Resin composition

Abstract

The present invention provides a resin composition and the like capable of obtaining a cured product having suppressed occurrence of warpage and low dielectric properties. A resin composition comprising (A) an aliphatic maleimide compound, (B) an aromatic maleimide compound, (C) a hollow inorganic filler, and (D) a radically polymerizable resin, when a is the content of the component (A) when the non-volatile components of the resin composition are 100% by mass, b is the content of the component (B) when the non-volatile components of the resin composition are 100% by mass, and d is the content of the component (D) when the non-volatile components of the resin composition are 100% by mass, a / b is 0.1-6, and d / b is 0.1-6.

Description

Technical Field

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

[0002] As a manufacturing technology for a printed wiring board, a manufacturing method based on a build-up method in which insulating layers and conductive layers are alternately stacked is known.

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

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2013-173841. Summary of the invention

[0007] Problems to be solved by the invention

[0008] In recent years, with the high functionality of printed wiring boards, it is required to further improve the dielectric loss tangent and dielectric constant of the insulating layer. In order to improve the dielectric loss tangent and dielectric constant, a method of adding a radical polymerizable resin having an ethylenically unsaturated group to the resin composition is considered.

[0009] However, the present inventors have conducted intensive studies and found that when a radical polymerizable resin is included in a resin composition, the curing shrinkage increases and the warpage of the cured product increases. Hereinafter, the dielectric loss tangent and the dielectric constant may be collectively referred to as dielectric properties.

[0010] The present invention is proposed in view of the above-mentioned problems, and its purpose is to provide: a resin composition that can obtain a cured product with reduced warping and low dielectric properties; a resin sheet containing the resin composition; and a printed wiring board and a semiconductor device having an insulating layer formed using the resin composition.

[0011] Means for solving problems

[0012] The present inventors have conducted in-depth studies on the above-mentioned issues and have found that the above-mentioned issues can be solved by adjusting the amount ratio of the aliphatic maleimide compound to the aromatic maleimide compound, and the amount ratio of the aromatic maleimide compound to the free radical polymerizable resin to within specified ranges, and then selecting a hollow inorganic filler material as the inorganic filler material, thereby completing the present invention.

[0013] That is, the present invention includes the following contents.

[0014] [1] A resin composition comprising (A) an aliphatic maleimide compound, (B) an aromatic maleimide compound, (C) a hollow inorganic filler material, and (D) a radical polymerizable resin,

[0015] When the content of the component (A) when the non-volatile component of the resin composition is 100% by mass is a, the content of the component (B) when the non-volatile component of the resin composition is 100% by mass is b, and the content of the component (D) when the non-volatile component of the resin composition is 100% by mass is d,

[0016] a / b is 0.1 or more and 6 or less,

[0017] d / b is 0.1 or more and 6 or less.

[0018] [2] The resin composition described in [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.

[0019] [3] The resin composition according to [1] or [2], wherein the content of the component (C) is 20% by volume or more and 70% by volume or less, when the non-volatile component of the resin composition is 100% by volume.

[0020] [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.

[0021] [5] The resin composition according to any one of [1] to [4], wherein a cured product obtained by thermally curing the resin composition at 190°C for 90 minutes has a thermal expansion coefficient of 35 ppm / °C or less.

[0022] [6] The resin composition according to any one of [1] to [5], wherein the component (A) comprises any one of an aliphatic maleimide compound represented by the formula (A-1) and an aliphatic maleimide compound represented by the formula (A-2):

[0023]

[0024] 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; p represents an integer of 1 to 15,

[0025] 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] [7] The resin composition according to any one of [1] to [6], wherein the component (B) comprises any one of an aromatic maleimide compound represented by the formula (B-1) and an aromatic maleimide compound represented by the formula (B-2):

[0027]

[0028] 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-, and 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 greater than 1, t1 each independently represents an integer from 0 to 5, u each independently represents an integer from 0 to 2,

[0029] 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 alkoxy 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, and R a2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy 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, and R a3 Each independently represents a divalent aliphatic hydrocarbon group, n a1 Represents the average number of repeating units from 0.95 to 10.0, n a2 Each independently represents an integer from 0 to 4, and n a3 Each independently represents an integer from 0 to 3.

[0030] [8] A resin sheet comprising: a support and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [7].

[0031] [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].

[0032]

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

[0033] Effects of the Invention

[0034] According to the present invention, there can be provided a resin composition capable of obtaining a cured product having reduced warpage and low dielectric properties, and a resin sheet, a printed wiring board, and a semiconductor device using the resin composition. DETAILED DESCRIPTION

[0035] Hereinafter, the present invention will be described in detail based on preferred embodiments of the present invention. However, the present invention is not limited to the following embodiments and examples, and can be implemented with any changes within the scope of the claims of the present invention and their equivalents.

[0036] [Resin composition]

[0037] The resin composition of the present invention comprises (A) aliphatic maleimide compound, (B) aromatic maleimide compound, (C) hollow inorganic filling material and (D) free radical polymerizable resin, when the content of (A) component is set to a when the non-volatile component of the resin composition is set to 100% by mass, the content of (B) component is set to b when the non-volatile component of the resin composition is set to 100% by mass, and the content of (D) component is set to d when the non-volatile component of the resin composition is set to 100% by mass, a / b is 0.1 or more and 6 or less, and d / b is 0.1 or more and 6 or less. In the present invention, by adjusting the amount ratio of (A) component and (B) component and the amount ratio of (B) component and (D) component to the above-mentioned range respectively, and then selecting (C) hollow inorganic filling material as inorganic filling material to contain, it is possible to obtain a cured product with suppressed warpage and excellent dielectric properties. In addition, a cured product with low thermal expansion coefficient and low elastic modulus can also be obtained in general.

[0038] The resin composition may further include optional components in combination with the components (A) to (D). Examples of the optional components include: (E) a curing agent, (F) a thermoplastic resin, (G) a curing accelerator, (H) a free radical initiator, (I) a solid inorganic filler, (J) other additives, and (K) a solvent. The following describes in detail the components contained in the resin composition of the present invention.

[0039] <(A) Aliphatic maleimide compound>

[0040] The resin composition contains (A) an aliphatic maleimide compound as the (A) component. The (A) aliphatic maleimide compound refers to 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 the 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. Regarding the (A) component, as long as the nitrogen atom of the maleimide group is directly bonded to the aliphatic group, an aromatic ring may be contained in the molecule. For example, it can be obtained by subjecting a component containing an aliphatic amine compound (a diamine compound having a dimer acid skeleton, etc.), maleic anhydride and, as required, a tetracarboxylic dianhydride to an imidization reaction.

[0041]

[0042] 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. In addition, the aliphatic groups may bond to each other to form a ring, and the ring structure may also include a spiro ring or a condensed ring. The (A) component preferably contains two or more aliphatic groups.

[0043] 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 further preferably 8 or more, and preferably 50 or less, more preferably 45 or less, and further preferably 40 or less. In this specification, when a group includes a substituent, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the group unless otherwise specified. Therefore, for example, when an aliphatic group having 5 or more carbon atoms includes 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.

[0044] 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 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.

[0045] The number of carbon atoms of the alkyl group is preferably 5 or more, more preferably 6 or more, further preferably 8 or more, preferably 50 or less, more preferably 45 or less, further preferably 40 or less. The alkyl group may be any of linear, branched, and cyclic, with linear being preferred. Examples of such alkyl groups include pentyl, hexyl, heptyl, octyl, nonyl, and decyl. An alkyl group having 5 or more carbon atoms may be present as a substituent of an alkylene group having 5 or more carbon atoms and an alkenylene group having 5 or more carbon atoms.

[0046] The number of carbon atoms of the alkylene group is preferably 5 or more, more preferably 6 or more, further preferably 8 or more, preferably 50 or less, more preferably 45 or less, further preferably 40 or less. The alkylene group may be any of a straight chain, a branched chain, or a cyclic group, wherein a straight chain is preferred. Here, a cyclic alkylene group refers to a group that includes not only a narrow sense group consisting only of a cyclic alkylene group, but also a broad sense group including both a straight chain alkylene group and a cyclic alkylene group. As such an alkylene group, for example, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, heptadecanylene, triheptadecylene, trihexadecylene, hexadecylene, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, etc.

[0047] The number of carbon atoms of 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 further preferably 40 or less. The alkenylene group may be any of linear, branched, and cyclic, with linear being preferred. Here, the cyclic alkenylene group refers to a concept including the case of being composed only of cyclic alkenylene groups and the case of including both linear and cyclic alkenylene groups. Examples of such alkenylene groups include pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene, heptadecenylene, hexatriaconchinylene, a group having an octenylene-cyclohexenylene structure, a group having an octenylene-cyclohexenylene-octenylene structure, and a group having a propenylene-cyclohexenylene-octenylene structure.

[0048] The aliphatic group may or may not have a substituent. There are no particular restrictions on the substituent, and examples thereof include a halogen atom, -OH, -OC 1-6 Alkyl, -N(C 1-10 Alkyl)2, C 1-20 Alkyl, C 6-10Aryl, -NH2, -CN, -C(O)OC 1-10 Alkyl, -COOH, -C(O)H, -NO2, etc. Here, the term "C p-q "(p and q are positive integers, satisfying p<q) means that the number of carbon atoms in the organic group recorded immediately after the term is p to q. For example, "C 1-10 The expression "alkyl" means 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 may also include a spiro ring or a condensed ring.

[0049] The above-mentioned substituent may further have a substituent (hereinafter, sometimes referred to as a "secondary substituent"). As the secondary substituent, the same substituents as those described above can be used unless otherwise specified.

[0050] Regarding component (A), as long as the aliphatic group is directly bonded to the nitrogen atom of the maleimide group, an aromatic ring may be included in the molecule. 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 carbocyclic ring or an aromatic heterocyclic ring. In addition, the aromatic ring may be a monocyclic aromatic ring or a condensed aromatic ring obtained by condensing two or more monocyclic aromatic rings. Examples of these aromatic rings include: monocyclic aromatic rings such as a benzene ring and a pyridine ring; and condensed aromatic rings such as an indane ring, a fluorene ring, and a naphthalene ring. Among them, the aromatic ring is preferably an aromatic carbocyclic ring. The number of carbon atoms in the aromatic carbocyclic ring is preferably 6 or more and 10 or less.

[0051] The number of maleimide groups per molecule of the 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 a component (A) having 2 or more maleimide groups per molecule, the effect of the present invention can be significantly obtained.

[0052] The component (A) is preferably any one of an aliphatic maleimide compound represented by the formula (A-1) and an aliphatic maleimide compound represented by the formula (A-2).

[0053]

[0054] 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 composed of a combination of two or more of these groups. p represents an integer of 1 to 15.

[0055] In formula (A-2), R4 , 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.

[0056] 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 divalent aliphatic group having 5 or more carbon atoms preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, preferably 50 or less, more preferably 45 or less, and further preferably 40 or less carbon atoms. The divalent aliphatic group may be any of linear, branched, and cyclic, wherein a linear one is preferred. Here, a cyclic aliphatic group refers to a concept including the following cases: a case consisting only of a cyclic aliphatic group, and a case containing both a linear aliphatic group and a cyclic aliphatic group. Examples of the divalent aliphatic group include an alkylene group, an alkenylene group, and the like.

[0057] Examples of the alkylene group include pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, heptadecylene, hexatriadecylene, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, and the like, preferably a hexatriadecylene.

[0058] Examples of the alkenylene group include pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene, heptadecenylene, trihexadecenylene, a group having an octenylene-cyclohexenylene structure, a group having an octenylene-cyclohexenylene-octenylene structure, a group having a propenylene-cyclohexenylene-octenylene structure, and the like, preferably a trihexadecenylene.

[0059] The divalent aliphatic group may have a substituent. Examples of the substituent include a halogen atom, -OH, -OC 1-10 Alkyl, -N(C 1-10 Alkyl)2, C 1-10 Alkyl, C 2-30 Alkenyl, C 2-30 Alkynyl, C 6-10 Aryl, -NH2, -CN, -C(O)OC 1-10Alkyl, -COOH, -C(O)H, -NO2, etc. Here, the term "C x-y "" (x and y are positive integers, satisfying x < y) means that the number of carbon atoms in the organic group recorded immediately after the term is x to y. For example, "C 1-10 The expression "alkyl" means 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 may also include a spiro ring or a condensed ring. The substituent is preferably an alkyl group having 5 or more carbon atoms.

[0060] In formula (A-1), R 10 Each independently represents an oxygen atom, an arylene group, an alkylene group, or a divalent group composed of a combination of two or more of these groups.

[0061] The number of carbon atoms in the arylene group is preferably 6 to 24, more preferably 6 to 18, further preferably 6 to 14, particularly preferably 6 to 10. Examples of the arylene group include a phenylene group, a naphthylene group, and an anthrylene group.

[0062] As a divalent group composed of a combination of two or more of these groups, there can be mentioned: a combination of an oxygen atom, an arylene group and an alkylene group. As a specific example of a divalent group composed of a combination of two or more of these groups, there can be mentioned: the following groups. In the formula, "*" represents a bond.

[0063]

[0064] In formula (A-1), R 10 , preferably a divalent group composed of a combination of two or more of these groups or an oxygen atom.

[0065] In the formula (A-1), p represents an integer of 1-15, and preferably represents an integer of 1-10.

[0066] 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. 4 , R 6 and R 7 With R in formula (A-1) 2 The divalent aliphatic group having 5 or more carbon atoms which may have a substituent is the same, and preferably a hexylene group, a heptylene group, an octylene group, a nonylene group, and a decylene group, and more preferably an octylene group.

[0067] In formula (A-2), R 5 Each independently represents a divalent group having an aromatic ring which may have a substituent. 5A group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic acid imide is preferred; a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group is more preferred, and a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic acid imide is more preferred. 2 The alkylene groups in the divalent aliphatic groups having 5 or more carbon atoms represented are the same.

[0068] In formula (A-2), R 5 Specific examples of the group represented by include the following groups. In the formula, "*" represents a bond.

[0069]

[0070] In formula (A-2), R 12 Each independently represents an alkyl group having 5 or more carbon atoms. The alkyl group having 5 or more carbon atoms preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, preferably 50 or less, more preferably 45 or less, and further preferably 40 or less carbon atoms. The alkyl group may be any of a straight chain, a branched chain, and a cyclic shape, wherein a straight chain shape is preferred. Examples of such an alkyl group include: pentyl, hexyl, heptyl, octyl, nonyl, decyl, and the like. An alkyl group having 5 or more carbon atoms may be present as a substituent of an alkylene group having 5 or more carbon atoms. Among them, hexyl, heptyl, octyl, nonyl, and decyl are preferred, and hexyl and octyl are more preferred.

[0071] In formula (A-2), q represents an integer of 0 to 10, preferably an integer of 0 to 8, and particularly preferably 0.

[0072] 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.

[0073] 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.

[0074]

[0075] As the component (A), commercial products can be used. Examples of commercial products of the component (A) include: "BMI1500" manufactured by Designer Molecules; "SLK-1500-T80" (a compound of formula (a1)), "BMI1700" (a compound of formula (a2)), and "BMI3000J" (a compound of formula (a3)) manufactured by Shin-Etsu Chemical Co., Ltd.; "BMI689" (a compound of formula (a4)) manufactured by Designer Molecules; "BMI-TMH" manufactured by Yamato Chemical Co., Ltd.; and "SLK-6895-T90" manufactured by Shin-Etsu Chemical Co., Ltd.

[0076] The weight average molecular weight (Mw) of the component (A) is preferably 150 to 5000, more preferably 300 to 2500. The weight average molecular weight can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0077] The maleimide group equivalent of the component (A) is preferably 50 g / eq. to 2000 g / eq., more preferably 100 g / eq. to 1000 g / eq., and further preferably 150 g / eq. to 500 g / eq. The maleimide group equivalent means the mass of the component (A) containing 1 equivalent of maleimide groups.

[0078] When the nonvolatile component in the resin composition is 100 mass %, the content of the component (A) is preferably 0.5 mass % or more, more preferably 1 mass % or more, and is preferably 50 mass % or less, more preferably 40 mass % or less, and further preferably 35 mass % or less.

[0079] In the present invention, unless otherwise specified, the content of each component in the resin composition is a value when the nonvolatile component in the resin composition is 100 mass %, and the nonvolatile component refers to the entire nonvolatile component excluding the solvent in the resin composition.

[0080] <(B) Aromatic maleimide compound>

[0081] The resin composition contains (B) an aromatic maleimide compound as the (B) component. The (B) aromatic maleimide compound as the (B) component does not include a substance corresponding to the (A) component. The (B) component may be used alone or in combination of two or more.

[0082] (B) Aromatic maleimide compounds refer to compounds 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. Regarding the (B) component, as long as the nitrogen atom of the maleimide group is directly bonded to the aromatic ring, an aliphatic group may be present in the molecule. The (B) component can be obtained, for example, by subjecting a component containing an aromatic amine compound (aromatic diamine compound, etc.) and maleic anhydride to an imidization reaction.

[0083] The aromatic ring directly bonded to the nitrogen atom of the maleimide group may be monovalent, divalent, or trivalent or higher. The aromatic ring may be a monocyclic ring, a condensed ring, or a heterocyclic ring.

[0084] The aromatic ring may be a carbon ring or a heterocyclic ring. Examples of the aromatic group include a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, Azole ring, iso Monocyclic aromatic rings such as azole ring, thiazole ring, imidazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, etc.; naphthalene ring, anthracene ring, benzofuran ring, isobenzofuran ring, indole ring, isoindole ring, benzothiophene ring, benzimidazole ring, indazole ring, benzo Azole ring, benzyl isocyanate A condensed ring obtained by condensing two or more monocyclic aromatic rings such as an oxazole ring, a benzothiazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, an acridine ring, a quinazoline ring, a cinnoline ring, and a phthalazine ring; a condensed ring obtained by condensing one or more monocyclic non-aromatic rings to one or more monocyclic aromatic rings such as an indane ring, a fluorene ring, and a tetralin ring, etc. Among them, the aromatic ring is preferably a monocyclic aromatic ring, and more preferably a benzene ring.

[0085] As one embodiment of the component (B), a compound represented by the following formula (B-1) is preferred.

[0086]

[0087] 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-, and 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 greater than 1, t1 each independently represents an integer of 0 to 5, and u each independently represents an integer of 0 to 2.

[0088] In formula (B-1), Rc Each independently represents a substituent, and the substituent is the same as the substituent which the aliphatic group in the component (A) may have.

[0089] In formula (B-1), X c 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.

[0090] The alkylene group may be any of a straight chain, a branched chain, or a cyclic group, preferably a straight chain or a branched chain hydrocarbon group, and more preferably a straight chain group. As the alkylene group, an alkylene group having 1 to 20 carbon atoms is preferred, an alkylene group having 1 to 10 carbon atoms is more preferred, and an alkylene group having 1 to 6 carbon atoms is further preferred. The number of carbon atoms does not include the number of carbon atoms of the substituent. As the alkylene group, for example, methylene, ethylene, 1-methylethylene, propylene, n-butylene, secondary butylene, tert-butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, etc. are preferred, and methylene, ethylene, propylene, n-butylene, secondary butylene, tert-butylene are more preferred, and methylene or ethylene is more preferred.

[0091] The alkenylene group may be any of a straight chain, a branched chain, or a cyclic group, preferably a straight chain or a branched chain hydrocarbon group, and more preferably a straight chain group. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferred, an alkenylene group having 2 to 6 carbon atoms is more preferred, and an alkenylene group having 3 or 4 carbon atoms is further preferred. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the alkenylene group include ethenylene, propenylene, butenylene, pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, and the like.

[0092] The alkylene group and the alkenylene group may have a substituent. The substituent is the same as the substituent which the aliphatic group in the component (A) may have.

[0093] In formula (B-1), Z c Each 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.

[0094] In formula (B-1), s represents an integer of 1 or greater, 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.

[0095] In formula (B-1), t1 each 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.

[0096] In formula (B-1), u each independently represents an integer of 0 to 2, and is preferably 0.

[0097] The compound represented by formula (B-1) is preferably a compound represented by formula (B-1-2) to (B-1-5).

[0098]

[0099] 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 greater than 1; t' represents an integer from 0 to 5; v1, v2 and v3 each independently represent an integer from 0 to 2. It should be noted that the s unit, t unit, t' unit, v unit, v1 unit, v2 unit and v3 unit may be the same or different.

[0100] 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 which the aliphatic group in the component (A) may have as a substituent.

[0101] 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 and X in formula (B-1) c The alkylene groups represented are the same.

[0102] In formulae (B-1-2) to (B-1-5), s represents an integer of 1 or greater, 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.

[0103] In formulae (B-1-2) to (B-1-5), t' represents an integer of 1 to 5, which is the same as t1 in formula (B-1).

[0104] In formulae (B-1-2) to (B-1-5), v1, v2 and v3 each independently represent an integer of 0 to 2, and preferably 0.

[0105] The compound represented by formula (B-1) is preferably a compound represented by formula (B-1-6).

[0106]

[0107] In the formula, R 31 , R 32 , R33 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 independently represent an integer of 1 to 10, and a represents an integer of 1 to 100.

[0108] 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.

[0109] 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 still more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be linear, branched, or cyclic. Examples of such an alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, and isopropyl.

[0110] 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 further preferably an aryl group having 6 to 10 carbon atoms. The aryl group may be a monocyclic ring or a condensed ring. Examples of such aryl groups include phenyl, naphthyl, anthracenyl, and the like.

[0111] The alkyl group and the aryl group may have a substituent. The substituent may be the same as the substituent that the aliphatic group in the component (A) may have.

[0112] In formula (B-1-6), E represents a divalent aromatic group. Examples of the divalent aromatic group include phenylene, naphthylene, anthrylene, aralkyl, biphenylene, biphenylaralkyl, etc., among which biphenylene and biphenylaralkyl are preferred, and biphenylene 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.

[0113] 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, further preferably 1 to 2, and further preferably 1.

[0114] In the formula (B-1-6), a represents an integer of 1 to 100, preferably 1 to 50, more preferably 1 to 20, and even more preferably 1 to 5.

[0115] As the component (B-1), a resin represented by the formula (B-1-7) is preferred.

[0116]

[0117] In the formula, a1 represents an integer of 1 to 100.

[0118] In the formula (B-1-7), a1 is the same as a in the formula (B-1-6), and the preferred range is also the same.

[0119] The compound represented by formula (B-1) can be a commercial product. Commercial products of the compound represented by formula (B-1) include, for example, "MIR-3000-70MT" (biphenyl aralkyl type maleimide resin) manufactured by Nippon Kayaku Co., Ltd.; "BMI-70", "BMI-80", "BMI-50P", "BMI-4,4'-BPE" manufactured by KI Chemicals Co., Ltd.; "BMI-1000", "BMI-1000H", "BMI-1100", "BMI-1100H", "BMI-4000", "BMI-5100", "BMI-2300" manufactured by Yamato Chemical Industries, Ltd.

[0120] The weight average molecular weight (Mw) of the compound represented by formula (B-1) is preferably 150 to 5,000, more preferably 300 to 2,500.

[0121] The functional group equivalent of the maleimide group of 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., further preferably 150 g / eq. to 500 g / eq., particularly preferably 200 g / eq. to 300 g / eq.

[0122] As another embodiment of the component (B), a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and a skeleton comprising an aromatic ring fused to an aliphatic hydrocarbon ring. As a skeleton obtained by condensing an aromatic ring with an aliphatic hydrocarbon ring, it can be cited: an indane skeleton, a trimethyl indane skeleton, a tetralin skeleton, a benzocyclobutene skeleton, an indene skeleton, etc. Among them, from the viewpoint of significantly obtaining the effect of the present invention, as a skeleton obtained by condensing an aromatic ring with an aliphatic hydrocarbon ring, a trimethyl indane skeleton is preferred. Therefore, as another embodiment of the component (B), a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and a trimethyl indane skeleton. The trimethyl indane skeleton represents the skeleton shown in the following formula (2).

[0123]

[0124] A substituent may be bonded to the benzene ring contained in the trimethylindan skeleton. The substituent may be the same as the substituent which the aliphatic group in the component (A) may have.

[0125] The number of substituents bonded to one benzene ring contained in the trimethylindane skeleton may be 1 or more. The number of substituents bonded to the benzene ring contained in the trimethylindane skeleton is usually 0 or more and 3 or less. When the number of substituents is 2 or more, the 2 or more substituents may be the same or different. It is preferred that no substituents are bonded to the benzene ring contained in the trimethylindane skeleton.

[0126] The number of trimethylindane skeletons contained in one molecule of the maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and containing a trimethylindane skeleton may be 1 or more than 2. The upper limit may be, for example, 10 or less, 8 or less, 7 or less, or 6 or less.

[0127] 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 carbon atoms in 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.

[0128] The number of aromatic ring skeletons contained in one molecule 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 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 4 or less, and particularly preferably 3 or less. When the maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and containing a trimethylindane skeleton further contains two or more aromatic ring skeletons in addition to the trimethylindane skeleton, these aromatic ring skeletons may be the same or different.

[0129] Substituents may be bonded to the aromatic ring contained in the aromatic ring skeleton. As substituents, for example, the above-mentioned substituents and nitro groups as substituents that may be bonded to the benzene ring contained in the trimethylindane skeleton may be mentioned. The number of substituents bonded to one aromatic ring may be 1 or 2 or more. The number of substituents bonded to the aromatic ring is usually 0 or more and 4 or less. When the number of substituents is 2 or more, these 2 or more substituents may be the same or different.

[0130] The maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and containing a trimethyl indane skeleton preferably contains a divalent aliphatic hydrocarbon group in addition to the above-mentioned trimethyl indane skeleton. In particular, in the case where the maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and containing a trimethyl indane skeleton contains an aromatic ring skeleton other than the benzene ring contained in the trimethyl indane skeleton, it is preferred that the maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group and containing a trimethyl indane skeleton contains a divalent aliphatic hydrocarbon group. In this case, the divalent aliphatic hydrocarbon group preferably connects the benzene ring contained in the trimethyl indane skeleton to the aromatic ring skeleton. In addition, the divalent aliphatic hydrocarbon group preferably connects the aromatic ring skeletons to each other.

[0131] The number of carbon atoms of 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 which is a saturated aliphatic hydrocarbon group is more preferred. As the divalent aliphatic hydrocarbon group, there can be mentioned: straight-chain alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; and branched-chain alkylene groups such as ethylene (-CH(CH3)-), propylene (-CH(CH2CH3)-), isopropylene (-C(CH3)2-), ethylmethylmethylene (-C(CH3)(CH2CH3)-), diethylmethylene (-C(CH2CH3)2-), and dimethylmethylene. When the 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, these divalent aliphatic hydrocarbon groups may be the same or different.

[0132] 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).

[0133]

[0134] 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 alkoxy 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, and R a2each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy 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, and R a3 Each 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 from 0 to 4, and n a3 Each independently represents an integer from 0 to 3.

[0135] In formula (B-2), Ar a1 Represents a divalent aromatic hydrocarbon group which may have a substituent. The number of carbon atoms of the divalent aromatic hydrocarbon group is preferably 6 or more, preferably 20 or less, and more preferably 16 or less. Examples of the divalent aromatic hydrocarbon group include: phenylene and naphthylene. Examples of substituents that the divalent aromatic hydrocarbon group may have include: alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkylthio groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, arylthio groups having 6 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, halogen atoms, hydroxyl groups, and mercapto groups. The hydrogen atoms of each substituent may be further substituted by a halogen atom. In addition, specific examples of these substituents include: the same examples as the substituents that can 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 number of substituents possessed by the divalent aromatic hydrocarbon group is 2 or more, these 2 or more substituents may be the same or different. a1 It is preferably a divalent aromatic hydrocarbon group having no substituent.

[0136] In formula (B-2), R a1 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy 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 alkoxy group, the alkylthio group, the aryl group, the aryloxy group, the arylthio group and the cycloalkyl group may be substituted by halogen atoms. 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 a1 More preferably, it is 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 particularly preferably, it is an alkyl group having 1 to 4 carbon atoms.

[0137] In formula (B-2), R a2 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy 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, alkoxy, alkylthio, aryl, aryloxy, arylthio and cycloalkyl groups may be substituted with halogen atoms. Specific examples of these groups include the same substituents as those that can be bonded to the benzene ring contained in the trimethylindane skeleton. Among them, R a2 More preferably, it is 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.

[0138] 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.

[0139] In formula (B-2), n a1 It represents the average number of repeating units from 0.95 to 10.0. a1 It is more preferably 0.98 or more, further preferably 1.0 or more, particularly preferably 1.1 or more, and is preferably 10.0 or less, more preferably 8.0 or less, further preferably 7.0 or less, particularly preferably 6.0 or less.

[0140] In formula (B-2), n a2 Each independently represents an integer from 0 to 4. a2 Preferably it is 2 or 3, more preferably 2. Multiple n a2 can be different, but are preferably the same. a2 When the number of R is an integer of 2 to 4, a1 They can be the same or different within the same ring.

[0141] In formula (B-2), n a3 Each independently represents an integer from 0 to 3. a3 Can be different, but preferably the same. a3 Preferably 0. a3 When R is 2 to 3, a2 They can be the same or different within the same ring.

[0142] The compound represented by formula (B-2) is preferably a compound represented by the following formula (B-2-1).

[0143]

[0144] In the formula, R b1R each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy 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; b2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group; n b1 represents the average number of repeating units from 0.95 to 10.0; n b2 Each independently represents an integer from 0 to 4; n b3 R each independently represents an integer of 0 to 3. b1 The hydrogen atoms of the alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group and cycloalkyl group may be substituted by halogen atoms. b2 The hydrogen atoms of the alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio and cycloalkyl groups may be substituted with halogen atoms. b2 When R is 2 to 4, b1 They can be the same or different in the same ring. b3 When R is 2 to 3, b2 They can be the same or different within the same ring.

[0145] In formula (B-2-1), R b1 , R b2 、n b1 、n b2 and n b3 Respectively with R in formula (B-2) a1 , R a2 、n a1 、n a2 and n a3 same.

[0146] 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, 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 1 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 effect of the present invention can be significantly obtained.

[0147] There is no particular restriction on the method for producing a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of a maleimide group and comprising a trimethyl indane skeleton. The maleimide compound having an aromatic ring directly bonded to the nitrogen atom of a maleimide group and comprising a trimethyl indane skeleton can be produced, for example, by the method described in the Japanese Invention Association's Public Technical Bulletin No. 2020-500211. According to the production method described in the Japanese Invention Association's Public Technical Bulletin No. 2020-500211, a maleimide compound having a distribution of the number of repeating units of the trimethyl indane skeleton can be obtained.

[0148] 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.

[0149]

[0150] From the viewpoint of significantly obtaining the desired effect of the present invention, the maleimide group equivalent of the component (B) is preferably 100 g / eq. to 10000 g / eq., more preferably 1100 g / eq. to 9000 g / eq., and even more preferably 120 g / eq. to 8000 g / eq. The maleimide group equivalent is the mass of the component (B) containing 1 equivalent of maleimide groups.

[0151] The weight average molecular weight (Mw) of the component (B) is preferably 150 to 16,000, more preferably 200 to 15,000.

[0152] The molecular weight of the component (B) 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, from the viewpoint of significantly obtaining the effects of the present invention.

[0153] When the non-volatile component in the resin composition is set to 100 mass %, the content of component (B) is preferably 1 mass % or more, more preferably 2 mass % or more. The upper limit is preferably 30 mass % or less, more preferably 25 mass % or less, and further preferably 20 mass % or less.

[0154] When the content of the (A) component when the non-volatile component in the resin composition is set to 100% by mass is a, and the content of the (B) component when the non-volatile component in the resin composition is set to 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 further preferably 4.5 or less or 4 or less. By adjusting the amount ratio of the (A) component to the (B) component to the above range, the warpage of the cured product can be reduced.

[0155] <(C)Hollow inorganic filling materials>

[0156] The resin composition contains (C) a hollow inorganic filler as the (C) component. By containing the (C) hollow inorganic filler in the resin composition, a cured product with suppressed warpage can be obtained. The (C) hollow inorganic filler is usually contained in the resin composition in the form of particles. The (C) hollow inorganic filler can be used alone or in combination of two or more.

[0157] As mentioned above, if a free radical polymerizable resin is contained in the resin composition, the curing shrinkage becomes larger, and the warping amount of the cured product becomes larger. In order to reduce the curing shrinkage, a method of containing an inorganic filler with an average porosity of 0 volume % in the resin composition (hereinafter, an inorganic filler with an average porosity of 0 volume % is sometimes referred to as a "solid inorganic filler") is considered, but the research results of the inventors have known: if a solid inorganic filler is contained, as the elastic modulus of the cured product rises, the stress generated during curing will increase, and the suppression of the warping amount cannot be 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 is reduced, and as a result, the generation of the warping amount can be suppressed.

[0158] As the material of the hollow inorganic filling material (C), an inorganic compound is used. As the material of the hollow inorganic filling material (C), for example, silicon dioxide, aluminum oxide, 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, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate.

[0159] In addition, as the material of the hollow inorganic filling material (C), an inorganic composite oxide can be used. The inorganic composite oxide represents an oxide containing two or more atoms selected from metal atoms and semi-metal atoms. As such an inorganic composite oxide, an oxide containing a combination of silicon and one or more atoms selected from metal atoms and semi-metal atoms other than silicon is preferred. As metal atoms combined with silicon, aluminum, lead, nickel, cobalt, copper, zinc, zirconium, iron, lithium, magnesium, barium, potassium, calcium, titanium, boron, sodium, etc. can be cited, among which aluminum is particularly preferred. Therefore, as an inorganic composite oxide, an oxide containing silicon and aluminum is preferred, and aluminosilicates are particularly preferred.

[0160] Among the materials of these (C) hollow inorganic fillers, silica, alumina and aluminosilicate are suitable, and silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. In addition, spherical silica is preferred as silica.

[0161] (C) The hollow inorganic filler may be a single hollow particle having only one pore inside the particle, may be a multi-hollow particle having two or more pores inside the particle, or may be a combination of a single hollow particle and a multi-hollow particle.

[0162] (C) hollow inorganic filling material has a porosity greater than 0 volume % because it has a hole. From the viewpoint of reducing the warpage of the cured product of the resin combination, the porosity of (C) hollow inorganic filling material is preferably more than 10 volume %, more preferably more than 15 volume %, and particularly preferably more than 20 volume %. In addition, from the viewpoint of the mechanical strength of the cured product of the resin combination, the porosity of the hollow inorganic filling material is preferably less than 95 volume %, more preferably less than 90 volume %, and particularly preferably less than 85 volume %.

[0163] The porosity P (volume %) of a particle is defined as the volume-based ratio of the total volume of one or more pores in the particle to the volume of the entire particle based on the outer surface of the particle (total volume of pores / volume of the particle). The porosity P can be measured using the actual density D of the particle. M (g / cm 3 ) and the theoretical value of the material density D of the material forming the particles T (g / cm 3 ), calculated by the following formula (1).

[0164]

[0165] (C) hollow inorganic filling material usually has a pore formed in the particle and an outer shell formed by an inorganic material surrounding the pore. Usually, the pore is distinguished from the particle outside by the outer shell. At this time, it is hoped that the pore is not connected to the particle outside. Therefore, it is hoped that the outer shell is a non-porous shell without a hole that connects the pore to the particle outside. The situation that the outer shell is non-porous can be confirmed by observing with a transmission electron microscope (TEM).

[0166] From the viewpoint of significantly obtaining the effects of the present invention, 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.

[0167] The average particle size of the particles can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the particles can be made on a volume basis by a laser diffraction scattering particle size distribution measuring device, and the median particle size can be measured as the average particle size. The sample for measuring the inorganic filler can be a sample obtained by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing the sample for 10 minutes by ultrasonic wave. For the sample, a laser diffraction particle size distribution measuring device is used, and the wavelength of the light source is set to blue and red, and the particle size distribution of the volume basis of the inorganic filler is measured by a flow cell (flow cell), and the average particle size as the median particle size can be calculated according to the obtained particle size distribution. As a laser diffraction particle size distribution measuring device, for example, "LA-960" manufactured by Horiba Manufacturing Co., Ltd. can be cited.

[0168] From the viewpoint of significantly obtaining the effects of the present invention, 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 using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, adsorbing nitrogen on the sample surface, and calculating the specific surface area by the BET multipoint method.

[0169] (C) A commercially available hollow inorganic filler can be used. Examples of commercially available hollow inorganic fillers (C) include "LHP-208" manufactured by Ube Exsymo Co., Ltd. and "MG-005" manufactured by Pacific Cement Co., Ltd.

[0170] In addition, the hollow inorganic filling material (C) can be manufactured, for example, by the method described in Japanese Patent Gazette No. 5940188 or a method based on the method. For example, hollow silica particles as an example of the hollow inorganic filling material (C) can be manufactured by a method including the following steps: a step of preparing an aqueous solution containing a substance that can form pores and an alkaline compound; a step of mixing and stirring the aqueous solution with an alkoxysilane to precipitate silica particles; a step of removing the substance that can form pores from the silica particles to obtain a hollow silica precursor; and a step of calcining the hollow silica precursor.

[0171] From the viewpoint of improving moisture resistance and dispersibility, the (C) hollow inorganic filling material is preferably treated with a surface treatment agent. As the surface treatment agent, for example, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. can be cited. The surface treatment agent can be used alone or in combination of two or more.

[0172] Commercially available products of the surface treatment agent include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.; "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.; "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.; "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.; "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd.; "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.; "KBM-4803" (long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd.; "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

[0173] From the viewpoint of improving dispersibility, the degree of surface treatment by the surface treatment agent is preferably limited to a specific range. Specifically, relative to 100% by mass of the hollow inorganic filler material, preferably 0.2% by mass to 8% by mass of the surface treatment agent is used for surface treatment, more preferably 0.2% by mass to 5% by mass of the surface treatment agent is used for surface treatment, and further preferably 0.3% by mass to 3% by mass of the surface treatment agent is used for surface treatment.

[0174] The degree of surface treatment by the surface treatment agent can be evaluated by the carbon content per unit surface area of ​​the hollow inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m 2 More preferably 0.1 mg / m 2 More preferably 0.2 mg / m 2 On the other hand, from the viewpoint of preventing the increase of the melt viscosity of the resin composition, 1.0 mg / m 2 Less than 0.8 mg / m 2 Below, more preferably 0.5 mg / m 2 the following.

[0175] The amount of carbon per unit surface area of ​​the hollow inorganic filling material can be measured after the surface-treated hollow inorganic filling material is cleaned with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the hollow inorganic filling material 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 components, the amount of carbon per unit surface area of ​​the hollow inorganic filling material can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd., etc. can be used.

[0176] When the non-volatile component of the resin composition is set to 100 volume %, the content (volume %) of the component (C) is preferably 10 volume % or more, more preferably 15 volume % or more, further preferably 30 volume % or more, and is preferably 80 volume % or less, more preferably 75 volume % or less, further preferably 70 volume % or less.

[0177] When the non-volatile component of the resin composition is set to 100 mass %, the content (mass %) of the component (C) is preferably 10 mass % or more, more preferably 15 mass % or more, further preferably 20 mass % or more, and is preferably 80 mass % or less, more preferably 75 mass % or less, further preferably 70 mass % or less.

[0178] <(D) Radical polymerizable resin>

[0179] The resin composition contains (D) a radical polymerizable resin as the (D) component. The (D) radical polymerizable resin as the (D) component does not include a substance corresponding to the (A) to (C) components. The (D) component may be used alone or in combination of two or more.

[0180] As described above, if a radical polymerizable resin is contained in the resin composition, the curing shrinkage increases and the warpage of the cured product increases. In the present invention, the warpage can be reduced by containing a radical polymerizable resin and adjusting the amount ratio of the radical polymerizable resin to the (B) aromatic maleimide compound to a predetermined range.

[0181] (D) The radical polymerizable resin may contain an ethylenically unsaturated bond. Therefore, the radical polymerizable resin (D) may have a radical polymerizable group containing an ethylenically unsaturated bond. Examples of the radical polymerizable group include unsaturated hydrocarbon groups such as vinyl, allyl, styryl, 1-propenyl, 3-cyclohexenyl, 3-cyclopentenyl, 2-vinylphenyl, 3-vinylphenyl, and 4-vinylphenyl; α,β-unsaturated carbonyl groups such as acryloyl and methacryloyl. Among them, as the ethylenically unsaturated bond, it is preferably one or more selected from allyl, styryl, vinylphenyl, acryloyl, and methacryloyl. The radical polymerizable resin (D) preferably has two or more radical polymerizable groups.

[0182] (D) As a radical polymerizable resin, a styrene-based radical polymerizable resin, a (meth)acrylic radical polymerizable resin, an allyl radical polymerizable resin etc. are mentioned, for example, A styrene-based radical polymerizable resin is preferable.

[0183] Styrene-based free radical polymerizable resins are compounds having one or more, preferably two or more vinyl groups directly bonded to aromatic carbon atoms. Examples of styrene-based free radical polymerizable resins include low molecular weight (molecular weight less than 1000) styrene-based 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; and high molecular weight (molecular weight greater than 1000) styrene-based compounds such as vinylbenzyl-modified polyphenylene ether resins and styrene-divinylbenzene copolymers. Examples of commercially available styrene-based free radical polymerizable resins include: "ODV-XET (X03)", "ODV-XET (X04)", and "ODV-XET (X05)" (styrene-divinylbenzene copolymers) manufactured by Nippon Steel Chemical Materials Co., Ltd.; and "OPE-2St 1200" and "OPE-2St 2200" (vinyl benzyl-modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0184] The (meth)acrylic radical polymerizable resin is, for example, a compound having one or more, preferably two or more, acryloyl and / or methacryloyl groups. Examples of the (meth)acrylic radical polymerizable resin include: aliphatic (meth)acrylate compounds of low molecular weight (molecular weight less than 1000) such as 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-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; low molecular weight (molecular weight) esters such as oxadiol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)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, etc. Ether-containing (meth)acrylate compounds having a molecular weight of less than 1000); low molecular weight (molecular weight less than 1000) isocyanurate group-containing (meth)acrylate compounds such as tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and ethoxylated isocyanuric acid tri(meth)acrylate; high molecular weight (molecular weight of 1000 or more) acrylate compounds such as (meth)acrylic acid-modified polyphenylene ether resin, etc. Examples of commercially available (meth)acrylic free radical polymerizable resins include: "A-DOG" (dimethacrylate) manufactured by Shin-Nakamura Chemical Industry 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" (dicyclodecane dimethanol dimethacrylate) manufactured by Nippon Kayaku Co., Ltd. "SA9000", "SA9000-111" (methacrylic acid modified polyphenylene ether) manufactured by SABIC, etc.

[0185] Allyl radical polymerizable resins are, for example, compounds having one or more, preferably two or more, allyl groups. Examples of allyl radical polymerizable resins include: aromatic carboxylic acid allyl compounds such as diallyl biphenyl dicarboxylate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalene dicarboxylate, and diallyl 2,3-naphthalene dicarboxylate; isocyanurate allyl compounds such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; aromatic allyl compounds containing epoxy groups such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzo[3-allyl-4-(3,4-dihydro-2H-1,3-benzo[3-allyl-4-(3,4-dihydro-2H-1,3-benzo[3-allyl-4-(3,4-dihydro-2H-1,3-benzo[3-allyl-4-(3,4-dihydro-2H-1,3-benzo[3-allyl- Oxazine-3-yl)phenyl]methane and other benzo Aromatic allyl compounds containing oxazine; ether-containing aromatic allyl compounds such as 1,3,5-triallyl ether benzene; allyl silane compounds such as diallyl diphenylsilane, etc. As commercially available products of allyl-based free radical polymerizable resins, for example, there can be mentioned: "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Chemical Industry Co., Ltd.; "DAD" (diallyl biphenyl dicarboxylate) manufactured by Nichido Techno Fine Chemical Co., Ltd.; "TRIAM-705" (triallyl trimellitate) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; "DAND" (diallyl 2,3-naphthalene dicarboxylate) manufactured by Nichido Techno Fine Chemical Co., Ltd.; "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzo ... "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 Chemical Co., Ltd.; "NE-V-1100-70T" (a compound containing multiple allyl groups and benzene rings, respectively) manufactured by DIC Corporation, etc.

[0186] (D) The ethylenically unsaturated bond equivalent of the radically 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 indicates the mass of the radically polymerizable resin per 1 equivalent of ethylenically unsaturated bonds.

[0187] The weight average molecular weight (Mw) of the (D) radical polymerizable resin 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, and may be, for example, 150 or more. The weight average molecular weight can be measured as a polystyrene conversion value by gel permeation chromatography (GPC).

[0188] When the non-volatile component in the resin composition is set to 100 mass %, the content of the component (D) is preferably 0.1 mass % or more, more preferably 1 mass % or more, preferably 35 mass % or less, more preferably 30 mass % or less, further preferably 25 mass % or less, 20 mass % or less.

[0189] When the content of the component (D) when the non-volatile component in the resin composition is 100% by mass is defined as d, 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 further preferably 4.8 or less. By adjusting the amount ratio of the component (B) to the component (D) within the above range, a cured product with suppressed warpage can be obtained.

[0190] <(E) Curing agent>

[0191] The resin composition may contain (E) a curing agent as an optional component. The (E) curing agent as the (E) component does not include substances corresponding to the above-mentioned (A) to (D) components. The (E) component generally has a function of curing the resin composition by reacting with the (A) component and the (B) component. The (E) component may be used alone or in combination of two or more in any ratio.

[0192] (E) The curing agent may be any of an anionic curing agent and a cationic curing agent, but an anionic curing agent is preferred from the viewpoint of significantly obtaining the effects of the present invention.

[0193] Examples of the component (E) include active ester curing agents, phenolic curing agents, benzoic acid curing agents, Oxazine-based curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, cyanate-based curing agents, etc. Among them, as component (E), from the viewpoint of significantly obtaining the effect of the present invention, it is preferred to include phenol-based curing agents, benzophenone-based curing agents, Any of an oxazine-based curing agent and a carbodiimide-based curing agent.

[0194] As phenolic curing agents, there can be mentioned: curing agents having one or more, preferably two or more hydroxyl groups bonded to aromatic rings (benzene rings, naphthalene rings, etc.) in one molecule. Among them, compounds having hydroxyl groups bonded to benzene rings are preferred. In addition, from the viewpoints of heat resistance and water resistance, phenolic curing agents having a novolac structure are preferred. Moreover, from the viewpoint of close adhesion, nitrogen-containing phenolic curing agents are preferred, and phenolic curing agents containing a triazine skeleton are more preferred. In particular, from the viewpoint of highly satisfying heat resistance, water resistance and close adhesion, phenolic novolac curing agents containing a triazine skeleton are preferred.

[0195] 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 Chemicals; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-495V", "SN-375", and "SN-395" manufactured by Nippon Steel Chemicals Co., Ltd.; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165" manufactured by DIC; "GDP-6115L", "GDP-6115H", "ELPC75" manufactured by Qunrong Chemical Co., Ltd.; "SA90" manufactured by SABIC, etc.

[0196] Specific examples of the carbodiimide-based curing agent include "V-03", "V-05", and "V-07" manufactured by Nisshinbo Chemical Co., Ltd. and Stabaxol (registered trademark) P manufactured by LANXESS.

[0197] As benzo Specific examples of the oxazine-based curing agent include "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Highpolymer Co., Ltd.; and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0198] Examples of the acid anhydride curing agent include curing agents 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, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, and homotrimethylol. Polymer-type acid anhydrides such as phthalic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, naphthalenetetracarboxylic anhydride, oxydiphthalic anhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic anhydride, 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(trimellitic anhydride ester), styrene-maleic acid resin obtained by copolymerization of styrene and maleic acid, etc. Acid anhydride-based curing agents can be commercially available products, for example, "MH-700" manufactured by Shin Nippon Rika Co., Ltd., etc.

[0199] As active ester curing agents, curing agents having more than one active ester group in one molecule can be cited. Among them, as active ester curing agents, compounds having more than two highly reactive ester groups in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxylamine esters, esters of heterocyclic hydroxyl compounds, etc., are preferably used. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxyl 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 hydroxyl compound is preferably used, and an active ester curing agent obtained from a carboxylic acid compound and a phenolic compound and / or a naphthol compound is more preferably used.

[0200] 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.

[0201] Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, 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, phloroglucinol, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0202] Preferred specific examples of active ester curing agents include active ester compounds containing a dicyclopentadiene diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing acetylated products of phenol novolac, and active ester compounds containing benzoylated products of phenol novolac. Among them, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene diphenol structure are more preferred. "Dicyclopentadiene diphenol structure" means a divalent structure composed of phenylene-dicyclopentenylene-phenylene.

[0203] Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", and "EXB-8000L-65TM" (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene-type diphenol structure; and "HPC-8150-60T", "HPC-8150-62T", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65T", and "EXB-8100L-65T". XB9416-70BK", "EXB-8151-62T" (manufactured by DIC Corporation); as an active ester compound containing an acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation) can be cited; as an active ester compound containing a benzoylated product of phenol novolac, "YLH1026" (manufactured by Mitsubishi Chemical Corporation) can be cited; regarding the active ester curing agent as an acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation) can be cited; regarding the active ester curing agent as a benzoylated product of phenol novolac, "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation) and the like can be cited.

[0204] As the amine curing agent, there can be mentioned: a curing agent having one or more amino groups in one molecule, for example, aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, aromatic amines are preferred from the viewpoint of exerting the desired effect of the present invention. The amine curing agent is preferably a primary amine or a secondary amine, and a primary amine is more preferred. Specific examples of the amine curing agent include: 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, metaphenylenediamine, metaphenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino- 4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. As the amine curing agent, commercially available products can be used, for example, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd.; "EPICURE W" manufactured by Mitsubishi Chemical Corporation, etc.

[0205] Examples of the cyanate curing agent include difunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylene))benzene, bis(4-cyanatephenyl)sulfide, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers obtained by partially triazinizing these cyanate resins. Specific examples of cyanate curing agents include: "PT30" and "PT60" manufactured by Arxada (both are phenol novolac-type multifunctional cyanate resins); "ULL-950S" (multifunctional cyanate resin); "BA230", "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is triazine-treated to become trimers), etc.

[0206] From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile component in the resin composition is set to 100 mass %, the content of the (E) curing agent is preferably 0.1 mass % or more, more preferably 0.3 mass % or more, further preferably 0.5 mass % or more, and is preferably 10 mass % or less, more preferably 8 mass % or less.

[0207] <(F) Thermoplastic resin>

[0208] The resin composition may contain (F) a thermoplastic resin as an optional component. The (F) thermoplastic resin as the component (F) does not include those corresponding to the components (A) to (E). The (F) component may be used alone or in combination of two or more.

[0209] (F) Examples of the thermoplastic resin include polyimide resins, phenoxy resins, polyvinyl acetal resins, polystyrene resins, polyolefin resins, polybutadiene resins, polyamide-imide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins.

[0210] As the phenoxy resin, for example, there can be mentioned a phenoxy resin having one or more skeletons selected from the following skeletons: bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone 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 phenolic hydroxyl group and epoxy group. Specific examples of phenoxy resins include: "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (a phenoxy resin containing a bisphenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (a phenoxy resin containing a bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel Chemical Materials Co., Ltd.; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation.

[0211] Specific examples of polyimide resins include: "PIAD200" manufactured by Arakawa Chemical Co., Ltd.; "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd.; "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Shin-Nippon Chemical Co., Ltd. Specific examples of these polyimide resins include: linear polyimide resins obtained by reacting difunctional hydroxyl-terminated polybutadiene, diisocyanate compounds and tetrabasic acid anhydrides (polyimide resins described in Japanese Patent Application Laid-Open No. 2006-37083), polyimide resins containing polysiloxane skeletons (polyimide resins described in Japanese Patent Application Laid-Open No. 2002-12667 and Japanese Patent Application Laid-Open No. 2000-319386, etc.), and other modified polyimide resins.

[0212] Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", and "Denka Butyral 6000-EP" manufactured by Denka; and 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.

[0213] Examples of the polystyrene resin include unmodified polystyrene resin, Modified polystyrene resins containing oxazoline groups, styrene block copolymers, etc. As styrene block copolymers, for example, 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), styrene-isobutylene-styrene block copolymers (SIBS resins), etc. Specific examples of polystyrene-based resins include "PX3-RP-37" and "RP-RX-61" (containing 1,1-dioxazoline) manufactured by Nippon Shokubai. "HYBRAR 5125" manufactured by Kuraray (SIS resin); "S1611" manufactured by Asahi Kasei Corporation (SEBS resin); "H1041", "Tuftec H1043", "Tuftec P2000", "Tuftec MP10" manufactured by Asahi Kasei Corporation (hydrogenated styrene-based thermoplastic resins); "EPOFRIEND AT501", "CT310" manufactured by Daicel (epoxidized styrene-butadiene thermoplastic resins); "SEPTON HG252" manufactured by Kuraray (modified polystyrene resin with hydroxyl group); "Tuftec N503M" manufactured by Asahi Kasei Corporation (modified polystyrene resin with carboxyl group); "Tuftec N501" manufactured by Asahi Kasei Corporation (modified polystyrene resin with amino group); "Tuftec M1913" (modified polystyrene resin with anhydride group); "SEPTON S8104" (unmodified polystyrene resin) manufactured by Kuraray; "FG1924" (styrene-ethylene / butylene-styrene block copolymer) manufactured by Kraton; "EF-40" (manufactured by CRAY VALLEY), etc. As polystyrene resins, preferably containing Azoline-modified styrene resin.

[0214] Examples of the polyolefin resin include ethylene copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, and ethylene-methyl acrylate copolymers; and polyolefin polymers such as polypropylene and ethylene-propylene block copolymers.

[0215] Examples of the polybutadiene resin include resins containing a hydrogenated polybutadiene skeleton, polybutadiene resins containing a hydroxyl group, polybutadiene resins containing a phenolic hydroxyl group, polybutadiene resins containing a carboxyl group, polybutadiene resins containing an acid anhydride group, polybutadiene resins containing an epoxy group, polybutadiene resins containing an isocyanate group, polybutadiene resins containing a urethane group, and polyphenylene ether-polybutadiene resins.

[0216] Specific examples of polyamideimide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamideimide resins include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing a polysiloxane skeleton) manufactured by Resonac.

[0217] Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. and the like.

[0218] Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0219] The polyphenylene ether resin may be a copolymer of polyphenylene ether and polybutadiene. Specific examples of the polyetherimide resin include "ULTEM" manufactured by GE.

[0220] Examples of polycarbonate resins include hydroxyl-containing carbonate resins, phenolic hydroxyl-containing carbonate resins, carboxyl-containing carbonate resins, anhydride-containing carbonate resins, isocyanate-containing carbonate resins, and urethane-containing carbonate resins. Specific examples of polycarbonate resins include "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Corporation, and "C-1090", "C-2090", and "C-3090" (polycarbonate diols) manufactured by Kuraray Co., Ltd. Specific examples of polyetheretherketone resins include "SUMIPLOY K" manufactured by Sumitomo Chemical Co., Ltd.

[0221] Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexanedimethylene terephthalate resin.

[0222] 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, particularly preferably 20,000 or more, and is preferably 70,000 or less, more preferably 60,000 or less, particularly preferably 50,000 or less.

[0223] When the nonvolatile component in the resin composition is 100 mass %, the content of the (F) thermoplastic resin is preferably 0.1 mass % or more, more preferably 0.5 mass % or more, further preferably 1 mass % or more, and preferably 15 mass % or less.

[0224] <(G) Curing accelerator>

[0225] The resin composition may contain (G) a curing accelerator as an optional component. The (G) curing accelerator as the (G) component does not include substances corresponding to the (A) to (F) components. Examples of the (G) curing accelerator include: phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Preferred are amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators. More preferred are amine-based curing accelerators and imidazole-based curing accelerators. One curing accelerator may be used alone, or two or more may be used in combination.

[0226] 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, and butyltriphenylphosphonium thiocyanate, and triphenylphosphonium thiocyanate is preferred.

[0227] Examples of the amine-based 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, and 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferred.

[0228] 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-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4 imidazole compounds such as -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 of 2-phenylimidazole, isocyanuric acid adduct of 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

[0229] As imidazole-based curing accelerators, commercially available products can be used, for example, "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", "C11Z-A" manufactured by Shikoku Chemical Industry Co., Ltd.; "P200-H50" manufactured by Mitsubishi Chemical Corporation, etc.

[0230] Examples of the guanidine-based 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, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine. Preferred examples include dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0231] As metal curing accelerators, for example, organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin can be cited. Specific examples of organic metal complexes include organic cobalt complexes such as cobalt acetylacetonate (II) and cobalt acetylacetonate (III), organic copper complexes such as copper acetylacetonate (II), organic zinc complexes such as zinc acetylacetonate (II), organic iron complexes such as iron acetylacetonate (III), organic nickel complexes such as nickel acetylacetonate (II), and organic manganese complexes such as manganese acetylacetonate (II). As organic metal salts, for example, zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like can be cited.

[0232] When the non-volatile component in the resin composition is set to 100 mass%, the content of the (G) curing accelerator is preferably 0.01 mass% or more, more preferably 0.03 mass% or more, particularly preferably 0.05 mass% or more, and is preferably 3 mass% or less, more preferably 1 mass% or less, particularly preferably 0.5 mass% or less.

[0233] <(H) Radical polymerization initiator>

[0234] The resin composition may contain (H) a radical polymerization initiator as an optional component. The (H) radical polymerization initiator as the (H) component does not include substances corresponding to the (A) to (G) components. The (H) radical polymerization initiator may be, for example, a thermal polymerization initiator that generates free radicals when heated. The (H) radical polymerization initiator may be a polymerization initiator of a radical reactive group. The (H) radical polymerization initiator may be used alone or in any combination of two or more.

[0235] (H) As a radical polymerization initiator, a peroxide radical polymerization initiator, an azo radical polymerization initiator etc. are mentioned, for example. Among them, a peroxide radical polymerization initiator is preferable.

[0236] Examples of the peroxide-based radical polymerization initiator include hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; dialkyl peroxide compounds such as tert-butyl isopropyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, diisopropyl peroxide, 1,4-bis(1-tert-butylperoxy-1-methylethyl)benzene, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) Peroxy diacyl compounds such as peroxy dicarbonates; peroxy ester compounds such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanoate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxylaurate, 1,1-dimethylpropyl 2-ethylperoxyhexanoate, tert-butyl 2-ethylperoxyhexanoate, tert-butyl 3,5,5-trimethylperoxyhexanoate, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-butyl peroxymaleate, etc.

[0237] Examples of the azo radical polymerization initiator include azo nitrile 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; and 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]. 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), 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);

[0238] (H) As commercially available products of the radical polymerization initiator, for example, there may be mentioned “PERBUTYL C”, “PERBUTYL A”, “PERBUTYL P”, “PERBUTYL L”, “PERBUTYL O”, “PERBUTYL ND”, “PERBUTYL Z”, “PERBUTYL I”, “PERCUMYL P”, “PERCUMYL D”, “PERHEXYL D”, “PERHEXYLA”, “PERHEXYL I”, “PERHEXYL Z”, “PERHEXYL ND”, “PERHEXYL O”, “PERHEXYL PV” and the like manufactured by NOF Corporation.

[0239] When the non-volatile component in the resin composition is set to 100 mass %, the content of the (H) radical polymerization initiator is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, further preferably 0.1 mass % or more, and is preferably 1.5 mass % or less, more preferably 1 mass % or less, further preferably 0.5 mass % or less.

[0240] <(I) Solid inorganic filler materials>

[0241] The resin composition may contain (I) a solid inorganic filler as an optional component within a range not impairing the effects of the present invention. A solid inorganic filler is an inorganic filler having substantially no voids or pores, and is a material having an average porosity of 0 volume %.

[0242] As the material of the component (I), an inorganic compound is used. The material of the component (I) is the same as the material of the component (C).

[0243] As commercially available products of component (I), for example, there can be mentioned: "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by ADMATECHS; "UFP-30", "DAW-03", and "FB-105FD" manufactured by Denka; "SILFIL NSS-3N", "SILFIL NSS-4N", and "SILFIL NSS-5N" manufactured by Tokuyama; "CellSpheres" and "MGH-005" manufactured by Pacific Cement Co., Ltd.

[0244] The average particle size of the component (I) is preferably 0.01 μm or more, more preferably 0.1 μm or more, and further preferably 0.3 μm or more, and is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 3 μm or less. The average particle size of the component (I) can be measured by the same method as the method for measuring the average particle size of the component (C).

[0245] 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 ​​the component (I) can be measured by the same method as the method for measuring the specific surface area of ​​the component (C).

[0246] From the viewpoint of improving moisture resistance and dispersibility, component (I) is preferably treated with a surface treatment agent. As the surface treatment agent, the surface treatment agent that can be surface treated is the same as that of component (C). In addition, the degree of surface treatment and the amount of carbon in the surface treatment are also the same as those of component (C).

[0247] When the nonvolatile component in the resin composition is 100 mass %, the content of the 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.

[0248] <(J) Other additives>

[0249] The resin composition may further contain other additives as optional components in addition to the above-mentioned components. Examples of (I) other additives include: organic metal 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 leveling agents and acrylic polymer leveling agents; thickeners such as Benton and montmorillonite; defoamers such as silicone defoamers, acrylic defoamers, fluorine defoamers, and vinyl resin defoamers; ultraviolet light absorbers such as benzotriazole ultraviolet light absorbers; adhesion enhancers such as urea silane; adhesion enhancers such as triazole adhesion enhancers, tetrazole adhesion enhancers, and triazine adhesion enhancers; antioxidants such as hindered phenol antioxidants; fluorescent agents such as stilbene derivatives. Optical brighteners; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, 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 initiation aids such as tertiary amines; photosensitizers such as pyrazolines, anthracenes, coumarins, xanthones, and thioxanthones. (J) Other additives may be used alone or in combination of two or more.

[0250] <(K)Solvent>

[0251] The resin composition may further contain an optional solvent as a volatile component in addition to the above-mentioned non-volatile components. As the (K) solvent, a known solvent may be suitably used, and its type is not particularly limited, but an organic solvent is preferred. Examples of the (K) solvent include: ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; tetrahydropyran, tetrahydrofuran, 1,4-dihydropyran, and 1,4-dihydrofuran. Ether solvents such as alkane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, anisole, etc.; alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, etc.; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, carbitol acetate (ethyl diglycol Ether ester solvents such as acetate, γ-butyrolactone, and methyl methoxypropionate; 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 (butyl carbitol); 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; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (K) The solvent may be used alone or in combination of two or more in any ratio.

[0252] Regarding the resin composition, from the viewpoint of significantly obtaining the effect of the present invention, it is preferred that the (K) solvent is contained in an amount of 0.5% by mass or more and 3% by mass or less relative to all the components of the resin composition of 100% by mass. Specifically, regarding the (K) solvent, it is preferred that the amount is contained in an amount of preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1.5% by mass or less, preferably 0.5% by mass or more, more preferably 0.8% by mass or more, further preferably 1% by mass or more relative to all the components of the resin composition of 100% by mass.

[0253] The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which a solvent or the like is added to the blended components as necessary, and the mixture is mixed and dispersed using a rotary mixer or the like.

[0254] <Physical properties and uses of resin composition>

[0255] The cured product obtained by heat curing the resin composition at 190°C for 90 minutes shows the property that the warpage amount is suppressed. Therefore, an insulating layer with suppressed warpage amount is provided. For example, when three points of a cured product with a width of 160 mm and a length of 120 mm are fixed and the warpage at the remaining one point is measured, the warpage amount may be preferably less than 30 mm, more preferably less than 25 mm, further preferably less than 20 mm, and particularly preferably less than 17 mm. The warpage amount can be measured by the method described in the examples described later.

[0256] The cured product obtained by heat curing the resin composition at 190° C. for 90 minutes shows the property of low dielectric constant. Therefore, an insulating layer with low dielectric constant is provided. The dielectric constant is preferably 3.5 or less, more preferably 3.4 or less, and further preferably 3.3 or less. There is no particular restriction on the lower limit, and it can be set to 0.01 or more. The dielectric constant can be measured by the method described in the examples described later.

[0257] The cured product obtained by heat curing the resin composition at 190° C. for 90 minutes shows the characteristic of low dielectric loss tangent. Therefore, an insulating layer with low dielectric loss tangent is provided. The dielectric loss tangent is preferably 0.003 or less, more preferably 0.0028 or less, and further preferably 0.0025 or less. There is no particular restriction on the lower limit, and it can be set to 0.0001 or more. The dielectric loss tangent can be measured by the method described in the embodiments described later.

[0258] The cured product obtained by heat curing the resin composition at 190°C for 90 minutes generally shows the property of low coefficient of thermal expansion (CTE). Therefore, an insulating layer with a low coefficient of thermal expansion is provided. The coefficient of thermal expansion is preferably 35 ppm / °C or less, more preferably 33 ppm / °C or less, and further preferably 30 ppm / °C or less. There is no particular restriction on the lower limit, and it can be set to 0.1 ppm / °C or more. The coefficient of thermal expansion can be measured by the method described in the examples described later.

[0259] The cured product obtained by heat curing the resin composition at 190° C. for 90 minutes generally shows the property of low elastic modulus. Therefore, an insulating layer with low elastic modulus is provided. The elastic modulus is preferably less than 10 GPa, more preferably less than 9.8 GPa, and further preferably less than 9.5 GPa or less than 9.3 GPa. There is no particular restriction on the lower limit, and it can be set to 0.1 GPa or more. The elastic modulus can be measured by the method described in the embodiments described later.

[0260] 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 insulating purposes. Specifically, it can be suitably used as: a resin composition for forming an insulating layer (a resin composition for forming an insulating layer for forming a conductor layer), and the insulating layer is used to form a conductor layer (including a rewiring layer) formed on the insulating layer.

[0261] In addition, in the multilayer printed wiring board described later, it 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).

[0262] 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 also be suitably used as a resin composition for a rewiring forming layer (resin composition for forming a rewiring forming layer) as an insulating layer for forming a rewiring layer and a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When manufacturing a semiconductor chip package, a rewiring layer can be further formed on the sealing layer.

[0263] (1) A step of laminating a temporary fixing film on a substrate;

[0264] (2) A process of temporarily fixing the semiconductor chip on a temporary fixing film;

[0265] (3) a step of forming a sealing layer on a semiconductor chip;

[0266] (4) a step of peeling the substrate and the temporary fixing film from the semiconductor chip;

[0267] (5) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been peeled off; and

[0268] (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0269] [Resin sheet]

[0270] The resin sheet of the present invention comprises a support and a resin composition layer formed from the resin composition of the present invention and provided on the support.

[0271] The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, and further preferably 50 μm or less, from the viewpoint of thinning the printed wiring board and providing 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, and can usually be set to 5 μm or more.

[0272] Examples of the support include films made of plastic materials, metal foils, and release papers, and films made of plastic materials and metal foils are preferred.

[0273] When a film made of a plastic material is used as a support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate (hereinafter sometimes referred to as "PEN"), polycarbonate (hereinafter sometimes referred to as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0274] When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, preferably copper foil. The copper foil may be a foil made of a single metal such as copper or an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0275] The surface of the support to be in contact with the resin composition layer may be subjected to matte treatment, corona treatment, or antistatic treatment.

[0276] In addition, as the support, a support with a release layer having a release layer on the surface bonded to the resin composition layer can be used. As a release agent for the release layer of the support with a release layer, for example, there can be mentioned: one or more release agents selected from alkyd resins, polyolefin resins, urethane resins and silicone resins. The support with a release layer can use commercially available products, for example, there can be mentioned: "SK-1", "AL-5", "AL-7" manufactured by LINTEC, which is a PET film having a release layer with an alkyd resin-based release agent as a main component; "Lumirror T60" manufactured by Toray Industries, Inc.; "Purex" manufactured by Teijin Co., Ltd.; "Unipeel" manufactured by UNITIKA Co., Ltd., etc.

[0277] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

[0278] In one embodiment, the resin sheet may further include other layers as needed. As the other layers, for example, a protective film selected according to the support and arranged on the surface of the resin composition layer that is not bonded to the support (i.e., the surface on the opposite side of the support) can be cited. The thickness of the protective film is not particularly limited, for example, 1 μm to 40 μm. By laminating the protective film, dust and the like can be prevented from adhering to the surface of the resin composition layer or causing damage to the surface of the resin composition layer.

[0279] The resin sheet can be produced, for example, by preparing a resin varnish obtained by dissolving a resin composition in a solvent, applying the resin varnish on a support using a die coater or the like, and further drying to form a resin composition layer. The solvent is as described above.

[0280] Drying can be carried out by known methods such as heating and blowing hot air. The drying conditions are not particularly limited, and the drying is performed in a manner such that the content of the solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the solvent in the resin varnish, for example, in the case of using a resin varnish containing 30% to 60% by mass of a solvent, a resin composition layer can be formed by drying at 50° C. to 150° C. for 3 minutes to 10 minutes.

[0281] The resin sheet can be stored by winding it into a roll. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0282] [Printed wiring board]

[0283] The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.

[0284] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet and by a method including the following steps (I) and (II).

[0285] (I) a step of laminating a resin sheet on the inner substrate in such a manner that the resin composition layer of the resin sheet is bonded to the inner substrate;

[0286] (II) A step of thermally curing the resin composition layer to form an insulating layer.

[0287] The "inner substrate" used in step (I) refers to a component that becomes a 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, a thermosetting polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may also be patterned. Sometimes an inner substrate having a conductor layer (circuit) formed on one or both sides of a substrate is referred to as an "inner circuit substrate". In addition, when manufacturing a printed wiring board, an intermediate product to be further formed with an insulating layer and / or a conductor layer is also included in the "inner substrate" described in the present invention. In the case where the printed wiring board is a circuit board with built-in components, an inner substrate with built-in components can be used.

[0288] The lamination of the inner substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet to the inner substrate from the support body side. As a member for heat-pressing the resin sheet to the inner substrate (hereinafter, also referred to as a "heat-pressing member"), for example, a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller, etc.) can be cited. It should be noted that it is preferred not to press the heat-pressing member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet fully follows the surface unevenness of the inner substrate.

[0289] The lamination of the inner substrate and the resin sheet can be implemented by vacuum lamination. In the vacuum lamination method, the heating and pressing temperature is preferably 60°C to 160°C, more preferably 80°C to 140°C, the heating and pressing pressure is preferably 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa, and the heating and pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably implemented under reduced pressure conditions of 26.7hPa or less.

[0290] Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurizing laminator manufactured by Meiki Mfg. Co., Ltd., a vacuum applicator manufactured by Nikko-Materials Co., Ltd., and a batch vacuum pressurizing laminator.

[0291] After lamination, the laminated resin sheet can be smoothed by pressing the heating and pressing member at normal pressure (atmospheric pressure), for example, from the support side. The pressing conditions for the smoothing treatment can be set to the same conditions as the heating and pressing conditions for the above-mentioned lamination. The smoothing treatment can be performed using a commercially available laminator. It should be noted that the lamination and smoothing treatment can be performed continuously using the above-mentioned commercially available vacuum laminator.

[0292] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0293] In step (II), the resin composition layer is thermally cured to form an insulating layer. The thermal curing conditions of the resin composition layer are not particularly limited, and conditions generally used when forming an insulating layer of a printed wiring board can be used.

[0294] For example, the heat curing conditions of the resin composition layer vary depending on the type of the resin composition, and 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.

[0295] 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, before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature of 50° C. or higher and lower than 120° C. (preferably 60° C. or higher and 115° C. or lower, more preferably 70° C. or higher and 110° C. or lower) 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).

[0296] When manufacturing a printed wiring board, the step (III) of opening a hole in the insulating layer; the step (IV) of roughening the insulating layer; and the step (V) of forming a conductor layer may be further implemented. These steps (III) to (V) may be implemented according to various methods known to those skilled in the art for manufacturing printed wiring boards. It should be noted that, in the case where the support body is removed after step (II), the removal of the support body may be implemented between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). In addition, as necessary, the formation of the insulating layer and the conductor layer of steps (II) to (V) may be repeatedly implemented to form a multilayer wiring board.

[0297] Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) can be implemented, for example, using a drill, laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The size or shape of the hole can be appropriately determined according to the design of the printed wiring board.

[0298] Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), contamination is also removed. There are no particular restrictions on the steps and conditions of the roughening treatment, and the known steps and conditions commonly used when forming the insulating layer of the printed wiring board can be adopted. For example, swelling treatment based on a swelling solution, roughening treatment based on an oxidant, and neutralization treatment based on a neutralizing solution can be sequentially implemented to roughen the insulating layer. The swelling solution used for the roughening treatment is not particularly limited, and examples include: alkaline solutions, surfactant solutions, etc., preferably alkaline solutions, and more preferably sodium hydroxide solutions and potassium hydroxide solutions. As commercially available swelling solutions, for example, "Swelling Dip Securiganth P", "Swelling Dip Securiganth SBU", "Swelling DipSecurigant P" manufactured by Atotech Japan Co., Ltd. are mentioned. There is no particular restriction on the swelling treatment based on the swelling solution, for example, it can be carried out by immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferred to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes. As the oxidizing agent used for the roughening treatment, there is no particular limitation, and examples thereof include: an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment based on an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. As commercially available oxidizing agents, for example, alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan can be cited. In addition, as a neutralizing solution used for the roughening treatment, an acidic aqueous solution is preferred, and as a commercially available product, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan can be cited. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. In view of operability, etc., it is preferable to immerse the object subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes.

[0299] 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 further preferably 200 nm or less. The lower limit is not particularly limited, but is preferably 30 nm or more, more preferably 40 nm or more, and further 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.

[0300] Step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. There is no particular limitation on the conductor material used for the conductor layer. In a suitable embodiment, the conductor layer comprises one or more metals selected from 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. As the alloy layer, for example, a layer formed by an alloy of two or more metals selected from the above (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) can be cited. Among them, from the viewpoints of versatility, cost, ease of patterning, etc., of the formation of the conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or 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 nickel-chromium alloy is more preferred, and a single metal layer of copper is further preferred.

[0301] 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 composed of different types of metals or alloys are stacked. In the case where the conductor layer is 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.

[0302] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is usually 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0303] In one embodiment, the conductor layer can be formed by electroplating. For example, the surface of the insulating layer can be electroplated using a conventionally known technique such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. From the perspective of manufacturing simplicity, it is preferably formed by a semi-additive method. An example of forming a conductor layer by a semi-additive method is shown below.

[0304] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, a mask pattern is formed on the formed plating seed layer to expose a portion 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, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

[0305] [Semiconductor devices]

[0306] 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 produced using the printed wiring board of the present invention.

[0307] Examples of the semiconductor device include various semiconductor devices provided for electrical products (eg, computers, mobile phones, digital cameras, and televisions) and vehicles (eg, motorcycles, cars, trains, ships, and airplanes).

[0308] 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. "Conductive portion" means "a portion in a printed wiring board that transmits an electrical signal", and the position may be a surface or an embedded portion, either of which is acceptable. In addition, the semiconductor chip is not particularly limited as long as it is a circuit element made of semiconductor.

[0309] Regarding the method for mounting a semiconductor chip when manufacturing a semiconductor device, there is no particular limitation as long as the semiconductor chip can function effectively. Specifically, there are: a wire bonding mounting method, a flip chip mounting method, a mounting method based on a built-in non-bumpless build-up layer (BBUL), a mounting method based on anisotropic conductive film (ACF), a mounting method based on a non-conductive film (NCF), etc. Here, the "mounting method based on a built-in non-bumpless layer (BBUL)" refers to "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board to connect the semiconductor chip to the wiring on the printed wiring board".

[0310] Example

[0311] Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. It should be noted that in the following description, "parts" and "%" refer to "parts by mass" and "mass %" respectively, unless otherwise explicitly stated.

[0312] <Synthesis Example 1: Synthesis of Maleimide X>

[0313] A MEK solution (70% by mass of non-volatile matter) 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 Japan Invention Association Publication No. 2020-500211 was prepared. Maleimide X has a structure represented by the following formula (1).

[0314]

[0315] <Synthesis Example 2: Synthesis of Elastomer A>

[0316] A reaction container was charged with 60 g of difunctional hydroxyl-terminated polybutadiene ("G-1000" manufactured by Nippon Soda Co., Ltd., number average molecular weight = 1400, hydroxyl 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., and the reaction was carried out for about 1 hour.

[0317] Next, 145 g of oligophenylene ether resin containing phenolic hydroxyl groups at both ends ("SA90-100" manufactured by SABIC, hydroxyl equivalent = 800 g / eq.) and 1 g of benzophenone tetracarboxylic dianhydride (BTDA) were added to the reactant, and the temperature was raised to 140°C while stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak of 2250 cm-1 was confirmed by FT-IR. The disappearance of the NCO peak was regarded as the end point of the reaction, and the reactant was cooled to room temperature. Then, the reactant was filtered with a 100-mesh filter cloth to obtain an elastomer having an oligophenylene ether skeleton (non-volatile component 50% by mass, 25°C viscosity 2.0 Pa·s).

[0318] <Manufacturing of resin varnish>

[0319] Each component was weighed to the mass fraction described in the table, and 30 parts of MEK and 30 parts of cyclohexanone were mixed and uniformly dispersed using a high-speed rotary mixer to obtain a resin varnish.

[0320] [Table 1]

[0321] (Table 1)

[0322]

[0323] The details of each component described in the table are as follows.

[0324] (A)Ingredients

[0325] SLK-6895-T90: functional group equivalent 345 g / eq., toluene solution containing 90% by mass of non-volatile components, manufactured by Shin-Etsu Chemical Co., Ltd.

[0326] SLK-1500-T80: functional group equivalent 752 g / eq., toluene solution with a non-volatile content of 80% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.

[0327] (B) Ingredients

[0328] ·MIR-3000-70MT: functional group equivalent 275 g / eq., toluene solution with non-volatile content of 70% by mass, manufactured by Nippon Kayaku Co., Ltd.

[0329] Maleimide X: the substance synthesized in Synthesis Example 1

[0330] (C) Ingredients

[0331] ·LHP-208: Spherical hollow silica, average particle size 0.5 μm, porosity 50% by volume, manufactured by Ube Exsymo

[0332] (D) Ingredients

[0333] OPE-2St: functional group equivalent 590 g / eq., non-volatile matter 65% by mass, toluene solution, manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0334] ·A-DOG: Functional group equivalent 163g / eq., manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

[0335] TAIC: Functional group equivalent 83g / eq., manufactured by Mitsubishi Chemical Corporation

[0336] ·DAD: Functional group equivalent 161g / eq., manufactured by Nichiku Techno Fine Chemical Co., Ltd.

[0337] (E) Ingredients

[0338] LA-3018-50P: phenol-based curing agent (functional group equivalent 151 g / eq., 1-methoxy-2-propanol solution with a non-volatile content of 50% by mass, manufactured by DIC Corporation)

[0339] SA90: Functional group equivalent 800g / eq., manufactured by SABIC

[0340] V-03: Carbodiimide curing agent (functional group equivalent 216 g / eq., toluene solution with a non-volatile content of 50% by mass, manufactured by Nisshinbo Chemical Co., Ltd.)

[0341] ·ODA-BOZ:Benzo Oxazine-based curing agent (functional group equivalent 218 g / eq., manufactured by JFE Chemical Co., Ltd.)

[0342] (F)Ingredients

[0343] PIAD200: Polyimide resin (mixed solution of cyclohexanone, ethylene glycol dimethyl ether and methylcyclohexane with a non-volatile content of 30%, manufactured by Arakawa Chemical Co., Ltd.)

[0344] ·YX7553BH30: phenoxy resin (a 1:1 solution of MEK and cyclohexanone containing 30% by mass of non-volatile matter, manufactured by Mitsubishi Chemical Corporation)

[0345] Elastomer A: the material synthesized in Synthesis Example 2

[0346] RP-RX-61: has Polystyrene resin with oxazoline skeleton, manufactured by Nippon Shokubai Co., Ltd.

[0347] ·P2000: Styrene butadiene elastomer, manufactured by Asahi Kasei Corporation

[0348] (G) Ingredients

[0349] 1B2PZ: Imidazole curing accelerator, manufactured by Shikoku Chemical Industry Co., Ltd.

[0350] (H) Ingredients

[0351] PERBUTYL C: Made by NOF Corporation

[0352] PERCUMYL P: Made by NOF Corporation

[0353] PERHEXYL D: Made by NOF Corporation

[0354] (I)Ingredients

[0355] SO-C2: Spherical silica surface-treated with an amine alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0.5 μm, specific surface area 5.8 m 2 / g, manufactured by ADMATECHS

[0356] <Measurement of dielectric constant, dielectric loss tangent, elastic modulus, coefficient of thermal expansion (CTE), and warpage>

[0357] (1) Preparation of Resin Sheet A with a Resin Composition Layer Thickness of 40 μm

[0358] As a support, a polyethylene terephthalate film ("AL5" manufactured by LINTEC, thickness 38 μm) having a release layer was prepared. The resin varnish obtained in the examples and comparative examples was evenly applied to the release layer of the support 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 comprising a support and a resin composition layer.

[0359] (2) Preparation of solidified material

[0360] The resin sheet A was cured in an oven at 190° C. for 90 minutes. The support was peeled off from the resin sheet A taken out of the oven to obtain a cured product of the resin composition layer.

[0361] (3) Determination of elastic modulus

[0362] The cured product was punched out with a dumbbell (Super Dumbbell Cutter (Model: SDMK-5889-01)", manufactured by Dumbbell) to prepare a test piece for tensile strength measurement. The support was peeled off from the test piece. A tensile test was performed using a Tensilon universal testing machine (RTM-500 manufactured by Orientex) at a temperature of 25°C, a humidity of 60%, and a tensile speed of 5 mm / min to measure the elastic modulus.

[0363] (4) Determination of coefficient of thermal expansion (CTE)

[0364] The cured product was cut into test pieces of about 5 mm in width and about 15 mm in length, and a thermomechanical analysis was performed using a thermomechanical analyzer ("Thermo Plus TMA8310" manufactured by Rigaku Corporation) by a tensile weighted method. After the test piece was mounted on the device, the thermal expansion coefficient (ppm) was continuously measured twice (the first time was from 25°C to 200°C, and the second time was from 20°C to 260°C) under the measurement conditions of 1g load and a heating rate of 5°C / min, and the second value was used as the linear expansion coefficient (ppm / °C).

[0365] (5) Determination of warpage

[0366] The resin sheet A was laminated on a laminate (copper foil etched product of MCL-E-700G manufactured by Resonac) using an intermittent vacuum pressurizing laminator ("MVLP-500" manufactured by Meiki Manufacturing Co., Ltd.). The lamination was performed as follows: After reducing the pressure for 30 seconds to make the air pressure below 13 hPa, the laminate was crimped at 120°C and a pressure of 0.74 MPa for 30 seconds. After that, the support was peeled off, and the resin composition layer was cured under curing conditions of 190°C and 90 minutes to obtain a cured product sample. The obtained cured product was cut into test pieces with a width of 160 mm and a length of 120 mm, and the warpage of the remaining 1 point was measured while fixing the 3 points.

[0367] [Table 2]

[0368] (Table 2)

[0369]

Claims

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

2. The resin composition according to claim 1, wherein (D) The component 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 claim 1, wherein When the nonvolatile component of the resin composition is 100% by volume, the content of the component (C) is 20% by volume or more and 70% by volume or less.

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

5. The resin composition according to claim 1, wherein The thermal expansion coefficient of a cured product obtained by thermally curing the resin composition at 190° C. for 90 minutes is 35 ppm / ° C. or less.

6. The resin composition according to claim 1, wherein The component (A) contains any one of an aliphatic maleimide compound represented by the formula (A-1) and an aliphatic maleimide compound represented by the formula (A-2): 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; 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) includes any one of an aromatic maleimide compound represented by the formula (B-1) and an aromatic maleimide compound represented by the formula (B-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-, -SO2-, -CONH-, -NHCO-, -COO- or -OCO-, and 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 greater than 1, t1 each independently represents an integer from 0 to 5, u each independently represents an integer from 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 alkoxy 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, and R a2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy 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, and R a3 Each independently represents a divalent aliphatic hydrocarbon group, n a1 Represents the average number of repeating units from 0.95 to 10.0, n a2 Each independently represents an integer from 0 to 4, and n a3 Each independently represents an integer from 0 to 3. 8 . A resin sheet comprising: a support and a resin composition layer provided on the support and containing the resin composition according to claim 1 . 9 . A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to claim 1 . 10 . A semiconductor device comprising the printed wiring board according to claim 9 .

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