KR20190022480A - Resin composition, resin sheet, multilayer printed wiring board and semiconductor device - Google Patents

Abstract

A resin composition excellent in coating film property and heat resistance when used in a multilayer printed circuit board, excellent in plating adhesion and developability, a resin sheet on which a support is formed, a multilayer printed wiring board using the same, and a semiconductor device. (A), a photocuring initiator (B), a compound (C) represented by the following formula (2) and an ethylenically unsaturated group other than the component (C) (D).

Description

Resin composition, resin sheet, multilayer printed wiring board and semiconductor device

The present invention relates to a resin composition, a resin sheet using the resin composition, a multilayer printed wiring board, and a semiconductor device.

As a result of miniaturization and high density of the multilayered printed circuit board, studies for thinning the laminated board used for the multilayered printed circuit board have been actively conducted. With thinning, a thin resin layer is required for the insulating layer, and a resin sheet containing no glass cloth is required. The resin composition to be the material of the insulating layer is mainly composed of a thermosetting resin, and punching to obtain conduction between the insulating layers is generally performed by laser processing. In a resin sheet using a thermosetting resin, a method of forming a conductor circuit by copper plating is generally used as a method of forming a conductor circuit on an insulating layer.

On the other hand, hole drilling by laser machining has a problem that the processing time becomes longer as the number of holes increases in a high-density substrate. Therefore, in recent years, there has been a demand for a resin sheet which can be subjected to a hole punching process in a developing step by using a resin composition which is cured by a light beam or the like and is dissolved as a development. Further, since the conductor circuit is formed by copper plating on the insulating layer, a high copper plating adhesion property to the insulating layer is required so that the conductor circuit is not peeled off.

In the resin composition used for such a laminate or resin sheet, an alkali developing type is the mainstream, and an acrylate containing an acid anhydride group or a carboxyl group is used for enabling development. In addition, an epoxy resin is used because of copper plating adhesion. For example, Patent Document 1 discloses a resin composition comprising a carboxyl-modified epoxy (meth) acrylate resin obtained by reacting a bisphenol-type epoxy resin with (meth) acrylic acid and then reacting with an acid anhydride, a biphenyl-type epoxy resin, Discloses a photosensitive thermosetting resin composition containing an initiator and a diluent. Patent Document 2 discloses an epoxy resin composition which contains an epoxy resin, a curing agent, and a silica component whose surface is treated with a silane coupling agent and does not contain a curing accelerator, or a total of 100 wt% Wherein the average particle diameter of the silica particles is 1 占 퐉 or less and the surface treatment amount B (g (g)) of the silane coupling agent per 1 g of the silica particles in the silica component is not more than 3.5 parts by weight, (X) (C (g) / silica particle 1 g = [specific surface area of silica particle (m 2 / g) / minimum coated area of silane coupling agent (m 2 / g) ) Is in the range of 10 to 80% based on the value C (g) per 1 g of the silica particles calculated by the following formula (1).

Japanese Laid-Open Patent Publication No. 2005-62450 Japanese Laid-Open Patent Publication No. 2011-174082

However, conventional cured products using an epoxy resin can not provide sufficient physical properties, and there is a limit to the formation of a protective film having high copper plating adhesion and an interlayer insulating layer while having high developing property.

The cured product obtained from the resin composition described in Patent Document 1 is limited to an etching resist or a solder resist for a printed wiring board and has excellent flexibility and heat resistance. However, when used as an interlayer insulating layer, It was not enough.

The cured product obtained from the resin composition described in Patent Document 2 is excellent in copper plating adhesion, but since the punching is limited to the laser processing, it is impossible to perform the punching by the developing step.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described problems, and it is an object of the present invention to provide a resin composition which is excellent in film formability and heat resistance when used for a multilayer printed wiring board and has excellent developability and copper plating adhesion, A multilayer printed wiring board, and a semiconductor device.

The inventors of the present invention have found that a resin composition comprising a biphenylaralkyl type epoxy resin (A) represented by the following formula (1), a photocuring initiator (B), a compound (C) represented by the following formula (2) The present inventors have found out that the above problems can be solved by using a resin composition containing a compound (D) having an unsaturated group, and have completed the present invention.

[Chemical Formula 1]

(In the formula (1), n represents an integer of 0 to 15).

(2)

(In the formula (2), a plurality of R _{1 s} each independently represents a hydrogen atom or a methyl group, the plurality of R _{2 s} each independently represent a hydrogen atom or a hydrocarbon group of 1 to 22 carbon atoms which may have a substituent , And the plurality of R ₃ independently represent a substituent represented by the following formula (3), a substituent represented by the following formula (4) or a hydroxy group.

(3)

[Chemical Formula 4]

(In the formula (4), R ₄ represents a hydrogen atom or a methyl group.).

That is, the present invention includes the following contents.

(1) A photosensitive resin composition comprising a biphenylaralkyl type epoxy resin (A), a photo-curing initiator (B) represented by the formula (1), a compound (C) represented by the formula (2) (D) having an ethylenic unsaturated group other than the ethylenic unsaturated group.

[2] The resin composition according to [1], further comprising a maleimide compound (E).

[3] The resin composition according to [1] or [2], further comprising a filler (F).

(4) a cyanate ester compound, a phenol resin, an oxetane resin, a benzoxazine compound, and an epoxy resin different from the biphenylaralkyl type epoxy resin (A) represented by the above (1) The resin composition according to any one of [1] to [3], further containing a compound (G).

[5] The resin composition according to any one of [1] to [4], wherein the acid value of the compound (C) represented by the formula (2) is 30 mgKOH / g or more and 120 mgKOH / g or less.

[6] The resin composition according to any one of [1] to [5], wherein the content of the component (A) is 3 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition.

[7] The resin composition according to any one of [1] to [6], wherein the ethylenically unsaturated group-containing compound (D) is a compound having a (meth) acryloyl group and / or a compound having a vinyl group.

[8] The resin composition according to [8], wherein the filler (F) is selected from the group consisting of silica, boehmite, barium sulfate, silicone powder, fluororesin filler, urethane resin filler, acrylic resin filler, polyethylene filler, styrene- The resin composition according to [3], wherein the resin composition is at least one kind.

[9] The resin composition according to any one of [1] to [8], further comprising a thermosetting accelerator (H).

[10] The resin composition according to any one of [1] to [9], further comprising a naphthalene type epoxy resin represented by the following formula (5).

[Chemical Formula 5]

[11] The resin composition according to any one of [1] to [10], wherein the photocuring initiator (B) contains a phosphine oxide compound represented by the following formula (6).

[Chemical Formula 6]

(In the formula (6), R ₅ to R ₁₀ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁₁ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. ).

[12] A resin sheet having a support and a resin composition according to any one of [1] to [11], which is disposed on the surface of the support.

[13] A multilayer printed wiring board comprising the resin composition according to any one of [1] to [11].

[14] A semiconductor device comprising the resin composition according to any one of [1] to [11].

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a resin composition which is excellent in plating adhesion, film formability, heat resistance and developability and which is cured by an active energy ray having preferable physical properties for a multilayered printed circuit board, a resin sheet on which a support is formed, Device can be provided.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as " present embodiment ") will be described in detail. The following embodiments are illustrative of the present invention and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified and carried out within the scope of the gist of the present invention.

In the present specification, the term "(meth) acryloyl group" means both "acryloyl group" and "methacryloyl group" corresponding thereto, and "(meth) acrylate" Methacrylate " means both of " methacrylic acid " and " methacrylate ", and " (meth) acrylic acid " In the present embodiment, the term "resin solid component" or "resin solid component in the resin composition" refers to components other than the solvent and the filler in the resin composition, unless otherwise specified. The term "resin solid content 100 parts by mass" Means that the total amount of components in the resin composition excluding the solvent and the filler is 100 parts by mass.

The resin composition of the present embodiment is obtained by mixing the biphenylaralkyl type epoxy resin (A), the photo-curing initiator (B), the compounds (C) and (C) represented by the above formula (1) Of a compound (D) having an ethylenic unsaturated group. Hereinafter, each component will be described.

≪ Biphenylaralkyl type epoxy resin (A) represented by the formula (1) >

The biphenyl aralkyl type epoxy resin (A) (also referred to as component (A)) used in the present embodiment is a compound having a biphenyl aralkyl skeleton having the structure of the above formula (1). The cured product including the resin (A) can preferably form a protective film having excellent developing property and an interlayer insulating layer while having high copper plating adhesion.

In the formula (1), n represents an integer of 0 to 15. Preferably, it is an integer of 0 to 5 in terms of developability.

In the resin composition of the present embodiment, the content of the component (A) is not particularly limited, but from the viewpoint of improving the copper plating adhesion, the total content of the component (A), the component (C) More preferably 3 parts by mass or more, more preferably 4 parts by mass or more, and further preferably 5 parts by mass or more. Further, it is preferably 90 parts by mass or less, more preferably 89 parts by mass or less, and further preferably 88 parts by mass or less from the viewpoint of sufficiently curing and improving heat resistance.

The content of the component (A) in the resin composition of the present embodiment is not particularly limited, but is preferably 3 parts by mass or more based on 100 parts by mass of the resin solid content in the resin composition from the viewpoint of improving copper plating adhesion and developability More preferably 5 parts by mass or more, further preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more. It is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and most preferably 30 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition, from the viewpoint of sufficiently curing and improving heat resistance More preferably 28 parts by mass or less, and still more preferably 28 parts by mass or less.

For example, NC3000FH (n = 8 to 10 in the formula (1)), NC3000H (n = 2 to 5 in the formula (1)), NC3000L (formula (1) (N = 1 to 3 in the formula (1)), NC3000 (n = 1 to 3 in the formula (1)) and CER3000L .

These may be used singly or in a mixture of two or more.

≪ Photo-curing initiator (B)

The photo-curing initiator (B) (also referred to as component (B)) used in the present embodiment is not particularly limited, but those known in the field used as a photo-curable resin composition can be used.

Examples thereof include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, perchlorobenzoyl peroxide, Di-tert-butylphthalate, di-tert-butyl-di-perphthalate, and the like, acylphosphine oxides, acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy- 1-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2- 2-methylpyrrolidin-1-yl, methylthio) phenyl] -2-morpholino-propan- Anthraquinones such as ethyl anthraquinone, 2-t-butyl anthraquinone, 2-chloro anthraquinone and 2-amylanthraquinone, 2,4-diethyl thioxanthone, Xanthone and 2-chlorothioxanthone, ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bis Benzophenones such as methylaminobenzophenone, and the like; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Oxime esters such as octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)], and the like, and photoinitiators such as p-methoxyphenyldiazonium fluorophosphonate , Diazonium salts of Lewis acids such as N, N-diethylaminophenyldiazonium hexafluorophosphonate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroantimonate and the like, Triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, and the like, such as iodonium salt of triphenylsulfonium hexafluorophosphate, Cationic photopolymerization such as phosphonium salts of Lewis acids such as sulfonium salts of acid, triphenylphosphonium hexafluoroantimonate, other halides, triazine initiators, borate initiators, and other photoacid generators Initiators.

Examples of the acylphosphine oxides include phosphine oxide compounds represented by the following formula (6) such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl- Pin oxide, and the like. In particular, the phosphine oxide compound represented by the following formula (6) has a high UV absorption rate at a long wavelength and is excellent in reaching the inside of the resin with UV light. Therefore, the biphenyl aralkyl type epoxy resin (A), the compound (C), the compound (D) and the like according to the present embodiment can be suitably reacted to produce a resin sheet having superior heat resistance and a multilayer printed wiring board .

(7)

In formula (6), R ₅ to R ₁₀ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁₁ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms include linear or branched alkyl groups such as methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, sec- Branched alkyl group.

Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, a n-hexyl group, an isopropyl group, an isobutyl group, butyl group, neopentyl group, 1,1-dimethylpropyl group, 1,1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, 1 , 1-dimethylbutyl group, 1,1,3-trimethylbutyl group, and other linear or branched alkyl groups.

Examples of the aryl group having 6 to 20 carbon atoms include an unsubstituted aryl group such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group; Substituted aryl groups such as a tolyl group, a dimethylphenyl group, an isopropylphenyl group, a t-butylphenyl group, and a di-t-butylphenyl group.

Among them, from the viewpoints of reactivity suitable for the use of multilayer printed wiring boards and high reliability for metal conductors, it is preferable to use acylphosphine oxides such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) (6) is more preferable, and bis (2, 3) -bis (2, 3) is more preferable because acetophenone type radical photo- 4,6-trimethylbenzoyl) -phenylphosphine oxide is more preferable.

These photo-curing initiators (B) may be used alone or in combination of two or more, and both radical initiators and cation initiators may be used together.

In addition, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6- Irgacure (registered trademark) 369 (manufactured by BASF Japan), Irgacure (registered trademark) 819 (manufactured by BASF Japan) and Irgacure (registered by BASF Japan) can be used as a commercially available product, and trimethylbenzoyldiphenylphosphine oxide TPO (manufactured by BASF Japan Ltd.) is preferably used.

The content of the photo-curing initiator (B) in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of sufficiently curing the resin composition with an active energy ray to improve the heat resistance, Is preferably 0.1 part by mass or more, more preferably 0.2 parts by mass or more, and further preferably 0.3 part by mass or more based on 100 parts by mass of the total content of the components (C) and (D). Further, it is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less, from the viewpoint of inhibiting thermal curing after photo-curing and lowering heat resistance.

The content of the photo-curing initiator (B) in the resin composition of the present embodiment is not particularly limited, but is preferably 0.1 part by mass or more, more preferably 0.2 parts by mass or more per 100 parts by mass of the resin solid content in the resin composition More preferably 0.3 part by mass or more, further preferably 1 part by mass or more, and still more preferably 1.8 part by mass or more. It is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and most preferably 20 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition, from the viewpoint of inhibiting thermal curing after photo- More preferably not more than 10 parts by mass, still more preferably not more than 10 parts by mass.

≪ Compound (C) >

The compound (C) (also referred to as component (C)) used in the present embodiment is a compound represented by the above formula (2). The compound (C) may be used alone, or may include isomers such as structural isomers and stereoisomers, or two or more kinds of compounds having mutually different structures may be appropriately used in combination.

In the formula (2), a plurality of R ₁ each independently represents a hydrogen atom or a methyl group. Among them, it is preferable to include a hydrogen atom from the viewpoint of improving the reactivity of the photo-curing reaction, and more preferably all of R ₁ is a hydrogen atom.

The plurality of R ₂ independently represent a hydrogen atom or a hydrocarbon group of 1 to 22 carbon atoms which may have a substituent.

Examples of the hydrocarbon group include a linear or branched aliphatic hydrocarbon group of 1 to 22 carbon atoms, preferably 1 to 14 carbon atoms, and more preferably 1 to 10 carbon atoms; An alicyclic hydrocarbon group of 3 to 22 carbon atoms, preferably 3 to 14 carbon atoms, and more preferably 3 to 10 carbon atoms; Aromatic hydrocarbon groups of 6 to 22 carbon atoms, preferably 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms.

Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, a n-hexyl group, an isopropyl group, an isobutyl group, , Neopentyl group, 1,1-dimethylpropyl group, 1,1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, A linear or branched alkyl group such as a methyl group, a butyl group or a 1,1,3-trimethyl butyl group; A linear or branched alkenyl group such as a vinyl group, an allyl group or an isopropenyl group; A straight chain or branched alkynyl group such as an ethynyl group and a propargyl group.

The alicyclic hydrocarbon group includes, for example, cyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 1-methyl-1-cyclohexyl group and adamantyl group; And cyclic unsaturated hydrocarbon groups such as a cyclopentadienyl group, an indenyl group and a fluorenyl group.

Examples of the aromatic hydrocarbon group include an unsubstituted aryl group such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group; Substituted aryl groups such as a tolyl group, a dimethylphenyl group, an isopropylphenyl group, a t-butylphenyl group, and a di-t-butylphenyl group; And the like.

These hydrocarbon groups may be substituted with at least one hydrogen atom by another hydrocarbon group. Examples of the hydrocarbon group in which at least one hydrogen atom is substituted with another hydrocarbon group include an aryl group substituted alkyl group such as a benzyl group and a cumyl group, and a cyclic saturated hydrocarbon substituted alkyl group such as a cyclohexylmethyl group.

The hydrocarbon group having 1 to 22 carbon atoms which may have a substituent is preferably a linear or branched alkyl group.

The plurality of R ₂ preferably includes a methyl group from the viewpoint of improving the heat resistance of the cured product, more preferably all of R ₂ is a methyl group.

The plural R _{3 s} each independently represent a substituent represented by the formula (3), a substituent represented by the formula (4) or a hydroxy group. Among them, it is preferable to include a hydroxyl group from the viewpoint of improving the heat resistance. In the present embodiment, it is also preferable to use a compound (C) containing a substituent represented by the above formula (3) among a plurality of R ₃ from the viewpoint of improving developability. In the present embodiment, it is also preferable to use a compound (C) containing a substituent represented by the above formula (4) among a plurality of R ₃ from the viewpoint of improving the heat resistance. In the formula (4), R ₄ represents a hydrogen atom or a methyl group. Among them, a hydrogen atom is preferable from the viewpoint of improving the reactivity of the photo-curing reaction.

A plurality of R ₃ is, in view of improving the developing property, of the substituents, of all R ₃ above formula (3) ratio in the range of less than 98%, 20% or more of the substituent groups represented by the substituent represented by the formula (4) The ratio is in the range of 5% or more and 98% or less, and the ratio of the hydroxyl group is in the range of 10% or more and 98% or less (the sum of the proportion of these substituents is 100%). Among them, from the viewpoint of improving developability, it is particularly preferable that at least one of the plurality of R ₃ is a substituent represented by the formula (3).

The compound (C) preferably contains at least one of the following compounds (C1) to (C5) because it can improve the reactivity of the photo-curing reaction, the heat resistance and developability of the cured product, More preferably at least two kinds of (C1) to (C5), more preferably at least one of the compounds (C1) and (C2) to (C5) . As the compound (C), it is also preferable to include at least the compounds (C2) and (C3).

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

Such compounds may be commercially available products such as KAYARAD (registered trademark) ZCR-6001H, KAYARAD (registered trademark) ZCR-6002H, KAYARAD (registered trademark) ZCR-6006H, KAYARAD (registered trademark) ZCR- KAYARAD (registered trademark) ZCR-601H (trade name, manufactured by Nippon Kayaku Co., Ltd.) and the like.

In the resin composition of the present embodiment, the acid value of the compound (C) is preferably 30 mgKOH / g or more from the viewpoint of improving developability, and more preferably 50 mgKOH / g or more More preferable. The acid value of the compound (A) is preferably 120 mgKOH / g or less from the viewpoint of preventing dissolution by the developing solution after curing with an active energy ray, and from the viewpoint of preventing further dissolution, 110 mgKOH / g or less. The " acid value " in this embodiment represents a value measured by a method according to JIS K 0070: 1992.

In the resin composition of the present embodiment, the content of the compound (C) is not particularly limited, but from the viewpoint of curing the resin composition with an active energy ray, the content of the component (A), the component (C) ) Is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more based on 100 parts by mass. Further, it is preferably 99 mass parts or less, more preferably 98 mass parts or less, and further preferably 97 mass parts or less from the viewpoint of sufficiently curing with an active energy ray to improve heat resistance.

The content of the compound (C) in the resin composition of the present embodiment is not particularly limited, but is preferably 1 part by mass or more based on 100 parts by mass of the resin solid content in the resin composition from the viewpoint of curing the resin composition with an active energy ray More preferably 2 parts by mass or more, further preferably 3 parts by mass or more, further preferably 10 parts by mass or more, still more preferably 25 parts by mass or more , And most preferably 30 parts by mass or more. From the viewpoint of sufficiently curing with an active energy ray to improve the heat resistance, the content is preferably 99 parts by mass or less, more preferably 98 parts by mass or less, and most preferably 97 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. More preferably 90 parts by mass or less, still more preferably 75 parts by mass or less, and most preferably 72 parts by mass or less.

<Compound (D) having an ethylenically unsaturated group other than the component (C)> [

(D) (component (D)) having an ethylenically unsaturated group other than the component (C) is added to the resin composition of the present embodiment in order to increase the reactivity to an active energy ray (for example, ultraviolet rays) Quot;). The compound (D) having an ethylenically unsaturated group used in the present embodiment is not particularly limited so long as it is a compound other than the compound (C) represented by the formula (2) and having at least one ethylenic unsaturated group in one molecule, For example, a compound having a (meth) acryloyl group, a vinyl group or the like. These may be used singly or in a mixture of two or more.

Examples of the compound having a (meth) acryloyl group include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol Acrylates such as glycol (meth) acrylate monomethyl ether, phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (Meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, (Meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) (Meth) acrylate, bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, epsilon -caprolactone-modified hydroxypivalic acid neophenol glycol di Caprolactone-modified dipentaerythritol poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, ε-caprolactone modified dipentaerythritol hexa (meth) acrylate, ε-caprolactone modified dipentaerythritol poly (Meth) acrylate, ethylene oxide adduct thereof, pentaerythritol tri (meth) acrylate, and ethylene oxide adduct thereof, pentaerythritol tetra (meth) acrylate, Acrylate, dipentaerythritol hexa (meth) acrylate, and ethylene oxide adduct thereof.

In addition, urethane (meth) acrylates which have a (meth) acryloyl group and a urethane bond in the same molecule, and polyester (meth) acrylates which also have an acryloyl group and an ester bond in the same molecule , Epoxy (meth) acrylates derived from an epoxy resin and having a (meth) acryloyl group, reactive oligomers in which these bonds are used in combination, and the like.

The above-mentioned urethane (meth) acrylates are reaction products of hydroxyl group-containing (meth) acrylate and polyisocyanate and other alcohols which are optionally used. Examples thereof include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate, glycerin mono (meth) (Meth) acrylate such as glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (Meth) acrylates such as trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate and erythritol hexa (meth) acrylate, and aliphatic diols such as toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, Added xylylene diisocyanate, dicyclohexane methylene diisocyanate, and their di Such as by reacting a polyisocyanate such as a cyanurate, biuret reagent, and a urethane (meth) acrylates.

Examples of the polyester (meth) acrylates include caprolactone modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide modified phthalic acid (meth) acrylate, ethylene oxide modified succinic acid (Poly) ester (meth) acrylates such as caprolactone-modified tetrahydrofurfuryl (meth) acrylate and caprolactone-modified tetrahydrofurfuryl (meth) acrylate; (Poly (meth) acrylates) such as hydroxypivalic acid esters neopentyl glycol di (meth) acrylate, caprolactone-modified hydroxy diacid ester neopentyl glycol di (meth) acrylate and epichlorohydrin modified phthalic acid di ) Ester (meth) acrylates; Mono-, di- or tri (meth) acrylate of a triol obtained by adding 1 mol or more of a cyclic lactone compound such as? -Caprolactone,? -Butyrolactone, or? -Valerolactone to 1 mol of trimethylolpropane or glycerin .

Further, a mono, di-triol of triol obtained by adding at least 1 mol of a cyclic lactone compound such as? -Caprolactone,? -Butyrolactone, or? -Valerolactone to 1 mole of pentaerythritol or ditrimethylolpropane Or a triol obtained by adding tetra (meth) acrylate, a cyclic lactone compound such as? -Caprolactone,? -Butyrolactone, or? -Valerolactone in an amount of 1 mole or more per mole of dipentaerythritol, or Mono (meth) acrylate or poly (meth) acrylate of polyhydric alcohols such as triols of poly (meth) acrylate, tetraol, pentanol or hexanol.

Further, it is also possible to use a diol component such as (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, 3-methyl-1,5-pentanediol, Examples of the reaction product with a polybasic acid such as acid, fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimeric acid, sebacic acid, azelaic acid, 5-sodium sulfoisophthalic acid, (Meth) acrylates of polyester polyols; (Poly) esters such as (meth) acrylates of a cyclic lactone-modified polyester diol composed of the diol component, a polybasic acid, and an anhydride thereof, and? -Caprolactone,? -Butyrolactone, (Meth) acrylates, and the like, but are not limited thereto.

The epoxy (meth) acrylates are carboxylate compounds of a compound having an epoxy group and a (meth) acrylic acid. Examples of the epoxy (meth) acrylate include phenol novolak type epoxy (meth) acrylate, cresol novolak type epoxy (meth) acrylate, trishydroxyphenyl methane type epoxy (meth) acrylate, dicyclopentadiene phenol type epoxy (Meth) acrylate, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, biphenol type epoxy (meth) acrylate, bisphenol A novolak type epoxy ) Acrylate, glyoxylic epoxy (meth) acrylate, heterocyclic epoxy (meth) acrylate, and acid anhydride-modified epoxy acrylates thereof.

Examples of the compound having a vinyl group include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of the styrene include styrene, methylstyrene, ethylstyrene, and divinylbenzene. Other examples of the vinyl compound include triallyl isocyanurate, trimethallyl isocyanurate, bisallylnadimide, and the like.

Among them, from the viewpoint of heat resistance, epoxy resins such as pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, cresol novolak epoxy (meth) acrylate, bisphenol A epoxy (meth) (Meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate, and bisallylnadiimide, and more preferably is dipentaerythritol hexa (meth) acrylate in that the heat resistance is improved . By including a compound having such an ethylenic unsaturated group, the heat resistance of the obtained cured product tends to be further improved.

The content of the ethylenically unsaturated group-containing compound (D) other than the component (C) in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of improving the developability, Is preferably 0.5 part by mass or more, more preferably 1.0 part by mass or more, and further preferably 1.5 parts by mass or more based on 100 parts by mass of the total content of the components (C) and (D). Further, from the viewpoint of improving the heat resistance of the cured product, the amount is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, and further preferably 50 parts by mass or less.

In the resin composition of the present embodiment, the content of the compound (D) is not particularly limited, but it is preferably 0.5 part by mass or more based on 100 parts by mass of the resin solid content in the resin composition More preferably 1.0 part by mass or more, further preferably 1.5 parts by mass or more, further preferably 5.0 parts by mass or more, and most preferably 10 parts by mass or more. From the viewpoint of improving the heat resistance of the cured product, the amount is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, and most preferably 50 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition More preferably 25 parts by mass or less, and most preferably 20 parts by mass or less.

&Lt; Maleimide compound (E) &gt;

In the resin composition of the present embodiment, the maleimide compound (E) (also referred to as component (E)) can be used. Hereinafter, the maleimide compound (E) will be described in detail.

The maleimide compound (E) used in the present embodiment is not particularly limited so long as it is a compound having at least one maleimide group in the molecule. Specific examples thereof include, for example, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) 4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, Bis (3, 5-diethyl-4-maleimidephenyl) methane, phenylmethane maleimide, o-phenylene bismaleimide, m- phenylene bismaleimide, Bis (4- (4-maleimidophenoxy) -phenyl) propane, 3,3-bis (p-phenylenebisetracycline) Dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide- (2,2,4- Trimethyl) hexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenylsulfone bismaleimide, 1,3-bis (3-maleimide Phenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, 4,4-diphenylmethane bis-citraconimide, 2,2-bis [4- ) Phenyl] propane, bis (3,5-dimethyl-4-citraconimidophenyl) methane, bis (3-ethyl- Maleimide compound represented by the following formula (7), a compound represented by the following formula (8), and a maleimide compound represented by the following formula (7) , And prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds, and the like.

Of these, novolak-type maleimide compounds and biphenylaralkyl-type maleimide compounds are particularly preferred. The maleimide compound represented by the following formula (7) and the maleimide compound represented by the following formula (8) are preferable from the viewpoint of obtaining a good film-like property and excellent heat resistance, and the maleimide represented by the following formula (7) Compounds are more preferable. As the maleimide compound represented by the following formula (7), a commercially available product may be used. For example, BMI-2300 (manufactured by Taiwasan Kogyo Co., Ltd.) can be used. As the maleimide compound represented by the following formula (8), a commercially available product may be used, and for example, MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.) can be used.

These maleimide compounds (C) may be used singly or in a mixture of two or more.

[Chemical Formula 13]

(In the formula (7), a plurality of R ₅ each independently represents a hydrogen atom or a methyl group.) N ₁ represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably 1 Represents an integer of 1 to 5).

[Chemical Formula 14]

(In the formula (8), a plurality of R ₆ each independently represents a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more, preferably an integer of 1 to 5).

These maleimide compounds (E) may be used alone or in combination of two or more.

The content of the maleimide compound (E) in the resin composition of the present embodiment is not particularly limited. From the viewpoint of sufficiently curing the resin composition and improving the heat resistance, the content of the maleimide compound (E) More preferably 0.02 part by mass or more, and still more preferably 0.03 part by mass or more based on 100 parts by mass of the total content of the component (A) and the component (D). From the viewpoint of improving developability, the amount is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and further preferably 40 parts by mass or less.

In the resin composition of the present embodiment, the content (E) of the maleimide compound is not particularly limited and is preferably 0.01 part by mass to 50 parts by mass, more preferably 0.02 mass parts per 100 parts by mass of the resin solid content More preferably from 0.03 mass parts to 20 mass parts, still more preferably from 0.1 mass parts to 10 mass parts, and most preferably from 1 mass part to 7 mass parts. When the content of the maleimide compound is within the above range, the heat resistance of the cured product tends to be further improved.

&Lt; Filler (F) &gt;

The resin composition of the present embodiment can also be used in combination with filler (F) (also referred to as component (F)) in order to improve various properties such as coatability and heat resistance. The filler (F) used in the present embodiment is not particularly limited as long as it has an insulating property. Examples of the filler include fillers such as silica (for example, natural silica, fused silica, amorphous silica, hollow silica, (E.g., magnesium hydroxide, magnesium hydroxide, etc.), calcium compounds (e.g., calcium carbonate), molybdenum compounds (e.g., molybdenum oxide, zinc molybdate, etc.) ), Barium compounds (such as barium sulfate and barium silicate), talc (e.g. natural talc, plastic talc, etc.), mica (mica), glass (for example monofilament glass, spherical glass, (For example, E glass, T glass, D glass, etc.), silicone powder, fluorocarbon resin filler, urethane resin filler, acrylic resin filler, polyethylene filler, styrene / butadiene Rubber and silicone rubber.

Among them, at least one selected from the group consisting of silica, boehmite, barium sulfate, silicone powder, fluororesin-based filler, urethane resin filler, acrylic resin filler, polyethylene filler, styrene-butadiene rubber and silicone rubber is preferable.

These fillers (F) may be surface-treated with a silane coupling agent or the like to be described later.

Particularly, from the viewpoint of improving the heat resistance of the cured product and obtaining good coatability, silica is preferable, and fused silica is particularly preferable. Specific examples of silica include SC2050-MB, SC1050-MLE, YA010C-MFN, and YA050C-MJA manufactured by Admatech Co., Ltd., such as SFP-130MC manufactured by DENKA CO., LTD.

These fillers (F) may be used singly or in a mixture of two or more.

In the resin composition of the present embodiment, the content of the filler (F) is not particularly limited, but it is preferably 5 parts by mass or more based on 100 parts by mass of the resin solid content in the resin composition from the viewpoint of improving the heat resistance of the cured product More preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more. From the viewpoint of improving the developability of the resin composition, the amount is preferably 400 parts by mass or less, more preferably 350 parts by mass or less, and most preferably 300 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition More preferably 200 parts by mass or less, and most preferably 100 parts by mass or less.

<Silane coupling agent and wet dispersant>

A silane coupling agent and / or a wetting and dispersing agent may be used in combination in the resin composition of the present embodiment in order to improve the dispersibility of the filler, the polymer and / or the resin, and the bonding strength of the filler.

These silane coupling agents are not particularly limited as long as they are silane coupling agents generally used for surface treatment of an inorganic material. Specific examples include aminosilanes such as? -Aminopropyltriethoxysilane and N -? - (aminoethyl) -? - aminopropyltrimethoxysilane; epoxy silane type such as? -glycidoxypropyltrimethoxysilane; acrylsilane type such as? -acryloxypropyltrimethoxysilane; N-β- (N-vinylbenzylaminoethyl) - γ-aminopropyltrimethoxysilane hydrochloride; Phenyl silane-based silane coupling agents. These silane coupling agents may be used singly or in combination of two or more.

In the resin composition of the present embodiment, the content of the silane coupling agent is not particularly limited, but is usually 0.1 to 10 parts by mass based on 100 parts by mass of the resin composition.

The wetting and dispersing agent is not particularly limited so long as it is a dispersion stabilizer used for coating. Specific examples include wet dispersants such as DISPERBYK (registered trademark) -110, 111, 118, 180, 161, BYK (registered trademark) -W996, W9010, W903 manufactured by Big Chem Japan Co., . These wetting and dispersing agents may be used singly or in a mixture of two or more kinds.

In the resin composition of the present embodiment, the content of the wetting and dispersing agent is not particularly limited, but is usually 0.1 to 10 parts by mass based on 100 parts by mass of the resin composition.

At least one compound selected from the group consisting of a cyanate ester compound, a phenol resin, an oxetane resin, a benzoxazine compound, and an epoxy resin different from the biphenylaralkyl type epoxy resin (A) represented by the above (1) G)>

The compound (G) (also referred to as component (G)) to be used in the present embodiment is excellent in flame retardancy, heat resistance and heat resistance of the cured cured product required in the fields where the resin composition is used in addition to the copper plating adhesion property obtained by using the component , Thermal expansion characteristics, and the like. For example, when heat resistance is required, a cyanic acid ester compound, a benzoxazine compound, and the like can be used, and a phenol resin, an oxetane resin, and the like can also be used. (Glass transition temperature), low thermal expansion property, and plating adhesion property can be obtained by using the cyanate ester compound together with the biphenylaralkyl type epoxy resin (A), the photo-curing initiator (B), the compound (C) And the like can be obtained. When a cyanate ester compound is used in combination with a maleimide compound, a resin composition having better plating adhesion can be obtained. When an epoxy resin different from the epoxy resin (A) is used together with the biphenylaralkyl type epoxy resin (A) represented by the above-mentioned (1), a resin composition excellent in developability and plating adhesion can be obtained.

These may be used singly or in a mixture of two or more kinds.

Hereinafter, details of these compounds and / or resin (G) will be described.

<Cyanate ester compound>

The cyanate ester compound is not particularly limited as long as it is a resin having an aromatic moiety in which at least one cyano group (cyanate ester group) is substituted.

For example, those represented by the general formula (9).

[Chemical Formula 15]

In the formula (9), Ar ₁ represents a benzene ring, a naphthalene ring or two benzene rings bonded together. When there are a plurality of them, they may be the same or different. Ra represents independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms and an alkyl group having 1 to 6 carbon atoms. The aromatic ring in Ra may have a substituent, and arbitrary positions of substituents in Ar ₁ and Ra may be selected. p is the number of cyano or earthenware binding to Ar _1, each independently represent an integer of 1-3. q represents the number of Ra bonded to Ar ₁ , and when Ar ₁ is a benzene ring, it is 4 - p, when it is a naphthalene ring, it is 6 - p, and when two benzene rings are only bonded, it is 8 - p. t represents an average number of repeats and is an integer of 0 to 50, and the cyanate ester compound may be a mixture of compounds differing in t. X represents a single bond, a divalent organic group having 1 to 50 carbon atoms (hydrogen atom may be substituted with a hetero atom), a divalent organic group having 1 to 10 nitrogen atoms (for example, -NRN - (wherein R represents an organic group), a carbonyl group (-CO-), a carboxy group (-C (= O) O-), a carbonyldioxide group (-OC ₂ -), a divalent sulfur atom or a divalent oxygen atom.

The alkyl group in Ra in the general formula (9) may have a linear or branched chain structure and a cyclic structure (for example, a cycloalkyl group or the like).

The alkyl group in the general formula (9) and the hydrogen atom in the aryl group in Ra are substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, a cyano group or the like .

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, , A cyclopentyl group, a hexyl group, a cyclohexyl group, and a trifluoromethyl group.

Specific examples of the aryl group include a phenyl group, a xylyl group, a mesityl group, a naphthyl group, a phenoxyphenyl group, an ethylphenyl group, an o-, m- or p-fluorophenyl group, a dichlorophenyl group, a dicyanophenyl group, A methoxyphenyl group, and an o-, m- or p-tolyl group. Examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group and a tert-butoxy group.

Specific examples of the divalent organic group having 1 to 50 carbon atoms represented by X in the general formula (9) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, A biphenylmethylene group, a dimethylmethylene-phenylene-dimethylmethylene group, a fluorenediyl group, and a phthalidyl group. The hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, or a cyano group.

Examples of the divalent organic group having 1 to 10 nitrogen atoms in X in the general formula (9) include an imino group and a polyimide group.

Examples of the organic group represented by X in the general formula (9) include those represented by the general formula (10) or the general formula (11) shown below.

[Chemical Formula 16]

In the formula (10), Ar ₂ represents a benzenetetrayl group, a naphthalenetetrayl group or a biphenyltetrayl group, and when u is 2 or more, they may be the same or different. Rb, Rc, Rf and Rg each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or an aryl group having at least one phenolic hydroxy group. Rd and Re are each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, or a hydroxyl group. u represents an integer of 0 to 5;

[Chemical Formula 17]

In the formula (11), Ar ₃ represents a benzenetetrayl group, a naphthalenetetrayl group or a biphenyltetrayl group, and when v is 2 or more, they may be the same or different. Ri and Rj each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxyl group having 1 to 4 carbon atoms, a hydroxyl group, a trifluoromethyl group, Represents an aryl group substituted with at least one substituent. v represents an integer of 0 to 5, but may be a mixture of compounds in which v is different.

As X in the general formula (9), a divalent group represented by the following formula may be mentioned.

[Chemical Formula 18]

Here, z represents an integer of 4 to 7. Rk each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Specific examples of Ar _{2 in the} general formula (10) and Ar _{3 in} the general formula (11) are those wherein two carbon atoms represented by the general formula (10) or two oxygen atoms represented by the general formula (11) A benzene tetrayl group bonded to the 4-position or the 1,3-position, the above-mentioned two carbon atoms or two oxygen atoms are bonded at the 4,4 'position, the 2,4' position, the 2,2 ' A biphenyltetrayl group which is bonded at the 3 'position or the 3,4' position, and the two carbon atoms or two oxygen atoms are bonded at the 2,6 position, 1,5 position, 1,6 position, 1,8 position , A 1,3-position, a 1,4-position, or a 2,7-position naphthalenetetrayl group.

The alkyl group and the aryl group in Rb, Rc, Rd, Re, Rf and Rg in the general formula (10) and Ri and Rj in the general formula (11) have the same meanings as in the general formula (9).

Specific examples of the cyanato-substituted aromatic compound represented by the general formula (9) include cyanato benzene, 1-cyanato-2-, 1-cyanato- 1-cyanato-2-, 1- cyanato-3-, or 1- cyanato-4-methoxybenzene, 1- cyanato- Cyanato-2,6-, 1-cyanato-3,4- or 1-cyanato-3,5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, (4-cyanophenyl) -2-phenylpropane (cyanate of 4-a-cumylphenyl), 1-cyanato-4-cyclohexylbenzene, 1- 4-vinylbenzene, 1-cyanato-2- or 1-cyanato-3-chlorobenzene, 1-cyanato-2,6-dichlorobenzene, 1-cyanato- Benzene, cyanato nitrobenzene, 1-cyanato-4-nitro-2-ethylbenzene, 1-cyanato-2-methoxy-4-allylbenzene (cyanate of augenol) Phenyl) sulphate Cyanatobenzaldehyde, 4-cyanatobenzaldehyde, 4-cyanatobenzaldehyde, 4-cyanatobenzaldehyde, Cyanatobenzoic acid phenyl ester, 1-cyanato-4-acetaminobenzene, 4-cyanatobenzophenone, 1-cyanato-2,6-di-tert- Dianatobenzene, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,4-dicyanato-2-tert-butylbenzene, 1,4- Dimethylbenzene, 1,4-dicyanato-2,3,4-dimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyano- 4-methoxynaphthalene, 2-cyanato-6-methylnaphthalene, 2-cyanato-7-methoxynaphthalene, 2,2'-dicyano 1,1'-binaphthyl, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7- Dicyanatobinaphthalene, 2,2'- or 4,4'-dicyanatobiphenyl, 4, (4-cyanato-3,5-dimethylphenyl) methane, 1,1-bis (4-cyanato-3,5-dimethylphenyl) Bis (4-cyanatophenyl) propane, 2,2-bis (4-cyanato-3-methylphenyl) Bis (4-cyanatophenyl) hexafluoropropane, 2,2-bis (4-cyanato- Bis (4-cyanatophenyl) butane, 1,1-bis (4-cyanatophenyl) isobutane, 1,1- Bis (4-cyanatophenyl) -3-methylbutane, 1,1-bis (4-cyanatophenyl) Bis (4-cyanatophenyl) pentane, 2,2-bis (4-cyanatophenyl) pentane, 2,2- Bis (4-cyanatophenyl) -3-methylbutane, 2,2-bis (4-cyanatophenyl) Bis (4-cyanatophenyl) hexane, 3,3-bis (4-cyanatophenyl) heptane, 3,3-bis Bis (4-cyanatophenyl) -2-methylhexane, 3,3-bis (4-cyanatophenyl) 4-cyanatophenyl) -3-methylheptane, 3,3-bis (4-cyanatophenyl) -2-methylheptane, Bis (4-cyanatophenyl) -2,2-dimethylhexane, 3,3-bis (4-cyanatophenyl) Phenyl) -2,2,4-trimethylpentane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, bis (4-cyanatophenyl) Bis (4-cyanatophenyl) cyclopentane, 1,1-bis (4-cyanatophenyl) 1-bis (4-cyanatophenyl) cyclohexane, 2,2-bis (4-cyanato-3-isopropylphenyl) propane, (4-cyanatophenyl) diphenylmethane, bis (4-cyanatophenyl) -2,2-dichloroethylene, 1,3-bis [2- Propyl] benzene, 1,1-bis (4-cyanatophenyl) -3,3,5-trimethylcyclohexane, Bis (4-cyanatophenyl) methyl] biphenyl, 4,4-dicyanatobenzophenone, 1,3-bis (4-cyanatophenyl) Cyanatophenyl) sulfone, 4-cyanatobenzoic acid-4-cyanatophenyl ester (4-cyanatophenyl) sulfide, bis Bis (4-cyanatophenyl) carbonate, 1,3-bis (4-cyanatophenyl) adamantane, 1,3- (4-cyanatophenyl) isobenzofuran-1 (3H) -one (cyanate of phenolphthalein), 3,3-bis (4-cyanato- Benzofuran-1 (3H) -one (o-cresol (4-cyanatophenyl) fluorene, 9,9-bis (4-cyanato-3-methylphenyl) fluorene, 9,9-bis (4-cyanatophenyl) methane, 1,1,1-tris (4-cyanatophenyl) ethane, 1,1,3-tris (4-cyanatophenyl) ) Propane, α, α, α'-tris (4-cyanatophenyl) -1-ethyl-4-isopropylbenzene, 1,1,2,2-tetrakis (4-cyanatophenyl) methane, 2,4,6-tris (N-methyl-4-cyanatoanilino) Cyanato anilino) -6- (N-methylanilino) -1,3,5-triazine, bis (N-4-cyanato-2-methylphenyl) -4,4'- Bis (N-3-cyanato-4-methylphenyl) -4,4'-oxydipallimide, bis -4-cyanato-2-methylphenyl) -4,4 '- (hexafluoroisopropylidene) diphthalimide, tris (3,5- (4-cyanatophenyl) phthalimidine, 2- (4-methylphenyl) -3,3-bis (4-cyanatophenyl) phthalate Phenyl-3,3-bis (4-cyanato-3-methylphenyl) phthalimidine, 1-methyl-3,3-bis (4-cyanatophenyl) indolin- , 2-phenyl-3,3-bis (4-cyanatophenyl) indolin-2-one.

These cyanate ester compounds may be used singly or in combination of two or more.

Other examples of the cyanic acid ester compound represented by the general formula (9) include phenol novolac resins and cresol novolak resins (phenol, alkyl-substituted phenol or halogen-substituted phenol, (Obtained by reacting a formaldehyde compound such as paraformaldehyde in an acidic solution), a trisphenol novolac resin (obtained by reacting hydroxybenzaldehyde with phenol in the presence of an acid catalyst), a fluoren novolac resin A phenol aralkyl resin, a cresol aralkyl resin, a naphthol aralkyl resin and a biphenyl aralkyl resin (obtained by reacting 9,9-bis (hydroxyaryl) fluorenes in the presence of an acidic catalyst) , Ar ₄ - (CH ₂ Y) ₂ (Ar ₄ represents a phenyl group and Y represents a halogen atom, hereinafter the same in this paragraph) Reacting a methyl compound with a phenol compound with an acidic catalyst or without a catalyst, reacting a bis (alkoxymethyl) compound represented by Ar ₄ - (CH ₂ OR) ₂ with a phenol compound in the presence of an acidic catalyst, (Hydroxymethyl) compound represented by Ar ₄ - (CH ₂ OH) ₂ and a phenol compound in the presence of an acidic catalyst, or an aromatic aldehyde compound, an aralkyl compound and a phenol compound ), A phenol-modified xylene formaldehyde resin (obtained by reacting a xylene formaldehyde resin with a phenol compound in the presence of an acid catalyst by a known method), a modified naphthalene formaldehyde resin (obtained by reacting naphthalene formaldehyde A resin obtained by reacting a resin and a hydroxy-substituted aromatic compound in the presence of an acidic catalyst), a phenol-modified dicyclopentadiene resin, a polynaphthylene ether (A polyhydric hydroxy naphthalene compound having two or more phenolic hydroxy groups in one molecule by a known method, which has been dehydrated and condensed in the presence of a basic catalyst) can be used in the same manner as the above description And the like, and prepolymers thereof, and the like. These are not particularly limited. These cyanate ester compounds may be used singly or in combination of two or more.

Among them, a phenol novolak type cyanic acid ester compound, a naphthol aralkyl type cyanic acid ester compound, a biphenyl aralkyl type cyanic acid ester compound, a naphthylene ether type cyanic acid ester compound, a xylene type cyanic acid ester compound, But a skeleton-type cyanate ester compound is preferable, and a naphthol aralkyl-type cyanate ester compound is particularly preferable in that excellent plating adhesion can be obtained while maintaining excellent heat resistance.

The method for producing these cyanate ester compounds is not particularly limited, and known methods can be used. An example of such a production method is a method of obtaining or synthesizing a hydroxy group-containing compound having a desired skeleton and modifying the hydroxy group by a known method to cyanate. As a method for cyanating a hydroxy group, for example, the method described in Ian Hamerton, " Chemistry and Technology of Cyanate Ester Resins, " Blackie Academic & Professional.

The resin cured products using these cyanate ester compounds have excellent properties such as glass transition temperature, low thermal expansion property, and plating adhesion.

In the resin composition of the present embodiment, the content of the cyanate ester compound is not particularly limited, but is preferably 0.01 part by mass to 50 parts by mass, based on 100 parts by mass of the resin solid content, from the viewpoint of obtaining better plating adhesion and heat resistance. More preferably 0.05 parts by mass to 40 parts by mass, still more preferably 0.1 parts by mass to 20 parts by mass, still more preferably 0.2 parts by mass to 5 parts by mass.

<Phenolic resin>

As the phenol resin, a generally known one can be used as long as it is a phenol resin having at least two hydroxyl groups in one molecule. For example, there may be mentioned bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolak resin, bisphenol A novolak type phenol resin, glycidyl ester type phenol resin, Naphthalene novolak resins, polyfunctional naphthol resins, anthracene-type phenol resins, naphthalene skeleton-modified novolacs, naphthalene skeleton-modified phenolic resins, Type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, phosphorus containing phenol resin, A hydrocarbon group-containing phenol resin, and a hydroxyl group-containing silicone resin. However, the present invention is not limited thereto. Among these phenol resins, a biphenylaralkyl type phenol resin, a naphthol aralkyl type phenol resin, a phosphorus containing phenol resin and a hydroxyl group containing silicone resin are preferable in view of flame retardancy. These phenol resins may be used singly or in a mixture of two or more.

The content of the phenol resin is not particularly limited and is preferably 0.1 part by mass to 50 parts by mass, more preferably 0.2 part by mass to 45 parts by mass, based on 100 parts by mass of the resin solid content. When the content of the phenol resin is within the above range, the heat resistance tends to be further improved.

<Oxetane Resin>

As the oxetane resin, generally known ones can be used. For example, alkyloxetanes such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane and 3,3-dimethyloxetane, 3-methyl- Cetane, 3,3-di (trifluoromethyl) perfluoroctane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl type oxetane, OXT- (Trade name), OXT-121 (trade name, manufactured by TOA Corporation), and the like. These may be used alone or in combination of two or more.

The content of the oxetane resin is not particularly limited and is preferably 0.1 part by mass to 50 parts by mass, more preferably 0.2 parts by mass to 45 parts by mass, based on 100 parts by mass of the resin solid content. When the content of the oxetane resin is within the above range, the heat resistance tends to be further improved.

<Benzoxazine Photographic Compound>

As the benzoxazine compound, any compound having two or more dihydrobenzoxazine rings in a molecule may be used. For example, bisphenol A type benzoxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd.) bisphenol F type benzoxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd.), bisphenol S type benzoxazine BS-BXZ , Trade name), phenolphthalein type benzoxazine, and the like, but there is no particular limitation. These may be used singly or in a mixture of two or more.

The content of the benzoxazine compound is not particularly limited and is preferably 0.1 part by mass to 50 parts by mass, more preferably 0.2 part by mass to 45 parts by mass, based on 100 parts by mass of the resin solid content. When the content of the benzoxazine compound is within the above range, the heat resistance tends to be further improved.

&Lt; Epoxy resin &

In order to improve the heat resistance of the cured product, the resin composition of the present embodiment may be used in combination with an epoxy resin different from the biphenylaralkyl type epoxy resin (A) represented by the above (1).

Such an epoxy resin is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule, unlike the epoxy resin (A). Specific examples thereof include, for example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, Naphthalene skeleton-modified novolac epoxy resin, naphthylene ether-type epoxy resin, phenol aralkyl-type epoxy resin, phenolic aralkyl-type epoxy resin, Type epoxy resin, trifunctional phenol-type epoxy resin, tetrafunctional phenol-type epoxy resin, triglycidylisocyanurate, glycidyl ester-type epoxy resin, alicyclic epoxy resin, dicyclopentadiene novolak Type epoxy resin, biphenyl novolak type epoxy resin, phenol aralkyl novolak type epoxy resin, naphthol aralkyl novolak type Epoxidized double bonds such as epoxy resins, aralkyl novolak type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, polyol type epoxy resins, phosphorus containing epoxy resins, glycidyl amines and butadiene Compounds obtained by reacting epichlorohydrin with a hydroxyl group-containing silicone resin, and halides thereof.

Among them, at least one selected from the group consisting of naphthylene ether type epoxy resin, polyfunctional phenol type epoxy resin and naphthalene type epoxy resin is preferable, and naphthalene type epoxy resin is more preferable. The inclusion of such an epoxy resin tends to further improve developability and plating adhesion.

As the naphthalene type epoxy resin, it is preferable to use a resin represented by the following formula (5) because the developability and the plating adhesion are further improved. As this epoxy resin, a commercially available product can be used, and HP-4710 (trade name) manufactured by DIC Corporation can be mentioned. The naphthalene type epoxy resin represented by the following formula (5) is low in molecular weight and polyfunctional, and therefore has excellent solubility in a developing solution. Therefore, it is considered that a resin composition having excellent developability can be obtained by using in combination with the biphenylaralkyl type epoxy resin (A).

[Chemical Formula 19]

These epoxy resins may be used singly or in a mixture of two or more.

The content of the epoxy resin is not particularly limited, but from the viewpoint of further improving the developability, the total amount of the epoxy resin (A) and the epoxy resin different from the epoxy resin (A) relative to 100 parts by mass of the resin solid content in the resin composition , Preferably 3 parts by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more. From the viewpoint of further improving copper plating adhesion, it is preferable that the total amount of the epoxy resin (A) and the epoxy resin different from the epoxy resin (A) is 50 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition More preferably 40 parts by mass or less, further preferably 30 parts by mass or less, further preferably 28 parts by mass or less.

The ratio of the epoxy resin (A) to the epoxy resin (A) and the epoxy resin different from the epoxy resin is not particularly limited, but is preferably 1 to 10: 1 to 3, more preferably 2: 4: 2 is more preferable.

&Lt; Thermal curing accelerator (H) &gt;

In the resin composition of the present embodiment, it is also possible to use a thermosetting accelerator (H) (also referred to as component (H)) within a range in which the characteristics of the present embodiment are not impaired. The heat curing accelerator (H) used in the present embodiment is not particularly limited, and examples thereof include benzoyl peroxide, lauroyl peroxide, acetyl peroxide, para-chlorobenzoyl peroxide, di-tert- Organic peroxides exemplified by phthalates and the like; Azo compounds such as azobisnitrile; N, N-dimethylaniline, N, N-dimethyltoluidine, 2-N-ethylanilino ethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine , Tertiary amines such as triethylenediamine, tetramethylbutanediamine and N-methylpiperidine; Phenols such as phenol, xylenol, cresol, resorcin and catechol; Organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate and iron acetyl acetone; Those obtained by dissolving these organic metal salts in a hydroxyl group-containing compound such as phenol and bisphenol; Inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; Organic tin compounds such as dioctyltin oxide, other alkyltin, and alkyltin oxide; Imidazole compounds such as 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-phenylimidazole and triphenylimidazole (TPIZ). Among them, imidazole compounds such as 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-phenylimidazole and triphenylimidazole (TPIZ) Ethyl-4-methylimidazole is preferred because of its high reactivity with the biphenylaralkyl type epoxy resin (A), the compound (C) and the compound (D) .

These thermal curing accelerators may be used alone or in combination of two or more.

In the resin composition of the present embodiment, the content of the thermosetting accelerator (H) is not particularly limited, but is usually 0.01 to 10 parts by mass, preferably 0.05 to 10 parts by mass, per 100 parts by mass of the resin solid content in the resin composition. 5 parts by mass.

<Organic solvents>

The resin composition of the present embodiment may contain a solvent as required. For example, when an organic solvent is used, the viscosity at the time of preparing the resin composition can be adjusted. The type of the solvent is not particularly limited as long as it can dissolve a part or all of the resin in the resin composition. Specific examples thereof include, but are not limited to, ketones such as acetone, methyl ethyl ketone and methyl cellosolve; Aromatic hydrocarbons such as toluene and xylene; Amides such as dimethylformamide; Propylene glycol monomethyl ether and its acetate.

These organic solvents may be used singly or in a mixture of two or more.

&Lt; Other components &gt;

The resin composition of the present embodiment may contain various polymeric compounds such as thermosetting resins, thermoplastic resins and oligomers and elastomers, etc., which have not been heretofore described, within the range in which the characteristics of the present embodiment are not impaired; Flame retardant compounds which have not been illustrated so far; Additives and the like can be used in combination. These are not particularly limited as long as they are generally used. Examples of the flame retardant compound include nitrogen-containing compounds such as melamine and benzoguanamine, compounds containing an oxazine ring, phosphate compounds of phosphorus compounds, aromatic condensed phosphoric acid esters, and halogenated condensed phosphoric acid esters. Examples of the additives include ultraviolet absorbers, antioxidants, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, surface conditioners, polishes, polymerization inhibitors and the like. These components may be used singly or in combination of two or more.

In the resin composition of the present embodiment, the content of the other components is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.

&Lt; Production method of resin composition &gt;

The resin composition of the present embodiment is obtained by mixing the biphenylaralkyl type epoxy resin (A), the photo-curing initiator (B), the compounds (C) and (C) represented by the above formula (1) (E), the filler (F), the compound (G), and other components, if necessary, with the compound (D) having an ethylenically unsaturated group. The resin composition of the present embodiment can be preferably used as a varnish for preparing a resin sheet of the present invention to be described later.

The method for producing the resin composition of the present embodiment is not particularly limited and, for example, a method of mixing the components described above sequentially in a solvent and sufficiently stirring may be mentioned.

In the production of the resin composition, known treatments (stirring, mixing, kneading treatment, etc.) for uniformly dissolving or dispersing the respective components can be carried out, if necessary. Concretely, the dispersibility of the inorganic filler (G) in the resin composition can be improved by performing the stirring dispersion treatment using a stirring tank provided with a stirrer having an appropriate stirring ability. The stirring, mixing and kneading treatments described above may be carried out, for example, by a device for mixing an agitator, a three-roll mill, a ball mill, a bead mill or a sand mill for the purpose of dispersion such as an ultrasonic homogenizer, , Or a known device such as an agitator or a self-ball type mixing device. In preparing the resin composition of the present embodiment, an organic solvent may be used if necessary. The kind of the organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition, and specific examples thereof are as described above.

<Applications>

The resin composition of the present embodiment can be used for applications requiring an insulating resin composition, and is not particularly limited. Examples of the resin composition include a photosensitive film, a photosensitive film on which a support is formed, an insulating resin sheet such as a prepreg, A multilayer printed wiring board, etc.), a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole-filling resin, and a component-embedded resin. Among them, it can be suitably used as a resin composition for an insulating layer of a multilayered printed circuit board and a solder resist.

<Resin Sheet>

The resin sheet of the present embodiment is a resin sheet comprising a support, a support formed on the surface of the support and comprising a resin composition layer containing the resin composition of the present embodiment, Is formed. The resin sheet can be produced by applying the resin composition onto a support and drying the resin composition.

The support used in the resin sheet of the present embodiment is not particularly limited, but known ones can be used, and resin films are preferable. Examples of the resin film include a polyimide film, a polyamide film, a polyester film, a polyethylene terephthalate (PET) film, a polybutylene terephthalate (PBT) film, a polypropylene (PP) film, a polyethylene (PE) Film, a polyethylene naphthalate film, a polyvinyl alcohol film, and a triacetyl acetate film. Among them, a PET film is preferable.

In order to facilitate peeling from the resin composition layer, the resin film may preferably be coated with a releasing agent on its surface. The thickness of the resin film is preferably in the range of 5 탆 to 100 탆, more preferably in the range of 10 탆 to 50 탆. When the thickness is less than 5 mu m, the support tends to be broken at the time of peeling the support before development. When the thickness exceeds 100 mu m, the resolution at the time of exposure from the support tends to decrease.

Further, in order to reduce scattering of light at the time of exposure by an active energy ray such as ultraviolet rays, the resin film is preferably excellent in transparency.

In the resin sheet in the present embodiment, the resin composition layer may be protected by a protective film.

By protecting the side of the resin composition layer with a protective film, it is possible to prevent adhesion and scratching of dust or the like on the surface of the resin composition layer. As the protective film, a film constituted by the same material as the above resin film can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 탆 to 50 탆, more preferably in the range of 5 탆 to 40 탆. If the thickness is less than 1 mu m, the handling property of the protective film tends to decrease, and if it exceeds 50 mu m, the cheapness tends to be inferior. It is preferable that the protective film has a small adhesive force between the resin composition layer and the protective film against the adhesive force between the resin composition layer and the support.

The method of producing the resin sheet of the present embodiment is not particularly limited. For example, a method of manufacturing a resin sheet by applying the resin composition of the present embodiment to a support such as PET film and removing the organic solvent by drying And the like.

The application can be carried out by a known method using, for example, a roll coater, a comma coater, a gravure coater, a die coater, a bar coater, a lip coater, a knife coater, a squeeze coater and the like. The drying can be carried out, for example, by heating in a drier at 60 to 200 DEG C for 1 to 60 minutes.

The amount of the residual organic solvent in the resin composition layer is preferably 5% by mass or less based on the total mass of the resin composition layer from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step. The thickness of the resin composition layer relative to the support is preferably 1.0 占 퐉 or more in terms of the resin composition layer thickness of the resin sheet from the viewpoint of improving handling properties. Further, from the viewpoint of improving the transmittance and improving the developing property, it is preferable that the thickness is 300 mu m or less.

The resin sheet of the present embodiment can be used as an interlayer insulating layer of a multilayer printed wiring board.

<Multilayer Printed Circuit Board>

The multilayered printed circuit board of the present embodiment is provided with an interlayer insulating layer containing the resin composition of the present embodiment and may be obtained by, for example, curing one or more of the above-described resin sheets. Specifically, it can be produced by the following method.

(Lamination process)

The side of the resin composition layer of the resin sheet of this embodiment is laminated on one side or both sides of the circuit board using a vacuum laminator. Examples of the circuit board include a glass epoxy substrate, a metal substrate, a ceramic substrate, a silicon substrate, a semiconductor encapsulating resin substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, have. Here, the circuit board refers to a substrate on which a conductor layer (circuit) patterned on one side or both sides of the above-described substrate is formed. In the multilayer printed wiring board in which the conductor layer and the insulating layer are alternately laminated, a substrate in which the outermost layer of the printed wiring board has a conductor layer (circuit) patterned on one side or on both sides is also included in the circuit board do. Further, the surface of the conductor layer may be roughened in advance by blackening treatment, copper etching, or the like. In the case where the resin sheet has a protective film in the lamination process, the protective film is peeled off and then the resin sheet and the circuit board are preheated, if necessary, and the resin composition layer is pressed and heated on the circuit board while being pressed and heated. In the resin sheet of the present embodiment, a method of laminating a circuit board under reduced pressure by a vacuum laminating method is preferably used.

For example, the pressing temperature (lamination temperature) is preferably 50 占 폚 to 140 占 폚, the pressing pressure is preferably 1 kgf / cm2 to 15 kgf / cm2, The pressing time is preferably 5 seconds to 300 seconds, and it is preferable that the lamination is performed under a reduced pressure such that the air pressure is 20 mmHg or less. The lamination process may be a batch process or a continuous process using a roll. The vacuum laminating method can be carried out using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a two-stage build-up laminator manufactured by Nikko Materials Co., Ltd. can be mentioned.

(Exposure step)

After the resin sheet is formed on the circuit board by the lamination process, an exposure process is performed in which a predetermined portion of the resin composition layer is irradiated with active energy rays and the resin composition layer of the irradiated portion is cured. The irradiation of the active energy ray may be conducted through the mask pattern, or a direct imaging method in which the active energy ray is directly irradiated may be used.

Examples of the active energy ray include ultraviolet rays, visible rays, electron rays and X-rays, and ultraviolet rays are particularly preferred. The dose of ultraviolet rays is approximately 10 mJ / cm 2 to 1000 mJ / cm 2. The exposure method for passing the mask pattern includes a contact exposure method in which the mask pattern is brought into close contact with the multilayer printed wiring board and a non-contact exposure method in which the exposure is performed using parallel rays without being closely contacted. When a support is present on the resin composition layer, the support may be exposed from the support, or the support may be exposed after being peeled off.

(Developing step)

After the exposure process, if a support is present on the resin composition layer, a pattern of the insulation layer can be formed by removing the support and then removing the portion that is not photo-cured (unexposed portion) have.

In the case of the wet phenomenon, a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent is used as the developer, as long as it selectively elutes the unexposed portion. In the present embodiment, a developing step with an alkaline aqueous solution is particularly preferable. These developers may be used alone or in combination of two or more. The developing method can be carried out by a known method such as spraying, swinging dipping, brushing, scraping or the like.

The alkali aqueous solution used as the developer is not particularly limited, and examples thereof include potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, sodium 4-borate, ammonia and amines.

The concentration of the alkali aqueous solution is preferably 0.1% by mass to 60% by mass relative to the total amount of the developer. Further, the temperature of the aqueous alkali solution can be adjusted according to developability. These alkali aqueous solutions may be used alone or in combination of two or more.

In the pattern formation of the present embodiment, two or more kinds of developing methods described above may be used in combination as occasion demands. The developing method includes a dipping method, a paddle method, a spraying method, a high-pressure spraying method, brushing, and slapping, and a high-pressure spraying method is preferable for improving the resolution. The spray pressure in the case of employing the spray method is preferably 0.02 MPa to 0.5 MPa.

(Post-bake process)

After the above-mentioned development process, a post-baking process is performed to form an insulating layer (cured product). Examples of the post-baking process include a UV irradiation process using a high-pressure mercury lamp and a heating process using a clean oven, and they can be used in combination. In the case of irradiating ultraviolet rays, the irradiation amount can be adjusted as necessary, and irradiation can be carried out at an irradiation dose of, for example, about 0.05 J / cm 2 to 10 J / cm 2. The heating conditions may be appropriately selected depending on the type and content of the resin component in the resin composition, and preferably from 150 ° C to 220 ° C for 20 minutes to 180 minutes, more preferably from 160 ° C to 200 ° C at 30 ° C Minute to 150 minutes.

(Plating process)

Next, a conductive layer is formed on the surface of the insulating layer by dry plating or wet plating. As the dry plating, known methods such as a vapor deposition method, a sputtering method, and an ion plating method can be used. In the vapor deposition method (vacuum vapor deposition method), for example, a metal film can be formed on an insulating layer by placing a support in a vacuum container and evaporating the metal by heating. A sputtering method is also applicable. For example, a support is placed in a vacuum container, an inert gas such as argon is introduced, a DC voltage is applied to collide the ionized inert gas against the target metal, Film formation can be performed.

In the case of wet plating, the surface of the insulating layer formed is roughened by swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order. The swelling treatment by the swelling liquid is carried out by immersing the insulating layer in the swelling liquid at 50 DEG C to 80 DEG C for 1 minute to 20 minutes. Examples of the swelling solution include an alkaline solution, and examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Commercially available swelling solutions include, for example, Upes (registered trademark) MDS-37 manufactured by Uemura Kogyo Co., Ltd. and the like.

The coarsening treatment with an oxidizing agent is carried out by immersing the insulating layer in an oxidizing agent solution at 60 ° C to 80 ° C for 5 minutes to 30 minutes. As the oxidizing agent, for example, an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like can be given. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Commercially available oxidizing agents include, for example, alkaline permanganic acid solutions such as Upes (registered trademark) MDE-40 and Upes (registered trademark) ELC-SH manufactured by Uemura Kogyo Co., The neutralization treatment by the neutralization liquid is carried out by immersing in a neutralizing liquid at 30 ° C to 50 ° C for 1 minute to 10 minutes. As the neutralizing solution, an acidic aqueous solution is preferable, and a commercially available product is Upes (registered trademark) MDN-62 manufactured by Uemura Kogyo Co., Ltd.

Subsequently, a conductor layer is formed by combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. As the pattern formation method thereafter, for example, a subtractive method or a semi-additive method can be used.

<Semiconductor Device>

The semiconductor device of the present embodiment includes an interlayer insulating layer containing the resin composition of the present embodiment, specifically, it can be manufactured by the following method. The semiconductor device can be manufactured by mounting the semiconductor chip at the conduction point of the multilayered printed circuit board of the present embodiment. Here, the conduction point is a point for transmitting electrical signals in the multilayered printed circuit board, and the point may be a surface, a buried point, or the like. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor material.

The method for mounting the semiconductor chip in manufacturing the semiconductor device of the present embodiment is not particularly limited as long as the semiconductor chip effectively functions. Specifically, the semiconductor chip mounting method, the flip chip mounting method, A mounting method using an up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like.

The semiconductor device can also be manufactured by laminating the resin sheet of the present embodiment to a semiconductor chip. After the lamination, the multilayer printed wiring board can be produced by the same method as the above-described multilayer printed wiring board.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples at all.

[Synthesis Example 1]

(Synthesis of cyanic acid ester compound)

300 g (1.28 mol in terms of OH group) and 194.6 g (1.92 mol) of triethylamine (1.5 mol with respect to 1 mol of hydroxyl group) of 1-naphthol aralkyl resin (manufactured by Shinnitetsu Kagaku Kagaku) were added to 1800 g of dichloromethane And this solution was designated as solution 1.

, 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol per 1 mol of the hydroxyl group) and 1205.9 g of water were added to a solution of 125.9 g (2.05 mol) of cyanogen chloride (1.6 mol with respect to 1 mol of hydroxyl group) , While stirring and maintaining the solution temperature at -2 to -0.5 占 폚, Solution 1 was sprinkled over 30 minutes. Solution 1 After completion of the stirring, the solution was stirred for 30 minutes at the same temperature, and a solution (solution 2) in which 65 g (0.64 mol) of triethylamine (0.5 mol with respect to 1 mol of the hydroxyl group) was dissolved in 65 g of dichloromethane was dissolved in 10 Min. Solution 2 After completion of stirring, stirring was carried out at the same temperature for 30 minutes to complete the reaction.

Thereafter, the reaction solution was allowed to stand to separate the organic phase and water phase. The obtained organic phase was washed 5 times with 1300 g of water. It was confirmed that the ionic compound which can be removed by the washing with water was sufficiently removed, and the electrical conductivity of the wastewater at the fifth washing with water was 5 μS / cm.

The washed organic phase was concentrated under reduced pressure, and finally concentrated to dryness at 90 DEG C for 1 hour to obtain 331 g of objective naphthol aralkyl type cyanate ester compound (SNCN) (orangeish viscous product). The mass average molecular weight Mw of the obtained SNCN was 600. In addition, the IR spectrum of SNCN showed absorption of 2250 cm ^-1 (cyanate ester group), and no absorption of hydroxyl group was shown.

[Example 1]

(Production of resin composition and resin sheet)

As the biphenylaralkyl type epoxy resin (A) represented by the formula (1), a biphenylaralkyl type epoxy resin (n in the formula (1) is 1 to 3) NC3000L (trade name), manufactured by Nippon Yakuhaku Co., (Irgacure (registered trademark) 369, manufactured by BASF Japan Co., Ltd.) as a photocuring initiator (B), 22.4 parts by mass of 2- (Hereinafter sometimes referred to as PGMEA) solution (KAYARAD (registered trademark) ZCR-6007H, nonvolatile matter (hereinafter referred to as &quot; PGMEA &quot;) solution) of TrisP-PA epoxy acrylate compound 77.5 parts by mass (50.4 parts by mass in terms of nonvolatile content), 65% by mass, acid value: 70 mgKOH / g, manufactured by Nippon Kayaku Co., Ltd.) as the compound (D) having an ethylenic unsaturated group other than the component 17.4 parts by mass of erythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Yaku Yakuhin Co., Ltd.), 10 parts by mass of maleimide compound (E) , 3.3 parts by mass of a maleimide compound (BMI-2300 (trade name), manufactured by Daiwa Hoso Industry Co., Ltd.), and a methyl ethyl ketone (hereinafter may be abbreviated as MEK) slurry of epoxy silane- And 71.4 parts by mass (50 parts by mass in terms of nonvolatile content) were mixed with an organic solvent (SC2050MB (trade name), average particle diameter 0.5 mu m, nonvolatile matter 70 mass%, Admatech Co., Ltd.), and the mixture was stirred with an ultrasonic homogenizer Solution of the resin composition). These varnishes were coated on a PET film (Unifyl (registered trademark) TR1-38, trade name, product name) having a thickness of 38 탆 by using an automatic coating machine (PI-1210, manufactured by Tester Industry Co., Ltd.) And dried by heating at 80 DEG C for 7 minutes to obtain a resin sheet having a resin composition layer having a thickness of 30 mu m using a PET film as a support.

The KAYARAD (registered trademark) ZCR-6007H is a mixture containing at least one of the compound (C1) and the compounds (C2) to (C5).

(Fabrication of inner layer circuit board)

Both sides of a glass cloth base BT resin double coated copper clad laminate (copper foil thickness 18 탆, thickness 0.2 탆, CCL (registered trademark) -HL832NS manufactured by Mitsubishi Gas Chemical Co., Ltd.) Surface roughening treatment was carried out to obtain an inner-layer circuit board.

(Preparation of laminate for evaluation)

The resin surface of the resin sheet was placed on the inner layer circuit board and exhausted (5.0 MPa or less) for 30 seconds using a vacuum laminator (manufactured by Nikko Industries Co., Ltd.) Followed by lamination molding at 70 DEG C for 30 seconds. Further, lamination molding was carried out at a pressure of 10 kgf / cm 2 and a temperature of 70 캜 for 60 seconds to obtain a laminate in which an inner layer circuit board, a resin composition layer and a support were laminated. The obtained laminate was subjected to an exposure step of irradiating ultraviolet light of 200 mJ / cm 2, the support was peeled off, developed with a 1% by mass aqueous solution of sodium carbonate and subjected to an exposure step of irradiating ultraviolet rays of 1000 mJ / Post baking step of heating treatment at 180 占 폚 for 120 minutes was carried out to obtain a laminate for evaluation.

(Preparation of cured product for evaluation)

A post-baking step of irradiating the resin sheet with ultraviolet rays of 200 mJ / cm &lt; 2 &gt; and irradiating ultraviolet rays of 1000 mJ / cm &lt; 2 &gt;, and performing a heat treatment at 180 DEG C for 120 minutes, .

[Example 2]

As the component (A), 21.9 parts by mass of a biphenylaralkyl type epoxy resin (NC3000L (trade name), manufactured by Nippon Yakasei Co., Ltd.) and 2 parts by mass of 2-benzyl-2-dimethylamino- 6.5 parts by mass of 4-morpholinophenyl) -butanone-1 (Irgacure (registered trademark) 369, manufactured by BASF Japan Ltd.), and PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD 77.5 parts by mass (50.4 parts by mass in terms of nonvolatile content)), and an ethylenic unsaturated group other than the component (C) (hereinafter referred to as &quot; ZCR-6007H &quot;, trade name of ZCR-6007H, 65% by mass of nonvolatile content, 70 mgKOH / g of acid value, , 17.4 parts by mass of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.) as the compound (D) having the maleimide compound (BMI-2300 ), 3.3 parts by mass of an epoxy resin (manufactured by Daikin Industries, Ltd.), and MEK slurry of epoxysilane-treated silica (SC2050MB (trade name) , 71.4 parts by mass (50 parts by mass in terms of nonvolatile content), 0.5 parts by mass of the cyanate ester compound SNCN obtained in Synthesis Example 1 And the mixture was stirred with an ultrasonic homogenizer to obtain a varnish (solution of a resin composition). These varnishes were coated on a PET film (Unifyl (registered trademark) TR1-38, trade name, product name) having a thickness of 38 탆 by using an automatic coating machine (PI-1210, manufactured by Tester Industry Co., Ltd.) And dried by heating at 80 DEG C for 7 minutes to obtain a resin sheet having a resin composition layer having a thickness of 30 mu m using a PET film as a support. Using this, a laminate for evaluation and a cured product for evaluation were obtained in the same manner as in Example 1.

[Example 3]

As the component (A), 21.9 parts by mass of a biphenylaralkyl type epoxy resin (NC3000L (trade name), manufactured by Nippon Yakitori Co., Ltd.) and 2,4,6-trimethylbenzoyl-diphenyl- 6.5 parts by mass of phosphine oxide (Irgacure (registered trademark) 819, manufactured by BASF Japan Ltd.), 10 parts by mass of a PGMEA solution of a TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H, 77.5 parts by mass (50.4 parts by mass in terms of nonvolatile content), 65% by mass, acid value: 70 mgKOH / g, manufactured by Nippon Kayaku Co., Ltd.) as the compound (D) having an ethylenic unsaturated group other than the component 17.4 parts by mass of maleimide compound (BMI-2300 (trade name), manufactured by Daiwa Hoso Ind. Co., Ltd.) as the maleimide compound (E) ) As a filler (F), a MEK slurry of epoxy silane-treated silica (SC2050MB (trade name), average particle diameter 0.5 (50 parts by mass in terms of nonvolatile content) and 0.5 parts by mass of the cyanate ester compound SNCN obtained in Synthesis Example 1 as a compound (G) were compounded , And the mixture was stirred with an ultrasonic homogenizer to obtain a varnish (solution of a resin composition). These varnishes were coated on a PET film (Unifyl (registered trademark) TR1-38, trade name, product name) having a thickness of 38 탆 by using an automatic coating machine (PI-1210, manufactured by Tester Industry Co., Ltd.) And dried by heating at 80 DEG C for 7 minutes to obtain a resin sheet having a resin composition layer having a thickness of 30 mu m using a PET film as a support. Using this, a laminate for evaluation and a cured product for evaluation were obtained in the same manner as in Example 1.

[Example 4]

15.8 parts by mass of a biphenylaralkyl type epoxy resin (NC3000L (trade name), manufactured by Nippon Yaku Yakuhin Co., Ltd.) as the component (A) and 20 parts by mass of a naphthalene type epoxy resin (HP-4710 6.1 parts by mass as a photo-curing initiator (B), 6.5 parts by mass of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Irgacure (registered trademark) 819, BASF Japan) , 77.5 parts by mass of a PGMEA solution of a TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H, nonvolatile content of 65% by mass, acid value: 70 mgKOH / g, manufactured by Nippon Yaku Yakuhin K.K.) as the compound (C) (KAYARAD (registered trademark) DPHA, manufactured by Nippon Yakugaku Co., Ltd.) as the compound (D) having an ethylenic unsaturated group other than the component (C) in a proportion of 17.4 (50.4 parts by mass in terms of non- , 3.3 parts by mass of a maleimide compound (BMI-2300 (trade name), manufactured by Daiwa Hoso Industry Co., Ltd.) as the maleimide compound (E) 71.4 parts by mass (50 parts by mass in terms of nonvolatile content) of a MEK slurry of epoxy silane-treated silica (SC2050MB (trade name), average particle size of 0.5 占 퐉, nonvolatile component of 70% by mass, , And 0.5 part by mass of the cyanate ester compound SNCN obtained in Synthesis Example 1 as a compound (G) were mixed and stirred with an ultrasonic homogenizer to obtain a varnish (solution of a resin composition). These varnishes were coated on a PET film (Unifyl (registered trademark) TR1-38, trade name, product name) having a thickness of 38 탆 by using an automatic coating machine (PI-1210, manufactured by Tester Industry Co., Ltd.) And dried by heating at 80 DEG C for 7 minutes to obtain a resin sheet having a resin composition layer having a thickness of 30 mu m using a PET film as a support. Using this, a laminate for evaluation and a cured product for evaluation were obtained in the same manner as in Example 1.

[Example 5]

15.8 parts by mass of a biphenylaralkyl type epoxy resin (NC3000L (trade name), manufactured by Nippon Yaku Yakuhin Co., Ltd.) as the component (A) and 20 parts by mass of a naphthalene type epoxy resin (HP-4710 6.1 parts by mass as a photo-curing initiator (B), 6.5 parts by mass of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Irgacure (registered trademark) 819, BASF Japan) , 77.5 parts by mass of a PGMEA solution of a TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H, nonvolatile content of 65% by mass, acid value: 70 mgKOH / g, manufactured by Nippon Yaku Yakuhin K.K.) as the compound (C) (KAYARAD (registered trademark) DPHA, manufactured by Nippon Yakugaku Co., Ltd.) as the compound (D) having an ethylenic unsaturated group other than the component (C) in a proportion of 17.4 (50.4 parts by mass in terms of non- , 3.3 parts by mass of a maleimide compound (BMI-2300 (trade name), manufactured by Daiwa Hoso Industry Co., Ltd.) as the maleimide compound (E) 71.4 parts by mass (50 parts by mass in terms of nonvolatile content) of a MEK slurry of epoxy silane-treated silica (SC2050MB (trade name), average particle size of 0.5 占 퐉, nonvolatile component of 70% by mass, , 0.5 part by mass of the cyanate ester compound SNCN obtained in Synthesis Example 1 and 2 parts by mass of 2-ethyl-4-methylimidazole (2E4MZ (trade name), manufactured by Shikoku Chemical Co., Ltd.) Ltd.), and the mixture was stirred with an ultrasonic homogenizer to obtain a varnish (solution of the resin composition). These varnishes were coated on a PET film (Unifyl (registered trademark) TR1-38, trade name, product name) having a thickness of 38 탆 by using an automatic coating machine (PI-1210, manufactured by Tester Industry Co., Ltd.) And dried by heating at 80 DEG C for 7 minutes to obtain a resin sheet having a resin composition layer having a thickness of 30 mu m using a PET film as a support. Using this, a laminate for evaluation and a cured product for evaluation were obtained in the same manner as in Example 1.

[Comparative Example 1]

Except that 74.1 parts by mass of bisphenol F type epoxy acrylate (KAYARAD (registered trademark) ZFR-1553H, nonvolatile matter 68% by mass, acid value 70 mgKOH / g, manufactured by Nippon Yaku Yakuhin KK) (50.4 parts by mass) was used in place of the resin composition of Example 1 to prepare a varnish, to obtain a resin sheet, a laminate for evaluation, and a cured product for evaluation.

In addition, KAYARAD (registered trademark) ZFR-1553H does not have the structure represented by the above formula (2).

[Comparative Example 2]

A varnish was prepared in the same manner as in Example 1 except that 22.4 parts by mass of a naphthalene type epoxy resin (HP-4710 (trade name), manufactured by DIC Corporation) was used in place of the component (A) And a cured product for evaluation were obtained.

[Comparative Example 3]

A varnish was prepared in the same manner as in Example 1 except that 22.4 parts by mass of a multifunctional epoxy resin (1031S (trade name), manufactured by Mitsubishi Chemical Corporation) was used instead of the component (A) to prepare a resin sheet, To obtain a cured product for evaluation.

The polyfunctional epoxy resin (1031S (trade name), manufactured by Mitsubishi Chemical Corporation) has the following structural formula (12).

[Chemical Formula 20]

[Evaluation of physical properties]

The resin sheet, the evaluation laminate and the cured product for evaluation were measured and evaluated by the following methods. The results are shown in Table 1.

<Film Formation>

The fingers were lightly pressed against the resin surface end portion of the resin sheet on which each support of A4 size was formed, and the degree of attachment to the fingers was evaluated according to the following criteria.

?: Almost no adhesion to the finger is confirmed. The end of the resin sheet on which the support is formed adheres to the finger, but peels off from the finger at a height less than 30 mm and drops.

X: Attachment to the finger is confirmed. The end portion of the resin sheet on which the support is formed is attached to the fingers and floats at a height of 30 mm or more.

&Lt; Heat resistance (glass transition temperature) &gt;

The cured product for evaluation was heated at a rate of 10 ° C / min using a DMA device (dynamic viscoelasticity measuring device DMAQ800 (trade name) manufactured by TA Instrument), and the peak position of the loss modulus was defined as a glass transition temperature (Tg, ° C).

<Developability>

The development surface of the evaluation laminate was observed with a scanning electron microscope (SEM) (magnification: 1000 times) after measuring the time from the start of the development process to the time when the residue disappears visually, and the presence or absence of the residue And evaluated according to the following criteria.

?: The time until the development residue in the naked eye disappears is 50 sec or less, and there is no developing residue in the range of 30 mm in width and after the SEM observation, and the developing property is excellent.

 ?: The time until the development residue in the naked eye disappears is more than 50 sec, but there is no developing residue in the range of 30 mm in width and after the SEM observation, and the developing property is excellent.

X: Developed residue exists in a range of 30 mm in length and width, resulting in poor developability.

Wet coarsening treatment of the cured product for evaluation and conductor layer plating:

The multilayer printed wiring boards obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were subjected to electroless copper plating process (use chemical name: MCD-PL, MDP-2, MAT-SP, MAB-4-C , MEL-3-APEA ver.2), electroless copper plating of about 0.8 μm was carried out, and drying was carried out at 130 ° C. for 1 hour. Subsequently, the electrolytic copper plating was carried out so that the thickness of the plating copper was 18 占 퐉, and the coating was dried at 180 占 폚 for 1 hour. Thus, a sample having a conductor layer (plated copper) having a thickness of 18 mu m formed on the insulating layer was prepared and provided for the following evaluation.

&Lt; Plating adhesion (kN / m) &gt;

Using the samples prepared in the above procedure, the adhesive strength of the plating copper was measured three times in accordance with JIS C 6481, and the average value was obtained. The samples swollen by the drying after the electrolytic copper plating were evaluated by using the portions which were not swelled.

As apparent from Table 1, Examples 1 to 5 are excellent in the plating adhesion. Among them, Examples 2 to 5 are excellent in heat resistance and plating adhesion, and in particular, Examples 3 to 5 are remarkably excellent in heat resistance and plating adhesion. In addition, Examples 4 and 5 are excellent in developing property. On the contrary, the coating adhesiveness of Comparative Examples 1 to 3 was insufficient. Therefore, according to the present invention, a resin composition excellent in adhesion to plating, excellent in heat resistance and developability, a resin sheet using the same, a multilayer printed wiring board, and a semiconductor device can be obtained.

Claims (14)

(B) other than the compound (C) represented by the following formula (2) and the compound (C) represented by the following formula (2) And a compound (D) having an ethylenically unsaturated group.
[Chemical Formula 1]

(In the formula (1), n represents an integer of 0 to 15.)
(2)

(In the formula (2), a plurality of R _{1 s} each independently represents a hydrogen atom or a methyl group, the plurality of R _{2 s} each independently represent a hydrogen atom or a hydrocarbon group of 1 to 22 carbon atoms which may have a substituent , And the plurality of R ₃ independently represent a substituent represented by the following formula (3), a substituent represented by the following formula (4) or a hydroxy group.
(3)

[Chemical Formula 4]

(In the formula (4), R ₄ represents a hydrogen atom or a methyl group.). The method according to claim 1,
And a maleimide compound (E). 3. The method according to claim 1 or 2,
And further contains a filler (F). 4. The method according to any one of claims 1 to 3,
(G) selected from the group consisting of a cyanate ester compound, a phenol resin, an oxetane resin, a benzoxazine compound, and an epoxy resin different from the biphenylaralkyl type epoxy resin (A) ). &Lt; / RTI &gt; 5. The method according to any one of claims 1 to 4,
Wherein the acid value of the compound (C) represented by the formula (2) is 30 mgKOH / g or more and 120 mgKOH / g or less. 6. The method according to any one of claims 1 to 5,
Wherein the content of the component (A) is 3 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition. 7. The method according to any one of claims 1 to 6,
Wherein the ethylenically unsaturated group-containing compound (D) is a compound having a (meth) acryloyl group and / or a compound having a vinyl group. The method of claim 3,
Wherein the filler (F) is at least one kind selected from the group consisting of silica, boehmite, barium sulfate, silicone powder, fluororesin filler, urethane resin filler, acrylic resin filler, polyethylene filler, styrene / butadiene rubber, By weight. 9. The method according to any one of claims 1 to 8,
And a thermosetting accelerator (H). 10. The method according to any one of claims 1 to 9,
A resin composition further comprising a naphthalene type epoxy resin represented by the following formula (5).
[Chemical Formula 5]

11. The method according to any one of claims 1 to 10,
Wherein the photo-curing initiator (B) contains a phosphine oxide compound represented by the following formula (6).
[Chemical Formula 6]

(In the formula (6), R ₅ to R ₁₀ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁₁ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. ) A resin sheet comprising the support and the resin composition according to any one of claims 1 to 11, which is disposed on the surface of the support. A multilayer printed wiring board comprising the resin composition according to any one of claims 1 to 11. A semiconductor device comprising the resin composition according to any one of claims 1 to 11.