JP6913305B2 - Resin composition, resin sheet, multilayer printed wiring board and semiconductor device - Google Patents

Description

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

Studies are being actively conducted to reduce the thickness of the laminated board used for the multi-layer printed wiring board by reducing the size and increasing the density of the multi-layer printed wiring board. Along with the thinning, the insulating layer is also required to be thinned, and a resin sheet containing no glass cloth is required. Thermosetting resin is the mainstream of the resin composition used as the material of the insulating layer, and drilling for obtaining continuity between the insulating layers is generally performed by laser processing. Further, 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, drilling by laser processing 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 that can be collectively drilled in a developing process by using a resin composition that is cured by light rays or the like and dissolved by development. Further, since the conductor circuit is formed by copper plating on the insulating layer, it is required to have high copper plating adhesion to the insulating layer so that the conductor circuit is not peeled off.

In the resin composition used for such a laminated board or a resin sheet, the alkali development type is the mainstream, and an acid anhydride group or a carboxyl group-containing acrylate is used to enable development. In addition, epoxy resin is used for copper plating adhesion. For example, Patent Document 1 describes 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, and the like. A photosensitive thermosetting resin composition containing a photopolymerization initiator and a diluent is described. Further, Patent Document 2 contains an epoxy resin, a curing agent, and a silica component in which silica particles are surface-treated with a silane coupling agent, and does not contain a curing accelerator, or the epoxy resin and the above. The curing accelerator is contained in a content of 3.5 parts by weight or less with respect to 100 parts by weight of the total amount of the curing agent, the average particle size of the silica particles is 1 μm or less, and per 1 g of the silica particles in the silica component. The surface treatment amount B (g) of the silane coupling agent is the formula (X) (C (g) / silica particles 1 g = [specific surface area of silica particles (m ² / g) / minimum coating area of the silane coupling agent). (M ² / g)] ... Disclosed is an epoxy resin composition in the range of 10 to 80% with respect to the value C (g) per 1 g of silica particles calculated by the formula (X)). There is.

JP-A-2005-62450 Japanese Unexamined Patent Publication No. 2011-174882

However, sufficient physical properties cannot be obtained with a cured product using a conventional epoxy resin, 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 developability.

Further, the cured product obtained from the resin composition described in Patent Document 1 is limited in its use to etching resists and solder resists for printed wiring boards, and is excellent in flexibility and heat resistance, but is an interlayer insulating layer. The copper plating adhesion was not sufficient to be used as.

The cured product obtained from the resin composition described in Patent Document 2 has excellent copper plating adhesion, but since drilling is limited to laser processing, batch drilling by a developing process is not possible.

Therefore, the present invention has been made in view of the above problems, and when used in a multilayer printed wiring board, a resin composition having excellent coating properties and heat resistance, and excellent developability and copper plating adhesion. It is an object of the present invention to provide a resin sheet with a support, a multilayer printed wiring board using them, and a semiconductor device.

The present inventors have a biphenyl aralkyl type epoxy resin (A) represented by the following formula (1), a photocuring initiator (B), a compound (C) represented by the following formula (2), and the (C). We have found that the above problems can be solved by using a resin composition containing a compound (D) having an ethylenically unsaturated group other than the components, and have completed the present invention.

(In equation (1), n represents an integer from 0 to 15.).

(In the formula (2), a plurality of R ₁ each independently represent a hydrogen atom or a methyl group, a plurality of R ₂ are each independently a hydrogen atom or a substituted carbon atoms which may based on have 1 It represents to 22 hydrocarbon group, a plurality of R ₃ each independently represents a substituent, or a hydroxy group represented by the following formula (4) represented by the following formula (3).).

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

That is, the present invention includes the following contents.
[1] The biphenyl aralkyl type epoxy resin (A) represented by the formula (1), the photocuring initiator (B), the compound (C) represented by the formula (2), and the formula (2). A resin composition containing a compound (D) having an ethylenically unsaturated group other than the compound (C).
[2] The resin composition according to [1], further containing the maleimide compound (E).
[3] The resin composition according to [1] or [2], further comprising a filler (F).
[4] Any one or more 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 biphenyl aralkyl type epoxy resin (A) represented by the above (1). The resin composition according to any one of [1] to [3], further containing the 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] 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 with respect to 100 parts by mass of the resin solid content in the resin composition. The resin composition according to.
[7] Described in any one of [1] to [6], wherein the compound (D) having an ethylenically unsaturated group is a compound having a (meth) acryloyl group and / or a compound having a vinyl group. Resin composition.
[8] The filler (F) is silica, boehmite, barium sulfate, silicone powder, fluororesin-based filler, urethane resin-based filler, acrylic resin-based filler, polyethylene-based filler, styrene / butadiene rubber and silicone. The resin composition according to [3], which is one or more selected from the group consisting of rubber.

[9] The resin composition according to any one of [1] to [8], which further contains a thermosetting accelerator (H).
[10]
The resin composition according to any one of [1] to [9], further containing a naphthalene-type epoxy resin represented by the following 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).

(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 is an alkyl group having 1 to 20 carbon atoms or 6 to 20 carbon atoms. Indicates the aryl group of.).
[12] A resin sheet having a support and the resin composition according to any one of [1] to [11] arranged on the surface of the support.
[13] A multilayer printed wiring board having the resin composition according to any one of [1] to [11].
[14] A semiconductor device having the resin composition according to any one of [1] to [11].

According to the present invention, a resin composition which is excellent in plating adhesion, coating property, heat resistance and developability, and which has physical properties suitable for a multilayer printed wiring board and is cured by active energy rays, a resin sheet with a support, and the like. It is possible to provide the multi-layer printed wiring board and the semiconductor device used.

Hereinafter, embodiments for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining 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 thereof.

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

The resin composition of the present embodiment includes a biphenyl aralkyl type epoxy resin (A) represented by the formula (1), a photocuring initiator (B), a compound (C) represented by the formula (2), and ( It contains a compound (D) having an ethylenically unsaturated group other than the component C). Hereinafter, each component will be described.

<Biphenyl aralkyl 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 structure of the above formula (1) and having a biphenyl aralkyl skeleton. The cured product obtained by containing the resin (A) can suitably form a protective film and an interlayer insulating layer having excellent developability while having high copper plating adhesion.

In equation (1), n represents an integer from 0 to 15. Preferably, it is an integer of 0 to 5 from the viewpoint 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) and the component (D) is contained. The amount is preferably 3 parts by mass or more, more preferably 4 parts by mass or more, and further preferably 5 parts by mass or more with respect to 100 parts by mass. Further, from the viewpoint of sufficiently curing and improving heat resistance, the content 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.

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

Commercially available products can also be used as the resin (A), for example, NC3000FH (n = 8 to 10 in the formula (1)), NC3000H (n = 2 to 5 in the formula (1)), NC3000L (formula). (1) n = 1-3), NC3000 (n = 1-3 in formula (1)), CER3000L (n = 0-2 in formula (1)) (above, trade name, Nippon Kayaku (Made by Co., Ltd.) and the like.
These can be used alone or in admixture of two or more.

<Photocuring initiator (B)>
The photocurable initiator (B) (also referred to as component (B)) used in the present embodiment is not particularly limited, but those known in the field generally used in the photocurable resin composition can be used.

For example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di- Organic peroxides exemplified by perphthalate and the like, acylphosphine oxides, acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2, -Hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyncrohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one , 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and other acetophenones, 2-ethylanthraquinone, 2-t-butylantraquinone, 2-chloroanthraquinone, 2-amylanthraquinone, etc. Anthraquinones, thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal, benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, Benzophenones such as 4,4'-bismethylaminobenzophenone, phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1,2 -Radical photocuring initiators such as oxime esters such as octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], p-methoxyphenyldiazonium fluorophosphonate, N, N- Diazonium salt of Lewis acid such as diethylaminophenyldiazonium hexafluorophosphonate, iodonium salt of Lewis acid such as diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroantimonate and the like Luisic acid sulfonium salt, triphenylphosphonium hexafluoroantimonay Examples thereof include phosphonium salts of Lewis acids such as G, other halides, triazine-based initiators, borate-based initiators, and cationic photopolymerization initiators such as other photoacid generators.

Examples of acylphosphine oxides include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and other phosphine oxide compounds represented by the following formula (6), 2,4,6-trimethylbenzoyl-diphenyl-phos. Examples include fin oxides. In particular, the phosphine oxide compound represented by the following formula (6) has a high UV absorption rate at long wavelengths and is excellent in allowing UV light to reach the inside of the resin. 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, and a resin sheet and a multilayer printed wiring board having excellent heat resistance can be produced. It will be possible.

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

Examples of the alkyl group having 1 to 4 carbon atoms include a linear group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. A branched alkyl group can be mentioned.

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, an n-hexyl group, an isopropyl group, an isobutyl group and a sec-butyl group. t-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 Examples thereof include linear or branched alkyl groups such as −dimethylbutyl group and 1,1,3-trimethylbutyl group.

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 anthrasenyl group; a trill group, a dimethylphenyl group, an isopropylphenyl group and a t-butyl. Examples thereof include alkyl group-substituted aryl groups such as phenyl group and di-t-butylphenyl group.

Among them, acylphosphine oxides, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl), are available from the viewpoint of reactivity suitable for multi-layer printed wiring board applications and high reliability for metal conductors. ) -A acetophenone radical photocuring initiator such as butanone-1 is preferable, and as described above, more heat resistance can be obtained. Therefore, the phosphenyl oxide compound represented by the above formula (6) is more preferable, and bis ( 2,4,6-trimethylbenzoyl) -phenylphosphine oxide is more preferred.

These photocuring initiators (B) may be used alone or in admixture of two or more, and both radical and cationic initiators may be used in combination.

In addition, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6-trimethylbenzoyl. Commercially available products of -diphenyl-phosphine oxide can also be used, respectively, Irgacure (registered trademark) 369 (manufactured by BASF Japan Ltd.), Irgacure (registered trademark) 819 (manufactured by BASF Japan Ltd.) and Irgacure (registered). Trademark) TPO (manufactured by BASF Japan Ltd.) is preferably used.

The content of the photocuring 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 active energy rays and improving heat resistance, the resin composition The total content of the component (A), the component (C) and the component (D) is preferably 0.1 part by mass or more, and more preferably 0.2 part by mass or more with respect to 100 parts by mass. , 0.3 parts by mass or more is more preferable. Further, from the viewpoint of inhibiting heat curing after photo-curing and lowering heat resistance, it is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and further preferably 20 parts by mass or less. preferable.

The content of the photocuring initiator (B) in the resin composition of the present embodiment is not particularly limited, but may be 0.1 part by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. It is preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, further preferably 1 part by mass or more, and even more preferably 1.8 parts by mass or more. Even more preferable. Further, from the viewpoint of inhibiting thermosetting after photocuring and lowering heat resistance, it is preferably 30 parts by mass or less, preferably 25 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less.

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

Formula (2), a plurality of R ₁ each independently represent a hydrogen atom or a methyl group. Among them, it is preferable to contain hydrogen atoms from the viewpoint of improving the reactivity of the photocuring reaction, and more preferably _{all of R 1} are hydrogen atoms.

A plurality of R ₂ each independently represent a hydrogen atom or have a substituent a good 1 to 22 carbon atoms hydrocarbon group.

The hydrocarbon group is a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms, preferably 1 to 14, more preferably 1 to 10 carbon atoms; 3 to 22 carbon atoms, preferably 3 to 10 carbon atoms. 14, more preferably 3 to 10 alicyclic hydrocarbon groups; 6 to 22, preferably 6 to 14, and even more preferably 6 to 10 aromatic hydrocarbon groups.
Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, isobutyl group, sec-butyl group and t-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 Linear or branched alkyl group such as group, 1,1,3-trimethylbutyl group; linear or branched alkenyl group such as vinyl group, allyl group, isopropenyl group; ethynyl group, propargyl group, etc. Examples include linear or branched alkynyl groups.
Examples of the alicyclic hydrocarbon group include cyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 1-methyl-1-cyclohexyl group and adamantyl group; cyclopentadienyl group and indenyl. Examples thereof include a cyclic unsaturated hydrocarbon group such as a 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 anthrasenyl group; a trill group, a dimethylphenyl group, an isopropylphenyl group and a t-butylphenyl. Examples include an alkyl group substituted aryl group such as a group and a di-t-butylphenyl group; and an aryl group such as.
In these hydrocarbon groups, at least one hydrogen atom may be substituted with 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 group-substituted alkyl group such as a cyclohexylmethyl group. Can be mentioned.

As the hydrocarbon group having 1 to 22 carbon atoms which may have a substituent, a linear or branched alkyl group is preferable.
A plurality of R ₂ preferably includes a methyl group from the viewpoint of improving the heat resistance of the cured product, and more preferably all R ₂ is a methyl group.
A plurality of R ₃ are each independently a substituted group represented by the formula (3) represents a substituted or hydroxy group represented by the formula (4). Among them, it is preferable to contain a hydroxyl group from the viewpoint of improving heat resistance. Further, in the present embodiment, it is also preferable to use the compound (C) containing the substituent represented by the above formula (3) among the _{plurality of R 3, from the viewpoint of improving the developability.} In the present embodiment, it is also preferable to use the compound (C) containing the substituent represented by the above formula (4) among the _{plurality of R 3, from the viewpoint of improving the heat resistance.} In the above 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 photocuring reaction.

A plurality of R _3, from the viewpoint of improving the developability, the substituents of all R _3, the formula (3) range ratio below 98% 20% or more substituents represented by the formula ( The ratio of the substituent represented by 4) is in the range of 5% or more and 98% or less, and the ratio of the hydroxy group is in the range of 10% or more and 98% or less (the sum of the ratios of these substituents is 100%). Is preferable. Among them, that at least one of the plurality of R ₃ from the viewpoint of improving the developability becomes substituent represented by the formula (3) is particularly preferred.

It is preferable that the compound (C) contains any one or more of the following compounds (C1) to (C5) because the reactivity of the photocuring reaction, the heat resistance of the cured product and the developability can be improved. , At least the compound (C1) is more preferably contained, and it is more preferable to contain any two or more of the compounds (C1) to (C5), and any one of the compound (C1) and the compounds (C2) to (C5) 1 More preferably, it contains more than a species. It is also preferable that the compound (C) contains at least the compounds (C2) and (C3).

Commercially available products can also be used as such compounds, for example, KAYARAD (registered trademark) ZCR-6001H, KAYARAD (registered trademark) ZCR-6002H, KAYARAD (registered trademark) ZCR-6006H, KAYARAD (registered trademark) ZCR- Examples thereof include 6007H and KAYARAD (registered trademark) ZCR-601H (above, trade name, manufactured by Nippon Kayaku Co., Ltd.).

In the resin composition of the present embodiment, the acid value of compound (C) is preferably 30 mgKOH / g or more from the viewpoint of improving developability, and 50 mgKOH / g or more from the viewpoint of further improving developability. Is even more preferable. Further, from the viewpoint of preventing dissolution by the developing solution after curing with active energy rays, the acid value of compound (A) is preferably 120 mgKOH / g or less, and since dissolution can be further prevented, 110 mgKOH / g or less. Is more preferable. The "acid value" in the present embodiment indicates a value measured by a method according to JISK 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 active energy rays, the components (A) and the components (C) in the resin composition ) And the total content of the component (D) of 100 parts by mass, preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 3 parts by mass or more. Further, from the viewpoint of sufficiently curing with active energy rays and improving heat resistance, the content is preferably 99 parts by mass or less, more preferably 98 parts by mass or less, and further preferably 97 parts by mass or less. preferable.

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 active energy rays, the content of the resin solid content in the resin composition is 100 parts by mass. It is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, further preferably 10 parts by mass or more, and 25 parts by mass or more. It is even more preferable that the amount is 30 parts by mass or more. Further, from the viewpoint of sufficiently curing with active energy rays and improving heat resistance, it is preferably 99 parts by mass or less, preferably 98 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferably 97 parts by mass or less, further preferably 90 parts by mass or less, further preferably 75 parts by mass or less, and most preferably 72 parts by mass or less. preferable.

<Compound (D) having an ethylenically unsaturated group other than the component (C)>
The resin composition of the present embodiment has a compound (D) (component) having an ethylenically unsaturated group other than the component (C) in order to increase the reactivity with active energy rays (for example, ultraviolet rays) and improve the heat resistance. (Also referred to as (D)). The compound (D) having an ethylenically unsaturated group used in the present embodiment is other than the compound (C) represented by the above formula (2) and has one or more ethylenically unsaturated groups in one molecule. The compound is not particularly limited, and examples thereof include compounds having a (meth) acryloyl group, a vinyl group, and the like. These can be used alone or in admixture 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 (meth) acrylate, and polyethylene 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, nonanediol di (meth) acrylate, glycol di (meth) acrylate, diethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol Di (meth) acrylate, epoxy di (meth) acrylate of adipate, bisphenolethylene oxide di (meth) acrylate, hydride bisphenolethylene oxide (meth) acrylate, bisphenoldi (meth) acrylate, ε-caprolactone-modified neopenglycolate hydroxypivalate Di (meth) acrylate, ε-caprolactone-modified dipentaerythritol hexa (meth) acrylate, ε-caprolactone-modified dipentaerythritol poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, trimethylolpropanthry (meth) acrylate, Trietyrole propantri (meth) acrylate and its ethylene oxide adduct, pentaerythritol tri (meth) acrylate and its ethylene oxide adduct, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Examples thereof include ethylene oxide adducts.

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

The urethane (meth) acrylates are a reaction product of a hydroxyl group-containing (meth) acrylate, a polyisocyanate, and other alcohols used as needed. For example, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate, and glycerin (meth) such as glycerin mono (meth) acrylate and glycerin di (meth) acrylate. ) Alcolate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and other sugar alcohol (meth) acrylates, and toluene diisocyanate. , Hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexanemethylene diisocyanate, and polyisocyanates such as their isocyanurates and burette reactants are reacted with urethane (meth). ) It becomes acrylates.

The polyester (meth) acrylates include, for example, caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide-modified phthalic acid (meth) acrylate, ethylene oxide-modified succinic acid (meth) acrylate, and caprolactone-modified. Monofunctional (poly) ester (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate; hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, caprolactone-modified hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, epichlorohydrin Di (poly) ester (meth) acrylates such as modified phthalic acid di (meth) acrylate; 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone and δ-valerolactone per 1 mol of trimetylolpropane or glycerin Examples of the triol mono, di or tri (meth) acrylate obtained by adding the above.

Furthermore, triol mono, di, tri or tetra (meth) obtained by adding 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone and δ-valerolactone to 1 mol of pentaerythritol or ditrimethylolpropane. ) Triol mono obtained by adding 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone to 1 mol of acrylate and dipentaerythritol, or triol and tetra of poly (meth) acrylate. Examples thereof include mono (meth) acrylates and poly (meth) acrylates of polyhydric alcohols such as all, pentaol and hexaol.

Furthermore, diol components such as (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, 3-methyl-1,5-pentanediol, and hexanediol and maleic acid. , Fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebatic acid, azelaic acid, polybasic acids such as 5-sodium sulfoisophthalic acid, and anhydrides thereof. (Meta) acrylate of polyester polyol which is a reaction product with a product; (meth) acrylate of a cyclic lactone-modified polyester diol composed of the diol component, a polybasic acid, an anhydride thereof, ε-caprolactone, γ-butyrolactone, δ-valerolactone and the like. Examples thereof include polyfunctional (poly) ester (meth) acrylates such as meta) acrylate, but the present invention is not limited thereto.

The epoxy (meth) acrylates are carboxylate compounds of a compound having an epoxy group and (meth) acrylic acid. For example, phenol novolac type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate, trishydroxyphenylmethane type epoxy (meth) acrylate, dicyclopentadienephenol 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 (meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate, glyoxal type epoxy (meth) acrylate, heterocyclic epoxy ( Examples thereof include meta) acrylates and the like, and these acid anhydride-modified epoxy acrylates and the like.

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 styrenes include styrene, methylstyrene, ethylstyrene, divinylbenzene and the like. Other vinyl compounds include triallyl isocyanurate, trimetaallyl isocyanurate, bisallyl nadiimide and the like.

Among these, from the viewpoint of heat resistance, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, cresol novolac type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate, naphthalene skeleton-containing epoxy () It is preferably one or more selected from the group consisting of meta) acrylate and bisallyl nadiimide, and dipentaerythritol hexa (meth) acrylate is more preferable from the viewpoint of further improving heat resistance. By including a compound having such an ethylenically unsaturated group, the heat resistance of the obtained cured product tends to be further improved.

In the resin composition of the present embodiment, the content of the compound (D) having an ethylenically unsaturated group other than the component (C) is not particularly limited, but from the viewpoint of improving the developability, it is contained in the resin composition. The total content of the component (A), the component (C) and the component (D) is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, based on 100 parts by mass. It is more preferably 1.5 parts by mass or more. Further, from the viewpoint of improving the heat resistance of the cured product, it 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 from the viewpoint of improving the developability, 0. It is preferably 5 parts by mass or more, more preferably 1.0 part by mass or more, further preferably 1.5 parts by mass or more, still more preferably 5.0 parts by mass or more. Most preferably, it is 10 parts by mass or more. Further, from the viewpoint of improving the heat resistance of the cured product, the content is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. , 50 parts by mass or less, more preferably 25 parts by mass or less, and most preferably 20 parts by mass or less.

<Maleimide compound (E)>
In the resin composition of the present embodiment, a maleimide compound (E) (also referred to as a component (E)) can be used. The maleimide compound (E) will be described in detail below.

The maleimide compound (E) used in the present embodiment is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule. Specific examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidephenoxy) -phenyl} propane, 4,4. -Diphenylmethane bismaleimide, bis (3,5-dimethyl-4-maleimidephenyl) methane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, bis (3,5-diethyl-4-maleimidephenyl) Methan, phenylmethane maleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene biscitraconimide, m-phenylene biscitraconimide, p-phenylene biscitraconimide, 2,2-bis (4- (4-Maleimidephenoxy) -phenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6- Bismaleimide- (2,2,4-trimethyl) hexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenylsulphon bismaleimide, 1,3-bis (3-maleimide phenoxy) benzene, 1,3-bis ( 4-maleimide phenoxy) benzene, 4,4-diphenylmethane biscitraconimide, 2,2-bis [4- (4-citraconimide phenoxy) phenyl] propane, bis (3,5-dimethyl-4-citraconimidephenyl) methane , Bis (3-ethyl-5-methyl-4-citraconimidephenyl) methane, bis (3,5-diethyl-4-citraconimidephenyl) methane, polyphenylmethane maleimide, novolac type maleimide compound, biphenyl aralkyl type maleimide compound , The maleimide compound represented by the following formula (7), the maleimide compound represented by the following formula (8), the prepolymer of these maleimide compounds, the prepolymer of the maleimide compound and the amine compound, and the like.

Of these, novolak-type maleimide compounds and biphenyl aralkyl-type maleimide compounds are particularly preferable. Further, from the viewpoint of obtaining good coating film properties and excellent heat resistance, a maleimide compound represented by the following formula (7) and a maleimide compound represented by the following formula (8) are preferable, and the following formula (7) is preferable. The maleimide compound represented by is more preferable. As the maleimide compound represented by the following formula (7), a commercially available product can also be used, and examples thereof include BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd.). As the maleimide compound represented by the following formula (8), a commercially available product can also be used, and examples thereof include MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.).
These maleimide compounds (C) can be used alone or in admixture of two or more.

(In the formula (7), the plurality of R _5, each independently, .n ₁ represents a hydrogen atom or a methyl group, represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably 1 Represents an integer of ~ 5.

(In the formula (8), a plurality of R ₆ are each independently, .n ₂ represents a hydrogen atom or a methyl group, represents an integer of 1 or more, preferably an integer of 1 to 5.).
These maleimide compounds (E) can be used alone or in admixture of two or more.

The content of the maleimide compound (E) in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of sufficiently curing the resin composition and improving heat resistance, the component (A) in the resin composition , 0.01 part by mass or more, more preferably 0.02 part by mass or more, and 0.03 part by mass with respect to 100 parts by mass of the total content of the component (C) and the component (D). The above is more preferable. Further, from the viewpoint of improving the developability, it 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 parts by mass to 50 parts by mass with respect to 100 parts by mass of the resin solid content, which is more preferable. Is 0.02 parts by mass to 45 parts by mass, more preferably 0.03 parts by mass to 20 parts by mass, still more preferably 0.1 parts by mass to 10 parts by mass, and most preferably 1 part by mass. ~ 7 parts by mass. When the content of the maleimide compound is within the above range, the heat resistance of the cured product tends to be further improved.

<Filler (F)>
In order to improve various properties such as coating film property and heat resistance, the resin composition of the present embodiment can also be used in combination with a filler (F) (also referred to as a component (F)). The filler (F) used in the present embodiment is not particularly limited as long as it has insulating properties, and is, for example, silica (for example, natural silica, molten silica, amorphous silica, hollow silica, etc.), aluminum compound (for example, boehmite). , Aluminum hydroxide, alumina, etc.), Magnesium compounds (eg, magnesium oxide, magnesium hydroxide, etc.), Calcium compounds (eg, calcium carbonate, etc.), Molybdenum compounds (eg, molybdenum oxide, zinc molybdate, etc.), Barium compounds (eg, barium sulfate) , Barium silicate, etc.), talc (for example, natural talc, fired talc, etc.), mica (mica), glass (for example, short fibrous glass, spherical glass, fine powder glass (for example, E glass, T glass, D glass, etc.)), etc. ), Silicone powder, fluororesin-based filler, urethane resin-based filler, acrylic resin-based filler, polyethylene-based filler, styrene / butadiene rubber, silicone rubber, and the like.
Among them, it is selected from the group consisting of silica, boehmite, barium sulfate, silicone powder, fluororesin-based filler, urethane resin-based filler, acrylic resin-based filler, polyethylene-based filler, styrene-butadiene rubber and silicone rubber. It is preferably one or more.
These fillers (F) may be surface-treated with a silane coupling agent or the like described later.

In particular, silica is preferable, and fused silica is particularly preferable, from the viewpoint of improving the heat resistance of the cured product and obtaining good coating film properties. Specific examples of silica include SFP-130MC manufactured by Denka Co., Ltd., SC2050-MB, SC1050-MLE, YA010C-MFN, YA050C-MJA manufactured by Admatex Co., Ltd., and the like.
These fillers (F) can be used alone or in admixture of two or more.

In the resin composition of the present embodiment, the content of the filler (F) is not particularly limited, but from the viewpoint of improving the heat resistance of the cured product, the content of the resin solid content in the resin composition is 100 parts by mass. It is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 20 parts by mass or more. Further, from the viewpoint of improving the developability of the resin composition, it is preferably 400 parts by mass or less, and more preferably 350 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferably 300 parts by mass or less, further preferably 200 parts by mass or less, and most preferably 100 parts by mass or less.

<Silane coupling agent and wet dispersant>
In the resin composition of the present embodiment, a silane coupling agent and / or a wet dispersant may be used in combination in order to improve the dispersibility of the filler and the adhesive strength between the polymer and / or the resin and the filler. It is possible.
These silane coupling agents are not particularly limited as long as they are silane coupling agents generally used for surface treatment of inorganic substances. Specific examples include aminosilanes such as γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane; epoxysilanes such as γ-glycidoxypropyltrimethoxysilane. Acrylic silanes such as γ-acryloxypropyltrimethoxysilane; Cationic silanes such as N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride; phenylsilane silane cups Ring agent can be mentioned. These silane coupling agents may be used alone 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 with respect to 100 parts by mass of the resin composition.
The wet dispersant is not particularly limited as long as it is a dispersion stabilizer used for paints. Specific examples include wet dispersants such as DISPERBYK (registered trademark) -110, 111, 118, 180, 161 and BYK (registered trademark) -W996, W9010, W903 manufactured by Big Chemie Japan Co., Ltd. .. These wet dispersants can be used alone or in admixture of two or more.
In the resin composition of the present embodiment, the content of the wet dispersant 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.

<Any one or more compounds 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 biphenyl aralkyl type epoxy resin (A) represented by (1) above ( G)>
The compound (G) (also referred to as the component (G)) used in the present embodiment is cured, which is required in the field where the resin composition is used, in addition to the copper plating adhesion obtained by using the component (A). Various types of cured products can be used depending on the characteristics such as flame retardancy, heat resistance, and thermal expansion characteristics of the cured product. For example, when heat resistance is required, cyanate ester compounds, benzoxazine compounds and the like can be mentioned, and phenol resins, oxetane resins and the like can also be used. When a cyanic acid ester compound is used together with a biphenyl aralkyl type epoxy resin (A), a photocuring initiator (B), a compound (C) and a compound (D), heat resistance (glass transition temperature), low thermal expansion, and plating adhesion are used. A resin composition having excellent properties can be obtained. Further, it is preferable to use the cyanate ester compound in combination with the maleimide compound because 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 biphenyl aralkyl type epoxy resin (A) represented by the above (1), a resin composition having particularly excellent developability and plating adhesion can be obtained. ..

In addition, these can be used alone or in admixture of two or more.
The details of these compounds and / or the resin (G) will be described below.

<Cyanic acid ester compound>
The cyanate ester compound is not particularly limited as long as it is a resin having an aromatic moiety in the molecule in which at least one cyanato group (cyanic acid ester group) is substituted.

For example, the one represented by the general formula (9) can be mentioned.

In formula (9), Ar ₁ represents a benzene ring, a naphthalene ring, or a single bond of two benzene rings. When there are a plurality of them, they may be the same or different from each other. Ra independently has 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, an alkyl group having 1 to 6 carbon atoms and 6 to 12 carbon atoms. Indicates a group to which an aryl group is bonded. The aromatic ring in Ra may have a _{substituent, and the substituent in Ar 1} and Ra can be selected at any position. p _{indicates the number of cyanato groups attached to Ar 1} , and each is an integer of 1 to 3 independently. q represents the number of Ra to bind to Ar _1, the 4-p when Ar ₁ is a benzene ring, when the naphthalene ring when those 6-p, 2 one benzene ring is a single bond is 8-p .. t indicates the average number of repetitions and is an integer of 0 to 50, and the cyanate ester compound may be a mixture of compounds having different t. When there are a plurality of X, each of them is independently a single bond, a divalent organic group having 1 to 50 carbon atoms (the hydrogen atom may be replaced with a hetero atom), and a divalent group having 1 to 10 nitrogen atoms. Organic group (for example, -N-RN- (where R indicates an organic group)), carbonyl group (-CO-), carboxy group (-C (= O) O-), carbonyl dioxyside group ( -OC (= O) O-), sulfonyl group (-SO _2- ), divalent sulfur atom or divalent oxygen atom.

The alkyl group in Ra of the general formula (9) may have either a linear or branched chain structure or a cyclic structure (for example, a cycloalkyl group).
Further, the hydrogen atom in the alkyl group in the general formula (9) and the aryl group in Ra is 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. May be good.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group and 2,2-dimethylpropyl group. Examples thereof include a group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a trifluoromethyl group and the like.
Specific examples of the aryl group include phenyl group, xsilyl group, mesityl group, naphthyl group, phenoxyphenyl group, ethylphenyl group, o-, m- or p-fluorophenyl group, dichlorophenyl group, dicyanophenyl group and trifluorophenyl. Groups, methoxyphenyl groups, o-, m- or p-tolyl groups and the like can be mentioned. Further, 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, a tert-butoxy group and the like.

Specific examples of the divalent organic group having 1 to 50 carbon atoms in X of the general formula (9) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, and a biphenylyl. Examples thereof include a methylene group, a dimethylmethylene-phenylene-dimethylmethylene group, a fluoranyl group, a phthalidodiyl group and the like. 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, a cyano group or the like.
Examples of the divalent organic group having a nitrogen number of 1 to 10 in X of the general formula (9) include an imino group and a polyimide group.

Further, examples of the organic group of X in the general formula (9) include those having a structure represented by the following general formula (10) or the following general formula (11).

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 from each other. Rb, Rc, Rf, and Rg each independently have 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 having at least one phenolic hydroxy group. Indicates a group. Rd and Re are independently selected from any one of 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, and a hydroxy group. .. u represents an integer from 0 to 5.

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 from each other. Ri and Rj are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 12 carbon atoms, benzyl groups, alkoxyl groups having 1 to 4 carbon atoms, hydroxy groups, trifluoromethyl groups, respectively. Alternatively, it indicates an aryl group in which at least one cyanato group is substituted. v represents an integer from 0 to 5, but may be a mixture of compounds in which v is different.

Further, as X in the general formula (9), a divalent group represented by the following formula can be mentioned.

Here, in the formula, z represents an integer of 4 to 7. Each Rk independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Specific examples of Ar ₃ of Ar ₂ and of the general formula (10) (11), two carbon atoms shown in the general formula (10), or two oxygen atoms shown in the general formula (11) , A benzenetetrayl group bonded to the 1,4 or 1,3 position, the above two carbon atoms or two oxygen atoms at the 4,4'position, 2,4'position, 2,2'position, 2 , 3'-position, 3,3'-position, or 3,4'-position-bonded biphenyltetrayl group, and the above two carbon atoms or two oxygen atoms are at the 2, 6-position, 1,5-position. , 1,6 position, 1,8 position, 1,3 position, 1,4 position, or naphthalenetetrayl group bonded to 2,7 position.
The alkyl and aryl groups in Rb, Rc, Rd, Re, Rf and Rg of the general formula (10) and Ri and Rj of the general formula (11) are synonymous with those in the above general formula (9).

Specific examples of the cyanato-substituted aromatic compound represented by the above general formula (9) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1 -Cyanato-2-, 1-Cyanato-3-, or 1-Cyanato-4-methoxybenzene, 1-Cyanato-2,3-,1-Cyanato-2,4-,1-Cyanato-2,5-, 1-Cyanato-2,6-, 1-Cyanato-3,4- or 1-Cyanato-3,5-dimethylbenzene, Cyanatoethylbenzene, Cyanatobutylbenzene, Cyanatooctylbenzene, Cyanatononylbenzene, 2- (4-Cianaphenyl) -2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-2- or 1- Cianato-3-chlorobenzene, 1-Cyanato-2,6-dichlorobenzene, 1-Cyanato-2-methyl-3-chlorobenzene, Cyanatonitrobenzene, 1-Cyanato-4-nitro-2-ethylbenzene, 1-Cyanato-2 − -4-Acetylbenzene, 4-Cyanatobenzaldehyde, 4-Cyanato benzoic acid methyl ester, 4-Cyanato benzoic acid phenyl ester, 1-Cyanato-4-acetaminobenzene, 4-Cyanatobenzophenone, 1-Cyanato-2, 6-di-tert-butylbenzene, 1,2-disyanatobenzene, 1,3-disianatobenzene, 1,4-disyanatobenzene, 1,4-disyanato-2-tert-butylbenzene, 1,4- Disianato-2,4-dimethylbenzene, 1,4-disyanato-2,3,4-dimethylbenzene, 1,3-disianato-2,4,6-trimethylbenzene, 1,3-disianato-5-methylbenzene, 1-Cyanato or 2-Cyanatonaphthalene, 1-Cyanato 4-methoxynaphthalene, 2-Cyanato-6-methylnaphthalene, 2-Cyanato-7-methoxynaphthalene, 2,2'-disicanato-1,1'-binaphthyl, 1,3-,1,4-,1,5-,1,6-,1,7-,2,3-,2,6-or 2,7-disianatocinaphthalene, 2,2'-or 4,4'-Benzene Anatobiphenyl, 4,4'-disianato octafluorobiphenyl, 2,4'-or 4,4'-disianatodiphenylmethane, bis (4-cyanato-3,5-dimethylphenyl) methane, 1,1-bis ( 4-Cyanatophenyl) ethane, 1,1-bis (4-cyanatophenyl) propane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (4-cyanato-3-methylphenyl) ) Propane, 2,2-bis (2-cyanato-5-biphenylyl) propane, 2,2-bis (4-cyanatophenyl) hexafluoropropane, 2,2-bis (4-cyanato-3,5-) Dimethylphenyl) propane, 1,1-bis (4-cyanatophenyl) butane, 1,1-bis (4-cyanatophenyl) isobutane, 1,1-bis (4-cyanatophenyl) pentane, 1,1 -Bis (4-Cyanatophenyl) -3-methylbutane, 1,1-bis (4-Cyanatophenyl) -2-methylbutane, 1,1-bis (4-Cyanatophenyl) -2,2-dimethylpropane , 2,2-bis (4-cyanatophenyl) butane, 2,2-bis (4-cyanatophenyl) pentane, 2,2-bis (4-cyanatophenyl) hexane, 2,2-bis (4) −Cyanatophenyl) -3-methylbutane, 2,2-bis (4-cyanatophenyl) -4-methylpentane, 2,2-bis (4-cyanatophenyl) -3,3-dimethylbutane, 3, 3-bis (4-cyanatophenyl) hexane, 3,3-bis (4-cyanatophenyl) heptane, 3,3-bis (4-cyanatophenyl) octane, 3,3-bis (4-cyanato) Phenyl) -2-methylpentane, 3,3-bis (4-cyanatophenyl) -2-methylhexane, 3,3-bis (4-cyanatophenyl) -2,2-dimethylpentane, 4,4- Bis (4-cyanatophenyl) -3-methylheptane, 3,3-bis (4-cyanatophenyl) -2-methylheptane, 3,3-bis (4-cyanatophenyl) -2,2-dimethyl Hexane, 3,3-bis (4-cyanatophenyl) -2,4-dimethylhexane, 3,3-bis (4-cyanatophenyl) -2,2,4-trimethylpentane, 2,2-bis ( 4-Cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, bis (4-cyanatophenyl) phenylmethane, 1,1-bis (4-cyanatophenyl) -1-phenyl Etan, Bis (4 -Cyanatophenyl) biphenylmethane, 1,1-bis (4-cyanatophenyl) cyclopentane, 1,1-bis (4-cyanatophenyl) cyclohexane, 2,2-bis (4-cyanato-3-isopropyl) Phenyl) propane, 1,1-bis (3-cyclohexyl-4-cyanatophenyl) cyclohexane, bis (4-cyanatophenyl) diphenylmethane, bis (4-cyanatophenyl) -2,2-dichloroethylene, 1,3 -Bis [2- (4-Cyanatophenyl) -2-propyl] benzene, 1,4-Bis [2- (4-Cyanatophenyl) -2-propyl] benzene, 1,1-Bis (4-Si) Anatophenyl) -3,3,5-trimethylcyclohexane, 4- [bis (4-cyanatophenyl) methyl] biphenyl, 4,4-disyanatobenzophenone, 1,3-bis (4-cyanatophenyl) -2 -Propen-1-one, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) sulfide, bis (4-cyanatophenyl) sulfone, 4-cyanato benzoic acid-4-cyanatophenyl ester ( 4-Cyanatophenyl-4-Cyanatobenzoate), bis- (4-Cyanatophenyl) carbonate, 1,3-bis (4-Cyanatophenyl) adamantan, 1,3-bis (4-Cyanatophenyl) -5,7-Dimethyladamantan, 3,3-bis (4-cyanatophenyl) isobenzofuran-1 (3H) -one (cyanate of phenolphthaline), 3,3-bis (4-cyanato-3-methyl) Phenyl) Isobenzofuran-1 (3H) -one (cyanate of o-cresolphthaline), 9,9'-bis (4-cyanatophenyl) fluorene, 9,9-bis (4-cyanato-3-methylphenyl) ) Fluoren, 9,9-bis (2-cyanato-5-biphenylyl) fluoren, tris (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-Tetrax (4-Si) Anatophenyl) ethane, tetrakis (4-cyanatophenyl) methane, 2,4,6-tris (N-methyl-4-cyanatoanilino) -1,3,5-triazine, 2,4-bis (N-methyl-) 4-Cyanatoanilino) -6- (N-methylanili) No) -1,3,5-triazine, bis (N-4-cyanato-2-methylphenyl) -4,4'-oxydiphthalimide, bis (N-3-cyanato-4-methylphenyl) -4, 4'-oxydiphthalimide, bis (N-4-cyanatophenyl) -4,4'-oxydiphthalimide, bis (N-4-cyanato-2-methylphenyl) -4,4'-(hexafluoroisopropi) Liden) diphthalimide, tris (3,5-dimethyl-4-cyanatobenzyl) isocyanurate, 2-phenyl-3,3-bis (4-cyanatophenyl) phthalimidine, 2- (4-methylphenyl) -3 , 3-Bis (4-Cyanatophenyl) Phenylimidine, 2-Phenyl-3,3-Bis (4-Cyanato-3-methylphenyl) Phenylimidine, 1-Methyl-3,3-Bis (4-Cyanatophenyl) Examples thereof include indolin-2-one and 2-phenyl-3,3-bis (4-cyanatophenyl) indolin-2-one.

These cyanate ester compounds can be used alone or in admixture of two or more.

Further, as another specific example of the cyanic acid ester compound represented by the above general formula (9), a phenol novolac resin and a cresol novolac resin (by a known method, a phenol, an alkyl-substituted phenol or a halogen-substituted phenol, and a formaldehyde or the like are used. Formaldehyde compounds such as paraformaldehyde reacted in an acidic solution), trisphenol novolac resin (hydroxybenzaldehyde and phenol reacted in the presence of an acidic catalyst), fluorennovolac resin (fluorenone compound and 9). , 9-bis (hydroxyaryl) that the fluorenes were reacted in the presence of an acid catalyst), phenol aralkyl resins, cresol aralkyl resin, a naphthol aralkyl resin and a biphenyl aralkyl resin (a known method, Ar ₄ - (CH ₂ Y) ₂ (Ar ₄ indicates a phenyl group and Y indicates a halogen atom. The same shall apply hereinafter in this paragraph). Reaction of a bishalogenomethyl compound and a phenol compound with an acidic catalyst or no catalyst. that is, Ar ₄ - (CH ₂ oR) expressed by such bis ₂ (alkoxymethyl) that a compound with a phenol compound is reacted in the presence of an acidic catalyst, or, Ar ₄ - (CH ₂ OH ) A _{reaction of a bis (hydroxymethyl) compound and a phenol compound as represented by 2} in the presence of an acidic catalyst, or a polycondensation of an aromatic aldehyde compound, an aralkyl compound and a phenol compound), Phenol-modified xyleneformaldehyde resin (a reaction of xyleneformaldehyde resin and phenol compound in the presence of an acidic catalyst by a known method), modified naphthalene formaldehyde resin (a naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound by a known method). (Reacted in the presence of an acidic catalyst), a phenol-modified dicyclopentadiene resin, and a phenol resin having a polynaphthylene ether structure (by a known method, a polyvalent having two or more phenolic hydroxy groups in one molecule). Examples thereof include those obtained by cyanating a phenol resin such as a hydroxynaphthalene compound dehydrated and condensed in the presence of a basic catalyst) by the same method as described above, and prepolymers thereof. These are not particularly limited. These cyanate ester compounds can be used alone or in admixture of two or more.

Among these, phenol novolac type cyanate ester compound, naphthol aralkyl type cyanate ester compound, biphenyl aralkyl type cyanate ester compound, naphthylene ether type cyanate ester compound, xylene resin type cyanate ester compound, adamantan skeleton type cyanate ester The compound is preferable, and the naphthol aralkyl type cyanate ester compound is particularly preferable from the viewpoint 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 in which a hydroxy group-containing compound having a desired skeleton is obtained or synthesized, and the hydroxy group is modified by a known method to cyanate. Examples of the method for cyanating a hydroxy group include the methods described in Ian Hamerton, "Chemistry and Technology of Cyanate Ester Resins," Blackie Academic & Professional.

The cured resin product using these cyanate ester compounds has 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 preferable with respect to 100 parts by mass of the resin solid content from the viewpoint of obtaining better plating adhesion and heat resistance. Is 0.01 parts by mass to 50 parts by mass, 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, and even more preferably 0.2 parts by mass. It is 5 parts by mass by mass.

<Phenol resin>
As the phenol resin, generally known phenol resins can be used as long as they have two or more hydroxyl groups in one molecule. For example, bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type phenol resin, biphenyl. Aralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolak type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type Examples include phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, phosphorus-containing phenol resin, polymerizable unsaturated hydrocarbon group-containing phenol resin and hydroxyl group-containing silicone resin. However, there are no particular restrictions. Among these phenol resins, biphenyl aralkyl type phenol resin, naphthol aralkyl type phenol resin, phosphorus-containing phenol resin, and hydroxyl group-containing silicone resin are preferable in terms of flame retardancy. These phenol resins can be used alone or in admixture 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, and more preferably 0.2 parts by mass to 45 parts by mass with respect to 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, alkyl oxetane such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3-di (trifluoro). Methyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl-type oxetane, OXT-101 (manufactured by Toa Synthetic, trade name), OXT-121 (manufactured by Toa Synthetic, trade name) Etc., and are not particularly limited. It is also possible to use one kind or a mixture of two or more kinds as appropriate.

The content of the oxetane resin is not particularly limited, and is preferably 0.1 part by mass to 50 parts by mass, and more preferably 0.2 parts by mass to 45 parts by mass with respect to 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 compound>
As the benzoxazine compound, a generally known compound can be used as long as it is a compound having two or more dihydrobenzoxazine rings in one molecule. For example, bisphenol A type benzoxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name) Bisphenol F type benzoxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), bisphenol S type benzoxazine BS-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name) ), Phenolphthaline type benzoxazine and the like, but are not particularly limited. These can be used alone or in admixture 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, and more preferably 0.2 parts by mass to 45 parts by mass with respect to 100 parts by mass of the resin solid content. be. When the content of the benzoxazine compound is within the above range, the heat resistance tends to be further improved.

<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 biphenyl aralkyl type epoxy resin (A) represented by the above (1).
Unlike the epoxy resin (A), such an epoxy resin is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. Specific examples thereof include 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, and phenol novolac type epoxy resin. Cresol novolac type epoxy resin, xylene novolac type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, naphthylene ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, Trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, triglycidyl isocyanurate, glycidyl ester type epoxy resin, alicyclic epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, phenol aralkylnovolac type epoxy Epoxy double bonds such as resin, naphthol aralkylnovolac type epoxy resin, aralkylnovolac type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, glycidylamine, butadiene, etc. Examples thereof include the above-mentioned compounds, compounds obtained by reacting hydroxyl group-containing silicone resins with epichlorohydrin, and epoxies thereof.

Among them, it is preferably one or more selected from the group consisting of a naphthylene ether type epoxy resin, a polyfunctional phenol type epoxy resin, and a naphthalene type epoxy resin, and a naphthalene type epoxy resin is more preferable. By including such a kind of epoxy resin, the developability and the plating adhesion tend to be further improved.
As the naphthalene type epoxy resin, it is preferable to use a resin represented by the following formula (5) because the developability and 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) has excellent solubility in a developing solution because it has a small molecule and is polyfunctional. Therefore, it is considered that a resin composition having excellent developability can be obtained by using it in combination with the biphenyl aralkyl type epoxy resin (A).

These epoxy resins can be used alone or in admixture of two or more.

The content of the epoxy resin is not particularly limited, but from the viewpoint of further improving the developability, the epoxy resin (A) and the epoxy resin (A) are added to 100 parts by mass of the resin solid content in the resin composition. The total amount of the different epoxy resins is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, and further preferably 15 parts by mass or more. preferable. Further, from the viewpoint of further improving the copper plating adhesion, the total amount of the epoxy resin (A) and the epoxy resin different from the epoxy resin (A) is based on 100 parts by mass of the resin solid content in the resin composition. It is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, further preferably 30 parts by mass or less, and further preferably 28 parts by mass or less.
The ratio of the epoxy resin (A) to the epoxy resin different from the epoxy resin (A) is not particularly limited, but is preferably 1 to 10: 1 to 3 and 2 to 4: 1 from the viewpoint of plating adhesion. ~ 2 is more preferable.

<Thermosetting accelerator (H)>
In the resin composition of the present embodiment, a thermosetting accelerator (H) (also referred to as a component (H)) can be used as long as the characteristics of the present embodiment are not impaired. The heat curing accelerator (H) used in the present embodiment is not particularly limited, and is, for example, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate. Organic peroxides exemplified by, etc .; azo compounds such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri. Tertiary amines such as -n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcin, catechol Kind: Organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetone; these organic metal salts are phenols and bisphenols. Those dissolved in hydroxyl group-containing compounds such as; inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; dioctyl tin oxide and other organic tin compounds such as alkyl tin and alkyl tin oxide; 2-ethyl-4- Examples thereof include imidazole compounds such as methyl imidazole, 1,2-dimethyl imidazole, 1-benzyl-2-phenyl imidazole and triphenyl imidazole (TPIZ). Among them, imidazole compounds such as 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-phenylimidazole, and triphenylimidazole (TPIZ) are preferable from the viewpoint of heat resistance, and 2-ethyl -4-Methylimidazole is more preferable because it has high reactivity with the biphenyl aralkyl type epoxy resin (A), the compound (C) and the compound (D), and more excellent heat resistance can be obtained.

These thermosetting accelerators can be used alone or in admixture 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 with respect to 100 parts by mass of the resin solid content in the resin composition. It is preferably 0.05 to 5 parts by mass.

<Organic solvent>
The resin composition of the present embodiment may contain a solvent, if necessary. For example, when an organic solvent is used, the viscosity of the resin composition at the time of preparation can be adjusted. The type of 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 are not particularly limited, but for example, ketones such as acetone, methyl ethyl ketone and methyl cell solve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol monomethyl ether and its acetate. Can be mentioned.
These organic solvents may be used alone or in admixture of two or more.

<Other ingredients>
The resin composition of the present embodiment contains various polymer compounds such as thermosetting resins, thermoplastic resins and their oligomers, elastomers, etc., which have not been mentioned so far, as long as the characteristics of the present embodiment are not impaired. Flame-retardant compounds not listed so far; Additives and the like can be used in combination. These are not particularly limited as long as they are generally used. For example, flame-retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, phosphate compounds of phosphorus compounds, aromatic condensed phosphoric acid esters, halogen-containing condensed phosphoric acid esters, and the like. Additives include UV absorbers, antioxidants, optical brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, surface conditioners, brighteners, polymerization inhibitors, etc. Be done. These components may be used alone or in admixture of two or more.
In the resin composition of the present embodiment, the content of 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.

<Manufacturing method of resin composition>
The resin composition of the present embodiment includes a biphenyl aralkyl type epoxy resin (A) represented by the formula (1), a photocuring initiator (B), a compound (C) represented by the formula (2), and ( Prepared by appropriately mixing a compound (D) having an ethylenically unsaturated group other than the component C) with a maleimide compound (E), a filler (F), a compound (G), and other components, if necessary. Will be done. The resin composition of the present embodiment can be suitably used as a varnish for producing the resin sheet of the present invention described later.

The method for producing the resin composition of the present embodiment is not particularly limited, and examples thereof include a method in which each of the above-mentioned components is sequentially added to a solvent and sufficiently stirred.

At the time of producing the resin composition, a known treatment (stirring, mixing, kneading treatment, etc.) for uniformly dissolving or dispersing each component can be performed, if necessary. Specifically, the dispersibility of the inorganic filler (G) in the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank equipped with a stirring machine having an appropriate stirring ability. The above-mentioned stirring, mixing, and kneading treatment may be performed on, for example, a stirring device for dispersing an ultrasonic homogenizer, a device for mixing three rolls, a ball mill, a bead mill, a sand mill, or a revolution or rotation type. It can be appropriately performed using a known device such as a mixing device. Further, when preparing the resin composition of the present embodiment, an organic solvent can be used if necessary. The type 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.

<Use>
The resin composition of the present embodiment can be used in applications that require an insulating resin composition, and is not particularly limited, but is an insulating resin sheet such as a photosensitive film, a photosensitive film with a support, and a prepreg. , Circuit boards (laminated board applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, component embedding resins, etc. Among them, it can be suitably used as a resin composition for an insulating layer of a multilayer printed wiring board or a solder resist.

<Resin sheet>
The resin sheet of the present embodiment comprises a support and a resin composition layer formed on the surface of the support and containing the resin composition of the present embodiment, and the above-mentioned resin composition is provided on one side or both sides of the support. It is a resin sheet with a support applied to. The resin sheet can be produced by applying the resin composition on the support and drying it.

The support used in the resin sheet of the present embodiment is not particularly limited, but known ones can be used, and a resin film is 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, and a polyvinyl alcohol. Examples thereof include resin films such as films and triacetyl acetate films. Among them, PET film is preferable.

As the resin film, a release agent coated on the surface can be preferably used in order to facilitate peeling from the resin composition layer. The thickness of the resin film is preferably in the range of 5 μm to 100 μm, and more preferably in the range of 10 μm to 50 μm. If the thickness is less than 5 μm, the support tends to be torn easily when the support is peeled off before development, and if the thickness exceeds 100 μm, the resolution when exposed from above the support tends to decrease. be.

Further, in order to reduce the scattering of light during exposure by active energy rays such as ultraviolet rays, it is preferable that the resin film has excellent transparency.

Further, in the resin sheet of the present embodiment, the resin composition layer may be protected by a protective film.
By protecting the resin composition layer side with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches. As the protective film, a film made of 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 μm to 50 μm, and more preferably in the range of 5 μm to 40 μm. If the thickness is less than 1 μm, the handleability of the protective film tends to decrease, and if it exceeds 50 μm, the cost tends to be inferior. The protective film preferably has a smaller adhesive force between the resin composition layer and the protective film than the adhesive force between the resin composition layer and the support.

The method for producing the resin sheet of the present embodiment is not particularly limited, but for example, the resin sheet is produced by applying the resin composition of the present embodiment to a support such as a PET film and removing the organic solvent by drying. How to do it.
The above coating 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 or the like. The drying can be performed, for example, by heating in a dryer at 60 to 200 ° 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 with respect to the total mass of the resin composition layer from the viewpoint of preventing the diffusion of the organic solvent in a later step. The thickness of the resin composition layer with respect to the support is preferably 1.0 μm or more in terms of the thickness of the resin composition layer of the resin sheet from the viewpoint of improving handleability. Further, from the viewpoint of improving the transmittance and improving the developability, the thickness is preferably 300 μm 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 wiring board>
The multilayer printed wiring board of the present embodiment includes an interlayer insulating layer containing the resin composition of the present embodiment, and can be obtained by, for example, stacking one or more of the above-mentioned resin sheets and curing them. Specifically, it can be produced by the following method.

(Laminating process)
The resin composition layer side of the resin sheet of the present 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 board, 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 heat-curable polyphenylene ether substrate, and the like. Here, the circuit board refers to a board on which a patterned conductor layer (circuit) is formed on one side or both sides of the board as described above. Further, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, a substrate in which one or both sides of the outermost layer of the printed wiring board is a patterned conductor layer (circuit) is also included here. It is included in the circuit board mentioned above. The surface of the conductor layer may be roughened in advance by blackening treatment, copper etching or the like. In the laminating step, if the resin sheet has a protective film, the protective film is peeled off and removed, and then the resin sheet and the circuit board are preheated as necessary, and the resin composition layer is pressurized and heated. Crimped to the circuit board. In the resin sheet of the present embodiment, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used.

The conditions of the laminating step are not particularly limited, but for example, the crimping temperature (lamination temperature) is preferably 50 ° C. to 140 ° C., the crimping pressure is preferably 1 kgf / cm ^{2 to} 15 kgf / cm ² , and the crimping time. Is preferably 5 seconds to 300 seconds, and the lamination is preferably performed under reduced pressure so that the air pressure is 20 mmHg or less. Further, the laminating step may be a batch type or a continuous type using a roll. The vacuum laminating method can be performed using a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a two-stage build-up laminator manufactured by Nikko Materials Co., Ltd.

(Exposure process)
After the resin sheet is provided on the circuit board by the laminating step, an exposure step is performed in which a predetermined portion of the resin composition layer is irradiated with active energy rays to cure the resin composition layer of the irradiated portion. Irradiation of the active energy rays may be performed through a mask pattern, or a direct drawing method of directly irradiating the active energy rays may be used.

Examples of the active energy ray include ultraviolet rays, visible rays, electron beams, X-rays and the like, and ultraviolet rays are particularly preferable. Dose of ultraviolet light is approximately ^{10mJ / cm 2 ~1000mJ / cm 2} . There are two types of exposure methods through which the mask pattern is passed: a contact exposure method in which the mask pattern is brought into close contact with a multilayer printed wiring board, and a non-contact exposure method in which the mask pattern is exposed using parallel rays without being brought into close contact. It doesn't matter. When the support is present on the resin composition layer, it may be exposed from above the support, or the support may be exposed after being peeled off.

(Development process)
After the exposure step, if a support is present on the resin composition layer, the support is removed, and then wet development is performed to remove the non-photocured portion (unexposed portion) for development. Therefore, the pattern of the insulating layer can be formed.

In the case of the above wet development, the developing solution is not particularly limited as long as it selectively elutes the unexposed portion, but a developing solution such as an alkaline aqueous solution, an aqueous developer, or an organic solvent is used. .. In the present embodiment, a developing step using an alkaline aqueous solution is particularly preferable. These developers can be used alone or in combination of two or more. Further, as a developing method, for example, a known method such as spraying, rocking dipping, brushing, scraping or the like can be performed.

The alkaline aqueous solution used as the developing solution is not particularly limited, but is, for example, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, sodium 4-borate, and ammonia. , Amines and the like.

The concentration of the alkaline aqueous solution is preferably 0.1% by mass to 60% by mass with respect to the total amount of the developing solution. Further, the temperature of the alkaline aqueous solution can be adjusted according to the developability. Further, these alkaline aqueous solutions can be used alone or in combination of two or more.

In the pattern formation of the present embodiment, if necessary, the above-mentioned two or more kinds of development methods may be used in combination. Development methods include a dip method, a paddle method, a spray method, a high-pressure spray method, brushing, slapping, and the like, and the high-pressure spray method is suitable for improving the resolution. When the spray method is adopted, the spray pressure is preferably 0.02 MPa to 0.5 MPa.

(Post-baking process)
After the development step is completed, a post-baking step is performed to form an insulating layer (cured product). Examples of the post-baking step include an ultraviolet irradiation step using a high-pressure mercury lamp and a heating step using a clean oven, and these can also be used in combination. When irradiating with ultraviolet rays, the irradiation amount can be adjusted as needed, and for example, irradiation can be performed with an irradiation amount of about ^{0.05 J / cm 2 to} 10 J / cm ^2. The heating conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but are preferably in the range of 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, and more preferably 160 ° C. It is selected in the range of 30 minutes to 150 minutes at ~ 200 ° C.

(Plating process)
Next, a conductor 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 thin film deposition method, a sputtering method, and an ion plating method can be used. In the thin-film 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 vessel and heating and evaporating the metal. In the sputtering method, for example, the support is placed in a vacuum vessel, an inert gas such as argon is introduced, a DC voltage is applied, the ionized inert gas is made to collide with the target metal, and the metal is beaten out. A metal film can be formed on the insulating layer.

In the case of wet plating, the surface of the formed insulating layer is roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. .. The swelling treatment with the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 ° C. to 80 ° 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. Examples of commercially available swelling liquids include Updes (registered trademark) MDS-37 manufactured by Uemura Kogyo Co., Ltd.

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

Next, electroless plating and electrolytic plating are combined to form a conductor layer. It is also possible to form a plating resist having a pattern opposite to that of the conductor layer, and to form the conductor layer only by electroless plating. As a method of subsequent pattern formation, for example, a subtractive method, a semi-additive method, or the like 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, and can be specifically produced by the following method. A semiconductor device can be manufactured by mounting a semiconductor chip on a conductive portion of the multilayer printed wiring board of the present embodiment. Here, the conductive portion is a portion of the multilayer printed wiring board that transmits an electric signal, and the location may be a surface or an embedded portion. Further, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting the semiconductor chip when manufacturing the semiconductor device of the present embodiment is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and a bump. None A mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like can be mentioned.

A semiconductor device can also be manufactured by laminating the resin sheet of the present embodiment on a semiconductor chip. After laminating, it can be manufactured by the same method as the above-mentioned multilayer printed wiring board.

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

[Synthesis Example 1]
(Synthesis of cyanate ester compound)
1-Naphthol aralkyl resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 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 hydroxy group) were dissolved in 1800 g of dichloromethane. This was designated as solution 1.
Cyanogen chloride 125.9 g (2.05 mol) (1.6 mol with respect to 1 mol of hydroxy group), dichloromethane 293.8 g, 36% hydrochloric acid 194.5 g (1.92 mol) (1.5 mol with respect to 1 mol of hydroxy group) ), 1205.9 g of water was poured over 30 minutes while maintaining the liquid temperature at -2 to -0.5 ° C. with stirring. After pouring 1 solution, the mixture was stirred at the same temperature for 30 minutes, and then a solution (solution 2) in which 65 g (0.64 mol) of triethylamine (0.5 mol with respect to 1 mol of hydroxy group) was dissolved in 65 g of dichloromethane was added for 10 minutes. I poured it over. After 2 pouring of the solution was completed, the reaction was completed by stirring at the same temperature for 30 minutes.
After that, the reaction solution was allowed to stand to separate the organic phase and the aqueous phase. The obtained organic phase was washed 5 times with 1300 g of water. The electrical conductivity of the wastewater after the fifth washing with water was 5 μS / cm, and it was confirmed that the ionic compounds that could be removed were sufficiently removed by washing with water.
The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated to dryness at 90 ° C. for 1 hour to obtain 331 g of the target naphthol aralkyl type cyanate ester compound (SNCN) (orange viscous substance). 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} (cyanic acid ester group) and no absorption of hydroxy group.

[Example 1]
(Preparation of resin composition and resin sheet)
As the biphenyl aralkyl type epoxy resin (A) represented by the formula (1), the biphenyl aralkyl type epoxy resin (n in the formula (1) is 1 to 3; NC3000L (trade name), Nippon Kayaku Co., Ltd. ) 22.4 parts by mass, as a photocuring initiator (B), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Epoxy® 369, BASF Japan) 6.5 parts by mass, compound (C), propylene glycol monomethyl ether acetate (hereinafter, may be abbreviated as PGMEA) solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H, Non-volatile content 65% by mass, acid value: 70 mgKOH / g, manufactured by Nippon Kayaku Co., Ltd. 77.5 parts by mass (50.4 parts by mass in terms of non-volatile content), ethylenically unsaturated groups other than component (C) Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 17.4 parts by mass as the compound (D), and the maleimide compound (BMI-2300 (trade name)) as the maleimide compound (E). ), 3.3 parts by mass of Daiwa Kasei Kogyo Co., Ltd., as a filler (F), a methyl ethyl ketone (hereinafter, sometimes abbreviated as MEK) slurry of epoxysilane-treated silica (SC2050MB (trade name), average particle size). Add 71.4 parts by mass (50 parts by mass in terms of non-volatile content) of 0.5 μm, 70% by mass of non-volatile content, manufactured by Admatex Co., Ltd., and stir with an ultrasonic homogenizer to make a varnish (solution of resin composition). Got These varnishes are applied on a 38 μm-thick PET film (Unipeal (registered trademark) TR1-38, manufactured by Unitika Ltd., trade name) using an automatic coating device (PI-1210, manufactured by Tester Sangyo Co., Ltd.). The coating was applied and dried by heating at 80 ° C. for 7 minutes to obtain a resin sheet having a PET film as a support and a resin composition layer having a thickness of 30 μm.

The KAYARAD (registered trademark) ZCR-6007H is a mixture containing any one or more of the above compounds (C1) and the above compounds (C2) to (C5).

(Creation of inner layer circuit board)
Both sides of a glass cloth base material BT resin double-sided copper-clad laminate (copper foil thickness 18 μm, thickness 0.2 mm, CCL (registered trademark) -HL832NS manufactured by Mitsubishi Gas Chemical Company, Inc.) on which an inner layer circuit is formed are both sides of MEC Co., Ltd. The copper surface was roughened with CZ8100 manufactured by CZ8100 to obtain an inner layer circuit board.

(Preparation of laminate for evaluation)
The resin surface of the resin sheet is placed on the inner layer circuit board, and after vacuuming (5.0 MPa or less) for 30 seconds using a vacuum laminator (manufactured by Nikko Materials Co., Ltd.), the pressure is 10 kgf / cm. ^2. Laminate molding was performed at a temperature of 70 ° C. for 30 seconds. Further, laminating molding was performed at a pressure of 10 kgf / cm ² and a temperature of 70 ° C. for 60 seconds to obtain a laminated body in which the inner layer circuit board, the resin composition layer and the support were laminated. The obtained laminate is ^{subjected to an exposure step of irradiating the obtained laminate with ultraviolet rays of 200 mJ / cm 2} , the support is peeled off, developed with a 1 mass% sodium carbonate aqueous solution, and further exposed with ultraviolet rays of ^{1000 mJ / cm 2.} After performing a post-baking step of heat-treating at 180 ° C. for 120 minutes, a laminate for evaluation was obtained.

(Preparation of cured product for evaluation)
The resin sheet is irradiated with ultraviolet rays of 200 mJ / cm ^{2 , further subjected to an exposure step of irradiating ultraviolet rays of 1000 mJ / cm 2} , a post-baking step of heat-treating at 180 ° C. for 120 minutes, and then the support is peeled off. It was used as a cured product for evaluation.

[Example 2]
As a component (A), 21.9 parts by mass of a biphenyl aralkyl type epoxy resin (NC3000L (trade name), manufactured by Nippon Kayaku Co., Ltd.), and as a photocuring initiator (B), 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butanone-1 (Irgacure (registered trademark) 369, manufactured by BASF Japan Co., Ltd.) 6.5 parts by mass, as compound (C), a PGMEA solution of a TrisP-PA epoxy acrylate compound ( KAYARAD (registered trademark) ZCR-6007H, non-volatile content 65% by mass, acid value: 70 mgKOH / g, manufactured by Nippon Kayaku Co., Ltd. 77.5 parts by mass (50.4 parts by mass in terms of non-volatile content), (C) As the compound (D) having an ethylenically unsaturated group other than the components, 17.4 parts by mass of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.), as a maleimide compound (E), Maleimide compound (BMI-2300 (trade name), manufactured by Daiwa Kasei Kogyo Co., Ltd.) 3.3 parts by mass, as filler (F), MEK slurry of epoxy silane treated silica (SC2050MB (trade name), average particle size 0 .5 μm, 70% by mass of non-volatile content, 71.4 parts by mass (50 parts by mass in terms of non-volatile content) of Admatex Co., Ltd., as compound (G), the cyanate ester compound SNCN0. 5 parts by mass were blended and stirred with an ultrasonic homogenizer to obtain a varnish (solution of the resin composition). These varnishes are applied on a 38 μm-thick PET film (Unipeal (registered trademark) TR1-38, manufactured by Unitika Ltd., trade name) using an automatic coating device (PI-1210, manufactured by Tester Sangyo Co., Ltd.). The coating was applied and dried by heating at 80 ° C. for 7 minutes to obtain a resin sheet having a PET film as a support and a resin composition layer having a thickness of 30 μm. Using this, an evaluation laminate and an evaluation cured product were obtained in the same manner as in Example 1.

[Example 3]
As a component (A), 21.9 parts by mass of a biphenyl aralkyl type epoxy resin (NC3000L (trade name), manufactured by Nippon Kayaku Co., Ltd.), and as a photocuring initiator (B), 2,4,6-trimethylbenzoyl- Diphenyl-phosphine oxide (Irgacure (registered trademark) 819, manufactured by BASF Japan Co., Ltd.) 6.5 parts by mass, as compound (C), PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H , Non-volatile content 65% by mass, acid value: 70 mgKOH / g, manufactured by Nippon Kayaku Co., Ltd. 77.5 parts by mass (50.4 parts by mass in terms of non-volatile content), ethylenically unsaturated groups other than the component (C) Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 17.4 parts by mass as the compound (D), and the maleimide compound (BMI-2300 (commodity)) as the maleimide compound (E). Name), manufactured by Daiwa Kasei Kogyo Co., Ltd., 3.3 parts by mass, as filler (F), MEK slurry of epoxy silane treated silica (SC2050MB (trade name), average particle size 0.5 μm, non-volatile content 70% by mass) , (Manufactured by Admatex Co., Ltd.) 71.4 parts by mass (50 parts by mass in terms of non-volatile content), 0.5 parts by mass of the cyanate ester compound SNCN obtained in Synthesis Example 1 was blended as compound (G), and super A varnish (solution of the resin composition) was obtained by stirring with a sonic homogenizer. These varnishes are applied on a 38 μm-thick PET film (Unipeal (registered trademark) TR1-38, manufactured by Unitika Ltd., trade name) using an automatic coating device (PI-1210, manufactured by Tester Sangyo Co., Ltd.). The coating was applied and dried by heating at 80 ° C. for 7 minutes to obtain a resin sheet having a PET film as a support and a resin composition layer having a thickness of 30 μm. Using this, an evaluation laminate and an evaluation cured product were obtained in the same manner as in Example 1.

[Example 4]
As component (A), biphenyl aralkyl type epoxy resin (NC3000L (trade name), manufactured by Nippon Kayaku Co., Ltd.) 15.8 parts by mass, and as component (G), naphthalene type epoxy resin (HP-4710 (trade name)) , DIC Co., Ltd.) 6.1 parts by mass, as a photocuring initiator (B), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Irgacure (registered trademark) 819, BASF Japan Co., Ltd.) (Manufactured by) 6.5 parts by mass, as compound (C), PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H, non-volatile content 65% by mass, acid value: 70 mgKOH / g, Nippon Kayaku (Nippon Kayaku) As a compound (D) having 77.5 parts by mass (50.4 parts by mass in terms of non-volatile content) and an ethylenically unsaturated group other than the component (C), dipentaerythritol hexaacrylate (KAYARAD®). ) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 17.4 parts by mass, as a maleimide compound (E), filled with a maleimide compound (BMI-2300 (trade name), manufactured by Daiwa Kasei Kogyo Co., Ltd.) 3.3 parts by mass. As the material (F), MEK slurry of epoxy silane treated silica (SC2050MB (trade name), average particle size 0.5 μm, non-volatile content 70% by mass, manufactured by Admatex Co., Ltd.) 71.4 parts by mass (in terms of non-volatile content) 50 parts by mass), 0.5 parts by mass of the cyanate ester compound SNCN obtained in Synthesis Example 1 was blended as the compound (G), and the mixture was stirred with an ultrasonic homogenizer to obtain a varnish (solution of the resin composition). These varnishes are applied on a 38 μm-thick PET film (Unipeal (registered trademark) TR1-38, manufactured by Unitika Ltd., trade name) using an automatic coating device (PI-1210, manufactured by Tester Sangyo Co., Ltd.). The coating was applied and dried by heating at 80 ° C. for 7 minutes to obtain a resin sheet having a PET film as a support and a resin composition layer having a thickness of 30 μm. Using this, an evaluation laminate and an evaluation cured product were obtained in the same manner as in Example 1.

[Example 5]
As component (A), biphenyl aralkyl type epoxy resin (NC3000L (trade name), manufactured by Nippon Kayaku Co., Ltd.) 15.8 parts by mass, and as component (G), naphthalene type epoxy resin (HP-4710 (trade name)) , DIC Co., Ltd.) 6.1 parts by mass, as a photocuring initiator (B), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Irgacure (registered trademark) 819, BASF Japan Co., Ltd.) (Manufactured by) 6.5 parts by mass, as compound (C), PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H, non-volatile content 65% by mass, acid value: 70 mgKOH / g, Nippon Kayaku (Nippon Kayaku) As a compound (D) having 77.5 parts by mass (50.4 parts by mass in terms of non-volatile content) and an ethylenically unsaturated group other than the component (C), dipentaerythritol hexaacrylate (KAYARAD®). ) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 17.4 parts by mass, as a maleimide compound (E), filled with a maleimide compound (BMI-2300 (trade name), manufactured by Daiwa Kasei Kogyo Co., Ltd.) 3.3 parts by mass. As the material (F), MEK slurry of epoxy silane treated silica (SC2050MB (trade name), average particle size 0.5 μm, non-volatile content 70% by mass, manufactured by Admatex Co., Ltd.) 71.4 parts by mass (in terms of non-volatile content) 50 parts by mass), 0.5 parts by mass of the cyanate ester compound SNCN obtained in Synthesis Example 1 as compound (G), and 2-ethyl-4-methylimidazole (2E4MZ (trade name)) as a thermal curing accelerator (H). ) And 0.2 parts by mass of Shikoku Kasei Co., Ltd., and stirred with an ultrasonic homogenizer to obtain a varnish (solution of the resin composition). These varnishes are applied on a 38 μm-thick PET film (Unipeal (registered trademark) TR1-38, manufactured by Unitika Ltd., trade name) using an automatic coating device (PI-1210, manufactured by Tester Sangyo Co., Ltd.). The coating was applied and dried by heating at 80 ° C. for 7 minutes to obtain a resin sheet having a PET film as a support and a resin composition layer having a thickness of 30 μm. Using this, an evaluation laminate and an evaluation cured product were obtained in the same manner as in Example 1.

[Comparative Example 1]
Instead of compound (C), bisphenol F type epoxy acrylate (KAYARAD (registered trademark) ZFR-1553H, non-volatile content 68% by mass, acid value: 70 mgKOH / g, manufactured by Nippon Kayaku Co., Ltd.) 74.1 parts by mass ( A varnish was prepared in the same manner as in Example 1 except that 50.4 parts by mass in terms of non-volatile content was used to obtain a resin sheet, an evaluation laminate, and an evaluation cured product.

KAYARAD (registered trademark) ZFR-1553H does not have a 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 instead of the component (A), and the resin was prepared. A sheet, a laminate for evaluation, 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 polyfunctional epoxy resin (1031S (trade name), manufactured by Mitsubishi Chemical Corporation) was used instead of the component (A), and the resin was prepared. A sheet, a laminate for evaluation, and a cured product for evaluation were obtained.

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

[Measurement and evaluation of physical properties]
The resin sheet, the evaluation laminate and the evaluation cured product were measured and evaluated by the following methods. The results are shown in Table 1.

<Coating film property>
A finger was lightly pressed against the resin surface edge of each A4 size resin sheet with a support, and the degree of sticking to the finger was evaluated according to the following criteria.
◯: There is almost no sticking to the finger. The end of the resin sheet with a support sticks to the finger, but if the height is less than 30 mm, it peels off from the finger and falls.
X: Sticking to the finger is recognized. The end of the resin sheet with a support sticks to the finger and rises at a height of 30 mm or more.

<Heat resistance (glass transition temperature)>
The cured product for evaluation was heated at 10 ° C./min using a DMA device (dynamic viscoelasticity measuring device DMAQ800 (trade name) manufactured by TA Instruments), and the peak position of Loss Modulus was set to the glass transition temperature (Tg, ° C.). ).

<Developability>
The developed surface of the evaluation laminate was visually measured for the time from the start of the developing process until the residue disappeared, and then observed with an SEM (scanning electron microscope) (magnification: 1000 times) to check for the presence or absence of the residue as follows. Evaluated by criteria.
⊚: The time until the development residue disappears visually is 50 sec or less, there is no development residue in the range of 30 mm square even after SEM observation, and the developability is very excellent.
◯: It takes more than 50 sec to visually eliminate the development residue, but there is no development residue in the range of 30 mm square even after SEM observation, and the developability is excellent.
X: There is a development residue in the range of 30 mm square, and the developability is inferior.

Wet roughening treatment of 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 an electroless copper plating process manufactured by Uyemura & Co., Ltd. (chemical solution names: MCD-PL, MDP-2, MAT-SP, MAB-4). -C, MEL-3-APEA
ver. In 2), electroless copper plating of about 0.8 μm was applied, and the mixture was dried at 130 ° C. for 1 hour. Subsequently, electrolytic copper plating was applied so that the thickness of the plated copper was 18 μm, and drying was performed at 180 ° C. for 1 hour. In this way, a sample in which a conductor layer (plated copper) having a thickness of 18 μm was formed on the insulating layer was prepared and used for the following evaluation.

<Plating adhesion (kN / m)>
Using the sample prepared by the above procedure, JIS the adhesive strength of plated copper
The measurement was performed three times according to C6481, and the average value was calculated. The sample that swelled due to drying after electrolytic copper plating was evaluated using the non-swelled part.

As is clear from Table 1, Examples 1 to 5 have excellent plating adhesion. Among them, Examples 2 to 5 have good heat resistance and plating adhesion, and in particular, Examples 3 to 5 have remarkably excellent heat resistance and plating adhesion. Further, Examples 4 and 5 are also excellent in developability. On the other hand, Comparative Examples 1 to 3 have insufficient plating adhesion. Therefore, according to the present invention, a resin composition having excellent plating adhesion, heat resistance and developability, a resin sheet using the same, a multilayer printed wiring board and a semiconductor device can be obtained.

Claims (13)

Biphenyl aralkyl type epoxy resin represented by the following formula (1) (A), photocuring initiator (B), of compound (C)及beauty the compound (C) a compound having an ethylenically unsaturated group other than ( containing D),
The photocuring initiator (B) contains a phosphine oxide compound represented by the following formula (6), and contains the phosphine oxide compound.
A resin in which the compound (C) contains one or more of a compound represented by the following formula (C1) and a compound represented by the following formula (C2) to a compound represented by the following formula (C5). Composition.

(In equation (1), n represents an integer from 0 to 15.)

(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 is an alkyl group having 1 to 20 carbon atoms or 6 to 20 carbon atoms. Indicates the aryl group of.)

The resin composition according to claim 1, further containing the maleimide compound (E). The resin composition according to claim 1 or 2, further containing a filler (F). Any one or more compounds (G) selected from the group consisting of cyanate ester compounds, phenol resins, oxetane resins, benzoxazine compounds and epoxy resins different from the biphenyl aralkyl type epoxy resin (A) represented by (1) above. ), The resin composition according to any one of claims 1 to 3. Before hear compounds acid value of (C) is not more than 30 mgKOH / g or more 120 mgKOH / g, the resin composition according to any one of claims 1-4. The resin composition 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 with respect to 100 parts by mass of the resin solid content in the resin composition. thing. The resin composition according to any one of claims 1 to 6, wherein the compound (D) having an ethylenically unsaturated group is a compound having a (meth) acryloyl group and / or a compound having a vinyl group. The filler (F) is composed of silica, boehmite, barium sulfate, silicone powder, fluororesin-based filler, urethane resin-based filler, acrylic resin-based filler, polyethylene-based filler, styrene / butadiene rubber, and silicone rubber. it is on any one or more kinds selected from the group, the resin composition according to claim 3. The resin composition according to any one of claims 1 to 8, further containing a thermosetting accelerator (H). The resin composition according to any one of claims 1 to 9, further containing a naphthalene-type epoxy resin represented by the following formula (5).

A resin sheet comprising the support and the resin composition according to any one of claims 1 to 10 arranged on the surface of the support. A multilayer printed wiring board having the resin composition according to any one of claims 1 to 10. A semiconductor device having the resin composition according to any one of claims 1 to 10.