resin sheets

Abstract

The objective of this invention is to provide resin sheets and the like that exhibit good mechanical strength while also possessing desired dielectric properties. The solution of this invention is a resin sheet for forming an insulating layer using vacuum pressing, comprising a support body and a resin composition layer disposed on the support body, the support body having a metal foil, and the resin composition layer containing (A) a free radical polymerizable compound.

Description

Technical Field

[0001] This invention relates to resin sheets. It further relates to printed wiring boards, semiconductor devices, and methods for manufacturing printed wiring boards using the resin sheets. Background Technology

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

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent document 1: Japanese Patent Application Publication No. 2017-59779. Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] With the recent trend towards high-speed transmission, there is a demand for further reductions in the dielectric constant and dielectric loss tangent of insulating materials. In improving these dielectric properties, free-radical polymerizable compounds are desirable curing compounds for use in insulating materials. However, when using these free-radical polymerizable compounds to form cured products (insulating layers), the resulting cured products sometimes exhibit poor mechanical strength, and sometimes fail to present the desired dielectric properties.

[0008] The present invention aims to provide a resin sheet that can be cured to exhibit good mechanical strength and desired dielectric properties; a printed wiring board and a semiconductor device formed using the resin sheet; and a method for manufacturing the printed wiring board.

[0009] Solution for solving the problem

[0010] The inventors have conducted intensive research on the above-mentioned problems and found that the above-mentioned problems can be solved by using the following resin sheet and forming an insulating layer by vacuum pressing. The resin sheet includes a support containing a metal foil and a resin composition layer containing a (A) free radical polymerizable compound disposed on the support, thereby completing the present invention.

[0011] That is, the present invention includes the following:

[0012] [1] A resin sheet, which is a resin sheet for forming an insulating layer using vacuum pressing.

[0013] The resin sheet includes a support and a resin composition layer disposed on the support.

[0014] The support has metal foil,

[0015] The resin composition layer contains (A) a free radical polymerizable compound;

[0016] [2] The resin sheet according to [1], wherein component (A) comprises: a free radical polymerizable compound containing maleimide groups;

[0017] [3] The resin sheet according to [1] or [2], wherein the metal foil comprises copper foil;

[0018] [4] The resin sheet according to any one of [1] to [3], wherein, in the dynamic viscoelasticity test of the resin composition layer from 60°C to 200°C, the maximum value of tanδ at 100°C or above is 2.0 or less;

[0019] [5] The resin sheet according to any one of [1] to [4], wherein the resin composition layer further comprises (B) a thermoplastic resin;

[0020] [6] The resin sheet according to any one of [1] to [5], wherein the resin composition layer further contains (C) an inorganic filler material;

[0021] [7] According to the resin sheet of [6], when the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (C) is 50% by mass or more;

[0022] [8] A printed wiring board, wherein it comprises an insulating layer formed by curing a resin composition layer of a resin sheet as described in any one of [1] to [7];

[0023] [9] A semiconductor device comprising the printed wiring board described in [8];

[0024]

[10] A method for manufacturing a printed wiring board, the method comprising:

[0025] (1) The process of laminating the resin sheet of any one of [1] to [7] onto the inner substrate by vacuum pressing, and

[0026] (2) The process of heat curing the resin composition layer to form an insulating layer.

[0027] The effects of the invention

[0028] According to the present invention, a resin sheet can be provided which exhibits good mechanical strength and desired dielectric properties in a cured form; a printed wiring board and a semiconductor device formed using the resin sheet; and a method for manufacturing the printed wiring board.

[0029] Brief description of the attached diagram

[0030] Figure 1 This is a schematic side view of an example of two test tubes used in determining the liquid, semi-solid, and solid states of free radical polymerizable compounds. Detailed Implementation

[0031] The present invention will now be described in detail according to its preferred embodiments. However, the present invention is not limited to the embodiments and examples described below, and may be implemented by any modifications without departing from the scope of the claims and their equivalents.

[0032] [Resin Sheets]

[0033] The resin sheet of the present invention is a resin sheet used for forming an insulating layer by vacuum pressing. The resin sheet is characterized by comprising a support body and a resin composition layer disposed on the support body, the support body having a metal foil, and the resin composition layer containing (A) a free radical polymerizable compound.

[0034] When improving dielectric properties, compounds having free radical polymerizable unsaturated groups with low-polarity reactive functional groups (free radical polymerizable compounds) are considered as curable compounds used in insulating materials. However, although a cured product (insulating layer) is formed using free radical polymerizable compounds, the resulting insulating layer sometimes has poor mechanical strength, and sometimes fails to exhibit the desired dielectric properties. In contrast, the inventors have discovered that by using the resin sheet of the present invention and forming an insulating layer (cured resin composition layer) using vacuum pressing, the resulting insulating layer exhibits good mechanical strength, excellent flexibility (MIT folding resistance), and the desired dielectric properties. The resin sheet of the present invention comprises: a support containing a metal foil, and a resin composition layer containing a free radical polymerizable compound disposed on the support. It should be noted that the inventors have identified a new problem: compared to the conventional vacuum lamination method used when forming an insulating layer using a resin sheet (resin composition layer), the pressure applied to the resin sheet (resin composition layer) during lamination is high in vacuum pressing, and due to resin exudation, the desired insulating layer thickness is sometimes not obtained. Regarding the deviation in the thickness of the insulating layer after vacuum pressing (the difference from the target thickness), it has been confirmed that it is related to the amount of residual solvent in the resin composition layer and 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 the loss modulus E'' (Pa) to the storage modulus E' (GPa) E'' / E'). Solutions based on these residual solvent amounts and the maximum value of tanδ will be described later.

[0035] The following is a detailed description of each layer that makes up the resin sheet.

[0036] <Support Body>

[0037] In the resin sheet of the present invention, the support has a metal foil. Thus, the conductor layer described later can be formed from the support.

[0038] Examples of metal foils include copper foil and aluminum foil, with copper foil being preferred. Copper foil can be used as a single metal, such as copper, or it can be an alloy of copper with other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0039] Metal foil can be a single-layer structure or a multi-layer structure obtained by stacking two or more single metal layers or alloy layers formed of different kinds of metals or alloys. Examples of multi-layer metal foils include, for instance, a metal foil comprising a carrier metal foil and an extremely thin metal foil bonded to the carrier metal foil. The multi-layer metal foil may also include a release layer between the carrier metal foil and the extremely thin metal foil, allowing the extremely thin metal foil to be peeled off from the carrier metal foil. The release layer is not particularly limited as long as it allows the extremely thin metal foil to be peeled off from the carrier metal foil; examples include, for instance, an alloy layer selected from elements selected from Cr, Ni, Co, Fe, Mo, Ti, W, and P; and an organic coating. It should be noted that when using a multi-layer metal foil as a support, a resin composition layer may be disposed on the extremely thin metal foil.

[0040] There are no particular limitations on the manufacturing method of metal foil; it can be manufactured using known methods such as electrolysis and rolling.

[0041] Commercially available products can be used as supports. Examples of commercially available products include "HLP foil" and "JXUT-III foil" manufactured by JX Minerals & Metals Corporation, and "MicroThin MT-Ex copper foil" and "TP-III foil" manufactured by Mitsui Metals & Mining Corporation.

[0042] From the viewpoint of achieving significant effects of the present invention, the thickness of the support is preferably 50 μm or less, more preferably 45 μm or less, further 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. It should be noted that when the metal foil has a multilayer structure, it is preferable that the overall thickness of the metal foil is within the aforementioned range, wherein the thickness of an extremely thin metal foil can, for example, be in the range of 0.1 μm or more and 10 μm or less.

[0043] <Resin Composition Layer>

[0044] In the resin sheet of the present invention, the resin composition layer disposed on the support contains (A) a free radical polymerizable compound.

[0045] The resin composition layer may also contain any other components in combination with component (A). Examples of such 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.

[0046] -(A) Free radical polymerizable compounds-

[0047] In the resin composition layer, a free radical polymerizable compound is included as component (A). By using the resin composition layer containing component (A) together with a support containing a metal foil, a cured product with excellent dielectric properties can be obtained. Component (A) can be used alone or in combination of two or more.

[0048] As component (A), a compound that can be polymerized using free radicals generated by heat or light, i.e., a compound having a free radical polymerizable unsaturated group, can be used. Examples of free radical polymerizable unsaturated groups include groups having olefinic double bonds that exhibit curability upon irradiation by active energy rays. Examples of such free radical polymerizable unsaturated groups include vinyl, allyl, vinylphenyl, acryloyl, methacryloyl, maleimide, fumaroyl, and maleyl, preferably selected from at least one of maleimide, allyl, vinylphenyl, acryloyl, and methacryloyl.

[0049] As component (A), it is preferable to have one or more free radical polymerizable unsaturated groups, and more preferably two or more. There is no particular limit to the upper limit, and it can be set to 10 or less, etc.

[0050] As a compound having a free radical polymerizable unsaturated group, it is preferable to include at least one selected from free radical polymerizable compounds containing a maleimide group (maleimide-based free radical polymerizable compounds), free radical polymerizable compounds containing a vinylphenyl group (vinylphenyl-based free radical polymerizable compounds), free radical polymerizable compounds containing a (meth)acryloyl group ((meth)acrylic acid-based free radical polymerizable compounds), free radical polymerizable compounds containing an allyl group (allyl-based free radical polymerizable compounds), and free radical polymerizable compounds containing a butadiene skeleton (butadiene-based free radical polymerizable compounds), more preferably including at least any one of maleimide-based free radical polymerizable compounds, vinylphenyl-based free radical polymerizable compounds, allyl-based free radical polymerizable compounds, and (meth)acrylic acid-based free radical polymerizable compounds, and even more preferably including maleimide-based free radical polymerizable compounds.

[0051] Maleimide-based free radical polymerizable compounds are compounds whose molecules contain a maleimide group as shown in formula (A-1);

[0052] [Chemical Formula 1]

[0053] .

[0054] The maleimide-based free radical polymerizable compound is preferably any one of the maleimide-based free radical polymerizable compounds (A1) to (A3) below. The resin composition layer is preferably composed of at least one of the maleimide-based free radical polymerizable compounds (A1) to (A3), more preferably composed of multiple maleimide-based free radical polymerizable compounds (A1) to (A3), and even more preferably composed of all of the maleimide-based free radical polymerizable compounds (A1) to (A3).

[0055] (A1) Solid maleimide-based free radical polymeric compound

[0056] (A2) Liquid or semi-solid maleimide-based free radical polymeric compounds

[0057] (A3) Maleimide-based free radical polymeric compounds containing a skeleton formed by the fusion of aromatic and aliphatic hydrocarbon rings.

[0058] However, for maleimide-based free radical polymers of (A1) and (A2), compounds belonging to (A3) are excluded.

[0059] Here, the determination of whether a substance is liquid, semi-solid, or solid can be made according to Appendix 2, "Method for Confirmation of Liquid State," of the Ministry Ordinance concerning the Testing and Properties of Hazardous Materials (Ministry of Housing and Urban-Rural Development Ordinance No. 1, 1962). The specific determination method is as follows.

[0060] (1) Apparatus

[0061] Constant temperature water tank:

[0062] A constant-temperature water bath with a depth of 150 mm or more, equipped with a stirrer, heater, thermometer, and automatic temperature controller (a device capable of temperature control in ±0.1℃), is used. It should be noted that in determining the liquid, semi-solid, and solid states, a combination of a low-temperature constant-temperature water bath (model BU300) and an immersion-type thermostat Thermomate (model BF500) manufactured by Yamato Scientific Co., Ltd., Japan, is used. Approximately 22 liters of tap water are added to the low-temperature constant-temperature water bath (model BU300), and the power supply to the Thermomate (model BF500) is connected. The set temperature (20℃ or 60℃) is used. The water temperature can be finely adjusted to ±0.1℃ using the Thermomate (model BF500), but any device capable of the same adjustment can be used.

[0063] test tube:

[0064] As a test tube, such as Figure 1 As shown, a liquid state determination test tube 10a and a temperature measurement test tube 10b are used. The liquid state determination test tube 10a is a flat-bottomed cylindrical transparent glass test tube with an inner diameter of 30 mm and a height of 120 mm. Markings 11A and 12B are placed at heights of 55 mm and 85 mm from the bottom of the tube, respectively. The mouth of the test tube is sealed with a rubber stopper 13a. The temperature measurement test tube 10b is a test tube of the same size as the liquid state determination test tube 10a and is marked with the same markings. The mouth of the test tube is sealed with a rubber stopper 13b, which has a hole in the center for inserting and supporting a thermometer. A thermometer 14 is inserted into the rubber stopper 13b. Hereinafter, the marking at a height of 55 mm from the bottom of the tube will be referred to as "line A", and the marking at a height of 85 mm from the bottom of the tube will be referred to as "line B". As thermometer 14, a thermometer for determining the freezing point (SOP-58 scale range 0 to 100°C) as specified in JIS B7410 (1982) "Glass thermometers for petroleum testing" is used, but any thermometer capable of measuring the temperature range of 0 to 100°C is acceptable.

[0065] (2) Experimental Implementation Steps

[0066] exist Figure 1 (a) shows the test tube 10a for determining the liquid state and Figure 1 (b) As shown in the temperature measurement test tube 10b, samples that have been placed at atmospheric pressure (60±5℃) for more than 24 hours are added to line 11A. In a low-temperature constant-temperature water bath, the two test tubes 10a and 10b are placed upright and stationary with line 12B below the water surface. The thermometer is set with its lower end 30mm below line 11A. After the sample temperature reaches the set temperature ±0.1℃, this state is maintained for 10 minutes. After 10 minutes, the liquid state judgment test tube 10a is removed from the low-temperature constant-temperature water bath and immediately laid horizontally on a level test platform. A stopwatch is used to measure the time it takes for the front of the liquid surface in the test tube to move from line 11A to line 12B, and this time is recorded.

[0067] Similarly, for samples placed at atmospheric pressure at a temperature of 20±5℃ for more than 24 hours, the same test was conducted as for samples placed at atmospheric pressure at a temperature of 60±5℃ for more than 24 hours. The time taken for the front of the liquid surface in the test tube to move from line 11A to line 12B was measured with a stopwatch and the time was recorded.

[0068] A liquid state is defined as a condition where the measurement time at 20℃ is less than 90 seconds.

[0069] Cases measured at 20°C for more than 90 seconds and at 60°C for less than 90 seconds are classified as semi-solid.

[0070] If the measurement time at 60℃ exceeds 90 seconds, it will be judged as solid.

[0071] From the viewpoint of achieving the desired effect of the present invention, the number of maleimide groups in each molecule of solid maleimide-based free radical polymerizable compound is preferably one or more, more preferably two or more, further preferably three or more, preferably ten or less, more preferably six or less, and particularly preferably three or less.

[0072] From the viewpoint of achieving the desired effect of the present invention, the solid maleimide-based free radical polymerizable compound preferably has either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably has both an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

[0073] As an aliphatic hydrocarbon group, it is preferably a divalent aliphatic hydrocarbon group, more preferably a divalent saturated aliphatic hydrocarbon group, and even more preferably an alkylene group. As an alkylene group, it is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, even more preferably an alkylene group having 1 to 3 carbon atoms, and particularly preferably a methylene group.

[0074] As an aromatic group, monovalent and divalent aromatic groups are preferred, and aryl and arylene groups are even more preferred. As an arylene group, arylene groups with 6 to 30 carbon atoms are preferred, arylene groups with 6 to 20 carbon atoms are even more preferred, and arylene groups with 6 to 10 carbon atoms are even more preferred. Examples of such arylene groups include phenylene, naphthylene, anthracene, aralkyl, biphenylene, and biphenylaralkyl, among which phenylene, aralkyl, biphenylene, and biphenylaralkyl are preferred, and phenylene, aralkyl, and biphenylene 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.

[0075] In solid maleimide-based free radical polymerizable compounds, from the viewpoint of significantly achieving the desired effects of the present invention, the nitrogen atom of the maleimide group is preferably directly bonded to a monovalent or divalent aromatic group. Here, "directly" means that there are no other groups between the nitrogen atom of the maleimide group and the aromatic group.

[0076] Solid maleimide-based free radical polymerizable compounds are preferably represented by the structure of the following formula (A-2);

[0077] [Chemical Formula 2]

[0078]

[0079] In equation (A-2), R31 and R 36 R represents maleimide group. 32 R 33 R 34 and R 35 Each of the following groups independently represents a hydrogen atom, an alkyl group, or an aryl group, and D independently represents a divalent aromatic group. m1 and m2 independently represent integers from 1 to 10, and a represents an integer from 1 to 100.

[0080] R in equation (A-2) 32 R 33 R 34 and R 35 Each can be represented independently as a hydrogen atom, alkyl group, or aryl group, preferably a hydrogen atom.

[0081] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group can be straight-chain, branched, or cyclic. Examples of such alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, and isopropyl.

[0082] 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 monocyclic or fused-ring. Examples of such aryl groups include phenyl, naphthyl, and anthracene.

[0083] Alkyl and aryl groups may optionally have substituents. There are no particular limitations on substituents; examples include halogen atoms, -OH, and -OC. 1-6 Alkyl, -N(C) 1-10 Alkyl)2, C 1-20 Alkyl, C 2-30 alkenyl, C 2-30 alkynyl group, C 6-10 Aryl, -NH2, -CN, -C(O)OC 1-10 Alkyl groups, -COOH, -C(O)H, -NO2, etc. Here, "C p-q (where p and q are positive integers, satisfying p < q.) Such a term indicates that the number of carbon atoms in the organic group immediately following the term is p to q. For example, "C 1-10 The term "alkyl" indicates an alkyl group having 1 to 10 carbon atoms. These substituents can combine with each other to form rings, and ring structures also include spirocyclic and fused rings.

[0084] The substituents described above may further have substituents (hereinafter, sometimes referred to as "secondary substituents"). As secondary substituents, the same substituents as those described above may be used unless otherwise specified.

[0085] In formula (A-2), D represents a divalent aromatic group. Examples of divalent aromatic groups include phenylene, naphthylene, anthraceneylene, aralkyl, biphenylene, and biphenylaralkyl, with biphenylene and biphenylaralkyl being preferred, and biphenylene being even more preferred. The divalent aromatic group may optionally have substituents. As substituents, they are related to R in general formula (A-2). 32 The alkyl group indicated has the same meaning if it has any of the substituents.

[0086] m1 and m2 independently represent integers from 1 to 10, preferably from 1 to 6, even better from 1 to 3, further better from 1 to 2, and even better from 1.

[0087] a represents an integer from 1 to 100, preferably 1 to 50, even better 1 to 20, and even better 1 to 5.

[0088] As a solid maleimide-based free radical polymerizable compound, the resin shown in formula (A-3) is preferred;

[0089] [Chemical Formula 3]

[0090]

[0091] In equation (A-3), R 37 and R 38 This indicates a maleimide group. a1 represents an integer from 1 to 100.

[0092] a1 has the same meaning as 'a' in equation (A-2), and the range of better values ​​is also the same.

[0093] 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.

[0094] Liquid or semi-solid maleimide-based free radical polymerizable compounds are preferably maleimide compounds having at least one maleimide group in the molecule and containing an aliphatic group with five or more carbon atoms optionally having substituents. Liquid or semi-solid maleimide-based free radical polymerizable compounds can be obtained, for example, by imidizing an aliphatic amine compound (such as a diamine compound having a dimer acid backbone), maleic anhydride, and, if desired, a tetracarboxylic dianhydride.

[0095] Aliphatic groups having 5 or more carbon atoms can be monovalent, divalent, or trivalent or higher. These groups can be saturated or unsaturated. Examples of aliphatic groups with 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 alkyl groups having 5 or more carbon atoms (optionally substituted), alkylene groups having 5 or more carbon atoms (optionally substituted), and alkenyl groups having 5 or more carbon atoms (optionally substituted). For example, liquid or semi-solid maleimide-based free radical polymerizable compounds are preferably maleimide compounds containing at least one hydrocarbon group selected from alkyl groups having 5 or more carbon atoms (optionally substituted), and alkylene groups having 5 or more carbon atoms (optionally substituted). In addition, the liquid or semi-solid maleimide-based free radical polymerizable compound is preferably a maleimide compound comprising at least one hydrocarbon group selected from alkyl groups having 5 or more carbon atoms and alkenyl groups having 5 or more carbon atoms.

[0096] The aliphatic group typically has 5 or more carbon atoms. From the viewpoint of achieving significant effects of the present invention, 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 group contains a substituent, unless otherwise specified, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the aforementioned group. Therefore, when an aliphatic group with 5 or more carbon atoms contains a substituent, unless otherwise specified, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the aliphatic group with 5 or more carbon atoms.

[0097] 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. This alkyl group can be straight-chain, branched, 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 alkylene group having 5 or more carbon atoms or an alkenyl group having 5 or more carbon atoms.

[0098] The alkylene group having 5 or more carbon atoms preferably has 6 or more carbon atoms, more preferably 8 or more, more preferably 50 or fewer, more preferably 45 or fewer, and even more preferably 40 or fewer. This alkylene group can be linear, branched, or cyclic, with linear being preferred. Here, cyclic alkylene is a concept that includes not only the narrow definition consisting solely of cyclic alkylene groups, but also the broad definition encompassing both linear and cyclic alkylene groups. Examples of such alkylene groups include, for instance, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, heptadecanylene, hexadecylene, octylene, octylene-cyclohexylene-octylene, propylene-cyclohexylene-octylene, etc.

[0099] The number of carbon atoms in an 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. Here, "cyclic alkenyl" includes both cases consisting solely of cyclic alkenyl groups and cases including both linear and cyclic alkenyl groups. Examples of such alkenyl groups include pentenyl, hexenyl, heptenyl, octeneyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, heptadecenyl, trihexadecenyl, octeneyl, groups having an octeneyl-cyclohexeneyl structure, groups having an octeneyl-cyclohexeneyl-octeneyl structure, and groups having a propeneyl-cyclohexeneyl-octeneyl structure.

[0100] In liquid or semi-solid maleimide-based free radical polymerizable compounds, the aliphatic group with 5 or more carbon atoms is preferably 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.

[0101] From the viewpoint of achieving significant effects of the present invention, the liquid or semi-solid maleimide-based free radical polymerizable compound preferably contains two or more aliphatic groups having five or more carbon atoms.

[0102] Aliphatic groups with five or more carbon atoms can combine to form rings, including spirocyclic and fused ring structures. Examples of rings formed by these combinations include the cyclohexane ring.

[0103] Aliphatic groups with 5 or more carbon atoms may or may not have substituents. As substituents, they interact with R in the general formula (A-2). 32 The alkyl group indicated has the same meaning if it has any of the substituents.

[0104] Liquid or semi-solid maleimide-based free radical polymerizable compounds preferably contain an aromatic ring in their molecules. Therefore, liquid or semi-solid maleimide-based free radical polymerizable compounds are preferably maleimide compounds containing an aliphatic group having 5 or more carbon atoms (optionally substituents) and an aromatic ring. The aromatic ring can be a monocyclic aromatic ring or a fused aromatic ring formed by the fusion of two or more monocyclic aromatic rings. Examples of such aromatic rings include monocyclic aromatic rings such as benzene rings and pyridine rings; and fused aromatic rings such as indene rings, fluorene rings, and naphthalene rings. Preferably, the aromatic ring is an aromatic carbon ring. The aromatic carbon ring preferably has 6 or more and 10 or fewer carbon atoms.

[0105] The number of maleimide groups per molecule of the liquid or semi-solid maleimide-based free radical polymerizable compound can be 1, preferably 2 or more, more preferably 10 or less, more preferably 6 or less, and particularly preferably 3 or less. The effects of the present invention can be significantly obtained by using liquid or semi-solid maleimide-based free radical polymerizable compounds having 2 or more maleimide groups per molecule.

[0106] From the viewpoint of achieving significant effects of the present invention, liquid or semi-solid maleimide-based free radical polymerizable compounds are preferably maleimide compounds represented by the following general formula (A-4);

[0107] [Chemical Formula 4]

[0108]

[0109] In general formula (A-4), R represents a divalent aliphatic group with 5 or more carbon atoms that may be substituted, and L represents a single bond or a divalent linking group.

[0110] In general formula (A-4), R represents a divalent aliphatic group having 5 or more carbon atoms, optionally with a substituent. The divalent aliphatic 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. This divalent aliphatic group can be linear, branched, or cyclic, with linear being preferred. Here, cyclic divalent aliphatic groups include both cases consisting solely of cyclic aliphatic groups and cases containing both linear and cyclic aliphatic groups. Examples of divalent aliphatic groups include alkylene groups and alkenyl groups. For alkylene and alkenyl groups, the above explanation applies.

[0111] As a substituent for R, it interacts with R in the general formula (A-2). 32 The alkyl group indicated has the same meaning if it has any of the substituents.

[0112] In general formula (A-4), L represents a single bond or a divalent linking group. Examples of divalent linking groups include alkylene, alkenylene, ynylene, arylene, -C(=O)-, -C(=O)-O-, and -NR. 0 -(R 0 It consists of hydrogen atoms, alkyl groups with 1 to 3 carbon atoms, oxygen atoms, sulfur atoms, and C(=O)NR. 0 - Divalent groups derived from phthalimide, divalent groups derived from pyromellitic diimide, and groups formed by combinations of two or more of these divalent groups. Alkylene, alkenylene, ynylene, arylene, divalent groups derived from phthalimide, divalent groups derived from pyromellitic diimide, and groups formed by combinations of two or more divalent groups, wherein an alkyl group having five or more carbon atoms is optionally used as a substituent. Divalent groups derived from phthalimide refer to divalent groups derived from phthalimide; as a specific example, the group shown in general formula (A-5) can be given. Divalent groups derived from pyromellitic diimide refer to divalent groups derived from pyromellitic diimide; as a specific example, the group shown in general formula (A-6) can be given. In the formula, "*" represents a chemical bond;

[0113] [Chemical Formula 5]

[0114] .

[0115] The alkylene group that forms the divalent linking group in the general formula (A-4) is preferably an alkylene group having 1 to 50 carbon atoms, more preferably an alkylene group having 1 to 45 carbon atoms, and particularly preferably an alkylene group having 1 to 40 carbon atoms. This alkylene group can be linear, branched, or cyclic. Examples of such alkylene groups include: methyl ethylene (2-propylene), cyclohexylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, heptadecanylene, hexadecylene, octylene, groups having an octylene-cyclohexylene-octylene structure, groups having an propylene-cyclohexylene-octylene structure, etc.

[0116] The alkenyl group, which is the divalent linking group in L of 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: methylvinylene (2-propenylene), cyclohexenylene, pentenylene, hexenylene, heptenylene, octene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene, heptadecenylene, trihexadecenylene, octeneylene, groups having an octene-cyclohexenyl-octene structure, groups having an octene-cyclohexenyl-octene structure, and groups having a propenyl-cyclohexenyl-octene structure.

[0117] The divalent linking group in L of general formula (A-4) is preferably an ynylene group with 2 to 50 carbon atoms, more preferably an ynylene group with 2 to 45 carbon atoms, and particularly preferably an ynylene group with 2 to 40 carbon atoms. This ynylene group can be linear, branched, or cyclic. Examples of such ynylene groups include 2-propynyl, cyclohexynyl, pentylyl, hexynyl, heptylyl, octylyl, nonynyl, decanynyl, undecynyl, dodecaynyl, tridecaynyl, heptadecynyl, trihexadecynyl, octylyl, groups having an octylyl-cyclohexynyl structure, groups having an octylyl-cyclohexynyl-octylyl structure, and groups having a propynyl-cyclohexynyl-octylyl structure.

[0118] The arylene group that is the divalent linking group in L of general formula (A-4) is preferably an arylene group with 6 to 24 carbon atoms, more preferably an arylene group with 6 to 18 carbon atoms, even more preferably an arylene group with 6 to 14 carbon atoms, and even more preferably an arylene group with 6 to 10 carbon atoms. Examples of arylene groups include phenylene, naphthylene, and anthracene.

[0119] The alkylene, alkenylene, ynylene, and arylene groups in L of general formula (A-4) may optionally have substituents. As substituents, they may be associated with R in general formula (A-2). 32 The alkyl group represented may optionally have the same substituents, but is preferably an alkyl group having 5 or more carbon atoms.

[0120] Examples of divalent groups in the L of general formula (A-4) that are composed of two or more divalent groups include: a divalent group composed of an alkylene group, a divalent group derived from phthalimide, and an oxygen atom; a divalent group composed of a divalent group derived from phthalimide, an oxygen atom, an aryl group, and an alkylene group; a divalent group composed of an alkylene group and a divalent group derived from pyromellitic diimide; a divalent group composed of an ynylene group, a divalent group derived from phthalimide, and an oxygen atom; a divalent group composed of a divalent group derived from phthalimide, an oxygen atom, an aryl group, and an ynylene group; a divalent group composed of an ynylene group and a divalent group derived from pyromellitic diimide; and so on. Groups composed of two or more divalent groups can form fused rings or other rings through the combination of these groups. Furthermore, groups composed of two or more divalent groups can be repeating units with a repeating unit number of 1 to 10.

[0121] Wherein, L in general formula (A-4) is preferably an oxygen atom, an arylene group having 6 to 24 carbon atoms with optional substituents, an alkylene group having 1 to 50 carbon atoms with optional substituents, an alkyne group having 1 to 50 carbon atoms with optional substituents, an alkenyl group having 1 to 50 carbon atoms with optional substituents, a divalent group derived from phthalimide, a divalent group derived from pyromellitic diimide, or a divalent group composed of two or more of these groups. Wherein, L is preferably alkylene; a divalent group having a structure of alkylene-divalent group derived from phthalimide-oxygen atom-divalent group derived from phthalimide; a divalent group having a structure of alkylene-divalent group derived from phthalimide-oxygen atom-arylene-alkylene-arylene-oxygen atom-divalent group derived from phthalimide; a divalent group having a structure of alkylene-divalent group derived from pyromellitic diimide; alkenyl; a divalent group having a structure of alkenyl-divalent group derived from phthalimide-oxygen atom-divalent group derived from phthalimide; an alkenyl-divalent group derived from phthalimide A divalent group of an amine with a divalent group - oxygen atom - arylene - alkenyl - arylene - oxygen atom - derived from the divalent group of phthalimide; a divalent group with an alkynyl - derived from the divalent group of pyromellitic diimide; a divalent group with an alkynyl - derived from the divalent group of phthalimide - oxygen atom - derived from the divalent group of phthalimide; a divalent group with an alkynyl - derived from the divalent group of phthalimide - oxygen atom - arylene - alkynyl - arylene - oxygen atom - derived from the divalent group of phthalimide; a divalent group with an alkynyl - derived from the divalent group of pyromellitic diimide.

[0122] The maleimide compound represented by general formula (A-4) is preferably the maleimide compound represented by general formula (A-7);

[0123] [Chemical Formula 6]

[0124]

[0125] In general formula (A-7), R 100 Each of the following groups independently represents a divalent aliphatic group with 5 or more carbon atoms that may be substituted, and A independently represents either a divalent aliphatic group with 5 or more carbon atoms that may be substituted, or a divalent group with an aromatic ring that may be substituted. n represents an integer from 1 to 10.

[0126] R in general formula (A-7) 100 Each of these groups independently represents a divalent aliphatic group with 5 or more carbon atoms that is optionally substituented. 1 The same as R in general formula (A-4).

[0127] In general formula (A-7), A independently represents either a divalent aliphatic group having 5 or more carbon atoms, optionally with substituents, or a divalent group having an aromatic ring, optionally with substituents. Examples of divalent aliphatic groups in A include alkylene groups and alkenylene groups. The divalent aliphatic group in A can be chain-like, branched, or cyclic, with cyclic being preferred, i.e., a cyclic divalent aliphatic group having 5 or more carbon atoms, optionally with substituents.

[0128] The alkylene group 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. Examples of such alkylene groups include groups having an octylene-cyclohexylene structure, groups having an octylene-cyclohexylene-octylene structure, and groups having a propylene-cyclohexylene-octylene structure.

[0129] The number of carbon atoms in an 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. Here, cyclic alkenyl groups include cases consisting solely of cyclic alkenyl groups and cases including both linear and cyclic alkenyl groups. Examples of such alkenyl groups include pentenyl, hexenyl, heptenyl, octeneyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, heptadecenyl, trihexadecenyl, octeneyl, groups having an octeneyl-cyclohexeneyl structure, groups having an octeneyl-cyclohexeneyl-octeneyl structure, and groups having a propenyl-cyclohexeneyl-octeneyl structure.

[0130] Examples of aromatic rings among the divalent groups containing aromatic rings represented by A include benzene rings, naphthalene rings, anthracene rings, phthalimide rings, pyromellitic diimide rings, and aromatic heterocycles, with benzene rings, phthalimide rings, and pyromellitic diimide rings being preferred. That is, the preferred divalent groups containing aromatic rings are either divalent groups containing benzene rings with optional substituents, divalent groups containing phthalimide rings with optional substituents, or divalent groups containing pyromellitic diimide rings with optional substituents. Examples of divalent groups with aromatic rings include groups composed of a divalent group derived from phthalimide and an oxygen atom; groups composed of a divalent group derived from phthalimide, an oxygen atom, an arylene, and an alkylene; groups composed of an alkylene and a divalent group derived from pyromellitic diimide; divalent groups derived from pyromellitic diimide; groups composed of a divalent group derived from phthalimide and an alkylene; etc. The aforementioned arylene groups are the same as the arylene groups represented by L in general formula (2) in the divalent linking group.

[0131] In general formula (A-7), A represents a divalent aliphatic group, and divalent groups having an aromatic ring may optionally have substituents. As substituents, they are related to R in general formula (A-2). 32 The alkyl group represented may optionally have the same substituents.

[0132] Wherein, A in general formula (A-7) preferably represents a cyclic alkylene group having 5 or more carbon atoms optionally having a substituent; a divalent group having a benzene ring optionally having a substituent; a divalent group having an phthalimide ring optionally having a substituent; or a divalent group having a pyromellitic diimide ring optionally having a substituent.

[0133] As specific examples of the group represented by A in general formula (A-7), the following groups can be cited. In the formula, "*" represents a chemical bond;

[0134] [Chemical Formula 7]

[0135]

[0136] [Chemical Formula 8]

[0137] .

[0138] The maleimide compound represented by general formula (A-4) is preferably any of the maleimide compounds represented by general formula (A-8) and general formula (A-9);

[0139] [Chemical Formula 9]

[0140]

[0141] In general formula (A-8), R 2a and R 3a Each of the following independently represents a divalent aliphatic group with 5 or more carbon atoms that is arbitrarily chosen to have substituents, R 10a Each group independently represents an oxygen atom, an aryl group, an alkyl group, an alkenyl group, or a divalent group composed of two or more of these groups. n1 represents an integer from 1 to 10.

[0142] In general formula (A-9), R 4a R 6a and R 7a Each of the following independently represents a divalent aliphatic group with 5 or more carbon atoms that is arbitrarily chosen to have substituents, R 5a Each of the following independently represents a divalent group with an aromatic ring, optionally with substituents: R 11a and R 12a Each of these characters independently represents an alkyl group having 5 or more carbon atoms. t2 represents an integer from 0 to 10, and m1 and m2 independently represent integers from 0 to 4.

[0143] R in general formula (A-8) 2a and R 3a Each of these groups independently represents a divalent aliphatic group with 5 or more carbon atoms that is optionally substituented. 2a and R 3a The same as the divalent aliphatic group with 5 or more carbon atoms represented by R in general formula (A-4), preferably hexadeceneyl or hexadecylyl.

[0144] R in general formula (A-8) 10a Each of these groups independently represents an oxygen atom, an arylene, an alkylene, an alkenyl group, or a group composed of two or more of these divalent groups. The arylene, alkylene, and alkenyl groups are identical to the arylene, alkylene, and alkenyl groups represented by L in general formula (A-4) as divalent linking groups. As R... 10a It is preferable that the group or oxygen atom is composed of two or more divalent groups.

[0145] R as general formula (A-8) 10a Groups composed of two or more divalent groups can be exemplified by combinations of oxygen atoms, aryl groups, and alkylene groups. Specific examples of groups composed of two or more divalent groups include the following groups. In the formula, "*" represents a chemical bond;

[0146] [Chemical Formula 10]

[0147] .

[0148] R in general formula (A-9) 4a R 6a and R 7a Each of these groups independently represents a divalent aliphatic group with 5 or more carbon atoms that is optionally substituented. 4a R 6a and R 7a The R in general formula (A-4) represents a divalent aliphatic group with 5 or more carbon atoms that may have a substituent, preferably hexane, heptane, octane, nonane, or decane, and more preferably octane.

[0149] R in general formula (A-9) 5a Each of these can be independently represented as a divalent group with an aromatic ring, optionally with a substituent. R 5a The alkylene group is the same as the optional substituent-containing divalent group with an aromatic ring represented by A in general formula (A-7), preferably a group composed of an alkylene group and a divalent group derived from pyromellitic diimide; a group composed of a divalent group derived from phthalimide and an alkylene group, more preferably a group composed of an alkylene group and a divalent group derived from pyromellitic diimide. The alkylene group is the same as the arylene and alkylene group in the divalent linking group represented by L in general formula (A-4).

[0150] As R in general formula (A-9) 5a Specific examples of the groups represented can be given, such as the following groups. In the formula, "*" represents a chemical bond;

[0151] [Chemical Formula 11]

[0152] .

[0153] R in general formula (A-9) 11a and R 12a Each of these can be used independently to represent an alkyl group having 5 or more carbon atoms. R 11a and R 12a Similar to the alkyl groups having 5 or more carbon atoms mentioned above, the preferred alkyl groups are hexyl, heptyl, octyl, nonyl, and decyl, and more preferably hexyl and octyl.

[0154] In the general formula (A-9), m1 and m2 independently represent integers from 1 to 15, preferably integers from 1 to 10.

[0155] Specific examples of liquid or semi-solid maleimide-based free radical polymerizable compounds include compounds (A-10) to (A-13) below. However, 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;

[0156] [Chemical Formula 12]

[0157]

[0158] [Chemical Formula 13]

[0159]

[0160] .

[0161] Commercially available products can be used for liquid or semi-solid maleimide-based free radical polymerizable compounds. Specific examples of liquid or semi-solid maleimide-based free radical polymerizable compounds include "BMI1500" (a compound of formula (A-10), "BMI1700" (a compound of formula (A-11), "BMI3000J", "BMI3000" (a compound of formula (A-12), and "BMI689" (a compound of formula (A-13)) manufactured by Designer Molecules.

[0162] As a maleimide-based free radical polymerizable compound (hereinafter sometimes referred to as "(3) component") having a skeleton composed of an aromatic ring and an aliphatic hydrocarbon ring fused together, examples of such a skeleton include the indane skeleton, trimethyl indane skeleton, tetrahydronaphthalene skeleton, benzocyclobutene skeleton, and indane skeleton, etc. From the viewpoint of significantly obtaining the effects of the present invention, the trimethyl indane skeleton is preferred. Therefore, component (3) is preferably a maleimide compound containing the trimethyl indane skeleton. The trimethyl indane skeleton represents the skeleton shown in the following formula (A-14);

[0163] [Chemical Formula 14]

[0164] .

[0165] Substituents can be attached 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.

[0166] The number of carbon atoms in an alkyl group is preferably 1 to 10. Examples of alkyl groups include methyl, ethyl, propyl, n-butyl, and tert-butyl.

[0167] The number of carbon atoms in an alkyloxy group is preferably 1 to 10. Examples of alkyloxy groups include methoxy, ethoxy, propoxy, and butoxy.

[0168] The number of carbon atoms in an alkyl thio group is preferably 1 to 10. Examples of alkyl thio groups include methyl thio, ethyl thio, propyl thio, and butyl thio.

[0169] The aryl group preferably has 6 to 10 carbon atoms. Examples of aryl groups include phenyl and naphthyl groups.

[0170] The number of carbon atoms in an aryloxy group is preferably 6 to 10. Examples of aryloxy groups include phenyloxy and naphthyloxy groups.

[0171] The number of carbon atoms in an aryl thio group is preferably 6 to 10. Examples of aryl thio groups include phenyl thio and naphthio.

[0172] The preferred number of carbon atoms in a cycloalkyl group is 3 to 10. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and cycloheptyl.

[0173] Examples of halogen atoms include fluorine, chlorine, and iodine.

[0174] In the aforementioned substituents, the hydrogen atoms of alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups may optionally be replaced by halogen atoms.

[0175] The number of substituents bonded to one benzene ring within the trimethylindane skeleton can be one or more. The number of substituents bonded to the benzene ring within the trimethylindane skeleton is typically zero to three. When the number of substituents is two or more, those two or more substituents can be the same or different. Preferably, no substituents are bonded to the benzene ring within the trimethylindane skeleton.

[0176] (3) The number of trimethylindene skeletons contained in one molecule of the component can be 1 or more. The upper limit can be, for example, less than 10, less than 8, less than 7, or less than 6.

[0177] (3) The component preferably contains, in addition to the trimethylindane skeleton described above, an aromatic ring skeleton. The number of cyclic carbon atoms 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 particularly preferably 3 or less. (3) When the component contains two or more aromatic ring skeletons in addition to the trimethylindane skeleton, those aromatic ring skeletons may be the same or different.

[0178] Substituents may be attached to the aromatic ring contained in the aforementioned aromatic ring skeleton. Examples of substituents include the aforementioned substituents and nitro groups, which can be attached to the benzene ring contained in the trimethylindene skeleton. The number of substituents attached to one aromatic ring may be one or more. The number of substituents attached to the aromatic ring is generally zero or more and four or less. When the number of substituents is two or more, those two or more substituents may be the same or different.

[0179] (3) Preferably, in addition to containing the trimethylindane skeleton described above, the component also contains a divalent aliphatic hydrocarbon group. Specifically, 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, the divalent aliphatic hydrocarbon group preferably connects the benzene ring containing the trimethylindane skeleton to the aromatic ring skeleton. Furthermore, the divalent aliphatic hydrocarbon group preferably connects the aromatic ring skeletons to each other.

[0180] 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 particularly preferably 5 or less. As a divalent aliphatic hydrocarbon group, it is more preferably an alkylene group derived from a saturated aliphatic hydrocarbon group. Examples of divalent aliphatic hydrocarbon groups include straight-chain alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; branched alkylene groups such as ethylidene (-CH(CH3)-), propylene (-CH(CH2CH3)-), isopropylene (-C(CH3)2-), ethylmethylmethylene (-C(CH3)(CH2CH3)-), and diethylmethylene (-C(CH2CH3)2-); etc. When a maleimide compound containing a trimethylindane skeleton (C-2b) contains two or more divalent aliphatic hydrocarbon groups in addition to the trimethylindane skeleton, those divalent aliphatic hydrocarbon groups may be the same or different.

[0181] (3) The component preferably comprises the structure shown in formula (A-15) below. (3) The component as a whole may have the structure shown in formula (A-15), or (3) a part of the component may have the structure shown in formula (A-15);

[0182] [Chemical Formula 15]

[0183] .

[0184] (where Ar) a1 R represents a divalent aromatic group with optional substituents; a1 Each of the following groups 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; R a2 Each of the following can independently represent 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 group, or a mercapto group; R a3Each independently represents a divalent aliphatic hydrocarbon group; n a1 n represents a positive integer; a2 Each of the integers from 0 to 4 can be represented independently; n a3 Each integer from 0 to 3 can be represented independently. R a1 The hydrogen atoms of alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups may optionally be replaced by halogen atoms. a2 The hydrogen atoms of alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups may optionally be replaced by halogen atoms. a2 When R is 2 to 4, a1 Within the same ring, they can be the same or different. a3 When R is 2-3, a2 (They can be the same or different within the same ring).

[0185] In equation (A-15), Ar a1 This refers to a divalent aromatic group optionally having substituents. The number of carbon atoms in this divalent aromatic group is preferably 6 or more, preferably 20 or less, and more preferably 16 or less. Examples of divalent aromatic groups include phenylene and naphthylene. Examples of substituents that may be present in the divalent aromatic 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 optionally be replaced by halogen atoms. Furthermore, specific examples of these substituents include those identical to those that can be bonded to the benzene ring contained in the trimethylindene skeleton. When the divalent aromatic group has substituents, the number of substituents is preferably 1 to 4. When a divalent aromatic hydrocarbon group has two or more substituents, those two or more substituents can be the same or different. Among them, Ar... a1 It is preferable to have a divalent aromatic group without substituents.

[0186] In equation (A-15), R a1 Each of these groups 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, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups may optionally be replaced by halogen atoms. Specific examples of these groups include substituents that can be attached to the benzene ring contained in the trimethylindene skeleton. Wherein, R a1More preferably, it is a group selected from one or more 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, especially alkyl groups having 1 to 4 carbon atoms.

[0187] In equation (A-15), R a2 Each of these groups 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 group, or a mercapto group. The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups may optionally be replaced by halogen atoms. Specific examples of these groups include substituents that can be attached to the benzene ring contained in the trimethylindene skeleton. Wherein, R a2 Preferably, it is one or more groups selected from 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.

[0188] In equation (A-15), R a3 Each divalent aliphatic hydrocarbon group is represented independently. The range of preferred divalent aliphatic hydrocarbon groups is shown above.

[0189] In equation (A-15), n a1 Represents a positive integer. n a1 A better value is above 1, a better value is below 10, and an even better value is below 8.

[0190] In equation (A-15), n a2 Each of the integers from 0 to 4 can be represented independently. a2 It's better to have 2 or 3, and even better to have 2. Multiple n's a2 They can be different, but it's better if they are the same. When n a2 When the value is 2 or higher, multiple R a1 Within the same ring, they can be the same or different.

[0191] In equation (A-15), n a3 Each n can be represented independently from an integer between 0 and 3. a3 They can be different, but it's better if they are the same. a3 The better value is 0.

[0192] (3) The component particularly preferably contains the structure shown in formula (A-16). (3) The component as a whole may have the structure shown in formula (A-16), or (3) a part of the component may have the structure shown in formula (A-16);

[0193] [Chemical Formula 16]

[0194]

[0195] (where R is in the formula) b1 Each of the following groups 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; R b2 Each of the following groups 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 group, or a mercapto group; n b1 n represents a positive integer; b2 Each of the integers from 0 to 4 can be represented independently; n b3 Each integer from 0 to 3 can be represented independently. R b1 The hydrogen atoms of alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups may optionally be replaced by halogen atoms. b2 The hydrogen atoms of alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups may be optionally replaced by halogen atoms. b2 When R is 2 to 4, b1 Within the same ring, they can be the same or different. When n b3 When R is 2-3, b2 (They can be the same or different within the same ring).

[0196] In equation (A-16), R b1 R b2 n b1 n b2 and n b3 respectively with R in equation (A-15) a1 R a2 n a1 n a2 and n a3 same.

[0197] (3) The components may also include the structure shown in the following formula (A-17);

[0198] [Chemical Formula 17]

[0199]

[0200] In equation (A-17), R c1 R c2 n c2 and nc3 respectively with R in equation (A-15) a1 R a2 n a2 and n a3 Same. Furthermore, in equation (A-17), n c1 The number of repeating units is represented by an integer from 1 to 20. Furthermore, in formula (A-17), * denotes a chemical bond. For example, for component (3), in formula (A-15), n a2 The number of groups is 3 or less, and in the ortho and para positions of the maleimide-bonded benzene ring relative to the maleimide group, there are more than 2 unbonded R groups. a1 In this case, it can be combined with the structure shown in equation (A-15) to include the structure shown in the aforementioned equation (A-17). Furthermore, for example, for component (3), in equation (A-16), n b2 In benzene rings with 3 or fewer maleimide groups, two or more of the ortho and para positions relative to the maleimide group are not bound by R. b1 In the case of [the structure shown in equation (A-16), it can be combined with the structure shown in equation (A-17) above.

[0201] (3) One ingredient can be used alone, or two or more ingredients can be combined in any proportion.

[0202] (3) There are no particular limitations on the manufacturing method of the component. (3) The component can be manufactured, for example, by the method described in Japanese Invention Publication No. 2020-500211. According to the manufacturing method described in Japanese Invention Publication No. 2020-500211, a maleimide compound with a distribution of the number of repeating units of the trimethylindene skeleton can be obtained. The maleimide compound obtained by this method contains the structure shown in the following formula (A-18). Therefore, the component (3) may contain: a maleimide compound containing the structure shown in formula (A-18);

[0203] [Chemical Formula 18]

[0204]

[0205] (where R is in the formula) 1 Each of the following groups 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; R 2Each of the following groups 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 hydroxyl group, or a mercapto group; n1 represents the average number of repeating units from 0.95 to 10.0; n2 independently represents an integer from 0 to 4; n3 independently represents an integer from 0 to 3. R 1 The hydrogen atoms of alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups are optionally replaced by halogen atoms. 2 The hydrogen atoms of alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups are optionally replaced by halogen atoms. When n2 is 2–4, R 1 Within the same ring, they can be the same or different. When n3 is 2 to 3, R 2 (They can be the same or different within the same ring).

[0206] In equation (A-18), R 1 R 2 n2 and n3 are respectively related to R in equation (A-15) a1 R a2 n a2 and n a3 same.

[0207] 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 Japanese Invention Publication No. 2020-500211, a group of maleimide compounds containing the structure shown in formula (A-18) can be obtained. As can be seen from the fact that the average number of repeating units n1 in formula (A-18) can become less than 1.00, the maleimide compounds containing the structure shown in formula (A-18) obtained in this way may contain maleimide compounds with a repeating unit number of 0 for the trimethylindane skeleton. Therefore, by purification, maleimide compounds with a repeating unit number of 0 for the trimethylindane skeleton are removed from the maleimide compounds containing the structure shown in formula (A-18), and component (3) is obtained, which may be the only component (3) contained in the resin composition layer. However, the effects of the present invention can be obtained even when the resin composition layer contains a maleimide compound with zero repeating units of the trimethylindane skeleton. Furthermore, costs can be controlled by omitting purification. Therefore, it is preferable not to remove the maleimide compound with zero repeating units of the trimethylindane skeleton, but to include a maleimide compound containing the structure shown in formula (A-18) in the resin composition layer.

[0208] In 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, the effects of the present invention can be significantly obtained. In particular, the glass transition temperature of the resin composition can be effectively increased.

[0209] As an example of the structure shown in equation (A-18), the following structure can be given;

[0210] [Chemical Formula 19]

[0211]

[0212] .

[0213] Maleimide compounds containing the structure shown in formula (A-18) may further contain the structure shown in formula (A-17). For example, for maleimide compounds containing the structure shown in formula (A-18), in formula (A-18), n2 is 3 or less, and in the benzene rings bonded to the maleimide group, at two or more of the ortho and para positions relative to the maleimide group are not bonded to R. 1 In the case of [the structure shown in equation (A-17)], it can be combined with the structure shown in equation (A-18) to include the structure shown in equation (A-17).

[0214] For maleimide compounds containing the structure shown in formula (A-18), the molecular weight distribution Mw / Mn calculated by gel permeation chromatography (GPC) is preferably within a specific range. The molecular weight distribution is the value obtained by dividing the weight-average molecular weight Mw by the number-average molecular weight Mn, and is represented by "Mw / Mn". Specifically, the molecular weight distribution Mw / Mn of the maleimide compound containing the structure shown in formula (A-18) is preferably 1.0 to 4.0, more preferably 1.1 to 3.8, further preferably 1.2 to 3.6, and particularly preferably 1.3 to 3.4. When the molecular weight distribution Mw / Mn of the maleimide compound containing the structure shown in formula (A-18) is within the aforementioned range, the effects of the present invention can be significantly obtained.

[0215] In maleimide compounds containing the structure shown in formula (A-18), the amount of maleimide compounds with an average repeating unit number n1 of 0 is preferably 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 an average repeating unit number n1 of 0 can be expressed as area % based on the results of its GPC determination. Specifically, in the chromatogram obtained using the aforementioned GPC determination, the amount of maleimide compounds with an average repeating unit number n1 of 0 can be expressed as the ratio (area %) of the peak area of ​​"maleimide compounds with an average repeating unit number n1 of 0" to the "total peak area of ​​maleimide compounds containing the structure shown in formula (A-18)". Specifically, the amount of maleimide compound with an average repeating unit number n1 of 0 relative to the total area of ​​the maleimide compound comprising the structure shown in formula (A-18) is preferably 32 area% or less, more preferably 30 area% or less, and even more preferably 28 area% or less. When the amount of maleimide compound with an average repeating unit number n1 of 0 is within the aforementioned range, the effects of the present invention can be significantly obtained.

[0216] 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, further preferably 120 g / eq. or more, 200 g / eq. or more, preferably 10000 g / eq. or less, more preferably 9000 g / eq. or less, further preferably 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 maleimide equivalent.

[0217] The weight-average molecular weight (Mw) of maleimide-based free radical polymerizable compounds is preferably 150–16000, and more preferably 200–15000.

[0218] From the viewpoint of significantly obtaining the effects of the present invention, the molecular weight of the maleimide-based free radical polymerizable compound is preferably 200 or more, more preferably 300 or more, even more preferably 400 or more, preferably 100,000 or less, more preferably 80,000 or less, and even more preferably 60,000 or less.

[0219] Vinylphenyl-based free radical polymerizable compounds are free radical polymerizable compounds having a vinylphenyl group. Vinylphenyl-based free radical polymerizable compounds are preferably liquid or semi-solid. The determination of liquid or semi-solid state is as described above. A vinylphenyl group is a group having the structure shown below;

[0220] [Chemical Formula 20]

[0221]

[0222] (* indicates a chemical bond)

[0223] From the viewpoint of obtaining cured products with excellent dielectric properties, vinylphenyl-based free radical polymerizable compounds are preferably those with more than two vinylphenyl groups per molecule.

[0224] From the viewpoint of obtaining cured products 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, multiple divalent cyclic groups may be present.

[0225] From the viewpoint of achieving the desired effects of the present invention, the divalent cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, even more preferably a 5-membered ring or more, preferably a 20-membered ring or less, more preferably a 15-membered ring or less, and even more preferably a 10-membered ring or less. Furthermore, the divalent cyclic group can be a monocyclic structure or a polycyclic structure.

[0226] In a divalent cyclic group, the ring, in addition to carbon atoms, can also be composed of heteroatoms forming the ring skeleton. Examples of heteroatoms include oxygen atoms, sulfur atoms, and nitrogen atoms, with oxygen atoms being preferred. The ring may contain one or more heteroatoms.

[0227] Specific examples of divalent cyclic groups include the following divalent groups (a) or (b);

[0228] [Chemical Formula 21]

[0229]

[0230] (In divalent groups (a) and (b), R) 51 R 52 R 55 R 56 R 57 R 61 and R 62 Each can independently represent a halogen atom, an alkyl group with 6 or fewer carbon atoms, or a phenyl group, R. 53 R 54 R 58 R 59 and R 60 Each can be independently represented by a hydrogen atom, a halogen atom, an alkyl group with 6 or fewer carbon atoms, or a phenyl group.

[0231] 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. As for R... 51 R 52 R 55 R 56 R 57 R 61 and R 62 , preferably to represent methyl. R 53 R 54 R 58 R 59 and R 60 It is better to have a hydrogen atom or a methyl group.

[0232] Furthermore, multiple divalent cyclic groups can be combined. As a specific example of combining divalent cyclic groups, the divalent cyclic group shown in formula (A-19) below can be cited;

[0233] [Chemical Formula 22]

[0234]

[0235] (where R is in the formula) 71 R 72 R 75 R 76 R 77 R 81 R 82 R 85 and R 86 Each can independently represent a halogen atom, an alkyl group with 6 or fewer carbon atoms, or a phenyl group, R. 73 R 74 R 78 R 79 R 80 R 83 and R 84 Each of these can be used independently to 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 (except when one of d1 or d2 is 0).

[0236] R 71 R 72 R 85 and R 86 R in equation (a) 510 Same. R 73 R 74 R 83 and R 84 R in equation (a) 530 Same. R 75R 76 R 77 R 81 and R 82 With R in equation (b) 550 Same. R 78 R 79 and R 80 With R in equation (b) 580 same.

[0237] d1 and d2 represent integers from 0 to 300. However, this does not apply if either d1 or d2 is 0. Preferably, d1 and d2 represent integers from 1 to 100, more preferably from 1 to 50, and even more preferably from 1 to 10. d1 and d2 may be the same or different.

[0238] The divalent cyclic group may optionally have substituents. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, arylalkyl groups, silyl groups, acyl groups, acyloxy groups, carboxyl groups, sulfonyl groups, cyano groups, nitro groups, hydroxyl groups, mercapto groups, oxo groups, etc., with alkyl groups being preferred.

[0239] Vinylphenyl groups can be directly bonded to divalent cyclic groups or bonded through divalent linking groups. Examples of divalent linking groups include alkylene, alkenylene, arylene, heteroarylene, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, etc., or groups composed of multiple combinations of these groups. Preferably, the alkylene group has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 5 carbon atoms, or 1 to 4 carbon atoms. The alkylene group can be straight-chain, branched, or cyclic. Examples of such alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, and 1,1-dimethylethylene, with methylene, ethylene, and 1,1-dimethylethylene being preferred. As an alkenyl group, it is preferably an alkenyl group with 2 to 10 carbon atoms, more preferably an alkenyl group with 2 to 6 carbon atoms, and even more preferably an alkenyl group with 2 to 5 carbon atoms. As an aryl or heteroaryl group, it is preferably an aryl or heteroaryl group with 6 to 20 carbon atoms, and even more preferably an aryl or heteroaryl group with 6 to 10 carbon atoms. As a divalent linking group, it is preferably an alkylene group, with methylene being a preferred choice.

[0240] Vinylphenyl free radical polymerizable compounds are preferably compounds represented by the following formula (A-20);

[0241] [Chemical Formula 23]

[0242]

[0243] (where R is in the formula) 91 and R 92 Each of these groups represents a divalent linker independently. (Cyclic A1 represents a divalent cyclic group).

[0244] R 91 and R 92 Each of these represents a divalent linker independently. As a divalent linker, it is the same as the divalent linkers described above.

[0245] Ring A1 represents a divalent cyclic group. Ring B is the same as the divalent cyclic group described above.

[0246] Cycle A1 may optionally have substituents. These substituents are the same as those optionally present in the divalent cyclic groups described above.

[0247] The following are specific examples of vinylphenyl-based free radical polymerizable compounds, but the present invention is not limited thereto;

[0248] [Chemical Formula 24]

[0249]

[0250] (q1 is the same as d1 in equation (A-19), and q2 is the same as d2 in equation (A-19).

[0251] Vinylphenyl radical polymerizable compounds are commercially available, such as "OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd. A single vinylphenyl radical polymerizable compound can be used, or two or more can be used in combination.

[0252] From the viewpoint of achieving the desired effects of the present invention, the number average molecular weight of the vinylphenyl-based free radical polymerizable compound is preferably 3000 or less, more preferably 2500 or less, and even more preferably 2000 or less and 1500 or less. The lower limit is preferably 100 or more, more preferably 300 or more, and even more preferably 500 or more and 1000 or more. The number average molecular weight is the number average molecular weight converted from polystyrene, determined using gel permeation chromatography (GPC).

[0253] (Meth)acrylic acid-based free radical polymerizable compounds are compounds comprising acryloyl groups and methacryloyl groups, and combinations thereof. From the viewpoint of significantly achieving the desired effects of the present invention, it is preferable that each molecule of a (meth)acrylic acid-based free radical polymerizable compound has two or more (meth)acryloyl groups. The term "(meth)acryloyl" includes acryloyl groups, methacryloyl groups, and combinations thereof.

[0254] From the viewpoint of significantly achieving the desired effects of the present invention, (meth)acrylic acid-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 any cyclic group comprising an alicyclic structure or a cyclic group comprising an aromatic ring structure. Of these, from the viewpoint of significantly achieving the desired effects of the present invention, a cyclic group comprising an alicyclic structure is preferred.

[0255] From the viewpoint of achieving the desired effects of the present invention, the divalent cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, even more preferably a 5-membered ring or more, preferably a 20-membered ring or less, more preferably a 15-membered ring or less, and even more preferably a 10-membered ring or less. Furthermore, the divalent cyclic group can be a monocyclic structure or a polycyclic structure.

[0256] In a divalent cyclic group, the ring, in addition to carbon atoms, can also have a heteroatom skeleton. Examples of heteroatoms include oxygen, sulfur, and nitrogen atoms, with oxygen being preferred. The ring may contain one or more heteroatoms.

[0257] Specific examples of divalent cyclic groups include the following divalent groups (i) to (xi). Among them, (x) or (xi) is preferred as a divalent cyclic group;

[0258] [Chemical Formula 25]

[0259]

[0260] .

[0261] The divalent cyclic group may optionally have substituents. Examples of such substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, arylalkyl groups, silyl groups, acyl groups, acyloxy groups, carboxyl groups, sulfonyl groups, cyano groups, nitro groups, hydroxyl groups, mercapto groups, oxo groups, etc., with alkyl groups being preferred.

[0262] (Meth)acryloyl groups can be directly bonded to divalent cyclic groups or bonded via divalent linking groups. Examples of divalent linking groups include alkylene, alkenylene, arylene, heteroarylene, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, etc., or groups composed of multiple combinations of these groups. Preferably, the alkylene group has 1 to 10 carbon atoms; more preferably, it has 1 to 6 carbon atoms; even more preferably, it has 1 to 5 carbon atoms, or 1 to 4 carbon atoms. The alkylene group can be straight-chain, branched, or cyclic. Examples of such alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, and 1,1-dimethylethylene, with methylene, ethylene, and 1,1-dimethylethylene being preferred. As an alkenyl group, it is preferably an alkenyl group with 2 to 10 carbon atoms, more preferably an alkenyl group with 2 to 6 carbon atoms, and even more preferably an alkenyl group with 2 to 5 carbon atoms. As an aryl or heteroaryl group, it is preferably an aryl or heteroaryl group with 6 to 20 carbon atoms, and more preferably an aryl or heteroaryl group with 6 to 10 carbon atoms. As a divalent linking group, it is preferably an alkylene group, with methylene and 1,1-dimethylethylene being preferred.

[0263] (Meth)acrylic acid-based free radical polymerizable compounds are preferably compounds represented by the following formula (A-21);

[0264] [Chemical Formula 26]

[0265]

[0266] (In the formula, R) 101 and R 104 Each can be independently represented by an acryloyl group or a methacryloyl group, R 102 and R 103 Each of these groups represents a divalent linker independently. (Cyclic A2 represents a divalent cyclic group).

[0267] R 101 and R 104 Acryloyl or methacryloyl, respectively, are represented independently, with acryloyl being preferred.

[0268] R 102 and R 103 Each divalent linker is represented independently. The same applies to divalent linkers that can combine with (meth)acryloyl groups.

[0269] Ring A2 represents a divalent cyclic group. Ring A2 is the same as the divalent cyclic groups described above. Ring A2 may optionally have substituents. These substituents are the same as those optionally present in the divalent cyclic groups described above.

[0270] Specific examples of (meth)acrylic acid-based free radical polymerizable compounds include the following compounds, but the present invention is not limited thereto;

[0271] [Chemical Formula 27]

[0272]

[0273] .

[0274] (Meth)acrylic acid-based free radical polymerizable compounds can be commercially available, such as "A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "DCP-A" manufactured by Kyoeisha 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.

[0275] From the viewpoint of achieving the desired effects of the present invention, the (meth)acryloyl equivalent of the (meth)acrylic acid-based free radical polymerizable compound is preferably 30 g / eq. to 400 g / eq., more preferably 50 g / eq. to 300 g / eq., and even more preferably 75 g / eq. to 200 g / eq. The (meth)acryloyl equivalent is the mass of the (meth)acrylic acid-based free radical polymerizable compound containing 1 equivalent of (meth)acryloyl groups.

[0276] Allyl-based free radical polymerizable compounds are compounds having at least one allyl group in their molecule. Preferably, each molecule of an allyl-based free radical polymerizable compound has more than one allyl group, and more preferably more than two allyl groups. There is no particular upper limit, but it can be set as preferably less than 10, and more preferably less than 5.

[0277] Furthermore, from the viewpoint of significantly achieving the desired effects of the present invention, the allyl-based free radical polymerizable compound is preferably any of the following in addition to having an allyl group: a benzoxazine ring, a phenolic ring, an isocyanuric acid ring, an epoxy group, and a carboxylic acid derivative having a cyclic structure.

[0278] Allyl radical polymerizable compounds having a benzoxazine ring are preferably bonded to either the nitrogen atom of the benzoxazine ring or the benzene ring, and more preferably to the nitrogen atom.

[0279] Examples of allyl-based free radical polymerizable compounds containing phenolic rings include cresol resin containing allyl groups, phenolic varnish-type phenolic resin containing allyl groups, and cresol varnish resin containing allyl groups.

[0280] For allyl-based free radical polymerizable compounds with an isocyanuric acid structure, it is preferable that the nitrogen atom of the isocyanuric acid structure is directly bonded to the allyl group. Examples of allyl-based free radical polymerizable compounds with an isocyanuric acid structure include allyl isocyanurate, diallyl isocyanurate, and triallyl isocyanurate.

[0281] Allyl-based free radical polymerizable compounds with epoxy groups preferably contain two or more epoxy groups per molecule. Furthermore, allyl-based free radical polymerizable compounds with epoxy groups preferably have an aromatic structure; when using two or more allyl-based free radical polymerizable compounds with epoxy groups, it is more preferable that at least one has an aromatic structure. An aromatic structure is a chemical structure generally defined as aromatic, 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.

[0282] As an allyl-based free radical polymerizable compound having a carboxylic acid derivative (the carboxylic acid derivative having a cyclic structure), it is preferably an allyl carboxylic acid ester having a cyclic structure. The cyclic structure can be any of a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. Furthermore, in addition to carbon atoms, heteroatoms can be used to form the ring skeleton. Examples of heteroatoms include oxygen atoms, sulfur atoms, and nitrogen atoms, with nitrogen atoms being preferred. The ring may contain one or more heteroatoms.

[0283] Examples of carboxylic acids with cyclic structures include isocyanuric acid, biphenyl acid, phthalic acid, and cyclohexanedicarboxylic acid. Examples of allyl-based free radical polymerizable compounds having carboxylic acid derivatives (the carboxylic acid derivatives having cyclic structures) include allyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate, diallyl biphenylate, allyl biphenylate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, allyl cyclohexanedicarboxylate, and diallyl cyclohexanedicarboxylate.

[0284] Allyl-based free radical polymerizable compounds can be commercially available. Commercially available examples include: Meiwa Chemical's "MEH-8000H" and "MEH-8005" (allyl-based free radical polymers with phenolic rings); Nippon Kayaku Co., Ltd.'s "RE-810NM" (allyl-based free radical polymers with epoxy groups); Shikoku Chemical Industry Co., Ltd.'s "ALP-d" (allyl-based free radical polymers with benzoxazine rings); Shikoku Chemical Industry Co., Ltd.'s "L-DAIC" (allyl-based free radical polymers with isocyanuric acid rings); Nippon Kasei Co., Ltd.'s "TAIC" (allyl-based free radical polymers with isocyanuric acid rings (tallyl isocyanurate)); Osaka SODA Co., Ltd.'s "MDAC" (allyl-based free radical polymers with cyclohexanedicarboxylic acid derivatives); Nippon Techno Fine Chemical Co., Ltd.'s "DAD" (diallyl biphenylate); and Osaka SODA Co., Ltd.'s "DAISO". DAP (registered trademark) MONOMER (dallyl phthalate), etc.

[0285] From the viewpoint of achieving the 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.

[0286] Butadiene-based free radical polymerizable compounds refer to compounds having at least one butadiene backbone in their molecule. The polybutadiene structure may be contained in the main chain or in the side chain. It should be noted that the polybutadiene structure may be partially or completely hydrogenated. Preferably, the butadiene-based free radical polymerizable compound is a resin selected from one or more of the following: resins containing a hydrogenated polybutadiene backbone, hydroxyl-containing butadiene resins, phenolic hydroxyl-containing butadiene resins, carboxyl-containing butadiene resins, anhydride-containing butadiene resins, epoxy-containing butadiene resins, isocyanate-containing butadiene resins, and urethane-containing butadiene resins.

[0287] Specific examples of butadiene-based free radical polymerizable compounds include "JP-100" manufactured by Nippon Soda, and "Ricon100", "Ricon150", "Ricon130MA8", "Ricon130MA13", "Ricon130MA20", "Ricon131MA5", "Ricon131MA10", "Ricon131MA17", "Ricon131MA20", and "Ricon 184MA6" manufactured by CRAY VALLEY.

[0288] From the viewpoint of obtaining a cured product with excellent dielectric properties, when the content of the non-volatile component in the resin composition layer is set to 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

[0289] -(B) Thermoplastic resin-

[0290] In addition to component (A), the resin composition layer may, as an optional component, further contain a thermoplastic resin as component (B). By including component (B) in the resin composition layer, a cured product exhibiting better mechanical strength can be obtained. Component (B) may be used alone or in combination of two or more.

[0291] From the viewpoint of obtaining a cured product with excellent dielectric properties, the weight-average molecular weight (Mw) of component (B) is preferably 5,000 or more, more preferably 8,000 or more, particularly preferably 10,000 or more, preferably 100,000 or less, more preferably 80,000 or less, and particularly preferably 50,000 or less. The weight-average molecular weight of component (B) is the weight-average molecular weight converted from polystyrene by gel permeation chromatography (GPC).

[0292] As component (B), a component with a high weight-average molecular weight can 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, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, and polyester resins; and elastomers. Among these, from the viewpoint of obtaining a cured product with excellent dielectric properties, component (B) is preferably selected from at least one of polyimide resins and elastomers.

[0293] Polyimide resins can be resins that have imide bonds in repeating units. Polyimide resins include products typically obtained by the imidization reaction of diamine compounds with acid anhydrides.

[0294] There are no particular limitations on the diamine compounds used to prepare polyimide resins; examples include aliphatic diamine compounds and aromatic diamine compounds.

[0295] 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.

[0296] Dimeric acid-type diamines refer to diamine compounds obtained by replacing the two terminal carboxylic acid groups (-COOH) of a dimer acid with aminomethyl (-CH2-NH2) or amino (-NH2). Dimeric acids are known compounds obtained by dimerizing unsaturated fatty acids (preferably unsaturated fatty acids with 11 to 22 carbon atoms, and particularly preferably unsaturated fatty acids with 18 carbon atoms), and their industrial manufacturing processes are largely standardized in the industry. In particular, dimer acids with a carbon number of 36, obtained by dimerizing inexpensive and readily available 18-carbon unsaturated fatty acids such as oleic acid and linoleic acid, are readily available. Furthermore, depending on the manufacturing method and the degree of purification, dimer acids may sometimes contain arbitrary amounts of monomeric acids, trimeric acids, other polymeric fatty acids, etc. In addition, although double bonds remain after the polymerization reaction of unsaturated fatty acids, in this specification, hydrides that have undergone further hydrogenation reactions to reduce the degree of unsaturation are also included in dimer acids. For dimeric acid type diamines, commercially available products are available, such as "PRIAMINE1073", "PRIAMINE1074", "PRIAMINE1075" manufactured by Croda Japan, and "Versamine551" and "Versamine 552" manufactured by Cognis Japan.

[0297] Examples of aromatic diamine compounds include phenylenediamine compounds, naphthylenediamine compounds, and diphenylamine compounds.

[0298] A phenylenediamine compound is a compound formed from a benzene ring having two amino groups, wherein the benzene ring may have 1 to 3 substituents. As substituents, they are related to R in the general formula (A-2). 32The alkyl group represented may optionally have the same 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.

[0299] Naphthalene diamine compounds refer to compounds formed from a naphthalene ring having two amino groups, where the naphthalene ring can have 1 to 3 substituents. As substituents, they are related to R in general formula (A-2). 32 The alkyl group represented may optionally have the same substituents. Examples of naphthyl diamine compounds include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, and 2,3-diaminonaphthalene.

[0300] A diphenylamine compound is a compound containing two aniline structures within its molecule. Furthermore, each of the two benzene rings in the two aniline structures can have 1 to 3 substituents. As substituents, they are related to R in the general formula (A-2). 32 The alkyl groups represented may optionally have the same substituents. The two aniline structures in a diphenylamine compound may be directly bonded and / or bonded via one or two linker structures having 1 to 100 skeletal atoms selected from carbon, oxygen, sulfur, and nitrogen atoms. Diphenylamine compounds also include compounds in which the two aniline structures are bonded by two bonds.

[0301] Specifically, 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-, and -SO. 2-, -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-, groups represented by formulas (I) and (II) below, and groups formed by combinations of these groups, etc. In this specification, "Ph" represents 1,4-phenylene, 1,3-phenylene, or 1,2-phenylene.

[0302] [Chemical Formula 28]

[0303] .

[0304] In one embodiment, examples of diphenylamine compounds include 4,4'-diamino-2,2'-bis(trifluoromethyl)-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoic acid, 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'-(isopropylidene)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-fluorenylidene))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, 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., preferably 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindene.

[0305] In other embodiments, examples of diphenylamine compounds include, for instance, diamine compounds represented by the following formula (B-1).

[0306] [Chemical Formula 29]

[0307]

[0308] (In equation (B-1), R) 1 ~R 8 Each can independently represent a hydrogen atom, halogen atom, cyano group, nitro group, or -X group. 9 -R 9 , or -X 10 -R 10 R 1 ~R 8 At least one of them is -X 10 -R 10 X 9 Each independently represents a single bond, -NR 9'-, -O-, -S-, -CO-, -SO2-, -NR 9' CO-、-CONR 9' -、-OCO-、or -COO-、R 9 Each independently represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, R 9' Each of these elements independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, X. 10 Each can independently represent a single bond, -(substituted or unsubstituted alkylene)-, -NH-, -O-, -S-, -CO-, -SO2-, -NHCO-, -CONH-, -OCO-, or -COO-, R 10 Each can independently represent a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0309] R in equation (B-1) 9 and R 9' The alkyl group referred to is a straight-chain, branched, or cyclic monovalent aliphatic saturated hydrocarbon group. Preferably, it is an alkyl group with 1 to 6 carbon atoms, and more preferably, it is an alkyl group with 1 to 3 carbon atoms. Examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, cyclopentyl, and cyclohexyl.

[0310] R in equation (B-1) 9 and R 9' The term "alkenyl" refers to a straight-chain, branched, or cyclic monovalent unsaturated hydrocarbon group having at least one carbon-carbon double bond. Preferably, the alkenyl group has 2 to 6 carbon atoms, and more preferably has 2 or 3 carbon atoms. 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. The substituents for the alkenyl group in "substituted or unsubstituted alkenyl" are not particularly limited, and examples include halogen atoms, cyano, alkoxy, aryl, heteroaryl, amino, nitro, hydroxyl, carboxyl, and sulfonyl groups. As a base number for substitution, it is preferable to have 1 to 3, and more preferably 1.

[0311] Substituents for alkyl groups in "substituted or unsubstituted alkyl groups" and substituents for alkenyl groups in "substituted or unsubstituted alkenyl groups" are not particularly limited, and examples include halogen atoms, cyano groups, alkoxy groups, amino groups, nitro groups, hydroxyl groups, carboxyl groups, sulfonyl groups, etc. The number of substituents is preferably 1 to 3, and more preferably 1.

[0312] An alkoxy group is a monovalent group (alkyl-O-) formed by bonding an alkyl group to an oxygen atom. Preferably, an alkoxy group has 1 to 6 carbon atoms, and more preferably, it has 1 to 3 carbon atoms. Examples of such alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and pentoxy.

[0313] X in equation (B-1) 10 The alkylene group referred to is a straight-chain, branched, or cyclic divalent aliphatic saturated hydrocarbon group, preferably an alkylene group with 1 to 6 carbon atoms, and more preferably an alkylene group with 1 to 3 carbon atoms. Examples of alkylene 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 for the alkylene group in "substituted or unsubstituted alkylene" 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, sulfonyl groups, etc. The number of substituents is preferably 1 to 3, and more preferably 1.

[0314] As R in equation (B-1) 10 The aryl group represented 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 the most preferred. The substituents for the aryl group in "substituted or unsubstituted aryl group" are not particularly limited, and examples include halogen atoms, cyano groups, alkyl groups, alkoxy groups, aryl groups, heteroaryl groups, amino groups, nitro groups, hydroxyl groups, carboxyl groups, and sulfonyl groups. The number of substituents is preferably 1 to 3, and more preferably 1.

[0315] R in equation (B-1) 10The term "heteroaryl" refers to an aromatic heterocyclic group having 1 to 4 heteroatoms selected from oxygen, nitrogen, and sulfur atoms. Preferably, the heteroaryl group is a 5- to 12-membered (preferably 5 or 6-membered) monocyclic, bicyclic, or tricyclic (preferably monocyclic) aromatic heterocyclic group. Examples of such heteroaryl groups include furanyl, thiopheneyl, pyrroleyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, furazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, pyridinyl, pyridinyl, pyrazinyl, triazinyl, etc. The substituents of heteroaryl in "substituted or unsubstituted heteroaryl" are the same as the substituents of aryl in "substituted or unsubstituted aryl".

[0316] R 1 ~R 8 Each can independently represent a hydrogen atom, halogen atom, cyano group, nitro group, or -X group. 9 -R 9 , or -X 10 -R 10 R 1 ~R 8 Ideally, each atom should be a hydrogen atom or -X. 10 -R 10 .

[0317] R 1 ~R 8 At least one of them is -X 10 -R 10 R is better. 1 ~R 8 One or both of them are -X 10 -R 10 It's better to be R 5 ~R 8 One or both of them are -X 10 -R 10 Further improvement is R 5 and R 7 One or both of them are -X 10 -R 10 .

[0318] In one implementation, R is preferred. 1 ~R 8 One or both of them are -X 10 -R 10 And R 1 ~R 8 The others are hydrogen atoms, preferably R. 5 ~R 8One or both of them are -X 10 -R 10 And R 1 ~R 8 The others are hydrogen atoms, and even better, R. 5 and R 7 One or both of them are -X 10 -R 10 And R 1 ~R 8 The others are hydrogen atoms.

[0319] X 9 Each independently represents a single bond, -NR 9' -, -O-, -S-, -CO-, -SO2-, -NR 9' CO-、-CONR 9' -、-OCO-、or -COO-. R 9 Each can independently represent a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. X 9 It is better to have a single bond.

[0320] R 9' Each of these independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. R 9 It is preferable to use substituted or unsubstituted alkyl groups.

[0321] X 10 Each can independently represent a single bond, -(substituted or unsubstituted alkylene)-, -NH-, -O-, -S-, -CO-, -SO2-, -NHCO-, -CONH-, -OCO-, or -COO-. X 10 It is better to have a single bond.

[0322] R 10 Each can independently represent a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R 10 It is preferable to have substituted or unsubstituted aryl groups.

[0323] 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 ester);

[0324] [Chemical Formula 30]

[0325]

[0326] (where R is in the formula) 1 ~R 6 and R 8Each can independently represent a hydrogen atom, halogen atom, cyano group, nitro group, or -X group. 9 -R 9 Other symbols are the same as in equation (B-1).

[0327] [Chemical Formula 31]

[0328] .

[0329] The diamine compound can be a commercially available product or a compound synthesized using known methods. For example, the diamine compound shown in formula (B-1) can be synthesized using the synthesis method described in Japanese Patent No. 6240798 or a method based thereon. A single diamine compound can be used alone, or in combination of two or more.

[0330] The acid 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 diphthalic dianhydride, with diphthalic dianhydride being preferred.

[0331] Benzenetetracarboxylic dianhydride refers to a dianhydride of benzene having four carboxyl groups. Further, the benzene ring may optionally have one to three substituents. Here, the substituents are preferably selected from halogen atoms, cyano groups, and -X groups. 13 -R 13 (The same group as defined in formula (B-4) below). Specific examples of phenyltetracarboxylic dianhydrides include pyromellitic dianhydride, 1,2,3,4-phenyltetracarboxylic dianhydride, etc.

[0332] Naphthalenetetracarboxylic dianhydride refers to a dianhydride of naphthalene having four carboxyl groups. Further, the naphthalene ring may optionally have one to three substituents. Here, the substituents are preferably selected from halogen atoms, cyano groups, and -X groups. 13 -R 13 (The same group as defined in formula (B-4) below). Examples of naphthalenetetracarboxylic dianhydrides include 1,4,5,8-naphthalenetetracarboxylic dianhydrides, 2,3,6,7-naphthalenetetracarboxylic dianhydrides, etc.

[0333] Anthracene tetracarboxylic dianhydride refers to the dianhydride of anthracene having four carboxyl groups. Further, the anthracene ring may optionally have one to three substituents. Here, the substituents are preferably selected from halogen atoms, cyano groups, and -X groups. 13 -R 13 (The same group as defined in formula (B-4) below). Examples of anthracene tetracarboxylic dianhydrides include 2,3,6,7-anthracite tetracarboxylic dianhydrides.

[0334] Diphthalic anhydride refers to a compound containing two phthalic anhydride atoms within its molecule. Further, each of the two benzene rings in the two phthalic anhydrides may optionally have one to three substituents. Here, the substituents are preferably selected from halogen atoms, cyano groups, and -X groups. 13 -R 13 (Same as the definition in formula (B-4) below) groups. The two phthalic anhydrides in phthalic dianhydrides can be directly bonded or can be linked through a linker structure having 1 to 100 skeletal atoms selected from carbon, oxygen, sulfur and nitrogen atoms.

[0335] Examples of phthalic anhydrides include compounds represented by formula (B-4);

[0336] [Chemical Formula 32]

[0337]

[0338] (where R is in the formula) 11 and R 12 Each can independently represent a halogen atom, cyano group, nitro group, or -X. 13 -R 13 ,

[0339] X 13 Each independently represents a single bond, -NR 13' -, -O-, -S-, -CO-, -SO2-, -NR 13' CO-、-CONR 13' -、-OCO-、or -COO-,

[0340] R 13 Each can independently represent a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group.

[0341] R 13' Each of these elements independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group.

[0342] Y represents a single bond, or a linkage structure with 1 to 100 skeleton atoms selected from carbon, oxygen, sulfur, and nitrogen atoms.

[0343] n1 and m1 each independently represent integers from 0 to 3.

[0344] Y preferably has a linker structure with 1 to 100 framework atoms selected from carbon, oxygen, sulfur, and nitrogen atoms. n1 and m1 are preferably 0.

[0345] The "linker structure" in Y has 1 to 100 framework atoms selected from carbon, oxygen, sulfur, and nitrogen atoms. A preferred "linker structure" is -[A-Ph]. a -A-[Ph-A] b - [where A independently represents a single bond, -(substituted or unsubstituted alkylene)-, -O-, -S-, -CO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-, and a and b independently represent integers from 0 to 2 (preferably 0 or 1).] This indicates a divalent group.

[0346] Specific examples of "linker structures" in Y include -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.

[0347] Examples of phthalic dianhydrides include: 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, and 2,3,3',4'-biphenyl tetracarboxylic dianhydride. 2,3,3',4'-Benzenone Tetracarboxylic Acid Dihydric Anhydride, 2,3,3',4'-Diphenyl Ether Tetracarboxylic Acid Dihydric Anhydride, 2,3,3',4'-Diphenyl Sulfone Tetracarboxylic Acid Dihydric Anhydride, 2,2'-Bis(3,4-Dicarboxyphenoxyphenyl)sulfone Dihydric Anhydride, Methylene-4,4'-Diphthalic Acid Dihydric Anhydride, 1,1-Ethylene-4,4'-Diphthalic Acid Dihydric Anhydride, 2,2-Propylene-4 4'-Diphthalic anhydride, 1,2-Ethylene-4,4'-Diphthalic anhydride, 1,3-Trimethylene-4,4'-Diphthalic anhydride, 1,4-Tetramethylene-4,4'-Diphthalic anhydride, 1,5-Pentamethylene-4,4'-Diphthalic anhydride, 1,3-Bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,4-Bis(diphthalic anhydride) (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) phthalic anhydride, etc.

[0348] Aromatic tetracarboxylic dianhydrides can be commercially available products or compounds synthesized using known methods or methods thereof. Aromatic tetracarboxylic dianhydrides can be used alone or in combination of two or more.

[0349] In one embodiment, the anhydride used to make the polyimide resin may contain other anhydrides besides aromatic tetracarboxylic dianhydride.

[0350] Other examples of acid anhydrides 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'-dicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, and methylene-4,4'-bis( Aliphatic tetracarboxylic dianhydrides such as cyclohexane-1,2-dicarboxylic acid dianhydride, 1,2-ethylidene-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 sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride.

[0351] The content of the structure derived from the aromatic tetracarboxylic dianhydride in all the structures of the anhydrides that constitute the polyimide resin is preferably 10 mol% or more, 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 particularly preferably 100 mol%.

[0352] The polyimide resin preferably has a structural unit having the following general formula (B);

[0353] [Chemical Formula 33]

[0354]

[0355] (In general formula (B), R) 51 R indicates a single bond or a residue derived from an anhydride. 52 This indicates a single bond or a residue originating from a diamine compound.

[0356] R 51 Represents a single bond or a residue derived from an anhydride, preferably a residue derived from an anhydride. R 51 The residues derived from acid anhydrides refer to the divalent groups obtained by removing two oxygen atoms from the acid anhydride. This is as described above regarding acid anhydrides.

[0357] R 52 Represents a single bond or a residue derived from a diamine compound, preferably a residue derived from a diamine compound. R 52The residues derived from diamine compounds refer to the divalent groups obtained by removing two amino groups from a diamine compound. This is as described above regarding diamine compounds.

[0358] Polyimide resins can be prepared using methods known in the art. One known method is to react a mixture of a diamine compound, an acid anhydride, and a solvent by heating. The amount of the diamine compound mixed is typically 0.5 to 1.5 molar equivalents relative to the acid anhydride, preferably 0.9 to 1.1 molar equivalents.

[0359] Examples of solvents that can be used in the preparation of polyimide resins include amide 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. Additionally, imidization catalysts, azeotropic dehydration solvents, and acid catalysts can be used in the preparation of polyimide resins as needed. Examples of imidization catalysts include tertiary amines such as triethylamine, triisopropylamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, N,N-dimethyl-4-aminopyridine, and pyridine. Examples of azeotropic dehydration solvents include toluene, xylene, and ethylcyclohexane. Examples of acid catalysts include acetic anhydride. The amounts of imidization catalyst, azeotropic dehydration solvent, acid catalyst, etc., can be appropriately set by those skilled in the art. The reaction temperature for preparing polyimide resins is typically 100–250°C.

[0360] Examples of phenoxy resins include those having one or more skeletons selected from the following: bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetylphenyl skeleton, phenolic skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal group of the phenoxy resin can be any functional group such as a phenolic hydroxyl group or an epoxy group. Preferably, the phenoxy resin has a weight-average molecular weight of 30,000 or more.

[0361] 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 acetylbenzene backbone); Nippon Steel Chemical Materials' "FX280" and "FX293"; and Mitsubishi Chemical's "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", and "YL7482", etc.

[0362] Polyamide-imide resin is a resin having an amide-imide structure. From the viewpoint of compatibility with other components in the resin composition layer, it is preferable to use polyamide-imide resins having an alicyclic structure in their molecular structure, polyamide-imide resins having a siloxane structure as described in Japanese Patent Application Publication No. 05-112760, polyamide-imide resins having a sterically hindered branched structure, polyamide-imide resins using asymmetric monomers as raw materials, and polyamide-imide resins having a multi-branched structure, etc.

[0363] Among these, for polyamide-imide resins, from the viewpoint of improving the compatibility and dispersibility of resin varnishes by having an isocyanuric ring structure, it is preferable to have: (i) a polyamide-imide resin having an isocyanuric ring structure in its molecular structure (i.e., a polyamide-imide resin having an "isocyanuric ring structure" and an "imide skeleton or amide skeleton"), (ii) a polyamide-imide resin having an isocyanuric ring structure and an alicyclic structure in its molecular structure (i.e., a polyamide-imide resin having an isocyanuric ring structure, an alicyclic structure, and an imide skeleton or amide skeleton), and (iii) a polyamide-imide resin having repeating units containing an isocyanuric ring structure and an alicyclic structure (i.e., a polyamide-imide resin having repeating units containing an isocyanuric ring structure, an alicyclic structure, and an imide skeleton or amide skeleton).

[0364] As a preferred embodiment of the polyamide-imide resin described in (i) to (iii) above, examples include: (1) a branched polyamide-imide containing a carboxylic acid group (hereinafter, sometimes referred to as "(compound B-b1)"), which is obtained by reacting a polyisocyanate compound containing an isocyanuric acid ring derived from an alicyclic diisocyanate with an anhydride of a polycarboxylic acid having three or more carboxyl groups; (2) a branched polymerizable polyamide-imide containing a carboxylic acid group (hereinafter, sometimes referred to as "compound (B-b2)"), which is obtained by reacting compound (B-b1) with a compound having one epoxy group and one or more free radical polymerizable unsaturated groups; or (3) a branched polymerizable polyamide-imide containing a carboxylic acid group (hereinafter, sometimes referred to as "compound (B-b3)"), which is obtained by reacting the isocyanate group remaining during the synthesis of compound (B-b1) with a compound having one hydroxyl group and one or more free radical polymerizable unsaturated groups.

[0365] Specifically, compounds represented by the general formula (I) can be cited as examples of compounds (B-b1). It should be noted that the repeating unit in the compound represented by general formula (I) is considered as the repeating unit (I-1);

[0366] [Chemical Formula 34]

[0367]

[0368] (In the formula, w represents 0 to 15).

[0369] As a compound (B-b2), a compound (II) having a structure (I-2) obtained by adding GMA (glycidyl methacrylate) to any part of the repeating unit (I-1) in general formula (I) and / or the terminal carboxyl group is given.

[0370] [Chemical Formula 35]

[0371]

[0372] (where R is in the formula) 40 Residues in expression (I).

[0373] Regarding the proportion of GMA modification of the carboxyl group, the range of added GMA relative to the molar number of carboxyl groups in compound (B-b1) is preferably 0.3 mol% or more, more preferably 0.5 mol% or more, further preferably 0.7 mol% or more, or 0.9 mol% or more. The upper limit is preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, or 20 mol% or less.

[0374] As a compound (B-b3), examples include compounds (III) having any part of the repeating unit (I-1) in the above formula (I) and / or terminal imide groups being isocyanate residues, with the addition of a hydroxyl group of pentaerythritol triacrylate to them.

[0375] [Chemical Formula 36]

[0376]

[0377] (In the formula, R' represents the residue in formula (I)).

[0378] Regarding the amount of pentaerythritol triacrylate added, relative to the molar number of isocyanate groups in the polyisocyanate at the time of charging, it is preferably 40 mol% or less, more preferably 38 mol% or less, and even more preferably 35 mol% or less. On the other hand, regarding the amount of pentaerythritol triacrylate added, from the viewpoint of fully obtaining the effect obtained by the addition, relative to the molar number of isocyanate groups in the polyisocyanate at the time of charging, it is preferably 0.3 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more.

[0379] Polyamide-imide resins can be synthesized using various known methods. For example, reference can be made to paragraphs 0020 to 0030 of International Publication No. 2010 / 074197, the contents of which are incorporated herein by reference.

[0380] Commercially available polyamide-imide resins are acceptable. Examples of commercially available products include "UNIDICV-8000" manufactured by DIC Corporation, "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Corporation, and "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane backbone) manufactured by Hitachi Chemical Corporation.

[0381] For polyester resins, from the viewpoint of compatibility with other components in the resin composition layer, it is preferable to have a fluorene structure in the molecular structure, and it is preferable to have structural units from diols and structural units from dicarboxylic acids in addition to the fluorene structure.

[0382] Specific examples of polyester resins include "OKP4HT" manufactured by Osaka Gas Chemical Co., Ltd.

[0383] Specific examples of polysulfone resins include polysulfones such as "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0384] Examples of polyvinyl acetal resins include, for example, polyvinyl formal resin and polyvinyl butyral resin, with polyvinyl butyral resin being preferred. Specific examples of polyvinyl acetal resins include: the S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemicals Co., Ltd.; etc.

[0385] Specific examples of polyethersulfone resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0386] (B) The elastomer in the composition refers to a flexible resin, preferably a resin that exhibits rubber elasticity by polymerization with a rubber-elastic resin or other components. Examples of such resins include those that, as a rubber elasticity, exhibit 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). The elastomer is typically an amorphous resin component soluble in organic solvents. This elastomer can be used alone or in combination of two or more in any proportion.

[0387] In one embodiment, the elastomer is preferably a resin having one or more structures selected from polybutadiene, polysiloxane, poly(meth)acrylate, polyalkylene, polyalkyleneoxy, polyisoprene, polyisobutylene, polycarbonate, and polystyrene within its molecule. "(meth)acrylate" refers to methacrylates and acrylates.

[0388] In another embodiment, the elastomer is preferably selected from one or more resins selected from those with a glass transition temperature (Tg) of 25°C or lower and those that are liquid at 25°C or lower. The glass transition temperature of the resin with a Tg of 25°C or lower is preferably 20°C or lower, more preferably 15°C or lower. There is no particular limitation on the lower limit of the glass transition temperature, and it can generally be -15°C or higher. Furthermore, as for the resin that is liquid at 25°C, it is preferable to have a resin that is liquid at 20°C or lower, more preferably a resin that is liquid at 15°C or lower. The glass transition temperature can be determined by DSC (differential scanning calorimetry).

[0389] Examples of elastomers include resins containing a polybutadiene structure. The polybutadiene structure can be contained in the main chain or in the side chains. Furthermore, some or all of the polybutadiene structure can be hydrogenated. Resins containing a polybutadiene structure are sometimes referred to as "polybutadiene resins." Specific examples of polybutadiene resins include: "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", and "Ricon 184MA6" (polybutadiene containing anhydride groups) manufactured by CrayValley; "GQ-1000" (polybutadiene with introduced hydroxyl and carboxyl groups), "G-1000", "G-2000", and "G-3000" (polybutadiene with two-terminated hydroxyl groups), "GI-1000", "GI-2000", and "GI-3000" (hydrogenated polybutadiene with two-terminated hydroxyl groups) manufactured by Nippon Soda; and "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin) manufactured by Nagase ChemteX. In addition, specific examples of polybutadiene resins include linear polyimides (as described in Japanese Patent Application Publication No. 2006-37083 and International Publication No. 2008 / 153208) made from hydroxyl-terminated polybutadiene, diisocyanate compounds, and tetrabasic anhydrides, 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 detailed information on this polyimide resin, please refer to the descriptions in Japanese Patent Application Publication No. 2006-37083 and International Publication No. 2008 / 153208, which are incorporated herein by reference.

[0390] Examples of elastomers include resins containing a poly(meth)acrylate structure. Resins containing a poly(meth)acrylate structure are sometimes referred to as "poly(meth)acrylate resins." Specific examples of poly(meth)acrylate resins include TEISANRESIN manufactured by Nagase ChemteX, and "ME-2000," "W-116.3," "W-197C," "KG-25," and "KG-3000" manufactured by Negami Kogyo Co., Ltd.

[0391] Examples of elastomers include resins containing a polycarbonate structure. Sometimes, resins containing a polycarbonate structure are 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 groups refer to functional groups such as hydroxyl, phenolic hydroxyl, carboxyl, acid anhydride, isocyanate, urethane, and epoxy groups that can react 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 Kuraray Co., Ltd. Additionally, linear polyimides made from hydroxyl-terminated polycarbonate, diisocyanate compounds, and tetrabasic anhydrides 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 detailed information on this polyimide resin, please refer to International Publication No. 2016 / 129541, the contents of which are incorporated herein by reference.

[0392] Examples of elastomers include resins containing polysiloxane structures. Resins containing polysiloxane structures are sometimes referred to as "siloxane resins." Specific examples of siloxane resins include "SMP-2006," "SMP-2003PGMEA," and "SMP-5005PGMEA" manufactured by Shin-Etsu Silicones Co., Ltd., and 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.).

[0393] Examples of elastomers include resins containing polyalkylene structures or polyalkylene oxide structures. Resins containing polyalkylene structures are sometimes referred to as "alkylene resins." Additionally, resins containing polyalkylene oxide structures are sometimes referred to as "alkylene oxide resins." The polyalkylene oxide structure is preferably a polyalkylene oxide structure with 2 to 15 carbon atoms, more preferably a polyalkylene oxide structure with 3 to 10 carbon atoms, and particularly preferably a polyalkylene oxide structure with 5 to 6 carbon atoms. Specific examples of alkylene resins and alkylene oxide resins include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Corporation.

[0394] Examples of elastomers include resins containing a polyisoprene structure. Resins containing a polyisoprene structure are sometimes referred to as "isoprene resins." Specific examples of isoprene resins include "KL-610" and "KL613" manufactured by Kuraray Co., Ltd.

[0395] As elastomers, examples include resins containing a polyisobutylene structure. Sometimes, resins containing a polyisobutylene structure are called "isobutylene resins." Specific examples of isobutylene resins include KANEKA's "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer).

[0396] Examples of elastomers include resins containing a polystyrene structure. Resins containing a polystyrene structure are sometimes referred to as "styrene resins." Styrene resins and polystyrene resins can be copolymers containing, in addition to styrene units, any repeating units different from the aforementioned styrene units, or they can be hydrogenated polystyrene resins.

[0397] Examples of repetitive units include, for instance, repetitive units having a structure obtained by polymerizing a conjugated diene (conjugated diene unit) and repetitive units having a structure obtained by hydrogenating a conjugated diene (hydrogenated conjugated diene unit). Examples of conjugated dienes include, for instance, 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. One type of conjugated diene may be used alone, or two or more may be used in combination. Furthermore, the polystyrene resin may be a random copolymer or a block copolymer.

[0398] Examples of styrene resins include: styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-butene-styrene block copolymer (SBBS), styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, hydrogenated styrene-butadiene random copolymer, and styrene-maleic anhydride copolymer. Specific examples of styrene resins include: hydrogenated styrene thermoplastic elastomers "H1041", "Tuftec H1043", "Tuftec P2000", and "Tuftec MP10" (manufactured by Asahi Kasei Corporation); epoxidized styrene-butadiene thermoplastic elastomers "Epofriend AT501" and "CT310" (manufactured by Daicel Corporation); hydroxyl-modified styrene elastomer "SEPTONHG252" (manufactured by Kuraray Corporation); carboxyl-modified styrene elastomers "Tuftec N503M", amino-modified styrene elastomers "Tuftec N501", and anhydride-modified styrene elastomers "Tuftec M1913" (manufactured by Asahi Kasei Chemicals); unmodified styrene elastomer "SEPTONS8104" (manufactured by Kuraray Corporation); styrene-ethylene / butene-styrene block copolymers "FG1924" (manufactured by Kraton Corporation) and "EF-40" (manufactured by CRAY Corporation). VALLEY Corporation.

[0399] 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, particularly preferably 5,000 or higher, more preferably 1,000,000 or lower, and even more preferably 900,000 or lower. The number-average molecular weight (Mn) can be determined using GPC (gel permeation chromatography) converted to polystyrene.

[0400] From the viewpoint of obtaining a cured product with excellent dielectric properties, when the content of the non-volatile component in the resin composition layer is set to 100% by mass, it is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

[0401] -(C) Inorganic filler materials-

[0402] In addition to the components mentioned above, the resin composition layer may further include inorganic filler material as component (C).

[0403] Inorganic compounds are used as inorganic filler materials. Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Furthermore, spherical silica is preferred as silica. (C) One inorganic filler material may be used alone or in combination of two or more.

[0404] Examples of commercially available products containing component (C) include: Denka's "UFP-30"; Nippon Steel & Sumitomo Metal Materials' "SP60-05" and "SP507-05"; Admatechs' "YC100C", "YA050C", "YA050C-MJE", and "YA010C"; Tokuyama's "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N"; and Admatechs' "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1".

[0405] The specific surface area of ​​component (C) is preferably 1 m². 2 / g or higher, preferably 2m 2 / g or higher, especially 3m 2 / g or above. There is no particular limit to the upper limit, but 60m is preferred. 2 / g or less, 50m 2 / g or less or 40m 2 / g or less. For specific surface area, it can be obtained by using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) to adsorb nitrogen gas onto the sample surface and then calculating the specific surface area using the BET multi-point method.

[0406] From the viewpoint of significantly achieving the desired effect of the present invention, the average particle size of component (C) is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly 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.

[0407] The average particle size of component (C) can be determined using laser diffraction-scattering based on the Mie scattering theory. Specifically, a laser diffraction-scattering particle size distribution measuring device can be used to prepare the particle size distribution of the inorganic filler material on a volume basis, and the median particle size can be used as the average particle size for measurement. The sample for testing can be prepared by weighing 100 mg of inorganic filler material and 10 g of methyl ethyl ketone into a vial and dispersing it ultrasonically for 10 minutes. For the sample to be tested, a laser diffraction-scattering particle size distribution measuring device is used, with blue and red light source wavelengths, to measure the volume-based particle size distribution of component (C) in a flow cell manner. The average particle size can be calculated from the obtained particle size distribution as the median particle size. Examples of laser diffraction-scattering particle size distribution measuring devices include the "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

[0408] From the viewpoint of improving moisture resistance and dispersibility, component (C) is preferably treated with a surface treatment agent. Examples of surface treatment agents include vinyl silane coupling agents, (meth)acrylic acid coupling agents, fluorinated silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. Among these, from the viewpoint of significantly achieving the effects of the present invention, aminosilane coupling agents are preferred. Furthermore, a single surface treatment agent or a combination of two or more agents can be used.

[0409] Commercially available surface treatment agents include, for example: Shin-Etsu Chemical Industry Co., Ltd.'s "KBM1003" (vinyltriethoxysilane), Shin-Etsu Chemical Industry Co., Ltd.'s "KBM503" (3-methacryloyloxypropyltriethoxysilane), Shin-Etsu Chemical Industry Co., Ltd.'s "KBM403" (3-epoxypropoxypropyltrimethoxysilane), Shin-Etsu Chemical Industry Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), and Shin-Etsu Chemical Industry Co., Ltd.'s "KBE903" (3-amino... Examples of silanes include N-phenyl-3-aminopropyltrimethoxysilane, KBM573 (N-phenyl-3-aminopropyltrimethoxysilane), SZ-31 (hexamethyldisilazane), KBM103 (phenyltrimethoxysilane), KBM-4803 (long-chain epoxy silane coupling agent), and KBM-7103 (3,3,3-trifluoropropyltrimethoxysilane).

[0410] From the perspective of improving the dispersibility of inorganic fillers, the degree of surface treatment by surface treatment agent is preferably within a specified range. Specifically, it is preferable that 100 parts by mass of inorganic filler are surface treated with 0.2 to 5 parts by mass of surface treatment agent, preferably with 0.2 to 3 parts by mass of surface treatment agent, and preferably with 0.3 to 2 parts by mass of surface treatment agent.

[0411] The degree of surface treatment by surface treatment agents can be evaluated by the carbon content per unit surface area of ​​the inorganic filler. From the perspective of improving the dispersibility of inorganic fillers, the preferred carbon content per unit surface area of ​​the inorganic filler is 0.02 mg / m². 2 The above is preferred, ideally 0.1 mg / m². 2 The above, and even better, is 0.2 mg / m². 2 That's all. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish and the melt viscosity in sheet form, 1 mg / m³ is preferable. 2 The following is preferable: 0.8 mg / m² 2 The following is even better: 0.5 mg / m² 2 the following.

[0412] The carbon content per unit surface area of ​​inorganic filler materials can be determined after cleaning the surface-treated inorganic filler material with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, sufficient MEK as a solvent is added to the surface-treated inorganic filler material, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid components, the carbon content per unit surface area of ​​the inorganic filler material can be determined using a carbon analyzer. A carbon analyzer such as the "EMIA-320V" manufactured by Horiba Corporation can be used.

[0413] From the viewpoint of achieving an insulating layer with a low dielectric loss tangent and reducing the maximum value of tanδ, when the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (C) 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, and even more preferably 70% by mass or less.

[0414] -(D) Polymerization initiator-

[0415] The resin composition layer may also contain (D) polymerization initiators as an optional component. By including (D) polymerization initiators, the curing of free radical polymerizable compounds can be effectively carried out.

[0416] There are no particular limitations on the types of polymerization initiators, but examples include free radical generators such as cyclohexanone peroxide, tert-butyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, dicumyl hydroperoxide, cumyl hydroperoxide, tert-butyl hydroperoxide, and 2,3-dimethyl-2,3-diphenylbutane. One or more of these polymerization initiators can be used.

[0417] Commercially available polymerization initiators can be used. Examples of commercially available initiators include "PERHEXYNE 25B" manufactured by Nippon Oil Company.

[0418] From the viewpoint of achieving significant effects of the present invention, when the content of the non-volatile component in the resin composition layer is set to 100% by mass, it 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.

[0419] -(E) Other Additives-

[0420] In addition to the components described above, the resin composition layer may, as an optional component, further include other additives. Examples of such additives include resin additives such as thickeners, defoamers, leveling agents, and adhesion promoters. These additives may be used individually or in combination of two or more. Those skilled in the art can appropriately determine their respective contents.

[0421] 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 varnish can be adjusted. Examples of solvents include organic solvents. However, it is preferable to exclude toluene, and when the resin composition layer is set to 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.

[0422] Examples of organic solvents include ketones such as methyl ethyl ketone (MEK) and cyclohexanone; aromatics such as xylene and tetramethylbenzene; glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, and diethylene glycol monoethyl ether acetate; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha. These solvents can be used alone or in combination of two or more.

[0423] As previously stated, the inventors have identified a new problem: compared to the conventional vacuum lamination method used when forming an insulating layer using a resin sheet (resin composition layer), the pressure applied to the resin sheet (resin composition layer) during lamination is high in vacuum pressing, and due to resin exudation, the desired insulating layer thickness is sometimes not obtained. Regarding the deviation in the thickness of the insulating layer after vacuum pressing (the difference from the target thickness), it has been confirmed that it is related to the amount of residual solvent in the resin composition layer and the maximum value of tanδ in a specific temperature range of the dynamic viscoelasticity of the resin composition layer (here, tanδ is the ratio of the loss modulus E'' (Pa) to the storage modulus E' (GPa) E'' / E'). Hereinafter, from the viewpoint of the amount of residual solvent and the maximum value of tanδ, a method for achieving the desired insulating layer thickness after vacuum hot pressing is presented.

[0424] From the viewpoint of adjusting the melt viscosity of the resin composition layer and achieving the desired insulation layer thickness after vacuum pressing, the less 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, further preferably 2% by mass or less, even more preferably 1.5% by mass or less, and particularly preferably 1% by mass or less. There is no particular limitation on the lower limit, and it can be set to 0.0001% by mass or more, etc. The residual solvent content can be determined by the method described in the examples described later.

[0425] From the viewpoint of achieving the desired insulation layer thickness after vacuum pressing, in the dynamic viscoelasticity measurement of the resin composition layer at 60°C to 200°C, the maximum value of tanδ at 100°C and above 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, the lower limit of this maximum value can be set to 0.3 or more, 0.4 or more, 0.5 or more, etc. The maximum value of tanδ at 100°C and above in the dynamic viscoelasticity can be measured according to the method described in the examples below.

[0426] From the viewpoint of achieving thinner printed wiring boards and providing a cured product with excellent insulation even when the cured resin composition is a thin film, the thickness of the resin composition layer is preferably 60 μm or less, more preferably 50 μm or less, and even more preferably 40 μm or less. There is no particular limitation on the lower limit of the resin composition layer thickness; it can typically be set to 5 μm or more, 10 μm or more, etc.

[0427] <Other Layers>

[0428] In one embodiment, the resin sheet may further contain other layers as needed. Examples of such other layers include, for instance, a protective film disposed on the side of the resin composition layer that is not bonded to the support (i.e., the side opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of debris or other contaminants to the surface of the resin composition layer, or to prevent damage from forming.

[0429] <Method for manufacturing resin sheets>

[0430] Resin sheets can be manufactured, for example, by preparing a resin varnish by dissolving a resin composition in an organic solvent, applying the resin varnish onto a support using a die coater or similar device, and then drying it to form a resin composition layer. The organic solvents described above can be used.

[0431] Drying can be carried out using known methods such as heating or blowing hot air. There are no particular limitations on drying conditions; drying is carried out when the content of organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although this varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% to 60% by mass of organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0432] Resin sheets can be stored in rolls. When resin sheets have a protective film, they can be used by peeling off the protective film.

[0433] <Properties and Applications of Resin Sheets>

[0434] The resin sheet of the present invention is a resin sheet for forming an insulating layer using vacuum pressing. It includes a support body and a resin composition layer disposed on the support body. The support body has a metal foil, and the resin composition layer contains component (A). By forming an insulating layer using a resin composition layer containing component (A) together with a support body containing a metal foil, and by vacuum pressing, an insulating layer exhibiting good mechanical strength, excellent tumble set resistance, and desired dielectric properties can be achieved.

[0435] The cured resin composition layer, formed by laminating a resin sheet layer onto a circuit board using vacuum pressing, heat-curing the resin composition layer at 100°C for 30 minutes, and then heat-curing it at 200°C for 120 minutes, exhibits a low dielectric loss tangent. Therefore, the aforementioned cured product provides an insulating layer with a low dielectric loss tangent. Preferably, the dielectric loss tangent is less than 0.0031, more preferably less than 0.0030, and even more preferably less than 0.0026 or less, or less than 0.0025. The lower limit of the dielectric loss tangent can be set to 0.0001 or higher. The dielectric loss tangent can be measured according to the method described in the examples below.

[0436] The cured resin composition layer, formed by laminating a resin sheet layer onto a circuit board using vacuum pressing, heat-curing the resin composition layer at 100°C for 30 minutes, and then heat-curing it at 200°C for 120 minutes, exhibits a low dielectric constant. Therefore, the aforementioned cured product provides an insulating layer with a low dielectric constant. Preferably, the dielectric constant is less than 2.95, more preferably less than 2.9, and even more preferably less than 2.9. The lower limit of the dielectric constant can be set to 1 or higher. The dielectric constant can be measured according to the method described in the examples below.

[0437] The cured resin composition layer, formed by laminating a resin sheet layer onto a circuit board using vacuum pressing, heat-curing the resin composition layer at 100°C for 30 minutes, and then heat-curing it at 200°C for 120 minutes, exhibits excellent mechanical strength and flexibility (MIT folding endurance). Therefore, the aforementioned cured product provides an insulating layer with excellent mechanical strength and flexibility. The folding endurance test apparatus preferably has 400 cycles or more, more preferably 410 cycles or more, and even more preferably 420 cycles or more. An upper limit can be set to 1000 cycles or less. MIT folding endurance can be measured according to the method described in the examples below.

[0438] By using the resin sheet of the present invention and forming an insulating layer using vacuum pressing, an insulating layer exhibiting good mechanical strength, excellent MIT (Medium-to-Fold) resistance, and desired dielectric properties can be obtained. Therefore, the resin sheet of the present invention can be suitably used as a resin sheet for forming an insulating layer using vacuum pressing (for forming an insulating layer using vacuum pressing). The resin sheet of the present invention can include a support comprising a metal foil, which is used to form a conductor layer. Therefore, the resin sheet of the present invention can be suitably used in the manufacture of printed wiring boards for forming both an insulating layer and a conductor layer using vacuum pressing (for forming an insulating layer and a conductor layer using vacuum pressing). The resin sheet of the present invention can be suitably used to form the insulating layer (and conductor layer) of a printed wiring board, preferably the interlayer insulating layer (and conductor layer) of a printed wiring board. In the present invention, the term "printed wiring board" also includes a rewiring substrate for semiconductor packaging.

[0439] [Printed wiring board, manufacturing method of printed wiring board]

[0440] The printed wiring board of the present invention comprises an insulating layer formed by a cured resin composition layer of the resin sheet of the present invention.

[0441] For printed wiring boards, for example, the resin sheet described above can be used to manufacture them by a method comprising the steps (I) and (II) below:

[0442] (I) The process of laminating resin sheets onto the inner substrate using vacuum pressing.

[0443] (II) The process of heat curing the resin composition layer to form an insulating layer.

[0444] The "inner layer substrate" used in process (I) refers to a component that becomes the substrate of a printed wiring board, such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, or a thermosetting polyphenylene ether substrate. Furthermore, this substrate may have a conductor layer on one or both sides, and this conductor layer may be patterned. Sometimes, an inner layer substrate with conductor layers (circuit) formed on one or both sides of the substrate is called an "inner layer circuit substrate." Additionally, intermediate products for which insulating layers and / or conductor layers are to be further formed during the manufacture of the printed wiring board are also included in the "inner layer substrate" as described in this invention. When the printed wiring board is a component-integrated circuit board, an inner layer substrate with the component integrated can be used.

[0445] Regarding the lamination of the inner layer substrate and the resin sheet, a vacuum pressing process is used to bond the resin composition layer of the resin sheet to the inner layer substrate. By using vacuum pressing to laminate the inner layer substrate and the resin composition layer, the dielectric properties, mechanical strength, and electrical properties can be improved.

[0446] First, the inner layer substrate and the resin sheet are placed in a vacuum pressing apparatus to bond the resin composition layer of the resin sheet to the inner layer substrate. Next, a vacuum pressing process is performed under reduced pressure to heat and press the inner layer substrate and the resin composition layer together. The vacuum pressing process is preferably a vacuum hot pressing process (vacuum heating pressing process) with applied heat.

[0447] The inner substrate and resin sheet are preferably disposed in a vacuum pressing device through metal plates such as cushion paper, stainless steel plates (SUS plates), and release films.

[0448] Vacuum pressing can be performed using existing vacuum pressing apparatuses that press the inner layer substrate and resin sheet from both sides of a heated metal plate, such as a SUS plate. Examples of commercially available vacuum pressing apparatuses include, for instance, the "VH1-1603" manufactured by Kitagawa Seiki Co., Ltd.

[0449] Vacuum pressing can be performed once or repeated two or more times. When repeated two or more times, the pressing pressure, heating temperature, pressing time, etc., can be the same or different.

[0450] In vacuum pressing, the pressing pressure is preferably above 0.49 MPa, more preferably above 0.98 MPa, preferably below 7.9 MPa, and even more preferably below 5.9 MPa.

[0451] In vacuum pressing, the atmospheric pressure, i.e., the pressure (decompression degree) during decompression within the chamber containing the stacked structure of the object being processed, is preferably 3 × 10⁻⁶. -2 Below MPa, 1×10 is better. -2Below MPa. There is no specific restriction on the lower limit; it can be set to 1×10. -10 MPa and above, etc.

[0452] In vacuum pressing, the heating temperature varies depending on the composition of the resin composition layer, typically above 150°C, preferably above 160°C, more preferably above 170°C, or above 180°C. There is no particular upper limit to the heating temperature; it can generally be set below 240°C, etc. It should be noted that, from the viewpoint of significantly obtaining the effects of the present invention, vacuum pressing can be performed by progressively or continuously increasing the temperature and / or progressively or continuously decreasing the temperature. Furthermore, as described later, the resin composition layer can be thermo-cured by heating during vacuum pressing to form an insulating layer.

[0453] In vacuum pressing, the pressing time is preferably 5 minutes or more, more preferably 10 minutes or more, and even more preferably 15 minutes or more. There is no specific upper limit, but it is preferably below 300 minutes, more preferably below 200 minutes, and even more preferably below 150 minutes.

[0454] After the resin sheet is laminated onto the inner substrate using vacuum pressing, the resin composition layer is thermally cured in step (II) to form an insulating layer. As a method for thermally curing the resin composition layer, for example, in the case of pressing using vacuum hot pressing, the resin composition layer is thermally cured using the heat from pressing to form an insulating layer.

[0455] There are no particular limitations on the thermosetting conditions of the resin composition layer; the conditions typically used when forming the insulating layer of a printed wiring board can be used.

[0456] For example, the thermosetting conditions of the resin composition layer vary depending on the type of resin composition, but the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C. The curing time is preferably set to 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0457] Before heat curing the resin composition layer, the resin composition layer can be preheated at a temperature lower than the curing temperature. For example, before heat curing the resin composition layer, the resin composition layer can be preheated for more than 5 minutes (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 to 120°C (preferably 60°C to 115°C, more preferably 70°C to 110°C).

[0458] As previously stated, the inventors have confirmed that, compared to vacuum lamination, the desired insulation layer thickness cannot always be achieved in vacuum pressing due to resin exudation during lamination. To address this, by setting the residual solvent amount and the maximum value of tanδ to the aforementioned preferred ranges, the desired insulation layer thickness after vacuum pressing can be achieved while maintaining good mechanical strength and dielectric properties. Specifically, when the designed insulation layer thickness is set to 15 μm, the deviation in the thickness of the insulation layer 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 set to 0%, ±0.1% or more, etc. The thickness of the insulation layer after vacuum pressing can be measured according to the method described in the examples below.

[0459] For the resin sheet used in this invention, since the support body contains metal foil, it may also include a process of forming a circuit by subtractive or modified semi-additive methods as process (III).

[0460] In process (III), a circuit can be formed using a support (metal foil) by a subtractive or modified semi-additive method.

[0461] In subtractive processing, unwanted portions (non-circuit forming portions) of a metal foil are selectively removed by etching or the like to form a circuit. Circuit formation using subtractive processing can be performed according to known steps. For example, circuit formation using subtractive processing can be performed by a method including the following steps: i) applying an etching resist to the surface of the metal foil (i.e., the side opposite to the side bonded to the resin composition layer); ii) exposing and developing the etching resist to form a wiring pattern; iii) etching away the exposed metal foil portions; and iv) removing the etching resist.

[0462] In the modified semi-additive process, a plating resist is used to protect the non-circuit forming portion of the metal foil. After electroplating a thickened metal such as copper onto the circuit forming portion, the plating resist is removed, and the metal foil outside the circuit forming portion is removed by etching to form a circuit. Circuit formation using the modified semi-additive process can be performed according to known steps. For example, circuit formation using the modified semi-additive process can be performed by a method including the following steps: i) applying a plating resist to the surface of the metal foil (i.e., the side opposite to the side bonded to the resin composition layer); ii) exposing and developing the plating resist to form a wiring pattern; iii) electroplating via the plating resist; iv) removing the plating resist; v) etching away the metal foil outside the circuit forming portion. It should be noted that if the metal foil is thick, before step i), the entire metal foil can be thinned by etching or the like to achieve the desired thickness (typically 5 μm or less, 4 μm or less, or 3 μm or less).

[0463] In the manufacturing of printed wiring boards, steps (IV) of opening holes and (V) of roughening the insulating layer can be further performed. These steps (IV) to (V) can be performed according to various methods known to those skilled in the art in the manufacture of printed wiring boards. In addition, the formation of insulating and conductor layers in steps (I) to (V) can be repeated as needed to form a multilayer wiring board.

[0464] [Semiconductor Devices]

[0465] 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.

[0466] Examples of semiconductor devices include various semiconductor devices used in electrical products (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trams, ships, and airplanes).

[0467] The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. A "conductive portion" refers to a portion that transmits electrical signals in the printed wiring board, and its location can be either on the surface or embedded. Furthermore, the semiconductor chip is not particularly limited to any electrical circuit element made of semiconductor material.

[0468] The mounting method for semiconductor chips during semiconductor device manufacturing is not particularly limited as long as it enables the semiconductor chip to function effectively. Examples include wire bonding mounting, flip-chip mounting, mounting using a bumpless build-up layer (BBUL), mounting using anisotropic conductive film (ACF), and mounting using non-conductive film (NCF). Here, "mounting using a bumpless build-up layer (BBUL)" refers to "a mounting method in which the semiconductor chip is directly embedded into a recess in a printed circuit board, connecting the semiconductor chip to the wiring on the printed circuit board." Example

[0469] The present invention will now be described in more detail using examples, but the invention is not limited to these examples. It should be noted that, unless otherwise expressly stated, "parts" and "%" refer to "parts by mass" and "% by mass," respectively.

[0470] <Inorganic filler material used>

[0471] Inorganic filler material 1: Spherical silica (UFP-30 manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 0.078 μm, specific surface area 30.7 m²). 2 100 parts (g) of a material that has been surface-treated with 2 parts of N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., KBM573);

[0472] Inorganic filler material 2: Spherical silica (Yarduma Corporation "SC2500SQ", average particle size 0.63μm, specific surface area 11.2m²). 2 100 parts (g) of a material that has been surface-treated with 1 part of N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., KBM573).

[0473] <Synthesis Example 1: Synthesis of Polyimide Resin 1>

[0474] In a 500 ml detachable flask equipped with a nitrogen inlet tube and a stirrer, 9.13 g (30 mmol) of 5-aminobenzoic acid 5-amino-1,1'-biphenyl-2-yl ester (a compound of formula (B-3)), 15.61 g (30 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic dianhydride, 94.64 g of N-methyl-2-pyrrolidone, 0.47 g (6 mmol) of pyridine, and 10 g of toluene were added. Under a nitrogen atmosphere, an imidization reaction was carried out at 180 °C for 4 hours, with toluene being removed from the system midway through the reaction, to obtain a polyimide solution containing polyimide resin 1 (20% by mass of non-volatile components). No precipitation of the synthesized polyimide resin 1 was observed in the polyimide solution. The weight-average molecular weight of polyimide resin 1 was 45,000.

[0475] <Synthesis Example 2: Synthesis of Polyimide Resin 2>

[0476] In a reaction vessel equipped with a stirrer, water separator, thermometer, and nitrogen inlet, 65.0 g of aromatic tetracarboxylic dianhydride (SABIC Japan, "BisDA-1000"), 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 an imidization reaction was carried out at 140°C for 1 hour. This yielded a polyimide solution containing polyimide resin 2 (30% by mass of non-volatile components). Furthermore, the weight-average molecular weight of polyimide resin 2 was 25,000.

[0477] <Synthesis Example 3: Synthesis of Polyimide Resin 3>

[0478] A 500 mL detachable flask equipped with a moisture metering receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer was prepared. 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 29.6 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindene were added to the flask. The reaction was carried out under a nitrogen stream at 45°C with stirring for 2 hours. Next, the reaction solution was heated to approximately 160°C, and the condensed water and toluene were azeotropically removed under a nitrogen stream. The presence of a specified amount of water in the moisture metering receiver and the observation of no further water outflow were confirmed. After confirmation, the reaction solution was further heated to 200°C with stirring for 1 hour. The solution was then cooled to obtain a polyimide solution (20% by mass of non-volatile component) containing a polyimide resin 3 having a 1,1,3-trimethylindene backbone. The obtained polyimide resin 3 has repeating units represented by formula (X1) and repeating units represented by formula (X2). Furthermore, the weight-average molecular weight of the aforementioned polyimide resin 3 is 12000.

[0479] [Chemical Formula 37]

[0480]

[0481] .

[0482] <Synthesis Example 4: Synthesis of Elastomers>

[0483] In a reaction vessel, 50 g of G-3000 (difunctional hydroxyl-terminated polybutadiene, number-average molecular weight = 5047 (GPC method), hydroxyl equivalent = 1798 g / eq., solid content 100% by mass: manufactured by Nippon Soda Co., Ltd.), 23.5 g of Ipzole 150 (aromatic mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.), and 0.005 g of dibutyltin laurate were mixed and dissolved uniformly. After homogenization, the temperature was raised to 50°C, and then 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq.) was added while stirring, 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 diethylene glycol monoethyl ether acetate (Daicel) were added. The mixture was stirred and heated to 130 °C for approximately 4 hours. The reaction was then carried out by FTIR at 2250 cm⁻¹. -1The disappearance of the NCO peak was confirmed. Based on the confirmation of the disappearance of the NCO peak, it was regarded as the endpoint of the reaction. After cooling the reactants to room temperature, they were filtered through a 100-mesh filter cloth to obtain an elastomer with an imide backbone, a urethane backbone, and a butadiene backbone.

[0484] Viscosity: 7.5 Pa·s (25℃, E-type viscometer)

[0485] Acid value: 16.9 mg KOH / g

[0486] Solid content: 50% by mass

[0487] Number average molecular weight: 13723

[0488] Glass transition temperature: -10℃

[0489] The content of the polybutadiene structural part is: 50 / (50+4.8+8.96)×100=78.4% by mass.

[0490] <Synthetic Example 5: Synthesis of Maleimide Resin A>

[0491] According to the method described in Synthesis Example 1 of Japan Invention Association 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.

[0492] [Chemical Formula 38]

[0493] .

[0494] <Preparation of Resin Composition 1>

[0495] While stirring, 5 parts of maleimide compound (Designer Molecules, "BMI-689"), 10 parts of maleimide resin containing a biphenyl backbone (Nippon Kayaku Co., Ltd., "MIR-3000"), 5 parts of maleimide resin A synthesized in Synthesis Example 5, and 20 parts of hydrogenated styrene-based thermoplastic elastomer (Asahi Kasei Corporation, "H1043", styrene / ethylene·butene·butadiene ratio = 67 / 33) were heated and dissolved 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 (Nippon Yushu Co., Ltd., "PERHEXYNE 25B") were mixed in, and the mixture was uniformly dispersed using a high-speed rotary mixer and filtered through a cartridge filter (ROKITECHNO, "SHP020") to prepare resin composition 1.

[0496] <Preparation of Resin Composition 2>

[0497] In the preparation of resin composition 1, polyimide resin 1 synthesized in Synthesis Example 1 was prepared by changing 20 parts of hydrogenated styrene-based thermoplastic elastomer (Asahi Kasei Corporation's "H1043" styrene / ethylene·butene·butadiene ratio = 67 / 33) to 100 parts. Except as described above, resin composition 2 was prepared in the same manner as resin composition 1.

[0498] <Preparation of Resin Composition 3>

[0499] In the preparation of resin composition 1, polyimide resin 2 was synthesized in Synthesis Example 2 by changing 20 parts of hydrogenated styrene-based thermoplastic elastomer (Asahi Kasei Corporation's "H1043" styrene / ethylene·butene·butadiene ratio = 67 / 33) to 67 parts. Except as described above, resin composition 3 was prepared in the same manner as resin composition 1.

[0500] <Preparation of Resin Composition 4>

[0501] In the preparation of resin composition 1, polyimide resin 3 was synthesized in Synthesis Example 3 by changing 20 parts of hydrogenated styrene-based thermoplastic elastomer (Asahi Kasei Corporation's "H1043" styrene / ethylene·butene·butadiene ratio = 67 / 33) to 100 parts. Except as described above, resin composition 4 was prepared in the same manner as resin composition 1.

[0502] <Preparation of Resin Composition 5>

[0503] In 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 replaced with 40 parts of the elastomer synthesized in Synthesis Example 4. Except for the above, resin composition 5 was prepared in the same manner as resin composition 1.

[0504] <Preparation of Resin Composition 6>

[0505] In 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.

[0506] <Preparation of Resin Composition 7>

[0507] In the preparation of resin composition 1, 5 parts of maleimide resin A were replaced with 4.5 parts of styrene-modified polyphenylene ether resin ("OPE-2St 1200", Mn=1200, toluene solution with 65% by mass of solids manufactured by Mitsubishi Gas Chemical Co., Ltd.). Except as described above, resin composition 7 was prepared in the same manner as resin composition 1.

[0508] <Preparation of Resin Composition 8>

[0509] In 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", molecular weight 326, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). Except as described above, resin composition 8 was prepared in the same manner as resin composition 1.

[0510] <Preparation of Resin Composition 9>

[0511] In the preparation of resin composition 1, 5 parts of maleimide resin A were replaced with 5 parts of a difunctional allyl compound having a benzoxazine ring ("ALP-d" manufactured by Shikoku Chemical Industry Co., Ltd.). Except as described above, resin composition 9 was prepared in the same manner as resin composition 1.

[0512] <Preparation of Resin Composition 10>

[0513] While stirring, 11 parts of styrene-modified polyphenylene ether resin ("OPE-2St 1200", Mn=1200, 65% by mass of toluene solution manufactured by Mitsubishi Gas Chemical Co., Ltd., a difunctional acrylate compound ("NK ester A-DOG", molecular weight 326 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., a difunctional allyl compound with a benzoxazine ring ("ALP-d", manufactured by Shikoku Chemical Industry Co., Ltd.), and 20 parts of hydrogenated styrene-based thermoplastic elastomer ("H1043", styrene / ethylene·butene·butadiene ratio = 67 / 33 manufactured by Asahi Kasei Corporation) were heated and dissolved in a mixed solvent of 20 parts naphtha and 10 parts cyclohexanone. After cooling to room temperature, 50 parts of inorganic filler material 1 and 0.1 parts of polymerization initiator (PERHEXYNE25B manufactured by Nippon Oil Co., Ltd.) are mixed in, and the mixture is evenly dispersed using a high-speed rotary mixer and then filtered through a cartridge filter (SHP020 manufactured by ROKITECHNO Co., Ltd.) to prepare resin composition 10.

[0514] <Preparation of Resin Composition 11>

[0515] In the preparation of resin composition 1, the amount of inorganic filler 1 was changed from 50 parts to 40 parts. Except as described above, resin composition 11 was prepared in the same manner as resin composition 1.

[0516] [Examples 1-11]

[0517] <Preparation of Resin Sheet A>

[0518] As a support, a copper foil with a carrier (Mitsui Metals & Minerals Co., Ltd. MicroThin MT-Ex copper foil (3μm thick ultrathin copper foil / 18μm thick carrier copper foil)) is prepared, comprising a carrier copper foil and an ultrathin copper foil. Resin compositions 1 to 11 are uniformly coated onto the ultrathin copper foil of the support using a die coater, so that the thickness of the dried resin composition layer is 20μm. The resin composition layer is obtained on the support by drying at 70°C to 120°C for 7 minutes. Next, on the surface of the resin composition layer that is not bonded to the support, a polypropylene film (Oji F-Tex Co., Ltd. "ALPHANMA-411", 15μm thick) serving as a protective film is laminated with the resin composition layer, with its rough surface bonded to the resin composition layer. Thus, a resin sheet A is obtained, consisting of a copper foil with a carrier (support), a resin composition layer, and a protective film in sequence.

[0519] <Preparation of Evaluation Cured Product A using Vacuum Pressing Process>

[0520] The protective film is peeled off from resin sheet A, exposing the resin composition layer. Next, the exposed resin composition layer is laminated with the ultrathin copper side of a copper foil with a carrier (Mitsui Metals & Minerals Co., Ltd. MicroThin MT-Ex copper foil (3μm thick ultrathin copper foil / 18μm thick carrier copper foil)) in a vacuum hot press (Kitagawa Seiki Co., Ltd., VH1-1603). The pressing conditions are set to a pressure reduction of 1×10⁻⁶. -3 Under pressure reduction conditions below MPa, the pressure condition is 20 kgf / cm². 2 As for the heating conditions, the first stage of pressing was carried out at a temperature of 100°C for 30 minutes, and the second stage of pressing was carried out at a temperature of 200°C for 120 minutes. After the resin composition layer was cured by utilizing the heating of pressing, the carrier foil was peeled off and an extremely thin copper was etched, thereby obtaining the evaluation cured product A.

[0521] [Comparative Example 1]

[0522] <Preparation of Resin Sheet B>

[0523] As a support, a PET film (Toray Industries, Ltd., "LUMIRROR R80", thickness 38 μm, softening point 130°C, "release PET") that has been released using an alkyd resin-based release agent (Lintec Corporation, "AL-5") was prepared. Resin composition 1 was uniformly coated onto the support using a die coater to achieve a dried resin composition layer thickness of 20 μm. The layer was dried at 70–120°C (average 100°C) for 3 minutes to form a resin composition layer on the support. Next, a polypropylene film (Oji F-Tex Corporation, "ALPHAN MA-411", thickness 15 μm) was laminated onto the surface of the resin composition layer that was not bonded to the support, using the rough surface of this film as a protective film. This resulted in a resin sheet B with the structure of support (38 μm PET film) / resin composition layer / protective film (MA-411).

[0524] <Preparation of Evaluation Cured Product B Using Lamination Process>

[0525] The untreated side of the release PET film (Lintec Corporation "501010", 38μm thick, 240mm square) is placed on the glass cloth substrate epoxy resin double copper clad laminate (Panasonic Electric Works Corporation "R5715ES", 0.7mm thick, 255mm square) in a way that connects to the surface of the film. The four sides of the release PET film are then fixed with polyimide adhesive tape (10mm wide).

[0526] Resin sheet B (167×107mm square) was laminated in the center using an intermittent vacuum pressure laminator (Nikko-Materials, 2-stage stacking laminator, CVP700), with the second resin composition layer in contact with the release surface of the release PET film. The lamination process was performed by depressurizing the pressure to below 13 hPa for 30 seconds, 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 thermocured at 190°C for 90 minutes. After thermocuring, the polyimide adhesive tape was peeled off, and the cured layer was removed from the glass cloth substrate epoxy resin double-sided copper-clad laminate. The release PET film was then peeled off from the cured layer to obtain the evaluation cured product B.

[0527] [evaluate]

[0528] <Determination of Residual Solvent Content>

[0529] The resin sheet, with the support and resin composition layers stacked, was cut into 10cm × 10cm pieces, and its initial mass was determined using an electronic balance. Next, the resin sheet was placed on a metal mesh and heated in an oven pre-set to 130°C for 15 minutes, then transferred to a desiccant and allowed to stand for 30 minutes to cool to room temperature. The dried mass of the resin sheet was then determined using an electronic balance. For three samples, both the initial mass and the dried mass were measured together, and the average value was used to calculate the amount of solvent contained in the resin composition layer (residual solvent content) using the following formula.

[0530] Residual solvent content (mass%) = 100 × (initial mass of resin sheet - dried mass of resin sheet) / (initial mass of resin sheet - mass of support).

[0531] <Determination of dielectric properties (dielectric constant, dielectric loss tangent)>

[0532] The cured material for evaluation was cut into specimens 2 mm wide and 80 mm long. For these specimens, the dielectric constant and dielectric loss tangent were measured using an Agilent Technologies HP8362B resonant cavity perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23 °C. The average values ​​of the dielectric constant and dielectric loss tangent were calculated for each of the three specimens, and the dielectric constant and dielectric loss tangent were further evaluated according to the following criteria.

[0533] -Dielectric loss tangent-

[0534] 〇: The dielectric loss tangent is less than 0.003

[0535] △: The dielectric loss tangent is greater than or equal to 0.003 and less than 0.0031.

[0536] ×: The dielectric loss tangent is above 0.0031.

[0537] -Dielectric constant-

[0538] 〇: Dielectric constant less than 2.9

[0539] △: Dielectric constant is 2.9 or higher and less than 2.95.

[0540] ×: Dielectric constant is 2.95 or higher.

[0541] <Evaluation of Flexibility (MIT Flexural Strength)>

[0542] Either the cured material A or cured material B for evaluation was cut into specimens 15 mm wide and 110 mm long. Using an MIT testing apparatus (MIT Flexural Fatigue Testing Machine "MIT-DA" manufactured by Toyo Seiki Co., Ltd.), in accordance with JIS C-5016, the number of flexural fatigue tests until the cured body fractured was measured under the following conditions: load 2.5 N, bending angle 90 degrees, bending radius 1.0 mm, and bending speed 175 times / minute. It should be noted that for 5 samples, the average of the top 3 results from highest to lowest was calculated, and the results were evaluated according to the following criteria.

[0543] 〇: The flexural strength is 405 cycles or more.

[0544] △: The number of folding resistances is 395 or more and less than 405.

[0545] ×: The number of folding cycles is less than 395.

[0546] <Determination of the maximum value of tanδ in dynamic viscoelasticity>

[0547] For the resin composition layer of resin sheet A or resin sheet B, dynamic viscoelasticity was measured using a dynamic viscoelasticity measuring device (UBM Rheosol-G3000). For a sample of 1 g of resin composition collected from the resin composition layer, using a parallel plate with a diameter of 18 mm, the temperature was increased from an initial temperature of 60 °C to 200 °C at a heating rate of 5 °C / min. The dynamic viscoelastic modulus was measured under the following conditions: a temperature interval of 2.5 °C, a vibration frequency of 1 Hz, and a deformation of 1 degree. Using the obtained storage modulus E' (GPa) and loss modulus E'' (Pa), tanδ was calculated using the following formula. Furthermore, the maximum value of tanδ at temperatures above 100 °C was determined.

[0548] tanδ=E'' / E'.

[0549] <Evaluation of the thickness of the insulation layer after vacuum pressing>

[0550] (1) Lamination of resin sheets using vacuum pressing on copper-clad laminate

[0551] As a copper-clad laminate, a glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil thickness 12μm, substrate thickness 0.15mm, Mitsubishi Gas Chemical Co., Ltd. "HL832NSF LCA", 255×340mm size) with circuit conductors (copper) formed on both sides by wiring patterns with a side length of 1mm and a residual copper ratio of 59% is prepared. The copper surface of both sides of this inner circuit substrate is roughened using MEC Co., Ltd. "CZ8201" (copper etching depth 0.5μm). The protective film is peeled off from resin sheet A, exposing the resin composition layer. Then, using a vacuum hot press (Kitagawa Seiki Co., Ltd., VH1-1603), the exposed resin composition layer is laminated on both sides of the copper-clad laminate in a manner that the resin composition layer is in contact with the copper-clad laminate. The pressing conditions are set to a pressure reduction of 1×10⁻⁶. -3 Under pressure reduction conditions below MPa, the pressure condition is 20 kgf / cm². 2 Under the specified heating conditions, the first stage of pressing was carried out at a temperature of 100°C for 30 minutes, and the second stage of pressing was carried out at a temperature of 190°C for 120 minutes. After the resin composition layer was cured by heating during pressing, an extremely thin copper layer was etched, thereby obtaining the evaluation substrate C.

[0552] (2) Observation of the thickness of the insulating layer after vacuum pressing.

[0553] Using a FIB-SEM composite apparatus (SII Nanotechnology Co., Ltd. "SMI3050SE"), cross-sectional observation of the evaluation substrate C was performed, and the thickness of the insulating layer (the thickness of the insulating layer directly above the circuit conductors of the copper-clad laminate) was measured. The evaluation was carried out according to the following criteria.

[0554] 〇: The thickness of the insulation layer is less than 15μm ± 20%.

[0555] △: The thickness of the insulation layer is greater than 15μm±20% and less than 15μm±30%.

[0556] ×: The thickness of the insulation layer is 15μm ± 30% or more.

[0557] [Table 1]

[0558] .

[0559] It was confirmed that in Examples 1 to 11, even without components (B) to (D), although there were differences in degree, the results were the same as those in the examples described above.

Claims

1. A resin sheet comprising a support and a resin composition layer disposed on the support, in, The support has metal foil, The resin composition layer contains (A) a free radical polymerizable compound and (C) an inorganic filler. When the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (C) is 52% by mass or more. (C) the specific surface area of the component is less than 40 m 2 / g.

2. The resin sheet according to claim 1, wherein, (A) The ingredient comprises at least one selected from the following: a free radical polymerizable compound containing a maleimide group, a free radical polymerizable compound containing a vinylphenyl group, a free radical polymerizable compound containing a (meth)acryloyl group, a free radical polymerizable compound containing an allyl group, and a free radical polymerizable compound containing a butadiene skeleton.

3. The resin sheet according to claim 1, wherein, (A) The ingredients include: free radical polymeric compounds containing maleimide groups.

4. The resin sheet according to claim 2, wherein, The free radical polymerizable compound containing a maleimide group includes at least one of the following (A1) to (A3): (A1) Solid maleimide-based free radical polymeric compounds, (A2) Liquid or semi-solid maleimide-based free radical polymeric compounds, and (A3) Maleimide-based free radical polymerizable compounds containing a skeleton formed by the fusion of aromatic rings and aliphatic hydrocarbon rings.

5. The resin sheet according to claim 4, wherein, Component (A1) has a structure represented by the following formula (A-2): In equation (A-2), R 31 and R 36 It represents maleimide group. R 32 R 33 R 34 and R 35 Each can be independently represented by a hydrogen atom, alkyl group, or aryl group. D independently represents a divalent aromatic group. m1 and m2 independently represent integers from 1 to 10. a represents an integer from 1 to 100.

6. The resin sheet according to claim 4, wherein, Component (A2) has a structure represented by the following formula (A-4): In equation (A-4), R represents an optional divalent aliphatic group with 5 or more carbon atoms having substituents. L represents a single bond or a divalent linker.

7. The resin sheet according to claim 4, wherein, Component (A2) has a structure represented by the following formula (A-7): In formula (A-7), R 100 Each can be independently represented by a divalent aliphatic group having 5 or more carbon atoms and being chosen as a substituent. A independently represents either a divalent aliphatic group with 5 or more carbon atoms that is optionally substituented, or a divalent group with an aromatic ring that is optionally substituented. n represents an integer from 1 to 10.

8. The resin sheet according to claim 7, wherein, In formula (A-7), A is selected from the following groups: 。 9. The resin sheet according to claim 4, wherein, (A2) The component is selected from the following compounds (A-10) to (A-13): In the formula, a represents an integer from 1 to 10.

10. The resin sheet according to claim 4, wherein, (A3) The component contains a structure represented by the following formula (A-15): In the formula, Ar a1 This indicates an optional divalent aromatic group with substituents; R a1 Each of the following can be independently represented: alkyl group with 1 to 10 carbon atoms, alkyloxy group with 1 to 10 carbon atoms, alkylthio group with 1 to 10 carbon atoms, aryl group with 6 to 10 carbon atoms, aryloxy group with 6 to 10 carbon atoms, arylthio group with 6 to 10 carbon atoms, cycloalkyl group with 3 to 10 carbon atoms, halogen atom, nitro group, hydroxyl group, or mercapto group; R a2 Each of the following can be independently represented: alkyl group with 1 to 10 carbon atoms, alkyloxy group with 1 to 10 carbon atoms, alkylthio group with 1 to 10 carbon atoms, aryl group with 6 to 10 carbon atoms, aryloxy group with 6 to 10 carbon atoms, arylthio group with 6 to 10 carbon atoms, cycloalkyl group with 3 to 10 carbon atoms, halogen atom, hydroxyl group, or mercapto group. R a3 Each can be independently represented by a divalent aliphatic hydrocarbon group; n a1 Represents positive integers; n a2 Each can independently represent an integer from 0 to 4; n a3 Each can independently represent an integer from 0 to 3; R a1 The hydrogen atoms of alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups may be optionally replaced by halogen atoms; R a2 The hydrogen atoms of alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups may be optionally replaced by halogen atoms; n a2 When R is 2 to 4, a1 Within the same ring, they can be the same or different; n a3 When R is 2-3, a2 Within the same ring, they can be the same or different.

11. The resin sheet according to claim 1, wherein, When the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (A) is 5% by mass or more.

12. The resin sheet according to claim 1, wherein, When the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (A) is 10% by mass or more.

13. The resin sheet according to claim 1, wherein, When the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (A) is 15% by mass or more.

14. The resin sheet according to claim 1, wherein, When the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (A) is less than 40% by mass.

15. The resin sheet according to claim 1, wherein, Metal foil includes copper foil.

16. The resin sheet according to claim 1, wherein, In the dynamic viscoelasticity test of the resin composition layer from 60°C to 200°C, the maximum value of tanδ at temperatures above 100°C is less than 2.

0.

17. The resin sheet according to claim 1, wherein, In the dynamic viscoelasticity test of the resin composition layer from 60°C to 200°C, the maximum value of tanδ at temperatures above 100°C is less than 1.

8.

18. The resin sheet according to claim 1, wherein, In the dynamic viscoelasticity test of the resin composition layer from 60°C to 200°C, the maximum value of tanδ at a temperature above 100°C is 0.3 or higher.

19. The resin sheet according to claim 1, wherein, The resin composition layer further contains (B) thermoplastic resin.

20. The resin sheet according to claim 19, wherein, (B) The weight average molecular weight of the component is above 5,000 and below 100,000.

21. The resin sheet according to claim 19, wherein, (B) Component is selected from at least one of polyimide resin and elastomer.

22. The resin sheet according to claim 19, wherein, When the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (B) is 10% by mass or more.

23. The resin sheet according to claim 19, wherein, When the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (B) is 15% by mass or more.

24. The resin sheet according to claim 19, wherein, When the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (B) is 40% by mass or less.

25. The resin sheet according to claim 1, wherein, When the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (C) is 55% by mass or more.

26. The resin sheet according to claim 1, wherein, When the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (C) is 80% by mass or less.

27. A printed wiring board, wherein, An insulating layer comprising a cured product of a resin composition layer of a resin sheet according to any one of claims 1 to 26.

28. A semiconductor device, wherein, It includes the printed wiring board of claim 27.

29. A method for manufacturing a printed wiring board, the method comprising: (1) The process of laminating the resin sheet of any one of claims 1 to 26 onto the inner substrate by vacuum pressing, and (2) The process of heat curing the resin composition layer to form an insulating layer.

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