Resin composition

Abstract

To provide a resin composition or the like capable of giving a cured product which suppresses the amount of warpage and has low dielectric characteristics.SOLUTION: The resin composition contains (A) an aliphatic maleimide compound, (B) an aromatic maleimide compound, (C) a hollow inorganic filler, and (D) a radically polymerizable resin. When the content of the component (A) is a based on 100 mass% of a nonvolatile component of the resin composition, the content of the component (B) is b based on 100 mass% of the nonvolatile component of the resin composition, and the content of the component (D) is d based on 100 mass% of the nonvolatile component of the resin composition, a / b is 0.1 or more and 6 or less and d / b is 0.1 or more and 6 or less.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 2013-173841 A Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, with the increasing functionality of printed wiring boards, there has been a demand for further improvements in the dielectric loss tangent and dielectric constant of insulating layers. In order to improve the dielectric loss tangent and dielectric constant, a method of including a radical polymerizable resin having an ethylenically unsaturated group in a resin composition can be considered.

[0006] However, as a result of intensive research by the present inventors, it was found that when a radical polymerizable resin is contained in a resin composition, the curing shrinkage increases and the amount of warping of the cured product increases. Hereinafter, the dielectric loss tangent and the dielectric constant may be collectively referred to as the dielectric properties.

[0007] The present invention has been devised in view of the above-mentioned problems, and aims to provide a resin composition which suppresses the amount of warping and which can give a cured product with low dielectric properties; a resin sheet containing the resin composition; and a printed wiring board and a semiconductor device which have an insulating layer formed using the resin composition. [Means for solving the problem]

[0008] As a result of intensive research into the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by adjusting the quantitative ratio of the aliphatic maleimide compound to the aromatic maleimide compound, and the quantitative ratio of the aromatic maleimide compound to the radical polymerizable resin, each to be within a predetermined range, and further by selecting and using a hollow inorganic filler as the inorganic filler, thereby completing the present invention.

[0009] That is, the present invention includes the following. [1] (A) an aliphatic maleimide compound, (B) an aromatic maleimide compound, (C) a hollow inorganic filler, and (D) A resin composition comprising a radical polymerizable resin, The content of the (A) component is represented by a when the non-volatile components of the resin composition are 100% by mass, The content of the (B) component is represented by b when the non-volatile components of the resin composition are 100% by mass, When the content of the (D) component is d when the non-volatile components of the resin composition are 100 mass%, a / b is 0.1 or more and 6 or less, A resin composition having a d / b ratio of 0.1 or more and 6 or less. [2] The resin composition according to [1], wherein the component (D) contains any one of a styrene-based radical polymerizable resin, a (meth)acrylic-based radical polymerizable resin, and an allyl-based radical polymerizable resin. [3] The resin composition according to [1] or [2], wherein the content of component (C) is 20 vol% or more and 70 vol% or less, when the non-volatile components of the resin composition are 100 vol%. [4] The resin composition according to any one of [1] to [3], wherein the elastic modulus of a cured product obtained by thermally curing the resin composition at 190° C. for 90 minutes is less than 10 GPa. [5] The resin composition according to any one of [1] to [4], wherein the resin composition is heat-cured at 190°C for 90 minutes and the cured product has a thermal expansion coefficient of 35 ppm / °C or less. [6] The resin composition according to any one of [1] to [5], wherein the component (A) contains either an aliphatic maleimide compound represented by formula (A-1) or an aliphatic maleimide compound represented by formula (A-2). [ka] In formula (A-1), R 2 and R 3 each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, R 10 each independently represents an oxygen atom, an arylene group, an alkylene group, an alkenylene group, or a divalent group formed from a combination of two or more of these groups. p represents an integer of 1 to 15. In formula (A-2), R 4 , R 6 and R 7 each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, R 5 each independently represents a divalent group having an aromatic ring which may have a substituent; R 12 each independently represents an alkyl group having 5 or more carbon atoms, q represents an integer of 0 to 10, and r1 and r2 each independently represent an integer of 0 to 4. [7] The resin composition according to any one of [1] to [6], wherein the component (B) contains either an aromatic maleimide compound represented by formula (B-1) or an aromatic maleimide compound represented by formula (B-2). [ka] In formula (B-1), R c each independently represents a substituent; X ceach independently represents a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-; Z c each independently represents a non-aromatic ring which may have a substituent, or an aromatic ring which may have a substituent. s represents an integer of 1 or more, each t1 independently represents an integer of 0 to 5, and each u independently represents an integer of 0 to 2. In formula (B-2), Ar a1 represents a divalent aromatic hydrocarbon group which may have a substituent, R a1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; R a2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; R a3 Each of n independently represents a divalent aliphatic hydrocarbon group. a1 represents the average number of repeating units from 0.95 to 10.0, and n a2 each independently represents an integer of 0 to 4; a3 each independently represents an integer of 0 to 3. [8] 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 [7]. [9] A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [7].

[10] A semiconductor device comprising the printed wiring board described in [9]. Effect of the Invention

[0010] According to the present invention, it is possible to provide a resin composition which can suppress the occurrence of warping and give a cured product with low dielectric properties; and a resin sheet, a printed wiring board, and a semiconductor device which use the resin composition. 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 includes (A) an aliphatic maleimide compound, (B) an aromatic maleimide compound, (C) a hollow inorganic filler, and (D) a radical polymerizable resin, and when the content of the (A) component when the non-volatile components of the resin composition are 100% by mass is a, the content of the (B) component when the non-volatile components of the resin composition are 100% by mass is b, and the content of the (D) component when the non-volatile components of the resin composition are 100% by mass is d, a / b is 0.1 to 6 and d / b is 0.1 to 6. In the present invention, the ratio of the amounts of the (A) component and the (B) component, and the ratio of the amounts of the (B) component and the (D) component are adjusted to be within the above-mentioned ranges, respectively, and further, the hollow inorganic filler (C) is selected and contained as the inorganic filler, thereby suppressing the amount of warping and making it possible to obtain a cured product with excellent dielectric properties. In addition, it is usually possible to obtain a cured product with a low thermal expansion coefficient and a low elastic modulus.

[0013] The resin composition may further contain optional components in combination with the components (A) to (D). Examples of the optional components include a curing agent (E), a thermoplastic resin (F), a curing accelerator (G), a radical initiator (H), a solid inorganic filler (I), other additives (J), and a solvent (K). Each component contained in the resin composition of the present invention will be described in detail below.

[0014] <(A) Aliphatic maleimide compound> The resin composition contains an aliphatic maleimide compound (A) as component (A). The aliphatic maleimide compound (A) is a compound containing a maleimide group represented by the following formula (1) in the molecule, and the nitrogen atom of the maleimide group represented by formula (1) is directly bonded to an aliphatic group. Here, "directly" means that there is no other group between the nitrogen atom of the maleimide group represented by the following formula (1) and the aliphatic group. The component (A) may contain an aromatic ring in the molecule, so long as the nitrogen atom of the maleimide group is directly bonded to the aliphatic group. For example, it can be obtained by imidization reaction of a component containing an aliphatic amine compound (such as a diamine compound having a dimer acid skeleton), maleic anhydride, and, if necessary, tetracarboxylic dianhydride. [ka]

[0015] The aliphatic group directly bonded to the nitrogen atom of the maleimide group may be monovalent, divalent, or trivalent or higher. The aliphatic group may be a saturated aliphatic group or an unsaturated aliphatic group. The aliphatic groups may be bonded to each other to form a ring, and the ring structure may include a spiro ring or a condensed ring. It is preferable that the component (A) contains two or more aliphatic groups.

[0016] From the viewpoint of obtaining a cured product with suppressed warpage, the number of carbon atoms of the aliphatic group is preferably 5 or more, more preferably 6 or more, and even more preferably 8 or more, and is preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. In this specification, when a group contains a substituent, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the group, unless otherwise specified. Thus, for example, when an aliphatic group having 5 or more carbon atoms contains a substituent, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the aliphatic group having 5 or more carbon atoms, unless otherwise specified.

[0017] Examples of the aliphatic group include an alkyl group, an alkylene group, an alkenylene group, etc. Therefore, the component (A) is preferably a maleimide compound containing at least one hydrocarbon group selected from the group consisting of an alkyl group having 5 or more carbon atoms which may have a substituent, an alkylene group having 5 or more carbon atoms which may have a substituent, and an alkenylene group having 5 or more carbon atoms which may have a substituent, and is preferably a maleimide compound in which at least one aliphatic hydrocarbon group selected from the group consisting of an alkyl group having 5 or more carbon atoms which may have a substituent, and an alkylene group having 5 or more carbon atoms which may have a substituent is directly bonded to the nitrogen atom of the maleimide group.

[0018] The number of carbon atoms of the alkyl group is preferably 5 or more, more preferably 6 or more, and even more preferably 8 or more, and is 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 is preferably linear. Examples of such alkyl groups include pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. The alkyl group having 5 or more carbon atoms may be used as a substituent of an alkylene group having 5 or more carbon atoms and an alkenylene group having 5 or more carbon atoms.

[0019] The number of carbon atoms of the alkylene group is preferably 5 or more, more preferably 6 or more, and even more preferably 8 or more, and is 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 not only a narrow definition of a cyclic alkylene group, but also a broad definition of 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.

[0020] The number of carbon atoms in the alkenylene group is preferably 5 or more, more preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. The alkenylene group may be linear, branched, or cyclic, and linear is preferred. Here, the cyclic alkenylene group refers to a concept including a case where the alkenylene group is composed of only a cyclic alkenylene group and a case where the alkenylene group contains both a linear alkenylene group and a cyclic alkenylene group. Examples of such alkenylene groups include a pentynylene group, a hexynylene group, a heptylenylene group, an octynylene group, a nonynylene group, a decynylene group, an undecynylene group, a dodecynylene group, a tridecynylene group, a heptadecynylene group, a hexatriacontinylene group, a group having an octynylene-cyclohexynylene structure, a group having an octynylene-cyclohexynylene-octynylene structure, and a group having a propynylene-cyclohexynylene-octynylene structure.

[0021] The aliphatic group may or may not have a substituent. The substituent is not particularly limited, and examples of the substituent include a halogen atom, -OH, -OC 1-6 Alkyl group, -N(C1-10 (alkyl group)2, C 1-20 alkyl group, C 6-10 aryl group, -NH2, -CN, -C(O)O-C 1-10 alkyl group, -COOH, -C(O)H, -NO2, etc. are exemplified. Here, the term "C p-q " (p and q are positive integers, and p < q is satisfied.) represents that the number of carbon atoms of the organic group described immediately after this term is p to q. For example, the expression "C 1-10 alkyl group" indicates an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure includes a spiro ring and a condensed ring.

[0022] The above-mentioned substituents may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). As the secondary substituent, the same ones as the above-mentioned substituents may be used unless otherwise specified.

[0023] (Component (A) may contain an aromatic ring in the molecule as long as an aliphatic group is directly bonded to the nitrogen atom of the maleimide group. Therefore, component (A) may be a maleimide compound containing an aliphatic group directly bonded to the nitrogen atom of the maleimide group and an aromatic ring not directly bonded to the nitrogen atom of the maleimide group. The aromatic ring may be an aromatic carbon ring or an aromatic heterocyclic ring. Further, the aromatic ring may be a monocyclic aromatic ring or a condensed aromatic ring in which two or more monocyclic aromatic rings are condensed. Examples of these aromatic rings include monocyclic aromatic rings such as a benzene ring and a pyridine ring; condensed aromatic rings such as an indane ring, a fluorene ring, and a naphthalene ring. Among them, the aromatic ring is preferably an aromatic carbon ring. The number of carbon atoms of the aromatic carbon ring is preferably 6 or more and 10 or less.

[0024] The number of maleimide groups per molecule of component (A) may be 1, but is preferably 2 or more, preferably 10 or less, more preferably 6 or less, and particularly preferably 3 or less. By using component (A) having two or more maleimide groups per molecule, the effects of the present invention can be remarkably obtained.

[0025] The component (A) is preferably either an aliphatic maleimide compound represented by formula (A-1) or an aliphatic maleimide compound represented by formula (A-2). [ka] In formula (A-1), R 2 and R 3 each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, R 10 each independently represents an oxygen atom, an arylene group, an alkylene group, an alkenylene group, or a divalent group formed from a combination of two or more of these groups. p represents an integer of 1 to 15. In formula (A-2), R 4 , R 6 and R 7 each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, R 5 each independently represents a divalent group having an aromatic ring which may have a substituent; R 12 each independently represents an alkyl group having 5 or more carbon atoms, q represents an integer of 0 to 10, and r1 and r2 each independently represent an integer of 0 to 4.

[0026] In formula (A-1), R 2 and R 3 Each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. The number of carbon atoms of the divalent aliphatic group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. This divalent aliphatic group may be linear, branched, or cyclic, and linear is preferred. Here, the concept of a cyclic aliphatic group includes a case where the group is composed of only a cyclic aliphatic group and a case where the group contains both a linear aliphatic group and a cyclic aliphatic group. Examples of the divalent aliphatic group include an alkylene group and an alkenylene group.

[0027] Examples of the alkylene group include 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, a group having a propylene-cyclohexylene-octylene structure, etc., and a hexatriacontylene group is preferred.

[0028] Examples of the alkenylene group include a pentynylene group, a hexynylene group, a heptylenylene group, an octynylene group, a nonynylene group, a decynylene group, an undecynylene group, a dodecynylene group, a tridecynylene group, a heptadecynylene group, a hexatriacontynylene group, a group having an octynylene-cyclohexynylene structure, a group having an octynylene-cyclohexynylene-octynylene structure, a group having a propynylene-cyclohexynylene-octynylene structure, etc., and a hexatriacontynylene group is preferred.

[0029] The divalent aliphatic group may have a substituent. Examples of the substituent include a halogen atom, -OH, -O-C 1-10 alkyl group, -N(C 1-10 alkyl group)2, C 1-10 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 6-10 aryl group, -NH2, -CN, -C(O)O-C 1-10 alkyl group, -COOH, -C(O)H, -NO2, etc. Here, the term "C x-y " (where x and y are positive integers and x < y) represents that the number of carbon atoms of the organic group described immediately after this term is x to y. For example, the expression "C 1-10 alkyl group" indicates an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure includes a spiro ring and a condensed ring. The substituent is preferably an alkyl group having 5 or more carbon atoms.

[0030] In formula (A-1), R10 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.

[0031] The number of carbon atoms in the arylene group is preferably 6 to 24, more preferably 6 to 18, further preferably 6 to 14, and particularly preferably 6 to 10. Examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.

[0032] Divalent groups formed by combining two or more of these groups include combinations of oxygen atoms, arylene groups, and alkylene groups. Specific examples of divalent groups formed by combining two or more of these groups include the following groups. In the formula, "*" represents a bond. [ka]

[0033] In formula (A-1), R 10 is preferably a divalent group formed by a combination of two or more of these groups, or an oxygen atom.

[0034] In formula (A-1), p represents an integer of 1 to 15, and preferably an integer of 1 to 10.

[0035] In formula (A-2), R 4 , R 6 and R 7 R each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. 4 , R 6 and R 7 is R in formula (A-1) 2 and is preferably a hexylene group, a heptylene group, an octylene group, a nonylene group, or a decylene group, and more preferably an octylene group.

[0036] In formula (A-2), R 5R each independently represents a divalent group having an aromatic ring which may have a substituent. 5 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. 2 is the same as the alkylene group in the divalent aliphatic group having 5 or more carbon atoms represented by

[0037] In formula (A-2), R 5 Specific examples of the group represented by the formula include the following groups: In the formula, "*" represents a bond.

[0038] [ka]

[0039] In formula (A-2), R 12 Each independently represents an alkyl group having 5 or more carbon atoms. 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 an alkyl group include a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. The alkyl group having 5 or more carbon atoms may be a substituent of an alkylene group having 5 or more carbon atoms. Among them, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group are preferred, and a hexyl group and an octyl group are more preferred.

[0040] In formula (A-2), q represents an integer of 0 to 10, preferably an integer of 0 to 8, and particularly preferably 0.

[0041] In formula (A-2), r1 and r2 each independently represent an integer of 0 to 4, preferably an integer of 1 to 3, and more preferably 2.

[0042] Specific examples of the component (A) include the following compounds (a1) to (a4). However, the component (A) is not limited to these specific examples. In the formula, n represents an integer of 1 to 10. [ka] [ka]

[0043] The component (A) may be a commercially available product. Examples of commercially available products of the component (A) include "BMI1500" manufactured by Designer Molecules, "SLK-1500-T80" (compound of formula (a1)) manufactured by Shin-Etsu Chemical Co., Ltd., "BMI1700" (compound of formula (a2)), "BMI3000J" (compound of formula (a3)), "BMI689" (compound of formula (a4)) manufactured by Designer Molecules, "BMI-TMH" manufactured by Daiwa Chemical Industry Co., Ltd., and "SLK-6895-T90" manufactured by Shin-Etsu Chemical Co., Ltd.

[0044] The weight average molecular weight (Mw) of the component (A) is preferably from 150 to 5000, and more preferably from 300 to 2500. The weight average molecular weight can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0045] The maleimide group equivalent of component (A) 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 represents the mass of component (A) containing one equivalent of a maleimide group.

[0046] The content of component (A) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less, based on 100% by mass of the non-volatile components in the resin composition.

[0047] In the present invention, unless otherwise specified, the content of each component in the resin composition is a value when the non-volatile components in the resin composition are taken as 100 mass%, and the non-volatile components mean all non-volatile components in the resin composition excluding the solvent.

[0048] <(B) Aromatic maleimide compound> The resin composition contains an aromatic maleimide compound (B) as component (B). The aromatic maleimide compound (B) as component (B) does not include those corresponding to component (A). The component (B) may be used alone or in combination of two or more kinds.

[0049] The (B) aromatic maleimide compound is a compound containing a maleimide group represented by the above formula (1) in the molecule, and the nitrogen atom of the maleimide group represented by the formula (1) is directly bonded to an aromatic ring. Here, "directly" means that there is no other group between the nitrogen atom of the maleimide group represented by the above formula (1) and the aromatic ring. The (B) component may have an aliphatic group in the molecule, so long as the nitrogen atom of the maleimide group is directly bonded to the aromatic ring. The (B) component can be obtained, for example, by imidization reaction of a component containing an aromatic amine compound (such as an aromatic diamine compound) and maleic anhydride.

[0050] The aromatic ring directly bonded to the nitrogen atom of the maleimide group may be monovalent, divalent, trivalent or higher, and may be a monocyclic, fused ring, or heterocyclic ring.

[0051] The aromatic ring can be a carbocyclic ring or a heterocyclic ring. Examples of the aromatic group include monocyclic aromatic rings such as benzene ring, furan ring, thiophene ring, pyrrole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, imidazole ring, pyridine ring, pyridazine ring, pyrimidine ring, and pyrazine ring; condensed rings in which two or more monocyclic aromatic rings are condensed, such as naphthalene ring, anthracene ring, benzofuran ring, isobenzofuran ring, indole ring, isoindole ring, benzothiophene ring, benzimidazole ring, indazole ring, benzoxazole ring, benzisoxazole ring, benzothiazole ring, quinoline ring, isoquinoline ring, quinoxaline ring, acridine ring, quinazoline ring, cinnoline ring, and phthalazine ring; condensed rings in which one or more monocyclic aromatic rings are condensed to one or more monocyclic non-aromatic rings, such as indane ring, fluorene ring, and tetralin ring. Among these, the aromatic ring is preferably a monocyclic aromatic ring, and more preferably a benzene ring.

[0052] As one embodiment of the component (B), a compound represented by the following formula (B-1) is preferable. [ka] In formula (B-1), 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-; Z c each independently represents a non-aromatic ring which may have a substituent, or an aromatic ring which may have a substituent. s represents an integer of 1 or more, each t1 independently represents an integer of 0 to 5, and each u independently represents an integer of 0 to 2.

[0053] In formula (B-1), R c each independently represents a substituent, and the substituents are the same as the substituents that the aliphatic group in component (A) may have.

[0054] In formula (B-1), Xc each independently represents a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-, and preferably represents a single bond or an alkylene group.

[0055] The alkylene group may be linear, branched, or cyclic, preferably linear or branched, more preferably linear. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 6 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the alkylene group include a methylene group, an ethylene group, a 1-methylethylene group, a propylene group, an n-butylene group, an s-butylene group, a t-butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, and a decylene group, and the like. The methylene group, the ethylene group, the propylene group, the n-butylene group, the s-butylene group, and the t-butylene group are preferred, and the methylene group or the ethylene group is more preferred.

[0056] The alkenylene group may be linear, branched, or cyclic, and is preferably a linear or branched hydrocarbon group, more preferably linear. The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms, and even more preferably an alkenylene group having 3 or 4 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the alkenylene group include an ethenylene group, a propenylene group, a butenylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, a nonenylene group, and a decenylene group.

[0057] The alkylene group and alkenylene group may have a substituent. The substituent is the same as the substituent that may be possessed by the aliphatic group in component (A).

[0058] In formula (B-1), Z cEach of the 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, and particularly preferably a benzene ring which may have a substituent. The aromatic ring is as described above.

[0059] In formula (B-1), s represents an integer of 1 or more, preferably an integer of 1 to 100, more preferably an integer of 1 to 50, and further preferably an integer of 1 to 20.

[0060] In formula (B-1), each t1 independently represents an integer of 0 to 5, preferably an integer of 1 to 5, and more preferably an integer of 0 or 1 or more.

[0061] In formula (B-1), each u independently represents an integer of 0 to 2, and is preferably 0.

[0062] The compound represented by formula (B-1) is preferably a compound represented by formulas (B-1-2) to (B-1-5). [ka] 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 greater; t' represents an integer of 0 to 5; and v1, v2, and v3 each independently represent an integer of 0 to 2. Note that the s unit, t unit, t' unit, v unit, v1 unit, v2 unit, and v3 unit may be the same or different for each unit.

[0063] In formulas (B-1-2) to (B-1-5), R c1 , R c2 and R c3 each independently represents an alkyl group, and the alkyl group is the same as the alkyl group that may be substituted on the aliphatic group in component (A).

[0064] In formulas (B-1-2) to (B-1-5), X c1 and X c2 each independently represents a single bond or an alkylene group, and the alkylene group is X c is the same as the alkylene group represented by the formula (I).

[0065] In formulas (B-1-2) to (B-1-5), 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.

[0066] In the formulas (B-1-2) to (B-1-5), t' represents an integer of 1 to 5 and is the same as t1 in the formula (B-1).

[0067] In formulas (B-1-2) to (B-1-5), v1, v2 and v3 each independently represent an integer of 0 to 2, and preferably 0.

[0068] The compound represented by formula (B-1) is preferably a compound represented by formula (B-1-6). [ka] In the formula, R 31 , R 32 , R 33 and R 34 each independently represents a hydrogen atom, an alkyl group, or an aryl group, and each E independently represents a divalent aromatic group. m1 and m2 each independently represent an integer of 1 to 10, and a represents an integer of 1 to 100.

[0069] In formula (B-1-6), R 31 , R 32 , R 33 and R 34 each independently represents a hydrogen atom, an alkyl group, or an aryl group, and is preferably a hydrogen atom.

[0070] The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be linear, branched, or cyclic. Examples of such alkyl groups include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an isopropyl group.

[0071] The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms. The aryl group may be a single ring or a condensed ring. Examples of such aryl groups include a phenyl group, a naphthyl group, and an anthracenyl group.

[0072] The alkyl group and aryl group may have a substituent. The substituents are the same as those that the aliphatic group in component (A) may have.

[0073] In formula (B-1-6), E 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. The substituent is the same as the substituent that the aliphatic group in component (A) may have.

[0074] In formula (B-1-6), 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.

[0075] In formula (B-1-6), a represents an integer of 1 to 100, preferably 1 to 50, more preferably 1 to 20, and further preferably 1 to 5.

[0076] The component (B-1) is preferably a resin represented by formula (B-1-7). [ka] In the formula, a1 represents an integer of 1 to 100.

[0077] In formula (B-1-7), a1 is the same as a in formula (B-1-6), and the preferred range is also the same.

[0078] The compound represented by formula (B-1) can be a commercially available product. Examples of the commercially available compound represented by formula (B-1) include "MIR-3000-70MT" (biphenylaralkyl-type maleimide resin) manufactured by Nippon Kayaku Co., Ltd.; "BMI-70", "BMI-80", "BMI-50P", and "BMI-4,4'-BPE" manufactured by Keiai Kasei Co., Ltd.; and "BMI-1000", "BMI-1000H", "BMI-1100", "BMI-1100H", "BMI-4000", "BMI-5100", and "BMI-2300" manufactured by Daiwa Kasei Co., Ltd.

[0079] The weight average molecular weight (Mw) of the compound represented by formula (B-1) is preferably 150-5,000, and more preferably 300-2,500.

[0080] The functional group equivalent of the maleimide group in the compound represented by formula (B-1) is preferably 50 g / eq. to 2000 g / eq., more preferably 100 g / eq. to 1000 g / eq., even more preferably 150 g / eq. to 500 g / eq., and particularly preferably 200 g / eq. to 300 g / eq.

[0081] Another embodiment of the component (B) is a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and including a skeleton in which the aromatic ring and the aliphatic hydrocarbon ring are condensed. Examples of the skeleton in which the aromatic ring and the aliphatic hydrocarbon ring are condensed include an indane skeleton, a trimethylindane skeleton, a tetralin skeleton, a benzocyclobutene skeleton, and an indene skeleton. Among them, from the viewpoint of obtaining the effect of the present invention remarkably, the skeleton in which the aromatic ring and the aliphatic hydrocarbon ring are condensed is preferably a trimethylindane skeleton. Therefore, another embodiment of the component (B) is a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and including a trimethylindane skeleton. The trimethylindane skeleton represents a skeleton shown in the following formula (2). [ka]

[0082] The benzene ring contained in the trimethylindane skeleton may have a substituent bonded thereto. The substituent is the same as the substituent that may be possessed by the aliphatic group in component (A).

[0083] The number of substituents bonded to one benzene ring contained in the trimethylindane skeleton may be 1 or 2 or more. The number of substituents bonded to a benzene ring contained in the trimethylindane skeleton is usually 0 to 3. When the number of substituents is 2 or more, the 2 or more substituents may be the same or different. In particular, it is preferable that no substituents are bonded to the benzene ring contained in the trimethylindane skeleton.

[0084] The number of trimethylindane skeletons contained in one molecule of a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of a maleimide group and including a trimethylindane skeleton may be 1 or more. The upper limit may be, for example, 10 or less, 8 or less, 7 or less, or 6 or less.

[0085] The maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and containing a trimethylindane skeleton further contains an aromatic ring skeleton in addition to the above-mentioned trimethylindane skeleton. The number of ring-constituting carbon atoms of the aromatic ring skeleton is preferably 6 to 10. Examples of the aromatic ring skeleton include a benzene ring skeleton and a naphthalene ring skeleton.

[0086] The number of aromatic ring skeletons contained in one molecule of a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and containing a trimethylindane skeleton is preferably 1 or more, more preferably 2 or more, and preferably 6 or less, more preferably 4 or less, and particularly preferably 3 or less. When a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and containing a trimethylindane skeleton contains two or more aromatic ring skeletons in addition to the trimethylindane skeleton, these aromatic ring skeletons may be the same or different.

[0087] The aromatic ring contained in the aromatic ring skeleton may have a substituent bonded thereto. Examples of the substituent include the above-mentioned substituents that may be bonded to the benzene ring contained in the trimethylindane skeleton, and a nitro group. The number of substituents bonded to one aromatic ring may be 1 or 2 or more. The number of substituents bonded to an aromatic ring is usually 0 to 4. When the number of substituents is 2 or more, the 2 or more substituents may be the same or different.

[0088] The maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and containing a trimethylindane skeleton preferably further contains a divalent aliphatic hydrocarbon group in addition to the above-mentioned trimethylindane skeleton. In particular, when the maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and containing a trimethylindane skeleton contains an aromatic ring skeleton other than the benzene ring contained in the trimethylindane skeleton, the maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and containing a trimethylindane skeleton preferably contains a divalent aliphatic hydrocarbon group. In this case, the divalent aliphatic hydrocarbon group preferably connects between the benzene ring and the aromatic ring skeleton contained in the trimethylindane skeleton. In addition, the divalent aliphatic hydrocarbon group preferably connects between the aromatic ring skeletons.

[0089] The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 or more, preferably 12 or less, more preferably 8 or less, and particularly preferably 5 or less. As the divalent aliphatic hydrocarbon group, an alkylene group as a saturated aliphatic hydrocarbon group is more preferable. As the divalent aliphatic hydrocarbon group, a straight-chain alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, or a hexamethylene group; a branched-chain alkylene group such as an ethylidene group (-CH(CH3)-), a propylidene group (-CH(CH2CH3)-), an isopropylidene group (-C(CH3)2-), an ethylmethylmethylene group (-C(CH3)(CH2CH3)-), a diethylmethylene group (-C(CH2CH3)2-), or a dimethylmethylene group; and the like. When a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and containing a trimethylindane skeleton contains two or more divalent aliphatic hydrocarbon groups in addition to the trimethylindane skeleton, those divalent aliphatic hydrocarbon groups may be the same or different.

[0090] The maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and containing a trimethylindane skeleton is preferably a compound represented by the following formula (B-2). [ka] In formula (B-2), Ar a1 represents a divalent aromatic hydrocarbon group which may have a substituent, R a1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; R a2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; R a3 Each of n independently represents a divalent aliphatic hydrocarbon group. a1 represents the average number of repeating units from 0.95 to 10.0, and n a2 each independently represents an integer of 0 to 4; a3 each independently represents an integer of 0 to 3.

[0091] In formula (B-2), Ar a1represents a divalent aromatic hydrocarbon group which may have a substituent. The number of carbon atoms in this divalent aromatic hydrocarbon group is preferably 6 or more, preferably 20 or less, more preferably 16 or less. Examples of the divalent aromatic hydrocarbon group include a phenylene group and a naphthylene group. Examples of the substituent that the divalent aromatic hydrocarbon group may have include an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, and a mercapto group. The hydrogen atom of each substituent may be further substituted with a halogen atom. Specific examples of these substituents include the same examples as the substituents which may be bonded to the benzene ring contained in the trimethylindane skeleton. When the divalent aromatic hydrocarbon group has a substituent, the number of the substituents is preferably 1 to 4. When the divalent aromatic hydrocarbon group has two or more substituents, the two or more substituents may be the same or different. a1 is preferably an unsubstituted divalent aromatic hydrocarbon group.

[0092] In formula (B-2), R a1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group. The hydrogen atoms of the alkyl group, the alkyloxy group, the alkylthio group, the aryl group, the aryloxy group, the arylthio group, and the cycloalkyl group may be substituted with a halogen atom. Specific examples of these groups include the same examples as the substituents that can be bonded to the benzene ring contained in the trimethylindane skeleton. Among them, R a1is more preferably one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms, and is particularly preferably an alkyl group having 1 to 4 carbon atoms.

[0093] In formula (B-2), R a2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group. The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with a halogen atom. Specific examples of these groups include the same examples as the substituents that can be bonded to the benzene ring contained in the trimethylindane skeleton. Among them, R a2 is more preferably one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

[0094] In formula (B-2), R a3 each independently represents a divalent aliphatic hydrocarbon group. The preferred range of the divalent aliphatic hydrocarbon group is as described above.

[0095] In formula (B-2), n a1 represents the average number of repeating units of 0.95 to 10.0. a1 is more preferably 0.98 or more, even more preferably 1.0 or more, and particularly preferably 1.1 or more, and is preferably 10.0 or less, more preferably 8.0 or less, even more preferably 7.0 or less, and particularly preferably 6.0 or less.

[0096] In formula (B-2), n a2 Each independently represents an integer of 0 to 4. a2is preferably 2 or 3, more preferably 2. a2 may be different, but are preferably the same. a2 When is an integer between 2 and 4, multiple R a1 may be the same or different within the same ring.

[0097] In formula (B-2), n a3 Each independently represents an integer of 0 to 3. a3 may be different, but are preferably the same. a3 is preferably 0. a3 If is 2-3, R a2 may be the same or different in the same ring.

[0098] The compound represented by formula (B-2) is preferably a compound represented by the following formula (B-2-1). [ka] In the formula, R b1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; R b2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; b1 represents the average number of repeating units from 0.95 to 10.0; n b2 each independently represents an integer of 0 to 4; b3 R each independently represents an integer of 0 to 3. b1The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group of R may be substituted with halogen atoms. b2 The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with halogen atoms. b2 If is between 2 and 4, R b1 may be the same or different in the same ring. b3 If is 2-3, R b2 may be the same or different in the same ring.

[0099] In formula (B-2-1), R b1 , R b2 , n b1 , n b2 and n b3 respectively represent R in formula (B-2). a1 , R a2 , n a1 , n a2 and n a3 is the same as:

[0100] The maleimide group equivalent of the maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and containing a trimethylindane skeleton is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, particularly preferably 200 g / eq. or more, and preferably 2000 g / eq. or less, more preferably 1000 g / eq. or less, particularly preferably 800 g / eq. or less. The maleimide group equivalent represents the mass of the maleimide compound per equivalent of maleimide group. When the maleimide group equivalent of the maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and containing a trimethylindane skeleton is within the above range, the effects of the present invention can be significantly obtained.

[0101] There is no particular limitation on the method for producing a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and containing a trimethylindane skeleton. A maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and containing a trimethylindane skeleton can be produced, for example, by the method described in the Japan Institute of Invention and Innovation Disclosure Technical Bulletin No. 2020-500211. According to the production method described in the Japan Institute of Invention and Innovation Disclosure Technical Bulletin No. 2020-500211, a maleimide compound having a distribution in the number of repeating units of the trimethylindane skeleton can be obtained.

[0102] Specific examples of the compound represented by formula (B-2) include the following compounds (b21) to (b23). However, the compound represented by formula (B-2) is not limited to these specific examples. In the formula, n represents the average number of repeating units of 0.95 to 10.0. [ka]

[0103] From the viewpoint of significantly obtaining the desired effects of the present invention, the maleimide group equivalent of the (B) component is preferably 100 g / eq. to 10,000 g / eq., more preferably 1,100 g / eq. to 9,000 g / eq., and even more preferably 120 g / eq. to 8,000 g / eq. The maleimide group equivalent is the mass of the (B) component containing one equivalent of a maleimide group.

[0104] The weight average molecular weight (Mw) of the component (B) is preferably 150 to 16,000, and more preferably 200 to 15,000.

[0105] From the viewpoint of obtaining a remarkable effect of the present invention, the molecular weight of the (B) component is preferably 200 or more, more preferably 300 or more, and even more preferably 400 or more, and is preferably 100,000 or less, more preferably 80,000 or less, and even more preferably 60,000 or less.

[0106] The content of the (B) component is preferably 1% by mass or more, more preferably 2% by mass or more, based on 100% by mass of the non-volatile components in the resin composition, and the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.

[0107] When the content of the (A) component when the nonvolatile components in the resin composition are 100% by mass is a and the content of the (B) component when the nonvolatile components in the resin composition are 100% by mass is b, a / b is 0.1 or more, preferably 0.15 or more. The upper limit is 6 or less, preferably 5.5 or less, more preferably 5 or less, and even more preferably 4.5 or less, or 4 or less. By adjusting the quantitative ratio of the (A) component and the (B) component to be within this range, it is possible to reduce the amount of warping of the cured product.

[0108] <(C) Hollow inorganic filler> The resin composition contains a hollow inorganic filler (C) as the component (C). By including the hollow inorganic filler (C) in the resin composition, it is possible to obtain a cured product with a reduced amount of warping. The hollow inorganic filler (C) is usually included in the resin composition in the form of particles. The hollow inorganic filler (C) may be used alone or in combination of two or more kinds.

[0109] As described above, when a radical polymerizable resin is contained in a resin composition, the curing shrinkage increases, and the cured product warps more. In order to reduce the curing shrinkage, a method of containing an inorganic filler with an average porosity of 0% by volume (hereinafter, an inorganic filler with an average porosity of 0% by volume may be referred to as a "solid inorganic filler") in the resin composition is considered. However, as a result of the study by the present inventors, it was found that when a solid inorganic filler is contained, the stress generated during curing increases with the increase in the elastic modulus of the cured product, and the suppression of the amount of warping is not improved. In the present invention, by using a hollow inorganic filler instead of a solid inorganic filler, the elastic modulus of the cured product of the resin composition decreases, and as a result, the occurrence of the amount of warping can be suppressed.

[0110] (C) An inorganic compound is used as the material of the hollow inorganic filler. Examples of the material of the hollow inorganic filler (C) 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.

[0111] In addition, inorganic complex oxides may be used as the material for the hollow inorganic filler (C). The inorganic complex oxide refers to an oxide containing two or more types of atoms selected from the group consisting of metal atoms and metalloid atoms. As such an inorganic complex oxide, an oxide containing a combination of silicon and one or more types of atoms selected from the group consisting of metal atoms and metalloid atoms other than silicon is preferable. Examples of metal atoms to be combined with silicon include aluminum, lead, nickel, cobalt, copper, zinc, zirconium, iron, lithium, magnesium, barium, potassium, calcium, titanium, boron, sodium, etc., and among them, aluminum is particularly preferable. Therefore, as the inorganic complex oxide, an oxide containing silicon and aluminum is preferable, and an aluminosilicate is particularly preferable.

[0112] Among these materials for the hollow inorganic filler (C), silica, alumina and aluminosilicate are preferred, with silica being particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. Furthermore, spherical silica is preferred as the silica.

[0113] The (C) hollow inorganic filler may be a monohollow particle having only one hole inside the particle, a multihollow particle having two or more holes inside the particle, or a combination of a monohollow particle and a multihollow particle.

[0114] Since the hollow inorganic filler (C) has pores, it usually has a porosity of more than 0 volume %. From the viewpoint of reducing the amount of warping of the cured product of the resin composition, the porosity of the hollow inorganic filler (C) is preferably 10 volume % or more, more preferably 15 volume % or more, and particularly preferably 20 volume % or more. In addition, from the viewpoint of the mechanical strength of the cured product of the resin composition, the porosity of the hollow inorganic filler is preferably 95 volume % or less, more preferably 90 volume % or less, and particularly preferably 85 volume % or less.

[0115] The porosity P (volume %) of a particle is defined as the volume ratio of the total volume of one or more pores present inside the particle to the total volume of the particle based on the outer surface of the particle (total volume of pores / volume of particle). This porosity P is calculated by multiplying the measured value of the actual density D of the particle by the volume ratio of the particle. M (g / cm 3 ), and the theoretical density of the material that forms the particle D T (g / cm 3 ) can be calculated using the following formula (1).

number

[0116] (C) Hollow inorganic filler generally has voids formed within the particle and an outer shell formed of an inorganic material surrounding the voids. Usually, the voids are separated from the outside of the particle by the outer shell. In this case, it is desirable that the voids do not communicate with the outside of the particle. Therefore, it is desirable that the outer shell is a non-porous shell that does not have holes that communicate the voids with the outside of the particle. The fact that the outer shell is non-porous can be confirmed by observation with a transmission electron microscope (TEM).

[0117] From the viewpoint of obtaining the effects of the present invention remarkably, the average particle size of the hollow inorganic filler (C) is preferably 0.01 μm or more, more preferably 0.1 μm or more, particularly preferably 0.3 μm or more, and is preferably 5 μm or less, more preferably 4 μm or less, particularly preferably 3 μm or less.

[0118] The average particle size of particles can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, a particle size distribution of particles 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 of the inorganic filler can be prepared by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing the inorganic filler 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 the inorganic filler 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.

[0119] In order to obtain the effects of the present invention remarkably, the BET specific surface area of ​​the hollow inorganic filler (C) is preferably 1 m 2 / g or more, more preferably 2m 2 / g or more, particularly preferably 5m 2 / g or more, preferably 100m 2 / g or less, more preferably 50m 2 / g or less, particularly preferably 30m 2 The BET specific surface area of ​​the particles can be measured by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multipoint method.

[0120] The hollow inorganic filler (C) may be a commercially available product. Examples of commercially available hollow inorganic filler (C) include "LHP-208" manufactured by Ube Exsymo Co., Ltd. and "MG-005" manufactured by Taiheiyo Cement Corporation.

[0121] The hollow inorganic filler (C) may be produced, for example, by the method described in Japanese Patent No. 5940188 or a method equivalent thereto. To give a specific example, hollow silica particles as one example of the hollow inorganic filler (C) can be produced by a method including the steps of: preparing an aqueous solution containing a substance capable of forming pores and a basic compound; mixing and stirring the aqueous solution with an alkoxysilane to precipitate silica particles; removing the substance capable of forming pores from the silica particles to obtain hollow silica precursors; and calcining the hollow silica precursors.

[0122] (C) The hollow inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. One type of surface treatment agent may be used alone, or two or more types may be used in any combination.

[0123] Examples of commercially available surface treatment agents include 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), 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).

[0124] From the viewpoint of improving dispersibility, the degree of surface treatment with the surface treatment agent is preferably within a specific range. Specifically, 100% by mass of the hollow inorganic filler is preferably surface-treated with 0.2% to 8% by mass of the surface treatment agent, more preferably with 0.2% to 5% by mass of the surface treatment agent, and even more preferably with 0.3% to 3% by mass of the surface treatment agent.

[0125] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the hollow 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 preventing an increase in the melt viscosity of the resin composition, it is more preferable that the content is 1.0 mg / m 2 Less than 0.8 mg / m is preferred. 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0126] The amount of carbon per unit surface area of ​​the hollow inorganic filler can be measured after the surface-treated hollow 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 hollow 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 hollow inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, the "EMIA-320V" manufactured by Horiba, Ltd., or the like can be used.

[0127] The content (volume %) of component (C) is preferably 10 vol% or more, more preferably 15 vol% or more, and even more preferably 30 vol% or more, and is preferably 80 vol% or less, more preferably 75 vol% or less, and even more preferably 70 vol% or less, assuming the non-volatile components of the resin composition to be 100 vol%.

[0128] The content (mass %) of component (C) is preferably 10 mass % or more, more preferably 15 mass % or more, and even more preferably 20 mass % or more, and is preferably 80 mass % or less, more preferably 75 mass % or less, and even more preferably 70 mass % or less, assuming the non-volatile components of the resin composition to be 100 mass %.

[0129] <(D) Radical polymerizable resin> The resin composition contains a radical polymerizable resin (D) as the component (D). The radical polymerizable resin (D) as the component (D) does not include those corresponding to the components (A) to (C). The component (D) may be used alone or in combination of two or more kinds.

[0130] As described above, when a radical polymerizable resin is contained in a resin composition, the curing shrinkage increases, and the amount of warping of the cured product increases. In the present invention, the amount of warping can be reduced by adjusting the amount of the radical polymerizable resin to the amount of the aromatic maleimide compound (B) so that the amount of the radical polymerizable resin is within a predetermined range.

[0131] (D) radical polymerizable resin may contain an ethylenically unsaturated bond. Therefore, (D) radical polymerizable resin may have a radical polymerizable group containing an ethylenically unsaturated bond. Examples of the radical polymerizable group include unsaturated hydrocarbon groups such as vinyl group, allyl group, styryl group, 1-propenyl group, 3-cyclohexenyl group, 3-cyclopentenyl group, 2-vinylphenyl group, 3-vinylphenyl group, and 4-vinylphenyl group; and α,β-unsaturated carbonyl groups such as acryloyl group and methacryloyl group. Among them, the ethylenically unsaturated bond is preferably one or more selected from an allyl group, a styryl group, a vinylphenyl group, an acryloyl group, and a methacryloyl group. (D) radical polymerizable resin preferably has two or more radical polymerizable groups.

[0132] Examples of the (D) radically polymerizable resin include styrene-based radically polymerizable resins, (meth)acrylic-based radically polymerizable resins, and allyl-based radically polymerizable resins, with styrene-based radically polymerizable resins being preferred.

[0133] The styrene radical polymerizable resin is, for example, a compound having one or more, preferably two or more, vinyl groups directly bonded to an aromatic carbon atom. Examples of the styrene radical polymerizable resin include low molecular weight (molecular weight less than 1000) styrene compounds such as divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl)ether; high molecular weight (molecular weight 1000 or more) styrene compounds such as vinylbenzyl-modified polyphenylene ether resin and styrene-divinylbenzene copolymer. Commercially available styrene-based radical polymerizable resins include, for example, "ODV-XET(X03)", "ODV-XET(X04)", and "ODV-XET(X05)" (styrene-divinylbenzene copolymers) manufactured by Nippon Steel Chemical & Material Co., Ltd., and "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Co., Inc.

[0134] The (meth)acrylic radical polymerizable resin is, for example, a compound having one or more, preferably two or more, acryloyl groups and / or methacryloyl groups. Examples of the (meth)acrylic radical polymerizable resin include cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonane dimethanol di(meth)acrylate, 1,2-dicyclohexane dimethanol di(meth)acrylate, 1,3-dicyclohexane dimethanol ... Low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylic acid ester compounds such as diol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; dioxane glycol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, ) acrylate, 3,6,9-trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, and other low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylic acid ester compounds; tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and other low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylic acid ester compounds; and high molecular weight (molecular weight 1000 or more) acrylic acid ester compounds such as (meth)acrylic modified polyphenylene ether resins.Commercially available (meth)acrylic radical polymerizable resins include, for example, "A-DOG" (dioxane glycol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" (tricyclodecane dimethanol diacrylate) and "DCP" (tricyclodecane dimethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., "KAYARAD R-684" (tricyclodecane dimethanol diacrylate) and "KAYARAD R-604" (dioxane glycol diacrylate) manufactured by Nippon Kayaku Co., Ltd., and "SA9000" and "SA9000-111" (methacrylic-modified polyphenylene ether) manufactured by SABIC.

[0135] The allyl-based radically polymerizable resin is, for example, a compound having one or more, preferably two or more, allyl groups. Examples of allyl radical polymerizable resins include aromatic carboxylic acid allyl ester compounds such as diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, and diallyl 2,3-naphthalenecarboxylate; isocyanuric acid allyl ester compounds such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; epoxy-containing aromatic allyl compounds such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; benzoxazine-containing aromatic allyl compounds such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane; ether-containing aromatic allyl compounds such as 1,3,5-triallyl ether benzene; and allyl silane compounds such as diallyl diphenyl silane. Commercially available allyl radical polymerizable resins include, for example, "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Chemical Industry Co., Ltd., "DAD" (diallyl diphenate) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., "TRIAM-705" (triallyl trimellitate) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., "DAND" (2,3-diallyl naphthalene carboxylate) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., and "ALP-d" (bis[3 Examples of such aryl groups include "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane) manufactured by Nippon Kayaku Co., Ltd., "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Kasei Corporation, and "NE-V-1100-70T" (a compound containing multiple allyl groups and multiple benzene rings) manufactured by DIC Corporation.

[0136] The ethylenically unsaturated bond equivalent of the (D) radical polymerizable resin is preferably 20 g / eq. to 3,000 g / eq., more preferably 50 g / eq. to 2,500 g / eq., further preferably 70 g / eq. to 2,000 g / eq., and particularly preferably 90 g / eq. to 1,500 g / eq. The ethylenically unsaturated bond equivalent represents the mass of the radical polymerizable resin per equivalent of the ethylenically unsaturated bond.

[0137] The weight average molecular weight (Mw) of the radical polymerizable resin (D) is preferably 40,000 or less, more preferably 10,000 or less, further preferably 5,000 or less, and particularly preferably 3,000 or less. The lower limit is not particularly limited, but may be, for example, 150 or more. The weight average molecular weight can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0138] The content of component (D) is preferably 0.1% by mass or more, more preferably 1% by mass or more, and is preferably 35% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and 20% by mass or less, based on 100% by mass of non-volatile components in the resin composition.

[0139] When the content of the (D) component is d when the non-volatile components in the resin composition are 100% by mass, d / b is 0.1 or more, preferably 0.15 or more. The upper limit is 6 or less, preferably 5.5 or less, more preferably 5 or less, and even more preferably 4.8 or less. By adjusting the ratio of the (B) component and the (D) component to be within this range, it is possible to obtain a cured product with reduced warpage.

[0140] <(E) Hardener> The resin composition may contain a curing agent (E) as an optional component. The curing agent (E) as the component (E) does not include those corresponding to the above-mentioned components (A) to (D). The component (E) usually has a function of curing the resin composition by reacting with the components (A) and (B). The component (E) may be used alone or in combination of two or more kinds in any ratio.

[0141] The (E) curing agent may be either an anionic curing agent or a cationic curing agent, but from the viewpoint of obtaining the effects of the present invention more prominently, an anionic curing agent is preferred.

[0142] Examples of the component (E) include active ester-based curing agents, phenol-based curing agents, benzoxazine-based curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, cyanate ester-based curing agents, etc. Among these, from the viewpoint of obtaining the effects of the present invention significantly, it is preferable that the component (E) contains any one of a phenol-based curing agent, a benzoxazine-based curing agent, and a carbodiimide-based curing agent.

[0143] The phenol-based curing agent may be a curing agent having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring (such as a benzene ring or a naphthalene ring) in one molecule. Among them, a compound having a hydroxyl group bonded to a benzene ring is preferred. From the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolac structure is preferred. From the viewpoint of adhesion, a nitrogen-containing phenol-based curing agent is preferred, and a triazine skeleton-containing phenol-based curing agent is more preferred. In particular, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, a triazine skeleton-containing phenol novolac curing agent is preferred.

[0144] Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Chemical Industry Co., Ltd.; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; and "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-495V", "SN-375", and "SN-39" manufactured by Nippon Steel Chemical & Material Co., Ltd. 5); DIC's "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", and "KA-1165"; Gun-ei Chemical's "GDP-6115L", "GDP-6115H", and "ELPC75"; and SABIC's "SA90".

[0145] Specific examples of carbodiimide-based curing agents include "V-03", "V-05", and "V-07" manufactured by Nisshinbo Chemical Inc.; and Stavaxol (registered trademark) P manufactured by Lanxess AG.

[0146] Specific examples of benzoxazine-based curing agents include "ODA-BOZ" manufactured by JFE Chemical Corporation, "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0147] Examples of the acid anhydride curing agent include a curing agent having one or more acid anhydride groups in one molecule.Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic 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 benzophenone. Examples of the acid anhydride include tetracarboxylic dianhydride, 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 resins in which styrene and maleic acid are copolymerized. Commercially available acid anhydride curing agents may be used, such as "MH-700" manufactured by New Japan Chemical Co., Ltd.

[0148] Examples of active ester curing agents include curing agents having one or more active ester groups in one molecule. Among them, active ester curing agents are preferably compounds 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 curing agent 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 curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred.

[0149] 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.

[0150] 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.

[0151] Preferred specific examples of the active ester curing agent include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structure consisting of phenylene-dicyclopentylene-phenylene.

[0152] Commercially available active ester curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", and "EXB-8000L-65TM" (manufactured by DIC Corporation); and active ester compounds containing a naphthalene structure, such as "HPC-8150-60T", "HPC-8150-62T", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65T", and "EXB9416- Examples of such curing agents include "70BK" and "EXB-8151-62T" (manufactured by DIC Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent which is an acetylated phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester curing agents which are benzoylated phenol novolac.

[0153] The amine-based curing agent may be a curing agent 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-based curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of amine-based curing agents 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)propanediamine, and the like. bis(4-aminophenyl)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. The amine-based curing agent may be a commercially available product, 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.

[0154] Examples of cyanate ester curing agents 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 curing agents include "PT30" and "PT60" manufactured by Arxada (both are 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); and the like.

[0155] From the viewpoint of significantly obtaining the effects of the present invention, the content of the (E) curing agent is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, and even more preferably 0.5 mass% or more, based on 100 mass% of the non-volatile components in the resin composition, and is preferably 10 mass% or less, more preferably 8 mass% or less.

[0156] <(F)Thermoplastic resin> The resin composition may contain a thermoplastic resin (F) as an optional component. The thermoplastic resin (F) as the component (F) does not include those corresponding to the components (A) to (E). The component (F) may be used alone or in combination of two or more kinds.

[0157] Examples of (F) thermoplastic resins include polyimide resins, phenoxy resins, polyvinyl acetal resins, polystyrene resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins.

[0158] 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. 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", "YL7482", and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation.

[0159] Specific examples of polyimide resins include "PIAD200" manufactured by Arakawa Chemical Industry Co., Ltd., "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., and "Rikacoat SN20" and "Rikacoat PN20" manufactured by New Japan Chemical Co., Ltd. Specific examples of these polyimide resins also include modified polyimide resins such as linear polyimide resins obtained by reacting bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (polyimide resins described in JP-A-2006-37083), and polysiloxane skeleton-containing polyimide resins (polyimide resins described in JP-A-2002-12667 and JP-A-2000-319386, etc.).

[0160] 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 "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", and "Denka Butyral 6000-EP" manufactured by Denka Co., Ltd.; 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.

[0161] Examples of polystyrene resins include unmodified polystyrene resins, oxazoline group-containing modified polystyrene resins, and styrene block copolymers. Examples of styrene block copolymers include styrene-isoprene-styrene block copolymers (SIS resins), styrene-ethylene-butylene-styrene block copolymers (SEBS resins), styrene-ethylene-propylene-styrene block copolymers (SEPS resins), styrene-butadiene-styrene block copolymers (SBS resins), and styrene-isobutylene-styrene block copolymers (SIBS resins). Specific examples of polystyrene resins include "PX3-RP-37" and "RP-RX-61" (oxazoline group-containing modified polystyrene resins) manufactured by Nippon Shokubai; and "HYBRAR 5125 (SIS resin); Asahi Kasei's "S1611" (SEBS resin); Asahi Kasei's "H1041", "Tuftec H1043", "Tuftec P2000", and "Tuftec MP10" (hydrogenated styrene-based thermoplastic resins); Daicel's "Epofriend AT501" and "CT310" (epoxidized styrene-butadiene thermoplastic resins); Kuraray's "Septon HG252" (modified polystyrene resin with hydroxyl groups); Asahi Kasei's "Tuftec N503M" (modified polystyrene resin with carboxyl groups); Asahi Kasei's "Tuftec N501" (modified polystyrene resin with amino groups); Asahi Kasei's "Tuftec M1913" (modified polystyrene resin with acid anhydride groups); Kuraray's "Septon S8104" (unmodified polystyrene resin); Kraton's "FG1924" (styrene-ethylene / butylene-styrene block copolymer); "EF-40" (CRAY VALLEY Co., Ltd. As the polystyrene resin, an oxazoline group-containing modified styrene resin is preferable.

[0162] Examples of polyolefin resins include ethylene-based copolymer resins such as low-density polyethylene, very low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; and polyolefin polymers such as polypropylene and ethylene-propylene block copolymer.

[0163] Examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxy group-containing polybutadiene resins, phenolic hydroxy group-containing polybutadiene resins, carboxy group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, isocyanate group-containing polybutadiene resins, urethane group-containing polybutadiene resins, polyphenylene ether-polybutadiene resins, and the like.

[0164] Specific examples of polyamide-imide resins include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide-imide resins also include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imide) manufactured by Resonac Corporation.

[0165] A specific example of the polyethersulfone resin is "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0166] Specific examples of polysulfone resins include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0167] The polyphenylene ether resin may be a copolymer of polyphenylene ether and polybutadiene. A specific example of the polyetherimide resin is "Ultem" manufactured by GE.

[0168] Examples of polycarbonate resins include 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, and urethane group-containing carbonate resins. Specific examples of polycarbonate resins include Mitsubishi Gas Chemical's "FPC0220," Asahi Kasei's "T6002" and "T6001" (polycarbonate diols), and Kuraray's "C-1090," "C-2090," and "C-3090" (polycarbonate diols). Specific examples of polyether ether ketone resins include Sumitomo Chemical's "Sumiploy K."

[0169] Examples of polyester resins include polyethylene terephthalate resins, polyethylene naphthalate resins, polybutylene terephthalate resins, polybutylene naphthalate resins, polytrimethylene terephthalate resins, polytrimethylene naphthalate resins, and polycyclohexane dimethyl terephthalate resins.

[0170] From the viewpoint of significantly obtaining the desired effects of the present invention, the weight average molecular weight (Mw) of the (F) thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, and particularly preferably 20,000 or more, and is preferably 70,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less.

[0171] The content of the (F) thermoplastic resin is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and is preferably 15% by mass or less, based on 100% by mass of the non-volatile components in the resin composition.

[0172] <(G) Curing accelerator> The resin composition may contain a curing accelerator (G) as an optional component. The curing accelerator (G) as the component (G) does not include those corresponding to the components (A) to (F). Examples of the curing accelerator (G) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. The amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferred, and either the amine-based curing accelerators or the imidazole-based curing accelerators are more preferred. The curing accelerator may be used alone or in combination of two or more types.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] As the imidazole-based curing accelerator, commercially available products may be used, such as "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", and "C11Z-A" manufactured by Shikoku Chemical Industry Co., Ltd.; and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0177] 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.

[0178] 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.

[0179] The content of the (G) curing accelerator, when the non-volatile components in the resin composition are taken as 100 mass%, is preferably 0.01 mass% or more, more preferably 0.03 mass% or more, and particularly preferably 0.05 mass% or more, and is preferably 3 mass% or less, more preferably 1 mass% or less, and particularly preferably 0.5 mass% or less.

[0180] <(H) Radical Polymerization Initiator> The resin composition may contain a radical polymerization initiator (H) as an optional component. The radical polymerization initiator (H) as this component (H) excludes those corresponding to the components (A) to (G). The radical polymerization initiator (H) may be, for example, a thermal polymerization initiator that generates free radicals when heated. The radical polymerization initiator (H) may be a polymerization initiator of a radical reactive group. The radical polymerization initiator (H) may be used alone or in any combination of two or more kinds.

[0181] (H) Examples of the radical polymerization initiator include peroxide-based radical polymerization initiators, azo-based radical polymerization initiators, etc. Among these, peroxide-based radical polymerization initiators are preferred.

[0182] Examples of the peroxide radical polymerization initiator include hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; dialkyl peroxide compounds such as tert-butylcumyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, dicumyl peroxide, 1,4-bis(1-tert-butylperoxy-1-methylethyl)benzene, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; and diacyl peroxide compounds such as dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, and bis(4-tert-butylcyclohexyl)peroxydicarbonate. peroxyester compounds such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanoate, tert-hexylperoxyisopropyl monocarbonate, tert-butyl peroxylaurate, (1,1-dimethylpropyl)2-ethylperhexanoate, tert-butyl 2-ethylperhexanoate, tert-butyl 3,5,5-trimethylperhexanoate, tert-butylperoxy-2-ethylhexyl monocarbonate, and tert-butylperoxymaleic acid.

[0183] Examples of the azo radical polymerization initiator include azonitrile compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, and 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile; 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], and the like. azo amide compounds such as 2,2'-azobis[2-methyl-N-[2-(1-hydroxybutyl)]-propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis(2-methylpropionamide) dihydrate, 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); alkyl azo compounds such as 2,2'-azobis(2,4,4-trimethylpentane) and 2,2'-azobis(2-methylpropane); and the like.

[0184] (H) Commercially available radical polymerization initiators include, for example, “Perbutyl C”, “Perbutyl A”, “Perbutyl P”, “Perbutyl L”, “Perbutyl O”, “Perbutyl ND”, “Perbutyl Z”, “Perbutyl I”, “Percumyl P”, “Percumyl D”, “Perhexyl D”, “Perhexyl A”, “Perhexyl I”, “Perhexyl Z”, “Perhexyl ND”, “Perhexyl O”, and “Perhexyl PV”, all manufactured by NOF Corporation.

[0185] The content of the (H) radical polymerization initiator is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 0.1 mass% or more, and is preferably 1.5 mass% or less, more preferably 1 mass% or less, even more preferably 0.5 mass% or less, based on 100 mass% of the non-volatile components in the resin composition.

[0186] <(I) Solid inorganic filler> The resin composition may contain (I) a solid inorganic filler as an optional component within a range that does not impair the effects of the present invention. The solid inorganic filler refers to an inorganic filler that does not substantially have voids or holes, and has an average porosity of 0 volume %.

[0187] The material for component (I) is an inorganic compound, and is the same as the material for component (C).

[0188] Examples of commercially available products of component (I) include "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" manufactured by Denka Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" manufactured by Tokuyama Corporation; and "Cellspheres" and "MGH-005" manufactured by Taiheiyo Cement Corporation.

[0189] The average particle size of component (I) is preferably 0.01 μm or more, more preferably 0.1 μm or more, and even more preferably 0.3 μm or more, and is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The average particle size of component (I) can be measured by the same method as that for measuring the average particle size of component (C).

[0190] The BET specific surface area of ​​component (I) is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, preferably 100m 2 / g or less, more preferably 70m 2 / g or less, more preferably 40m 2 The specific surface area of ​​component (I) can be measured by the same method as that for measuring the specific surface area of ​​component (C).

[0191] From the viewpoint of improving moisture resistance and dispersibility, it is preferable that the (I) component is treated with a surface treatment agent. The surface treatment agent is the same as the surface treatment agent that may be used to treat the (C) component. The degree of surface treatment and the amount of carbon are also the same as those of the (C) component.

[0192] The content of component (I) is preferably 70 mass% or less, more preferably 65 mass% or less, particularly preferably 60 mass% or less, and preferably 5 mass% or more, assuming the non-volatile components in the resin composition to be 100 mass%.

[0193] <(J) Other Additives> The resin composition may further contain other additives as optional components in addition to the above-mentioned components. (I) Other additives include, for example, organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentone and montmorillonite; defoamers such as silicone-based defoamers, acrylic-based defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion imparters such as triazole-based adhesion imparters, tetrazole-based adhesion imparters, and triazine-based adhesion imparters; and hindered phenol-based antioxidants. Antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers; photopolymerization initiator assistants such as tertiary amines; and photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones, and thioxanthones. (J) Other additives may be used alone or in combination of two or more.

[0194] <(K) Solvent> The resin composition may further contain an arbitrary solvent as a volatile component in addition to the non-volatile components described above. As the (K) solvent, a known solvent can be appropriately used, and the type is not particularly limited, and it is preferable that the solvent is an organic solvent. As the (K) solvent, for example, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, etc.; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, anisole, etc.; alcohol-based solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, etc.; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate, etc. Examples of the solvent include ether ester solvents such as ethyl acetate, ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate, ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butylcarbitol), amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone, sulfoxide solvents such as dimethyl sulfoxide, nitrile solvents such as acetonitrile and propionitrile, aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane, and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. The (K) solvent may be used alone or in combination of two or more in any ratio.

[0195] From the viewpoint of obtaining the effect of the present invention significantly, the resin composition preferably contains 0.5% by mass or more and 3% by mass or less of the (K) solvent, based on 100% by mass of all the components of the resin composition. Specifically, the (K) solvent is preferably contained in an amount of 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1.5% by mass or less, based on 100% by mass of all the components of the resin composition, and is preferably contained in an amount of 0.5% by mass or more, more preferably 0.8% by mass or more, and even more preferably 1% by mass or more.

[0196] 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.

[0197] <Physical properties and applications of resin compositions> The cured product obtained by thermally curing the resin composition at 190°C for 90 minutes exhibits the characteristic of suppressing the amount of warping. This results in an insulating layer with a suppressed amount of warping. For example, when three points of a cured product having a width of 160 mm and a length of 120 mm are fixed and the warping at the remaining point is measured, the amount of warping may be preferably less than 30 mm, more preferably less than 25 mm, even more preferably less than 20 mm, and particularly preferably less than 17 mm. The amount of warping may be measured by the method described in the Examples below.

[0198] The cured product obtained by thermally curing the resin composition at 190°C for 90 minutes exhibits the characteristic of a low dielectric constant. Thus, an insulating layer with a low dielectric constant is obtained. The dielectric constant is preferably 3.5 or less, more preferably 3.4 or less, and even more preferably 3.3 or less. There is no particular lower limit, but it may be 0.01 or more. The dielectric constant can be measured by the method described in the examples below.

[0199] The resin composition is thermally cured at 190°C for 90 minutes to produce a cured product with a low dielectric tangent. This results in an insulating layer with a low dielectric tangent. The dielectric tangent is preferably 0.003 or less, more preferably 0.0028 or less, and even more preferably 0.0025 or less. There is no particular lower limit, but it may be 0.0001 or more. The dielectric tangent can be measured by the method described in the examples below.

[0200] A cured product obtained by thermally curing a resin composition at 190°C for 90 minutes usually exhibits the characteristic of a low coefficient of thermal expansion (CTE). Thus, an insulating layer having a low coefficient of thermal expansion is obtained. The coefficient of thermal expansion is preferably 35 ppm / °C or less, more preferably 33 ppm / °C or less, and even more preferably 30 ppm / °C or less. There is no particular lower limit, but it may be 0.1 ppm / °C or more. The coefficient of thermal expansion can be measured by the method described in the examples below.

[0201] A cured product obtained by thermally curing a resin composition at 190°C for 90 minutes usually exhibits the characteristic of low elastic modulus. Thus, an insulating layer with low elastic modulus is obtained. The elastic modulus is preferably less than 10 GPa, more preferably 9.8 GPa or less, further preferably 9.5 GPa or less, or 9.3 GPa or less. There is no particular limit to the lower limit, but it may be 0.1 GPa or more. The elastic modulus can be measured by the method described in the examples below.

[0202] The resin composition of the present invention can obtain a cured product with suppressed warpage and excellent dielectric properties. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulation 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 an insulating layer.

[0203] 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).

[0204] 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.

[0205] [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.

[0206] The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 50 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.

[0207] 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.

[0208] 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.

[0209] 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.

[0210] 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.

[0211] 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.

[0212] 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.

[0213] 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.

[0214] The resin sheet can be produced, for example, by preparing a resin varnish by dissolving the resin composition in a solvent, applying the resin varnish onto a support using a die coater or the like, and then drying the varnish to form a resin composition layer. The solvent is as described above.

[0215] Drying may be performed by a known method such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is performed so that the content of the 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 solvent in the resin varnish, for example, when a resin varnish containing 30 mass % to 60 mass % of the solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0216] 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.

[0217] [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.

[0218] 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

[0219] 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.

[0220] 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.

[0221] 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.

[0222] 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.

[0223] 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.

[0224] The support may be removed between step (I) and step (II) or after step (II).

[0225] 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.

[0226] 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.

[0227] 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).

[0228] 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.

[0229] 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.

[0230] 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.

[0231] 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.

[0232] 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.

[0233] 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.

[0234] 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.

[0235] 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.

[0236] 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.

[0237] [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.

[0238] Examples of the semiconductor device include various semiconductor devices used in electric appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

[0239] 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.

[0240] 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

[0241] 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.

[0242] <Synthesis Example 1: Synthesis of Maleimide X> An MEK solution (70% by mass of non-volatile components) of maleimide X (Mw / Mn=1.81, t''=1.47 (mainly 1, 2 or 3)) synthesized by the method described in Synthesis Example 1 of the Japan Institute of Invention and Innovation Disclosure Technical Journal No. 2020-500211 was prepared. This maleimide X has a structure represented by the following formula (1). [ka]

[0243] <Synthesis Example 2: Synthesis of Elastomer A> A reaction vessel was charged with 60 g of bifunctional hydroxyl-terminated polybutadiene ("G-1000" manufactured by Nippon Soda Co., Ltd., number average molecular weight = 1400, hydroxyl group equivalent = 800 g / eq.), 220 g of anisole as a solvent, and 14 g of isophorone diisocyanate (IPDI), and the temperature was raised to 50°C to carry out the reaction for approximately 1 hour.

[0244] Next, 145 g of oligophenylene ether resin containing phenolic hydroxyl groups at both ends (SABIC SA90-100, hydroxyl group equivalent = 800 g / eq.) and 1 g of benzophenonetetracarboxylic dianhydride (BTDA) were added to the reaction mixture, and the mixture was heated to 140°C with stirring and reacted for about 4 hours. The disappearance of the NCO peak at 2250 cm-1 was confirmed by FT-IR. The disappearance of the NCO peak was regarded as the end of the reaction, and the reaction mixture was cooled to room temperature. The reaction mixture was then filtered through a 100-mesh filter cloth to obtain an elastomer having an oligophenylene ether skeleton (non-volatile content 50% by mass, viscosity at 25°C 2.0 Pa·s).

[0245] <Production of resin varnish> Each component was weighed out in the amount of parts by mass shown in the table, and then mixed with 30 parts of MEK and 30 parts of cyclohexanone. The mixture was uniformly dispersed using a high-speed rotating mixer to obtain a resin varnish. [Table 1]

[0246] Details of each component listed in the table are as follows. Component (A) SLK-6895-T90: functional group equivalent weight 345g / eq., non-volatile content 90% by mass in toluene solution, manufactured by Shin-Etsu Chemical Co., Ltd. SLK-1500-T80: functional group equivalent weight 752g / eq., non-volatile content 80% by mass in toluene solution, manufactured by Shin-Etsu Chemical Co., Ltd. (B) Component MIR-3000-70MT: Functional group equivalent weight 275g / eq., non-volatile content 70% by mass in toluene solution, manufactured by Nippon Kayaku Co., Ltd. Maleimide X: Synthesized in Synthesis Example 1 (C) Component LHP-208: Spherical hollow silica, average particle size 0.5 μm, porosity 50% by volume, manufactured by Ube Exsymo Co., Ltd. (D) Component OPE-2St: functional group equivalent weight 590g / eq., non-volatile content 65% by mass in toluene solution, manufactured by Mitsubishi Gas Chemical Co., Ltd. ·A-DOG: Functional group equivalent 163g / eq., manufactured by Shin-Nakamura Chemical Industry Co., Ltd. TAIC: Functional group equivalent weight 83g / eq., manufactured by Mitsubishi Chemical Corporation DAD: Functional group equivalent weight 161g / eq., manufactured by Nisshoku Techno Fine Chemical Co., Ltd. (E) Component LA-3018-50P: Phenol-based hardener (functional group equivalent weight 151g / eq., non-volatile content 50% by mass in 1-methoxy-2-propanol solution, manufactured by DIC Corporation) SA90: Functional group equivalent weight 800g / eq., manufactured by SABIC V-03: Carbodiimide-based curing agent (functional group equivalent weight 216g / eq., non-volatile content 50% by mass in toluene solution, manufactured by Nisshinbo Chemical Co., Ltd.) ODA-BOZ: Benzoxazine-based curing agent (functional group equivalent weight 218g / eq., manufactured by JFE Chemical Corporation) Ingredient (F) PIAD200: Polyimide resin (a mixed solution of cyclohexanone, dimethyl glycol, and methylcyclohexane with a non-volatile content of 30%, manufactured by Arakawa Chemical Industries, Ltd.) YX7553BH30: Phenoxy resin (1:1 solution of MEK with 30% non-volatile content and cyclohexanone, manufactured by Mitsubishi Chemical Corporation) Elastomer A: Synthesized in Synthesis Example 2 RP-RX-61: Polystyrene resin with oxazoline structure, manufactured by Nippon Shokubai Co., Ltd. P2000: Styrene butadiene elastomer, manufactured by Asahi Kasei Corporation (G) Component 1B2PZ: Imidazole-based curing accelerator, manufactured by Shikoku Chemical Industry Co., Ltd. (H) Component Perbutyl C: NOF Corp. Parkmill P: NOF Corp. Perhexyl D: NOF Corp. Component (I) SO-C2: Spherical silica surface-treated with an amine-based alkoxysilane compound (Shin-Etsu Chemical Co., Ltd.'s "KBM573"), with an average particle size of 0.5 μm and a specific surface area of ​​5.8 m 2 / g, manufactured by Admatechs Co., Ltd.

[0247] <Measurement of dielectric constant, dielectric tangent, elastic modulus, coefficient of thermal expansion (CTE), and warpage> (1) Preparation of resin sheet A having a resin composition layer thickness of 40 μm A polyethylene terephthalate film with a release layer ("AL5" manufactured by Lintec Corporation, thickness 38 μm) was prepared as a support. On the release layer of this support, the resin varnish obtained in the examples and comparative examples was uniformly applied so that the thickness of the resin composition layer after drying was 40 μm. Thereafter, the resin composition was dried at 80°C to 100°C (average 90°C) for 2 minutes to obtain a resin sheet A including a support and a resin composition layer.

[0248] (2) Preparation of hardened product Resin sheet A was cured for 90 minutes in an oven at 190° C. The support was peeled off from resin sheet A taken out of the oven to obtain a cured resin composition layer.

[0249] (3) Measurement of elastic modulus The cured product was punched out with a dumbbell (Super Dumbbell Cutter (Model: SDMK-5889-01), manufactured by Dumbbell Co., Ltd.) to prepare a test specimen for measuring tensile strength. The support was peeled off from the test specimen. A tensile test was carried out using a Tensilon universal testing machine (manufactured by Orientec Co., Ltd., RTM-500) under conditions of a temperature of 25°C, humidity of 60%, and a tensile speed of 5 mm / min to measure the elastic modulus.

[0250] (4) Measurement of coefficient of thermal expansion (CTE) The cured product was cut into test pieces with a width of about 5 mm and a length of about 15 mm, and a thermomechanical analysis was performed by the tensile load method using a thermomechanical analyzer (Rigaku's "Thermo Plus TMA8310"). After mounting the test pieces on the device, the thermal expansion coefficient (ppm) was measured twice consecutively under the measurement conditions of a load of 1 g and a temperature rise rate of 5°C / min (the first time was from 25°C to 200°C, and the second time was from 20°C to 260°C), and the value measured the second time was taken as the linear expansion coefficient (ppm / °C).

[0251] (5) Measurement of warpage Resin sheet A was laminated onto a laminate (Resonac's MCL-E-700G copper foil etched-out product) using a batch-type vacuum pressure laminator (Meiki Seisakusho's "MVLP-500"). The laminate was depressurized for 30 seconds to a pressure of 13 hPa or less, and then pressed at 120°C for 30 seconds at a pressure of 0.74 MPa. The support was then peeled off, and the resin composition layer was cured at 190°C for 90 minutes to obtain a cured product sample. The obtained cured product was cut into a test piece with a width of 160 mm and a length of 120 mm, and the amount of warping at the remaining point was measured while the three points were fixed.

[0252] [Table 2]

Claims

1. (A) an aliphatic maleimide compound, (B) an aromatic maleimide compound, (C) a hollow inorganic filler, and (D) a radical polymerizable resin, The content of the (A) component is represented by a when the non-volatile components of the resin composition are 100% by mass, The content of the (B) component is represented by b when the non-volatile components of the resin composition are 100% by mass, When the content of the (D) component is d when the non-volatile components of the resin composition are 100 mass%, a / b is 0.1 or more and 6 or less, A resin composition having a d / b ratio of 0.1 or more and 6 or less.

2. The resin composition according to claim 1, wherein the component (D) comprises any one of a styrene-based radical polymerizable resin, a (meth)acrylic-based radical polymerizable resin, and an allyl-based radical polymerizable resin.

3. 2. The resin composition according to claim 1, wherein the content of the component (C) is 20% by volume or more and 70% by volume or less, when the non-volatile components of the resin composition are taken as 100% by volume.

4. The resin composition according to claim 1, wherein the elastic modulus of the cured product obtained by thermally curing the resin composition at 190°C for 90 minutes is less than 10 GPa.

5. 2. The resin composition according to claim 1, wherein the resin composition has a thermal expansion coefficient of 35 ppm / °C or less when heat-cured at 190°C for 90 minutes.

6. The resin composition according to claim 1, wherein the component (A) contains either an aliphatic maleimide compound represented by formula (A-1) or an aliphatic maleimide compound represented by formula (A-2). 【Chemistry 1】 In formula (A-1), R ２ and R ３ each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent; R １０ each independently represents an oxygen atom, an arylene group, an alkylene group, an alkenylene group, or a divalent group consisting of a combination of two or more of these groups, and p represents an integer of 1 to 15. In formula (A-2), R ４ , R ６ and R ７ each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent; R ５ each independently represents a divalent group having an aromatic ring which may have a substituent; R １２ each independently represents an alkyl group having 5 or more carbon atoms, q represents an integer of 0 to 10, and r1 and r2 each independently represent an integer of 0 to 4.

7. The resin composition according to claim 1, wherein the component (B) contains either an aromatic maleimide compound represented by formula (B-1) or an aromatic maleimide compound represented by formula (B-2). 【Chemistry 2】 In formula (B-1), 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-, or -SO ２ represents -, -CONH-, -NHCO-, -COO-, or -OCO-; Z ｃ each independently represents a non-aromatic ring which may have a substituent, or an aromatic ring which may have a substituent, s represents an integer of 1 or more, each t1 independently represents an integer of 0 to 5, and each u independently represents an integer of 0 to 2. In formula (B-2), Ar ａ１ represents a divalent aromatic hydrocarbon group which may have a substituent; R ａ１ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; R ａ２ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; R ａ３ Each of n independently represents a divalent aliphatic hydrocarbon group. ａ１ represents the average number of repeating units from 0.95 to 10.0, n ａ２ Each independently represents an integer of 0 to 4; ａ３ each independently represents an integer of 0 to 3.

8. 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 7.

9. 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 7.

10. A semiconductor device comprising the printed wiring board according to claim 9.

Images