extrudes the inner substrate and resin sheet from both sides of a heated metal plate such as a SUS plate. Examples of commercially available vacuum pressure devices include the "VH1-1603" manufactured by Kitagawa Seiki Co., Ltd.

[0297] The vacuum pressure treatment may be performed only once, or it may be repeated two or more times. When it is repeated two or more times, the pressing pressure, heating temperature, pressing time, etc. may be the same or different.

[0298] In vacuum pressure treatment, the pressing pressure (extrusion pressure) is preferably above 0.49MPa, more preferably above 0.98MPa, and preferably below 7.9MPa, more preferably below 5.9MPa.

[0299] For vacuum pressure treatment, the ambient pressure, i.e., the pressure (pressure reduction degree) of the indoor pressure when depressurizing the laminated structure containing the object to be treated, is preferably below 3×10-2 MPa, and more preferably below 1×10-2 MPa. Although there is no particular limitation on the lower limit, it can be above 1×10-10 MPa, etc.

[0300] For vacuum pressure processing, the heating temperature varies depending on the composition of the resin composition layer, but is generally 150°C or higher, preferably 160°C or higher, and more preferably 170°C or higher or 180°C or higher. While there is no particular upper limit to the heating temperature, it can generally be 240°C or lower. Furthermore, from the viewpoint that significant effects of the present invention can be obtained through vacuum pressure processing, the temperature can be increased in stages or continuously, and / or decreased in stages or continuously. Also, as described later, by heating during vacuum pressure processing, the resin composition layer can be thermocured to form an insulating layer.

[0301] During vacuum pressure treatment, the pressing time is preferably 5 minutes or more, preferably 10 minutes or more, and even more preferably 15 minutes or more. Although there is no specific upper limit, it is preferably below 300 minutes, preferably below 200 minutes, and even more preferably below 150 minutes.

[0302] After laminating a resin sheet subjected to vacuum pressure treatment onto the inner substrate, an insulating layer is formed by thermosetting the resin composition layer in step (II). For example, a method for thermosetting the resin composition layer can be described as using the heat during vacuum hot pressing to thermoset the resin composition layer and form an insulating layer.

[0303] Although there are no particular limitations on the thermosetting conditions of the resin composition layer, the conditions generally used when forming the insulating layer of a printed wiring board can also be used.

[0304] For example, although the thermosetting conditions of the resin composition layer vary depending on the type of resin composition, the curing temperature is preferably 120℃ to 240℃, more preferably 150℃ to 220℃, and even more preferably 170℃ to 210℃. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0305] Before heat curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, the resin composition layer may be heat cured first, and preheated 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) at a temperature of 50°C or higher but not exceeding 120°C (preferably 60°C to 115°C, and more preferably 70°C to 110°C).

[0306] As mentioned above, the inventors have confirmed that, compared with vacuum lamination, resin leakage during lamination in vacuum pressure processing sometimes occurs, resulting in an inability to obtain the desired insulation layer thickness. From this perspective, by setting the maximum residual solvent amount or tanδ within the aforementioned preferred range, the desired insulation layer thickness after vacuum pressure processing can be achieved while maintaining good mechanical strength or dielectric properties. Specifically, when the designed insulation layer thickness is set to 15 μm, the insulation layer thickness deviation after hot pressing is preferably less than ±30%, more preferably less than ±20%, and even more preferably less than ±15%. The lower limit can be 0%, ±0.1% or more, etc. The insulation layer thickness after vacuum pressure processing can be evaluated according to the method described in the examples below.

[0307] Since the support of the resin sheet used in this invention contains metal foil, step (III) may also include a step of forming a circuit by means of a reduction method or a modification semi-addition method.

[0308] For step (III), a circuit can be formed using a support (metal foil) by a subtraction method or a modified semi-addition method.

[0309] For the reduction method, the unwanted portion (non-loop forming portion) of the metal foil can be selectively removed by etching or the like to form a loop. The loop formation by the reduction method can be performed according to a known procedure. For example, the loop formation by the reduction method can be performed by a method comprising: i) a step of applying an etching resist to the surface of the metal foil (i.e., the side opposite to the surface bonded to the resin composition layer), ii) a step of exposing and developing the etching resist to form a wiring pattern, iii) a step of etching and removing the exposed metal foil portion, and iv) a step of removing the etching resist.

[0310] In the modified semi-additive method, the non-circuit-forming portion of the metal foil is protected by plating resist, the circuit-forming portion is thickened by electroplating with a metal such as copper, and then the plating resist is removed. The metal foil outside the circuit-forming portion is then etched away to form a circuit. The circuit formation by the modified semi-additive method can be performed according to a known procedure. For example, the circuit formation by the modified semi-additive method can be performed by a method including: i) applying plating resist to the surface of the metal foil (i.e., the side opposite to the surface bonded to the resin composition layer), ii) exposing and developing the plating resist to form a wiring pattern, iii) electroplating the plating resist, iv) removing the plating resist, and v) removing the metal foil outside the circuit-forming portion by etching. When the metal foil is thick, before i), the metal foil is thinned by etching or the like to achieve the desired thickness (usually 5 μm or less, 4 μm or less, or 3 μm or less).

[0311] In the manufacture of printed wiring boards, steps (IV) of opening holes and (V) of roughening the insulation layer can be further performed. These steps (IV) to (V) can be performed according to various methods known to those in the industry for the manufacture of printed wiring boards. Furthermore, as necessary, the formation of the insulation layer and conductor layer in steps (I) to (V) can be repeated to form a multilayer wiring board.

[0312] [Semiconductor Device] The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

[0313] As semiconductor devices, examples include various semiconductor devices provided in electrical products (such as computers, mobile phones, digital cameras and televisions) and vehicles (such as electric vehicles, automobiles, trams, ships and airplanes).

[0314] The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) at the conductive point of a printed circuit board. The term "conductive point" refers to "the location where electrical signals in the printed circuit board are transmitted," and this location can be either a surface or an embedded location. Furthermore, there is no particular limitation as long as the semiconductor chip is an electrical circuit element that uses semiconductors as the material.

[0315] The method for mounting semiconductor wafers during the manufacture of semiconductor devices is not particularly limited as long as it enables the semiconductor wafer to effectively perform its function. Examples include wire bonding mounting methods, flip chip mounting methods, mounting methods using a bumpless buildup layer (BBUL), mounting methods using anisotropic conductive films (ACF), and mounting methods using non-conductive films (NCF). The term "mounting method using a bumpless buildup layer (BBUL)" refers to "a mounting method in which the semiconductor wafer is directly embedded in a recess of a printed circuit board, connecting the semiconductor wafer to the wiring on the printed circuit board." [Example]

[0316] The present invention will be described in more detail below using the embodiments, but the present invention is not limited to these embodiments. In the following description, unless otherwise stated, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

[0317] <Inorganic fillers used> Inorganic filler 1: Surface-treated with 2 parts of N-phenyl-3-aminopropyltrimethoxysilane (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) relative to 100 parts of spherical silica (UFP-30 manufactured by Denki Kagaku Kogyo Co., Ltd., with an average particle size of 0.078 μm and a specific surface area of ​​30.7 m² / g). Inorganic filler 2: Surface-treated with 1 part of N-phenyl-3-aminopropyltrimethoxysilane (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) relative to 100 parts of spherical silica (SC2500SQ manufactured by Admatechs Co., Ltd., with an average particle size of 0.63 μm and a specific surface area of ​​11.2 m² / g).

[0318] <Synthesis Example 1: Synthesis of Polyimide Resin 1> In a 500ml separable flask equipped with a nitrogen inlet tube and a stirrer, 9.13g (30 mmol) of 4-aminobenzoic acid 5-amino-1,1'-biphenyl-2-yl (a compound of formula (B-3)), 15.61g (30 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic dianhydride, 94.64g of N-methyl-2-pyrrolidone, 0.47g (6 mmol) of pyridine, and 10g of toluene were added. The amide reaction was carried out under nitrogen at 180°C for 4 hours while the toluene was being purged from the system. A polyimide solution (20% by mass) containing polyimide resin 1 was obtained. No precipitation of the synthesized polyimide resin 1 was observed in the polyimide solution. The weight average molecular weight of polyimide resin 1 is 45,000.

[0319] <Synthesis Example 2: Synthesis of Polyimide Resin 2> In a reaction vessel equipped with a stirrer, water separator, thermometer, and nitrogen inlet tube, 65.0 g of aromatic tetracarboxylic acid dianhydride (SABIC JAPAN "BisDA-1000", 4,4'-(4,4'-isopropylidene diphenoxy)bisphthalic acid dianhydride), 266.5 g of cyclohexanone, and 44.4 g of methylcyclohexane were added, and the solution was heated to 60°C. Next, 43.7 g of dimer diamine (Croda Japan "PRIAMINE 1075") and 5.4 g of 1,3-bis(aminomethyl)cyclohexane were added dropwise, and the amide reaction was carried out at 140°C for 1 hour. A polyimide solution containing polyimide resin 2 (30% by mass of non-volatile matter) was obtained. Furthermore, the weight average molecular weight of polyimide resin 2 is 25,000.

[0320] <Synthesis Example 3: Synthesis of Polyimide Resin 3> A 500 mL separable flask equipped with a water metering receiver connected to a reflux cooler, 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-trimethylindene were added to the flask, and the reaction was carried out under a nitrogen stream at 45°C with stirring for 2 hours. The reaction solution was then heated to approximately 160°C, and the condensed water was removed by azeotropic extraction with toluene under a nitrogen stream. The metered amount of water was confirmed to have accumulated in the water metering receiver, and no water flow was observed. After confirmation, the reaction solution was further heated to 200°C with stirring for 1 hour. After cooling, a polyimide solution (20% by mass of non-volatile matter) containing polyimide resin 3 having a 1,1,3-trimethylindene backbone was obtained. The obtained polyimide resin 3 has repeating units as shown in formula (X1) and repeating units as shown in formula (X2). Furthermore, the weight average molecular weight of the aforementioned polyimide resin 3 is 12,000.

[0321] <Synthesis Example 4: Synthesis of Elastomer> 50 g of G-3000 (difunctional hydroxyl-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl equivalent = 1798 g / eq., solids content 100% by mass: manufactured by Nippon Soda Co., Ltd.), 23.5 g of Ipsol 150 (aromatic hydrocarbon mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.), and 0.005 g of dibutyltin laurate were mixed and dissolved uniformly in a reaction vessel. After homogenization, the temperature was raised to 50°C, and while stirring further, 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq.) was added, and the reaction was carried out for about 3 hours. Next, after cooling the reactants to room temperature, 8.96 g of benzophenone tetracarboxylic dianhydride (anhydride equivalent = 161.1 g / eq.), 0.07 g of triethylenediamine, and 40.4 g of ethyl diethylene glycol acetate (manufactured by Daicel Chemical Industries, Ltd.) were added. The mixture was stirred and heated to 130°C for approximately 4 hours. The disappearance of the NCO absorption peak at 2250 cm⁻¹ was confirmed by FTIR. The reaction endpoint was considered reached when the NCO absorption peak disappeared. After cooling the reactants to room temperature, the mixture was filtered through a 100-mesh filter cloth to obtain an elastomer with an imine backbone, a carbamate backbone, and a butadiene backbone. Viscosity: 7.5 Pa·s (25℃, E-type viscometer) Acid value: 16.9 mg KOH / g Solid content: 50% by mass Number average molecular weight: 13723 Glass transition temperature: -10℃ Content of polybutadiene structural moieties: 50 / (50+4.8+8.96)×100 = 78.4% by mass

[0322] <Synthesis Example 5: Synthesis of Maleimide Resin A> According to the method described in Synthesis Example 1 of the Patent Application Publication No. 2020-500211, a MEK solution (70% by mass of non-volatile component) of maleimide resin A (Mw / Mn=1.81, u'=1.47 (mainly 1, 2 or 3)) as shown in the following formula (1) was prepared.

[0323] <Preparation of Resin Composition 1> 5 parts of maleimide compound (Designer Moleculars "BMI-689"), 10 parts of maleimide resin containing biphenyl skeleton (Nippon Kayaku Co. "MIR-3000", a 1:1 solution of toluene and MEK with 70% by mass of non-volatile matter), 5 parts of maleimide resin A synthesized in Synthesis Example 5, and 20 parts of hydrogenated styrene thermoplastic elastomer (Asahi Kasei Corporation "H1043", styrene / ethylene·butene·butadiene ratio = 67 / 33) were stirred and heated to dissolve. After cooling to room temperature, 50 parts of inorganic filler 1 and 0.1 parts of polymerization initiator (Perhexin 25B manufactured by Nippon Oil Co., Ltd.) are mixed together and uniformly dispersed in a high-speed rotating mixer. The mixture is then filtered through a cartridge filter (SHP020 manufactured by ROKITECHNO Co., Ltd.) to prepare resin composition 1.

[0324] <Preparation of Resin Composition 2> For the preparation of resin composition 1, the 20 parts of hydrogenated styrene-based thermoplastic elastomer (Asahi Kasei Corporation "H1043" styrene / ethylene·butene·butadiene ratio = 67 / 33) synthesized in Synthesis Example 1 were changed to 100 parts. Resin composition 2 was prepared in the same manner as the preparation of resin composition 1, except for the above.

[0325] <Preparation of Resin Composition 3> For the preparation of resin composition 1, 20 parts of hydrogenated styrene-based thermoplastic elastomer (Asahi Kasei Corporation "H1043" styrene / ethylene·butene·butadiene ratio = 67 / 33) were changed to 67 parts to prepare polyimide resin 2 synthesized in Synthesis Example 2. Except for the above, resin composition 3 was prepared in the same manner as resin composition 1.

[0326] <Preparation of Resin Composition 4> Regarding the preparation of resin composition 1, 20 parts of hydrogenated styrene-based thermoplastic elastomer (Asahi Kasei Corporation "H1043", styrene / ethylene·butene·butadiene ratio = 67 / 33) were changed to 100 parts to synthesize polyimide resin 3 as in Synthesis Example 3. Except as described above, resin composition 4 was prepared in the same manner as resin composition 1.

[0327] <Preparation of Resin Composition 5> Regarding the preparation of resin composition 1, 20 parts of the hydrogenated styrene-based thermoplastic elastomer (Asahi Kasei Corporation "H1043" styrene / ethylene·butene·butadiene ratio = 67 / 33) were replaced with 40 parts of the elastomer synthesized in Synthesis Example 4. Except as described above, resin composition 5 was prepared in the same manner as resin composition 1.

[0328] <Preparation of Resin Composition 6> For the preparation of resin composition 1, 50 parts of inorganic filler 1 are replaced with 50 parts of inorganic filler 2. Except as described above, resin composition 6 is prepared in the same manner as resin composition 1.

[0329] <Preparation of Resin Composition 7> For the preparation of resin composition 1, 5 parts of maleimide resin A were replaced with 4.5 parts of styrene-modified polyphenylene ether resin (Mitsubishi Gas Chemical Co., Ltd. "OPE-2St 1200", Mn=1200, toluene solution with 65% by mass of solids). Resin composition 7 was prepared in the same manner as resin composition 1, except as otherwise provided above.

[0330] <Preparation of Resin Composition 8> For the preparation of resin composition 1, 5 parts of maleimide resin A were replaced with 5 parts of a difunctional acrylate compound ("NK ester A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight 326). Except for the above, resin composition 8 was prepared in the same manner as resin composition 1.

[0331] <Preparation of Resin Composition 9> For the preparation of resin composition 1, 5 parts of maleimide resin A were replaced with 5 parts of a difunctional allyl compound (manufactured by Shikoku Chemical Industry Co., Ltd., "ALP-d") having a benzoxazine ring. Except for the above, resin composition 9 was prepared in the same manner as resin composition 1.

[0332] <Preparation of Resin Composition 10> 11 parts of styrene-modified polyphenylene ether resin ("OPE-2St 1200", manufactured by Mitsubishi Gas Chemical Co., Ltd., Mn=1200, toluene solution with 65% by mass of solids) 5 parts of difunctional acrylate compound ("NK ester A-DOG", manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 326) 5 parts of difunctional allyl compound with benzoxazine ring ("ALP-d", manufactured by Shikoku Chemical Co., Ltd.) 20 parts of hydrogenated styrene-based thermoplastic elastomer ("H1043", manufactured by Asahi Kasei Corporation, styrene / ethylene·butene·butadiene ratio = 67 / 33) were dissolved by heating while stirring in a mixed solvent of 20 parts naphtha and 10 parts cyclohexanone. After cooling to room temperature, 50 parts of inorganic filler 1 and 0.1 parts of polymerization initiator (Perhexin 25B manufactured by Nippon Oil Co., Ltd.) are mixed together and uniformly dispersed in a high-speed rotating mixer. After filtration through a cartridge filter (SHP020 manufactured by ROKITECHNO Co., Ltd.), resin composition 10 is prepared.

[0333] <Preparation of Resin Composition 11> For the preparation of resin composition 1, the amount of inorganic filler 1 was changed from 50 parts to 40 parts. Except for the above, resin composition 11 was prepared in the same manner as the preparation of resin composition 1.

[0334] [Examples 1-11] <Preparation of Resin Sheet A> As a support, a copper foil with a carrier (Microsin MT-Ex copper foil manufactured by Mitsui Metals & Mining Co., Ltd. (3μm thick ultrathin copper foil / 18μm thick carrier copper foil)) was prepared, comprising a carrier copper foil and an ultrathin copper foil. Resin compositions 1-11 were uniformly coated onto the ultrathin copper foil of the support using a mold until the thickness of the dried resin composition layer was 20μm. After drying at 70°C to 120°C for 7 minutes, a resin composition layer was obtained on the support. Next, on the surface of the support that was not bonded to the resin composition layer, a polypropylene film (AlfanMA-411 manufactured by Oji F-Tex Co., Ltd., 15μm thick) was laminated to form a protective film, and the rough surface was bonded to the resin composition layer. In this way, a resin sheet A was obtained, which was formed in the order of a carrier-attached copper foil (support), a resin composition layer, and a protective film.

[0335] <Preparation of Evaluation Hardened Material A using Vacuum Pressure Processing> The protective film is peeled off from resin sheet A, exposing the resin composition layer. Next, lamination is performed by bringing the exposed resin composition layer into contact with the extremely thin copper side of a copper foil (Mitsui Metals & Minerals Co., Ltd. Microsin MT-Ex copper foil (3μm thick ultrathin copper foil / 18μm thick carrier copper foil)) attached to a carrier, using a vacuum hot press (Kitagawa Seiki Co., Ltd. VH1-1603). Pressing conditions are a reduced pressure of 1×10⁻³ MPa or less, a pressure of 20 kgf / cm², and heating conditions: the first stage of pressing is performed at 100°C for 30 minutes, and the second stage at 200°C for 120 minutes. After the resin composition layer hardens through the pressing heating, the carrier foil is peeled off, and the extremely thin copper is etched to obtain evaluation hardened material A.

[0336] [Comparative Example 1] <Preparation of Resin Sheet B> As a support, a PET film (Toray's "Le Miller R80", thickness 38 μm, softening point 130°C, "release PET") was prepared and released using an alkyd resin-based release agent (Lintec's "AL-5"). To achieve a 20 μm thickness of the dried resin composition layer on the support, resin composition 1 was uniformly coated using a mold coating method and dried at 70–120°C (average 100°C) for 3 minutes to form a resin composition layer on the support. Next, on the surface of the support not bonded to the resin composition layer, a rough layer of a polypropylene film (Oji F-Tex's "AlfanMA-411", thickness 15 μm) was synthesized and bonded to the resin composition layer. In this way, a resin sheet B consisting of a support (38μm PET film) / resin composition layer / protective film (MA-411) is obtained.

[0337] <Preparation of Evaluation Hardened Material B Using Lamination Treatment> To place the untreated side of the release PET film (Lintec "501010", thickness 38μm, side length 240mm) on the glass cloth substrate epoxy resin double-sided copper laminate (Panasonic Electric Works "R5715ES", thickness 0.7mm, side length 255mm) on the glass cloth substrate epoxy resin double-sided copper laminate, the four sides of the release PET film are fixed with polyimide adhesive tape (width 10mm).

[0338] A resin sheet B (167 × 107 mm side length) was laminated in the center of the release surface of the release PET film using a batch vacuum pressure laminator (Nikko Materials, CVP700, a two-stage accumulation laminator). The lamination process involved depressurizing the pressure for 30 seconds to below 13 hPa, followed by pressing at 100°C and 0.74 MPa for 30 seconds. Next, the support was peeled off, and the resin sheet layer was thermo-cured at 190°C for 90 minutes. After thermo-curing, the polyimide adhesive tape was peeled off, and the cured layer was removed from the epoxy resin double-sided copper laminate on the glass cloth substrate. The release PET film was then peeled off from the cured layer to obtain the cured product B for evaluation.

[0339] [Evaluation] <Determination of Residual Solvent Content> A 10cm × 10cm resin sheet was cut from the laminated support and resin composition layers, and its initial mass was measured using an electronic balance. Next, the resin sheet was placed on a gold mesh and heated in an oven pre-set to 130°C for 15 minutes, then transferred to a desiccator and allowed to stand for 30 minutes to cool to room temperature. The dried mass of the resin sheet was then measured using an electronic balance. The initial and dried masses of three samples were measured simultaneously, and the average value was used to calculate the amount of solvent contained in the resin composition layers (residual solvent content) using the following formula: Residual solvent content (mass %) = 100 × (Initial mass of resin sheet - Dried mass of resin sheet) / (Initial mass of resin sheet - Mass of support)

[0340] <Determination of Dielectric Properties (Dielectric Strength, Dielectric Loss Tangent)> The hardened material used for evaluation was cut into test pieces 2 mm wide and 80 mm long. For these test pieces, the dielectric strength and dielectric loss tangent were measured using an Agilent Technologies HP8362B instrument at a frequency of 5.8 GHz and a measurement temperature of 23 °C using the void resonance perturbation method. After measuring three test pieces, the average values ​​of each dielectric strength and dielectric loss tangent were calculated. The dielectric strength and dielectric loss tangent were further evaluated according to the following criteria: -Dielectric Loss Tangent- 〇: Dielectric loss tangent less than 0.003 △: Dielectric loss tangent greater than or equal to 0.0031 ×: Dielectric loss tangent greater than or equal to 0.0031 -Dielectric Strength- 〇: Dielectric strength less than 2.9 △: Dielectric strength greater than or equal to 2.95 ×: Dielectric strength greater than or equal to 2.95

[0341] <Evaluation of Flexibility (MIT Flexural Strength)> Evaluation hardened material A or B was cut into test pieces 15mm wide and 110mm long. Using an MIT testing apparatus (MIT Flexural Strength Fatigue Testing Machine "MIT-DA" manufactured by Toyo Seiki Co., Ltd.), according to JIS C-5016, the number of flexural cycles until fracture was measured under the following conditions: load 2.5N, bending angle 90 degrees, bending radius 1.0mm, and bending speed 175 cycles / minute. Five samples were tested, and the average of the top three points was calculated. Evaluation was performed based on the following criteria: ○: Flexural strength ≥ 405 cycles △: Flexural strength ≥ 395 cycles but less than 405 cycles ×: Flexural strength less than 395 cycles

[0342] <Determination of the maximum value of tanδ in dynamic viscoelasticity> For resin composition layers of resin sheet A or resin sheet B, dynamic viscoelasticity was measured using a dynamic viscoelasticity measuring device (Rheosol-G3000, manufactured by YouBM). For a sample of 1g of resin composition taken from the resin composition layer, using a parallel plate with a diameter of 18mm, the temperature was increased from an initial temperature of 60°C to 200°C at a heating rate of 5°C / min. The dynamic viscoelasticity was measured under the following conditions: a temperature interval of 2.5°C, a vibration number of 1Hz, and a strain of 1deg. Using the obtained storage elasticity E' (GPa) and loss elasticity E' (Pa), tanδ was calculated using the following formula. The maximum value of tanδ above 100°C was obtained. tanδ = E” / E'

[0343] <Evaluation of the thickness of the insulating layer after vacuum pressure treatment> (1) The resin sheet of the copper laminate was laminated into a copper laminate by vacuum pressure treatment. A glass cloth substrate epoxy resin double-sided copper laminate (copper foil thickness 12μm, substrate thickness 0.15mm, Mitsubishi Gas Chemical Co., Ltd. "HL832NSF LCA", 255×340mm size) with a wiring pattern of 1mm side length grid on both sides was prepared. The copper surface of the inner circuit board was roughened by MEC Co., Ltd. "CZ8201" (copper etching amount 0.5μm). The protective film was peeled off from the resin sheet A to expose the resin composition layer. The exposed resin composition layer was then laminated to both sides of the copper laminate by vacuum hot pressing machine (Kitagawa Seiki Co., Ltd. VH1-1603). The pressing conditions were set to a decompression of less than 1×10⁻³ MPa and a pressure of 20 kgf / cm². For heating, the first stage of pressing was at 100°C for 30 minutes, and the second stage was at 190°C for 120 minutes. After the resin composition layer was hardened by pressing and heating, an extremely thin copper layer was etched to obtain the evaluation substrate C.

[0344] (2) The thickness of the insulating layer after vacuum pressure treatment was observed using a FIB-SEM composite device (SII Nanotechnology Co., Ltd. "SMI3050SE"). The cross-section of the evaluation substrate C was observed to measure the thickness of the insulating layer (the thickness of the insulating layer directly above the circuit conductor of the copper laminate). The evaluation was based on the following criteria: ○: The thickness of the insulating layer is less than 15μm±20%. △: The thickness of the insulating layer is more than 15μm±20% but less than 30%. ×: The thickness of the insulating layer is more than 15μm±30%.

[0345]

[0346] For Examples 1 to 11, even if components (B) to (D) are not present, although there are differences in degree, the same results as those in the above examples were confirmed. [Simplified Explanation of the Diagram]

[0010] [Figure 1] Figure 1 shows a schematic side view of an example of two test tubes used to determine the liquid, semi-solid and solid states of free radical polymerizable compounds.

Claims

1. A resin sheet, characterized in that it comprises a support and a resin composition layer disposed on the support, the support having a metal foil, the resin composition layer comprising (A) a free radical polymerizable compound, (B) a thermoplastic resin with a weight average molecular weight of 50,000 or less (but other than 50,000), and (C) an inorganic filler, wherein the content of component (C) is 52% by mass or more when the non-volatile components in the resin composition layer are taken as 100% by mass, and the specific surface area of ​​component (C) is 40 m² / g or less (but excluding 40 m² / g).

2. The resin sheet of claim 1, wherein component (A) contains a free radical polymerizable compound comprising maleimide groups.

3. The resin film of claim 1, wherein component (A) contains at least one of a maleimine compound containing an aliphatic group having 5 or more carbon atoms that may have substituents, and a maleimine compound containing an indane skeleton.

4. The resin sheet of claim 1, wherein component (A) comprises at least one selected from maleimine compounds represented by the following general formula (A-7) and maleimine compounds containing an indane skeleton; in the general formula (A-7), each R¹⁰⁰ independently represents a divalent aliphatic group having 5 or more carbon atoms that may have substituents, each A independently represents a divalent cyclic aliphatic group having 5 or more carbon atoms that may have substituents; n represents an integer from 1 to 10.

5. The resin sheet of claim 1, wherein the metal foil contains copper foil.

6. The resin sheet of claim 1, wherein the maximum value of tanδ of the resin composition layer in the dynamic viscoelasticity test from 60°C to 200°C is 2.0 or less above 100°C.

7. The resin sheet of claim 1, wherein component (B) contains at least one selected from polyimide resin, phenoxy resin, polyolefin resin, polyamide-imide resin, polyether-imide resin, polyurethane resin, polyether ether ketone resin, polyester resin and elastomer.

8. A printed wiring board, characterized in that it contains an insulating layer made of a hardened resin composition layer of resin sheets as claimed in any one of claims 1 to 7.

9. A semiconductor device, characterized in that it includes a printed wiring board as claimed in claim 8.

10. A method for manufacturing a printed wiring board, comprising (1) laminating a resin sheet of any one of claims 1 to 7 onto an inner substrate by vacuum pressure treatment, and (2) forming an insulating layer by thermosetting the resin composition layer.

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