Resin composition

Abstract

An object of the present invention is to provide a resin composition capable of obtaining a cured product that can suppress the generation of cracks after defouling treatment and suppress the dielectric loss tangent (Df) to a low value. The solution of the present invention is a resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler. Among them, the component (A) includes: (A-1) a modified epoxy resin obtained by reacting an epoxy resin having two or more epoxy groups in one molecule with an ester compound represented by the formula (1) (each symbol in the formula (1) is as described in the specification). When the non-volatile components in the resin composition are set to 100% by mass, the content of the component (C) is 50% by mass or more.

Description

Technical Field

[0001] The present invention relates to a resin composition containing an epoxy resin. Furthermore, it relates to a cured product, a sheet-like laminate, a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition. Background Art

[0002] As a manufacturing technique for printed wiring boards, a manufacturing method based on a build-up method of alternately overlapping an insulating layer and a conductor layer is known. In the manufacturing method based on the build-up method, usually, the insulating layer is formed by curing a resin composition.

[0003] For printed wiring boards, they are usually exposed to a wide range of temperature environments from a low temperature environment such as room temperature to a high temperature environment such as reflow soldering. Therefore, if the dimensional stability is poor, the resin material of the insulating layer expands and contracts repeatedly, and cracks are generated due to its deformation. In addition, in recent years, further improvement of dielectric properties such as the dielectric loss tangent of the insulating layer has been required.

[0004] So far, ester-modified epoxy resins have been known (Patent Document 1).

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2020-111735. Summary of the Invention

[0008] Technical Problem to be Solved by the Invention

[0009] The technical problem to be solved by the present invention is to provide: a resin composition capable of obtaining a cured product that can suppress the generation of cracks after desmear treatment and suppress the dielectric loss tangent (Df) to a lower value.

[0010] Means for Solving the Technical Problem

[0011] To solve the technical problem of the present invention, the present inventors conducted in-depth research and found that, as a component of the resin composition, by using an ester-modified epoxy resin and setting the content of the inorganic filler to 50% by mass or more, a cured product that can unexpectedly suppress the generation of cracks after desmear treatment and suppress the dielectric loss tangent (Df) to a lower value can be obtained, and thus the present invention was completed.

[0012] That is, the present invention includes the following content,

[0013] [1] A resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler, wherein,

[0014] (A) component contains: a modified epoxy resin obtained by reacting an epoxy resin having two or more epoxy groups in one molecule with an ester compound represented by formula (1).

[0015] [Chemical formula 1]

[0016]

[0017] [In the formula, R 1 represents an optionally substituted alkyl group or an optionally substituted aryl group, and R 2 represents an optionally substituted aryl group],

[0018] When the non-volatile component in the resin composition is set to 100% by mass, the content of component (C) is 50% by mass or more.

[0019] [2] A resin composition comprising an (A) epoxy resin, a (B) reactive ester compound, and a (C) inorganic filler, wherein

[0020] (A) component contains: (A-1) a modified epoxy resin having a group represented by formula (2-1) and a group represented by formula (2-2),

[0021] [Chemical formula 2]

[0022]

[0023] [In the formula, * represents the bonding site].

[0024] [Chemical formula 3]

[0025]

[0026] [In the formula, R 1 represents an optionally substituted alkyl group or an optionally substituted aryl group, R 2 represents an optionally substituted aryl group, and * represents the bonding site],

[0027] When the non-volatile component in the resin composition is set to 100% by mass, the content of component (C) is 50% by mass or more.

[0028] [3] The resin composition according to [1] or [2] above, wherein the (A-1) component is a modified epoxy resin having a structural unit represented by formula (4-1) and a structural unit represented by formula (4-2).

[0029] [Chemical formula 4]

[0030]

[0031] [Where R 4 [a] each independently represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and a represents 0, 1, 2 or 3.

[0032] [Chemical formula 5]

[0033]

[0034] [Where R 1 represents an alkyl group optionally having a substituent, or an aryl group optionally having a substituent, R 2 represents an aryl group optionally having a substituent, R 4 [a] each independently represents an alkyl group optionally having a substituent, or an aryl group optionally having a substituent, and a represents 0, 1, 2 or 3;

[0035] [4] The resin composition according to any one of [1] to [3] above, wherein the content of the component (A-1) is 1% by mass to 20% by mass, based on 100% by mass of the non-volatile component in the resin composition;

[0036] [5] The resin composition according to any one of [1] to [4] above, wherein the content of the component (B) is 5% to 30% by mass, based on 100% by mass of the non-volatile component in the resin composition;

[0037] [6] The resin composition described in any one of [1] to [5] above, wherein the component (A) further comprises (A-2) an epoxy resin that is liquid at 20°C;

[0038] [7] The resin composition according to any one of [1] to [6] above, further comprising (D) a thermoplastic resin;

[0039] [8] The resin composition described in [7] above, wherein the component (D) comprises a thermoplastic resin selected from a polyimide resin and a phenoxy resin;

[0040] [9] The resin composition described in [7] or [8] above, wherein the weight average molecular weight (Mw) of the component (D) is 5,000 or more;

[0041]

[10] The resin composition according to any one of [1] to [9] above, further comprising (E) a radical polymerizable compound;

[0042]

[11] The resin composition described in

[10] above, wherein the component (E) comprises a (meth)acrylic radical polymerizable compound;

[0043]

[12] The resin composition according to any one of [1] to

[11] above, further comprising (F) an elastomer;

[0044]

[13] The resin composition according to

[12] above, wherein the component (F) comprises core-shell rubber particles;

[0045]

[14] The resin composition according to any one of [1] to

[13] above, further comprising (G) a curing accelerator;

[0046]

[15] The resin composition according to any one of [1] to

[14] above, wherein when measured under the conditions of 5.8 GHz and 23 °C, the dielectric loss tangent (Df) of the cured product of the resin composition is 0.0030 or less;

[0047]

[16] A cured product which is a cured product of the resin composition according to any one of [1] to

[15] above;

[0048]

[17] A sheet-like laminated material containing the resin composition according to any one of [1] to

[15] above;

[0049]

[18] A resin sheet having: a support, and a resin composition layer formed of the resin composition according to any one of [1] to

[15] above provided on the support;

[0050]

[19] A printed wiring board having an insulating layer formed of a cured product of the resin composition according to any one of [1] to

[15] above;

[0051]

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

[19] above.

[0052] Effects of the Invention

[0053] According to the resin composition of the present invention, a cured product can be obtained that can suppress the generation of cracks after defouling treatment and suppress the dielectric loss tangent (Df) to a lower value. Detailed Embodiments

[0054] Hereinafter, the present invention will be described in detail according to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented within the scope not exceeding the claims of the present invention and their equivalents.

[0055] <Resin Composition>

[0056] The resin composition of the present invention contains (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler. The (A) epoxy resin contains an (A-1) ester-modified epoxy resin described below. When the non-volatile components in the resin composition are set to 100% by mass, the content of the (C) inorganic filler is 50% by mass or more. By using such a resin composition, a cured product can be obtained that can suppress the generation of cracks after the stain removal treatment and suppress the dissipation factor (Df) to a lower value.

[0057] In addition to containing (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler, the resin composition of the present invention may further contain optional components. Examples of the optional components include (D) a thermoplastic resin, (E) a radically polymerizable compound, (F) an elastomer, (G) a curing accelerator, (H) other additives, and (I) an organic solvent. Hereinafter, each component contained in the resin composition will be described in detail.

[0058] <(A) Epoxy resin>

[0059] The resin composition of the present invention contains (A) an epoxy resin. The (A) epoxy resin refers to a resin having one or more epoxy groups in one molecule. The (A) epoxy resin may be used alone or two or more thereof may be used in any ratio in combination.

[0060] <(A-1) Ester-modified epoxy resin>

[0061] In the resin composition of the present invention, the (A) epoxy resin contains an (A-1) ester-modified epoxy resin.

[0062] In the first embodiment, the (A-1) ester-modified epoxy resin is a modified epoxy resin obtained by reacting an epoxy resin having two or more epoxy groups in one molecule with an ester compound represented by the formula (1).

[0063] [Chemical formula 6]

[0064]

[0065] [In the formula, R 1 represents an optionally substituted alkyl group or an optionally substituted aryl group, and R 2 represents an optionally substituted aryl group].

[0066] R 1 represents an optionally substituted alkyl group or an optionally substituted aryl group.

[0067] In this specification, examples of the "substituent" in the "optionally substituted alkyl" include monovalent substituents such as a halogen atom, an aryl group, an alkyl-aryl group (an aryl group optionally substituted by an alkyl group), an alkyl-oxy group, an aryl-oxy group, an alkyl-carbonyl group, and an aryl-carbonyl group. The number of substituents in the "optionally substituted alkyl" is not particularly limited, and is preferably 0 to 5, more preferably 0, 1, or 2.

[0068] In this specification, examples of the "substituent" in the "optionally substituted aryl" include monovalent substituents such as a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group (an alkyl group optionally substituted by an aryl group), an alkyl-oxy group, an aryl-oxy group, an alkyl-carbonyl group, and an aryl-carbonyl group. The number of substituents in the "optionally substituted aryl" is not particularly limited, and is preferably 0 to 5, more preferably 0, 1, or 2.

[0069] An alkyl group refers to a straight-chain, branched-chain, and / or cyclic monovalent aliphatic saturated hydrocarbon group. For an alkyl group, unless otherwise specified, an alkyl group having 1 to 14 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, and an alkyl group having 1 to 6 carbon atoms is particularly preferred. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a trimethylcyclohexyl group, a cyclopentylmethyl group, and a cyclohexylmethyl group. An aryl group refers to a monovalent aromatic hydrocarbon group formed by removing one hydrogen atom from an aromatic carbocyclic ring. For an aryl group, unless otherwise specified, an aryl group having 6 to 14 carbon atoms is preferred, and an aryl group having 6 to 10 carbon atoms is particularly preferred. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. A halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0070] R 1 It is preferably an optionally substituted aryl group, more preferably an aryl group optionally substituted by a group selected from a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group, and an aryl-oxy group, and further preferably (1) a phenyl group optionally substituted by a group selected from a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group, and an aryl-oxy group, (2) a 1-naphthyl group optionally substituted by a group selected from a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group, and an aryl-oxy group, or (3) a 2-naphthyl group optionally substituted by a group selected from a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group, and an aryl-oxy group. Even more preferably, it is a phenyl group optionally substituted by a group selected from a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group, and an aryl-oxy group, and particularly preferably a phenyl group.

[0071] R 2 represents an optionally substituted aryl group.

[0072] R 2 Preferably, it is an aryl group optionally substituted with a group selected from a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group, and an aryl-oxy group. More preferably, it is (1) a phenyl group optionally substituted with a group selected from a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group, and an aryl-oxy group, (2) a 1-naphthyl group optionally substituted with a group selected from a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group, and an aryl-oxy group, or (3) a 2-naphthyl group optionally substituted with a group selected from a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group, and an aryl-oxy group. Further preferably, it is a 2-naphthyl group optionally substituted with a group selected from a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group, and an aryl-oxy group. Particularly preferably, it is a 2-naphthyl group.

[0073] As the "epoxy resin having two or more epoxy groups in one molecule" that reacts with the ester compound represented by the formula (1) to obtain the (A-1) ester-modified epoxy resin, known epoxy resins can be widely used and there is no particular limitation. Examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy resin having an ester skeleton, bisphenol Z type epoxy resin, anthracene type epoxy resin, naphthalene type epoxy resin, naphthalene tetrafunctional epoxy resin, naphthol type epoxy resin, phenol novolac type epoxy resin, bisphenol A type novolac epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, bixylenol type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene type epoxy resin; among them, naphthalene tetrafunctional epoxy resin, naphthol type epoxy resin, phenol novolac type epoxy resin, bisphenol A type novolac epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, bixylenol type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene type epoxy resin are preferred; phenol novolac type epoxy resin, bisphenol A type novolac epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, bixylenol type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene type epoxy resin are more preferred. The "epoxy resin having two or more epoxy groups in one molecule" that reacts with the ester compound represented by the formula (1) to obtain the (A-1) ester-modified epoxy resin can be a single type or a combination of two or more types.

[0074] From the viewpoint of improving heat resistance, the epoxy equivalent of the "epoxy resin having two or more epoxy groups in one molecule" that reacts with the ester compound represented by the formula (1) to obtain the (A-1) ester-modified epoxy resin is preferably 400 g / eq. or less, more preferably 350 g / eq. or less, and still more preferably 300 g / eq. or less. From the viewpoint of sufficiently ensuring the reactivity with the ester compound, it is preferably 100 g / eq. or more, more preferably 120 g / eq. or more, and still more preferably 150 g / eq. or more. The epoxy equivalent is the mass of the resin per 1 equivalent of epoxy groups. This epoxy equivalent can be measured in accordance with JIS K7236.

[0075] The reaction equivalent ratio of the epoxy resin and the ester compound represented by the formula (1) in the reaction for obtaining the (A-1) ester-modified epoxy resin, based on the ratio of the number of moles of the epoxy groups of the epoxy resin to the number of moles of the ester groups (-CO-O-) of the ester compound (epoxy group / ester group), is preferably 1.60 or more, more preferably 1.62 or more, further preferably 1.63 or more, particularly preferably 1.65 or more, and preferably 6.0 or less, more preferably 5.5 or less, further preferably 5.0 or less, particularly preferably 4.5 or less.

[0076] In the reaction for obtaining the (A-1) ester-modified epoxy resin, the following catalysts can be used: for example, tertiary amines such as 4-(dimethylamino)pyridine and 1,4-diazabicyclo[2,2,2]octane; imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; organophosphorus compounds such as triphenylmethylphosphine; quaternary ammonium salts, etc. The usage amount of the catalyst is preferably 0.001 to 1% by weight based on the reaction solid components. In the reaction for obtaining the (A-1) ester-modified epoxy resin, the following solvents can be used: for example, aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol), etc. When using a solvent in the reaction for obtaining the (A-1) ester-modified epoxy resin, it is preferably used under the condition that the reaction solid component concentration becomes 35 to 95% by mass. After the reaction is completed, the solvent can be removed as needed, or a solvent can be further added. The reaction temperature in the reaction for obtaining the (A-1) ester-modified epoxy resin is preferably 50 to 200 °C, more preferably 100 or 180 °C, further preferably 120 °C to 160 °C. The reaction time in the reaction for obtaining the (A-1) ester-modified epoxy resin is usually 1 to 12 hours, preferably 3 to 10 hours.

[0077] In the second embodiment, the (A-1) ester-modified epoxy resin is a modified epoxy resin having a group represented by the formula (2-1) and a group represented by the formula (2-2).

[0078] [Chemical formula 7]

[0079]

[0080] [In the formula, * represents the bonding site].

[0081] [Chemical formula 8]

[0082]

[0083] [In the formula, each symbol has the same meaning as described above.]

[0084] In this embodiment, in addition to the groups represented by formula (2-1) and the groups represented by formula (2-2), this modified epoxy resin sometimes further has the groups represented by formula (2-3).

[0085] [Chemical formula 9]

[0086]

[0087] [In the formula, each symbol has the same meaning as described above.]

[0088] The molar ratio of the groups represented by formula (2-2) to the groups represented by formula (2-1) in the modified epoxy resin (formula (2-2) / formula (2-1)) is preferably 1 or less. The number of the groups represented by formula (2-1) in one molecule of the modified epoxy resin is preferably 2 or more.

[0089] In this embodiment, the groups represented by formula (2-1), the groups represented by formula (2-2), and the groups represented by formula (2-3) are each preferably directly bonded to the aromatic carbon atoms in the aromatic ring.

[0090] An aromatic ring is a ring that follows Hückel's rule and has 4p + 2 electrons (where p is a natural number) in the π-electron system of the ring. The aromatic ring can be an aromatic carbocyclic ring with carbon atoms as ring-forming atoms, or an aromatic heterocyclic ring having heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms in addition to carbon atoms as ring-forming atoms. In one embodiment, it is preferably an aromatic carbocyclic ring. For the aromatic ring, in one embodiment, it is preferably a 5- to 14-membered aromatic ring, more preferably a 5- to 10-membered aromatic ring, and further preferably a 5- or 6-membered aromatic ring. Suitable specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, etc., more preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring.

[0091] The (A-1) ester-modified epoxy resin in this embodiment can be obtained, for example, by reacting an epoxy resin having two or more groups represented by formula (2-1) in one molecule with the ester compound represented by formula (1) described above. The reaction conditions can be the same as the reaction conditions for obtaining the (A-1) ester-modified epoxy resin in the first embodiment. As the "epoxy resin having two or more groups represented by formula (2-1) in one molecule", a substance having two or more groups represented by formula (2-1) in the "epoxy resin having two or more epoxy groups in one molecule" described above can be cited.

[0092] In the second embodiment, the (A-1) ester-modified epoxy resin is preferably a modified epoxy resin having a structural unit represented by the formula (3-1) and a structural unit represented by the formula (3-2).

[0093] [Chemical formula 10]

[0094]

[0095] [In the formula, the ring Ar represents an aromatic ring optionally having a substituent, and R 3 each independently represents a hydrogen atom, an alkyl group optionally having a substituent, or an aryl group optionally having a substituent].

[0096] [Chemical formula 11]

[0097]

[0098] [In the formula, each symbol has the same meaning as described above.]

[0099] In this embodiment, in addition to having the structural unit represented by the formula (3-1) and the structural unit represented by the formula (3-2), this modified epoxy resin sometimes further has a structural unit represented by the formula (3-3).

[0100] [Chemical formula 12]

[0101]

[0102] [In the formula, each symbol has the same meaning as described above.]

[0103] The molar ratio of the structural unit represented by the formula (3-2) to the structural unit represented by the formula (3-1) in the modified epoxy resin (formula (3-2) / formula (3-1)) is preferably 1 or less. The number of the structural units represented by the formula (3-1) in one molecule of the modified epoxy resin is preferably 2 or more.

[0104] The ring Ar represents an aromatic ring optionally having a substituent.

[0105] In this specification, examples of the "substituent" in the "aromatic ring optionally having a substituent" include monovalent substituents such as a halogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, an alkyl-oxy group optionally having a substituent, an aryl-oxy group optionally having a substituent, an alkyl-carbonyl group optionally having a substituent, and an aryl-carbonyl group optionally having a substituent. The number of substituents in the "aromatic ring optionally having a substituent" is not particularly limited, and is preferably 0 to 5, more preferably 0, 1, or 2.

[0106] Ring Ar is preferably (1) a benzene ring optionally substituted with a group selected from "optionally substituted alkyl" and "optionally substituted aryl", or (2) a naphthalene ring optionally substituted with "optionally substituted alkyl" and "optionally substituted aryl", more preferably a benzene ring optionally substituted with a group selected from "optionally substituted alkyl" and "optionally substituted aryl", still more preferably a benzene ring optionally substituted with "optionally substituted alkyl", and particularly preferably a benzene ring optionally substituted with alkyl.

[0107] R 3 each independently represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group. R 3 is preferably a hydrogen atom.

[0108] The (A-1) ester-modified epoxy resin in this embodiment can be obtained, for example, by reacting an epoxy resin having two or more structural units represented by the formula (3-1) in one molecule with the ester compound represented by the formula (1) described above. The reaction conditions can be the same as those for obtaining the (A-1) ester-modified epoxy resin in the first embodiment. As the "epoxy resin having two or more groups represented by the formula (3-1) in one molecule", substances having two or more structural units represented by the formula (3-1) in the "epoxy resin having two or more epoxy groups in one molecule" described above can be cited.

[0109] In the second embodiment, the (A-1) ester-modified epoxy resin is more preferably a modified epoxy resin having a structural unit represented by the formula (4-1) and a structural unit represented by the formula (4-2).

[0110] [Chemical formula 13]

[0111]

[0112] [In the formula, R 4 each independently represents an optionally substituted alkyl group or an optionally substituted aryl group, and a represents 0, 1, 2, or 3].

[0113] [Chemical formula 14]

[0114]

[0115] [In the formula, each symbol has the same meaning as described above.]

[0116] In this embodiment, in addition to having a structural unit represented by the formula (4-1) and a structural unit represented by the formula (4-2), such a modified epoxy resin may further have a structural unit represented by the formula (4-3).

[0117] [Chemical formula 15]

[0118]

[0119] [In the formula, each symbol has the same meaning as described above.]

[0120] The molar ratio of the structural unit represented by formula (4-2) to the structural unit represented by formula (4-1) in the modified epoxy resin (formula (4-2) / formula (4-1)) is preferably 1 or less. The number of the structural units represented by formula (4-1) in one molecule of the modified epoxy resin is preferably 2 or more.

[0121] R 4 Each independently represents an optionally substituted alkyl group or an optionally substituted aryl group.

[0122] R 4 Each is independently preferably (1) an alkyl group optionally substituted with a group selected from a halogen atom, an aryl group, an alkyl-aryl group, an alkyl-oxy group, and an aryl-oxy group, or (2) an aryl group optionally substituted with a group selected from a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group, and an aryl-oxy group, more preferably an alkyl group optionally substituted with a group selected from a halogen atom, an aryl group, an alkyl-aryl group, an alkyl-oxy group, and an aryl-oxy group, still more preferably an alkyl group, and particularly preferably a methyl group.

[0123] a represents 0, 1, 2, or 3, preferably 0 or 1.

[0124] The (A-1) ester-modified epoxy resin in this embodiment can be obtained, for example, by reacting an epoxy resin having two or more structural units represented by formula (4-1) in one molecule with the ester compound represented by formula (1) described above. The reaction conditions can be the same as the reaction conditions for obtaining the (A-1) ester-modified epoxy resin in the first embodiment. As the "epoxy resin having two or more groups represented by formula (4-1) in one molecule", a substance having two or more structural units represented by formula (4-1) in the "epoxy resin having two or more epoxy groups in one molecule" described above can be cited.

[0125] The (A-1) ester-modified epoxy resin is preferably solid at 20°C. When the (A-1) ester-modified epoxy resin is solid at 20°C, regarding its softening point, from the viewpoint of improving the processability of the resin, it is preferably 60°C or higher, more preferably 65°C or higher, still more preferably 70°C or higher, and particularly preferably 75°C or higher. From the viewpoint of sufficiently ensuring solvent solubility, it is preferably 130°C or lower, more preferably 125°C or lower, still more preferably 120°C or lower, and particularly preferably 115°C or lower. The softening point can be measured according to JIS K7234.

[0126] (A-1) The weight average molecular weight (Mw) of the ester-modified epoxy resin, from the viewpoint of further improving the dielectric properties, is preferably 500 or more, more preferably 600 or more, further preferably 700 or more, and particularly preferably 1,000 or more. From the viewpoint of good processability, it is preferably 10,000 or less, more preferably 8,000 or less, further preferably 7,000 or less, and particularly preferably 6,000 or less. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a value in terms of polystyrene conversion.

[0127] (A-1) The epoxy equivalent of the ester-modified epoxy resin, from the viewpoint of improving heat resistance, is preferably 1,000 g / eq. or less, more preferably 900 g / eq. or less, and particularly preferably 800 g / eq. or less. From the viewpoint of further improving the dielectric properties, it is preferably 300 g / eq. or more, more preferably 330 g / eq. or more, and further preferably 360 g / eq. or more.

[0128] The content of the (A-1) ester-modified epoxy resin in the resin composition is not particularly limited. When the non-volatile components in the resin composition are set to 100% by mass, it is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, further more preferably 15% by mass or less, and particularly preferably 12% by mass or less. The lower limit of the content of the (A-1) ester-modified epoxy resin in the resin composition is not particularly limited. When the non-volatile components in the resin composition are set to 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, further more preferably 3% by mass or more, and particularly preferably 5% by mass or more.

[0129] <(A-2) Liquid epoxy resin>

[0130] In the resin composition of the present invention, for the (A) epoxy resin, in addition to containing the (A-1) ester-modified epoxy resin, it sometimes further contains, as an optional component, the (A-2) epoxy resin that is liquid at 20°C (sometimes simply referred to as "liquid epoxy resin" in this specification). The (A-2) liquid epoxy resin described here is an epoxy resin that does not belong to the (A-1) ester-modified epoxy resin.

[0131] (A-2) The liquid epoxy resin preferably contains a liquid epoxy resin having 1 or more epoxy groups in 1 molecule and 2 or more epoxy groups in 1 molecule. The proportion of the liquid epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more with respect to 100% by mass of the liquid epoxy resin.

[0132] Examples of the (A-2) liquid epoxy resin include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, and epoxy resins having a butadiene structure, etc.

[0133] Specific examples of the (A-2) liquid epoxy resin include: "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", "EPIKOTE 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidyl amine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (Glycirol type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L", "EP-3980S" (glycidyl amine type epoxy resin) manufactured by ADEKA Corporation; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA Corporation; "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation; "CELLOXIDE 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation; "PB-3600", "JP-100", "JP-200" (epoxy resins having a butadiene structure) manufactured by Nippon Soda Co., Ltd.; "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd., etc. They can be used individually by one kind, or two or more kinds can be used in combination.

[0134] The epoxy equivalent of the (A-2) liquid epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 2,000 g / eq., further preferably 70 g / eq. to 1,000 g / eq., and further more preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of the resin per 1 equivalent of epoxy group. This epoxy equivalent can be measured in accordance with JIS K7236.

[0135] (A-2) The weight-average molecular weight (Mw) of the liquid epoxy resin is preferably 100 to 5,000, more preferably 150 to 3,000, and still more preferably 200 to 1,500. The weight-average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a value in terms of polystyrene conversion.

[0136] The content of the (A-2) liquid epoxy resin in the resin composition is not particularly limited. When the non-volatile components in the resin composition are set to 100% by mass, it is preferably 40% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 7% by mass or less. The lower limit of the content of the (A-2) liquid epoxy resin in the resin composition is not particularly limited. When the non-volatile components in the resin composition are set to 100% by mass, it is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 3% by mass or more.

[0137] The mass ratio of the (A-2) liquid epoxy resin to the (A-1) ester-modified epoxy resin in the resin composition ((A-2) component / (A-1) component) is not particularly limited, and is preferably 0.05 or more, more preferably 0.1 or more, and particularly preferably 0.3 or more. The upper limit of the mass ratio of the (A-2) liquid epoxy resin to the (A-1) ester-modified epoxy resin in the resin composition ((A-2) component / (A-1) component) is not particularly limited, and is preferably 5 or less, more preferably 2 or less, and particularly preferably 1 or less.

[0138] <(A-3) Solid epoxy resin>

[0139] In the resin composition of the present invention, for the (A) epoxy resin, in addition to containing the (A-1) ester-modified epoxy resin, it may further contain, as an optional component, the (A-3) epoxy resin that is solid at 20°C (sometimes simply referred to as "solid epoxy resin" in this specification). The (A-3) solid epoxy resin described here is an epoxy resin that does not belong to the (A-1) ester-modified epoxy resin.

[0140] (A-3) The solid epoxy resin preferably contains a solid epoxy resin having one or more epoxy groups in one molecule and two or more epoxy groups in one molecule. The proportion of the solid epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more based on 100% by mass of the solid epoxy resin.

[0141] As the (A-3) solid epoxy resin, it is preferably a xylenol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a naphthol novolac type epoxy resin, a cresol novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a naphthalene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, a phenol aralkyl type epoxy resin, a tetraphenylethane type epoxy resin, a phenol phthalimidine type epoxy resin, a phenolphthalein type epoxy resin.

[0142] As specific examples of the (A-3) solid epoxy resin, the following can be cited: "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolak-type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak-type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene-type epoxy resin) manufactured by DIC Corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthalene ether-type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (triphenol-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolak-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V", "ESN4100V" (naphthalene-type epoxy resin) manufactured by Nippon Steel Chemical Co., Ltd.; "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical Co., Ltd.; "ESN375" (dihydroxynaphthalene-type epoxy resin) manufactured by Nippon Steel Chemical Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (xylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenol aralkyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR991S" (phenol benzopyrrolidone-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., etc. They can be used alone or in combination of two or more kinds.

[0143] (A-3) The epoxy equivalent of the solid epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 2,000 g / eq., further preferably 70 g / eq. to 1,000 g / eq., and still further preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of the resin per 1 equivalent of epoxy groups. The epoxy equivalent can be measured in accordance with JIS K7236.

[0144] (A-3) The weight-average molecular weight (Mw) of the solid epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and further preferably 400 to 1,500. The weight-average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC) method.

[0145] The content of the (A-3) solid epoxy resin in the resin composition is not particularly limited. When the non-volatile components in the resin composition are set to 100% by mass, it is preferably 40% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and still further preferably 5% by mass or less.

[0146] The mass ratio of the (A-3) solid epoxy resin to the (A-1) ester-modified epoxy resin in the resin composition ((A-3) component / (A-1) component) is not particularly limited, and is preferably 3 or less, more preferably 2 or less, and particularly preferably 1 or less.

[0147] <(B) Active ester compound>

[0148] The resin composition of the present invention contains a (B) active ester compound. The (B) active ester compound can be used alone or two or more thereof can be used in any ratio in combination. The (B) active ester compound can function as an epoxy resin curing agent that reacts with the (A) epoxy resin to cure it.

[0149] As the (B) active ester compound, it is generally preferable to use compounds having two or more ester groups (ester groups with high reactivity) in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. The active ester compound is preferably a compound obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, pyrogallol, dicyclopentadiene-type diphenol compound, 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.

[0150] Specifically, as the (B) active ester compound, a dicyclopentadiene-type active ester compound, a naphthalene-type active ester compound containing a naphthalene structure, an active ester compound of an acetylated product containing a phenol novolac, and an active ester compound of a benzoylated product containing a phenol novolac are preferred, and at least one selected from the dicyclopentadiene-type active ester compound and the naphthalene-type active ester compound is more preferred, and the dicyclopentadiene-type active ester compound is further preferred. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferred.

[0151] Regarding commercially available products of the (B) active ester compound, as the active ester compound containing a dicyclopentadiene-type diphenol structure, examples include "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC Corporation); as the active ester compound containing a naphthalene structure, examples include "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); as the active ester compound containing phosphorus, an example is "EXB9401" (manufactured by DIC Corporation), as the active ester compound which is an acetylated product of a linear phenolic resin, an example is "DC808" (manufactured by Mitsubishi Chemical Corporation), as the active ester compound which is a benzoylated product of a linear phenolic resin, examples include "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation), as the active ester compound containing a styryl group and a naphthalene structure, an example is "PC1300-02-65MA" (manufactured by AIRWATER Corporation), etc.

[0152] The active ester group equivalent of the (B) active ester compound is preferably 50 g / eq. to 500 g / eq., more preferably 50 g / eq. to 400 g / eq., and further preferably 100 g / eq. to 300 g / eq. The active ester group equivalent is the mass of the active ester compound per 1 equivalent of the active ester group.

[0153] The content of the (B) active ester compound in the resin composition is not particularly limited. When the non-volatile components in the resin composition are set to 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, further more preferably 25% by mass or less, and particularly preferably 20% by mass or less. The lower limit of the content of the (B) active ester compound in the resin composition is not particularly limited. When the non-volatile components in the resin composition are set to 100% by mass, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 5% by mass or more, further more preferably 8% by mass or more, and particularly preferably 10% by mass or more.

[0154] The mass ratio of the (B) active ester compound to the (A-1) ester-modified epoxy resin in the resin composition ((B) component / (A-1) component) is not particularly limited, preferably 0.5 or more, more preferably 1 or more, and particularly preferably 1.2 or more. The upper limit of the mass ratio of the (B) active ester compound to the (A-1) ester-modified epoxy resin in the resin composition ((B) component / (A-1) component) is not particularly limited, preferably 5 or less, more preferably 3 or less, and particularly preferably 2 or less.

[0155] <(B') Other curing agents>

[0156] The resin composition of the present invention may further contain, as an optional component, a (B') curing agent other than the (B) component. The (B') other curing agent may be used alone or in any combination of two or more. The (B') other curing agent, like the (B) active ester compound, can have the function of an epoxy resin curing agent that reacts with the (A) epoxy resin to cure it.

[0157] There is no particular limitation on the (B') other curing agent, and examples thereof include phenolic curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanate ester curing agents, and mercaptan curing agents. The (B') other curing agent particularly preferably contains a phenolic curing agent.

[0158] As the phenolic curing agent, from the viewpoints of heat resistance and water resistance, a phenolic curing agent having a novolac structure is preferred. In addition, from the viewpoint of adhesion to the adherend, a nitrogen-containing phenolic curing agent is preferred, and a phenolic curing agent containing a triazine skeleton is more preferred. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, a linear phenolic resin containing a triazine skeleton is preferred. Specific examples of the phenolic curing agent include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meito Kasei Co., Ltd., "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd., "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "TD-2090-60M" manufactured by DIC Corporation, etc.

[0159] As the carbodiimide-based curing agent, a curing agent having one or more, preferably two or more carbodiimide structures in one molecule can be mentioned. Examples include aliphatic biscarbodiimides such as tetramethylene-bis(tert-butylcarbodiimide) and cyclohexane bis(methylene-tert-butylcarbodiimide); biscarbodiimides such as phenylenedi(bixylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylene carbodiimide, poly(methylenebiscyclohexylene carbodiimide), and poly(isophorone carbodiimide); and aromatic polycarbodiimides such as poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(benzylidenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylenecarbodiimide)].

[0160] Examples of commercially available products of the carbodiimide-based curing agent include "CARBODILITE V-02B", "CARBODILITE V-03", "CARBODILITE V-04K", "CARBODILITE V-07", and "CARBODILITE V-09" manufactured by Nisshinbo Chemical Inc.; "Stabaxol P", "Stabaxol P400", "Hycasyl510", etc. manufactured by Rhein Chemie.

[0161] As the acid anhydride-based curing agent, curing agents having one or more acid anhydride groups in one molecule can be cited, and curing agents having two or more acid anhydride groups in one molecule are preferred. Specific examples of the acid anhydride-based curing agent include: phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(trimellitate), polymer-type acid anhydrides such as styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid, etc. Commercially available products of the acid anhydride-based curing agent include: "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Shin Nippon Rika Co., Ltd., "YH-306", "YH-307" manufactured by Mitsubishi Chemical Corporation, "HN-2200", "HN-5500" manufactured by Hitachi Chemical Co., Ltd., "EF-30", "EF-40", "EF-60", "EF-80" manufactured by Cray Valley Company, etc.

[0162] As the amine-based curing agent, curing agents having one or more, preferably two or more amino groups in one molecule can be cited. Examples include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, from the viewpoint of achieving the effects expected by the present invention, aromatic amines are preferred. The amine-based curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine-based curing agent include: 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylenediamine, 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. Commercially available products of the amine-based curing agent can be used. Examples include "SEIKACURE-S" manufactured by SEIKA Corporation, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S" manufactured by Nippon Kayaku Co., Ltd., "Epicure W" manufactured by Mitsubishi Chemical Corporation, etc.

[0163] Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D", "ODA-BOZ" manufactured by JFE Chemical Corporation; "HFB2006M" manufactured by Showa Highpolymer Co., Ltd.; "P-d", "F-a", etc. manufactured by Shikoku Kasei Kogyo Co., Ltd.

[0164] As the cyanate ester-based curing agent, for example, bifunctional cyanate ester resins such as bisphenol A dicyanate, polyphenol cyanate (oligomeric (3-methylidene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanatophenyl)propane, 1,1-bis(4-cyanatophenyl)methane, bis(4-cyanato-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl) sulfide, and bis(4-cyanatophenyl) ether; polyfunctional cyanate ester resins derived from phenol novolac resins, cresol novolac resins, etc.; prepolymers obtained by triazine formation of a part of these cyanate ester resins, etc. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both are phenol novolac type polyfunctional cyanate ester resins), "BA230", "BA230S75" (prepolymers in which a part or all of bisphenol A dicyanate is triazine-formed to form a trimer), etc. manufactured by Lonza Japan Co., Ltd.

[0165] As the thiol-based curing agent, for example, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), tris(3-mercaptopropyl) isocyanurate, etc. can be cited.

[0166] (B') The reactive group equivalent of other curing agents is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., still more preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The reactive group equivalent is the mass of the curing agent per 1 equivalent of the reactive group.

[0167] The content of (B') other curing agents in the resin composition is not particularly limited. When the non-volatile components in the resin composition are set to 100% by mass, it is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The lower limit of the content of (B') other curing agents in the resin composition is not particularly limited. When the non-volatile components in the resin composition are set to 100% by mass, for example, it can be 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.5% by mass or more, etc.

[0168] The mass ratio of (B') other curing agents to (A-1) ester-modified epoxy resin in the resin composition ((B') component / (A-1) component) is not particularly limited, and is preferably 1 or less, more preferably 0.5 or less, and particularly preferably 0.2 or less.

[0169] When the total amount of the (B) active ester compound and the (B') other curing agent in the resin composition is 100% by mass, the content of the (B) active ester compound in the resin composition is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and particularly preferably 50% by mass or more.

[0170] <(C) Inorganic filler>

[0171] The resin composition of the present invention contains a (C) inorganic filler. When the non-volatile components in the resin composition are 100% by mass, the content of the (C) inorganic filler is 50% by mass or more. The (C) inorganic filler is contained in the resin composition in a particulate state.

[0172] As the material of the (C) inorganic filler, an inorganic compound is used. Examples of the material of the (C) inorganic filler include, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among them, silica is particularly preferred. Examples of silica include, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, as silica, spherical silica is preferred. The (C) inorganic filler may be used alone or two or more thereof may be combined in any ratio.

[0173] Examples of commercially available products of the (C) inorganic filler include, for example, "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05", "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30" manufactured by DENKA Co., Ltd.; "SILFIL(シルフィル)NSS-3N", "SILFIL NSS-4N", "SILFIL NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatechs Co., Ltd.; "DAW-03", "FB-105FD" manufactured by DENKA Co., Ltd.

[0174] (C) The average particle diameter of the inorganic filler is not particularly limited, preferably 10 μm or less, more preferably 5 μm or less, further preferably 2 μm or less, still further preferably 1 μm or less, and particularly preferably 0.7 μm or less. The lower limit of the average particle diameter of the inorganic filler is not particularly limited, preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. The average particle diameter of the inorganic filler can be measured by the laser diffraction-scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared based on volume using a laser diffraction scattering type particle size distribution measuring device, and the median particle size can be used as the average particle diameter for measurement. As the measurement sample, a sample obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a test tube and dispersing them ultrasonically for 10 minutes can be used. For the measurement sample, using a laser diffraction type particle size distribution measuring device, the light source wavelength is set to blue and red, and the volume-based particle size distribution of the inorganic filler is measured in a flow cell manner, and the average particle diameter is calculated as the median particle size based on the obtained particle size distribution. As the laser diffraction type particle size distribution measuring device, for example, "LA-960" manufactured by Horiba, Ltd. can be cited.

[0175] (C) The specific surface area of the inorganic filler is not particularly limited, preferably 0.1 m 2 / g or more, more preferably 0.5 m 2 / g or more, further preferably 1 m 2 / g or more, particularly preferably 3 m 2 / g or more. The upper limit of the specific surface area of the inorganic filler is not particularly limited, preferably 100 m 2 / g or less, more preferably 70 m 2 / g or less, further preferably 50 m 2 / g or less, particularly preferably 40 m 2 / g or less. The specific surface area of the inorganic filler can be calculated by the following method: According to the BET method, nitrogen is adsorbed on the surface of the sample using a specific surface area measuring device ("Macsorb HM-1210" manufactured by Mountech Co., Ltd.), and the specific surface area is calculated using the BET multi-point method.

[0176] (C) The inorganic filler is preferably surface-treated with a suitable surface treatment agent. By performing the surface treatment, the moisture resistance and dispersibility of the (C) inorganic filler can be improved. Examples of the surface treatment agent include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy-based silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; styryl-based silane coupling agents such as p-styryltrimethoxysilane; methacrylic acid-based silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; acrylic acid-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane; amino-based silane coupling agents such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanurate-based silane coupling agents such as tris(trimethoxysilylpropyl)isocyanurate; ureido-based silane coupling agents such as 3-ureidopropyltrialkoxysilane; mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatopropyltriethoxysilane; anhydride-based silane coupling agents such as 3-trimethoxysilylpropylsuccinic anhydride; and other silane coupling agents; alkylalkoxysilane compounds such as methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, and 3,3,3-trifluoropropyltrimethoxysilane. In addition, the surface treatment agent can be used alone or two or more thereof can be used in any ratio in combination.

[0177] Examples of commercially available surface treatment agents include, for example, "KBM-1003", "KBE-1003" (vinyl-based silane coupling agents) manufactured by Shin-Etsu Chemical Co., Ltd.; "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403" (epoxy-based silane coupling agents); "KBM-1403" (styryl-based silane coupling agent); "KBM-502", "KBM-503", "KBE-502", "KBE-503" (methacrylic acid-based silane coupling agents); "KBM-5103" (acrylic acid-based silane coupling agent); "KBM-602", "KBM-603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575" (amino-based silane coupling agents); "KBM-9659" (isocyanurate-based silane coupling agent); "KBE-585" (urea-based silane coupling agent); "KBM-802", "KBM-803" (mercapto-based silane coupling agents); "KBE-9007N" (isocyanate-based silane coupling agent); "X-12-967C" (anhydride-based silane coupling agent); "KBM-13", "KBM-22", "KBM-103", "KBE-13", "KBE-22", "KBE-103", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" (alkylalkoxysilane compounds), etc.

[0178] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably controlled within a specified range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably surface-treated with 0.2% to 3% by mass, and further preferably surface-treated with 0.3% to 2% by mass.

[0179] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and even more preferably 0.2 mg / m 2 or more. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, the amount of carbon per unit surface area of the inorganic filler is preferably 1.0 mg / m2 More preferably, it is 0.8 mg / m or less 2 Even more preferably, it is 0.5 mg / m or less 2 or less.

[0180] (C) The amount of carbon per unit surface area of the inorganic filler can be measured after cleaning the surface-treated inorganic filler with a solvent (such as methyl ethyl ketone (MEK)). Specifically, add a sufficient amount of MEK as a solvent to the inorganic filler surface-treated with a surface treatment agent, and perform ultrasonic cleaning at 25 °C for 5 minutes. Remove the supernatant, dry the solid component, and then the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0181] When the non-volatile components in the resin composition are set to 100% by mass, the content of the (C) inorganic filler in the resin composition can be 50% by mass or more, preferably 55% by mass or more, more preferably 60% by mass or more, further preferably 62% by mass or more, and particularly preferably 64% by mass or more. The upper limit of the content of the (C) inorganic filler in the resin composition is not particularly limited. When the non-volatile components in the resin composition are set to 100% by mass, it can be preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 75% by mass or less, and particularly preferably 70% by mass or less.

[0182] The mass ratio of the (C) inorganic filler to the (A-1) ester-modified epoxy resin in the resin composition ((C) component / (A-1) component) is not particularly limited, preferably 2 or more, more preferably 4 or more, and particularly preferably 5 or more. The upper limit of the mass ratio of the (C) inorganic filler to the (A-1) ester-modified epoxy resin in the resin composition ((C) component / (A-1) component) is not particularly limited, preferably 30 or less, more preferably 20 or less, and particularly preferably 10 or less.

[0183] <(D) Thermoplastic resin>

[0184] The resin composition of the present invention may further contain (D) a thermoplastic resin as an optional component. By containing (D) a thermoplastic resin in the resin composition of the present invention, the adhesion to copper that can be used as a conductor layer can be further improved.

[0185] Examples of the (D) thermoplastic resin include, for example, polyimide resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, polyester resins, etc. In one embodiment, the (D) thermoplastic resin preferably contains a thermoplastic resin selected from polyimide resins and phenoxy resins. Further, the thermoplastic resin may be used alone or two or more thereof may be used in combination.

[0186] Specific examples of the polyimide resin include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Nippon Rika Kogyo Co., Ltd., etc.

[0187] Examples of the phenoxy resin include, for example, a phenoxy resin having one or more skeletons selected from a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a phenol formaldehyde skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

[0188] Specific examples of the phenoxy resin include: "1256" and "4250" (both are phenoxy resins containing a bisphenol A skeleton) manufactured by Mitsubishi Chemical Corporation; "YX8100" (a phenoxy resin containing a bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation; "YX6954" (a phenoxy resin containing a bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation; "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation; etc.

[0189] Examples of the polyvinyl acetal resin include, for example, 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", "Denka Butyral 6000-EP" manufactured by Denki Kagaku Kogyo Kabushiki Kaisha; S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, BM series manufactured by Sekisui Chemical Co., Ltd.; etc.

[0190] As the polyolefin resin, examples thereof include ethylene-based copolymer resins such as low-density polyethylene, ultra-low density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; polyolefin-based polymers such as polypropylene and ethylene-propylene block copolymer, etc.

[0191] As the polybutadiene resin, examples thereof 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, polyphenylene ether-polybutadiene resins, etc.

[0192] Specific examples of the polyamideimide resin include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd.

[0193] Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., etc.

[0194] Specific examples of the polysulfone resin include polysulfones "P1700", "P3500", etc. manufactured by Solvay Advanced Polymers.

[0195] Specific examples of the polyphenylene ether resin include "NORYL SA90" manufactured by SABIC, etc. Specific examples of the polyetherimide resin include "ULTEM" manufactured by GE, etc.

[0196] As the polycarbonate resin, examples thereof include carbonate resins containing a hydroxyl group, carbonate resins containing a phenolic hydroxyl group, carbonate resins containing a carboxyl group, carbonate resins containing an acid anhydride group, carbonate resins containing an isocyanate group, carbonate resins containing a urethane group, etc. Specific examples of the polycarbonate resin include "FPC0220" manufactured by Mitsubishi Gas Chemical Company, "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals Corporation, "C-1090", "C-2090", "C-3090" (polycarbonate diol) manufactured by Kuraray Co., Ltd., etc. Specific examples of the polyetheretherketone resin include "SUMIPLOYK" manufactured by Sumitomo Chemical Co., Ltd., etc.

[0197] Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polypropylene terephthalate resin, polypropylene naphthalate resin, polycyclohexanedimethylene terephthalate resin, and the like.

[0198] From the viewpoint of significantly obtaining the effects of the present invention, the weight average molecular weight (Mw) of the (D) thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, further preferably 10,000 or more, particularly preferably 20,000 or more, and preferably 100,000 or less, more preferably 70,000 or less, further preferably 60,000 or less, particularly preferably 50,000 or less.

[0199] The content of the (D) thermoplastic resin in the resin composition is not particularly limited. When the non-volatile components in the resin composition are set to 100% by mass, it is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, particularly preferably 2% by mass or less. The lower limit of the content of the (D) thermoplastic resin in the resin composition is not particularly limited. When the non-volatile components in the resin composition are set to 100% by mass, for example, it can be 0% by mass or more, 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and the like.

[0200] <(E) Free-radical polymerizable compound>

[0201] The resin composition of the present invention may further contain (E) a free-radical polymerizable compound as an optional component. By containing the (E) free-radical polymerizable compound in the resin composition of the present invention, the stain removability based on the defouling treatment can be further improved. The (E) free-radical polymerizable compound may be used alone or in any combination of two or more.

[0202] In one embodiment, the (E) free-radical polymerizable compound is a free-radical polymerizable compound having an ethylenic unsaturated bond. The (E) free-radical polymerizable compound is not particularly limited and may have, for example, an unsaturated hydrocarbon group such as allyl, 3-cyclohexenyl, 3-cyclopentenyl, p-vinylphenyl, m-vinylphenyl, o-vinylphenyl; a free-radical polymerizable group such as acryloyl, methacryloyl, maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl), etc. The (E) free-radical polymerizable compound preferably has 2 or more free-radical polymerizable groups in 1 molecule.

[0203] As the (E) radically polymerizable compound, for example, (meth)acrylic radically polymerizable compounds, styrenic radically polymerizable compounds, allylic radically polymerizable compounds, maleimide-based radically polymerizable compounds, etc. can be used.

[0204] (Meth)acrylic radically polymerizable compounds are, for example, compounds having one or more, preferably two or more acryloyl groups and / or methacryloyl groups. Examples of the (meth)acrylic radically polymerizable compound include aliphatic (meth)acrylate compounds 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, pentaerythritol tetra(meth)acrylate; (meth)acrylate compounds containing an ether such as dioxane glycol 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; (meth)acrylate compounds containing isocyanurate such as tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, etc. Commercially available products of (meth)acrylic radically polymerizable compounds include, for example, "A-DOG" (dioxane glycol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" (tricyclodecane dimethanol diacrylate), "DCP" (tricyclodecane dimethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., "KAYARAD R-684" (tricyclodecane dimethanol diacrylate), "KAYARAD R-604" (dioxane glycol diacrylate) of Nippon Kayaku Co., Ltd., etc.

[0205] Styrene-based free-radical polymerizable compounds are, for example, compounds having one or more, preferably two or more vinyl groups directly bonded to aromatic carbon atoms. Examples of styrene-based free-radical polymerizable compounds include 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, bis(4-vinylphenyl) ether, and the like.

[0206] Allyl-based free-radical polymerizable compounds are, for example, compounds having one or more, preferably two or more allyl groups. Examples of allyl-based free-radical polymerizable compounds include aromatic carboxylic acid allyl ester compounds such as diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, diallyl 2,3-naphthoate; allyl isocyanurate compounds such as 1,3,5-triallyl isocyanurate, 1,3-diallyl-5-glycidyl isocyanurate; aromatic allyl compounds containing an epoxy group such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; aromatic allyl compounds containing a benzoxazine such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane; aromatic allyl compounds containing an ether such as 1,3,5-triallyl ether benzene; allyl silane compounds such as diallyl diphenylsilane, and the like. Examples of commercially available allyl-based free-radical polymerizable compounds include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kayaku Co., Ltd., "DAD" (diallyl diphenate) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., "TRIAM-705" (triallyl trimellitate) manufactured by Wako Pure Chemical Industries, Ltd., "DAND" (diallyl 2,3-naphthoate) with the trade name manufactured by Nippon Sharyo Co., Ltd., "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) manufactured by Shikoku Kasei Kogyo Co., Ltd., "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane) manufactured by Nippon Kayaku Co., Ltd., "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Kasei Co., Ltd., and the like.

[0207] The maleimide-based radically polymerizable compound is, for example, a compound having one or more, preferably two or more maleimide groups. The maleimide-based radically polymerizable compound may be an aliphatic maleimide compound containing an aliphatic amine skeleton or an aromatic maleimide compound containing an aromatic amine skeleton. Examples of commercially available products include "SLK-2600" manufactured by Shin-Etsu Chemical Co., Ltd., "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", "BMI-2500" (maleimide compound containing a dimer diamine structure) manufactured by Designer Molecules, Inc., "BMI-6100" (aromatic maleimide compound) manufactured by Designer Molecules, Inc., "MIR-5000-60T", "MIR-3000-70MT" (biphenyl aralkyl type maleimide compound) manufactured by Nippon Kayaku Co., Ltd., "BMI-70", "BMI-80" manufactured by K.I. Kasei Co., Ltd., "BMI-2300", "BMI-TMH" manufactured by Daiwa Kasei Kogyo Co., Ltd., etc. In addition, as the maleimide-based radically polymerizable compound, a maleimide resin (maleimide compound containing an indane ring skeleton) disclosed in Japanese Invention Association Publication Technical Report Public Technology No. 2020-500211 can be used.

[0208] (E) The vinyl unsaturated bond equivalent of the radically polymerizable compound is preferably 20 g / eq. to 1000 g / eq., more preferably 50 g / eq. to 750 g / eq., still more preferably 70 g / eq. to 500 g / eq., and particularly preferably 90 g / eq. to 400 g / eq. The vinyl unsaturated bond equivalent is the mass of the radically polymerizable compound per 1 equivalent of vinyl unsaturated bond.

[0209] (E) The molecular weight of the radically polymerizable compound is preferably 10,000 or less, more preferably 5,000 or less, still more preferably 1,000 or less, and particularly preferably 500 or less. The lower limit is not particularly limited and may be, for example, 150 or more.

[0210] The content of the (E) radically polymerizable compound in the resin composition is not particularly limited. When the nonvolatile components in the resin composition are set to 100% by mass, it is preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The lower limit of the content of the (E) radically polymerizable compound in the resin composition is not particularly limited. When the nonvolatile components in the resin composition are set to 100% by mass, it is, for example, 0% by mass or more, 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1% by mass or more.

[0211] <(F) Elastomer>

[0212] The resin composition of the present invention may sometimes contain an (F) elastomer as an optional component. By containing the (F) elastomer in the resin composition of the present invention, the crack resistance after stain removal treatment can be further improved. The (F) elastomer refers to a resin having flexibility, preferably a resin exhibiting rubber elasticity or a resin that exhibits rubber elasticity by reacting with other components. Examples of the resin exhibiting rubber elasticity include resins having an elastic modulus of 1 GPa or less when a tensile test is performed under the conditions of a temperature of 25°C and a humidity of 40% RH in accordance with Japanese Industrial Standard (JIS K7161).

[0213] (F) The elastomer may be a particulate elastomeric component (particulate elastomer) that maintains a particulate form in the resin composition, or an amorphous non-particulate elastomeric component (non-particulate elastomer) that has a tendency to mix or dissolve in the resin composition. The (F) elastomer preferably contains a particulate elastomer. The particulate elastomer is preferably spherical.

[0214] The granular elastomer is preferably a silicone-based elastomer containing, for example, polydimethylsiloxane; olefin-based thermoplastic elastomers such as polybutadiene, polyisoprene, polychloroprene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutene copolymer, isobutene-butadiene copolymer, ethylene-propylene-diene terpolymer, ethylene-propylene-butene terpolymer, etc.; acrylic-based thermoplastic elastomers such as poly(propyl methacrylate), poly(butyl methacrylate), poly(cyclohexyl methacrylate), poly(octyl methacrylate), etc., as rubber particles as the rubber component. Further, a silicone-based rubber such as polyorganosiloxane rubber can be mixed in the rubber component. The glass transition temperature of the rubber component contained in the rubber particles is, for example, 0 °C or lower, preferably -10 °C or lower, more preferably -20 °C or lower, and further preferably -30 °C or lower.

[0215] From the viewpoint of significantly obtaining the desired effects of the present invention, the granular elastomer preferably contains core-shell rubber particles. The core-shell rubber particles are granular elastomers composed of "core particles containing the rubber components exemplified above" and "one or more shell parts covering them". Further, the core-shell rubber particles are preferably core-shell graft copolymer rubber particles composed of "core particles containing the rubber components exemplified above" and "a shell part obtained by graft copolymerizing a monomer component capable of copolymerizing with the rubber component contained in the core particles". The core-shell mentioned here does not necessarily refer only to those in which the core particles and the shell parts can be clearly distinguished, but also includes those in which the boundary between the core particles and the shell parts is not clear, and the core particles may not be completely covered by the shell parts.

[0216] The core-shell rubber particles preferably contain 40% by mass or more of the rubber component, more preferably 50% by mass or more of the rubber component, and further preferably 60% by mass or more of the rubber component. The upper limit of the content of the rubber component in the core-shell rubber particles is not particularly limited, and from the viewpoint of sufficiently covering the core particles with the shell part, it is, for example, 95% by mass or lower, preferably 90% by mass or lower.

[0217] The monomer components forming the shell of the core-shell rubber particles include, for example, (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, glycidyl (meth)acrylate; (meth)acrylic acid; N-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; maleimide; α,β-unsaturated carboxylic acids such as maleic acid and itaconic acid; aromatic vinyl compounds such as styrene, 4-vinyltoluene, and α-methylstyrene; (meth)acrylonitrile, etc. Among them, (meth)acrylates are preferably included, and methyl (meth)acrylate is more preferably included. It should be noted that “(meth)acrylic acid” is methacrylic acid or acrylic acid.

[0218] Examples of commercially available core-shell rubber particles include, for example, “CHT” manufactured by Cheil Industries; “B602” manufactured by UMGABS; “PARALOID EXL-2602”, “PARALOID EXL-2603”, “PARALOID EXL-2655”, “PARALOID EXL-2311”, “PARALOID-EXL2313”, “PARALOID EXL-2315”, “PARALOID KM-330”, “PARALOID KM-336P”, “PARALOIDKCZ-201” manufactured by Dow Chemical Japan; “METABLEN C-223A”, “METABLEN E-901”, “METABLEN S-2001”, “METABLEN W-450A”, “METABLEN SRK-200” manufactured by Mitsubishi Rayon; “KaneAce M-511”, “Kane Ace M-600”, “Kane Ace M-400”, “KaneAce M-580”, “KaneAce MR-01” manufactured by Kaneka, etc.

[0219] The average particle diameter (average primary particle diameter) of the granular elastomer is not particularly limited, preferably 20 nm or more, more preferably 30 nm or more, and further preferably 50 nm or more. The upper limit of the average particle diameter (average primary particle diameter) of the granular elastomer is not particularly limited, preferably 5,000 nm or less, more preferably 2,000 nm or less, and further preferably 1,000 nm or less. The average particle diameter (average primary particle diameter) of the granular elastomer can be measured using a Zeta potential particle size distribution measuring device, etc.

[0220] The content of the (F) elastomer in the resin composition is not particularly limited. When the non-volatile components in the resin composition are set to 100% by mass, it is preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The lower limit of the content of the (F) elastomer in the resin composition is not particularly limited. When the non-volatile components in the resin composition are set to 100% by mass, it is, for example, 0% by mass or more, 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more.

[0221] <(G) Curing Accelerator>

[0222] The resin composition of the present invention may sometimes contain a (G) curing accelerator as an optional component. The (G) curing accelerator has the function of promoting the curing of the (A) epoxy resin.

[0223] Examples of the curing accelerator include, for example, phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, and the like. The (G) curing accelerator can be used alone or in combination of two or more.

[0224] Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate and other aliphatic phosphonium salts; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, para- Aromatic phosphonium salts such as tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants; tributylphosphine, tri-tert-butylphosphine, and trioctylphosphine. , di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl-2-butenyl) phosphine, tricyclohexyl phosphine and the like; dibutylphenyl phosphine, di-tert-butylphenyl phosphine, methyldiphenyl phosphine, ethyldiphenyl phosphine, butyldiphenyl phosphine, diphenylcyclohexyl phosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(4-tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,5-dimethylphenyl)phosphine, tri( Aromatic phosphines such as 2,6-dimethylphenyl)phosphine, tri(3,5-dimethylphenyl)phosphine, tri(2,4,6-trimethylphenyl)phosphine, tri(2,6-dimethyl-4-ethoxyphenyl)phosphine, tri(2-methoxyphenyl)phosphine, tri(4-methoxyphenyl)phosphine, tri(4-ethoxyphenyl)phosphine, tri(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether.

[0225] As the urea-based curing accelerator, for example, 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea; aromatic dimethylureas such as 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea], etc.

[0226] As the guanidine-based curing accelerator, for example, 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-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc.

[0227] As imidazole-based curing accelerators, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-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 other imidazole compounds and adducts of imidazole compounds and epoxy resins can be cited.

[0228] As imidazole-based curing accelerators, commercially available products can be used. For example, "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Kasei Kogyo Co., Ltd., "P200-H50" manufactured by Mitsubishi Chemical Corporation, etc. can be cited.

[0229] As metal-based curing accelerators, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, tin, etc. can be cited. Specific examples of organometallic complexes include: organocobalt complexes such as cobalt(II) acetylacetonate, cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, organomanganese complexes such as manganese(II) acetylacetonate, etc. As organometallic salts, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc. can be cited.

[0230] As amine-based curing accelerators, for example, trialkylamines such as triethylamine, tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5.4.0)undecene, etc. can be cited.

[0231] As the amine-based curing accelerator, commercially available products can be used. For example, "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd. etc. can be cited.

[0232] The content of the (G) curing accelerator in the resin composition is not particularly limited. When the non-volatile components in the resin composition are set to 100% by mass, it is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 2% by mass or less. The lower limit of the content of the (G) curing accelerator in the resin composition is not particularly limited. When the non-volatile components in the resin composition are set to 100% by mass, for example, it can be 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.5% by mass or more, etc.

[0233] <(H) Other additives>

[0234] The resin composition of the present invention may further contain optional additives as non-volatile components. Examples of such additives include radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; thermosetting resins other than epoxy resins such as epoxy acrylate resins, polyurethane acrylate resins, polyurethane resins, cyanate ester resins, thermosetting polyimide resins, benzoxazine resins, unsaturated polyester resins, phenolic resins, melamine resins, and silicone resins; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; homogenizers such as silicone-based homogenizers and acrylic polymer-based homogenizers; thickeners such as Benton and montmorillonite; defoamers such as silicone-based defoamers, acrylic-based defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as ureidosilane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenol-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate compounds, phosphazene compounds, phosphonic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic-based flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate / borate-based stabilizers, titanate / titanate-based stabilizers, aluminate / aluminate-based stabilizers, zirconate / zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers, etc. (H) Other additives may be used alone or two or more of them may be used in any ratio in combination. Regarding the content of (H) other additives, those skilled in the art can appropriately set it.

[0235] <(I) Organic solvents>

[0236] For the resin composition of the present invention, in addition to containing the above-mentioned non-volatile components, as volatile components, optional organic solvents may sometimes be further contained. As the (I) organic solvent, known organic solvents can be appropriately used, and the types thereof are not particularly limited. Examples of the (I) organic 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, isopentyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyldiglycol 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. The (I) organic solvent may be used alone or two or more thereof may be used in combination at any ratio.

[0237] In one embodiment, the content of the (I) organic solvent is not particularly limited. When all the components in the resin composition are set to 100% by mass, for example, it may be 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, etc.

[0238] <Manufacturing method of resin composition>

[0239] The resin composition of the present invention can be produced, for example, by adding and / or simultaneously adding part or all of (A) an epoxy resin, (B) an active ester compound, (C) an inorganic filler, (D) a thermoplastic resin as needed, (E) a radically polymerizable compound as needed, (F) an elastomer as needed, (G) a curing accelerator as needed, (H) other additives as needed, and (I) an organic solvent as needed in any order into an arbitrary preparation container and mixing them. Further, during the process of adding each component and mixing them, the temperature can be appropriately set, and heating and / or cooling can be performed temporarily or throughout the process. Further, during the process of adding and mixing, or after this process, the resin composition can be stirred or shaken using a stirring device or a shaking device such as a mixer, etc., so as to be uniformly dispersed. Further, defoaming can be performed under a low pressure condition such as under vacuum simultaneously with stirring or shaking.

[0240] <Properties of the resin composition>

[0241] The resin composition of the present invention contains (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler. The (A) epoxy resin contains (A-1) an ester-modified epoxy resin. When the non-volatile components in the resin composition are 100% by mass, the content of the (C) inorganic filler is 50% by mass or more. By using such a resin composition, a cured product that can suppress the generation of cracks after a defouling treatment and suppress the dielectric loss tangent (Df) to a lower value can be obtained.

[0242] The cured product of the resin composition of the present invention can suppress the generation of cracks after a defouling treatment. Therefore, in one embodiment, when a circuit board is produced as in Test Example 2 below and subjected to a defouling treatment, and 100 copper pad portions of the circuit board are observed, the number of cracks is preferably 10 or less.

[0243] The cured product of the resin composition of the present invention can have a feature of a low dielectric loss tangent (Df). Therefore, in one embodiment, when measured under the conditions of 5.8 GHz and 23°C as in Test Example 1 below, the dielectric loss tangent (Df) of the cured product of the resin composition is preferably 0.0200 or less, 0.0100 or less, more preferably 0.0090 or less, 0.0080 or less, 0.0070 or less, further preferably 0.0060 or less, 0.0050 or less, 0.0040 or less, and particularly preferably 0.0035 or less, 0.0030 or less, 0.0027 or less.

[0244] <Uses of the resin composition>

[0245] The resin composition of the present invention can be suitably used as a resin composition for insulating purposes, particularly as a resin composition for forming an insulating layer. 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) for forming a conductor layer (including a rewiring layer), where the conductor layer is formed on the insulating layer. In addition, in the printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of the printed wiring board (a resin composition for forming an insulating layer of the printed wiring board). The resin composition of the present invention can also be widely used in applications that require a resin composition, such as sheet-like laminated materials such as resin sheets and prepregs, solder resists, underfill materials, chip bonding materials, semiconductor encapsulants, via filling resins, component embedding resins, etc.

[0246] In addition, for example, in the case of manufacturing a semiconductor chip package through the following steps (1) to (6), the resin composition of the present invention can also be suitably used as: a resin composition for forming a rewiring formation layer as an insulating layer for forming a rewiring layer (a resin composition for forming a rewiring formation layer), and a resin composition for encapsulating a semiconductor chip (a resin composition for encapsulating a semiconductor chip). When manufacturing a semiconductor chip package, a rewiring layer can be further formed on the encapsulation layer;

[0247] (1) A step of laminating a temporary fixing film on a substrate,

[0248] (2) A step of temporarily fixing a semiconductor chip on the temporary fixing film,

[0249] (3) A step of forming an encapsulation layer on the semiconductor chip,

[0250] (4) A step of peeling the substrate and the temporary fixing film from the semiconductor chip,

[0251] (5) A step of 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, and

[0252] (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0253] In addition, for the resin composition of the present invention, since it provides an insulating layer with good component embedding properties, it can also be suitably used in the case where the printed wiring board is a circuit board with built-in components.

[0254] <Sheet-like laminated material>

[0255] The resin composition of the present invention can also be used by coating it in a varnish state, but industrially, it is generally preferably used in the form of a sheet-like laminated material containing the resin composition.

[0256] As the sheet-like laminated material, a resin sheet, a prepreg shown below are preferable.

[0257] In one embodiment, the resin sheet includes a support and a resin composition layer provided on the support, and the resin composition layer is formed of the resin composition of the present invention.

[0258] From the viewpoints of thinning of the printed wiring board and providing a cured product having excellent insulation even if the cured product of the resin composition is a thin film, the thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and usually can be 5 μm or more, 10 μm or more, etc.

[0259] Examples of the support include a film formed of a plastic material, a metal foil, and a release paper, and a film formed of a plastic material and a metal foil are preferable.

[0260] When a film formed of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes simply referred to as "PET"), polyethylene naphthalate (hereinafter sometimes simply referred to as "PEN"), polycarbonate (hereinafter sometimes simply referred to as "PC"), acrylic polymers 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 preferable, and inexpensive polyethylene terephthalate is particularly preferable.

[0261] When a metal foil is used as the support, examples of the metal foil include a copper foil, an aluminum foil, etc., and a copper foil is preferable. As the copper foil, a foil formed of single metal of copper or a foil formed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

[0262] For the support, the surface joined to the resin composition layer can be subjected to a matting treatment, a corona treatment, an antistatic treatment.

[0263] In addition, as the support, a support with a release layer having a release layer on the surface joined to the resin composition layer can be used. As the release agent used in the release layer of the support with a release layer, for example, one or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins can be cited. Commercially available products can be used as the support with a release layer. For example, "SK-1", "AL-5", "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, "Unipeel" manufactured by Unitika Ltd., etc., which are PET films having a release layer mainly composed of an alkyd resin-based release agent.

[0264] The thickness of the support is not particularly limited, and is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. It should be noted that when using a support with a release layer, it is preferable that the overall thickness of the support with a release layer is in the above range.

[0265] In one embodiment, if necessary, the resin sheet may further include an arbitrary layer. As the arbitrary layer, for example, a protective film selected according to the support provided on the surface of the resin composition layer not joined to the support (that is, the surface on the side opposite to the support) can be cited. The thickness of the protective film is not particularly limited, for example, it is 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of dust and the like to the surface of the resin composition layer or the generation of damage on the surface of the resin composition layer.

[0266] The resin sheet can be manufactured, for example, by directly coating a liquid resin composition on a support using a die coater or the like, or by preparing a resin varnish in which the resin composition is dissolved in an organic solvent and coating it on the support using a die coater or the like, and then drying it to form a resin composition layer.

[0267] As the organic solvent, the same organic solvents as those described as components of the resin composition can be cited. The organic solvent can be used alone or in combination of two or more.

[0268] Drying can be carried out by known methods such as heating and blowing hot air. The drying conditions are not particularly limited, and drying is carried out so that the content of the organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although it also varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when using a resin composition or resin varnish containing 30% to 60% by mass of an organic solvent, a resin composition layer can be formed by drying at 50 °C to 150 °C for 3 minutes to 10 minutes.

[0269] The resin sheet can be wound into a roll for storage. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0270] In one embodiment, the prepreg is formed by impregnating a sheet-shaped fiber substrate with the resin composition of the present invention.

[0271] The sheet-shaped fiber substrate used in the prepreg is not particularly limited, and glass cloth, aramid non-woven fabric, liquid crystal polymer non-woven fabric, etc., which are commonly used sheet-shaped fiber substrates as prepreg substrates, can be used. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-shaped fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, and particularly preferably 20 μm or less. There is no particular limitation on the lower limit of the thickness of the sheet-shaped fiber substrate. Usually, it is 10 μm or more.

[0272] The prepreg can be manufactured by known methods such as the hot melt method and the solvent method.

[0273] The thickness of the prepreg can be in the same range as the resin composition layer in the above-mentioned resin sheet.

[0274] The sheet-like laminate of the present invention can be suitably used to form an insulating layer of a printed wiring board (for the insulating layer of a printed wiring board), and can be more suitably used to form an interlayer insulating layer of a printed wiring board (for the interlayer insulating layer of a printed wiring board).

[0275] <Printed Wiring Board>

[0276] The printed wiring board of the present invention includes an insulating layer formed of a cured product obtained by curing the resin composition of the present invention.

[0277] The printed wiring board can be manufactured, for example, using the above-mentioned resin sheet by a method including the following steps (I) and (II).

[0278] (I) A step of laminating the resin sheet on the inner layer substrate in such a manner that the resin composition layer of the resin sheet is joined to the inner layer substrate, and (II) a step of curing (for example, thermally curing) the resin composition layer to form an insulating layer.

[0279] 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, and a thermosetting polyphenylene ether substrate. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner substrate having a conductor layer (circuit) formed on one or both sides of the substrate is sometimes 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" referred to in the present invention. When the printed wiring board is a component-built-in circuit board, an inner substrate with built-in components can be used.

[0280] The inner substrate and the resin sheet can be laminated, for example, by heat-pressing the resin sheet onto the inner substrate from the support side. As a member for heat-pressing the resin sheet onto 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) can be cited. It should be noted that it is preferred that the heat-pressing member is not pressed directly onto the resin sheet, but rather pressed through an elastic material such as heat-resistant rubber so that the resin sheet fully follows the surface irregularities of the inner substrate.

[0281] Lamination of the inner layer substrate and the resin sheet can be performed by vacuum lamination. In vacuum lamination, 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 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa, and the heating and pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure of 26.7 hPa or less.

[0282] Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Meiki Mfg. Co., Ltd., a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressure laminator.

[0283] After lamination, the laminated resin sheets can be smoothed by, for example, pressing a heat-pressing member from the support side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing treatment can be set to the same conditions as the heat-pressing conditions for the lamination described above. The smoothing treatment can be performed using a commercially available laminator. It should be noted that lamination and smoothing treatment can be performed continuously using the above-mentioned commercially available vacuum laminator.

[0284] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0285] In step (II), the resin composition layer is cured (e.g., thermally cured) to form an insulating layer formed of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and conditions generally employed in forming an insulating layer of a printed wiring board can be used.

[0286] For example, the thermal curing conditions of the resin composition layer also vary depending on the type of the resin composition and the like. In one embodiment, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and still more preferably 170°C to 210°C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and still more preferably 15 minutes to 100 minutes.

[0287] Before thermally curing the resin composition layer, the resin composition layer can be preheated at a temperature lower than the curing temperature. For example, before thermally curing the resin composition layer, the resin composition layer is preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and still more preferably 15 minutes to 100 minutes.

[0288] When manufacturing a printed wiring board, step (III) of opening holes in the insulating layer, step (IV) of roughening the insulating layer, and step (V) of forming a conductor layer can be further implemented. These steps (III) to (V) can be implemented according to various methods known to those skilled in the art and usable in the manufacture of printed wiring boards. It should be noted that when removing the support after step (II), the removal of the support can be implemented between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). In addition, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) can be repeatedly implemented to form a multilayer wiring board.

[0289] In other embodiments, the printed wiring board of the present invention can be manufactured using the above-described prepreg. The manufacturing method is basically the same as that in the case of using a resin sheet.

[0290] Step (III) is a step of opening holes in the insulating layer, whereby holes such as vias and through-holes can be formed in the insulating layer. For step (III), depending on the composition of the resin composition used in the formation of the insulating layer and the like, it can be implemented using, for example, a drill, a laser, a plasma, etc. The size or shape of the holes can be appropriately determined according to the design of the printed wiring board.

[0291] Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), removal of contamination is also performed. The steps and conditions for the roughening treatment are not particularly limited, and known steps and conditions generally used when forming the insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by sequentially performing a swelling treatment using a swelling liquid, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing liquid.

[0292] The swelling liquid used in the roughening treatment is not particularly limited, and examples thereof include an alkali solution and a surfactant solution. An alkali solution is preferred, and among them, a sodium hydroxide solution and a potassium hydroxide solution are more preferred. Examples of commercially available swelling liquids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan Co., Ltd. The swelling treatment using the swelling liquid is not particularly limited. For example, it can be performed by immersing the insulating layer in the swelling liquid 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 the swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0293] The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganic acid solution prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in the oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "DosingSolution Securiganth P" manufactured by Atotech Japan Co., Ltd.

[0294] In addition, as the neutralizing liquid used in the roughening treatment, an acidic aqueous solution is preferred. Examples of commercially available products include "Reduction Solution Securiganth P" manufactured by Atotech Japan Co., Ltd.

[0295] The treatment using the neutralizing liquid can be performed by immersing the treated surface that has completed the roughening treatment using the oxidizing agent in the neutralizing liquid at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of operability and the like, a method of immersing the object that has completed the roughening treatment using the oxidizing agent in the neutralizing liquid at 40°C to 70°C for 5 minutes to 20 minutes is preferred.

[0296] In one embodiment, the arithmetic mean roughness (Ra) of the surface of the roughened insulating layer is preferably 500 nm or less, more preferably 400 nm or less, and still more preferably 300 nm or less. There is no particular limitation on the lower limit, and it can be, for example, 1 nm or more, 2 nm or more, etc. In addition, the root mean square roughness (Rq) of the surface of the roughened insulating layer is preferably 500 nm or less, more preferably 400 nm or less, and still more preferably 300 nm or less. There is no particular limitation on the lower limit, and it can be, for example, 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) and the root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

[0297] Process (V) is a process 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 in the conductor layer. In a preferred embodiment, the conductor layer contains 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 can be a single metal layer or an alloy layer. As the alloy layer, for example, a layer formed of an alloy of two or more metals selected from the above metals (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy) can be cited. Among them, from the viewpoints of the versatility of conductor layer formation, cost, ease of patterning, etc., 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, and 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 still more preferred.

[0298] The conductor layer can have a single-layer structure or a multilayer structure formed by laminating two or more single metal layers or alloy layers formed of different metals or alloys. When the conductor layer has a multilayer 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 nickel-chromium alloy.

[0299] The thickness of the conductor layer depends on the design of the desired printed wiring board and is usually 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0300] In one embodiment, the conductor layer can be formed by plating. For example, using conventionally known techniques such as semi-additive method and full-additive method, plating can be performed on the surface of the insulating layer to form a conductor layer having a desired wiring pattern. From the viewpoint of manufacturing simplicity, it is preferably formed by the semi-additive method. Hereinafter, an example of forming a conductor layer by the semi-additive method is shown.

[0301] First, an electroless plating is used to form a plating seed layer on the surface of the insulating layer. Next, on the formed plating seed layer, corresponding to the desired wiring pattern, a mask pattern is formed to expose a part of the plating seed layer. On the exposed plating seed layer, an electrolytic plating is used to form a metal layer, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having the desired wiring pattern can be formed.

[0302] In other embodiments, the conductor layer can be formed using a metal foil. In the case of forming the conductor layer using a metal foil, step (V) is preferably carried out between step (I) and step (II). For example, after step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil can be carried out by a vacuum lamination method. The lamination conditions can be the same as those described for step (I). Next, step (II) is carried out to form an insulating layer. Then, using the metal foil on the insulating layer, a conductor layer having the desired wiring pattern can be formed by a known technique such as a subtractive method or a modified semi-additive method.

[0303] The metal foil can be manufactured by known methods such as an electrolytic method or a rolling method. As commercially available products of the metal foil, for example, HLP foil, JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, 3EC-III foil, TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd. etc. can be cited.

[0304] <Semiconductor Device>

[0305] The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

[0306] As the semiconductor device, various semiconductor devices for electrical products (for example, computers, mobile phones, digital cameras, and televisions, etc.) and transportation means (for example, motorcycles, automobiles, trams, ships, and airplanes, etc.) can be cited.

[0307] Examples

[0308] Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited by these examples. It should be noted that hereinafter, unless otherwise clearly specified, "parts" and "%" indicating amounts respectively refer to "parts by mass" and "mass%". The temperature conditions and pressure conditions in the case of not particularly specifying the temperature and pressure are room temperature (23°C) and atmospheric pressure (1 atm).

[0309] <Example 1>

[0310] 10 parts of epoxy resin A (a modified epoxy resin having a structure represented by the following formula (A) synthesized by the method described in Example 1 of JP-A-2020-111735; according to FD / MS measurement results, 1 ≤ x ≤ 5, 0 ≤ y ≤ 1, 0 ≤ z ≤ 1, and the maximum peak is m / z = 588.3 (x = z = 1, y = 0), epoxy equivalent is about 455 g / eq.) and 5 parts of an epoxy resin containing a naphthalene skeleton ("HP-4032-D" manufactured by DIC Corporation, epoxy equivalent is about 140 g / eq.) were dissolved in 15 parts of MEK. To this, 65 parts of spherical silica (average particle diameter 0.5 μm, "SO-C2" manufactured by Admatechs Co., Ltd.) surface-treated with an amino-based silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.), 1 part of core-shell rubber particles ("EXL-2655" manufactured by Dow Chemical Company), 24 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active ester equivalent 223, toluene solution with a solid content of 65% by mass), 2 parts of an acrylate compound ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd.), 5 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, MEK / cyclohexanone mixed solution with a solid content of 30% by mass), and 0.1 part of a curing accelerator ("4-dimethylaminopyridine" manufactured by Wako Pure Chemical Industries, Ltd.) were uniformly dispersed using a high-speed rotary mixer to prepare a resin composition.

[0311] [Chemical formula 16]

[0312]

[0313] <Example 2>

[0314] Instead of using 24 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, toluene solution with a solid content of 65% by mass), 25 parts of an active ester curing agent ("HPC-8150-62T" manufactured by DIC Corporation, active ester equivalent 234, toluene solution with a solid content of 62%) were used, and a resin composition was prepared in the same manner as in Example 1 except for this.

[0315] <Example 3>

[0316] Instead of using 24 parts of an active ester-based curing agent (“HPC-8000-65T” manufactured by DIC Corporation, toluene solution with a solid content of 65% by mass), 25 parts of an active ester curing agent (“HPC-8150-62T” manufactured by DIC Corporation, active ester equivalent 234, toluene solution with a solid content of 62%) were used. Instead of using 5 parts of a phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK / cyclohexanone mixed solution with a solid content of 30% by mass), 6 parts of a polyimide resin (“SLK-6100” manufactured by Shin-Etsu Chemical Co., Ltd., anisole solution with a solid content of 25%) were used. Otherwise, a resin composition was prepared in the same manner as in Example 1.

[0317] <Example 4>

[0318] Instead of using 24 parts of an active ester-based curing agent (“HPC-8000-65T” manufactured by DIC Corporation, toluene solution with a solid content of 65% by mass), 24 parts of an active ester curing agent (“HPC-8150-62T” manufactured by DIC Corporation, active ester equivalent 234, toluene solution with a solid content of 62%) were used. Further, 2 parts of a cresol novolak resin containing triazine (“LA-3018-50P” manufactured by DIC Corporation, nitrogen content 18%, propylene glycol monomethyl ether solution with a solid content of 50%) were added. Otherwise, a resin composition was prepared in the same manner as in Example 1.

[0319] <Example 5>

[0320] Instead of using 24 parts of an active ester-based curing agent (“HPC-8000-65T” manufactured by DIC Corporation, toluene solution with a solid content of 65% by mass), 24 parts of an active ester curing agent (“HPC-8150-62T” manufactured by DIC Corporation, active ester equivalent 234, toluene solution with a solid content of 62%) were used. The amount of spherical silica (average particle size 0.5 μm, “SO-C2” manufactured by Admatechs Co., Ltd.) surface-treated with an amino-based silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 65 parts to 82 parts. Further, 2 parts of a cresol novolak resin containing triazine (“LA-3018-50P” manufactured by DIC Corporation, nitrogen content 18%, propylene glycol monomethyl ether solution with a solid content of 50%) were added. Otherwise, a resin composition was prepared in the same manner as in Example 1.

[0321] <Comparative Example 1>

[0322] Instead of using epoxy resin A, 9 parts of naphthalene-type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 330) were used. Instead of 24 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, toluene solution with a solid content of 65% by mass), 26 parts of an active ester curing agent ("HPC-8150-62T" manufactured by DIC Corporation, active ester equivalent 234, toluene solution with a solid content of 62%) were used. Further, 2 parts of a cresol novolac resin containing triazine ("LA-3018-50P" manufactured by DIC Corporation, nitrogen content 18%, propylene glycol monomethyl ether solution with a solid content of 50% by mass) were added. Otherwise, a resin composition was prepared in the same manner as in Example 1.

[0323] <Comparative Example 2>

[0324] Instead of 24 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, toluene solution with a solid content of 65% by mass), 25 parts of an active ester curing agent ("HPC-8150-62T" manufactured by DIC Corporation, active ester equivalent 234, toluene solution with a solid content of 62%) were used. The amount of spherical silica (average particle size 0.5 μm, "SO-C2" manufactured by Admatechs Co., Ltd.) surface-treated with an amino-based silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 65 parts to 35 parts. Further, 2 parts of a cresol novolac resin containing triazine ("LA-3018-50P" manufactured by DIC Corporation, nitrogen content 18%, propylene glycol monomethyl ether solution with a solid content of 50% by mass) were added. Otherwise, a resin composition was prepared in the same manner as in Example 1.

[0325] <Production Example 1: Resin Sheet with a Resin Composition Layer Thickness of 40 μm>

[0326] As a support, a polyethylene terephthalate film with a release layer ("AL5" manufactured by Lintec Corporation, thickness 38 μm) was prepared. The resin compositions obtained in the examples and comparative examples were uniformly coated on the release layer of the support so that the thickness of the dried resin composition layer became 40 μm. Then, the resin composition was dried at 80°C to 100°C (average 90°C) for 4 minutes to obtain a resin sheet including the support and the resin composition layer.

[0327] <Production Example 2: Resin Sheet with a Resin Composition Layer Thickness of 25 μm>

[0328] In the same manner as in Production Example 1, the resin compositions obtained in the Examples and Comparative Examples were uniformly coated so that the thickness of the dried resin composition layer became 25 μm, and dried at 70°C to 80°C (average 75°C) for 2.5 minutes to obtain resin sheets each comprising a support and a resin composition layer.

[0329] <Test Example 1: Measurement of Dielectric Loss Tangent>

[0330] The resin sheet produced in Production Example 1 was heated at 190°C for 90 minutes to thermally cure the resin composition layer. Then, the support was peeled off to obtain a cured product of the resin composition. This cured product was cut into test pieces having a width of 2 mm and a length of 80 mm. For these test pieces, the dielectric loss tangent (Df) was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C by the cavity perturbation method using "HP8362B" manufactured by Agilent Technologies, Inc. The measurement was performed on 3 test pieces, and the average value is shown in Table 1 below.

[0331] <Test Example 2: Evaluation of Crack Resistance after Defouling Treatment>

[0332] On both sides of a core material (Hitachi Chemical Co., Ltd.'s "E705GR", thickness 400 μm) formed by arranging circular copper pads (copper thickness 35 μm) with a diameter of 350 μm in a lattice pattern at intervals of 400 μm with a residual copper rate of 60%, a discontinuous vacuum pressure laminator (Nikko-Materials Co., Ltd.'s 2-stage stacked laminator "CVP700") was used to laminate the resin sheets with a thickness of 25 μm obtained in Production Example 2 on both sides of the inner substrate in such a manner that the resin composition layer was joined to the inner substrate. This lamination was carried out as follows: The pressure was reduced for 30 seconds to make the air pressure 13 hPa or less, and then, crimping was carried out for 30 seconds under the conditions of a temperature of 100 °C and a pressure of 0.74 MPa. It was put into an oven at 130 °C and heated for 30 minutes, and then transferred to an oven at 170 °C and heated for 30 minutes. Further, the support layer (support) was peeled off, and the obtained circuit board was immersed in Swelling Dip Securiganth P manufactured by Atotech Japan Co., Ltd. as a swelling liquid at 60 °C for 10 minutes. Then, it was immersed in Concentrate Compact P (aqueous solution of KMnO4: 60 g / L, NaOH: 40 g / L) manufactured by Atotech Japan Co., Ltd. as a roughening liquid at 80 °C for 30 minutes. Finally, it was immersed in Reduction Solution Securiganth P manufactured by Atotech Japan Co., Ltd. as a neutralizing liquid at 40 °C for 5 minutes. One hundred copper pad portions of the circuit boards after the roughening treatment were observed to confirm the presence or absence of cracks in the resin composition layer. If the number of cracks was 10 or less, it was evaluated as "〇"; if the number of cracks was more than 10, it was evaluated as "×".

[0333] The usage amounts of the raw materials of the resin compositions of the examples and comparative examples, the contents of the non-volatile components, and the measurement results and evaluation results of the test examples are shown in Table 1 below.

[0334] [Table 1]

[0335]

[0336] Referring to Table 1, it can be seen that in Comparative Example 1 where an ester-modified epoxy resin was not used, the evaluation of crack resistance was poor; in addition, in Comparative Example 2 where the usage amount of the inorganic filler was less than 50% by mass, the evaluation of crack resistance was poor and the dielectric loss tangent was a relatively high value. In contrast, when using a resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler, (A) the epoxy resin contains an ester-modified epoxy resin, and (C) the content of the inorganic filler is 50% by mass or more, these problems can be overcome.

Claims

1. A resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler. Among them, (A) The component contains: (A-1) a modified epoxy resin obtained by reacting an epoxy resin having two or more epoxy groups in one molecule with an ester compound represented by formula (1). In formula (1), R 1 represents an optionally substituted alkyl group or an optionally substituted aryl group, and R 2 represents an optionally substituted aryl group. (A) The component further contains (A-2) an epoxy resin that is liquid at 20 °C, and the (A-2) component does not include substances belonging to the (A-1) component. (A-2) The component has a weight average molecular weight (Mw) of 100 to 5,000. (A-2) The mass ratio of the content of the component to the content of the (A-1) component, that is, (A-2) component / (A-1) component, is 0.3 or more and 2 or less, and the mass ratio of the content of the (B) component to the content of the (A-1) component, that is, (B) component / (A-1) component, is 1 or more and 5 or less. When the non-volatile components in the resin composition are set to 100% by mass, the content of the (C) component is 60% by mass or more.

2. A resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler. Among them, (A) The component contains: (A-1) a modified epoxy resin having a group represented by formula (2-1) and a group represented by formula (2-2). In formula (2-1), * represents a bonding site. In formula (2-2), R 1 represents an optionally substituted alkyl group or an optionally substituted aryl group, R 2 represents an optionally substituted aryl group, and * represents a bonding site. (A) The component further contains (A-2) an epoxy resin that is liquid at 20 °C, and the (A-2) component does not include substances belonging to the (A-1) component. (A-2) The component has a weight average molecular weight (Mw) of 100 to 5,000. (A-2) The mass ratio of the content of the component to the content of the (A-1) component, that is, (A-2) component / (A-1) component, is 0.3 or more and 2 or less. (B) The mass ratio of the content of the component to the content of the (A-1) component, that is, (B) component / (A-1) component, is 1 or more and 5 or less. When the non-volatile components in the resin composition are set to 100% by mass, the content of the (C) component is 60% by mass or more.

3. The resin composition according to claim 1 or 2, wherein R 1 is an optionally substituted aryl group.

4. The resin composition according to claim 3, wherein R 1 is optionally a phenyl group having substituents, an optionally substituted 1-naphthyl group, or an optionally substituted 2-naphthyl group.

5. The resin composition according to claim 4, wherein, R 1 is an optionally substituted phenyl group.

6. The resin composition according to claim 5, wherein, R 1 is phenyl.

7. The resin composition according to claim 1 or 2, wherein R 2 is optionally a phenyl group having a substituent, an optionally substituted 1-naphthyl group, or an optionally substituted 2-naphthyl group.

8. The resin composition according to claim 7, wherein, R 2 is an optionally substituted 2-naphthyl group.

9. The resin composition according to claim 8, wherein, R 2 is 2-naphthyl.

10. The resin composition according to claim 1 or 2, wherein (A-1) The component is a modified epoxy resin having a structural unit represented by formula (4-1) and a structural unit represented by formula (4-2). In formula (4-1), R 4 each independently represents an optionally substituted alkyl group or an optionally substituted aryl group, and a represents 0, 1, 2, or 3. In formula (4-2), R 1 represents an optionally substituted alkyl group or an optionally substituted aryl group, R 2 represents an optionally substituted aryl group, R 4 each independently represents an optionally substituted alkyl group or an optionally substituted aryl group, and a represents 0, 1, 2 or 3.

11. The resin composition according to claim 10, wherein, R 4 is an optionally substituted alkyl group.

12. The resin composition according to claim 11, wherein, R 4 is an alkyl group.

13. The resin composition according to claim 12, wherein, R 4 is methyl.

14. The resin composition according to claim 1 or 2, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of the (A-1) component is 0.1% by mass or more.

15. The resin composition according to claim 1 or 2, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of the (A-1) component is 50% by mass or less.

16. The resin composition according to claim 1 or 2, wherein When the non-volatile components in the resin composition are set to 100% by mass, the content of the (A-1) component is 1% by mass to 20% by mass.

17. The resin composition according to claim 1 or 2, wherein When the non-volatile components in the resin composition are set to 100% by mass, the content of the (A-1) component is 5% by mass or more.

18. The resin composition according to claim 1 or 2, wherein When the non-volatile components in the resin composition are set to 100% by mass, the content of the (A-1) component is 12% by mass or less.

19. The resin composition according to claim 1 or 2, wherein When the non-volatile components in the resin composition are set to 100% by mass, the content of the (B) component is 0.1% by mass or more.

20. The resin composition according to claim 1 or 2, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of component (B) is 50% by mass or less.

21. The resin composition according to claim 1 or 2, wherein When the non-volatile components in the resin composition are set to 100% by mass, the content of component (B) is 5% to 30% by mass.

22. The resin composition according to claim 1 or 2, wherein When the non-volatile components in the resin composition are set to 100% by mass, the content of component (B) is 10% by mass or more.

23. The resin composition according to claim 1 or 2, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of component (B) is 20% by mass or less.

24. The resin composition according to claim 1 or 2, wherein When the non-volatile components in the resin composition are set to 100% by mass, the content of component (A-2) is 0.01% by mass or more.

25. The resin composition according to claim 1 or 2, wherein When the non-volatile components in the resin composition are set to 100% by mass, the content of component (A-2) is 3% by mass or more.

26. The resin composition according to claim 1 or 2, wherein When the non-volatile components in the resin composition are set to 100% by mass, the content of component (A-2) is 40% by mass or less.

27. The resin composition according to claim 1 or 2, wherein When the non-volatile components in the resin composition are set to 100% by mass, the content of component (A-2) is 7% by mass or less.

28. The resin composition according to claim 1 or 2, wherein When the non-volatile components in the resin composition are set to 100% by mass, the content of component (C) is 64% by mass or more.

29. The resin composition according to claim 1 or 2, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of component (C) is 90% by mass or less.

30. The resin composition according to claim 1 or 2, wherein When the non-volatile components in the resin composition are set to 100% by mass, the content of component (C) is 70% by mass or less.

31. The resin composition according to claim 1 or 2, wherein, Further contains (D) thermoplastic resin.

32. The resin composition according to claim 31, wherein, Component (D) contains a thermoplastic resin selected from polyimide resin and phenoxy resin.

33. The resin composition according to claim 31, wherein, The weight-average molecular weight (Mw) of component (D) is 5000 or more.

34. The resin composition according to claim 31, wherein, The weight-average molecular weight (Mw) of component (D) is 20000 or more.

35. The resin composition according to claim 31, wherein, The weight-average molecular weight (Mw) of component (D) is 100000 or less.

36. The resin composition according to claim 31, wherein, The weight-average molecular weight (Mw) of component (D) is 50000 or less.

37. The resin composition according to claim 31, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of component (D) is 0.001% by mass or more.

38. The resin composition according to claim 31, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of component (D) is 1% by mass or more.

39. The resin composition according to claim 31, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of component (D) is 20% by mass or less.

40. The resin composition according to claim 31, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of component (D) is 2% by mass or less.

41. The resin composition according to claim 1 or 2, wherein Further contains (E) radically polymerizable compound.

42. The resin composition according to claim 41, wherein, Component (E) contains a (meth)acrylic radically polymerizable compound.

43. The resin composition according to claim 41, wherein When the non-volatile components in the resin composition are set to 100% by mass, the content of component (E) is 0.001% by mass or more.

44. The resin composition according to claim 41, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of component (E) is 1% by mass or more.

45. The resin composition according to claim 41, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of component (E) is 30% by mass or less.

46. The resin composition according to claim 41, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of component (E) is 3% by mass or less.

47. The resin composition according to claim 1 or 2, wherein, Further contains (F) elastomer.

48. The resin composition according to claim 47, wherein, Component (F) contains core-shell rubber particles.

49. The resin composition according to claim 47, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of the (F) component is 0.001% by mass or more.

50. The resin composition according to claim 47, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of the (F) component is 0.5% by mass or more.

51. The resin composition according to claim 47, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of the (F) component is 30% by mass or less.

52. The resin composition according to claim 47, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of the (F) component is 3% by mass or less.

53. The resin composition according to claim 1 or 2, wherein Further includes a (G) curing accelerator.

54. The resin composition according to claim 53, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of the (G) component is 0.01% by mass or more.

55. The resin composition according to claim 53, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of the (G) component is 0.5% by mass or more.

56. The resin composition according to claim 53, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of the (G) component is 15% by mass or less.

57. The resin composition according to claim 53, wherein When the non-volatile components in the resin composition are set to 100% by mass, the content of the (G) component is 2% by mass or less.

58. The resin composition according to claim 1 or 2, wherein When measured under the conditions of 5.8 GHz and 23 °C, the dielectric loss tangent (Df) of the cured product of the resin composition is 0.0200 or less.

59. The resin composition according to claim 1 or 2, wherein, When measured under the conditions of 5.8 GHz and 23 °C, the dielectric loss tangent (Df) of the cured product of the resin composition is 0.0030 or less.

60. The resin composition according to claim 1 or 2, wherein, When measured under the conditions of 5.8 GHz and 23 °C, the dielectric loss tangent (Df) of the cured product of the resin composition is 0.0027 or less.

61. A cured product which is a cured product of the resin composition according to any one of claims 1 to 60.

62. A sheet-like laminated material which contains the resin composition according to any one of claims 1 to 60.

63. A resin sheet having: a support, and a resin composition layer provided on the support and formed of the resin composition according to any one of claims 1 to 60.

64. A printed wiring board which includes an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 60.

65. A semiconductor device which includes the printed wiring board according to claim 64.

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