Resin sheet

Abstract

To provide a resin sheet or the like that can give a cured product having excellent mechanical strength and having desired dielectric properties.SOLUTION: The present invention discloses a resin sheet for forming an insulating layer by vacuum pressing. The resin sheet has a support, and a resin composition layer provided on the support. The support has metal foil. The resin composition layer contains (A) a radical-polymerizable compound.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin sheet, and further to a printed wiring board, a semiconductor device, and a method for producing a printed wiring board, which are obtained by using the resin sheet. [Background technology]

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

[0003] [Patent Document 1] JP 2017-59779 A DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0004] With the recent trend toward high-speed transmission, insulating materials are required to have a lower dielectric constant and a lower dielectric loss tangent. To improve such dielectric properties, radically polymerizable compounds are expected to be used as curable compounds for insulating materials. However, when such radically polymerizable compounds are used to form a cured product (insulating layer), the obtained cured product may have poor mechanical strength and may not exhibit the desired dielectric properties.

[0005] An object of the present invention is to provide a resin sheet which can give a cured product exhibiting good mechanical strength and desired dielectric properties; a printed wiring board and a semiconductor device formed using the resin sheet; and a method for producing a printed wiring board. [Means for solving the problem]

[0006] Means for Solving the Problems The present inventors have intensively investigated the above-mentioned problems and have found that the above-mentioned problems can be solved by forming an insulating layer by a vacuum press treatment using a resin sheet including a support containing a metal foil and, provided on the support, (A) a resin composition layer containing a radically polymerizable compound, and have thus completed the present invention.

[0007] That is, the present invention includes the following. [1] A resin sheet for forming an insulating layer using a vacuum press process, A support and a resin composition layer provided on the support, The support has a metal foil, A resin sheet, wherein the resin composition layer contains (A) a radically polymerizable compound. [2] The resin sheet according to [1], wherein the component (A) contains a radical polymerizable compound containing a maleimide group. [3] The resin sheet according to [1] or [2], wherein the metal foil includes copper foil. [4] The resin sheet according to any one of [1] to [3], wherein in dynamic viscoelasticity measurement of the resin composition layer from 60° C. to 200° C., the maximum value of tan δ at 100° C. or higher is 2.0 or lower. [5] The resin sheet according to any one of [1] to [4], wherein the resin composition layer further contains a thermoplastic resin (B). [6] The resin sheet according to any one of [1] to [5], wherein the resin composition layer further contains (C) an inorganic filler. [7] The resin sheet according to [6], wherein the content of the component (C) is 50% by mass or more when the total amount of non-volatile components in the resin composition layer is 100% by mass. [8] A printed wiring board comprising an insulating layer made of a cured product of the resin composition layer of the resin sheet according to any one of [1] to [7]. [9] A semiconductor device comprising the printed wiring board according to [8].

[10] (1) A step of laminating the resin sheet according to any one of [1] to [7] on an inner layer substrate by vacuum pressing; (2) a step of thermally curing the resin composition layer to form an insulating layer; A method for manufacturing a printed wiring board, comprising: Effect of the Invention

[0008] According to the present invention, it is possible to provide a resin sheet which can give a cured product exhibiting 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 a printed wiring board. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic side view showing an example of two test tubes used for determining whether a radically polymerizable compound is in a liquid state, a semi-solid state, or a solid state. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present invention will be described in detail below with reference to preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be modified and implemented as desired without departing from the scope of the claims of the present invention and their equivalents.

[0011] [Resin sheet] The resin sheet of the present invention is a resin sheet for forming an insulating layer using a vacuum press treatment, which includes a support and a resin composition layer provided on the support, the support having a metal foil, and the resin composition layer containing (A) a radical polymerizable compound.

[0012] In order to improve the dielectric properties, it is possible to use a compound (radical polymerizable compound) having a radically polymerizable unsaturated group, which is a reactive functional group with low polarity, as a curable compound used in an insulating material. However, when a cured product (insulating layer) is formed using a radical polymerizable compound, the obtained insulating layer may have poor mechanical strength and may not exhibit the desired dielectric properties. In contrast, the present inventors have found that by forming an insulating layer (cured product of the resin composition layer) by vacuum press processing using the resin sheet of the present invention, which includes a support containing a metal foil and a resin composition layer containing a radical polymerizable compound provided on the support, the obtained insulating layer exhibits good mechanical strength, excellent flexibility (MIT folding resistance), and desired dielectric properties. The present inventors have confirmed that, compared to the vacuum lamination method conventionally used for forming an insulating layer using a resin sheet (resin composition layer), the vacuum press processing causes a new problem that the pressure applied to the resin sheet (resin composition layer) during lamination is high, and the desired insulating layer thickness may not be obtained due to the exudation of the resin. Regarding the deviation in thickness of the insulating layer after such vacuum press processing (difference from the target thickness), it has been confirmed that this is related to the amount of residual solvent in the resin composition layer and the maximum value of tan δ in a specific temperature range in the dynamic viscoelasticity of the resin composition layer (here, tan δ is the ratio E'' / E' of the storage modulus E' (GPa) to the loss modulus E'' (Pa). This will be discussed later together with solution guidelines based on the amount of residual solvent and the maximum value of tan δ.

[0013] Each layer constituting the resin sheet will be described in detail below.

[0014] <Support> In the resin sheet of the present invention, the support has a metal foil, which allows a conductor layer, which will be described later, to be formed from the support.

[0015] Examples of the metal foil include copper foil and aluminum foil, and copper foil is preferred. The copper foil may be a foil made of a single metal such as copper, or may be a foil made of an alloy of copper and another metal (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0016] The metal foil may be a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. Examples of multi-layer metal foils include metal foils containing a carrier metal foil and an ultra-thin metal foil bonded to the carrier metal foil. Such multi-layer metal foils may include a release layer between the carrier metal foil and the ultra-thin metal foil that allows the ultra-thin metal foil to be peeled off from the carrier metal foil. The release layer is not particularly limited as long as it can peel off the ultra-thin metal foil from the carrier metal foil, and examples of the release layer include an alloy layer of an element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, and P; an organic coating, and the like. When a multi-layer metal foil is used as the support, the resin composition layer is provided on the ultra-thin metal foil.

[0017] The method for producing the metal foil is not particularly limited, but it can be produced by known methods such as electrolysis and rolling.

[0018] The support may be a commercially available product, such as "HLP foil" and "JXUT-III foil" manufactured by JX Nippon Mining & Metals Corporation, and "Microthin MT-Ex copper foil" and "TP-III foil" manufactured by Mitsui Mining & Smelting Co., Ltd.

[0019] From the viewpoint of obtaining the effects of the present invention significantly, the thickness of the support is preferably 50 μm or less, more preferably 45 μm or less, even more preferably 40 μm or less, 35 μm or less, 30 μm or less, and may be preferably 1 μm or more, more preferably 5 μm or more, even more preferably 10 μm or more, etc. When the metal foil has a multilayer structure, it is preferable that the thickness of the entire metal foil is in this range, and the thickness of the ultrathin metal foil may be, for example, in the range of 0.1 μm or more and 10 μm or less.

[0020] <Resin composition layer> In the resin sheet of the present invention, the resin composition layer provided on the support contains (A) a radically polymerizable compound.

[0021] The resin composition layer may further contain optional components in combination with the component (A). Examples of the optional components include a thermoplastic resin (B), an inorganic filler (C), a polymerization initiator (D), and other additives (E). Each component contained in the resin composition layer will be described in detail below.

[0022] -(A) Radical polymerizable compound- The resin composition layer contains a radical polymerizable compound as component (A). By using a resin composition layer containing component (A) together with a support containing a metal foil, it is possible to obtain a cured product with excellent dielectric properties. The component (A) may be used alone or in combination of two or more types.

[0023] As the component (A), a compound that can be polymerized by radicals generated by heat or light, that is, a compound having a radically polymerizable unsaturated group, can be used. Examples of the radically polymerizable unsaturated group include a group having an ethylenic double bond that exhibits curability upon irradiation with active energy rays. Examples of such radically polymerizable unsaturated groups include a vinyl group, an allyl group, a vinylphenyl group, an acryloyl group, a methacryloyl group, a maleimide group, a fumaroyl group, and a maleoyl group, and it is preferable that the radically polymerizable unsaturated group is at least one selected from a maleimide group, an allyl group, a vinylphenyl group, an acryloyl group, and a methacryloyl group.

[0024] The component (A) preferably has one or more radically polymerizable unsaturated groups, and more preferably has two or more. There is no particular upper limit, but it may be 10 or less.

[0025] The compound having a radically polymerizable unsaturated group preferably contains at least one selected from a radically polymerizable compound containing a maleimide group (maleimide-based radically polymerizable compound), a radically polymerizable compound containing a vinylphenyl group (vinylphenyl-based radically polymerizable compound), a radically polymerizable compound containing a (meth)acryloyl group ((meth)acrylic-based radically polymerizable compound), a radically polymerizable compound containing an allyl group (allyl-based radically polymerizable compound), and a radically polymerizable compound containing a butadiene skeleton (butadiene-based radically polymerizable compound), more preferably contains at least one of a maleimide-based radically polymerizable compound, a vinylphenyl-based radically polymerizable compound, an allyl-based radically polymerizable compound, and a (meth)acrylic-based radically polymerizable compound, and even more preferably contains a maleimide-based radically polymerizable compound.

[0026] The maleimide radically polymerizable compound is a compound containing a maleimide group represented by the following formula (A-1) in the molecule. [ka]

[0027] The maleimide-based radical polymerizable compound is preferably any one of the following maleimide-based radical polymerizable compounds (A1) to (A3). The resin composition layer preferably contains at least one of the maleimide-based radical polymerizable compounds (A1) to (A3), more preferably contains a plurality of the maleimide-based radical polymerizable compounds (A1) to (A3), and further preferably contains all of the maleimide-based radical polymerizable compounds (A1) to (A3). (A1) A solid maleimide-based radical polymerizable compound. (A2) A liquid or semi-solid maleimide-based radical polymerizable compound. (A3) A maleimide-based radically polymerizable compound containing a skeleton in which an aromatic ring and an aliphatic hydrocarbon ring are condensed. However, the maleimide radical polymerizable compounds (A1) and (A2) exclude those that fall under the maleimide radical polymerizable compound (A3).

[0028] Here, the determination of liquid, semi-solid, and solid state is made in accordance with the "Method of Confirming Liquid State" in Appendix 2 of the Ministerial Ordinance on the Testing and Properties of Hazardous Materials (Ministry of Home Affairs Ordinance No. 1 of 1989). The specific determination method is as follows.

[0029] (1) Equipment Thermostatic water bath: Use a container equipped with an agitator, heater, thermometer, and automatic temperature controller (capable of controlling temperature to within ±0.1°C) and with a depth of 150 mm or more. In determining whether a substance is liquid, semi-solid, or solid, a combination of a low-temperature constant temperature water bath (model BU300) and an input type constant temperature device Thermomate (model BF500) manufactured by Yamato Scientific Co., Ltd. is used. Approximately 22 liters of tap water is placed into the low-temperature constant temperature water bath (model BU300), the Thermomate (model BF500) attached to it is turned on and set to the set temperature (20°C or 60°C), and the water temperature can be fine-tuned using the Thermomate (model BF500) to within ±0.1°C of the set temperature; however, any device capable of similar adjustments can be used.

[0030] Test tube: The test tubes used are cylindrical, flat-bottomed transparent glass tubes with an inner diameter of 30 mm and a height of 120 mm, as shown in Fig. 1, with marked lines 11A and 12B at heights of 55 mm and 85 mm from the bottom of the tube, respectively, and a test tube 10a for liquid determination, with the mouth of the test tube sealed with a rubber stopper 13a, and a test tube 10b for temperature measurement, with the mouth of the test tube sealed with a rubber stopper 13b of the same size and marked lines with a hole in the center for inserting and supporting a thermometer, and a thermometer 14 inserted into the rubber stopper 13b. Hereinafter, the marked line at a height of 55 mm from the bottom of the tube will be referred to as "line A", and the marked line at a height of 85 mm from the bottom of the tube will be referred to as "line B". As the thermometer 14, a thermometer for measuring the freezing point (SOP-58 scale range 0 to 100°C) as specified in JIS B7410 (1982) "Glass thermometer for testing petroleum products" is used, but any thermometer that can measure temperatures in the range of 0 to 100°C will do.

[0031] (2) Test procedure The sample that has been left for 24 hours or more under atmospheric pressure at a temperature of 60±5°C is poured into the liquid determination test tube 10a shown in Figure 1(a) and the temperature measurement test tube 10b shown in Figure 1(b) up to the 11A line. The two test tubes 10a and 10b are placed upright in a low-temperature constant temperature water bath so that the 12B line is below the water surface. The thermometer is placed so that its bottom end is 30 mm below the 11A line. After the sample temperature reaches the set temperature ±0.1° C., maintain the state for 10 minutes. After 10 minutes, remove the liquid state determination test tube 10a from the low-temperature constant temperature water bath and immediately lay it horizontally on a horizontal test table. Use a stopwatch to measure and record the time it takes for the tip of the liquid level in the test tube to move from line 11A to line 12B.

[0032] Similarly, for samples that have been left for 24 hours or more under atmospheric pressure at a temperature of 20±5°C, the test is carried out in the same manner as for samples that have been left for 24 hours or more under atmospheric pressure at a temperature of 60±5°C, and the time it takes for the tip of the liquid level in the test tube to move from line 11A to line 12B is measured and recorded with a stopwatch.

[0033] At 20°C, a liquid is determined to be in a state where the measurement time is within 90 seconds. A sample that has a measured time of more than 90 seconds at 20°C and 90 seconds or less at 60°C is judged to be semi-solid. At 60°C, a specimen that lasts for more than 90 seconds is considered to be solid.

[0034] The number of maleimide groups per molecule of a solid maleimide-based radically polymerizable compound is, from the viewpoint of significantly obtaining the desired effects of the present invention, preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and is preferably 10 or less, more preferably 6 or less, and particularly preferably 3 or less.

[0035] From the viewpoint of significantly obtaining the desired effects of the present invention, the solid maleimide-based radically polymerizable compound preferably has either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably has an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0036] The aliphatic hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, more preferably a divalent saturated aliphatic hydrocarbon group, and further preferably an alkylene group. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, further preferably an alkylene group having 1 to 3 carbon atoms, and particularly preferably a methylene group.

[0037] As the aromatic hydrocarbon group, monovalent and divalent aromatic hydrocarbon groups are preferred, and aryl and arylene groups are more preferred. As the arylene group, an arylene group having 6 to 30 carbon atoms is preferred, an arylene group having 6 to 20 carbon atoms is more preferred, and an arylene group having 6 to 10 carbon atoms is even more preferred. Examples of such an arylene group include a phenylene group, a naphthylene group, an anthracenylene group, an aralkyl group, a biphenylene group, and a biphenylaralkyl group, and among these, a phenylene group, an aralkyl group, a biphenylene group, and a biphenylaralkyl group are preferred, and a phenylene group, an aralkyl group, and a biphenylene group are even more preferred. As the aryl group, an aryl group having 6 to 30 carbon atoms is preferred, an aryl group having 6 to 20 carbon atoms is more preferred, an aryl group having 6 to 10 carbon atoms is even more preferred, and a phenyl group is particularly preferred.

[0038] In a solid maleimide-based radically polymerizable compound, from the viewpoint of significantly achieving the desired effects of the present invention, it is preferred that the nitrogen atom of the maleimide group is directly bonded to a monovalent or divalent aromatic hydrocarbon group, where "directly" means that there is no other group between the nitrogen atom of the maleimide group and the aromatic hydrocarbon group.

[0039] The solid maleimide radical polymerizable compound preferably has a structure represented by the following formula (A-2), for example. [ka] In formula (A-2), R 31 and R 36 represents a maleimide group, and R 32 , R 33, R 34 and R 35 each independently represents a hydrogen atom, an alkyl group, or an aryl group, and each D independently represents a divalent aromatic group. m1 and m2 each independently represent an integer of 1 to 10, and a represents an integer of 1 to 100.

[0040] R in formula (A-2) 32 , R 33 , R 34 and R 35 each independently represents a hydrogen atom, an alkyl group, or an aryl group, and is preferably a hydrogen atom.

[0041] 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 may be linear, branched, or cyclic. Examples of such alkyl groups include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an isopropyl group.

[0042] The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms. The aryl group may be a single ring or a condensed ring. Examples of such aryl groups include a phenyl group, a naphthyl group, and an anthracenyl group.

[0043] The alkyl group and the aryl group may have a substituent. The substituent is not particularly limited, and examples of the substituent include a halogen atom, -OH, -OC 1-6 Alkyl group, -N(C 1-10 Alkyl group) 2, C 1-20 Alkyl group, C 2-30 Alkenyl group, C 2-30 Alkynyl group, C 6-10 Aryl groups, -NH2, -CN, -C(O)OC 1-10 Examples of the alkyl group include alkyl groups, -COOH, -C(O)H, and -NO2. p-qThe term “(where p and q are positive integers satisfying p < q)” indicates that the number of carbon atoms in the organic group described immediately after this term is from p to q. For example, the expression “C 1-10 alkyl group” indicates an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure includes spiro rings and fused rings.

[0044] The above-mentioned substituents may further have a substituent (hereinafter sometimes referred to as a “secondary substituent”). As the secondary substituent, the same ones as the above-mentioned substituents may be used unless otherwise specified.

[0045] D in formula (A-2) represents a divalent aromatic group. Examples of the divalent aromatic group include a phenylene group, a naphthylene group, an anthracenylene group, an aralkyl group, a biphenylene group, a biphenylaralkyl group, etc. Among them, a biphenylene group and a biphenylaralkyl group are preferred, and a biphenylene group is more preferred. The divalent aromatic group may have a substituent. The substituents are the same as those that the alkyl group represented by R 32 in general formula (A-2) may have.

[0046] m1 and m2 each independently represent an integer from 1 to 10, preferably from 1 to 6, more preferably from 1 to 3, still more preferably from 1 to 2, and 1 is even more preferred.

[0047] a represents an integer from 1 to 100, preferably from 1 to 50, more preferably from 1 to 20, still more preferably from 1 to 5.

[0048] As the solid maleimide-based radically polymerizable compound, a resin represented by formula (A-3) is preferred.

Chemical formula

[0049] a1 is the same as a in formula (A-2), and the preferred range is also the same.

[0050] As the solid maleimide radical polymerizable compound, a commercially available product can be used, for example, "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.

[0051] The liquid or semi-solid maleimide radical polymerizable compound is preferably a maleimide compound having at least one maleimide group in the molecule and including an aliphatic group having 5 or more carbon atoms which may have a substituent. The liquid or semi-solid maleimide radical polymerizable compound can be obtained, for example, by imidization reaction of a component including an aliphatic amine compound (such as a diamine compound having a dimer acid skeleton), maleic anhydride, and, if necessary, tetracarboxylic dianhydride.

[0052] The aliphatic group having 5 or more carbon atoms may be monovalent, divalent, or trivalent or more. The aliphatic group having 5 or more carbon atoms may be a saturated aliphatic group or an unsaturated aliphatic group. Examples of the aliphatic group having 5 or more carbon atoms include an alkyl group, an alkylene group, and an alkenylene group. The liquid or semi-solid maleimide radical polymerizable compound is preferably a maleimide compound containing at least one hydrocarbon group selected from the group consisting of an alkyl group having 5 or more carbon atoms which may have a substituent, an alkylene group having 5 or more carbon atoms which may have a substituent, and an alkenylene group having 5 or more carbon atoms which may have a substituent. For example, the liquid or semi-solid maleimide radical polymerizable compound is preferably a maleimide compound containing at least one hydrocarbon group selected from the group consisting of an alkyl group having 5 or more carbon atoms which may have a substituent, and an alkylene group having 5 or more carbon atoms which may have a substituent. In addition, the liquid or semi-solid maleimide-based radically polymerizable compound is preferably a maleimide compound containing at least one hydrocarbon group selected from the group consisting of an alkyl group having 5 or more carbon atoms which may have a substituent, and an alkenylene group having 5 or more carbon atoms which may have a substituent.

[0053] The number of carbon atoms in the aliphatic group is usually 5 or more. From the viewpoint of obtaining the effect of the present invention remarkably, the number of carbon atoms in the aliphatic group is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. In this specification, when a group contains a substituent, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the group, unless otherwise specified. Therefore, when an aliphatic group having 5 or more carbon atoms contains a substituent, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the aliphatic group having 5 or more carbon atoms, unless otherwise specified.

[0054] The number of carbon atoms of the alkyl group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. The alkyl group may be linear, branched, or cyclic, and linear is preferred. Examples of such alkyl groups include pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. The alkyl group having 5 or more carbon atoms may be used as a substituent of an alkylene group having 5 or more carbon atoms and an alkenylene group having 5 or more carbon atoms.

[0055] The number of carbon atoms of the alkylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. The alkylene group may be linear, branched, or cyclic, and linear is preferable. Here, the cyclic alkylene group is not only a narrow definition consisting of only cyclic alkylene groups, but also a broad definition including both linear and cyclic alkylene groups. Examples of such alkylene groups include pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, heptadecylene, hexatriacontylene, groups having an octylene-cyclohexylene structure, groups having an octylene-cyclohexylene-octylene structure, groups having a propylene-cyclohexylene-octylene structure, and the like.

[0056] The number of carbon atoms in the alkenylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. The alkenylene group may be linear, branched, or cyclic, and linear is preferred. Here, the cyclic alkenylene group refers to a concept including a case where the alkenylene group is composed only of a cyclic alkenylene group and a case where the alkenylene group contains both a linear alkenylene group and a cyclic alkenylene group. Examples of such alkenylene groups include a pentynylene group, a hexynylene group, a heptylenylene group, an octynylene group, a nonynylene group, a decynylene group, an undecynylene group, a dodecynylene group, a tridecynylene group, a heptadecynylene group, a hexatriacontinylene group, a group having an octynylene-cyclohexynylene structure, a group having an octynylene-cyclohexynylene-octynylene structure, and a group having a propynylene-cyclohexynylene-octynylene structure.

[0057] In a liquid or semi-solid maleimide radically polymerizable compound, the aliphatic group having 5 or more carbon atoms is preferably directly bonded to the nitrogen atom of the maleimide group, where "directly" means that there is no other group between the nitrogen atom of the maleimide group and the aliphatic group.

[0058] From the viewpoint of achieving the effects of the present invention remarkably, the liquid or semi-solid maleimide-based radically polymerizable compound preferably contains two or more aliphatic groups having 5 or more carbon atoms.

[0059] Aliphatic groups having 5 or more carbon atoms may be bonded to each other to form a ring, and the ring structure includes a spiro ring and a condensed ring. Examples of the ring formed by bonding to each other include a cyclohexane ring.

[0060] The aliphatic group having 5 or more carbon atoms may or may not have a substituent. The substituent is, for example, R 32 The substituents are the same as those that the alkyl group represented by the formula (I) may have.

[0061] The liquid or semi-solid maleimide radical polymerizable compound preferably contains an aromatic ring in the molecule. Therefore, the liquid or semi-solid maleimide radical polymerizable compound is preferably a maleimide compound containing an aliphatic group having 5 or more carbon atoms and an aromatic ring, which may have a substituent. The aromatic ring may be a monocyclic aromatic ring, or a condensed aromatic ring in which two or more monocyclic aromatic rings are condensed. Examples of these aromatic rings include monocyclic aromatic rings such as a benzene ring and a pyridine ring; and condensed aromatic rings such as an indane ring, a fluorene ring, and a naphthalene ring. Among them, the aromatic ring is preferably an aromatic carbon ring. The number of carbon atoms in the aromatic carbon ring is preferably 6 or more and 10 or less.

[0062] The number of maleimide groups per molecule of a liquid or semi-solid maleimide radically polymerizable compound may be 1, but is preferably 2 or more, and is preferably 10 or less, more preferably 6 or less, and particularly preferably 3 or less. By using a liquid or semi-solid maleimide radically polymerizable compound having 2 or more maleimide groups per molecule, the effects of the present invention can be significantly obtained.

[0063] From the viewpoint of achieving the remarkable effects of the present invention, the liquid or semi-solid maleimide-based radically polymerizable compound is preferably a maleimide compound represented by the following general formula (A-4). [ka] In formula (A-4), R represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and L represents a single bond or a divalent linking group.

[0064] R in the general formula (A-4) represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. The number of carbon atoms of the divalent aliphatic group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. This divalent aliphatic group may be linear, branched, or cyclic, and linear is preferred. Here, the concept of a cyclic divalent aliphatic group includes a case where the group is composed of only a cyclic aliphatic group and a case where the group contains both a linear aliphatic group and a cyclic aliphatic group. Examples of the divalent aliphatic group include an alkylene group and an alkenylene group. The alkylene group and the alkenylene group are as described above.

[0065] The substituent of R is R in the general formula (A-2). 32 The substituents are the same as those that the alkyl group represented by the formula (I) may have.

[0066] In formula (A-4), L represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -C(=O)-, -C(=O)-O-, -NR 0 -(R 0 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom, or C(=O)NR 0 -, a divalent group derived from phthalimide, a divalent group derived from pyromellitic diimide, and a group consisting of a combination of two or more of these divalent groups. The alkylene group, alkenylene group, alkynylene group, arylene group, divalent group derived from phthalimide, divalent group derived from pyromellitic diimide, and a group consisting of a combination of two or more of these divalent groups may have an alkyl group having 5 or more carbon atoms as a substituent. The divalent group derived from phthalimide represents a divalent group derived from phthalimide, and a specific example thereof is a group represented by the general formula (A-5). The divalent group derived from pyromellitic diimide represents a divalent group derived from pyromellitic diimide, and a specific example thereof is a group represented by the general formula (A-6). In the formula, "*" represents a bond. [ka]

[0067] The alkylene group as the divalent linking group in L 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 may be linear, branched, or cyclic. Examples of such alkylene groups include a methylethylene group (2-propylene group), a cyclohexylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecylene group, a hexatriacontylene group, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure.

[0068] The alkenylene group as the divalent linking group in L in general formula (A-4) is preferably an alkenylene group having 2 to 50 carbon atoms, more preferably an alkenylene group having 2 to 45 carbon atoms, and particularly preferably an alkenylene group having 2 to 40 carbon atoms. This alkenylene group may be linear, branched, or cyclic. Examples of such alkenylene groups include a methylethylenylene group (2-propenylene group), a cyclohexenylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, a nonenylene group, a decenylene group, an undecenylene group, a dodecenylene group, a tridecenylene group, a heptadecenylene group, a hexatriacontenylene group, a group having an octynylene-cyclohexynylene structure, a group having an octynylene-cyclohexynylene-octynylene structure, and a group having a propynylene-cyclohexynylene-octynylene structure.

[0069] The alkynylene group as the divalent linking group in L in general formula (A-4) is preferably an alkynylene group having 2 to 50 carbon atoms, more preferably an alkynylene group having 2 to 45 carbon atoms, and particularly preferably an alkynylene group having 2 to 40 carbon atoms. This alkynylene group may be linear, branched, or cyclic. Examples of such alkynylene groups include 2-propynylene, cyclohexynylene, pentynylene, hexynylene, heptynylene, octynylene, nonynylene, decynylene, undecynylene, dodecynylene, tridecynylene, heptadecynylene, hexatriacontinylene, groups having an octynylene-cyclohexynylene structure, groups having an octynylene-cyclohexynylene-octynylene structure, and groups having a propynylene-cyclohexynylene-octynylene structure.

[0070] The arylene group as the divalent linking group in L in general formula (A-4) is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, still more preferably an arylene group having 6 to 14 carbon atoms, and even more preferably an arylene group having 6 to 10 carbon atoms. Examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.

[0071] The alkylene group, alkenylene group, alkynylene group, and arylene group, which are the divalent linking groups in L in the general formula (A-4), may have a substituent. 32 The substituents are the same as those that the alkyl group represented by the formula (I) may have, and are preferably alkyl groups having 5 or more carbon atoms.

[0072] Examples of the group consisting of a combination of two or more divalent groups in L in the general formula (A-4) include a divalent group consisting of a combination of an alkylene group, a divalent group derived from phthalimide, and an oxygen atom; a divalent group consisting of a combination of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a divalent group consisting of a combination of a divalent group derived from an alkylene group and a divalent group derived from pyromellitic diimide; a divalent group consisting of a combination of an alkynylene group, a divalent group derived from phthalimide, and an oxygen atom; a divalent group consisting of a combination of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkynylene group; a divalent group consisting of a combination of a divalent group derived from an alkynylene group and a divalent group derived from pyromellitic diimide; and the like. The group consisting of a combination of two or more divalent groups may form a ring such as a condensed ring by the combination of the respective groups. In addition, the group consisting of a combination of two or more divalent groups may be a repeating unit having a repeating unit number of 1 to 10.

[0073] Among them, L in general formula (A-4) is preferably an oxygen atom, an arylene group having 6 to 24 carbon atoms which may have a substituent, an alkylene group having 1 to 50 carbon atoms which may have a substituent, an alkynylene group having 1 to 50 carbon atoms which may have a substituent, an alkenylene group having 1 to 50 carbon atoms which may have a substituent, a divalent group derived from phthalimide, a divalent group derived from pyromellitic diimide, or a divalent group consisting of a combination of two or more of these groups. Among these, L is preferably an alkylene group; a divalent group having a structure of an alkylene group-phthalimide-derived divalent group-oxygen atom-phthalimide-derived divalent group; a divalent group having a structure of an alkylene group-phthalimide-derived divalent group-oxygen atom-arylene group-alkylene group-arylene group-oxygen atom-phthalimide-derived divalent group; a divalent group having a structure of an alkylene-pyromellitic diimide-derived divalent group; an alkenyl group; a divalent group having a structure of an alkenyl group-phthalimide-derived divalent group-oxygen atom-phthalimide-derived divalent group; an alkenyl group-phthalimide-derived divalent group-oxygen atom -A divalent group having the structure of a divalent group derived from an arylene group-alkenylene group-arylene group-oxygen atom-phthalimide; a divalent group having the structure of a divalent group derived from an alkylene-pyromellitic diimide; a divalent group having the structure of a divalent group derived from an alkynylene group-phthalimide-oxygen atom-phthalimide; a divalent group having the structure of a divalent group derived from an alkynylene group-phthalimide-oxygen atom-arylene group-alkynylene group-arylene group-oxygen atom-phthalimide; a divalent group having the structure of a divalent group derived from an alkynylene-pyromellitic diimide is more preferred.

[0074] The maleimide compound represented by general formula (A-4) is preferably a maleimide compound represented by general formula (A-7). [ka] In general formula (A-7), R 100each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, each A independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent or a divalent group having an aromatic ring which may have a substituent, and n represents an integer of 1 to 10.

[0075] R in general formula (A-7) 100 R each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. 1 is the same as R in general formula (A-4).

[0076] In general formula (A-7), A each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, or a divalent group having an aromatic ring which may have a substituent. Examples of the divalent aliphatic group in A include an alkylene group and an alkenylene group. The divalent aliphatic group in A may be any of linear, branched, and cyclic, and among these, a cyclic divalent aliphatic group having 5 or more carbon atoms which may have a substituent is preferred.

[0077] The number of carbon atoms in the alkylene group is preferably 6 or more, more preferably 8 or more, and 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.

[0078] The number of carbon atoms in the alkenylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. The alkenylene group may be linear, branched, or cyclic, and linear is preferred. Here, the cyclic alkenylene group refers to a concept including a case where the alkenylene group is composed only of a cyclic alkenylene group and a case where the alkenylene group contains both a linear alkenylene group and a cyclic alkenylene group. Examples of such alkenylene groups include a pentynylene group, a hexynylene group, a heptylenylene group, an octynylene group, a nonenylene group, a decynylene group, an undecynylene group, a dodecynylene group, a tridecynylene group, a heptadecynylene group, a hexatriacontinylene group, a group having an octynylene-cyclohexynylene structure, a group having an octynylene-cyclohexynylene-octynylene structure, and a group having a propynylene-cyclohexynylene-octynylene structure.

[0079] Examples of the aromatic ring in the divalent group having an aromatic ring represented by A include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic diimide ring, and an aromatic heterocycle, and the like are mentioned, with a benzene ring, a phthalimide ring, and a pyromellitic diimide ring being preferred. That is, the divalent group having an aromatic ring is preferably a divalent group having a benzene ring which may have a substituent, a divalent group having a phthalimide ring which may have a substituent, or a divalent group having a pyromellitic diimide ring which may have a substituent. Examples of the divalent group having an aromatic ring include a group consisting of a combination of a divalent group derived from phthalimide and an oxygen atom; a group consisting of a combination of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; a divalent group derived from pyromellitic diimide; a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group; and the like. The above arylene group is the same as the arylene group in the divalent linking group represented by L in general formula (2).

[0080] The divalent aliphatic group and the divalent group having an aromatic ring represented by A in the general formula (A-7) may have a substituent. 32 The substituents are the same as those that the alkyl group represented by the formula (I) may have.

[0081] Among these, A in the general formula (A-7) preferably represents a cyclic alkylene group having 5 or more carbon atoms which may have a substituent; a divalent group having a benzene ring which may have a substituent; a divalent group having a phthalimide ring which may have a substituent; or a divalent group having a pyromellitic diimide ring which may have a substituent.

[0082] Specific examples of the group represented by A in the general formula (A-7) include the following groups: In the formula, "*" represents a bond. [ka] [ka]

[0083] The maleimide compound represented by general formula (A-4) is preferably any one of a maleimide compound represented by general formula (A-8) and a maleimide compound represented by general formula (A-9). [ka] In general formula (A-8), R 2a and R 3a each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, R 10a each independently represents an oxygen atom, an arylene group, an alkylene group, an alkenylene group, or a divalent group consisting of a combination of two or more of these groups. n1 represents an integer of 1 to 10. In general formula (A-9), R 4a , R 6a and R 7a each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, R5a each independently represents a divalent group having an aromatic ring which may have a substituent; R 11a and R 12a each independently represents an alkyl group having 5 or more carbon atoms. t2 represents an integer of 0 to 10, and m1 and m2 each independently represent an integer of 0 to 4.

[0084] R in general formula (A-8) 2a and R 3a R each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. 2a and R 3a is the same as the divalent aliphatic group having 5 or more carbon atoms represented by R in general formula (A-4), and a hexatriacontinylene group or a hexatriacontylene group is preferred.

[0085] R in general formula (A-8) 10a R each independently represents an oxygen atom, an arylene group, an alkylene group, an alkenylene group, or a group consisting of a combination of two or more of these divalent groups. The arylene group, alkylene group, and alkenylene group are the same as the arylene group, alkylene group, and alkenylene group in the divalent linking group represented by L in general formula (A-4). 10a is preferably an oxygen atom or a group formed from a combination of two or more divalent groups.

[0086] R in general formula (A-8) 10a In the formula, examples of the group consisting of a combination of two or more divalent groups include a combination of an oxygen atom, an arylene group, and an alkylene group. Specific examples of the group consisting of a combination of two or more divalent groups include the following groups. In the formula, "*" represents a bond. [ka]

[0087] R in general formula (A-9) 4a , R 6a and R 7aR each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. 4a , R 6a and R 7a is the same as the divalent aliphatic group having 5 or more carbon atoms which may have a substituent represented by R in general formula (A-4), and is preferably a hexylene group, a heptylene group, an octylene group, a nonylene group, or a decylene group, and more preferably an octylene group.

[0088] R in general formula (A-9) 5a R each independently represents a divalent group having an aromatic ring which may have a substituent. 5a is the same as the divalent group having an aromatic ring which may have a substituent represented by A in the general formula (A-7), and is preferably a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group, and more preferably a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide. The alkylene group is the same as the arylene group and alkylene group in the divalent linking group represented by L in the general formula (A-4).

[0089] R in general formula (A-9) 5a Specific examples of the group represented by the formula include the following groups: In the formula, "*" represents a bond. [ka]

[0090] R in general formula (A-9) 11a and R 12a R each independently represents an alkyl group having 5 or more carbon atoms. 11a and R 12a is the same as the above-mentioned alkyl group having 5 or more carbon atoms, and is preferably a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group, and more preferably a hexyl group or an octyl group.

[0091] In formula (A-9), m1 and m2 each independently represent an integer of 1 to 15, and an integer of 1 to 10 is preferable.

[0092] Specific examples of the liquid or semi-solid maleimide radical polymerizable compound include the following compounds (A-10) to (A-13). However, the liquid or semi-solid maleimide radical polymerizable compound is not limited to these specific examples. In the formula, a represents an integer of 1 to 10. [ka] [ka]

[0093] Commercially available liquid or semi-solid maleimide radical polymerizable compounds can be used. Specific examples of liquid or semi-solid maleimide radical polymerizable compounds include "BMI1500" (compound of formula (A-10)), "BMI1700" (compound of formula (A-11)), "BMI3000J", "BMI3000" (compound of formula (A-12)), and "BMI689" (compound of formula (A-13)) manufactured by Designer Molecules.

[0094] Examples of the skeleton of an aromatic ring and an aliphatic hydrocarbon ring condensed in a maleimide-based radical polymerizable compound (hereinafter sometimes referred to as "component (3)") include an indane skeleton, a trimethylindane skeleton, a tetralin skeleton, a benzocyclobutene skeleton, and an indene skeleton, but from the viewpoint of obtaining the effects of the present invention more significantly, a trimethylindane skeleton is preferable. Therefore, component (3) is preferably a maleimide compound containing a trimethylindane skeleton. The trimethylindane skeleton represents a skeleton represented by the following formula (A-14). [ka]

[0095] The benzene ring contained in the trimethylindane skeleton may have a substituent bonded thereto, for example, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a halogen atom, a hydroxyl group, and a mercapto group. The number of carbon atoms in the alkyl group is preferably 1 to 10. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a t-butyl group. The number of carbon atoms in the alkyloxy group is preferably 1 to 10. Examples of the alkyloxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The number of carbon atoms in the alkylthio group is preferably 1 to 10. Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, and a butylthio group. The number of carbon atoms in the aryl group is preferably 6 to 10. Examples of the aryl group include a phenyl group and a naphthyl group. The number of carbon atoms in the aryloxy group is preferably 6 to 10. Examples of the aryloxy group include a phenyloxy group and a naphthyloxy group. The number of carbon atoms in the arylthio group is preferably 6 to 10. Examples of the arylthio group include a phenylthio group and a naphthylthio group. The number of carbon atoms in the cycloalkyl group is preferably 3 to 10. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and an iodine atom.

[0096] Of the above-mentioned substituents, the hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group and cycloalkyl group may be substituted with halogen atoms.

[0097] The number of substituents bonded to one benzene ring contained in the trimethylindane skeleton may be 1 or 2 or more. The number of substituents bonded to a benzene ring contained in the trimethylindane skeleton is usually 0 to 3. When the number of substituents is 2 or more, the 2 or more substituents may be the same or different. In particular, it is preferable that no substituents are bonded to the benzene ring contained in the trimethylindane skeleton.

[0098] The number of trimethylindane structures contained in one molecule of the component (3) may be 1, or may be 2 or more. The upper limit can be, for example, 10 or less, 8 or less, 7 or less, or 6 or less.

[0099] The component (3) preferably further contains an aromatic ring skeleton in addition to the above-mentioned trimethylindane skeleton. The number of ring-constituting carbon atoms of the aromatic ring skeleton is preferably 6 to 10. Examples of aromatic ring skeletons include a benzene ring skeleton and a naphthalene ring skeleton. The number of the aromatic ring skeletons contained in one molecule of the component (3) is preferably 1 or more, more preferably 2 or more, and preferably 6 or less, more preferably 4 or less, and particularly preferably 3 or less. When the component (3) contains two or more aromatic ring skeletons in addition to the trimethylindane skeleton, the aromatic ring skeletons may be the same or different.

[0100] The aromatic ring contained in the aromatic ring skeleton may have a substituent bonded thereto. Examples of the substituent include the above-mentioned substituents that may be bonded to the benzene ring contained in the trimethylindane skeleton, and a nitro group. The number of substituents bonded to one aromatic ring may be 1 or 2 or more. The number of substituents bonded to an aromatic ring is usually 0 to 4. When the number of substituents is 2 or more, the 2 or more substituents may be the same or different.

[0101] The component (3) preferably further contains a divalent aliphatic hydrocarbon group in addition to the above-mentioned trimethylindane skeleton. In particular, when the component (3) contains an aromatic ring skeleton other than the benzene ring contained in the trimethylindane skeleton, the component (3) preferably contains a divalent aliphatic hydrocarbon group. In this case, the divalent aliphatic hydrocarbon group preferably connects between the benzene ring and the aromatic ring skeleton contained in the trimethylindane skeleton. In addition, the divalent aliphatic hydrocarbon group preferably connects between the aromatic ring skeletons.

[0102] 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 the divalent aliphatic hydrocarbon group, an alkylene group as a saturated aliphatic hydrocarbon group is more preferable. As the divalent aliphatic hydrocarbon group, linear alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group; branched alkylene groups such as ethylidene group (-CH(CH3)-), propylidene group (-CH(CH2CH3)-), isopropylidene group (-C(CH3)2-), ethylmethylmethylene group (-C(CH3)(CH2CH3)-), and diethylmethylene group (-C(CH2CH3)2-); and the like. (C-2b) When the maleimide compound containing a trimethylindane skeleton 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.

[0103] The component (3) preferably contains a structure represented by the following formula (A-15): The entire component (3) may have the structure represented by formula (A-15), or a portion of the component (3) may have the structure represented by formula (A-15). [ka]

[0104] (In the formula, Ar a1 represents a divalent aromatic hydrocarbon group which may have a substituent; R a1each 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 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; R a3 each independently represents a divalent aliphatic hydrocarbon group; a1 represents a positive integer; n a2 each independently represents an integer of 0 to 4; a3 R each independently represents an integer of 0 to 3. a1 The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group of R may be substituted with halogen atoms. a2 The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with halogen atoms. a2 If is between 2 and 4, R a1 may be the same or different in the same ring. a3 If is 2-3, R a2 may be the same or different in the same ring.

[0105] In formula (A-15), Ar a1represents a divalent aromatic hydrocarbon group which may have a substituent. The number of carbon atoms in this divalent aromatic hydrocarbon group is preferably 6 or more, preferably 20 or less, more preferably 16 or less. Examples of the divalent aromatic hydrocarbon group include a phenylene group and a naphthylene group. Examples of the substituent that the divalent aromatic hydrocarbon group may have include 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, and a mercapto group. The hydrogen atom of each substituent may be further substituted with a halogen atom. Specific examples of these substituents include the same examples as the substituents which may be bonded to the benzene ring contained in the trimethylindane skeleton. When the divalent aromatic hydrocarbon group has a substituent, the number of the substituents is preferably 1 to 4. When the divalent aromatic hydrocarbon group has two or more substituents, the two or more substituents may be the same or different. a1 is preferably an unsubstituted divalent aromatic hydrocarbon group.

[0106] In formula (A-15), R a1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group. The hydrogen atoms of the alkyl group, the alkyloxy group, the alkylthio group, the aryl group, the aryloxy group, the arylthio group, and the cycloalkyl group may be substituted with a halogen atom. Specific examples of these groups include the same examples as the substituents that can be bonded to the benzene ring contained in the trimethylindane skeleton. Among them, R a1is more preferably one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms, and is particularly preferably an alkyl group having 1 to 4 carbon atoms.

[0107] In formula (A-15), R a2 each 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 group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with a halogen atom. Specific examples of these groups include the same examples as the substituents that can be bonded to the benzene ring contained in the trimethylindane skeleton. Among them, R a2 is more preferably one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

[0108] In formula (A-15), R a3 each independently represents a divalent aliphatic hydrocarbon group. The preferred range of the divalent aliphatic hydrocarbon group is as described above.

[0109] In formula (A-15), n a1 represents a positive integer. a1 is preferably 1 or more, and preferably 10 or less, more preferably 8 or less.

[0110] In formula (A-15), n a2 Each independently represents an integer of 0 to 4. a2 is preferably 2 or 3, more preferably 2. a2 may be different, but are preferably the same. a2If is 2 or more, multiple R a1 may be the same or different within the same ring.

[0111] In formula (A-15), n a3 Each independently represents an integer of 0 to 3. a3 may be different, but are preferably the same. a3 is preferably 0.

[0112] It is particularly preferable that the component (3) contains a structure represented by the following formula (A-16): The entire component (3) may have the structure represented by formula (A-16), or a portion of the component (3) may have the structure represented by formula (A-16). [ka] (In the formula, R b1 each 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 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; b1 represents a positive integer; n b2 each independently represents an integer of 0 to 4; b3 R each independently represents an integer of 0 to 3. b1 The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group of R may be substituted with halogen atoms. b2The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with halogen atoms. b2 If is between 2 and 4, R b1 may be the same or different in the same ring. b3 If is 2-3, R b2 may be the same or different in the same ring.

[0113] In formula (A-16), R b1 , R b2 , n b1 , n b2 and n b3 are R in formula (A-15), a1 , R a2 , n a1 , n a2 and n a3 is the same as:

[0114] The component (3) may further contain a structure represented by the following formula (A-17). [ka] In formula (A-17), R c1 , R c2 , n c2 and n c3 are R in formula (A-15), a1 , R a2 , n a2 and n a3 In addition, in formula (A-17), n c1 is the number of repeating units and is an integer of 1 to 20. Furthermore, in formula (A-17), * represents a bond. For example, the component (3) is a compound represented by formula (A-15), a2 is 3 or less, and R is present at two or more of the ortho and para positions relative to the maleimide group of the benzene ring to which the maleimide group is bonded. a1 When no bond is bonded, the structure represented by formula (A-15) may be combined with the structure represented by formula (A-17).b2 is 3 or less, and R is present at two or more of the ortho and para positions relative to the maleimide group of the benzene ring to which the maleimide group is bonded. b1 When is not bonded, the structure represented by formula (A-16) may include the structure represented by formula (A-17) in combination with the structure represented by formula (A-16).

[0115] (3) The component may be used alone or in any combination of two or more kinds in any ratio.

[0116] The method for producing component (3) is not particularly limited. Component (3) can be produced, for example, by the method described in Japan Institute of Invention and Innovation's Technical Journal No. 2020-500211. According to the production method described in Japan Institute of Invention and Innovation's Technical Journal No. 2020-500211, a maleimide compound having a distribution in the number of repeating units of the trimethylindane skeleton can be obtained. The maleimide compound obtained by this method contains a structure represented by the following formula (A-18). Therefore, component (3) may contain a maleimide compound containing a structure represented by formula (A-18). [ka] (In the formula, R 1 each 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 2 each 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; n1 represents the average number of repeating units of 0.95 to 10.0; each independently represents an integer of 0 to 4; and each independently represents an integer of 0 to 3. R1 The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group of R may be substituted with halogen atoms. 2 The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with halogen atoms. 1 may be the same or different in the same ring. When n3 is 2 to 3, R 2 may be the same or different in the same ring.

[0117] In formula (A-18), R 1 , R 2 , n2 and n3 are R in formula (A-15), a1 , R a2 , n a2 and n a3 is the same as:

[0118] In formula (A-18), n1 represents the average number of repeating units, and its range is 0.95 to 10.0. According to the manufacturing method described in the Japan Institute of Invention and Innovation Disclosure Technical Bulletin No. 2020-500211, a group of maleimide compounds containing a structure represented by 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 be smaller than 1.00, the maleimide compound containing the structure represented by formula (A-18) thus obtained can contain a maleimide compound having a trimethylindane skeleton repeating unit number of 0. Therefore, the maleimide compound containing the structure represented by formula (A-18) can be purified to obtain component (3) by removing the maleimide compound having a trimethylindane skeleton repeating unit number of 0, and the resin composition layer may contain only the obtained component (3). However, even if the maleimide compound having a trimethylindane skeleton repeating unit number of 0 is contained in the resin composition layer, the effect of the present invention can be obtained. In addition, when purification is omitted, it is possible to suppress costs. Therefore, it is preferable that the resin composition layer contains a maleimide compound containing a structure represented by formula (A-18), without excluding any maleimide compound having a trimethylindane skeleton with zero repeating units.

[0119] 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, and is preferably 10.0 or less, more preferably 8.0 or less, even more preferably 7.0 or less, particularly preferably 6.0 or less. When the average number of repeating units n1 is within the above 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.

[0120] Examples of the structure represented by formula (A-18) include the following: [ka]

[0121] The maleimide compound containing the structure represented by formula (A-18) may further contain the structure represented by formula (A-17) above. For example, the maleimide compound containing the structure represented by formula (A-18) is a compound in which n2 is 3 or less and R is present at two or more of the ortho and para positions relative to the maleimide group of the benzene ring to which the maleimide group is bonded. 1 When is not bonded, the structure represented by formula (A-18) may include a structure represented by formula (A-17) in combination.

[0122] The maleimide compound containing the structure represented by formula (A-18) preferably has a molecular weight distribution Mw / Mn calculated by gel permeation chromatography (GPC) measurement in a specific range. The molecular weight distribution is a value obtained by dividing the weight average molecular weight Mw by the number average molecular weight Mn, and is expressed as "Mw / Mn". Specifically, the molecular weight distribution Mw / Mn of the maleimide compound containing the structure represented by formula (A-18) is preferably 1.0 to 4.0, more preferably 1.1 to 3.8, even more preferably 1.2 to 3.6, and particularly preferably 1.3 to 3.4. When the molecular weight distribution Mw / Mn of the maleimide compound containing the structure represented by formula (A-18) is in the above range, the effects of the present invention can be significantly obtained.

[0123] Of the maleimide compounds containing a structure represented by formula (A-18), the amount of the maleimide compound having an average repeating unit number n1 of 0 is preferably within a specific range. When the GPC measurement of the maleimide compound containing a structure represented by formula (A-18) is performed, the amount of the maleimide compound having an average repeating unit number n1 of 0 can be expressed in area % based on the results of the GPC measurement. In detail, the amount of the maleimide compound having an average repeating unit number n1 of 0 can be expressed by the ratio (area %) of the peak area of ​​the maleimide compound containing a structure represented by formula (A-18) to the total area of ​​the peaks of the maleimide compound containing a structure represented by formula (A-18) in the chromatogram obtained by the GPC measurement. Specifically, the amount of the maleimide compound having an average repeating unit number n1 of 0 is preferably 32 area % or less, more preferably 30 area % or less, and even more preferably 28 area % or less, relative to the total amount of the maleimide compound containing a structure represented by formula (A-18) (100 area %). When the amount of the maleimide compound having an average repeating unit number n1 of 0 is within the above range, the effects of the present invention can be significantly obtained.

[0124] The maleimide group equivalent of the maleimide radical polymerizable compound is preferably 50 g / eq or more, more preferably 100 g / eq or more, even more preferably 120 g / eq or more, 200 g / eq or more, and preferably 10,000 g / eq or less, more preferably 9,000 g / eq or less, even more preferably 8,000 g / eq or less, 2,000 g / eq or less, 1,000 g / eq or less, 800 g / eq or less. The maleimide group equivalent is the mass of the maleimide radical polymerizable compound containing one equivalent of maleimide group.

[0125] The weight average molecular weight (Mw) of the maleimide radically polymerizable compound is preferably 150 to 16,000, and more preferably 200 to 15,000.

[0126] From the viewpoint of obtaining the remarkable effects of the present invention, the molecular weight of the maleimide-based radically polymerizable compound is preferably 200 or more, more preferably 300 or more, and even more preferably 400 or more, and is preferably 100,000 or less, more preferably 80,000 or less, and even more preferably 60,000 or less.

[0127] The vinylphenyl radical polymerizable compound is a radical polymerizable compound having a vinylphenyl group. The vinylphenyl radical polymerizable compound is preferably liquid or semi-solid. The liquid or semi-solid state is determined as described above. The vinylphenyl group is a group having the structure shown below. [ka]

[0128] From the viewpoint of obtaining a cured product having excellent dielectric properties, the vinylphenyl radical polymerizable compound preferably has two or more vinylphenyl groups per molecule.

[0129] From the viewpoint of obtaining a cured product having excellent dielectric properties, the vinyl phenyl radical polymerizable compound preferably has a cyclic structure. The cyclic structure is preferably a divalent cyclic group. The divalent cyclic group may be either a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. In addition, the compound may have a plurality of divalent cyclic groups.

[0130] From the viewpoint of significantly obtaining the desired effects of the present invention, the divalent cyclic group is preferably a 3-membered or larger ring, more preferably a 4-membered or larger ring, and even more preferably a 5-membered or larger ring, and is preferably a 20-membered or smaller ring, more preferably a 15-membered or smaller ring, and even more preferably a 10-membered or smaller ring. In addition, the divalent cyclic group may be a monocyclic structure or a polycyclic structure.

[0131] The ring in the divalent cyclic group may have a ring skeleton constituted by a heteroatom other than carbon atoms. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom, and an oxygen atom is preferred. The ring may have one or more heteroatoms.

[0132] Specific examples of the divalent cyclic group include the following divalent groups (a) and (b). [ka] (In the divalent groups (a) and (b), R 51 , R 52 , R 55 , R 56 , R 57 , R 61 , and R 62 each independently represents a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group; R 53 , R 54 , R 58 , R 59 , and R 60 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.

[0133] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Examples of alkyl groups having 6 or less carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups, with methyl being preferred. 51 , R 52 , R 55 , R 56 , R 57 , R 61 , and R 62 R preferably represents a methyl group. 53 , R 54 , R 58 , R 59 , and R 60 is preferably a hydrogen atom or a methyl group.

[0134] In addition, the divalent cyclic group may be a combination of a plurality of divalent cyclic groups. Specific examples of the combination of divalent cyclic groups include the divalent cyclic groups represented by the following formula (A-19). [ka] (In the formula, R 71 , R 72 , R 75 , R 76 , R 77 , R 81 , R 82 , R 85 and R 86 each independently represents a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group; R 73 , R 74 , R 78 , R 79 , R 80 , R 83 and R 84 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. d1 and d2 each represent an integer of 0 to 300, except for the case where one of d1 and d2 is 0.

[0135] R 71 , R 72 , R 85 and R 86 is R in formula (a). 510 is the same as R 73 , R 74 , R 83 and R 84 is R in formula (a). 530 is the same as R 75 , R 76 , R 77 , R 81 , and R 82 is R in formula (b). 550 is the same as R 78 , R 79 , and R 80 is R in formula (b). 580 is the same as:

[0136] d1 and d2 represent an integer of 0 to 300, except when one of d1 and d2 is 0. d1 and d2 preferably represent an integer of 1 to 100, more preferably an integer of 1 to 50, and even more preferably an integer of 1 to 10. d1 and d2 may be the same or different.

[0137] The divalent cyclic group may have a substituent, such as a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, or an oxo group, and an alkyl group is preferred.

[0138] The vinylphenyl group may be directly bonded to the divalent cyclic group, or may be bonded via a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, and the like, and may be a group in which a plurality of these are combined. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms or an alkylene group having 1 to 4 carbon atoms. The alkylene group may be linear, branched, or cyclic. Examples of such alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, and 1,1-dimethylethylene groups, and are preferably methylene, ethylene, or 1,1-dimethylethylene. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferred, an alkenylene group having 2 to 6 carbon atoms is more preferred, and an alkenylene group having 2 to 5 carbon atoms is even more preferred. As the arylene group or heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferred, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferred. As the divalent linking group, an alkylene group is preferred, and among them, a methylene group is preferred.

[0139] The vinylphenyl radical polymerizable compound is preferably represented by the following formula (A-20). [ka] (In the formula, R 91 and R 92 each independently represents a divalent linking group. Ring A1 represents a divalent cyclic group.

[0140] R 91 and R 92 each independently represents a divalent linking group. The divalent linking group is the same as the divalent linking group described above.

[0141] Ring A1 represents a divalent cyclic group. Ring B is the same as the above divalent cyclic group.

[0142] Ring A1 may have a substituent. The substituent is the same as the substituent that the above divalent cyclic group may have.

[0143] Specific examples of the vinylphenyl radical polymerizable compound are shown below, but the present invention is not limited thereto. [ka] (q1 is the same as d1 in formula (A-19), and q2 is the same as d2 in formula (A-19).)

[0144] The vinylphenyl radical polymerizable compound may be a commercially available product, such as "OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd. The vinylphenyl radical polymerizable compound may be used alone or in combination of two or more kinds.

[0145] From the viewpoint of significantly obtaining the desired effects of the present invention, the number average molecular weight of the vinylphenyl radical polymerizable compound is preferably 3000 or less, more preferably 2500 or less, even more preferably 2000 or less, or 1500 or less. The lower limit is preferably 100 or more, more preferably 300 or more, even more preferably 500 or more, or 1000 or more. The number average molecular weight is a polystyrene-equivalent number average molecular weight measured using gel permeation chromatography (GPC).

[0146] The (meth)acrylic radical polymerizable compound is a compound including an acryloyl group, a methacryloyl group, and a combination thereof. In order to significantly obtain the desired effects of the present invention, the (meth)acrylic radical polymerizable compound preferably has two or more (meth)acryloyl groups per molecule. The term "(meth)acryloyl group" includes an acryloyl group, a methacryloyl group, and a combination thereof.

[0147] The (meth)acrylic radical polymerizable compound preferably has a cyclic structure from the viewpoint of significantly obtaining the desired effect of the present invention. The cyclic structure is preferably a divalent cyclic group. The divalent cyclic group may be either a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. Among them, from the viewpoint of significantly obtaining the desired effect of the present invention, a cyclic group containing an alicyclic structure is preferable.

[0148] From the viewpoint of significantly obtaining the desired effects of the present invention, the divalent cyclic group is preferably a 3-membered or larger ring, more preferably a 4-membered or larger ring, and even more preferably a 5-membered or larger ring, and is preferably a 20-membered or smaller ring, more preferably a 15-membered or smaller ring, and even more preferably a 10-membered or smaller ring. In addition, the divalent cyclic group may be a monocyclic structure or a polycyclic structure.

[0149] The ring in the divalent cyclic group may have a ring skeleton constituted by a heteroatom other than carbon atoms. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom, and an oxygen atom is preferred. The ring may have one or more heteroatoms.

[0150] Specific examples of the divalent cyclic group include the following divalent groups (i) to (xi). Among them, the divalent cyclic group is preferably (x) or (xi). [ka]

[0151] The divalent cyclic group may have a substituent, such as a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, or an oxo group, and an alkyl group is preferred.

[0152] The (meth)acryloyl group may be directly bonded to the divalent cyclic group, or may be bonded via a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, and the like, and may be a group in which a plurality of these are combined. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms or an alkylene group having 1 to 4 carbon atoms. The alkylene group may be linear, branched, or cyclic. Examples of such alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, and 1,1-dimethylethylene groups, and are preferably methylene, ethylene, or 1,1-dimethylethylene. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferred, an alkenylene group having 2 to 6 carbon atoms is more preferred, and an alkenylene group having 2 to 5 carbon atoms is even more preferred. As the arylene group or heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferred, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferred. As the divalent linking group, an alkylene group is preferred, and among them, a methylene group or a 1,1-dimethylethylene group is preferred.

[0153] The (meth)acrylic radically polymerizable compound is preferably represented by the following formula (A-21). [ka] (In the formula, R 101 and R 104 each independently represents an acryloyl group or a methacryloyl group, R 102 and R 103 each independently represents a divalent linking group. Ring A2 represents a divalent cyclic group.

[0154] R 101 and R 104each independently represents an acryloyl group or a methacryloyl group, and an acryloyl group is preferred.

[0155] R 102 and R 103 each independently represents a divalent linking group. The divalent linking group is the same as the divalent linking group which may have a (meth)acryloyl group bonded thereto.

[0156] Ring A2 represents a divalent cyclic group. Ring A2 is the same as the divalent cyclic group. Ring A2 may have a substituent. The substituent is the same as the substituent that the divalent cyclic group may have.

[0157] Specific examples of the (meth)acrylic radically polymerizable compound include the following, but the present invention is not limited thereto. [ka]

[0158] The (meth)acrylic radical polymerizable compound may be a commercially available product, and examples thereof include "A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" manufactured by Kyoeisha Chemical Co., Ltd., "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", and "DPHA" manufactured by Nippon Kayaku Co., Ltd., and "NK Ester DCP" manufactured by Shin-Nakamura Chemical Co., Ltd.

[0159] From the viewpoint of significantly obtaining the desired effects of the present invention, the (meth)acryloyl group equivalent of the (meth)acrylic radical polymerizable compound is preferably 30 g / eq. to 400 g / eq., more preferably 50 g / eq. to 300 g / eq., and further preferably 75 g / eq. to 200 g / eq. The (meth)acryloyl group equivalent is the mass of the (meth)acrylic radical polymerizable compound containing one equivalent of a (meth)acryloyl group.

[0160] The allyl radical polymerizable compound is a compound having at least one allyl group in the molecule. The allyl radical polymerizable compound preferably has one or more allyl groups per molecule, more preferably has two or more allyl groups. The lower limit is not particularly limited, but it is preferably 10 or less, more preferably 5 or less.

[0161] In addition, from the viewpoint of significantly obtaining the desired effects of the present invention, the allyl-based radical polymerizable compound preferably has, in addition to the allyl group, any one of a benzoxazine ring, a phenol ring, an isocyanuric ring, an epoxy group, and a carboxylic acid derivative having a cyclic structure.

[0162] The allyl radically polymerizable compound having a benzoxazine ring is preferably bonded to either the nitrogen atom of the benzoxazine ring or the benzene ring, and more preferably bonded to the nitrogen atom.

[0163] Examples of the allyl radical polymerizable compound having a phenol ring include a cresol resin containing an allyl group, a novolac type phenol resin containing an allyl group, and a cresol novolac resin containing an allyl group.

[0164] In the allyl radical polymerizable compound having an isocyanuric structure, the nitrogen atom of the isocyanuric structure and the allyl group are preferably directly bonded to each other. Examples of the allyl radical polymerizable compound having an isocyanuric structure include allyl isocyanurate, diallyl isocyanurate, and triallyl isocyanurate.

[0165] The allyl radical polymerizable compound having an epoxy group preferably contains two or more epoxy groups in one molecule. The allyl radical polymerizable compound having an epoxy group preferably has an aromatic structure, and when two or more allyl radical polymerizable compounds having an epoxy group are used, it is more preferable that at least one of them has an aromatic structure. The aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatic rings and aromatic heterocycles. The allyl radical polymerizable compound having an epoxy group preferably has a bisphenol structure, and examples of the bisphenol structure include bisphenol A type, bisphenol F type, and bisphenol AF type.

[0166] The allyl radical polymerizable compound having a carboxylic acid derivative with a cyclic structure is preferably an allyl carboxylate with a cyclic structure. The cyclic structure may be either a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. In addition, the cyclic group may have a ring skeleton formed by heteroatoms other than carbon atoms. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom, and the nitrogen atom is preferred. The ring may have one or more heteroatoms.

[0167] Examples of carboxylic acids having a cyclic structure include isocyanuric acid, diphenic acid, phthalic acid, cyclohexanedicarboxylic acid, etc. Examples of allyl radical polymerizable compounds having a carboxylic acid derivative having a cyclic structure include allyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate, diallyl diphenate, allyl diphenate, ortho-diallyl phthalate, meth-diallyl phthalate, para-diallyl phthalate, allyl cyclohexanedicarboxylate, diallyl cyclohexanedicarboxylate, etc.

[0168] The allyl radical polymerizable compound may be a commercially available product. Examples of commercially available products include "MEH-8000H" and "MEH-8005" (allyl radical polymerizable compound having a phenol ring) manufactured by Meiwa Kasei Co., Ltd.; "RE-810NM" (allyl radical polymerizable compound having an epoxy group) manufactured by Nippon Kayaku Co., Ltd.; "ALP-d" (allyl radical polymerizable compound having a benzoxazine ring) manufactured by Shikoku Kasei Kogyo Co., Ltd.; "L-DAIC" (allyl radical polymerizable compound having an isocyanuric ring) manufactured by Shikoku Kasei Kogyo Co., Ltd.; "TAIC" (allyl radical polymerizable compound having an isocyanuric ring (triallyl isocyanurate) manufactured by Nippon Kasei Co., Ltd.; "MDAC" (allyl radical polymerizable compound having a cyclohexanedicarboxylic acid derivative) manufactured by Osaka Soda Co., Ltd.; "DAD" (diallyl diphenate) manufactured by Nissho Techno Fine Chemical Co., Ltd.; and "Daiso DAP Monomer" (ortho-diallyl phthalate) manufactured by Osaka Soda Co., Ltd.

[0169] From the viewpoint of significantly obtaining the desired effects of the present invention, the allyl group equivalent of the allyl radical polymerizable compound is preferably 20 g / eq. to 1000 g / eq., more preferably 50 g / eq. to 500 g / eq., and further preferably 100 g / eq. to 300 g / eq. The allyl group equivalent is the mass of the allyl radical polymerizable compound containing one equivalent of an allyl group.

[0170] The butadiene radical polymerizable compound is a compound having at least one butadiene skeleton in the molecule. The polybutadiene structure may be included in the main chain or in the side chain. The polybutadiene structure may be partially or entirely hydrogenated. As the butadiene radical polymerizable compound, one or more resins selected from the group consisting of hydrogenated polybutadiene skeleton-containing resin, hydroxyl group-containing butadiene resin, phenolic hydroxyl group-containing butadiene resin, carboxyl group-containing butadiene resin, acid anhydride group-containing butadiene resin, epoxy group-containing butadiene resin, isocyanate group-containing butadiene resin, and urethane group-containing butadiene resin are more preferable.

[0171] Specific examples of the butadiene-based radical polymerizable compound include "JP-100" manufactured by Nippon Soda Co., Ltd., and "Ricon100", "Ricon150", "Ricon130MA8", "Ricon130MA13", "Ricon130MA20", "Ricon131MA5", "Ricon131MA10", "Ricon131MA17", "Ricon131MA20", and "Ricon 184MA6" manufactured by CRAY VALLEY.

[0172] From the viewpoint of obtaining a cured product with excellent dielectric properties, the content of component (A) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, and is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, assuming that the non-volatile components in the resin composition layer are 100% by mass.

[0173] -(B)Thermoplastic resin- The resin composition layer may further contain a thermoplastic resin as a component (B) as an optional component in addition to the component (A). By including the component (B) in the resin composition layer, it is possible to obtain a cured product exhibiting better mechanical strength. The component (B) may be used alone or in combination of two or more kinds.

[0174] From the viewpoint of obtaining a cured product with excellent dielectric properties, the weight average molecular weight (Mw) of component (B) is preferably at least 5000, more preferably at least 8000, particularly preferably at least 10000, and is preferably at most 100000, more preferably at most 80000, particularly preferably at most 50000. The weight average molecular weight of component (B) is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

[0175] As the (B) component, those having 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, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, and polyester resins; and elastomers. Among them, from the viewpoint of obtaining a cured product having excellent dielectric properties, it is preferable that the (B) component is at least one selected from polyimide resins and elastomers.

[0176] The polyimide resin may be a resin having an imide bond in the repeating unit, and generally includes a polyimide resin obtained by an imidization reaction between a diamine compound and an acid anhydride.

[0177] The diamine compound for preparing the polyimide resin is not particularly limited, but examples thereof include aliphatic diamine compounds and aromatic diamine compounds.

[0178] Examples of the aliphatic diamine compound 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 dimer acid diamines (hereinafter also referred to as "dimer diamines"). Among these, dimer acid diamines are preferred.

[0179] The dimer acid type diamine means a diamine compound obtained by substituting two terminal carboxylic acid groups (-COOH) of a dimer acid with an aminomethyl group (-CH2-NH2) or an amino group (-NH2). Dimer acid is a known compound obtained by dimerizing an unsaturated fatty acid (preferably one having 11 to 22 carbon atoms, particularly preferably one having 18 carbon atoms), and its industrial production process is almost standardized in the industry. Dimer acid is easily obtained, mainly consisting of a dimer acid having 36 carbon atoms obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms, such as oleic acid and linoleic acid, which are particularly inexpensive and easily available. In addition, dimer acid may contain any amount of monomer acid, trimer acid, other polymerized fatty acid, etc., depending on the production method, degree of purification, etc. In addition, although double bonds remain after the polymerization reaction of unsaturated fatty acid, in this specification, hydrogenated products in which the degree of unsaturation is reduced by further hydrogenation reaction are also included in dimer acid. Dimer acid type diamines are commercially available, for example, "PRIAMINE 1073", "PRIAMINE 1074", and "PRIAMINE 1075" manufactured by Croda Japan; "VERSAMINE 551" and "VERSAMINE 552" manufactured by Cognis Japan; and the like.

[0180] Examples of the aromatic diamine compound include a phenylenediamine compound, a naphthalenediamine compound, and a dianiline compound.

[0181] The phenylenediamine compound means a compound consisting of a benzene ring having two amino groups, and the benzene ring here may have 1 to 3 optional substituents. Examples of the substituents include R 32 The substituents are the same as those that may be possessed by the alkyl group represented by the formula (1). Specific examples of the phenylenediamine compound 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.

[0182] The naphthalene diamine compound means a compound consisting of a naphthalene ring having two amino groups, and the naphthalene ring here may have 1 to 3 optional substituents. The substituents include R 32 The substituents are the same as those that may be possessed by the alkyl group represented by the formula: Specific examples of the naphthalene diamine compound include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, and 2,3-diaminonaphthalene.

[0183] The dianiline compound means a compound containing two aniline structures in the molecule, and each of the two benzene rings in the two aniline structures may further have 1 to 3 optional substituents. Examples of the substituents include R 32 The two aniline structures in the dianiline compound may be bonded via a direct bond and / or one or two linker structures having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. The dianiline compound also includes one in which two aniline structures are bonded via two bonds.

[0184] Specific examples of the "linker structure" in a dianiline compound include -NHCO-, -CONH-, -OCO-, -COO-, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH(CH3)-, -C(CH3)2-, -C(CF3)2-, -CH=CH-, -O-, -S-, -CO-, and -SO2-. , -NH-, -Ph-, -Ph-Ph-, -C(CH3)2-Ph-C(CH3)2-, -O-Ph-O-, -O-Ph-Ph-O-, -O-Ph-SO2-Ph-O-, -O-Ph-C(CH3)2-Ph-O-, -Ph-CO-O-Ph-, -C(CH3)2-Ph-C(CH3)2-, groups represented by the following formulas (I) and (II), and groups consisting of combinations thereof. In this specification, "Ph" represents a 1,4-phenylene group, a 1,3-phenylene group, or a 1,2-phenylene group.

[0185] [ka]

[0186] In one embodiment, the dianiline compound specifically includes 4,4'-diamino-2,2'-ditrifluoromethyl-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-aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropylidene)dianiline, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, α,α-biphenyl, ... α,α-bis[4-(4-aminophenoxy)phenyl]-1,3-diisopropylbenzene, α,α-bis[4-(4-aminophenoxy)phenyl]-1,4-diisopropylbenzene, 4,4'-(9-fluorenylidene)dianiline, 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 Examples of such fluorenes include 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl)fluorene, and 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindan, and preferably 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindan.

[0187] In another embodiment, the dianiline compound may, for example, be a diamine compound represented by the following formula (B-1).

[0188] [ka] (In formula (B-1), R 1 ~R 8 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X 9 -R 9 , or -X 10 -R 10 R 1 ~R 8 At least one of the -X 10 -R 10 and 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 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group; X 10 each independently represents a single bond, -(substituted or unsubstituted alkylene group), -NH-, -O-, -S-, -CO-, -SO2-, -NHCO-, -CONH-, -OCO-, or -COO-; R 10 each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0189] R in formula (B-1) 9 and R 9’ The alkyl group represented by refers to a linear, branched, or cyclic monovalent aliphatic saturated hydrocarbon group. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a cyclopentyl group, and a cyclohexyl group.

[0190] R in formula (B-1) 9 and R 9’ The alkenyl group represented by refers to a linear, branched or cyclic monovalent unsaturated hydrocarbon group having at least one carbon-carbon double bond. The alkenyl group is preferably an alkenyl group having 2 to 6 carbon atoms, more preferably an alkenyl group having 2 or 3 carbon atoms. Examples of such an alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 3-methyl-2-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 4-methyl-3-pentenyl group, a 1-hexenyl group, a 3-hexenyl group, a 5-hexenyl group, and a 2-cyclohexenyl group. The substituent of the alkenyl group in the "substituted or unsubstituted alkenyl group" is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group, an aryl group, a heteroaryl group, an amino group, a nitro group, a hydroxy group, a carboxy group, a sulfo group, etc. The number of the substituents is preferably 1 to 3, and more preferably 1.

[0191] The substituent of the alkyl group in the "substituted or unsubstituted alkyl group" and the substituent of the alkenyl group in the "substituted or unsubstituted alkenyl group" are not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group, an amino group, a nitro group, a hydroxy group, a carboxy group, a sulfo group, etc. The number of the substituents is preferably 1 to 3, and more preferably 1.

[0192] An alkoxy group refers to a monovalent group (alkyl-O-) formed by bonding an alkyl group to an oxygen atom. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms. Examples of such an alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and a pentyloxy group.

[0193] X in formula (B-1) 10 The alkylene group represented by refers to a linear, branched or cyclic divalent aliphatic saturated hydrocarbon group, preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group 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-, and the like. The substituent of the alkylene group in the "substituted or unsubstituted alkylene group" is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group, an aryl group, a heteroaryl group, an amino group, a nitro group, a hydroxy group, a carboxy group, a sulfo group, etc. The number of the substituents is preferably 1 to 3, and more preferably 1.

[0194] R in formula (B-1) 10 The aryl group represented by is preferably an aryl group having 6 to 14 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. Examples of such aryl groups include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group, and preferably a phenyl group. The substituent of the aryl group in the "substituted or unsubstituted aryl group" is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, an amino group, a nitro group, a hydroxy group, a carboxy group, and a sulfo group. The number of substituents is preferably 1 to 3, and more preferably 1.

[0195] R in formula (B-1) 10The heteroaryl group represented by the formula (I) is an aromatic heterocyclic group having 1 to 4 heteroatoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom. The heteroaryl group is preferably 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 a furyl group, a thienyl group, a pyrrolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, a pyrazolyl group, a 1,2,3-oxadiazolyl group, a 1,2,4-oxadiazolyl group, a 1,3,4-oxadiazolyl group, a furazanyl group, a 1,2,3-thiadiazolyl group, a 1,2,4-thiadiazolyl group, a 1,3,4-thiadiazolyl group, a 1,2,3-triazolyl group, a 1,2,4-triazolyl group, a tetrazolyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, etc. The substituents of the heteroaryl group in the "substituted or unsubstituted heteroaryl group" are the same as the substituents of the aryl group in the "substituted or unsubstituted aryl group".

[0196] R 1 ~R 8 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X 9 -R 9 , or -X 10 -R 10 R 1 ~R 8 are preferably each independently a hydrogen atom or -X 10 -R 10 It is.

[0197] R 1 ~R 8 At least one of the following is -X 10 -R 10 Preferably, R 1 ~R 8 One or two of the following are -X 10 -R 10 and more preferably, R 5 ~R 8 One or two of the following are -X 10 -R 10and more preferably, R 5 and R 7 One or two of the following are -X 10 -R 10 It is.

[0198] In one embodiment, preferably, R 1 ~R 8 One or two of the following are -X 10 -R 10 and R 1 ~R 8 The other is a hydrogen atom, and more preferably, R 5 ~R 8 One or two of the following are -X 10 -R 10 and R 1 ~R 8 The other is preferably a hydrogen atom, and more preferably R 5 and R 7 One or two of the following are -X 10 -R 10 and R 1 ~R 8 The rest are hydrogen atoms.

[0199] 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 of X independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group. 9 is preferably a single bond.

[0200] R 9’ R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. 9 is preferably a substituted or unsubstituted alkyl group.

[0201] X 10each independently represents a single bond, -(substituted or unsubstituted alkylene group), -NH-, -O-, -S-, -CO-, -SO2-, -NHCO-, -CONH-, -OCO-, or -COO-. X 10 is preferably a single bond.

[0202] R 10 R each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. 10 is preferably a substituted or unsubstituted aryl group.

[0203] In one embodiment, the diamine compound represented by formula (B-1) is preferably a compound represented by the following formula (B-2), and more preferably a compound represented by the following formula (B-3) (5-amino-1,1'-biphenyl-2-yl 4-aminobenzoate). [ka] (In the formula, R 1 ~R 6 and R 8 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X 9 -R 9 and the other symbols are the same as in formula (B-1). [ka]

[0204] The diamine compound may be a commercially available product or may be synthesized by a known method. For example, the diamine compound represented by formula (B-1) may be synthesized by the synthesis method described in Japanese Patent No. 6240798 or a method equivalent thereto. The diamine compound may be used alone or in combination of two or more kinds.

[0205] The acid anhydride for preparing the polyimide resin is not particularly limited, but in a preferred embodiment, it is an aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic dianhydride include benzenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, anthracenetetracarboxylic dianhydride, and diphthalic dianhydride, and diphthalic dianhydride is preferred.

[0206] Benzenetetracarboxylic dianhydride means a dianhydride of benzene having four carboxy groups, and further, the benzene ring here may have 1 to 3 optional substituents. Here, the substituents include halogen atoms, cyano groups, and -X 13 -R 13 (The same definition as in the following formula (B-4)) is preferable. Specific examples of the benzenetetracarboxylic dianhydride include pyromellitic dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride.

[0207] Naphthalenetetracarboxylic dianhydride means a dianhydride of naphthalene having four carboxy groups, and further, the naphthalene ring here may have 1 to 3 optional substituents, where the substituents are halogen atoms, cyano groups, and -X 13 -R 13 (The same definition as in the following formula (B-4)) is preferable. Specific examples of the naphthalenetetracarboxylic dianhydride include 1,4,5,8-naphthalenetetracarboxylic dianhydride and 2,3,6,7-naphthalenetetracarboxylic dianhydride.

[0208] Anthracenetetracarboxylic dianhydride means a dianhydride of anthracene having four carboxy groups, and further, the anthracene ring here may have 1 to 3 optional substituents. Here, the substituents include halogen atoms, cyano groups, and -X 13 -R 13(The same definition as in the following formula (B-4)) is preferable. Specific examples of the anthracenetetracarboxylic dianhydride include 2,3,6,7-anthracenetetracarboxylic dianhydride.

[0209] Diphthalic dianhydride means a compound containing two phthalic anhydrides in the molecule, and further, each of the two benzene rings in the two phthalic anhydrides may have one to three optional substituents. Here, the substituents include halogen atoms, cyano groups, and -X 13 -R 13 (The same definition as in the following formula (B-4)) is preferable. Two phthalic anhydrides in the diphthalic dianhydride can be bonded directly or via a linker structure having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms.

[0210] An example of the diphthalic dianhydride is a compound represented by the formula (B-4). [ka] (In the formula, R 11 and R 12 each independently represents a halogen atom, a cyano group, a nitro group, or -X 13 -R 13 indicates, X 13 each independently represents a single bond, -NR 13’ -, -O-, -S-, -CO-, -SO2-, -NR 13’ CO-, -CONR 13’ -, -OCO-, or -COO-; R 13 each independently represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, R 13’ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, Y represents a single bond or a linker structure having 1 to 100 skeletal atoms selected from a carbon atom, an oxygen atom, a sulfur atom, and a nitrogen atom, n1 and m1 each independently represent an integer of 0 to 3.

[0211] Y is preferably a linker structure having 1 to 100 skeletal atoms selected from a carbon atom, an oxygen atom, a sulfur atom, and a nitrogen atom. n1 and m1 are preferably 0.

[0212] The "linker structure" in Y has 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. The "linker structure" is preferably -[A-Ph] a -A-[Ph-A] b - (wherein, each A independently represents a single bond, -(substituted or unsubstituted alkylene group)-, -O-, -S-, -CO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-, and each a and b independently represents an integer of 0 to 2 (preferably 0 or 1).) is a divalent group represented by the formula.

[0213] Specific examples of the "linker structure" for 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-, and the like.

[0214] Specific examples of diphthalic dianhydride 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, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl sulfone tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethynylidene-4,4'-diphthalic Acid dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenyl)benzene dianhydride 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic dianhydride, and the like.

[0215] The aromatic tetracarboxylic dianhydride may be a commercially available product, or may be synthesized by a known method or a method similar thereto. The aromatic tetracarboxylic dianhydride may be used alone or in combination of two or more kinds.

[0216] In one embodiment, the acid anhydride for preparing the polyimide resin may include other acid anhydrides in addition to the aromatic tetracarboxylic dianhydride.

[0217] Specific examples of other acid anhydrides include aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic acid dianhydride, cyclohexane-1,2,3,4-tetracarboxylic acid dianhydride, cyclohexane-1,2,4,5-tetracarboxylic acid dianhydride, 3,3',4,4'-bicyclohexyl tetracarboxylic acid dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-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.

[0218] The content of structures derived from aromatic tetracarboxylic dianhydrides in all structures derived from acid anhydrides constituting 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 %.

[0219] The polyimide resin preferably has a structural unit represented by the following general formula (B). [ka] (In general formula (B), R 51 represents a single bond or a residue derived from an acid anhydride, R 52 represents a single bond or a residue derived from a diamine compound.

[0220] R 51 R represents a single bond or a residue derived from an acid anhydride, and is preferably a residue derived from an acid anhydride. 51The residue derived from an acid anhydride represented by the formula (I) refers to a divalent group obtained by removing two oxygen atoms from an acid anhydride. The acid anhydride is as described above.

[0221] R 52 R represents a single bond or a residue derived from a diamine compound, and is preferably a residue derived from a diamine compound. 52 The residue derived from a diamine compound represented by the formula (I) refers to a divalent group obtained by removing two amino groups from a diamine compound. The diamine compound is as described above.

[0222] The polyimide resin can be prepared by a conventional method. For example, a method of heating a mixture of a diamine compound, an acid anhydride and a solvent to react them is mentioned. The amount of the diamine compound to be mixed can be, for example, usually 0.5 to 1.5 molar equivalents, preferably 0.9 to 1.1 molar equivalents, relative to the acid anhydride.

[0223] Examples of the solvent used in the preparation of the polyimide resin include amide-based solvents such as N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone; ketone-based solvents such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; ester-based solvents such as γ-butyrolactone; and hydrocarbon-based solvents such as cyclohexane and methylcyclohexane. In addition, in the preparation of the polyimide resin, an imidization catalyst, an azeotropic dehydrating solvent, an acid catalyst, and the like may be used as necessary. Examples of the imidization catalyst include tertiary amines such as triethylamine, triisopropylamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, N,N-dimethyl-4-aminopyridine, and pyridine. Examples of the azeotropic dehydrating solvent include toluene, xylene, and ethylcyclohexane. Examples of the acid catalyst include acetic anhydride. The amounts of the imidization catalyst, the azeotropic dehydrating solvent, and the acid catalyst can be appropriately set by those skilled in the art. The reaction temperature for preparing the polyimide resin is usually 100 to 250°C.

[0224] Examples of the phenoxy resin include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin is preferably a phenoxy resin having a weight average molecular weight of 30,000 or more.

[0225] Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both of which are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", and "YL7482" manufactured by Mitsubishi Chemical Corporation.

[0226] The 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 a polyamide-imide resin having an alicyclic structure in the molecular structure, a polyamide-imide resin having a siloxane structure described in JP-A-05-112760, a polyamide-imide resin having a bulky branched chain structure, a polyamide-imide resin made from an asymmetric monomer, a polyamide-imide resin having a multi-branched structure, or the like.

[0227] Among these, from the viewpoint that the polyamideimide resin has an isocyanuric ring structure, which improves compatibility and dispersibility with resin varnish, (i) polyamideimide resins having an isocyanuric ring structure in their molecular structure (i.e., polyamideimide resins having an isocyanuric ring structure and an imide skeleton or an amide skeleton), (ii) polyamideimide resins having an isocyanuric ring structure and an alicyclic structure in their molecular structure (i.e., polyamideimide resins having an isocyanuric ring structure, an alicyclic structure, and an imide skeleton or an amide skeleton), and (iii) polyamideimide resins having repeating units containing an isocyanuric ring structure and an alicyclic structure (i.e., polyamideimide resins having repeating units containing an isocyanuric ring structure, an alicyclic structure, and an imide skeleton or an amide skeleton).

[0228] A preferred embodiment of the polyamide-imide resins (i) to (iii) includes (1) a carboxylic acid group-containing branched polyamide-imide obtained by reacting an isocyanuric ring-containing polyisocyanate compound derived from an alicyclic diisocyanate with an acid anhydride of a polycarboxylic acid having three or more carboxyl groups (hereinafter, the compound may be referred to as "(compound B-b1)"); (2) a carboxylic acid group-containing branched polymerizable polyamide-imide obtained by reacting compound (B-b1) with a compound having one epoxy group and one or more radically polymerizable unsaturated groups (hereinafter, the compound may be referred to as "compound (B-b2)"); or (3) a carboxylic acid group-containing branched polymerizable polyamide-imide obtained by reacting a compound having one hydroxyl group and one or more radically polymerizable unsaturated groups with a remaining isocyanate group in the synthesis process of compound (B-b1) (hereinafter, the compound may be referred to as "compound (B-b3)").

[0229] Specific examples of the compound (B-b1) include compounds represented by the following general formula (I): The repeating unit in the compound represented by the general formula (I) is referred to as repeating unit (I-1). [ka] (In the formula, w represents 0 to 15.)

[0230] An example of the compound (B-b2) is a compound (II) having a structure (I-2) in which GMA (glycidyl methacrylate) is added to any part of the carboxyl groups and / or terminal carboxyl groups of the repeating unit (I-1) in the general formula (I). [ka] (In the formula, R 40 represents a residue in formula (I).

[0231] The ratio of GMA modification of carboxyl groups is preferably 0.3 mol% or more, more preferably 0.5 mol% or more, even more preferably 0.7 mol% or more, or 0.9 mol% or more, based on the moles of carboxyl groups of compound (B-b1). The upper limit is preferably 50 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, or 20 mol% or less.

[0232] An example of the compound (B-b3) is a compound (III) having a structure (I-3) in which any part of the repeating unit (I-1) and / or the terminal imide group in the above formula (I) is an isocyanate residue to which a hydroxyl group of pentaerythritol triacrylate is added. [ka] (In the formula, R' represents a residue in formula (I).)

[0233] The amount of pentaerythritol triacrylate added is preferably 40 mol% or less, more preferably 38 mol% or less, and even more preferably 35 mol% or less, based on the number of moles of isocyanate groups in the polyisocyanate at the time of charging. On the other hand, from the viewpoint of fully obtaining the effect of the addition, the amount of pentaerythritol triacrylate added is preferably 0.3 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, based on the number of moles of isocyanate groups in the polyisocyanate at the time of charging.

[0234] The polyamide-imide resin can be synthesized by various known methods. For the synthesis method of the polyamide-imide resin, for example, the description in paragraphs 0020 to 0030 of WO 2010 / 074197 can be referred to, the contents of which are incorporated herein by reference.

[0235] The polyamide-imide resin may be a commercially available product, such as modified polyamide-imide such as "UNIDIC V-8000" manufactured by DIC Corporation, "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo Co., Ltd., and "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imide) manufactured by Hitachi Chemical Co., Ltd.

[0236] From the viewpoint of compatibility with other components in the resin composition layer, the polyester resin preferably has a fluorene structure in its molecular structure, and preferably has, in addition to the fluorene structure, a structural unit derived from a diol and a structural unit derived from a dicarboxylic acid.

[0237] A specific example of the polyester resin is "OKP4HT" manufactured by Osaka Gas Chemicals Co., Ltd.

[0238] Specific examples of polysulfone resins include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0239] Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of polyvinyl acetal resins include S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

[0240] A specific example of the polyethersulfone resin is "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0241] The elastomer in component (B) is a resin having flexibility, preferably a resin having rubber elasticity or a resin exhibiting rubber elasticity by polymerization with other components. Examples of rubber elasticity include resins exhibiting an elastic modulus of 1 GPa or less when a tensile test is performed at a temperature of 25°C and a humidity of 40% RH according to the Japanese Industrial Standards (JIS K7161). Elastomers are usually amorphous resin components that can be dissolved in organic solvents. The elastomer (e) may be used alone or in combination of two or more types in any ratio.

[0242] In one embodiment, the elastomer is preferably a resin having, in the molecule, one or more structures selected from a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, a polycarbonate structure, and a polystyrene structure. "(Meth)acrylate" refers to methacrylate and acrylate.

[0243] In another embodiment, the elastomer is preferably one or more selected from a resin having a glass transition temperature (Tg) of 25° C. or less and a resin that is liquid at 25° C. or less. The glass transition temperature of the resin having a glass transition temperature (Tg) of 25° C. or less is preferably 20° C. or less, more preferably 15° C. or less. The lower limit of the glass transition temperature is not particularly limited, but can usually be −15° C. or more. The resin that is liquid at 25° C. is preferably a resin that is liquid at 20° C. or less, more preferably a resin that is liquid at 15° C. or less. The glass transition temperature can be measured by DSC (differential scanning calorimetry).

[0244] The elastomer may be, for example, a resin containing a polybutadiene structure. The polybutadiene structure may be contained in the main chain or in the side chain. The polybutadiene structure may be partially or entirely hydrogenated. A resin containing a polybutadiene structure may be called a "polybutadiene resin." 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 an acid anhydride group) manufactured by Cray Valley Corporation; "GQ-1000" (polybutadiene having hydroxyl groups and carboxyl groups introduced therein), "G-1000", "G-2000", and "G-3000" (polybutadiene having hydroxyl groups at both ends), "GI-1000", "GI-2000", and "GI-3000" (polybutadiene having hydrogenated hydroxyl groups at both ends) manufactured by Nippon Soda Co., Ltd.; and "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin) manufactured by Nagase ChemteX Corporation. Specific examples of polybutadiene resins include hydroxyl-terminated polybutadiene, linear polyimides made from diisocyanate compounds and tetrabasic acid anhydrides (polyimides described in JP 2006-37083 A and WO 2008 / 153208 A), and phenolic hydroxyl-containing butadiene. The content of the butadiene structure in the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. For details of the polyimide resin, refer to the descriptions in JP 2006-37083 A and WO 2008 / 153208 A, the contents of which are incorporated herein by reference.

[0245] Examples of elastomers include resins containing a poly(meth)acrylate structure. Resins containing a poly(meth)acrylate structure are sometimes called "poly(meth)acrylic resins." Specific examples of poly(meth)acrylic resins include Teisan Resin manufactured by Nagase ChemteX Corporation, and ME-2000, W-116.3, W-197C, KG-25, and KG-3000 manufactured by Negami Chemical Industries, Ltd.

[0246] Examples of elastomers include resins containing a polycarbonate structure. Resins containing a polycarbonate structure are sometimes called "polycarbonate resins". Examples of such resins include carbonate resins that do not have a reactive group, hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, urethane group-containing carbonate resins, and epoxy group-containing carbonate resins. The reactive group here refers to a functional group that can react with other components, such as a hydroxyl group, a phenolic hydroxyl group, a carboxyl group, an acid anhydride group, an isocyanate group, a urethane group, and an epoxy group. Specific examples of polycarbonate resins include "FPC0220" and "FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Chemicals Corporation, and "C-1090", "C-2090", and "C-3090" (polycarbonate diols) manufactured by Kuraray Co., Ltd. In addition, linear polyimides made from hydroxyl-terminated polycarbonate, diisocyanate compounds, and tetrabasic acid anhydrides can also be used. The content of the carbonate structure in the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. For details of the polyimide resin, refer to the description in International Publication No. 2016 / 129541, the contents of which are incorporated herein by reference.

[0247] Examples of elastomers include resins containing a polysiloxane structure. Resins containing a polysiloxane structure are sometimes called "siloxane resins." Specific examples of siloxane resins include "SMP-2006," "SMP-2003PGMEA," and "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd., and linear polyimides made from amine-terminated polysiloxanes and tetrabasic acid anhydrides (see International Publication No. 2010 / 053185, JP 2002-12667 A, JP 2000-319386 A, etc.).

[0248] Examples of the elastomer include resins containing a polyalkylene structure or a polyalkyleneoxy structure. A resin containing a polyalkylene structure may be referred to as an "alkylene resin". A resin containing a polyalkyleneoxy structure may be referred to as an "alkyleneoxy resin". The polyalkyleneoxy structure is preferably a polyalkyleneoxy structure having 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure having 3 to 10 carbon atoms, and particularly preferably a polyalkyleneoxy structure having 5 to 6 carbon atoms. Specific examples of the alkylene resin and the alkyleneoxy resin include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers Corporation.

[0249] Examples of elastomers include resins containing a polyisoprene structure. Resins containing a polyisoprene structure are sometimes called "isoprene resins." Specific examples of isoprene resins include "KL-610" and "KL613" manufactured by Kuraray Co., Ltd.

[0250] Examples of elastomers include resins containing a polyisobutylene structure. Resins containing a polyisobutylene structure are sometimes called "isobutylene resins." Specific examples of isobutylene resins include Kaneka Corporation's "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer).

[0251] An example of the elastomer is a resin containing a polystyrene structure. A resin containing a polystyrene structure is sometimes called a "styrene resin." The styrene resin may be a copolymer containing an arbitrary repeating unit other than the styrene unit in combination with the styrene unit, or may be a hydrogenated polystyrene resin.

[0252] Examples of the optional repeating unit include a repeating unit (conjugated diene unit) having a structure obtained by polymerizing a conjugated diene, and a repeating unit (hydrogenated conjugated diene unit) having a structure obtained by hydrogenating the same. Examples of the conjugated diene include aliphatic conjugated dienes such as butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, and 1,3-hexadiene; and halogenated aliphatic conjugated dienes such as chloroprene. As the conjugated diene, an aliphatic conjugated diene is preferable, and butadiene is more preferable, from the viewpoint of obtaining the effects of the present invention significantly. The conjugated diene may be used alone or in combination of two or more kinds. The polystyrene resin may be a random copolymer or a block copolymer.

[0253] Examples of styrene resins include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), styrene-ethylene-butylene-styrene block copolymers (SEBS), styrene-ethylene-propylene-styrene block copolymers (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymers (SEEPS), styrene-butadiene-butylene-styrene block copolymers (SBBS), styrene-butadiene diblock copolymers, hydrogenated styrene-butadiene block copolymers, hydrogenated styrene-isoprene block copolymers, hydrogenated styrene-butadiene random copolymers, and styrene-maleic anhydride copolymers. Specific examples of styrene resins include hydrogenated styrene-based 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); modified styrene-based elastomers having hydroxyl groups "Septon HG252" (manufactured by Kuraray Co., Ltd.); modified styrene-based elastomers having carboxyl groups "Tuftec N503M", modified styrene-based elastomers having amino groups "Tuftec N501", modified styrene-based elastomers having acid anhydride groups "Tuftec M1913" (manufactured by Asahi Kasei Chemicals Corporation); unmodified styrene-based elastomers "Septon S8104" (manufactured by Kuraray Co., Ltd.); styrene-ethylene / butylene-styrene block copolymers "FG1924" (manufactured by Kraton Corporation), and "EF-40" (manufactured by CRAY VALLEY Co., Ltd.).

[0254] The number average molecular weight (Mn) of the elastomer is preferably 1,000 or more, more preferably 1,500 or more, even more preferably 3,000 or more, particularly preferably 5,000 or more, and is preferably 1,000,000 or less, more preferably 900,000 or less. The number average molecular weight (Mn) can be measured in terms of polystyrene using GPC (gel permeation chromatography).

[0255] From the viewpoint of obtaining a cured product with excellent dielectric properties, the content of the (B) component is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, and is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, assuming that the non-volatile components in the resin composition layer are 100% by mass.

[0256] -(C)Inorganic filler- The resin composition layer may further contain an inorganic filler as component (C) in addition to the above-mentioned components.

[0257] As the material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as the silica, spherical silica is preferable. (C) The inorganic filler may be used alone or in combination of two or more types.

[0258] Examples of commercially available products of component (C) include "UFP-30" manufactured by Denka Company; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs Co., Ltd.; "Silfill NSS-3N", "Silfill NSS-4N", and "Silfill NSS-5N" manufactured by Tokuyama Corporation; and "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs Co., Ltd.

[0259] The specific surface area of ​​component (C) is preferably 1 m 2 / g or more, more preferably 2m 2 / g or more, particularly preferably 3m 2 / g or more. There is no particular upper limit, but it is preferably 60m 2 / g or less, 50m 2 / g or less or 40m 2 The specific surface area is determined by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multipoint method.

[0260] From the viewpoint of significantly obtaining the desired effects 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, and particularly preferably 0.1 μm or more, and is preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less.

[0261] The average particle size of component (C) can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, a particle size distribution of the inorganic filler is created on a volume basis using a laser diffraction / scattering particle size distribution measuring device, and the median diameter is used as the average particle size. The measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing the mixture by ultrasonic waves for 10 minutes. The measurement sample is measured using a laser diffraction particle size distribution measuring device with blue and red light wavelengths as the light source, and the volume-based particle size distribution of component (C) is measured using a flow cell method, and the average particle size can be calculated as the median diameter from the particle size distribution obtained. An example of a laser diffraction particle size distribution measuring device is the "LA-960" manufactured by Horiba, Ltd.

[0262] From the viewpoint of improving moisture resistance and dispersibility, it is preferable that the (C) component is treated with a surface treatment agent. Examples of the surface treatment agent include vinylsilane coupling agents, (meth)acrylic coupling agents, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. Among them, aminosilane coupling agents are preferable from the viewpoint of obtaining the effects of the present invention significantly. Moreover, the surface treatment agent may be used alone or in any combination of two or more types.

[0263] Commercially available surface treatment agents include, for example, Shin-Etsu Chemical Co., Ltd.'s "KBM1003" (vinyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM503" (3-methacryloxypropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxysilane), ... Examples of such silane coupling agents include Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy-type silane coupling agent), and Shin-Etsu Chemical Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane).

[0264] The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 parts by mass to 5 parts by mass of the surface treatment agent, more preferably 0.2 parts by mass to 3 parts by mass, and even more preferably 0.3 parts by mass to 2 parts by mass.

[0265] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2 On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, it is more preferable that the content is 1 mg / m 2 Less than 0.8 mg / m is preferred. 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0266] The amount of carbon per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. The carbon analyzer that can be used is the "EMIA-320V" manufactured by Horiba, Ltd.

[0267] From the viewpoint of realizing an insulating layer with a low dielectric tangent and reducing the maximum value of tan δ, the content of the (C) component is preferably 50 mass% or more, more preferably 52 mass% or more or 54 mass% or more, even more preferably 55 mass% or more, and is preferably 90 mass% or less, more preferably 80 mass% or less, even more preferably 70 mass% or less, when the non-volatile components in the resin composition layer are taken as 100 mass%.

[0268] -(D) Polymerization initiator- The resin composition layer may contain a polymerization initiator (D) as an optional component. By containing the polymerization initiator (D), the radical polymerizable compound can be cured efficiently.

[0269] The type of polymerization initiator is not particularly limited, and examples thereof include radical generators such as cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, and 2,3-dimethyl-2,3-diphenylbutane. These may be used alone or in combination of two or more.

[0270] The polymerization initiator may be a commercially available product, such as "Perhexine 25B" manufactured by NOF Corporation.

[0271] From the viewpoint of obtaining the effects of the present invention prominently, the content of the polymerization initiator is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and is preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, based on 100% by mass of the non-volatile components in the resin composition layer.

[0272] -(E) Other additives- The resin composition layer may further contain other additives as optional components in addition to the above-mentioned components. Examples of such additives include resin additives such as thickeners, defoamers, leveling agents, and adhesion-imparting agents. These additives may be used alone or in combination of two or more. The content of each additive can be appropriately set by a person skilled in the art.

[0273] The resin composition layer may further contain any solvent as a volatile component. The resin composition used to form the resin composition layer may contain a solvent to adjust the varnish viscosity. Examples of the solvent include organic solvents. However, it is preferable that the resin composition layer does not contain toluene, and when the entire resin composition layer is taken as 100 mass, the content of toluene is preferably 0.1 mass% or less, 0.01 mass% or less, 0.001 mass% or less, or 0.0001 mass% or less.

[0274] Examples of organic solvents include ketones such as methyl ethyl ketone (MEK) and cyclohexanone, aromatic hydrocarbons 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 ethyl diglycol acetate, aliphatic hydrocarbons such as octane and decane, and petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These may be used alone or in combination of two or more.

[0275] As mentioned above, the present inventors have confirmed that, compared with the vacuum lamination method conventionally used for forming an insulating layer using a resin sheet (resin composition layer), the vacuum press treatment generates a new problem that the pressure applied to the resin sheet (resin composition layer) during lamination is high, and the desired insulating layer thickness may not be obtained due to the exudation of resin. It has been confirmed that such deviation in the thickness of the insulating layer after the vacuum press treatment (difference from the target thickness) is related to the amount of residual solvent in the resin composition layer and the maximum value of tan δ in a specific temperature range in the dynamic viscoelasticity of the resin composition layer (here, tan δ is the ratio E'' / E' of the storage modulus E' (GPa) and the loss modulus E'' (Pa). Below, a guideline for achieving the desired insulating layer thickness after the vacuum hot press treatment is shown in terms of the amount of residual solvent and the maximum value of tan δ.

[0276] From the viewpoint of adjusting the melt viscosity of the resin composition layer and realizing the desired insulating layer thickness after vacuum press processing, the amount of solvent in the resin composition layer is preferably as small as possible. The amount of solvent in the resin composition layer (residual solvent amount) is preferably 3 mass% or less, more preferably 2.5 mass% or less, even more preferably 2 mass% or less, even more preferably 1.5 mass% or less, and particularly preferably 1 mass% or less. There is no particular lower limit, but it may be 0.0001 mass% or more. The residual solvent amount can be measured by the method described in the examples below.

[0277] From the viewpoint of realizing a desired insulating layer thickness after vacuum press treatment, in dynamic viscoelasticity measurement of the resin composition layer at 60°C to 200°C, the maximum value of tan δ at 100°C or higher is preferably 2.0 or less, more preferably 1.9 or less, and even more preferably 1.8 or less. From the viewpoint of realizing good circuit embedding properties, the lower limit of the maximum value may be 0.3 or more, 0.4 or more, 0.5 or more, etc. The maximum value of tan δ at 100°C or higher in dynamic viscoelasticity can be measured according to the method described in the examples below.

[0278] 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, from the viewpoint of making the printed wiring board thinner and being able to provide a cured product with excellent insulation even if the cured product of the resin composition is a thin film. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more, 10 μm or more, etc.

[0279] <Other layers> In one embodiment, the resin sheet may further include other layers as necessary. Examples of such other layers include a protective film provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface 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 adhesion of dirt and scratches on the surface of the resin composition layer.

[0280] <Method of manufacturing resin sheet> The resin sheet can be produced, for example, by preparing a resin varnish by dissolving the resin composition in an organic solvent, applying the resin varnish onto a support using a die coater or the like, and then drying the varnish to form a resin composition layer. The organic solvent may be any of those described above.

[0281] Drying may be performed by a known method such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is performed so that the content of organic solvent in the resin composition layer becomes 10 mass % or less, preferably 5 mass % or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30 mass % to 60 mass % of organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0282] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0283] <Physical properties and applications of resin sheets> The resin sheet of the present invention is a resin sheet for forming an insulating layer using a vacuum press treatment, and includes a support and a resin composition layer provided on the support, the support having a metal foil, and the resin composition layer containing component (A). By forming an insulating layer by vacuum press treatment using a support containing metal foil and a resin composition layer containing component (A), an insulating layer that exhibits good mechanical strength, is excellent in MIT folding resistance, and exhibits desired dielectric properties can be realized.

[0284] The resin composition layer of the resin sheet and the circuit board are laminated by vacuum pressing, and the resin composition layer is thermally cured at 100°C for 30 minutes and then at 200°C for 120 minutes to obtain a cured product of the resin composition layer that exhibits a low dielectric tangent. Thus, the cured product provides an insulating layer with a low dielectric tangent. The dielectric tangent is preferably less than 0.0031, more preferably less than 0.0030, and even more preferably 0.0026 or less or 0.0025 or less. The lower limit of the dielectric tangent may be 0.0001 or more. The dielectric tangent can be measured according to the method described in the examples below.

[0285] The resin composition layer of the resin sheet is laminated on a circuit board by vacuum pressing, and the resin composition layer is thermally cured at 100°C for 30 minutes and then at 200°C for 120 minutes. The cured product of the resin composition layer exhibits a low dielectric constant. Thus, the cured product provides an insulating layer with a low dielectric constant. The dielectric constant is preferably less than 2.95, more preferably 2.9 or less, and even more preferably less than 2.9. The lower limit of the dielectric constant may be 1 or more. The dielectric constant can be measured according to the method described in the examples below.

[0286] The resin composition layer of the resin sheet and the circuit board are laminated by vacuum pressing, and the resin composition layer is thermally cured at 100°C for 30 minutes and then at 200°C for 120 minutes to obtain a cured resin composition layer that exhibits good mechanical strength and excellent flexibility (MIT folding resistance). Thus, the cured product provides an insulating layer that exhibits good mechanical strength and excellent flexibility. The number of folding times in the MIT testing device is preferably 400 times or more, more preferably 410 times or more, and even more preferably 420 times or more. The upper limit can be 1000 times or less. The MIT folding resistance can be measured according to the method described in the examples below.

[0287] By using the resin sheet of the present invention to form an insulating layer by vacuum press processing, an insulating layer exhibiting good mechanical strength, excellent MIT folding 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 by vacuum press processing (for forming an insulating layer by vacuum press processing). The resin sheet of the present invention has a support containing a metal foil, and the metal foil can be used to form a conductor layer. Therefore, the resin sheet of the present invention can be suitably used as a resin sheet for forming both an insulating layer and a conductor layer by vacuum press processing in the manufacture of a printed wiring board (for forming an insulating layer and a conductor layer by vacuum press processing). The resin sheet of the present invention can be suitably used to form an insulating layer (and a conductor layer) of a printed wiring board, preferably an interlayer insulating layer (and a conductor layer) of a printed wiring board. In the present invention, the term "printed wiring board" also includes a rewiring board of a semiconductor package.

[0288] [Printed wiring boards and methods of manufacturing printed wiring boards] The printed wiring board of the present invention includes an insulating layer made of a cured product of the resin composition layer of the resin sheet of the present invention.

[0289] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet by a method including the following steps (I) and (II). (I) A process of laminating a resin sheet on an inner layer substrate by vacuum pressing. (II) A step of thermally curing the resin composition layer to form an insulating layer

[0290] The "inner layer substrate" used in step (I) is a member that becomes the substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. The substrate may have a conductor layer on one or both sides, and the conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be called an "inner layer circuit substrate". In addition, an intermediate product on which an insulating layer and / or a conductor layer is to be further formed during the manufacture of a printed wiring board is also included in the "inner layer substrate" of the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0291] The inner layer substrate and the resin sheet are laminated by vacuum pressing so that the resin composition layer of the resin sheet is bonded to the inner layer substrate. By laminating the inner layer substrate and the resin composition layer by vacuum pressing, it is possible to improve the dielectric properties, mechanical strength, and electrical properties.

[0292] First, the inner layer substrate and the resin sheet are set in a vacuum press device so that the resin composition layer of the resin sheet and the inner layer substrate are bonded. Next, a vacuum press treatment is performed to heat and press the inner layer substrate and the resin composition layer under reduced pressure conditions. The vacuum press treatment is preferably a vacuum heat press treatment (vacuum hot press treatment) in which heat is applied.

[0293] The inner layer substrate and the resin sheet are preferably set in a vacuum press device via cushion paper, a metal plate such as a stainless steel plate (SUS plate), a release film, or the like.

[0294] The vacuum press treatment can be carried out using a conventionally known vacuum press device that presses the inner layer substrate and the resin sheet from both sides with a heated metal plate such as a SUS plate. An example of a commercially available vacuum press device is "VH1-1603" manufactured by Kitagawa Seiki Co., Ltd.

[0295] The vacuum pressing treatment may be carried out only once, or may be carried out repeatedly two or more times. When the vacuum pressing treatment is carried out repeatedly two or more times, the pressure, heating temperature, pressing time, etc. may be the same or different.

[0296] In the vacuum press treatment, the compression pressure (pressing force) is preferably 0.49 MPa or more, more preferably 0.98 MPa or more, and is preferably 7.9 MPa or less, more preferably 5.9 MPa or less.

[0297] In the vacuum press process, the atmospheric pressure, i.e., the pressure (degree of vacuum) during decompression in the chamber in which the laminated structure to be processed is stored, is preferably 3×10 -2 MPa or less, more preferably 1×10 -2 MPa or less. There is no particular lower limit, but it is 1×10 -10 MPa or more.

[0298] In the vacuum press treatment, the heating temperature varies depending on the composition of the resin composition layer, but is usually 150°C or higher, preferably 160°C or higher, more preferably 170°C or higher, or 180°C or higher. The upper limit of the heating temperature is not particularly limited, but it can usually be 240°C or lower. In addition, the vacuum press treatment may be performed while increasing the temperature stepwise or continuously and / or decreasing the temperature stepwise or continuously from the viewpoint of obtaining the effects of the present invention significantly. In addition, as described later, the resin composition layer may be thermally cured by heating in the vacuum press treatment to form an insulating layer.

[0299] In the vacuum press treatment, the pressing time is preferably 5 minutes or more, more preferably 10 minutes or more, and even more preferably 15 minutes or more. The upper limit is not particularly limited, but is preferably 300 minutes or less, more preferably 200 minutes or less, and even more preferably 150 minutes or less.

[0300] After laminating a resin sheet on an inner layer substrate by vacuum pressing, in step (II), the resin composition layer is thermally cured to form an insulating layer. For example, when performing pressing by vacuum hot pressing, a method of thermally curing the resin composition layer by using heat generated during pressing to form an insulating layer can be mentioned as a method of thermally curing the resin composition layer.

[0301] The conditions for thermally curing the resin composition layer are not particularly limited, and conditions that are usually employed when forming an insulating layer for a printed wiring board may be used.

[0302] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, etc., 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 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0303] Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50° C. or more and less than 120° C. (preferably 60° C. or more and 115° C. or less, more preferably 70° C. or more and 110° C. or less) for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes).

[0304] As mentioned above, the present inventors have confirmed that, compared with the vacuum lamination method, the vacuum press treatment may not provide the desired insulating layer thickness due to the exudation of resin during lamination. In this regard, by setting the amount of residual solvent and the maximum value of tan δ within the above-mentioned preferred range, the desired insulating layer thickness can be achieved after the vacuum press treatment while maintaining good mechanical strength and dielectric properties. Specifically, when the designed thickness of the insulating layer is 15 μm, the variation in the thickness of the insulating layer after the heat press treatment is preferably less than ±30%, more preferably less than ±20%, and even more preferably ±15% or less. The lower limit may be 0%, ±0.1% or more, etc. The evaluation of the thickness of the insulating layer after the vacuum press treatment can be measured according to the method described in the examples below.

[0305] The resin sheet used in the present invention has a support that includes a metal foil, and therefore may include, as step (III), a step of forming a circuit by a subtractive process or a modified semi-additive process.

[0306] In the step (III), a circuit can be formed by a subtractive method or a modified semi-additive method using a support (metal foil).

[0307] In the subtractive method, unnecessary parts (non-circuit forming parts) of the metal foil are selectively removed by etching or the like to form a circuit. The circuit formation by the subtractive method may be carried out according to a known procedure. For example, the circuit formation by the subtractive method can be carried out by a method including: i) providing an etching resist on the surface of the metal foil (i.e., the surface opposite to the surface bonded to the resin composition layer); ii) exposing and developing the etching resist to form a wiring pattern; iii) etching and removing the exposed metal foil parts; and iv) removing the etching resist.

[0308] In the modified semi-additive method, the non-circuit forming portion of the metal foil is protected by a plating resist, and a metal such as copper is thickly applied to the circuit forming portion by electrolytic plating, and then the plating resist is removed, and the metal foil other than the circuit forming portion is removed by etching to form a circuit. The circuit formation by the modified semi-additive method may be carried out according to a known procedure. For example, the circuit formation by the modified semi-additive method can be carried out by a method including: i) providing a plating resist on the surface of the metal foil (i.e., the surface opposite to the surface bonded to the resin composition layer), ii) exposing and developing the plating resist to form a wiring pattern, iii) electroplating through the plating resist, iv) removing the plating resist, and v) etching and removing the metal foil other than the circuit forming portion. In addition, when the metal foil is thick, the entire surface of the metal foil may be thinned by etching or the like before the above i) so that the metal foil has a desired thickness (usually 5 μm or less, 4 μm or less, or 3 μm or less).

[0309] In manufacturing a printed wiring board, a step (IV) of drilling holes and a step (V) of roughening the insulating layer may be further carried out. These steps (IV) to (V) may be carried out according to various methods known to those skilled in the art and used in manufacturing printed wiring boards. Furthermore, if necessary, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated to form a multilayer wiring board.

[0310] [Semiconductor Devices] 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 by using the printed wiring board of the present invention.

[0311] Examples of the semiconductor device include various semiconductor devices used in electric appliances (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircraft).

[0312] 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. The "conductive portion" refers to a portion of a printed wiring board that transmits an electric signal, and the portion may be either on the surface or embedded. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of semiconductor material.

[0313] The method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively, but specific examples include a wire bonding mounting method, a flip chip mounting method, a bumpless buildup layer (BBUL) mounting method, an anisotropic conductive film (ACF) mounting method, a non-conductive film (NCF) mounting method, etc. Here, the "bumpless buildup layer (BBUL) mounting method" refers to "a mounting method in which a semiconductor chip is directly embedded in a recess in a printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board." EXAMPLES

[0314] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

[0315] <Inorganic fillers used> Inorganic filler 1: Spherical silica (Denki Kagaku Kogyo Co., Ltd. "UFP-30", average particle size 0.078 μm, specific surface area 30.7 m 2 The surface was treated with 2 parts of N-phenyl-3-aminopropyltrimethoxysilane (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) per 100 parts of silica gel (100 parts per million / g). Inorganic filler 2: Spherical silica (Admatechs "SC2500SQ", average particle size 0.63 μm, specific surface area 11.2 m 2 The surface was treated with 1 part of N-phenyl-3-aminopropyltrimethoxysilane (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) per 100 parts of silica gel (g).

[0316] <Synthesis Example 1: Synthesis of Polyimide Resin 1> In a 500 ml separable flask equipped with a nitrogen inlet tube and a stirrer, 9.13 g (30 mmol) of 5-amino-1,1'-biphenyl-2-yl 4-aminobenzoate (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, and the mixture was subjected to an imidization reaction under a nitrogen atmosphere at 180°C for 4 hours while removing toluene from the system, thereby obtaining a polyimide solution (non-volatile content 20% by mass) containing polyimide resin 1. 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.

[0317] <Synthesis Example 2: Synthesis of Polyimide Resin 2> A reaction vessel equipped with a stirrer, a water divider, a thermometer, and a nitrogen gas inlet tube was charged with 65.0 g of aromatic tetracarboxylic dianhydride (SABIC Japan "BisDA-1000", 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic dianhydride), 266.5 g of cyclohexanone, and 44.4 g of methylcyclohexane, 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 dropped, and then the imidization reaction was carried out at 140 ° C. for 1 hour. As a result, a polyimide solution (non-volatile content 30% by mass) containing polyimide resin 2 was obtained. The weight average molecular weight of polyimide resin 2 was 25,000.

[0318] <Synthesis Example 3: Synthesis of polyimide resin 3> A 500 mL separable flask equipped with a water content receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer was prepared. 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 29.6 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane were added to this flask, and the mixture was stirred at 45°C for 2 hours under a nitrogen stream to carry out a reaction. Next, the reaction solution was heated and, while maintaining the temperature at about 160°C, condensed water was azeotropically removed together with toluene under a nitrogen stream. It was confirmed that a predetermined amount of water had accumulated in the water content receiver and that no water was flowing out. After confirmation, the reaction solution was further heated and stirred at 200°C for 1 hour. The mixture was then cooled to obtain a polyimide solution (non-volatile content 20% by mass) containing polyimide resin 3 having a 1,1,3-trimethylindane skeleton. The obtained polyimide resin 3 had a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). The weight average molecular weight of the polyimide resin 3 was 12,000. [ka]

[0319] <Synthesis Example 4: Synthesis of elastomer> In a reaction vessel, 50 g of G-3000 (bifunctional hydroxyl group-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl group equivalent = 1798 g / eq., solid content 100 mass%: manufactured by Nippon Soda Co., Ltd.), 23.5 g of Ipsol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.), and 0.005 g of dibutyltin laurate were mixed and dissolved uniformly. When the mixture became uniform, the temperature was raised to 50°C, and 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq.) was added while further stirring, and the reaction was carried out for about 3 hours. Next, the reaction mixture was cooled to room temperature, and 8.96 g of benzophenonetetracarboxylic dianhydride (acid anhydride equivalent = 161.1 g / eq.), 0.07 g of triethylenediamine, and 40.4 g of ethyl diglycol acetate (manufactured by Daicel Corporation) were added thereto, and the mixture was heated to 130°C with stirring and reacted for about 4 hours. -1 The disappearance of the NCO peak was confirmed. The disappearance of the NCO peak was regarded as the end point of the reaction, and the reaction mixture was cooled to room temperature and filtered through a 100 mesh filter cloth to obtain an elastomer having an imide skeleton, a urethane skeleton, and a butadiene skeleton. Viscosity: 7.5Pa s (25℃, E-type viscometer) Acid value: 16.9mgKOH / g Solid content: 50% by mass Number average molecular weight: 13723 Glass transition temperature: -10℃ Polybutadiene structural portion content: 50 / (50+4.8+8.96)×100=78.4% by mass

[0320] <Synthesis Example 5: Synthesis of Maleimide Resin A> According to the method described in Synthesis Example 1 of the Japan Institute of Invention and Innovation's Technical Journal Publication No. 2020-500211, an MEK solution (70% by mass of non-volatile components) of maleimide resin A (Mw / Mn = 1.81, u' = 1.47 (mainly 1, 2 or 3)) represented by the following formula (1) was prepared. [ka]

[0321] <Preparation of Resin Composition 1> 5 parts of a maleimide compound (Designer Molecules' "BMI-689"), 10 parts of a biphenyl skeleton-containing maleimide resin (Nippon Kayaku's "MIR-3000", a 1:1 solution of toluene:MEK with a non-volatile content of 70% by mass), 5 parts of the maleimide resin A synthesized in Synthesis Example 5, and 20 parts of a hydrogenated styrene-based thermoplastic elastomer (Asahi Kasei's "H1043", styrene / ethylene-butylene-butadiene ratio = 67 / 33) were dissolved in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone with stirring. After cooling to room temperature, 50 parts of inorganic filler 1 and 0.1 parts of a polymerization initiator (NOF Corp.'s "Perhexine 25B") were mixed therein, uniformly dispersed in a high-speed rotating mixer, and then filtered with a cartridge filter (ROKITECHNO's "SHP020") to prepare a resin composition 1.

[0322] <Preparation of Resin Composition 2> In the preparation of resin composition 1, 20 parts of the hydrogenated styrene-based thermoplastic elastomer ("H1043" manufactured by Asahi Kasei Corporation, styrene / ethylene-butylene-butadiene ratio = 67 / 33) was changed to 100 parts of polyimide resin 1 synthesized in Synthesis example 1. Resin composition 2 was prepared in the same manner as in the preparation of resin composition 1, except for the above-mentioned points.

[0323] <Preparation of Resin Composition 3> In the preparation of resin composition 1, 20 parts of hydrogenated styrene-based thermoplastic elastomer ("H1043" manufactured by Asahi Kasei Corporation, styrene / ethylene-butylene-butadiene ratio = 67 / 33) was changed to 67 parts of polyimide resin 2 synthesized in Synthesis example 2. Resin composition 3 was prepared in the same manner as in the preparation of resin composition 1, except for the above-mentioned points.

[0324] <Preparation of Resin Composition 4> In the preparation of resin composition 1, 20 parts of the hydrogenated styrene-based thermoplastic elastomer ("H1043" manufactured by Asahi Kasei Corporation, styrene / ethylene-butylene-butadiene ratio = 67 / 33) was changed to 100 parts of polyimide resin 3 synthesized in Synthesis example 3. Resin composition 4 was prepared in the same manner as in the preparation of resin composition 1, except for the above-mentioned points.

[0325] <Preparation of Resin Composition 5> In the preparation of resin composition 1, 20 parts of the hydrogenated styrene-based thermoplastic elastomer ("H1043" manufactured by Asahi Kasei Corporation, styrene / ethylene-butylene-butadiene ratio = 67 / 33) was changed to 40 parts of the elastomer synthesized in Synthesis Example 4. Resin composition 5 was prepared in the same manner as in the preparation of resin composition 1, except for the above-mentioned points.

[0326] <Preparation of Resin Composition 6> Resin composition 6 was prepared in the same manner as in the preparation of resin composition 1, except that 50 parts of inorganic filler 1 was changed to 50 parts of inorganic filler 2. Except for the above, resin composition 6 was prepared in the same manner as in the preparation of resin composition 1.

[0327] <Preparation of Resin Composition 7> In the preparation of resin composition 1, 5 parts of maleimide resin A was changed to 4.5 parts of a styrene-modified polyphenylene ether resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., Mn=1200, toluene solution with a solid content of 65 mass %). Resin composition 7 was prepared in the same manner as in the preparation of resin composition 1, except for the above.

[0328] <Preparation of Resin Composition 8> In the preparation of resin composition 1, 5 parts of maleimide resin A was changed to 5 parts of a bifunctional acrylate compound ("NK Ester A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 326). Resin composition 8 was prepared in the same manner as in the preparation of resin composition 1 except for the above.

[0329] <Preparation of Resin Composition 9> In the preparation of resin composition 1, 5 parts of maleimide resin A was changed to 5 parts of a bifunctional allyl compound having a benzoxazine ring ("ALP-d" manufactured by Shikoku Chemical Industry Co., Ltd.). Resin composition 9 was prepared in the same manner as in the preparation of resin composition 1 except for the above.

[0330] <Preparation of Resin Composition 10> Eleven parts of a styrene-modified polyphenylene ether resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., Mn=1200, toluene solution with solid content of 65% by mass), 5 parts of a bifunctional acrylate compound ("NK Ester A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 326), 5 parts of a bifunctional allyl compound having a benzoxazine ring ("ALP-d" manufactured by Shikoku Chemical Industry Co., Ltd.), and 20 parts of a hydrogenated styrene-based thermoplastic elastomer ("H1043" manufactured by Asahi Kasei Corporation, styrene / ethylene-butylene-butadiene ratio=67 / 33) were dissolved in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone by heating with stirring. After cooling to room temperature, 50 parts of inorganic filler 1 and 0.1 parts of a polymerization initiator ("Perhexyne 25B" manufactured by NOF Corporation) were mixed thereto, and the mixture was uniformly dispersed using a high-speed rotating mixer. The mixture was then filtered through a cartridge filter ("SHP020" manufactured by ROKITECHNO Corporation) to prepare resin composition 10.

[0331] <Preparation of Resin Composition 11> In the preparation of resin composition 1, the amount of inorganic filler 1 was changed from 50 parts to 40 parts. Resin composition 11 was prepared in the same manner as in the preparation of resin composition 1 except for the above-mentioned points.

[0332] [Examples 1 to 11] <Preparation of resin sheet A> As a support, a carrier-attached copper foil (Mitsui Mining & Smelting Co., Ltd. Microthin MT-Ex copper foil (3 μm thick ultrathin copper foil / 18 μm thick carrier copper foil)) having a carrier copper foil and an ultrathin copper foil was prepared. Resin compositions 1 to 11 were uniformly applied to the ultrathin copper foil of the support by a die coater so that the thickness of the resin composition layer after drying was 20 μm, and dried at 70 ° C to 120 ° C for 7 minutes to obtain a resin composition layer on the support. Next, a rough surface of a polypropylene film (Oji F-Tex Co., Ltd. "Alphan MA-411", thickness 15 μm) was laminated as a protective film on the surface of the resin composition layer not bonded to the support so as to be bonded to the resin composition layer. As a result, a resin sheet A consisting of a carrier-attached copper foil (support), a resin composition layer, and a protective film in this order was obtained.

[0333] <Preparation of Cured Material A for Evaluation Using Vacuum Press Treatment> The protective film was peeled off from the resin sheet A to expose the resin composition layer. Next, the exposed resin composition layer was laminated so that the ultra-thin copper side of a carrier-attached copper foil (Microthin MT-Ex copper foil (3 μm thick ultra-thin copper foil / 18 μm thick carrier copper foil) manufactured by Mitsui Mining & Smelting Co., Ltd.) was in contact with the resin composition layer, and the laminate was made using a vacuum hot press machine (VH1-1603 manufactured by Kitagawa Seiki Co., Ltd.). The pressing conditions were a vacuum pressure of 1×10 -3 The pressure is reduced to 20kgf / cm2 or less. 2 The heating conditions for the first pressing were a temperature of 100° C. and a time of 30 minutes, and for the second pressing were a temperature of 200° C. and a time of 120 minutes. After the resin composition layer was cured by heating with the press, the carrier foil was peeled off and the ultrathin copper was etched to obtain a cured product A for evaluation.

[0334] [Comparative Example 1] <Preparation of Resin Sheet B> As a support, a PET film (Toray Industries, Inc., "Lumirror R80", thickness 38 μm, softening point 130° C., "release PET") that had been subjected to release treatment with an alkyd resin-based release agent (Lintec Corporation, "AL-5") was prepared. Resin composition 1 was uniformly applied onto the support with a die coater so that the thickness of the resin composition layer after drying was 20 μm, and the resin composition layer was dried at 70 to 120° C. (average 100° C.) for 3 minutes to form a resin composition layer on the support. Next, a rough surface of a polypropylene film (Oji F-Tex Co., Ltd., "Alphan MA-411", thickness 15 μm) was laminated as a protective film on the surface of the resin composition layer that was not bonded to the support so as to be bonded to the resin composition layer. This resulted in a resin sheet B having a configuration of support (38 μm PET film) / resin composition layer / protective film (MA-411).

[0335] <Preparation of Cured Product B for Evaluation Using Lamination Treatment> A release PET film ("501010" manufactured by Lintec Corporation, thickness 38 μm, 240 mm square) was placed on a glass cloth-based epoxy resin double-sided copper-clad laminate ("R5715ES" manufactured by Panasonic Electric Works, Ltd., thickness 0.7 mm, 255 mm square) so that the untreated surface of the release PET film was in contact with the glass cloth-based epoxy resin double-sided copper-clad laminate, and the four sides of the release PET film were fixed with polyimide adhesive tape (width 10 mm).

[0336] Resin sheet B (167 x 107 mm square) was laminated in the center using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., 2-stage build-up laminator, CVP700) so that the second resin composition layer was in contact with the release surface of the release PET film. The lamination was performed by reducing the pressure for 30 seconds to 13 hPa or less, and then pressing at 100 ° C and a pressure of 0.74 MPa for 30 seconds. Next, the support was peeled off, and the resin sheet layer was thermally cured under curing conditions of 190 ° C for 90 minutes. After thermal curing, the polyimide adhesive tape was peeled off, and the cured layer was removed from the glass cloth-based epoxy resin double-sided copper-clad laminate. The release PET film was further peeled off from the cured layer to obtain a cured product B for evaluation.

[0337] [evaluation] <Measurement of residual solvent amount> The resin sheet in which the support and the resin composition layer were laminated was cut into 10 cm x 10 cm, and the initial mass was measured using an electronic balance. Next, the resin sheet was placed on a wire mesh, heated in an oven previously set at 130 ° C. for 15 minutes, then transferred to a desiccator and left to stand for 30 minutes, and cooled to room temperature. Then, the dry mass of the resin sheet was measured using an electronic balance. The initial mass and dry mass were both measured for three samples, and the average value was used to calculate the amount of solvent (residual solvent amount) contained in the resin composition layer using the following formula. Residual solvent amount (mass%)=100×(initial mass of resin sheet−dry mass of resin sheet) / (initial mass of resin sheet−mass of support)

[0338] <Measurement of dielectric properties (dielectric constant, dielectric tangent)> The cured product for evaluation was cut into a test piece having a width of 2 mm and a length of 80 mm. The dielectric constant and dielectric loss tangent of the test piece were measured by a cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C using an "HP8362B" manufactured by Agilent Technologies. The average values ​​of the dielectric constant and dielectric loss tangent were calculated by measuring three test pieces, and the dielectric constant and dielectric loss tangent were further evaluated according to the following criteria. -Dielectric loss tangent- ○: Dielectric tangent is less than 0.003 △: Dielectric tangent is 0.003 or more and less than 0.0031 ×: Dielectric tangent is 0.0031 or more -Dielectric constant- ○: Dielectric constant is less than 2.9 △: Dielectric constant is 2.9 or more and less than 2.95 ×: Dielectric constant is 2.95 or more

[0339] <Evaluation of flexibility (MIT folding endurance)> Cured material A or cured material B for evaluation was cut into a test piece with a width of 15 mm and a length of 110 mm, and the number of times the cured material could be folded until it broke was measured using an MIT testing device (MIT folding fatigue tester "MIT-DA" manufactured by Toyo Seiki Seisakusho Co., Ltd.) under the measurement conditions of a load of 2.5 N, a folding angle of 90 degrees, a folding radius of 1.0 mm, and a folding speed of 175 times / min in accordance with JIS C-5016. Note that the measurement was performed on five samples, and the average of the top three points was calculated and evaluated according to the following criteria. 〇: Fold resistance 405 times or more △: Fold resistance is 395 to less than 405 ×: Fold resistance less than 395 times

[0340] <Measurement of maximum tan δ in dynamic viscoelasticity> The dynamic viscoelasticity of the resin composition layer of the resin sheet A or the resin sheet B was measured using a dynamic viscoelasticity measuring device (UBM's "Rheosol-G3000"). 1 g of the sample resin composition taken from the resin composition layer was heated from the starting temperature of 60°C to 200°C at a heating rate of 5°C / min using a parallel plate with a diameter of 18 mm, and the dynamic viscoelasticity was measured under the measurement conditions of a measurement temperature interval of 2.5°C, a vibration frequency of 1 Hz, and a strain of 1 deg. The obtained values ​​of the storage modulus E' (GPa) and the loss modulus E'' (Pa) were used to calculate tan δ using the following formula. The maximum value of tan δ at 100°C or higher was then obtained. tan δ=E'' / E'

[0341] <Evaluation of insulation layer thickness after vacuum press processing> (1) Lamination of resin sheet onto copper-clad laminate using vacuum pressing process As the copper-clad laminate, a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 12 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemical Company's "HL832NSF LCA", 255 × 340 mm size) was prepared, which has a circuit conductor (copper) formed on both sides in a wiring pattern of 1 mm square lattice (copper remaining rate 59%). Both sides of the inner layer circuit board were subjected to a copper surface roughening treatment (copper etching amount 0.5 μm) using MEC's ​​"CZ8201". The protective film was peeled off from the resin sheet A to expose the resin composition layer. Next, the exposed resin composition layer was laminated on both sides of the copper-clad laminate using a vacuum hot press machine (Kitagawa Seiki Co., Ltd., VH1-1603) so that the resin composition layer was in contact with the copper-clad laminate. The pressing conditions were a vacuum pressure of 1 × 10 -3 The pressure is reduced to 20kgf / cm2 or less. 2 Under the above conditions, the heating conditions for the first pressing were a temperature of 100° C. and a time of 30 minutes, and for the second pressing were a temperature of 190° C. and a time of 120 minutes. After the resin composition layer was cured by heating with the press, the ultrathin copper was etched to obtain a substrate C for evaluation.

[0342] (2) Observation of the thickness of the insulation layer after vacuum pressing A FIB-SEM composite device ("SMI3050SE" manufactured by SII Nanotechnology) was used to observe the cross section of evaluation substrate C, and the thickness of the insulating layer (the thickness of the insulating layer directly above the circuit conductor of the copper-clad laminate) was measured and evaluated according to the following criteria. ○: Insulation layer thickness is less than 15μm±20%. △: Insulation layer thickness is 15μm±20% or more but less than 30%. ×: Insulation layer thickness is 15 μm ± 30% or more.

[0343] [Table 1]

[0344] In Examples 1 to 11, it was confirmed that even when components (B) to (D) were not contained, the same results as those in the above Examples were obtained, although to a different extent.

Claims

1. A resin sheet for forming an insulating layer using a vacuum press treatment, A support and a resin composition layer provided on the support, The support has a metal foil, the resin composition layer contains (A) a radically polymerizable compound and (B) at least one thermoplastic resin selected from a polyimide resin and an elastomer having a polybutadiene structure or a polystyrene structure, The content of the component (B) is 10% by mass or more and 40% by mass or less, when the non-volatile components in the resin composition layer are taken as 100% by mass, A resin sheet, in which, in dynamic viscoelasticity measurement of a resin composition layer from 60° C. to 200° C., the maximum value of tan δ at 100° C. or higher is 2.0 or less.

2. The resin sheet according to claim 1 , wherein the component (A) comprises a radically polymerizable compound containing a maleimide group.

3. The resin sheet according to claim 1 or 2, wherein the metal foil comprises a copper foil.

4. The resin sheet according to any one of claims 1 to 3, wherein the resin composition layer further contains (C) an inorganic filler.

5. The resin sheet according to claim 4 , wherein the content of the component (C) is 50% by mass or more when the content of the nonvolatile components in the resin composition layer is 100% by mass.

6. A printed wiring board comprising an insulating layer made of a cured product of the resin composition layer of the resin sheet according to any one of claims 1 to 5.

7. A semiconductor device comprising the printed wiring board according to claim 6.

8. (1) a step of laminating the resin sheet according to any one of claims 1 to 5 on an inner layer substrate by vacuum pressing; and (2) A step of thermally curing the resin composition layer to form an insulating layer; A method for manufacturing a printed wiring board, comprising:

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