Resin composition

Abstract

To provide: a resin composition that can suppress the unevenness occurring in a curing substrate and gives a cured product with excellent dielectric properties and peel strength; a resin sheet containing the resin composition; and a printed wiring board and a semiconductor device having an insulating layer formed using the resin composition.SOLUTION: A resin composition contains (A) a compound containing an aromatic ester skeleton and an unsaturated bond, and (B) a radical-polymerizable compound. The (A) component content is 0.1 mass% or more and 30 mass% or less when a nonvolatile content in the resin composition is 100 mass%.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] 2. Description of the Related Art A known manufacturing technique for printed wiring boards is a build-up method in which insulating layers and conductor layers are alternately stacked.

[0003] As an insulating material for a printed wiring board used in such an insulating layer, for example, Patent Document 1 discloses a resin composition. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2019-6869 A DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0005] In recent years, there has been a demand for further improvement in the dielectric properties of the insulating layer, such as the dielectric constant and dielectric loss tangent, as well as further improvement in the peel strength between the insulating layer and the conductor layer formed by plating. In addition, when an insulating layer is formed by laminating a resin sheet on a substrate having irregularities, the surface of the insulating layer opposite the substrate may follow the irregularities of the substrate, reducing the flatness of the insulating layer, and causing unevenness in the cured substrate (unevenness in the surface of the insulating layer). If the cured substrate has irregularities, the composition of the insulating layer becomes non-uniform, which may result in poor wiring formability.

[0006] An object of the present invention is to provide a resin composition capable of suppressing unevenness occurring on a cured substrate and giving a cured product having excellent dielectric properties and peel strength; a resin sheet containing the resin composition; and a printed wiring board and a semiconductor device having an insulating layer formed using the resin composition. [Means for solving the problem]

[0007] Means for Solving the Problems The present inventors have conducted intensive research into the above-mentioned problems and have found that the above-mentioned problems can be solved by incorporating predetermined amounts of (A) a compound containing an aromatic ester skeleton and an unsaturated bond, and (B) a radically polymerizable compound, thereby completing the present invention.

[0008] That is, the present invention includes the following. [1] (A) a compound containing an aromatic ester skeleton and an unsaturated bond, and (B) A resin composition containing a radical polymerizable compound, A resin composition, the content of component (A) being 0.1% by mass or more and 30% by mass or less, when the total amount of non-volatile components in the resin composition is taken as 100% by mass. [2] The resin composition according to [1], wherein the component (A) is either a compound represented by the following general formula (A-1) or a compound represented by the following general formula (A-2): [ka] (In general formula (A-1), Ar 11 each independently represents a monovalent aromatic hydrocarbon group which may have a substituent, Ar 12 each independently represents a divalent aromatic hydrocarbon group which may have a substituent; Ar 13 each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof. n represents an integer of 0 to 10. [ka] (In general formula (A-2), Ar 21 represents an aromatic hydrocarbon group having a valence of m which may have a substituent, Ar 22 each independently represents a monovalent aromatic hydrocarbon group which may have a substituent; and m represents an integer of 2 or 3. [3] The resin composition according to [1] or [2], further comprising (C) an inorganic filler. [4] The resin composition according to [3], wherein the content of component (C) is 50% by mass or more, relative to 100% by mass of the non-volatile components in the resin composition. [5] The resin composition according to any one of [1] to [4], further comprising (D) a thermoplastic resin. [6] The resin composition according to any one of [1] to [5], further comprising (E) a thermosetting resin. [7] The resin composition according to any one of [1] to [6], wherein the component (B) contains either a maleimide-based radical polymerizable compound containing a maleimide group, or a vinylphenyl-based radical polymerizable compound containing a vinylphenyl group. [8] The resin composition according to any one of [1] to [7], which is for forming an insulating layer. [9] The resin composition according to any one of [1] to [8], which is for forming an insulating layer for forming a conductor layer.

[10] A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition layer comprising the resin composition according to any one of [1] to [9].

[11] A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [9].

[12] A semiconductor device comprising the printed wiring board according to

[11] . Effect of the Invention

[0009] According to the present invention, it is possible to provide a resin composition that can suppress unevenness occurring on a cured substrate and give a cured product that is excellent in dielectric properties, peel strength, and elongation at break; a resin sheet that includes the resin composition; a printed wiring board that includes an insulating layer formed using the resin composition, and a semiconductor device. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic side view showing an example of two test tubes used to determine whether a thermosetting resin is in a liquid state, a semi-solid state, or a solid state. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] 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.

[0012] [Resin composition] The resin composition of the present invention is a resin composition containing (A) an aromatic ester skeleton and unsaturated bond-containing compound, and (B) a radical polymerizable compound, and the content of the (A) component is 0.1% by mass or more and 30% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass. In the present invention, by containing a predetermined amount of the (A) component and further containing the (B) component, it is possible to suppress unevenness occurring on the cured substrate, and to obtain a cured product having excellent dielectric properties and peel strength. In addition, it is usually possible to obtain a cured product having excellent elongation at break.

[0013] The resin composition may further contain optional components in combination with the components (A) and (B). Examples of the optional components include an inorganic filler (C), a thermoplastic resin (D), a thermosetting resin (E), a curing accelerator (F), and other additives (G). Each component contained in the resin composition will be described in detail below.

[0014] <(A) Compound containing an aromatic ester skeleton and an unsaturated bond> The resin composition contains an aromatic ester skeleton and an unsaturated bond-containing compound as component (A). By including component (A) in the resin composition, it is possible to suppress unevenness on the cured substrate and obtain a cured product with excellent dielectric properties. The component (A) may be used alone or in combination of two or more.

[0015] The content of component (A), from the viewpoint of suppressing unevenness on the cured substrate and obtaining a cured product with excellent dielectric properties, is 0.1% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and 30% by mass or less, preferably 28% by mass or less, and even more preferably 25% by mass or less, based on 100% by mass of non-volatile components in the resin composition.

[0016] The component (A) has an aromatic ester skeleton. The aromatic ester skeleton refers to a skeleton having an ester bond and an aromatic ring bonded to one end or both ends of the ester bond. Among them, those having aromatic rings at both ends of the ester bond are preferred. Examples of groups having such a skeleton include an arylcarbonyloxy group, an aryloxycarbonyl group, an arylenecarbonyloxy group, an aryleneoxycarbonyl group, an arylcarbonyloxyarylene group, an aryloxycarbonylarylene group, an arylenecarbonyloxyarylene group, and an aryleneoxycarbonylarylene group. The number of carbon atoms in the group having such a skeleton is preferably 7 to 20, more preferably 7 to 15, and even more preferably 7 to 11. The aromatic hydrocarbon group such as an aryl group and an arylene group may have a substituent.

[0017] The aryl group is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms. Examples of such aryl groups include those obtained by removing one hydrogen atom from a monocyclic aromatic compound such as a phenyl group, a furanyl group, a pyrrolyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a pyridinyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, or a triazinyl group; and those obtained by removing one hydrogen atom from a condensed ring aromatic compound such as a naphthyl group, anthracenyl group, a phenalenyl group, a phenanthrenyl group, a quinolinyl group, an isoquinolinyl group, a quinazolyl group, a phthalazinyl group, a pteridinyl group, a coumarinyl group, an indole group, a benzimidazolyl group, a benzofuranyl group, or an acridinyl group.

[0018] The arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms, and further preferably an arylene group having 6 to 10 carbon atoms. Examples of such arylene groups include a phenylene group, a naphthylene group, an anthracenylene group, and a biphenylene group (-C6H4-C6H4-).

[0019] The component (A) contains an unsaturated bond. This unsaturated bond is preferably a carbon-carbon unsaturated bond. The unsaturated bond is preferably present as a substituent having at least one unsaturated bond. Examples of the unsaturated bond include unsaturated hydrocarbon groups such as an alkenyl group having 2 to 30 carbon atoms and an alkynyl group having 2 to 30 carbon atoms. The unsaturated bond is preferably present as a substituent of an aromatic hydrocarbon group at a terminal, and more preferably present as a substituent of aromatic hydrocarbon groups at both terminals.

[0020] Examples of the alkenyl group having 2 to 30 carbon atoms include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, a 5-hexenyl group, a 1-octenyl group, a 2-octenyl group, a 1-undecenyl group, a 1-pentadecenyl group, a 3-pentadecenyl group, and a 4-pentadecenyl group. Examples of such an alkyl group include a 7-pentadecenyl group, a 1-octadecenyl group, a 2-octadecenyl group, a cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, a 1,3-butadienyl group, a 1,4-butadienyl group, a hexa-1,3-dienyl group, a hexa-2,5-dienyl group, a pentadeca-4,7-dienyl group, a hexa-1,3,5-trienyl group, and a pentadeca-1,4,7-trienyl group.

[0021] Examples of the alkynyl group having 2 to 30 carbon atoms include an ethynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 3-pentynyl group, a 4-pentynyl group, and a 1,3-butadiynyl group.

[0022] Of these, the unsaturated bond is preferably an alkenyl group having 2 to 30 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms, even more preferably an alkenyl group having 2 to 5 carbon atoms, even more preferably an allyl group, an isopropenyl group, or a 1-propenyl group, and particularly preferably an allyl group.

[0023] In addition to the aromatic ester skeleton, component (A) may have any of an aromatic hydrocarbon group, an aliphatic hydrocarbon group, an oxygen atom, a sulfur atom, and a group consisting of a combination thereof. The term "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring, and the aromatic ring may be any of a monocyclic, polycyclic, and heterocyclic ring.

[0024] The aromatic hydrocarbon group is preferably a divalent aromatic hydrocarbon group, more preferably an arylene group or an aralkylene group, and even more preferably an arylene group. The arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms, and even more preferably an arylene group having 6 to 10 carbon atoms. Examples of such an arylene group include a phenylene group, a naphthylene group, an anthracenylene group, and a biphenylene group. The aralkylene group is preferably an aralkylene group having 7 to 30 carbon atoms, more preferably an aralkylene group having 7 to 20 carbon atoms, and even more preferably an aralkylene group having 7 to 15 carbon atoms. Among these, a phenylene group is preferable.

[0025] 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 or a cycloalkylene group. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and further preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, and a hexylene group.

[0026] The cycloalkylene group is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 3 to 15 carbon atoms, and even more preferably a cycloalkylene group having 5 to 10 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclopentylene group, a cycloheptylene group, and cycloalkylene groups represented by the following formulas (a) to (d). In the formulas (a) to (d), "*" represents a bond. [ka]

[0027] The aromatic ester skeleton, aromatic hydrocarbon group, aliphatic hydrocarbon group, and unsaturated hydrocarbon group may have a substituent. Examples of the substituent include an unsaturated hydrocarbon group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom. The substituent may be contained alone or in combination of two or more kinds.

[0028] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an isohexyl group, an n-nonyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclononyl group.

[0029] Examples of the alkoxy group having 1 to 10 carbon atoms include, but are not limited to, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group.

[0030] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. The above-mentioned substituents may further have a substituent (hereinafter, sometimes referred to as a "secondary substituent"). The unsaturated hydrocarbon group is as described above. Unless otherwise specified, the same secondary substituents as those described above may be used.

[0031] The component (A) is preferably either a compound represented by the following general formula (A-1) or a compound represented by the following general formula (A-2). [ka] (In general formula (A-1), Ar 11 each independently represents a monovalent aromatic hydrocarbon group which may have a substituent, Ar 12 each independently represents a divalent aromatic hydrocarbon group which may have a substituent; Ar 13 each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof. n represents an integer of 0 to 10. [ka] (In general formula (A-2), Ar 21 represents an aromatic hydrocarbon group having a valence of m which may have a substituent, Ar 22 each independently represents a monovalent aromatic hydrocarbon group which may have a substituent; and m represents an integer of 2 or 3.

[0032] In general formula (A-1), Ar 11 Each of the groups independently represents a monovalent aromatic hydrocarbon group which may have a substituent. Examples of the monovalent aromatic hydrocarbon group include a phenyl group, a furanyl group, a pyrrolyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a pyridinyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, a triazinyl group, and other monocyclic aromatic compounds from which one hydrogen atom has been removed; a naphthyl group, an anthracenyl group, a phenalenyl group, a phenanthrenyl group, a quinolinyl group, an isoquinolinyl group, a quinazolyl group, a phthalazinyl group, a pteridinyl group, a coumarinyl group, an indole group, a benzimidazolyl group, a benzofuranyl group, a condensed ring aromatic compound from which one hydrogen atom has been removed; and the like. Among these, from the viewpoint of obtaining the effects of the present invention remarkably, a phenyl group is preferred. Ar 11 The monovalent aromatic hydrocarbon group represented by may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton may have. Among them, Ar 11 The substituent preferably contains an unsaturated bond.

[0033] In general formula (A-1), Ar 12each independently represents a divalent aromatic hydrocarbon group which may have a substituent. Examples of the divalent aromatic hydrocarbon group include an arylene group and an aralkylene group, and an arylene group is preferred. As the arylene group, an arylene group having 6 to 30 carbon atoms is preferred, an arylene group having 6 to 20 carbon atoms is more preferred, and an arylene group having 6 to 10 carbon atoms is even more preferred. Examples of such an arylene group include a phenylene group, a naphthylene group, an anthracenylene group, and a biphenylene group. As the aralkylene group, an aralkylene group having 7 to 30 carbon atoms is preferred, an aralkylene group having 7 to 20 carbon atoms is more preferred, and an aralkylene group having 7 to 15 carbon atoms is even more preferred. Among these, a phenylene group is preferred.

[0034] Ar 12 The divalent aromatic hydrocarbon group represented by may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton may have.

[0035] In general formula (A-1), Ar 13 each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof, and a divalent group consisting of a combination thereof is preferable. 12 The divalent aromatic hydrocarbon group represented by the formula (I) is the same as the divalent aromatic hydrocarbon group represented by the formula (I).

[0036] As the divalent aliphatic hydrocarbon group, a divalent saturated aliphatic hydrocarbon group is more preferable, an alkylene group or a cycloalkylene group is preferable, and a cycloalkylene group is more preferable.

[0037] 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 further preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, and a hexylene group.

[0038] The cycloalkylene group is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 3 to 15 carbon atoms, and even more preferably a cycloalkylene group having 5 to 10 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclopentylene group, a cycloheptylene group, and cycloalkylene groups represented by the above formulas (a) to (d), and the cycloalkylene group represented by formula (c) is preferred.

[0039] The divalent group formed by these combinations is preferably a divalent group formed by combining a divalent aromatic hydrocarbon group which may have a substituent and a divalent aliphatic hydrocarbon group which may have a substituent, and more preferably a divalent group formed by alternately combining a plurality of divalent aromatic hydrocarbon groups which may have a substituent and a plurality of divalent aliphatic hydrocarbon groups which may have a substituent. Specific examples of the divalent group include the following divalent groups (A1) to (A8). In the formula, a1 to a8 represent integers of 0 to 10, preferably integers of 0 to 5. "*" represents a bond, and the wavy line represents a structure obtained by reaction of an aromatic compound, an acid halide of an aromatic compound, or an ester of an aromatic compound used in synthesizing the component (A). [ka] [ka]

[0040] Ar 13 The divalent aromatic hydrocarbon group and the divalent aliphatic hydrocarbon group represented by may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton may have.

[0041] In general formula (A-1), n ​​represents an integer of 0 to 10, preferably an integer of 0 to 5, and more preferably an integer of 0 to 3. When the compound represented by general formula (A-1) is an oligomer or polymer, n represents the average value thereof.

[0042] In general formula (A-2), Ar 21 represents an m-valent aromatic hydrocarbon group which may have a substituent. As the m-valent aromatic hydrocarbon group, an m-valent aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, an m-valent aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, and an m-valent aromatic hydrocarbon group having 6 to 10 carbon atoms is even more preferable. Ar 21 The aromatic hydrocarbon group having a valence of m represented by the formula (I) may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton may have.

[0043] In general formula (A-2), Ar 22 each independently represents a monovalent aromatic hydrocarbon group which may have a substituent. 22 represents Ar in general formula (A-1). 11 The aromatic hydrocarbon group represented by Ar 22 The monovalent aromatic hydrocarbon group represented by may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton may have.

[0044] In formula (A-2), m represents an integer of 2 or 3, with 2 being preferred.

[0045] Specific examples of the component (A) include the following compounds. Specific examples of the component (A) include the compounds described in paragraphs 0068 to 0071 of International Publication No. 2018 / 235424 and paragraphs 0113 to 0115 of International Publication No. 2018 / 235425. However, the component (A) is not limited to these specific examples. In the formula, s represents an integer of 0 or 1 or more, and r represents an integer of 1 to 10. [ka]

[0046] The component (A) may be synthesized by a known method. The component (A) can be synthesized by, for example, the method described in WO 2018 / 235424 or WO 2018 / 235425.

[0047] From the viewpoint of significantly obtaining the effects of the present invention, the weight average molecular weight of the component (A) is preferably at least 150, more preferably at least 200, and even more preferably at least 250, and is preferably at most 3000, more preferably at most 2000, and even more preferably at most 1500. The weight average molecular weight of the component (A) is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

[0048] From the viewpoint of obtaining the effects of the present invention remarkably, the unsaturated bond equivalent of the component (A) is preferably 50 g / eq or more, more preferably 100 g / eq or more, even more preferably 150 g / eq, and is preferably 2000 g / eq or less, more preferably 1000 g / eq or less, even more preferably 500 g / eq or less. The unsaturated bond equivalent is the mass of the component (A) containing one equivalent of an unsaturated bond.

[0049] <(B) Radical Polymerizable Compound> The resin composition contains a radically polymerizable compound (B) as the component (B). However, the component (B) does not include those that fall under the category of the component (A). By including the component (B) in the resin composition, it is possible to suppress unevenness that occurs on the cured substrate, and to obtain a cured product that is excellent in dielectric properties and peel strength. The component (B) may be used alone or in combination of two or more types.

[0050] As the component (B), a compound that generates radicals by heat or light and has the function of curing the component (A), that is, a compound having at least one of radically polymerizable unsaturated groups, can be used. As such a compound, it is preferable to use at least one selected from a maleimide-based radical polymerizable compound containing a maleimide group, a vinylphenyl-based radical polymerizable compound containing a vinylphenyl group, a (meth)acrylic-based radical polymerizable compound, an allyl-based radical polymerizable compound, a butadiene-based radical polymerizable compound, and a benzocyclobutene-based radical polymerizable compound, and it is more preferable to use at least one of a maleimide-based radical polymerizable compound, a vinylphenyl-based radical polymerizable compound, a (meth)acrylic-based radical polymerizable compound, and a benzocyclobutene-based radical polymerizable compound, and it is more preferable to use any one of a maleimide-based radical polymerizable compound, a vinylphenyl-based radical polymerizable compound, and a benzocyclobutene-based radical polymerizable compound.

[0051] The (B) component may have a radically polymerizable unsaturated group. 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 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 group is at least one selected from an allyl group, a vinylphenyl group, an acryloyl group, and a methacryloyl group.

[0052] The component (B) 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.

[0053] The maleimide radical polymerizable compound is a compound containing a maleimide group represented by the following formula (B-1) in the molecule. The maleimide radical polymerizable compound includes a solid maleimide radical polymerizable compound and a liquid or semi-solid maleimide radical polymerizable compound. [ka]

[0054] 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.

[0055] (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.

[0056] 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.

[0057] (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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] The solid maleimide compound preferably has a structure represented by the following formula (Ba), for example. [ka]

[0066] [In the formula, R c each independently represents a substituent; X c each independently represents a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO- (preferably a single bond or an alkylene group); Z ceach independently represents a non-aromatic ring which may have a substituent, or an aromatic ring which may have a substituent (preferably an aromatic ring which may have a substituent, particularly preferably an aromatic ring which may have a substituent); s represents an integer of 1 or more (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, and still more preferably an integer of 1 to 20); t represents 0 or an integer of 1 or more; and u represents an integer of 0 to 2 (preferably 0).], and particularly preferably the maleimide compounds represented by the formulae (Ba-1) to (Ba-4):

[0067] [ka]

[0068] [In the formula, R c1 , R c2 and R c3 each independently represents an alkyl group; X c1 and X c2 each independently represents a single bond or an alkylene group; s represents an integer of 1 or more (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, and even more preferably an integer of 1 to 20); t' represents an integer of 1 to 5; and u1, u2, and u3 each independently represent an integer of 0 to 2 (preferably 0). The maleimide compound is represented by the following formula. Note that the s unit, t unit, t' unit, u unit, u1 unit, u2 unit, and u3 unit may be the same or different for each unit.

[0069] In another embodiment, the solid maleimide radical polymerizable compound preferably has a structure represented by the following formula (B-2). [ka] In formula (B-2), R 31 and R 36 represents a maleimide group, and R 32 , R 33 , R 34 and R 35each independently represents a hydrogen atom, an alkyl group, or an aryl group, and D each independently represents a divalent aromatic group. m1 and m2 each independently represent an integer from 1 to 10, and a represents an integer from 1 to 100.

[0070] R in formula (B-2) 32 R 33 R 34 and R 35 each independently represents a hydrogen atom, an alkyl group, or an aryl group, and a hydrogen atom is preferred.

[0071] As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 3 carbon atoms is even more preferred. The alkyl group may be linear, branched, or cyclic. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, and the like.

[0072] The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms. The aryl group may be a monocyclic ring or a condensed ring. Examples of such an aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and the like.

[0073] The alkyl group and the aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom, -OH, -O-C 1-6 alkyl group, -N(C 1-10 alkyl group)2, C 1-10 alkyl group, C 6-10 aryl group, -NH2, -CN, -C(O)O-C 1-10 alkyl group, -COOH, -C(O)H, -NO2, and the like. Here, the term "C p-q " (p and q are positive integers and satisfy p < q) represents that the number of carbon atoms of the organic group described immediately after this term is p to q. For example, "C 1-10The expression "alkyl group" refers to 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 also includes a spiro ring and a fused ring.

[0074] The above-mentioned substituents may further have a substituent (hereinafter, sometimes referred to as a "secondary substituent"). Unless otherwise specified, the secondary substituent may be the same as the above-mentioned substituent.

[0075] D in formula (B-2) represents a divalent aromatic group. Examples of the divalent aromatic group include a phenylene group, a naphthylene group, an anthracenylene group, an aralkyl group, a biphenylene group, and a biphenylaralkyl group. Among them, a biphenylene group and a biphenylaralkyl group are preferred, and a biphenylene group is more preferred. The divalent aromatic group may have a substituent. As the substituent, R in formula (B-2) may be used. 32 The substituents are the same as those that the alkyl group represented by the formula (I) may have.

[0076] m1 and m2 each independently represent an integer of 1 to 10, preferably 1 to 6, more preferably 1 to 3, even more preferably 1 or 2, and still more preferably 1.

[0077] "a" represents an integer of 1 to 100, preferably 1 to 50, more preferably 1 to 20, and further preferably 1 to 5.

[0078] As the solid maleimide-based radically polymerizable compound, a resin represented by formula (B-3) is preferable. [ka] In formula (B-3), R 37 and R 38 represents a maleimide group. a1 represents an integer of 1 to 100.

[0079] a1 is the same as a in formula (B-2), and the preferred range is also the same.

[0080] The weight average molecular weight (Mw) of the solid maleimide-based radically polymerizable compound is preferably 150-5,000, and more preferably 300-2,500.

[0081] The functional group equivalent of the maleimide group in the maleimide-based radically polymerizable compound is preferably 50 g / eq. to 2000 g / eq., more preferably 100 g / eq. to 1000 g / eq., further preferably 150 g / eq. to 500 g / eq., and particularly preferably 200 g / eq. to 300 g / eq.

[0082] The solid maleimide radical polymerizable compound may be a commercially available product. Examples of the commercially available product include "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.; "BMI-50P" manufactured by KI Kasei Co., Ltd.; "BMI-1000", "BMI-1000H", "BMI-1100", "BMI-1100H", "BMI-4000", and "BMI-5100" manufactured by Daiwa Kasei Co., Ltd.; "BMI-4,4'-BPE", "BMI-70" manufactured by KI Kasei Co., Ltd., and "BMI-80" manufactured by KI Kasei Co., Ltd.

[0083] The liquid or semi-solid maleimide radically polymerizable compound is a compound having at least one maleimide group in the molecule.

[0084] The liquid or semi-solid maleimide radically polymerizable compound preferably contains at least one of an alkyl group having 5 or more carbon atoms, an alkylene group having 5 or more carbon atoms, and an alkynylene group having 5 or more carbon atoms.

[0085] 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 a substituent of an alkylene group having 5 or more carbon atoms.

[0086] The number of carbon atoms of the alkylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. The alkylene group may be linear, branched, or cyclic, and linear is preferred. Here, the cyclic alkylene group is a concept that includes the case where it is composed of only a cyclic alkylene group and the case where it contains both a linear alkylene group and a cyclic alkylene group. Examples of such alkylene groups include pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, heptadecylene, hexatriacontylene, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure. The number of carbon atoms in the alkynylene group having 5 or more carbon atoms 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. The alkynylene group may be linear, branched, or cyclic, and linear is preferred. Here, the cyclic alkynylene group is a concept that includes a case where the alkynylene group is only a cyclic alkynylene group and a case where the cyclic alkynylene group contains both a linear alkynylene group and a cyclic alkynylene group. Examples of such alkynylene groups include a pentynylene group, a hexynylene group, a heptynylene 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.

[0087] From the viewpoint of achieving the effects of the present invention remarkably, the liquid or semi-solid maleimide-based radically polymerizable compound preferably contains both an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms.

[0088] The alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring. Examples of the ring formed by bonding to each other include a cyclohexane ring.

[0089] The alkyl group having 5 or more carbon atoms, the alkylene group having 5 or more carbon atoms, and the alkynylene group having 5 or more carbon atoms preferably have no substituent, but may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton in component (A) may have.

[0090] In a liquid or semi-solid maleimide-based radically polymerizable compound, it is preferred that the alkyl group having 5 or more carbon atoms, the alkylene group having 5 or more carbon atoms, and the alkynylene group having 5 or more carbon atoms are directly bonded to a nitrogen atom of the maleimide group.

[0091] 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.

[0092] The liquid or semi-solid maleimide-based radically polymerizable compound is preferably represented by the following general formula (B-4). [ka] In formula (B-4), M represents an aliphatic group having 5 or more carbon atoms which may have a substituent, and L represents a single bond or a divalent linking group.

[0093] M represents an aliphatic group having 5 or more carbon atoms which may have a substituent. Examples of the divalent aliphatic group of M include an alkylene group having 5 or more carbon atoms and an alkynylene group having 5 or more carbon atoms, and the alkylene group having 5 or more carbon atoms and the alkynylene group having 5 or more carbon atoms are as described above. The substituent of M is the same as the substituent that the aromatic ester skeleton in component (A) may have, and the substituent is preferably an alkyl group having 5 or more carbon atoms.

[0094] L represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -C(=O)-, -C(=O)-O-, -NR 0 -(R 0 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom, or C(=O)NR 0-, a divalent group derived from phthalimide, a divalent group derived from pyromellitic diimide, and a group consisting of a combination of two or more of these divalent groups. The alkylene group, alkenylene group, alkynylene group, arylene group, divalent group derived from phthalimide, divalent group derived from pyromellitic diimide, and a group consisting of a combination of two or more of these divalent groups may have an alkyl group having 5 or more carbon atoms as a substituent. The divalent group derived from phthalimide represents a divalent group derived from phthalimide, specifically a group represented by general formula (B-5). The divalent group derived from pyromellitic diimide represents a divalent group derived from pyromellitic diimide, specifically a group represented by general formula (B-6). In the formula, "*" represents a bond. [ka]

[0095] The alkylene group as the divalent linking group in L is preferably an alkylene group having 1 to 50 carbon atoms, more preferably an alkylene group having 1 to 45 carbon atoms, and particularly preferably an alkylene group having 1 to 40 carbon atoms. This alkylene group may be linear, branched, or cyclic. Examples of such alkylene groups include a methylethylene group, a cyclohexylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecylene group, a hexatriacontylene group, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure.

[0096] The alkenylene group as the divalent linking group in L is preferably an alkenylene group having 2 to 20 carbon atoms, more preferably an alkenylene group having 2 to 15 carbon atoms, and particularly preferably an alkenylene group having 2 to 10 carbon atoms. This alkenylene group may be linear, branched, or cyclic. Examples of such alkenylene groups include a methylethylenylene group, a cyclohexenylene group, a pentenylene group, a hexenylene group, a heptenylene group, and an octenylene group.

[0097] The alkynylene group as the divalent linking group in L is preferably an alkynylene group having 2 to 20 carbon atoms, more preferably an alkynylene group having 2 to 15 carbon atoms, and particularly preferably an alkynylene group having 2 to 10 carbon atoms. This alkynylene group may be linear, branched, or cyclic. Examples of such alkynylene groups include a methylethynylene group, a cyclohexynylene group, a pentynylene group, a hexynylene group, a heptynylene group, and an octynylene group.

[0098] The arylene group as the divalent linking group in L is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, still more preferably an arylene group having 6 to 14 carbon atoms, and even more preferably an arylene group having 6 to 10 carbon atoms. Examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.

[0099] The alkylene group, alkenylene group, alkynylene group, and arylene group which are the divalent linking groups in L may have a substituent. The substituent is the same as the substituent which the aromatic ester skeleton in component (A) may have, and is preferably an alkyl group having 5 or more carbon atoms.

[0100] Examples of the group consisting of a combination of two or more divalent groups in L include a divalent group consisting of a combination of an alkylene group, a divalent group derived from phthalimide, and an oxygen atom; a divalent group consisting of a combination of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a divalent group consisting of a combination of 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 alkenylene 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 alkenylene group; a divalent group consisting of a combination of a divalent group derived from an alkenylene group and a divalent group derived from pyromellitic diimide. 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.

[0101] Among them, L in the general formula (B-4) is preferably an oxygen atom, an arylene group having 6 to 24 carbon atoms which may have a substituent, an alkylene group having 1 to 50 carbon atoms which may have a substituent, an alkyl group having 5 or more carbon atoms, a divalent group derived from phthalimide, a divalent group derived from pyromellitic diimide, or a divalent group consisting of a combination of two or more of these groups. Among them, L is more preferably an alkylene group; a divalent group having a structure of an alkylene group-a divalent group derived from phthalimide-oxygen atom-a divalent group derived from phthalimide; a divalent group having a structure of an alkylene group-a divalent group derived from phthalimide-oxygen atom-arylene group-alkylene group-arylene group-oxygen atom-a divalent group derived from phthalimide; or a divalent group having a structure of an alkylene-a divalent group derived from pyromellitic diimide.

[0102] The liquid or semi-solid maleimide radically polymerizable compound represented by general formula (B-4) is preferably represented by general formula (B-7). [ka] In general formula (B-7), M 1each independently represents an aliphatic group having 5 or more carbon atoms which may have a substituent, each Z independently represents an alkylene group having 5 or more carbon atoms which may have a substituent or a divalent group having an aromatic ring which may have a substituent, and t represents an integer of 1 to 10.

[0103] M 1 Each of M independently represents an aliphatic group having 5 or more carbon atoms which may have a substituent. 1 is the same as M in general formula (B-4).

[0104] Each Z independently represents an alkylene group having 5 or more carbon atoms which may have a substituent, or a divalent group having an aromatic ring which may have a substituent. The alkylene group in Z may be any of linear, branched, and cyclic, and among them, a cyclic alkylene group having 5 or more carbon atoms which may have a substituent is preferred. The number of carbon atoms of the alkylene group is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. Examples of such alkylene groups include a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure.

[0105] Examples of the aromatic ring in the divalent group having an aromatic ring represented by Z 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 arylene group and alkylene group are the same as the arylene group and alkylene group in the divalent linking group represented by L in general formula (B-4).

[0106] The alkylene group and the divalent group having an aromatic ring represented by Z may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton in the component (A) may have.

[0107] Specific examples of the group represented by Z include the following groups: In the formula, "*" represents a bond. [ka] [ka]

[0108] The maleimide-based radical polymerizable compound represented by general formula (B-4) is preferably any one of a liquid or semi-solid maleimide-based radical polymerizable compound represented by general formula (B-8) and a liquid or semi-solid maleimide-based radical polymerizable compound represented by general formula (B-9). [ka] In general formula (B-8), M 2 and M 3 each independently represents an aliphatic group having 5 or more carbon atoms which may have a substituent; R 40 each independently represents an oxygen atom, an arylene group, an alkylene group, or a divalent group consisting of a combination of two or more of these groups. t1 represents an integer of 1 to 10. In general formula (B-9), M 4 , M 6 and M 7 each independently represents an aliphatic group having 5 or more carbon atoms which may have a substituent; M 5 each independently represents a divalent group having an aromatic ring which may have a substituent; R 41 and R 42 each independently represents an alkyl group having 5 or more carbon atoms. t2 represents an integer of 0 to 10, and u1 and u2 each independently represent an integer of 0 to 4.

[0109] M 2 and M 3 Each of M independently represents an aliphatic group having 5 or more carbon atoms which may have a substituent. 2 and M 3 is the same as the aliphatic group having 5 or more carbon atoms represented by M in general formula (B-4), and a hexatriacontylene group or a hexatriacontinylene group is preferred.

[0110] R 40 R each independently represents an oxygen atom, an arylene group, an alkylene group, or a group consisting of a combination of two or more of these divalent groups. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (B-4). 40 is preferably an oxygen atom or a group formed from a combination of two or more divalent groups.

[0111] R 40In 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]

[0112] M 4 , M 6 and M 7 Each of M independently represents an aliphatic group having 5 or more carbon atoms which may have a substituent. 4 , M 6 and M 7 is the same as the aliphatic group having 5 or more carbon atoms which may have a substituent represented by M in general formula (B-4), and is preferably a hexylene group, a heptylene group, an octylene group, a nonylene group, or a decylene group, more preferably an octylene group, a hexynylene group, a heptynylene group, an octynylene group, a nonynylene group, or a decynylene group, and more preferably an octynylene group.

[0113] M 5 Each of M independently represents a divalent group having an aromatic ring which may have a substituent. 5 is the same as the divalent group having an aromatic ring which may have a substituent represented by Z in general formula (B-7), and is preferably a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group, and more preferably a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide. The arylene group and alkylene group are the same as the arylene group and alkylene group in the divalent linking group represented by L in general formula (B-4).

[0114] M 5 Specific examples of the group represented by the formula include the following groups: In the formula, "*" represents a bond. [ka]

[0115] R 41 and R 42 R each independently represents an alkyl group having 5 or more carbon atoms. 41 and R 42 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.

[0116] Each of u1 and u2 independently represents an integer of 1 to 15, and an integer of 1 to 10 is preferable.

[0117] Specific examples of the liquid or semi-solid maleimide radical polymerizable compound include the following compounds (B1) to (B3). However, the liquid or semi-solid maleimide radical polymerizable compound is not limited to these specific examples. In the formula, v represents an integer of 1 to 10. [ka] [ka]

[0118] Specific examples of liquid or semi-solid maleimide radical polymerizable compounds include "BMI1500" (compound of formula (B1)), "BMI1700" (compound of formula (B2)), and "BMI689" (compound of formula (B3)), all of which are manufactured by Designer Molecules.

[0119] From the viewpoint of significantly obtaining the desired effects of the present invention, the maleimide group equivalent of the liquid or semi-solid maleimide radical polymerizable compound is preferably 50 g / eq. to 2000 g / eq., more preferably 100 g / eq. to 1000 g / eq., and even more preferably 150 g / eq. to 500 g / eq. The maleimide group equivalent is the mass of the liquid or semi-solid maleimide radical polymerizable compound containing one equivalent of maleimide group.

[0120] 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] (* represents a bond.)

[0121] The vinylphenyl radical polymerizable compound preferably has two or more vinylphenyl groups per molecule, from the viewpoint of obtaining a cured product with a low dielectric tangent.

[0122] The vinylphenyl radical polymerizable compound preferably has a cyclic structure from the viewpoint of obtaining a cured product with a low dielectric tangent. The cyclic structure is preferably a divalent cyclic group. The divalent cyclic group may be 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.

[0123] 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.

[0124] 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.

[0125] Specific examples of the divalent cyclic group include the following divalent groups (xii) and (xiii). [ka] (In the divalent groups (xii) and (xiii), R 51 , R 52 , 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.

[0126] 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.

[0127] In addition, the divalent cyclic group may be a combination of a plurality of divalent cyclic groups. Specific examples of the combination of divalent cyclic groups include the divalent cyclic group represented by the following formula (B4) (divalent group (a)). [ka] (In formula (B4), 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.

[0128] R 71 , R 72 , R 85 and R 86 R in formula (xii) 51 is the same as R 73 , R 74 , R 83 and R 84 R in formula (xii) 53 is the same as R 75 , R 76 , R 77 , R 81 , and R 82 R in formula (xiii) 55 is the same as R 78 , R 79 , and R 80 R in formula (xiii) 58 is the same as:

[0129] 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.

[0130] 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.

[0131] 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.

[0132] The vinylphenyl radical polymerizable compound is preferably represented by the following formula (B-10). [ka] (In formula (B-10), R 91 and R92 each independently represents a divalent linking group. Ring B1 represents a divalent cyclic group.

[0133] 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.

[0134] Ring B1 represents a divalent cyclic group. Ring B is the same as the above divalent cyclic group.

[0135] Ring B1 may have a substituent. The substituent is the same as the substituent that the above divalent cyclic group may have.

[0136] In another embodiment, the vinylphenyl radical polymerizable compound is preferably a compound having a repeating unit represented by formula (B-11) (the number of repeating units is preferably 2 to 200). The compound may be a copolymer further having other styrene skeleton units such as a styrene unit or an ethylstyrene unit. When the compound has other styrene skeleton units, the proportion of the repeating unit of formula (B-11) is preferably 5 to 70 mol% based on the total styrene skeleton units. [ka]

[0137] [In the formula, R e5 , R e6 and R e7 each independently represents a hydrogen atom or a substituent (preferably a hydrogen atom).

[0138] 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 (B4), and q2 is the same as d2 in formula (B4).)

[0139] The vinylphenyl radical polymerizable compound may be a commercially available product, for example, "OPE-2St", "OPE-2St 1200", and "OPE-2St 2200" (vinylbenzyl modified polyphenylene ether) manufactured by Mitsubishi Gas Chemical Company, Inc.; "ODV-XET-X03", "ODV-XET-X04", and "ODV-XET-X05" (divinylbenzene polymer) manufactured by Nippon Steel Chemical & Material Co., Ltd. The vinylphenyl radical polymerizable compound may be used alone or in combination of two or more kinds.

[0140] 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).

[0141] The (meth)acrylic radical polymerizable compound is a compound including an acryloyl group, a methacryloyl group, and a combination thereof. From the viewpoint of significantly obtaining the desired effect 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. The (meth)acrylic radical polymerizable compound is preferably liquid or semi-solid. The determination of liquid or semi-solid is as described above.

[0142] 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.

[0143] 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.

[0144] 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.

[0145] 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]

[0146] 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.

[0147] 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.

[0148] The (meth)acrylic radically polymerizable compound is preferably represented by the following formula (B-11). [ka] (In formula (B-11), R 101 and R 104 each independently represents an acryloyl group or a methacryloyl group, R 102 and R 103 each independently represents a divalent linking group. Ring B2 represents a divalent cyclic group.

[0149] R 101 and R104 each independently represents an acryloyl group or a methacryloyl group, and an acryloyl group is preferred.

[0150] 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.

[0151] Ring B2 represents a divalent cyclic group. Ring B2 is the same as the divalent cyclic group. Ring B2 may have a substituent. The substituent is the same as the substituent that the divalent cyclic group may have.

[0152] Specific examples of the (meth)acrylic radically polymerizable compound include the following, but the present invention is not limited thereto. [ka]

[0153] 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.

[0154] 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.

[0155] The allyl radical polymerizable compound is a compound having at least one allyl group in the molecule. The allyl radical polymerizable compound is preferably liquid or semi-solid. The liquid or semi-solid state is determined as described above. 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 can be preferably 10 or less, more preferably 5 or less.

[0156] 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.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] 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.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] 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.

[0165] 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.

[0166] 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.

[0167] The butadiene-based radical polymerizable compound is preferably in a liquid or semi-solid state. Whether the compound is in a liquid or semi-solid state is determined as described above.

[0168] The benzocyclobutene radical polymerizable compound is a compound having a benzocyclobutene ring. The benzocyclobutene ring may be included in the main chain or in the side chain. Specific examples of the benzocyclobutene radical polymerizable compound include "CYCLOTENE 3022" manufactured by Dow Chemical Company.

[0169] The content of component (B), relative to 100 mass% of the nonvolatile components in the resin composition, is preferably 1 mass% or more, more preferably 5 mass% or more, and even more preferably 10 mass% or more, and is preferably 40 mass% or less, more preferably 35 mass% or less, and even more preferably 30 mass% or less, from the viewpoint of suppressing unevenness on the cured substrate and obtaining a cured product that is excellent in dielectric properties, peel strength, and elongation at break.

[0170] When the content of the (A) component when the nonvolatile components in the resin composition are taken as 100% by mass is a and the content of the (B) component when the nonvolatile components in the resin composition are taken as 100% by mass is b, a / b is preferably 0.05 or more, more preferably 0.1 or more, and even more preferably 0.15 or more, and is preferably 3 or less, more preferably 2 or less, and even more preferably 1.5 or less. By adjusting a / b to be within this range, it is possible to obtain the effects of the present invention significantly.

[0171] <(C) Inorganic filler> In addition to the above-mentioned components, the resin composition may further contain an inorganic filler as an optional component (C).

[0172] 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.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] 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.

[0177] 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, from the viewpoint of obtaining the effects of the present invention remarkably, vinylsilane coupling agents, (meth)acrylic coupling agents, and aminosilane coupling agents are preferred. Moreover, the surface treatment agent may be used alone or in any combination of two or more types.

[0178] 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).

[0179] 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.

[0180] 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:

[0181] 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.

[0182] From the viewpoint of reducing the dielectric properties, the content of the (C) component is preferably 50% by mass or more, more preferably 53% by mass or more, and even more preferably 55% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass, and is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

[0183] <(D) Thermoplastic resin> In addition to the above-mentioned components, the resin composition may further contain a thermoplastic resin as an optional component (D). However, those corresponding to the component (B) are excluded. By including the component (D) in the resin composition, the stress of the resin composition is relaxed, and as a result, it becomes possible to obtain a cured product with excellent dielectric properties. The component (D) may be used alone or in combination of two or more types.

[0184] From the viewpoint of obtaining a cured product with excellent dielectric properties, the weight average molecular weight (Mn) of component (D) 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 (D) is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

[0185] As the (D) component, those having a high weight average molecular weight can be used. Examples of such components include thermoplastic resins such as polyimide resins, polycarbonate resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, polystyrene resins, polyester resins, and bisphenol ether resins. Among them, the (D) component is preferably at least one selected from polyimide resins, polycarbonate resins, phenoxy resins, and bisphenol ether resins, from the viewpoint of obtaining a cured product having excellent dielectric properties.

[0186] The polyimide resin may be a resin having an imide structure, and generally includes those obtained by an imidization reaction between a diamine compound and an acid anhydride.

[0187] The diamine compound for preparing the polyimide resin is not particularly limited, but examples thereof include aliphatic diamine compounds and aromatic diamine compounds.

[0188] 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"). The dimer acid diamine refers to 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.

[0189] Examples of the aromatic diamine compound include a phenylenediamine compound, a naphthalenediamine compound, and a dianiline compound.

[0190] The phenylenediamine compound means a compound consisting of a benzene ring having two amino groups, and further, the benzene ring here may have 1 to 3 optional substituents. The substituents here are not particularly limited. 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.

[0191] 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 here are not particularly limited. Specific examples of the naphthalene diamine compound include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, and 2,3-diaminonaphthalene.

[0192] The dianiline compound means a compound containing two aniline structures in the molecule, and further, each of the two benzene rings in the two aniline structures may further have 1 to 3 optional substituents. The substituents here are not particularly limited. 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 by two bonds.

[0193] Specific examples of the "linker structure" in the 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-, -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-, -C(CH3)2-Ph-C(CH3)2-,

[0194] [ka]

[0195] In this specification, "Ph" represents a 1,4-phenylene group, a 1,3-phenylene group, or a 1,2-phenylene group.

[0196] 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]propane,

[0036] 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, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl)fluorene, 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane, and the like.

[0197] The diamine compound may be a commercially available product or may be synthesized by a known method. The diamine compound may be used alone or in combination of two or more kinds.

[0198] 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.

[0199] 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 330 -R 330 (The same definition as in the following formula (1D)) is preferable. Specific examples of the benzenetetracarboxylic dianhydride include pyromellitic dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride.

[0200] 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 330 -R 330 (The same definition as in the following formula (1D)) is preferable. Specific examples of the naphthalenetetracarboxylic dianhydride include 1,4,5,8-naphthalenetetracarboxylic dianhydride and 2,3,6,7-naphthalenetetracarboxylic dianhydride.

[0201] 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 330 -R 330(The same definition as in the following formula (1D)) is preferable. Specific examples of the anthracenetetracarboxylic dianhydride include 2,3,6,7-anthracenetetracarboxylic dianhydride.

[0202] 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 330 -R 330 (The same definition as in the following formula (1D)) is preferable. Two phthalic anhydrides in the diphthalic dianhydride may 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.

[0203] As the diphthalic dianhydride, for example, a compound represented by the formula (1D):

[0204] [ka]

[0205] [In the formula, R 201 and R 202 each independently represents a halogen atom, a cyano group, a nitro group, or -X 330 -R 330 indicates, X 330 each independently represents a single bond, -NR 330’ -, -O-, -S-, -CO-, -SO2-, -NR 330’ CO-, -CONR 330’ -, -OCO-, or -COO-; R 330 each independently represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, R 330’ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, Y1 represents a single bond or a linker structure having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms, n10 and n11 each independently represent an integer of 0 to 3.] Examples of the compound include compounds represented by the following formula:

[0206] Y 1 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. n10 and n11 are preferably 0.

[0207] Y 1 The "linker structure" in the formula (I) has 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. The "linker structure" is preferably -[A1-Ph] a10 -A1-[Ph-A1] b10 - (wherein, A1 each independently represents a single bond, -(substituted or unsubstituted alkylene group)-, -O-, -S-, -CO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-, and a10 and b10 each independently represent an integer of 0 to 2 (preferably 0 or 1).) is a divalent group represented by the formula.

[0208] Y 1 Specific examples of the "linker structure" in the above formula include -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH(CH3)-, -C(CH3)2-, -O-, -CO-, -SO2-, -Ph-, -O-Ph-O-, -O-Ph-SO2-Ph-O-, -O-Ph-C(CH3)2-Ph-O-, etc. In the present specification, "Ph" represents a 1,4-phenylene group, a 1,3-phenylene group, or a 1,2-phenylene group.

[0209] Specific examples of diphthalic dianhydrides include 4,4'-oxydiphthalic anhydride, 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'-Biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-diphenylethertetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfonetetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethynylidene-4 ,4'-Diphthalic 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 Examples of such anhydrides include 1,3-bis(3,4-dicarboxyphenyl)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, and 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic dianhydride.

[0210] The acid anhydride may be a commercially available product, or may be synthesized by a known method or a method similar thereto. The acid anhydride may be used alone or in combination of two or more kinds.

[0211] The polyimide resin may be a commercially available product, such as "Rikacoat SN20" and "Rikacoat PN20" manufactured by New Japan Chemical Co., Ltd.

[0212] Polycarbonate resins are resins having a carbonate structure. Examples of such resins include carbonate resins having no reactive group, hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, urethane group-containing carbonate resins, and epoxy group-containing carbonate resins. The reactive group here refers to a functional group that can react with other components, such as a hydroxyl group, a phenolic hydroxyl group, a carboxyl group, an acid anhydride group, an isocyanate group, a urethane group, and an epoxy group.

[0213] Commercially available carbonate resins can be used, including "FPC0220" and "FPC2136" manufactured by Mitsubishi Gas Chemical Co., "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Chemicals Corporation, and "C-1090", "C-2090", and "C-3090" (polycarbonate diols) manufactured by Kuraray Co., Ltd.

[0214] 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.

[0215] 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.

[0216] The polyamide-imide resin is a resin having an amide-imide structure. From the viewpoint of compatibility with other components in the resin composition, 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.

[0217] 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).

[0218] A preferred embodiment of the polyamideimide resins (i) to (iii) includes (1) a carboxylic acid group-containing branched polyamideimide 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, this compound may be referred to as "(compound D-1)"); (2) a carboxylic acid group-containing branched polymerizable polyamideimide obtained by reacting a compound having one epoxy group and one or more radically polymerizable unsaturated groups with compound (D-1) (hereinafter, this may be referred to as "compound (D-2)"); or (3) a carboxylic acid group-containing branched polymerizable polyamideimide 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 (D-1) (hereinafter, this may be referred to as "compound (D-3)").

[0219] Specific examples of the compound (D-1) 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.)

[0220] An example of the compound (D-2) 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).

[0221] 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 number of moles of carboxyl groups in compound (D-1). 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.

[0222] An example of the compound (D-3) 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).)

[0223] 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.

[0224] 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.

[0225] 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.

[0226] As the polystyrene resin, any elastomer containing a repeating unit (styrene unit) having a structure obtained by polymerizing styrene can be used. The polystyrene resin may be a copolymer containing any repeating unit different from the styrene unit in combination with the styrene unit, or may be a hydrogenated polystyrene resin.

[0227] 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.

[0228] Examples of polystyrene 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, styrene-maleic anhydride copolymers, etc. Among these, styrene-maleic anhydride copolymers are preferred as polystyrene resins.

[0229] Specific examples of polystyrene resins include "EF-40" manufactured by CRAY VALLEY and "H1043" manufactured by Asahi Kasei Corporation.

[0230] From the viewpoint of compatibility with other components in the resin composition, 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.

[0231] A specific example of the polyester resin is "OKP4HT" manufactured by Osaka Gas Chemicals Co., Ltd.

[0232] Specific examples of polysulfone resins include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0233] 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.

[0234] A specific example of the polyethersulfone resin is "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0235] The bisphenol ether resin is a resin having a bisphenol ether structure. From the viewpoint of obtaining the effects of the present invention more prominently, the bisphenol ether resin preferably contains a repeating unit represented by the following formula (Da): [ka]

[0236] [In the formula, ring A represents an optionally substituted nitrogen-containing aromatic ring; ring B and ring C each independently represent an optionally substituted aromatic ring; and X represents a single bond or a divalent non-aromatic hydrocarbon group.]

[0237] Ring A represents a nitrogen-containing aromatic ring which may have a substituent. The aromatic ring means a ring according to Huckel's rule in which the number of electrons contained in the π electron system on the ring is 4n+2 (n is a natural number). The nitrogen-containing aromatic ring represented by ring A has, in addition to carbon atoms, one or more (preferably two or more, particularly preferably two) nitrogen atoms as ring-constituting atoms, and may further have a heteroatom other than a nitrogen atom, such as an oxygen atom or a sulfur atom. The nitrogen-containing aromatic ring represented by ring A is preferably a 5-14-membered nitrogen-containing aromatic ring, more preferably a 5-10-membered nitrogen-containing aromatic ring, further preferably a 5- or 6-membered nitrogen-containing aromatic ring, and particularly preferably a 6-membered nitrogen-containing aromatic ring. The nitrogen-containing aromatic ring represented by ring A includes not only a monocyclic aromatic ring and a fused ring in which two or more monocyclic aromatic rings are fused, but also a fused ring in which one or more monocyclic non-aromatic rings are fused to one or more monocyclic aromatic rings.

[0238] Specific preferred examples of the nitrogen-containing aromatic ring represented by ring A include monocyclic nitrogen-containing aromatic rings such as a pyrrole ring, an imidazole ring, a pyrazole ring, a 1,2,3-triazole ring, a 1,2,4-triazole ring, a tetrazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a 1,2,3-triazine ring, a 1,2,4-triazine ring, and a 1,3,5-triazine ring; condensed rings of monocyclic nitrogen-containing aromatic rings and benzene rings such as an indole ring, an isoindole ring, a benzimidazole ring, an indazole ring, a benzotriazole ring, a quinoxaline ring, a cinnoline ring, a quinazoline ring, and a phthalazine ring; a pteridine ring, Examples of the ring include a condensed ring between monocyclic nitrogen-containing aromatic rings such as a phosphorus ring, a 4-azaindole ring, a 5-azaindole ring, a 6-azaindole ring, a 7-azaindole ring, a 7-azaindazole ring, a pyrazolo[1,5-a]pyrimidine ring, a 1,8-naphthyridine ring, a pyrido[3,2-d]pyrimidine ring, a pyrido[4,3-d]pyrimidine ring, a pyrido[3,4-b]pyrazine ring, and a pyrido[2,3-b]pyrazine ring. A monocyclic nitrogen-containing aromatic ring is preferred, a 6-membered monocyclic nitrogen-containing aromatic ring is more preferred, a pyrimidine ring or pyridazine ring is even more preferred, and a pyrimidine ring is particularly preferred.

[0239] The nitrogen-containing aromatic ring may have a substituent. The substituent is not particularly limited, but includes monovalent substituents such as alkyl group, alkenyl group, aryl group, alkyl-aryl group (aryl group substituted with one or more alkyl groups), aryl-aryl group (aryl group substituted with one or more aryl groups), aryl-alkyl group (alkyl group substituted with one or more aryl groups), alkyl-oxy group, alkenyl-oxy group, aryl-oxy group, alkyl-carbonyl group, alkenyl-carbonyl group, aryl-carbonyl group, alkyl-oxy-carbonyl group, alkenyl-oxy-carbonyl group, aryl-oxy-carbonyl group, alkyl-carbonyl-oxy group, alkenyl-carbonyl-oxy group, aryl-carbonyl-oxy group, and the like, and may also include divalent substituents such as oxo group (=O) if substitutable.

[0240] The alkyl group refers to a linear, branched, and / or cyclic monovalent aliphatic saturated hydrocarbon group. The alkyl group preferably has 1 to 14 carbon atoms, more preferably has 1 to 10 carbon atoms, and even more preferably has 1 to 6 or 4 to 10 carbon atoms. The alkenyl group refers to a linear, branched, and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The alkenyl group preferably has 2 to 14 carbon atoms, more preferably has 2 to 10 carbon atoms, and even more preferably has 2 to 6 or 4 to 10 carbon atoms. The aryl group refers to a monovalent aromatic hydrocarbon group. The aryl group is preferably an aryl group having 6 to 14 carbon atoms.

[0241] Ring B and ring C each independently represent an aromatic ring which may have a substituent. The aromatic ring represented by ring B or ring C may be a carbocyclic ring having a carbon atom as a ring-constituting atom, or a heterocyclic ring having a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom in addition to a carbon atom as a ring-constituting atom, but in one embodiment, it is preferably a carbocyclic ring. The aromatic ring represented by ring B or ring C is preferably a 5-14-membered aromatic ring, more preferably a 5-10-membered aromatic ring, further preferably a 5- or 6-membered aromatic ring, and particularly preferably a 6-membered aromatic ring. The aromatic ring represented by ring B or ring C includes not only a monocyclic aromatic ring and a fused ring in which two or more monocyclic aromatic rings are fused, but also a fused ring in which one or more monocyclic non-aromatic rings are fused to one or more monocyclic aromatic rings.

[0242] Specific preferred examples of the aromatic ring represented by ring B or ring C include monocyclic aromatic rings such as a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring; a naphthalene ring, an anthracene ring, a benzofuran ring, an isobenzofuran ring, an indole ring, an isoindole ring, a benzothiophene ring, a benzimidazole ring, an indazole ring, and a benzoxazole ring. , a fused ring in which two or more monocyclic aromatic rings, such as a benzisoxazole ring, a benzothiazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, an acridine ring, a quinazoline ring, a cinnoline ring, or a phthalazine ring, are fused; and a fused ring in which one or more monocyclic aromatic rings, such as an indane ring, a fluorene ring, or a tetralin ring, are fused to one or more monocyclic non-aromatic rings. Of these, a monocyclic aromatic ring is preferred, a 6-membered monocyclic aromatic ring is more preferred, and a benzene ring is particularly preferred.

[0243] X is a single bond or a divalent non-aromatic hydrocarbon group. The divalent non-aromatic hydrocarbon group represented by X is a saturated or unsaturated linear, branched and / or cyclic divalent non-aromatic hydrocarbon group. The divalent non-aromatic hydrocarbon group represented by X is, for example, a divalent non-aromatic hydrocarbon group having 1 to 100 carbon atoms, preferably 1 to 50 carbon atoms, more preferably 1 to 30 carbon atoms, and further preferably 1 to 20 carbon atoms.

[0244] X is preferably a divalent non-aromatic hydrocarbon group, more preferably a group represented by the formula (X1):

[0245] [ka]

[0246] [In the formula, R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, or an alkenyl group, or R 1 and R 2are bonded together to form a cycloalkane ring which may have a group selected from an alkyl group and an alkenyl group, or a cycloalkene ring which may have a group selected from an alkyl group and an alkenyl group; * indicates a bonding site.

[0247] [ka]

[0248] [In the formula, R 3 , R 4 , and R 5 each independently represents an alkyl group; x represents an integer of 0 to 5 (preferably 1 to 5, more preferably 2 to 4); and * represents a bonding site.] and particularly preferably a divalent group represented by formula (X2-1).

[0249] The cycloalkane ring refers to a cyclic aliphatic saturated hydrocarbon ring. The cycloalkane ring is preferably a cycloalkane ring having 3 to 8 carbon atoms, more preferably a cycloalkane ring having 5 or 6 carbon atoms. Examples of the cycloalkane ring include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring. The cycloalkene ring refers to a cyclic aliphatic unsaturated hydrocarbon ring having at least one carbon-carbon double bond. The cycloalkene ring is preferably a cycloalkene ring having 4 to 8 carbon atoms, more preferably a cycloalkene ring having 5 or 6 carbon atoms. Examples of the cycloalkene ring include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, a cyclopentadiene ring, and a cyclohexadiene ring.

[0250] The compound containing a repeating unit represented by formula (Da) is preferably represented by formula (1A) or (1B):

[0251] [ka]

[0252] [In the formula, X 1 , X 2 , X 3 and X 4 each independently represents N, CH, or CR a (preferably N or CH) and X 1 , X 2 , X 3 and X 4 at least one (preferably at least two, particularly preferably two) of R a , R b and R c each independently represents a substituent (preferably an alkyl group, an alkenyl group, an aryl group, an alkyl-aryl group, an aryl-aryl group, or an aryl-alkyl group, more preferably an alkyl group, an alkenyl group, or an aryl group, particularly preferably an aryl group); b and c each independently represent an integer of 0 to 3 (preferably 0); and other symbols are the same as in formula (X1). More preferably, the compound is a compound having a repeating unit represented by the formulas (1A-1) to (1B-3):

[0253] [ka]

[0254] [In the formula, a represents an integer of 0 to 2 (preferably 0); the other symbols are the same as in formulae (1A), (1B), and (X2-1) to (X2-3).] and particularly preferably a compound containing a repeating unit represented by formula (1A-1).

[0255] In one embodiment, the compound containing the repeating unit represented by formula (Da) may have a reactive group such as a phenolic hydroxyl group, a thiol group, an amino group, a carboxyl group, a sulfo group, etc., and preferably has a phenolic hydroxyl group. In one embodiment, it is preferable that one molecule has two or more reactive groups.

[0256] In a compound containing a repeating unit represented by formula (Da), the number of repeating units is preferably 5 or more, more preferably 10 or more, even more preferably 30 or more, and particularly preferably 50 or more. The upper limit of the number of repeating units is not particularly limited, and may be, for example, 10,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, etc.

[0257] The glass transition temperature (Tg) of the compound containing a repeating unit represented by formula (Da) is not particularly limited, but may be preferably from 100 to 300°C, more preferably from 150 to 250°C.

[0258] The compound containing a repeating unit represented by formula (Da) can be synthesized, for example, using the method described in WO2019 / 054335 or WO2020 / 021827 or a method equivalent thereto.

[0259] From the viewpoint of obtaining a cured product with excellent dielectric properties, the content of the (D) component, relative to 100 mass% of the non-volatile components in the resin composition, is preferably 0.5 mass% or more, more preferably 1 mass% or more, and even more preferably 1.5 mass% or more, and is preferably 10 mass% or less, more preferably 5 mass% or less, and even more preferably 3 mass% or less.

[0260] <(E) Thermosetting resin> In addition to the above-mentioned components, the resin composition may further contain a thermosetting resin as an optional component (E). However, those corresponding to the components (A) and (B) are excluded. Examples of the thermosetting resin (E) include epoxy resins, phenolic resins, naphthol resins, benzoxazine resins, active ester resins, cyanate ester resins, carbodiimide resins, amine resins, and acid anhydride resins. The component (E) may be used alone or in combination of two or more in any ratio. Hereinafter, resins that can react with epoxy resins to cure the resin composition, such as phenolic resins, naphthol resins, benzoxazine resins, active ester resins, cyanate ester resins, carbodiimide resins, amine resins, and acid anhydride resins, may be collectively referred to as "curing agents".

[0261] Examples of epoxy resins as component (E) include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, etc. The epoxy resins may be used alone or in combination of two or more.

[0262] The resin composition preferably contains, as component (E), an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of significantly obtaining the desired effects of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the non-volatile components of component (E) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0263] Epoxy resins include epoxy resins that are liquid at a temperature of 20° C. (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20° C. (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may contain only a liquid epoxy resin as component (E), may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin.

[0264] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0265] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidyl amine type epoxy resin, and epoxy resin having a butadiene structure are preferred, and bisphenol A type epoxy resin and bisphenol F type epoxy resin are more preferred.

[0266] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "Epicoat 828EL" (bisphenol A type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "630" and "630LSD" (glycidylamine type epoxy resins) manufactured by Mitsubishi Chemical Corporation. ); "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation; "PB-3600" (epoxy resin having a butadiene structure) manufactured by Daicel Corporation; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd. These may be used alone or in combination of two or more types.

[0267] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

[0268] As the solid epoxy resin, bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferred, and naphthalene type epoxy resin is more preferred.

[0269] As the solid epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, and tetraphenylethane-type epoxy resin are preferred, and naphthalene-type tetrafunctional epoxy resin, naphthol-type epoxy resin, and biphenyl-type epoxy resin are more preferred. Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "N" manufactured by Nippon Kayaku Co., Ltd. C3000, "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthalene type epoxy resin) and "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF type epoxy resin), "YL7800" (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), etc. may be mentioned. These may be used alone or in combination of two or more.

[0270] When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (E), the ratio of the amounts thereof (liquid epoxy resin:solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.3 to 1:15, and particularly preferably 1:0.5 to 1:10, in terms of mass ratio. When the ratio of the liquid epoxy resin to the solid epoxy resin is within such a range, the desired effects of the present invention can be significantly obtained. Furthermore, when the composition is used in the form of an adhesive film, appropriate adhesion is usually obtained. Furthermore, when the composition is used in the form of an adhesive film, sufficient flexibility is usually obtained, and handling is improved. Furthermore, a cured product having sufficient breaking strength can usually be obtained.

[0271] The epoxy equivalent of the epoxy resin as component (E) is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., even more preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. Within this range, a cured product having sufficient crosslink density of the cured product of the resin composition can be obtained. The epoxy equivalent is the mass of an epoxy resin containing one equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

[0272] From the viewpoint of significantly obtaining the desired effects of the present invention, the weight average molecular weight (Mw) of the epoxy resin as component (E) is preferably 100 to 5000, more preferably 250 to 3000, and further preferably 400 to 1500. The weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

[0273] The content of the epoxy resin as component (E) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, based on 100% by mass of the non-volatile components in the resin composition, from the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability. The upper limit of the content of the epoxy resin is preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

[0274] As the active ester resin as component (E), a resin having one or more active ester groups in one molecule can be used. Among them, the active ester resin is preferably a resin having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. The active ester resin is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred.

[0275] Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0276] Examples of phenol compounds or naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, etc. Here, the term "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0277] Preferred specific examples of the active ester resin include active ester resins containing a dicyclopentadiene-type diphenol structure, active ester resins containing a naphthalene structure, active ester resins containing an acetylated product of phenol novolac, and active ester resins containing a benzoylated product of phenol novolac. Among them, active ester resins containing a naphthalene structure and active ester resins containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0278] Commercially available active ester resins include active ester resins containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", and "EXB-8000L-65TM" (manufactured by DIC Corporation); active ester resins containing a naphthalene structure, such as "EXB9416-70BK", "EXB-8100L-65T", "EXB-8150L-65T", "EXB-8150-65T", "HPC-8150-60T", and "HPC-8150-62T" (manufactured by DIC Corporation); and phenol novo Examples of active ester resins containing acetylated phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of active ester resins containing benzoylated phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation); examples of active ester resins which are acetylated phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of active ester resins which are benzoylated phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation); and "EXB-8500-65T" (manufactured by DIC Corporation).

[0279] As the phenolic resin and naphtholic resin as component (E), those having a novolak structure are preferred from the viewpoints of heat resistance and water resistance, and from the viewpoint of adhesion to the conductor layer, nitrogen-containing phenolic curing agents are preferred, and triazine skeleton-containing phenolic resins are more preferred.

[0280] Specific examples of phenol-based resins and naphthol-based resins include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemical Industry Co., Ltd.; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", and "SN395" manufactured by Nippon Steel Chemical & Material Co., Ltd.; and "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", and "EXB-9500" manufactured by DIC Corporation.

[0281] Specific examples of benzoxazine-based resins as component (b) include "JBZ-OD100" (benzoxazine ring equivalent: 218), "JBZ-OP100D" (benzoxazine ring equivalent: 218), and "ODA-BOZ" (benzoxazine ring equivalent: 218) manufactured by JFE Chemical Corporation; "Pd" (benzoxazine ring equivalent: 217) and "Fa" (benzoxazine ring equivalent: 217) manufactured by Shikoku Chemical Industry Co., Ltd.; and "HFB2006M" (benzoxazine ring equivalent: 432) manufactured by Showa Polymer Co., Ltd.

[0282] Examples of the cyanate ester resin as component (E) include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl)thioether, and bis(4-cyanate phenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate ester resins include "PT30", "PT30S" and "PT60" (phenol novolac type multifunctional cyanate ester resins), "ULL-950S" (multifunctional cyanate ester resin), "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been converted to triazine to form a trimer), all of which are manufactured by Lonza Japan.

[0283] Specific examples of carbodiimide-based resins as component (E) include Carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216, V-05 (carbodiimide group equivalent: 216), V-07 (carbodiimide group equivalent: 200), V-09 (carbodiimide group equivalent: 200), manufactured by Nisshinbo Chemical Inc.; and Stavaxol (registered trademark) P (carbodiimide group equivalent: 302), manufactured by Rhein Chemie.

[0284] The amine resin as component (E) may be a resin having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc., and among them, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine resin is preferably a primary amine or secondary amine, and more preferably a primary amine. Specific examples of amine resins include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)-2,2'-diphenylpropanediamine, 2,2' ... phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. As the amine-based resin, commercially available products may be used, for example, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

[0285] Examples of the acid anhydride resin as component (E) include resins having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride. Examples of acid anhydrides include anhydrides, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymeric acid anhydrides such as styrene-maleic acid resin, which is a copolymer of styrene and maleic acid.

[0286] When the epoxy resin and the curing agent are contained as the component (E), the ratio of the amount of the epoxy resin to the total amount of the curing agent is preferably in the range of 1:0.01 to 1:5, more preferably 1:0.3 to 1:3, and even more preferably 1:0.5 to 1:2, in terms of the ratio of [total number of epoxy groups in the epoxy resin]:[total number of reactive groups in the curing agent]. Here, the "number of epoxy groups in the epoxy resin" refers to the total value obtained by dividing the mass of the non-volatile components of the epoxy resin present in the resin composition by the epoxy equivalent. In addition, the "number of active groups in the curing agent" refers to the total value obtained by dividing the mass of the non-volatile components of the curing agent present in the resin composition by the active group equivalent. By setting the ratio of the amount of the epoxy resin to the curing agent as the component (E) within this range, a cured product having excellent flexibility can be obtained.

[0287] From the viewpoint of obtaining a cured product having excellent flexibility, the content of the curing agent as component (E) is preferably 1 mass % or more, more preferably 3 mass % or more, and even more preferably 5 mass % or more, relative to 100 mass % of the non-volatile components in the resin composition, and is preferably 20 mass % or less, more preferably 15 mass % or less, and even more preferably 10 mass % or less.

[0288] From the viewpoint of obtaining a cured product having excellent flexibility, the content of the (E) component is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, relative to 100% by mass of the non-volatile components in the resin composition, and is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0289] <(F) Curing accelerator> In addition to the above-mentioned components, the resin composition may further contain a curing accelerator as an optional component (F). By including the component (F), it becomes possible to further accelerate the polymerization by heat.

[0290] Examples of the component (F) include epoxy resin curing accelerators such as phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators; thermal polymerization curing accelerators such as peroxide-based curing accelerators, etc. The component (F) may be used alone or in combination of two or more.

[0291] Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

[0292] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.

[0293] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2, 4-Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-furan Examples of the imidazole compounds include imidazole compounds such as 2-ethyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds and epoxy resins. Of these, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

[0294] As the imidazole-based curing accelerator, a commercially available product may be used, for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0295] Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene. Examples of such biguanide include o-[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide. Of these, dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

[0296] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0297] Examples of peroxide-based curing accelerators include peroxides such as di-t-butyl peroxide, t-butylcumyl peroxide, t-butyl peroxyacetate, α,α'-di(t-butylperoxy)diisopropylbenzene, t-butyl peroxylaurate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, and t-butyl peroxybenzoate.

[0298] Commercially available peroxide curing accelerators include, for example, NOF Corp.'s "Perhexyl D," "Perbutyl C," "Perbutyl A," "Perbutyl P," "Perbutyl L," "Perbutyl O," "Perbutyl ND," "Perbutyl Z," "Percumyl P," and "Percumyl D."

[0299] From the viewpoint of significantly obtaining the desired effects of the present invention, the content of the (F) component, relative to 100 mass% of the non-volatile components in the resin composition, is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, even more preferably 0.3 mass% or more, and is preferably 1 mass% or less, more preferably 0.8 mass% or less, even more preferably 0.5 mass% or less.

[0300] <(G) Other Additives> The resin composition 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 promoters. 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.

[0301] The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which the blending components are mixed and dispersed using a rotary mixer or the like, with the addition of a solvent or the like as necessary.

[0302] <Physical properties and applications of resin compositions> The resin composition contains a predetermined amount of component (A) and component (B). This makes it possible to suppress unevenness occurring on the cured substrate, and to obtain a cured product having excellent dielectric properties, peel strength, and elongation at break. Usually, when the content of the inorganic filler is increased, unevenness occurring on the cured substrate tends to occur easily. However, by containing a combination of predetermined amounts of component (A) and component (B), it becomes possible to suppress the occurrence of unevenness occurring on the cured substrate even if the content of the inorganic filler is high. Furthermore, it becomes possible to obtain a cured product having excellent dielectric properties, peel strength, and elongation at break.

[0303] The resin composition exhibits the characteristic of being able to suppress unevenness occurring on the cured substrate. Specifically, a resin composition layer of a resin sheet is laminated on a glass cloth-based epoxy resin double-sided copper-clad laminate having a copper foil thickness of 18 μm, and then heat-cured at 130° C. for 30 minutes and then at 170° C. for 30 minutes to form an insulating layer. The insulating layer in the portion where the resin sheet is laminated is visually observed, and the surface uniformity of the surface opposite to the glass cloth-based epoxy resin double-sided copper-clad laminate is observed. At this time, the portion inside the portion 1 cm from the outer periphery of the portion where the resin sheet is laminated is usually a uniform surface. Preferably, the entire surface of the insulating layer opposite to the laminate is a uniform surface. Details of the evaluation of unevenness of the cured substrate can be measured according to the method described in the examples described below.

[0304] The resin composition is thermally cured at 130°C for 30 minutes and then at 170°C for 30 minutes to produce a cured product that exhibits excellent peel strength between the resin composition and a conductor layer (plated conductor layer) formed by plating. Thus, the cured product provides an insulating layer that exhibits excellent peel strength between the resin composition and the plated conductor layer. The peel strength is preferably 0.3 kgf / cm or more, more preferably 0.35 kgf / cm or more, and even more preferably 0.4 kgf / cm or more. The upper limit of the peel strength may be 10 kgf / cm or less. The peel strength of the plated conductor layer can be measured according to the method described in the Examples below.

[0305] The cured product obtained by thermally curing the resin composition at 200°C for 90 minutes exhibits the characteristic of a low dielectric constant. Thus, the cured product provides an insulating layer with a low dielectric constant. The dielectric constant is preferably 4 or less, more preferably 3.5 or less, and even more preferably 3 or less. The lower limit of the dielectric constant may be 0.001 or more. The dielectric constant can be measured according to the method described in the examples below.

[0306] The cured product obtained by thermally curing the resin composition at 200°C for 90 minutes exhibits the characteristic of a low dielectric loss tangent. Thus, the cured product provides an insulating layer with a low dielectric loss tangent. The dielectric loss tangent is preferably 0.005 or less, more preferably 0.004 or less, and even more preferably 0.003 or less. The lower limit of the dielectric loss tangent may be 0.0001 or more. The dielectric loss tangent can be measured according to the method described in the examples below.

[0307] A cured product obtained by thermally curing a resin composition at 200°C for 90 minutes exhibits the characteristic of having high toughness and therefore high elongation at break. Thus, the cured product provides an insulating layer with high elongation at break. The elongation at break is preferably 0.5% or more, more preferably 0.8% or more, and even more preferably 1% or more. On the other hand, the upper limit of the elongation at break is not particularly limited, but may be 10% or less. The elongation at break can be evaluated according to the method described in the examples below.

[0308] The resin composition of the present invention can suppress unevenness occurring on the cured substrate, and can provide an insulating layer having excellent dielectric properties, peel strength, and elongation at break. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating purposes. Specifically, it can be suitably used as a resin composition for forming an insulating layer (resin composition for forming an insulating layer) for forming a conductor layer (including a rewiring layer) formed on the insulating layer.

[0309] Furthermore, in the multilayer printed wiring board described below, the resin composition can be suitably used as a resin composition for forming an insulating layer of a multilayer printed wiring board (resin composition for forming an insulating layer of a multilayer printed wiring board) and a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for forming an interlayer insulating layer of a printed wiring board).

[0310] In addition, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for a rewiring formation layer (resin composition for forming a rewiring formation layer) as an insulating layer for forming a rewiring layer, and as a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When a semiconductor chip package is manufactured, a rewiring layer may be further formed on the sealing layer. (1) A step of laminating a temporary fixing film onto a substrate; (2) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (3) forming an encapsulation layer on the semiconductor chip; (4) peeling the substrate and the temporary fixing film from the semiconductor chip; (5) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off; and (6) A process of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0311] [Resin sheet] The resin sheet of the present invention includes a support and a resin composition layer formed from the resin composition of the present invention provided on the support.

[0312] The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 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.

[0313] Examples of the support include films made of plastic materials, metal foils, and release papers, with films made of plastic materials and metal foils being preferred.

[0314] When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0315] When a metal foil is used as the support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferred. As the copper foil, a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0316] The surface of the support to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0317] In addition, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the support with a release layer may be, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. The support with a release layer may be a commercially available product, for example, "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Unipeel" manufactured by Unitika Limited, which are PET films having a release layer mainly composed of an alkyd resin-based release agent.

[0318] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, it is preferable that the total thickness of the support with a release layer is in the above range.

[0319] In one embodiment, the resin sheet may further include other layers as necessary. Examples of such other layers include a protective film equivalent to the support 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, adhesion of dirt and the like to the surface of the resin composition layer and scratches can be suppressed.

[0320] The resin sheet can be produced, for example, by preparing a resin varnish by dissolving a resin composition in an organic solvent, applying this resin varnish onto a support using a die coater or the like, and then drying the same to form a resin composition layer.

[0321] Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. The organic solvents may be used alone or in combination of two or more.

[0322] 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.

[0323] 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.

[0324] [Printed wiring board] The printed wiring board of the present invention includes an insulating layer formed from a cured product of the resin composition of the present invention.

[0325] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet by a method including the following steps (I) and (II). (I) A step of laminating a resin sheet on an inner layer substrate so that a resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) A step of thermally curing the resin composition layer to form an insulating layer

[0326] 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.

[0327] The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as the "thermocompression bonding member") include a heated metal plate (such as a SUS plate) or a metal roll (SUS roll). It is preferable to press the thermocompression member not directly onto the resin sheet, but via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface irregularities of the inner layer substrate.

[0328] The lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably performed under reduced pressure conditions of 26.7hPa or less.

[0329] The lamination can be performed by a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch type vacuum pressure laminator.

[0330] After lamination, the laminated resin sheet may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression conditions for the lamination. The smoothing treatment may be performed using a commercially available laminator. The lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0331] The support may be removed between step (I) and step (II) or after step (II).

[0332] In step (II), the resin composition layer is thermally cured to form an insulating layer. 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.

[0333] 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.

[0334] 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).

[0335] In manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art for use in manufacturing printed wiring boards. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). In addition, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board, as necessary.

[0336] Step (III) is a step of drilling holes in the insulating layer, which allows holes such as via holes and through holes to be formed in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined depending on the design of the printed wiring board.

[0337] Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smears are also removed. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling liquid used in the roughening treatment is not particularly limited, but includes an alkaline solution, a surfactant solution, and the like, and is preferably an alkaline solution, and as the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include "Swelling Dip Securigans P", "Swelling Dip Securigans SBU", and "Swelling Dip Securigant P" manufactured by Atotech Japan. The swelling treatment using a swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan. The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and a commercially available product is, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan. Treatment with a neutralizing solution can be performed by immersing the surface that has been roughened with an oxidizing agent in the neutralizing solution at 30°C to 80°C for 1 to 30 minutes.From the viewpoint of workability etc., a method in which the object that has been subjected to roughening treatment with an oxidizing agent is immersed in a neutralizing solution at 40° C. to 70° C. for 5 minutes to 20 minutes is preferred.

[0338] In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after the roughening treatment is preferably 300 nm or less, more preferably 250 nm or less, and even more preferably 200 nm or less. There is no particular limit to the lower limit, but it is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more. The arithmetic mean roughness (Ra) of the insulating layer surface can be measured using a non-contact surface roughness meter.

[0339] Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among these, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

[0340] The conductor layer may be a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of a nickel-chromium alloy.

[0341] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, and preferably 5 μm to 30 μm.

[0342] In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method, and from the viewpoint of ease of production, it is preferable to form the conductor layer by the semi-additive method. An example of forming the conductor layer by the semi-additive method will be described below.

[0343] First, a plating seed layer is formed on the surface of an insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to a desired wiring pattern. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0344] [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.

[0345] 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).

[0346] 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.

[0347] 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

[0348] 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.

[0349] [Synthesis Example 1: Synthesis of Compound A containing an aromatic ester skeleton and an unsaturated bond (Compound A)] In a reaction vessel, 89 parts by mass of ortho-allylphenol, 110 parts by mass of dicyclopentadiene-phenol copolymer resin (softening point 85°C, hydroxyl equivalent approximately 165g / eq.), and 1000 parts by mass of toluene were charged, and dissolved while the inside of the vessel was purged with nitrogen under reduced pressure. Then, 135 parts by mass of isophthalic acid chloride was charged and dissolved. Next, 0.5g of tetrabutylammonium bromide was added, and 309g of 20% aqueous sodium hydroxide solution was dropped over 3 hours while purging the inside of the vessel with nitrogen. At that time, the temperature in the system was controlled to 60°C or less. Then, the mixture was stirred for 1 hour to react. After the reaction was completed, the reaction mixture was separated and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer became 7, and toluene, etc. were distilled off under heating and reduced pressure conditions to obtain an aromatic ester skeleton and unsaturated bond-containing compound A. The unsaturated bond equivalent of the obtained aromatic ester skeleton and unsaturated bond-containing compound A was 428g / eq. calculated from the charge ratio. Compound A is represented by the following formula, where s is an integer of 0 or 1 or more, and the average value of r calculated from the charge ratio is 1. The wavy line represents a structure obtained by reaction of isophthalic acid chloride with a polyaddition reaction resin of phenol and / or ortho-allylphenol. [ka]

[0350] [Synthesis Example 2: Synthesis of Compound B containing an aromatic ester skeleton and an unsaturated bond (Compound B)] 201 parts by mass of ortho-allylphenol and 1000 parts by mass of toluene were charged into a reaction vessel, and dissolved while the inside of the vessel was purged with nitrogen under reduced pressure. Then, 152 parts by mass of isophthalic acid chloride was charged and dissolved. While purging the inside of the vessel with nitrogen, 309 g of 20% aqueous sodium hydroxide solution was dropped over 3 hours. At that time, the temperature inside the system was controlled to 60°C or less. Then, the mixture was stirred for 1 hour to react. After the reaction was completed, the reaction product was separated and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer became 7, and toluene and the like were distilled off under heating and reduced pressure conditions to obtain an aromatic ester skeleton and unsaturated bond-containing compound B. The unsaturated bond equivalent of the obtained aromatic ester skeleton and unsaturated bond-containing compound B was 199 g / eq. calculated from the charge ratio. Compound B has a structure represented by the following formula. [ka]

[0351] [Synthesis Example 3: Synthesis of polyimide resin] A 500 mL separable flask equipped with a water content receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer was prepared. 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 29.6 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane were added to this flask, and the mixture was stirred at 45°C for 2 hours under a nitrogen stream to carry out a reaction. Next, the reaction solution was heated and maintained at about 160°C, while the condensed water was azeotropically removed together with toluene under a nitrogen stream. It was confirmed that a predetermined amount of water had accumulated in the water content receiver, and that no water was flowing out. After confirmation, the reaction solution was further heated and stirred at 200°C for 1 hour. The mixture was then cooled to obtain a polyimide solution (non-volatile content 20% by mass) containing a polyimide resin having a 1,1,3-trimethylindane skeleton. The obtained polyimide resin 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 was 12,000.

[0352] [ka]

[0353] [ka]

[0354] [Synthesis Example 4: Synthesis of bisphenol ether resin] Into a four-neck flask, 894.96 mmol of dichloropyrimidine, 900.00 mmol of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1.2 mol of potassium carbonate, and N-methyl-2-pyrrolidone (450 g) were placed. After replacing the atmosphere in the flask with nitrogen, the contents of the flask were heated at 130° C. for 6 hours, and water generated during heating was removed from the Dean-Stark tube as needed. After cooling the contents of the flask to room temperature, the precipitated solid was filtered off, methanol was added to the filtrate, the precipitated solid was washed with methanol, and these solids were dried to obtain a bisphenol ether resin (weight average molecular weight (Mw); 87,000 (polystyrene equivalent)). The obtained bisphenol ether resin was 13 The product was confirmed by C-NMR. The bisphenol ether resin has the structure shown in the following formula: [ka]

[0355] [Synthesis Example 5: Synthesis of maleimide resin] An MEK solution (70% by mass of non-volatile components) of a maleimide compound synthesized by the method described in Synthesis Example 1 described in Japan Institute of Invention and Innovation Disclosure Technical Journal Publication No. 2020-500211 was prepared. This maleimide compound has a structure represented by the following formula. [ka]

[0356] When the FD-MS spectrum of the maleimide compound was measured, M +Peaks at n=560, 718 and 876 were confirmed. These peaks correspond to the cases where n1 is 0, 1 and 2, respectively. Furthermore, when the maleimide compound was analyzed by GPC and the value of the number of repeating units n1 of the indane skeleton portion was calculated based on the number average molecular weight, n1=1.47, and the molecular weight distribution (Mw / Mn)=1.81. Furthermore, the content of maleimide compounds having an average number of repeating units n1 of 0 was 26.5 area % in the total amount of maleimide compounds (100 area %).

[0357] [Example 1. Preparation of resin composition 1] 10 parts of compound A obtained in Synthesis Example 1 were dissolved in 10 parts of toluene and 10 parts of MEK under heating while stirring. The obtained solution was cooled to room temperature, and then 80 parts of biphenylaralkyl-type maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g / eq., MEK / toluene mixed solution with non-volatile content of 70%), 15 parts of varnish containing 20 mass% of polyimide resin obtained in Synthesis Example 3, 1 part of curing accelerator ("Perhexyl D" manufactured by NOF Corp.), and 130 parts of inorganic filler (spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) surface-treated with amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)) were mixed and uniformly dispersed in a high-speed rotating mixer to obtain resin composition 1.

[0358] [Example 2. Preparation of resin composition 2] In Example 1, 1) The amount of compound A was changed from 10 parts to 50 parts. 2) The amount of biphenyl aralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g / eq., MEK / toluene mixed solution with 70% non-volatile content) was changed from 80 parts to 70 parts. 3) 7 parts of liquid bismaleimide (Designer Molecules' "BMI689", maleimide group equivalent: 345 g / eq.) 4) 15 parts of the varnish containing 20% ​​by mass of the polyimide resin obtained in Synthesis Example 3 was changed to 12.5 parts of a polyamideimide resin (DIC Corporation's "Unidic V-8000", weight average molecular weight 11,000, ethyl diglycol acetate solution containing 40% by mass of non-volatile components). Resin composition 2 was prepared in the same manner as in Example 1 except for the above.

[0359] [Example 3. Preparation of resin composition 3] In Example 1, 1) The amount of compound A was changed from 10 parts to 20 parts. 2) 80 parts of biphenyl aralkyl type maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g / eq., MEK / toluene mixed solution with 70% non-volatile content) was replaced with 60 parts of oligophenylene ether-styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene solution with 65% non-volatile content), 3) 5 parts of a bifunctional acrylate ((meth)acrylic radical polymerizable compound, "NK Ester A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 326) was used. 4) 15 parts of the varnish containing 20% ​​by mass of the polyimide resin obtained in Synthesis Example 3 was changed to 5 parts of a polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Company, Inc., weight average molecular weight 30,000). Resin composition 3 was prepared in the same manner as in Example 1 except for the above.

[0360] [Example 4. Preparation of resin composition 4] In Example 1, 1) The amount of biphenyl aralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g / eq., MEK / toluene mixed solution with 70% non-volatile content) was changed from 80 parts to 40 parts. 2) 15 parts of the varnish containing 20% ​​by mass of the polyimide resin obtained in Synthesis Example 3 was replaced with 10 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 35,000, 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass); 3) 10 parts of a naphthalene-type epoxy resin (DIC Corporation, "HP4032SS"), 10 parts of a carbodiimide-based resin (Nisshinbo Chemical Corporation, "V-03", active group equivalent of about 216, toluene solution with 50% solids by mass), 20 parts of an active ester-based resin (DIC Corporation, "HPC-8000-65T", active group equivalent of 223, toluene solution with 65% solids by mass), and 1 part of a curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with 10% solids by mass). Resin composition 4 was prepared in the same manner as in Example 1 except for the above.

[0361] [Example 5. Preparation of resin composition 5] In Example 1, 10 parts of Compound A obtained in Synthesis Example 1 was changed to 10 parts of Compound B obtained in Synthesis Example 2. Resin composition 5 was prepared in the same manner as in Example 1 except for the above-mentioned points.

[0362] [Example 6. Preparation of resin composition 6] In Example 3, 20 parts of Compound A obtained in Synthesis Example 1 was changed to 20 parts of Compound B obtained in Synthesis Example 2. Resin composition 6 was prepared in the same manner as in Example 3 except for the above.

[0363] [Example 7. Preparation of resin composition 7] In Example 3, 20 parts of Compound A obtained in Synthesis Example 1 was changed to 50 parts of Compound B obtained in Synthesis Example 2. Resin composition 7 was prepared in the same manner as in Example 3 except for the above.

[0364] [Example 8. Preparation of resin composition 8] In Example 4, 1) 10 parts of compound A obtained in Synthesis Example 1 was replaced with 20 parts of compound B obtained in Synthesis Example 2, 2) 40 parts of biphenyl aralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g / eq., MEK / toluene mixed solution with 70% non-volatile content) was changed to 30 parts of oligophenylene ether-styrene resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene solution with 65% non-volatile content). Resin composition 8 was prepared in the same manner as in Example 4 except for the above.

[0365] [Comparative Example 1. Preparation of Comparative Resin Composition 1] In Example 1, 10 parts of Compound A obtained in Synthesis Example 1 was not used. Comparative resin composition 1 was prepared in the same manner as in Example 1 except for the above-mentioned points.

[0366] [Comparative Example 2. Preparation of Comparative Resin Composition 2] In Example 1, the amount of Compound A obtained in Synthesis Example 1 was changed from 10 parts to 85 parts. Comparative resin composition 2 was prepared in the same manner as in Example 1 except for the above-mentioned points.

[0367] [Comparative Example 3. Preparation of Comparative Resin Composition 3] In Example 6, the amount of compound B obtained in Synthesis Example 2 was changed from 20 parts to 85 parts. Comparative resin composition 3 was prepared in the same manner as in Example 6 except for the above-mentioned points.

[0368] [Example 9. Preparation of resin composition 9] In Example 1, 15 parts of the polyimide resin of Synthesis Example 3 was changed to 15 parts of a cyclohexanone solution of the bisphenol ether resin with a non-volatile content of 20% of Synthesis Example 4. Resin composition 9 was prepared in the same manner as in Example 1 except for the above.

[0369] [Example 10. Preparation of resin composition 10] In Example 1, 80 parts of the biphenylaralkyl-type maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g / eq., MEK / toluene mixed solution with 70% nonvolatile content) was changed to 80 parts of the maleimide resin of Synthesis Example 5 (MEK solution with 70% by mass nonvolatile content). A resin composition 10 was prepared in the same manner as in Example 1 except for the above points.

[0370] [Example 11. Preparation of resin composition 11] In Example 3, the amount of compound A obtained in Synthesis Example 1 was changed from 20 parts to 50 parts, 60 parts of oligophenylene ether-styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Inc. (toluene solution with non-volatile content of 65%) was changed to 67.7 parts of "ODV-XET-X04" manufactured by Nippon Steel Chemical & Material Co., Ltd. (weight average molecular weight 3110, 65 mass% solution), and no bifunctional acrylate ((meth)acrylic radical polymerizable compound, "NK Ester A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 326) was used. Resin composition 11 was prepared in the same manner as in Example 3 except for the above.

[0371] [Example 12. Preparation of resin composition 12] In Example 3, 60 parts of the oligophenylene ether-styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a non-volatile content of 65% was replaced with 44 parts of the benzocyclobutene resin ("CYCLOTENE 3022" manufactured by Dow Chemical Co., Ltd.), and 5 parts of the polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., a weight average molecular weight of 30,000) was replaced with 16.7 parts of the phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., a weight average molecular weight of 35,000, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass). Resin composition 12 was prepared in the same manner as in Example 3, except for the above items.

[0372] [Example 13. Preparation of resin composition 13] In Example 9, 10 parts of Compound A obtained in Synthesis Example 1 was changed to 10 parts of Compound B obtained in Synthesis Example 2. Resin composition 13 was prepared in the same manner as in Example 9 except for the above.

[0373] [Example 14. Preparation of resin composition 14] In Example 10, 10 parts of Compound A obtained in Synthesis Example 1 was changed to 10 parts of Compound B obtained in Synthesis Example 2. Resin composition 14 was prepared in the same manner as in Example 10 except for the above.

[0374] [Example 15. Preparation of resin composition 15] In Example 11, 50 parts of Compound A obtained in Synthesis Example 1 was changed to 20 parts of Compound B obtained in Synthesis Example 2. Resin composition 15 was prepared in the same manner as in Example 11 except for the above.

[0375] [Example 16. Preparation of resin composition 16] In Example 12, 20 parts of Compound A obtained in Synthesis Example 1 was changed to 50 parts of Compound B obtained in Synthesis Example 2. Resin composition 16 was prepared in the same manner as in Example 12 except for the above.

[0376] [Preparation of resin sheet] As a support, a polyethylene terephthalate film ("Lumirror R80" manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130° C.) that had been subjected to a release treatment with an alkyd resin-based release agent ("AL-5" manufactured by Lintec Corporation) was prepared.

[0377] Resin compositions 1 to 16 and comparative resin compositions 1 to 3 were each uniformly applied onto a support by a die coater so that the thickness of the resin composition layer after drying was 40 μm, and dried at 70° C. to 95° C. for 4 minutes to form a resin composition layer on the support. Next, the rough surface of a polypropylene film (Oji F-Tex Co., Ltd. "Alphan MA-411", thickness 15 μm) was attached as a protective film to the surface of the resin composition layer that was not bonded to the support. This resulted in a resin sheet having a support, a resin composition layer, and a protective film in this order.

[0378] [Evaluation of unevenness on cured substrates, measurement of peel strength of plated conductor layer] (1) Preparation of inner layer board Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic "R1515A") with an inner layer circuit formed were etched 1 μm with a microetching agent (Mec "CZ8101") to roughen the copper surface.

[0379] (2) Lamination of resin sheet The protective film was peeled off from the resin sheet to expose the resin composition layer. Using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., 2-stage build-up laminator "CVP700"), the resin composition layer was laminated on both sides of the inner layer substrate so that it was in contact with the inner layer substrate. The lamination was performed by reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less, and then pressing at 120°C and a pressure of 0.74 MPa for 30 seconds. Next, a heat press was performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

[0380] (3) Thermal curing of the resin composition layer Thereafter, the inner layer substrate laminated with the resin sheet was placed in an oven at 130°C and heated for 30 minutes, and then transferred to an oven at 170°C and heated for 30 minutes to thermally cure the resin composition layer and form an insulating layer. Thereafter, the support was peeled off to obtain a cured substrate A having the insulating layer, the inner layer substrate, and the insulating layer in this order.

[0381] <Evaluation of unevenness on cured substrate> For both sides of cured substrate A, the surface uniformity of the portions where the resin sheets were laminated (the surfaces opposite the laminated plate) was visually observed and evaluated as follows. ⊚: No unevenness was observed at all, and the surface was completely uniform. ◯: Unevenness was observed only in the area 1 cm from the outer periphery of the part where the resin sheet was laminated, and the area inside this had a completely uniform surface. ×: Uneven areas were observed in the area 1 cm inside from the outer periphery of the area where the resin sheet was laminated.

[0382] (4) Roughening treatment A desmear treatment was carried out as a roughening treatment on the cured substrate A. The desmear treatment was the following wet desmear treatment. (Wet desmear treatment) The cured substrate A was immersed in a swelling liquid (Atotech Japan's "Swelling Dip Securigant P", an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, then immersed in an oxidizing agent solution (Atotech Japan's "Concentrate Compact CP", an aqueous solution of potassium permanganate at approximately 6% and sodium hydroxide at approximately 4%) at 80°C for 15 minutes, and then immersed in a neutralizing liquid (Atotech Japan's "Reduction Solution Securigant P", an aqueous sulfuric acid solution) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

[0383] (5) Formation of the conductor layer A conductor layer was formed on the roughened surface of the insulating layer according to the semi-additive method. That is, the substrate after the roughening treatment was immersed in an electroless plating solution containing PdCl2 at 40°C for 5 minutes, and then immersed in an electroless copper plating solution at 25°C for 20 minutes. Next, an annealing treatment was performed by heating at 150°C for 30 minutes, and then an etching resist was formed and a pattern was formed by etching. Then, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm, and an annealing treatment was performed at 200°C for 60 minutes. The obtained substrate is called "evaluation substrate B".

[0384] <Measurement of peel strength of plated conductor layer> The peel strength of the insulating layer and the conductor layer was measured in accordance with the Japanese Industrial Standard (JIS C6481). Specifically, a cut was made in the conductor layer of evaluation board B, measuring 10 mm wide and 100 mm long, and one end of the cut was peeled off and held with a gripper. The load (kgf / cm) was measured when 35 mm was peeled off vertically at a speed of 50 mm / min at room temperature, and the peel strength was calculated. A tensile tester (TSE's "AC-50C-SL") was used for the measurement.

[0385] [Measurement of dielectric properties (dielectric constant, dielectric tangent)] The protective film was peeled off from the resin sheet produced in the examples and comparative examples, and the resin composition layer was thermally cured by heating at 200°C for 90 minutes, and then the support was peeled off. The obtained cured product was referred to as "evaluation cured product C". The evaluation cured product C 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 at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C by a cavity resonance perturbation method using an Agilent Technologies "HP8362B". Measurements were performed on three test pieces, and the average value was calculated.

[0386] [Measurement of elongation at break] For the cured product C for evaluation, a tensile test was carried out in accordance with Japanese Industrial Standards (JIS K7127) using a Tensilon universal testing machine ("RTC-1250A" manufactured by Orientec Co., Ltd.) to measure the elongation at break (%).

[0387] [Table 1] [Table 2] *In the table, "content of component (A)" represents the content of component (A) when the total amount of non-volatile components in the resin composition is 100 mass%, and "content of component (C)" represents the content of component (A) when the total amount of non-volatile components in the resin composition is 100 mass%.

[0388] In Examples 1 to 16, it was confirmed that even when components (C) to (F) were not contained, the results were similar to those of the above Examples, although to different degrees.

Claims

1. (A) a compound containing an aromatic ester skeleton and an unsaturated bond, (B) a radical polymerizable compound (excluding those corresponding to component (A)), (C) an inorganic filler, and (D) A resin composition containing a thermoplastic resin (excluding those corresponding to component (B)), The component (A) is either a compound represented by the following general formula (A-1) or a compound represented by the following general formula (A-2), The weight average molecular weight of the (A) component is 150 or more and 3,000 or less, the component (B) is at least one selected from the group consisting of a maleimide-based radical polymerizable compound containing a maleimide group, a vinylphenyl-based radical polymerizable compound containing a vinylphenyl group, a (meth)acrylic-based radical polymerizable compound, an allyl-based radical polymerizable compound, a butadiene-based radical polymerizable compound, and a benzocyclobutene-based radical polymerizable compound, the component (C) is at least one inorganic compound selected from 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; The component (D) is at least one selected from the group consisting of polyimide resins, polycarbonate resins, phenoxy resins, polyamideimide resins, and bisphenol ether resins, The content of the component (A) is 0.1% by mass or more and 30% by mass or less, when the total amount of non-volatile components in the resin composition is 100% by mass, The content of the (B) component is 1% by mass or more and 40% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass, The content of the (C) component is 50% by mass or more, based on 100% by mass of the non-volatile components in the resin composition; A resin composition, wherein the content of the (D) component is 0.5% by mass or more and 40% by mass or less, when the total amount of non-volatile components in the resin composition is 100% by mass. 【Chemistry 1】 (In general formula (A-1), Ar １１ each independently represents a monovalent aromatic hydrocarbon group which may have a substituent; Ar １２ each independently represents a divalent aromatic hydrocarbon group which may have a substituent; Ar １３ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, or a divalent group formed by combining a divalent aromatic hydrocarbon group which may have a substituent and a divalent aliphatic hydrocarbon group which may have a substituent, and n represents an integer of 0 to 10. 【Chemistry 2】 (In general formula (A-2), Ar ２１ represents an m-valent aromatic hydrocarbon group which may have a substituent; Ar ２２ each independently represents a monovalent aromatic hydrocarbon group which may have a substituent; and m represents an integer of 2 or 3.

2. The resin composition described in claim 1, wherein the polyimide resin is a resin obtained by an imidization reaction between an aromatic diamine compound and an aromatic tetracarboxylic dianhydride.

3. A resin composition as described in claim 2, wherein the aromatic diamine compound is a dianiline compound and the aromatic tetracarboxylic dianhydride is diphthalic dianhydride.

4. A resin composition as described in claim 1, wherein the polyamide-imide resin has an isocyanuric ring structure and an alicyclic structure in its molecular structure.

5. The resin composition described in claim 1, wherein the polyamideimide resin has a repeating unit including an isocyanuric ring structure and an alicyclic structure.

6. The resin composition described in claim 1, wherein the bisphenol ether resin contains a repeating unit represented by the following formula (D-a): 【Chemistry 3】 (In formula (D-a), ring A represents an optionally substituted nitrogen-containing aromatic ring; ring B and ring C each independently represent an optionally substituted aromatic ring; and X represents a single bond or a divalent non-aromatic hydrocarbon group.) 7. The resin composition according to claim 6, wherein, in formula (D-a), ring A is a monocyclic nitrogen-containing aromatic ring; rings B and C are monocyclic aromatic rings; and X is a divalent non-aromatic hydrocarbon group.

8. The resin composition according to any one of claims 1 to 6, further comprising (E) a thermosetting resin (excluding those corresponding to the components (A) and (B)).

9. The resin composition according to claim 8 , wherein the component (E) contains an active ester resin.

10. The resin composition according to any one of claims 1 to 9, wherein the resin composition is heat-cured at 200°C for 90 minutes and the cured product has an elongation at break of 1% or more.

11. The resin composition according to any one of claims 1 to 10, which is for forming an insulating layer.

12. The resin composition according to any one of claims 1 to 11, which is for forming an insulating layer for forming a conductor layer.

13. A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition layer comprising the resin composition according to any one of claims 1 to 12.

14. A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 12.

15. A semiconductor device comprising the printed wiring board according to claim 14.

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