WO2018003314A1

WO2018003314A1 - Resin composition, resin sheet, multilayer printed circuit board, and semiconductor device

Info

Publication number: WO2018003314A1
Application number: PCT/JP2017/018045
Authority: WO
Inventors: 慎也喜多村; 鈴木　卓也; 誠司四家
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2016-06-29
Filing date: 2017-05-12
Publication date: 2018-01-04
Also published as: KR102324898B1; JP6913305B2; KR20190022480A; TWI744332B; CN109415491A; TW201800473A; CN109415491B; JPWO2018003314A1

Abstract

Provided is a resin composition that, when used in a multilayer printed circuit board, exhibits superior heat resistance and coating, and exhibits superior plating adhesion and developability. Also provided are a resin sheet with a support body, and a multilayer printed circuit board and a semiconductor device that use said resin composition and said resin sheet with a support body. The resin composition includes a biphenyl aralkyl-type epoxy resin (A) expressed by formula (1), a photocuring initiator (B), a compound (C) expressed by formula (2), and a compound (D) that has an ethylenically unsaturated group other than the (C) component.

Description

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

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

2. Description of the Related Art Thinning of a laminated board used for a multilayer printed wiring board has been actively conducted by downsizing and increasing the density of the multilayer printed wiring board. As the thickness is reduced, the insulating layer is also required to be reduced in thickness, and a resin sheet that does not include glass cloth is required. A thermosetting resin is mainly used as a resin composition as a material for the insulating layer, and a hole for obtaining conduction between insulating layers is generally performed by laser processing. Moreover, in the resin sheet using a thermosetting resin, the method of forming a conductor circuit by copper plating is common as a method of forming a conductor circuit on an insulating layer.

On the other hand, the drilling by laser processing has a problem that the processing time becomes longer as the number of holes becomes higher. Therefore, in recent years, there has been a demand for a resin sheet that can be collectively punched in a development process by using a resin composition that is cured by light or the like and dissolved by development. Furthermore, since the conductor circuit is formed on the insulating layer by copper plating, it is required that the copper plating adherence to the insulating layer is high so that the conductor circuit is not peeled off.

In resin compositions used for such laminates and resin sheets, the alkali development type is the mainstream, and acid anhydride group- or carboxyl group-containing acrylates are used to enable development. In addition, epoxy resin is used for copper plating adhesion. For example, in Patent Document 1, 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, A photosensitive thermosetting resin composition containing a photopolymerization initiator and a diluent is described. Patent Document 2 contains an epoxy resin, a curing agent, and a silica component whose 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 a total of 100 parts by weight of the curing agent, the average particle diameter of the silica particles is 1 μm or less, and the silica component per 1 g of the silica particles. The surface treatment amount B (g) of the silane coupling agent is the formula (X) (C (g) / silica particle 1 g = [specific surface area of silica particle (m ² / g) / minimum coverage area of the silane coupling agent] (M ² / g)]... An epoxy resin composition in the range of 10 to 80% with respect to the value C (g) per gram of silica particles calculated by the formula (X)) is disclosed. Yes.

Japanese Patent Laid-Open No. 2005-62450 JP 2011-174082 A

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

Further, the cured product obtained from the resin composition described in Patent Document 1 is limited in use to an etching resist or a solder resist for printed wiring boards, and is excellent in flexibility and heat resistance, but is an interlayer insulating layer. As a result, the copper plating adhesion was not sufficient.

Although the cured product obtained from the resin composition described in Patent Document 2 is excellent in adhesion to copper plating, since drilling is limited to laser processing, batch drilling by a development process cannot be performed.

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 to provide a resin sheet with a support, a multilayer printed wiring board using them, and a semiconductor device.

The present inventors include 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) By using the resin composition containing the compound (D) having an ethylenically unsaturated group other than the components, it was found that the above problems can be solved, and the present invention has been completed.

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

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

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

That is, the present invention includes the following contents.
[1] Biphenyl aralkyl type epoxy resin (A) represented by formula (1), photocuring initiator (B), compound (C) represented by formula (2), and formula (2) The resin composition containing the compound (D) which has ethylenically unsaturated groups other than the compound (C) made.
[2] The resin composition according to [1], further containing a maleimide compound (E).
[3] The resin composition according to [1] or [2], further including 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 comprising a compound (G).

[5] The resin composition according to any one of [1] to [4], wherein the acid value of the compound (C) represented by the formula (2) is 30 mgKOH / g or more and 120 mgKOH / g or less. .
[6] 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 described in 1.
[7] The compound according to 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 filler, urethane resin filler, acrylic resin filler, polyethylene filler, styrene / butadiene rubber and silicone. The resin composition according to [3], which is at least one selected from the group consisting of rubber.

[9] The resin composition according to any one of [1] to [8], further containing 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 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁₁ represents an alkyl group having 1 to 20 carbon atoms or 6 to 20 carbon atoms. An aryl group of
[12] A resin sheet comprising the support and the resin composition according to any one of [1] to [11] disposed on the surface of the support.
[13] A multilayer printed wiring board comprising the resin composition according to any one of [1] to [11].
[14] A semiconductor device comprising the resin composition according to any one of [1] to [11].

According to the present invention, a resin composition that is excellent in plating adhesion, coating properties, heat resistance and developability, and is cured with active energy rays having physical properties suitable for a multilayer printed wiring board, a resin sheet with a support, and The multilayer printed wiring board and semiconductor device used can be provided.

Hereinafter, a mode 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 within the scope of the gist.

In the present specification, “(meth) acryloyl group” means both “acryloyl group” and the corresponding “methacryloyl group”, and “(meth) acrylate” means “acrylate” and the corresponding “methacrylate”. "(Meth) acrylic acid" means both "acrylic acid" and the corresponding "methacrylic acid". Further, in this embodiment, “resin solid content” or “resin solid content in the resin composition” means a component in the resin composition excluding the solvent and the filler, unless otherwise specified. The term “solid content of 100 parts by mass” means that the total of the components excluding the solvent and filler in the resin composition is 100 parts by mass.

The resin composition of this 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 ( The compound (D) which has ethylenically unsaturated groups other than C) component is contained. Hereinafter, each component will be described.

<Biphenylaralkyl type epoxy resin (A) represented by 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 including the resin (A) can suitably form a protective film having excellent developability and an interlayer insulating layer while having high copper plating adhesion.

In the formula (1), n represents an integer of 0 to 15. Preferably, it is an integer of 0 to 5 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 copper plating adhesion, the total content of the component (A), the component (C) and the component (D). The amount is preferably 3 parts by mass or more, more preferably 4 parts by mass or more, and still more preferably 5 parts by mass or more with respect to 100 parts by mass. Moreover, it is preferable to set it as 90 mass parts or less from a viewpoint of making it fully harden | cure and improving heat resistance, it is more preferable to set it as 89 mass parts or less, and it is still more preferable to set it as 88 mass parts or less.

Although content of the component (A) in the resin composition of this embodiment is not specifically limited, From a viewpoint of improving copper plating adhesiveness and developability, it is with respect to 100 mass parts of resin solid content in a resin composition. It is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more. Further, from the viewpoint of sufficiently curing and improving heat resistance, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. Preferably, it is more preferably 30 parts by mass or less, and still more preferably 28 parts by mass or less.

As the resin (A), a commercially available product can be used. For example, NC3000FH (n = 8 to 10 in the formula (1)), NC3000H (n = 2 to 5 in the formula (1)), NC3000L (formula N = 1-3 in (1), NC3000 (n = 1-3 in formula (1)), CER3000L (n = 0-2 in formula (1)) (above, trade name, Nippon Kayaku Etc.).
These can be used alone or in combination of two or more.

<Photocuring initiator (B)>
The photocuring initiator (B) (also referred to as component (B)) used in the present embodiment is not particularly limited, and those generally known in the field used in photocurable resin compositions 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, 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-hydroxyn cyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl Acetophenones such as -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-ethylanthraquinone, 2-t-butylanthraquinone, Anthraquinones such as 2-chloroanthraquinone and 2-amylanthraquinone, thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone, 4 Benzophenones such as benzoyl-4'-methyldiphenyl sulfide, 4,4'-bismethylaminobenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6- Radical light such as phosphine oxides such as limethylbenzoyl) -phenylphosphine oxide, oxime esters such as 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] Curing initiator, Lewis acid diazonium salt such as p-methoxyphenyldiazonium fluorophosphonate, N, N-diethylaminophenyldiazonium hexafluorophosphonate, iodonium salt of Lewis acid such as diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroantimonate , Sulfonium salts of Lewis acids such as triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroantimonate, triphenylphosphonium hexafluoroantimonate Examples include phosphonium salts of Lewis acids such as carbonates, other halides, triazine-based initiators, borate-based initiators, and other cationic photopolymerization initiators such as photoacid generators.

Acylphosphine oxides include phosphine oxide compounds represented by the following formula (6) such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phos Examples include fin oxide. In particular, the phosphine oxide compound represented by the following formula (6) has a high long wavelength UV absorption 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 the production of a resin sheet and a multilayer printed wiring board that are superior in heat resistance can be achieved. It becomes possible.

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

Examples of the alkyl group having 1 to 4 carbon atoms include a straight chain such as methyl group, ethyl group, n-propyl group, n-butyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, etc. A branched alkyl group is exemplified.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, sec-butyl, 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 -Linear or branched alkyl groups such as dimethylbutyl group and 1,1,3-trimethylbutyl group.

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

Among them, acylphosphine oxides, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) are suitable from the viewpoint of reactivity suitable for multilayer printed wiring board applications and high reliability for metal conductors. ) -Butanone-1 and other radical type photocuring initiators of acetophenones are preferable, and as described above, more heat resistance is obtained, so that the phosphine oxide compound represented by the formula (6) is more preferable, and bis ( More preferred is 2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

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

Also, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6-trimethylbenzoyl -Diphenyl-phosphine oxide may be a commercially available product, and 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. From the viewpoint of sufficiently curing the resin composition with active energy rays and improving heat resistance, the resin composition. The total content of component (A), component (C) and component (D) in the content is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, relative to 100 parts by mass. More preferably, the content is 0.3 parts by mass or more. Further, from the viewpoint of inhibiting heat curing after photocuring and reducing 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.

Although content of the photocuring initiator (B) in the resin composition of this embodiment is not specifically limited, It shall be 0.1 mass part or more with respect to 100 mass parts of resin solid content in a resin composition. Preferably, it is more preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, still more preferably 1 part by mass or more, and more preferably 1.8 parts by mass or more. Even more preferred. Further, from the viewpoint of inhibiting heat curing after photocuring and reducing heat resistance, it is preferably 30 parts by mass or less, and 25 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. More preferably, it is more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less.

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

In said formula (2), several R < ₁ > represents a hydrogen atom or a methyl group each independently. Among these, it is preferable that a hydrogen atom is contained from a viewpoint of improving the reactivity of photocuring reaction, More preferably, all of R < ₁ > is a hydrogen atom.

A plurality of R ₂ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent.

As the hydrocarbon group, a linear or branched aliphatic hydrocarbon group having 1 to 22, preferably 1 to 14, and more preferably 1 to 10 carbon atoms; 3 to 22 carbon atoms, preferably 3 to 14 and more preferably an alicyclic hydrocarbon group having 3 to 10 carbon atoms; an aromatic hydrocarbon group having 6 to 22 carbon atoms, preferably 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms.
Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. 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, branched alkyl group such as 1,1,3-trimethylbutyl group; linear or branched alkenyl group such as vinyl group, allyl group, isopropenyl group; ethynyl group, propargyl group, etc. And a linear or branched alkynyl group.
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, indenyl And cyclic unsaturated hydrocarbon groups such as a fluorenyl group.
Examples of aromatic hydrocarbon groups include unsubstituted aryl groups such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl groups; tolyl, dimethylphenyl, isopropylphenyl, and t-butylphenyl. And aryl groups such as alkyl group-substituted aryl groups such as di-t-butylphenyl group;
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 aryl group-substituted alkyl groups such as benzyl group and cumyl group, and cyclic saturated hydrocarbon group-substituted alkyl groups such as cyclohexylmethyl group. Can be mentioned.

The hydrocarbon group having 1 to 22 carbon atoms which may have a substituent is preferably a linear or branched alkyl group.
The plurality of R ₂ preferably contain a methyl group from the viewpoint of improving the heat resistance of the cured product, and more preferably all of R ₂ are methyl groups.
Several R < ₃ > represents the substituent represented by the said Formula (3), the substituent represented by the said Formula (4), or a hydroxy group each independently. Among these, it is preferable that a hydroxyl group is included from a viewpoint of improving heat resistance. Moreover, in this embodiment, it is also preferable from a viewpoint of improving developability to use the compound (C) containing the substituent represented by said Formula (3) among several R < ₃ >. In this embodiment, it is also preferable to use the compound (C) containing a substituent represented by the formula (4) among the plurality of R ₃ from the viewpoint of improving heat resistance. In the formula _(4), R 4 represents a hydrogen atom or a methyl group. Among these, a hydrogen atom is preferable from the viewpoint of improving the reactivity of the photocuring reaction.

From the viewpoint of improving developability, the plurality of R _{3 s} are in the range where the ratio of the substituent represented by the formula (3) is 20% or more and 98% or less among all the substituents of R ₃ , The ratio of the substituent represented by 4) is in the range of 5% to 98% and the ratio of the hydroxy group is in the range of 10% to 98% (the sum of the ratios of these substituents is 100%). Is preferred. Among these, from the viewpoint of improving developability, at least one of the plurality of R ₃ is particularly preferably a substituent represented by the above formula (3).

The compound (C) preferably 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. More preferably, it contains at least compound (C1), more preferably any two or more of (C1) to (C5), and any one of compound (C1) and compounds (C2) to (C5). More preferably, it contains more than one species. As the compound (C), it is also preferable that at least the compounds (C2) and (C3) are included.

Such compounds may be commercially available, for example, KAYARAD (registered trademark) ZCR-6001H, KAYARAD (registered trademark) ZCR-6002H, KAYARAD (registered trademark) ZCR-6006H, KAYARAD (registered trademark) ZCR- 6007H, KAYARAD (registered trademark) ZCR-601H (above, trade name, manufactured by Nippon Kayaku Co., Ltd.), and the like.

In the resin composition of the present embodiment, the acid value of the compound (C) is preferably 30 mgKOH / g or more from the viewpoint of improving developability, and more preferably 50 mgKOH / g or more because developability is further improved. More preferably. In addition, from the viewpoint of preventing dissolution by a developer after curing with active energy rays, the acid value of the compound (A) is preferably 120 mgKOH / g or less, and more preferably 110 mgKOH / g or less because dissolution can be further prevented. More preferably. 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 component (A) and component (C) in the resin composition ) And the total content of component (D) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably 3 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, 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 resin solid content in the resin composition is 100 parts by mass. 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, still more preferably 10 parts by mass or more, even more preferably 25 parts by mass or more. It is still more preferable, and it is most preferable to set it as 30 mass parts 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, and 98 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. More preferably, it is more preferably 97 parts by mass or less, still more preferably 90 parts by mass or less, still more preferably 75 parts by mass or less, and most preferably 72 parts by mass or less. preferable.

<Compound (D) having an ethylenically unsaturated group other than component (C)>
The resin composition of the present embodiment is a compound (D) (component (component) having an ethylenically unsaturated group other than the component (C) in order to increase the reactivity to active energy rays (for example, ultraviolet rays) and improve 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 formula (2), and has one or more ethylenically unsaturated groups in one molecule. Although it will not specifically limit if it is a compound, For example, the compound which has a (meth) acryloyl group, a vinyl group, etc. is mentioned. These can be used alone or in combination of two or more.

As a compound having a (meth) acryloyl group, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, 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, diethylenedi (meth) a Relate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate, adipic acid epoxy di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogenated bisphenol ethylene oxide (Meth) acrylate, bisphenol di (meth) acrylate, ε-caprolactone modified hydroxypivalic acid neopent glycol di (meth) acrylate, ε-caprolactone modified dipentaerythritol hexa (meth) acrylate, ε-caprolactone modified dipentaerythritol poly ( (Meth) acrylate, dipentaerythritol poly (meth) acrylate, trimethylolpropane tri (meth) a Relate, triethylolpropane tri (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 ethylene oxide adducts thereof.

In addition, urethane (meth) acrylates that have (meth) acryloyl groups and urethane bonds in the same molecule, polyester (meth) acrylates that have (meth) acryloyl groups and ester bonds in the same molecule, and epoxy resins Epoxy (meth) acrylates derived from the above and having a (meth) acryloyl group, and reactive oligomers in which these bonds are used in combination.

The urethane (meth) acrylate is a reaction product of a hydroxyl group-containing (meth) acrylate, a polyisocyanate, and other alcohols used as necessary. For example, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerin (meta) such as glycerin mono (meth) acrylate, glycerin di (meth) acrylate, etc. ) Sugars (meth) acrylates such as acrylates, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and toluene diisocyanate , Hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, Down diisocyanate, hydrogenated xylene diisocyanate, dicyclohexane diisocyanate, and their isocyanurate, by reacting polyisocyanates such as buret reactants, the urethane (meth) acrylates.

Examples of the polyester (meth) acrylates include caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide-modified phthalic acid (meth) acrylate, ethylene oxide-modified succinic acid (meth) acrylate, and caprolactone-modified. Monofunctional (poly) ester (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate; hydroxypivalate ester neopentyl glycol di (meth) acrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol di (meth) acrylate, epichlorohydrin Di (poly) ester (meth) acrylates such as modified phthalic acid di (meth) acrylate; 1 mole of trimethylolpropane or glycerin Mol of ε- caprolactone, .gamma.-butyrolactone, a triol obtained by adding a cyclic lactone compound such as δ- valerolactone mono- include di- or tri (meth) acrylate.

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

Still further, diol components such as (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, 3-methyl-1,5-pentanediol, hexanediol and maleic acid , Fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, polybasic acids such as 5-sodium sulfoisophthalic acid, and anhydrides thereof (Meth) acrylate of a polyester polyol which is a reaction product with a product of a cyclic lactone-modified polyester diol composed of the diol component and a polybasic acid and their anhydrides and ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. Many officials such as (meth) acrylate Can be mentioned (poly) ester (meth) acrylates such as, but not limited thereto.

The above 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 ( And (meth) acrylates and the like, and acid anhydride-modified epoxy acrylates thereof.

Examples of the compound having a vinyl group include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of styrenes include styrene, methyl styrene, ethyl styrene, divinyl benzene and the like. Other vinyl compounds include triallyl isocyanurate, trimethallyl 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 ( One or more selected from the group consisting of (meth) acrylates and bisallylnadiimides are preferred, and dipentaerythritol hexa (meth) acrylates are more preferred from the viewpoint of further improving heat resistance. By including the compound having such an ethylenically unsaturated group, the heat resistance of the resulting 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 developability in the resin composition. The total content of 100 parts by mass of component (A), component (C) and component (D) is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, More preferably, it is 1.5 parts by mass or more. Moreover, from a viewpoint of making the heat resistance of hardened | cured material favorable, it is preferable to set it as 90 mass parts or less, It is more preferable to set it as 70 mass parts or less, It is still more preferable to set it as 50 mass parts or less.

In the resin composition of the present embodiment, the content of the compound (D) is not particularly limited. However, from the viewpoint of improving the developability, the content of the compound (D) is 0.1% with respect to 100 parts by mass of the resin solid content in the resin composition. It is preferably 5 parts by mass or more, more preferably 1.0 part by mass or more, still more 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, it is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, with respect to 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 this embodiment, a maleimide compound (E) (also referred to as component (E)) can be used. The maleimide compound (E) is 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, for example, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, 4,4 -Diphenylmethane bismaleimide, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) Methane, phenylmethanemaleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene biscitraconimide, m-phenylene biscitraconimide, p-phenylene biscitraconimide, 2,2-bis (4- (4-Maleimido Noxy) -phenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide- (2,2 , 4-trimethyl) hexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, 4,4-diphenylmethane biscitraconimide, 2,2-bis [4- (4-citraconimidophenoxy) phenyl] propane, bis (3,5-dimethyl-4-citraconimidophenyl) methane, bis (3-ethyl- 5-methyl-4-citraconimidophenyl) methane, bis (3,5-die Ru-4-citraconimidophenyl) methane, polyphenylmethanemaleimide, novolac-type maleimide compound, biphenylaralkyl-type maleimide compound, maleimide compound represented by the following formula (7), maleimide compound represented by the following formula (8), And prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds.

Of these, novolac maleimide compounds and biphenylaralkyl maleimide compounds are particularly preferred. Further, from the viewpoint of obtaining good coating 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 preferred, and the following formula (7) The maleimide compound represented by these is more preferable. A commercially available product can be used as the maleimide compound represented by the following formula (7), and examples thereof include BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd.). A commercially available product may be used as the maleimide compound represented by the following formula (8), and examples thereof include MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.).
These maleimide compounds (C) can be used singly or in appropriate combination of two or more.

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

(In the formula (8), each of R ₆ independently represents a hydrogen atom or a methyl group. N ₂ represents an integer of 1 or more, preferably an integer of 1 to 5).
These maleimide compounds (E) can be used singly or in appropriate combination 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. The total content of component (C) and component (D) is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and 0.03 parts by mass with respect to 100 parts by mass. More preferably, the above is used. Moreover, from a viewpoint of making developability favorable, it is preferable to set it as 50 mass parts or less, It is more preferable to set it as 45 mass parts or less, It is still more preferable to set it as 40 mass parts 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 to 50 parts by mass, more preferably 100 parts by mass of the resin solid content. 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 the resin composition of this embodiment, a filler (F) (also referred to as component (F)) can be used in combination in order to improve various properties such as coating properties and heat resistance. The filler (F) used in the present embodiment is not particularly limited as long as it has insulating properties. For example, silica (for example, natural silica, fused silica, amorphous silica, hollow silica, etc.), an 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, etc.) , Barium silicate, etc.), talc (eg, natural talc, calcined talc, etc.), mica (mica), glass (eg, short fiber glass, spherical glass, fine powder glass (eg, E glass, T glass, D glass, etc.), etc. ), Silicone powder, Fluororesin filler, C Tan resin filler, an acrylic resin-based filler, polyethylene fillers, such as styrene-butadiene rubber and silicone rubber.
Among them, it is selected from the group consisting of silica, boehmite, barium sulfate, silicone powder, fluorine resin filler, urethane resin filler, acrylic resin filler, polyethylene filler, styrene / butadiene rubber and silicone rubber. One or more are preferred.
These fillers (F) may be surface-treated with a silane coupling agent 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 properties. Specific examples of silica include SFP-130MC manufactured by Denka Corporation, SC2050-MB, SC1050-MLE, YA010C-MFN, YA050C-MJA manufactured by Admatechs Corporation.
These fillers (F) can be used singly or in appropriate combination 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 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 still more 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, more preferably 350 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. Preferably, it is more preferably 300 parts by mass or less, still more preferably 200 parts by mass or less, and most preferably 100 parts by mass or less.

<Silane coupling agent and wetting and dispersing agent>
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, the polymer and / or resin, and the adhesive strength between the filler. Is possible.
These silane coupling agents are not particularly limited as long as they are silane coupling agents generally used for inorganic surface treatment. Specific examples include, for example, 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 A ring agent is mentioned. These silane coupling agents can 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 wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for coatings. Specific examples include wet dispersing agents such as DISPERBYK (registered trademark) -110, 111, 118, 180, 161, BYK (registered trademark) -W996, W9010, and W903 manufactured by Big Chemie Japan Co., Ltd. . These wetting and dispersing agents can be used singly or in appropriate combination of two or more.
In the resin composition of the present embodiment, the content of the wetting and dispersing agent is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.

<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 biphenylaralkyl type epoxy resin (A) represented by (1) above ( G) ＞
The compound (G) (also referred to as 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 kinds of materials can be used according to the properties of the cured product such as flame retardancy, heat resistance, and thermal expansion properties. For example, when heat resistance is required, a cyanate ester compound, a benzoxazine compound, and the like can be used, and a phenol resin, an oxetane resin, and the like can also be used. When cyanate ester compound is used together with biphenyl aralkyl type epoxy resin (A), photocuring initiator (B), compound (C) and compound (D), heat resistance (glass transition temperature), low thermal expansion, plating adhesion A resin composition having excellent properties and the like can be obtained. Furthermore, it is preferable to use a cyanate ester compound in combination with a 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 excellent in developability and plating adhesion can be obtained. .

Moreover, these can also be used individually by 1 type or in mixture of 2 or more types as appropriate.
Hereinafter, the detail of these compounds and / or resin (G) is demonstrated.

<Cyanate ester compound>
The cyanate ester compound is not particularly limited as long as it is a resin having in its molecule an aromatic moiety substituted with at least one cyanate group (cyanate ester group).

For example, what is represented by General formula (9) is mentioned.

In formula (9), Ar ₁ represents a single bond of a benzene ring, a naphthalene ring or two benzene rings. When there are a plurality, they may be the same or different. Each Ra is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 6 carbon atoms and an alkyl group having 6 to 12 carbon atoms. A group to which an aryl group is bonded is shown. The aromatic ring in Ra may have a substituent, and the substituent in Ar ₁ and Ra can be selected at any position. p represents the number of cyanato groups bonded to Ar ₁ , and each independently represents an integer of 1 to 3. q represents the number of Ra bonded to Ar _1, and is 4-p when Ar ₁ is a benzene ring, 6-p when Ar ₁ is a naphthalene ring, and 8-p when two benzene rings are a single bond. . t represents an 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 Xs, each independently represents a single bond, a divalent organic group having 1 to 50 carbon atoms (a hydrogen atom may be substituted with a hetero atom), a divalent group having 1 to 10 nitrogen atoms. An organic group (eg, —N—R—N— (where R represents an organic group)), a carbonyl group (—CO—), a carboxy group (—C (═O) O—), a carbonyl dioxide group ( —OC (═O) O—), a sulfonyl group (—SO ₂ —), a divalent sulfur atom or a divalent oxygen atom.

The alkyl group in Ra in the general formula (9) may have any of a linear or branched chain structure and a cyclic structure (for example, a cycloalkyl group).
In addition, 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. Also 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, 2,2-dimethylpropyl group. Group, cyclopentyl group, hexyl group, cyclohexyl group, trifluoromethyl group and the like.
Specific examples of the aryl group include phenyl group, xylyl group, mesityl group, naphthyl group, phenoxyphenyl group, ethylphenyl group, o-, m- or p-fluorophenyl group, dichlorophenyl group, dicyanophenyl group, trifluorophenyl. Group, methoxyphenyl group, and o-, m- or p-tolyl group. 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, and a tert-butoxy group.

Specific examples of the divalent organic group having 1 to 50 carbon atoms in X in the general formula (9) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, and biphenylyl. Examples include a methylene group, a dimethylmethylene-phenylene-dimethylmethylene group, a fluorenediyl group, and a phthalidodiyl group. The hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, a cyano group, or the like.
Examples of the divalent organic group having 1 to 10 nitrogen atoms 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 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 as or different from each other. Rb, Rc, Rf, and Rg are each independently an aryl having at least one hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or a phenolic hydroxy group. Indicates a group. Rd and Re are each 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 of 0 to 5.

Wherein (11), Ar ₃ represents a benzene tetracarboxylic yl group, naphthalene tetracarboxylic yl group or a biphenyl tetracarboxylic yl group, when v is 2 or more, may be the same or different from each other. Ri and Rj are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxyl group having 1 to 4 carbon atoms, a hydroxy group, a trifluoromethyl group, Or an aryl group substituted with at least one cyanato group. v represents an integer of 0 to 5, but may be a mixture of compounds having different v.

Furthermore, examples of X in the general formula (9) include a divalent group represented by the following formula.

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 _{2 in the} general formula (10) and Ar _{3 in} the general formula (11) include two carbon atoms represented by the general formula (10) or two oxygen atoms represented by the general formula (11). A benzenetetrayl group bonded to the 1,4-position or the 1,3-position, the two carbon atoms or the two oxygen atoms are 4,4′-position, 2,4′-position, 2,2′-position, 2 , 3′-position, 3,3′-position, or 3,4′-position, and the above two carbon atoms or two oxygen atoms are in the 2,6-position, 1,5-position , 1,6-position, 1,8-position, 1,3-position, 1,4-position, or 2,7-position.
Rb, Rc, Rd, Re, Rf and Rg in the general formula (10), and the alkyl group and aryl group in Ri and Rj in the general formula (11) have the same meanings as those in the general formula (9).

Specific examples of the cyanato-substituted aromatic compound represented by the 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-cyanaphenyl) -2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylben 1-cyanato-2- or 1-cyanato-3-chlorobenzene, 1-cyanato-2,6-dichlorobenzene, 1-cyanato-2-methyl-3-chlorobenzene, cyanatonitrobenzene, 1-cyanato-4- Nitro-2-ethylbenzene, 1-cyanato-2-methoxy-4-allylbenzene (eugenol cyanate), methyl (4-cyanatophenyl) sulfide, 1-cyanato-3-trifluoromethylbenzene, 4-cyanatobiphenyl 1-cyanato-2- or 1-cyanato-4-acetylbenzene, 4-cyanatobenzaldehyde, 4-cyanatobenzoic acid methyl ester, 4-cyanatobenzoic acid phenyl ester, 1-cyanato-4-acetaminobenzene, 4 -Cyanatobenzophenone, 1-cyanato-2,6-di-ter t-butylbenzene, 1,2-dicyanatobenzene, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,4-dicyanato-2-tert-butylbenzene, 1,4-dicyanato-2, 4-dimethylbenzene, 1,4-dicyanato-2,3,4-dimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyanato-5-methylbenzene, 1-cyanato or 2-cyanatonaphthalene, 1-cyanato-4-methoxynaphthalene, 2-cyanato-6-methylnaphthalene, 2-cyanato-7-methoxynaphthalene, 2,2′-dicyanato-1,1′-binaphthyl, 1,3- , 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-dicyanatosinaphthalene, 2,2'- or 4,4 ' -The Anatobiphenyl, 4,4′-dicyanatooctafluorobiphenyl, 2,4′- or 4,4′-dicyanatodiphenylmethane, 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-cyanato) Enyl) 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-shear Natophenyl) -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 Ethane, screw ( -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-dicyanato Nzophenone, 1,3-bis (4-cyanatophenyl) -2-propen-1-one, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) sulfide, bis (4-cyanatophenyl) ) Sulfone, 4-cyanatobenzoic acid-4-cyanatophenyl ester (4-cyanatophenyl-4-cyanatobenzoate), bis- (4-cyanatophenyl) carbonate, 1,3-bis (4-cyanato) Phenyl) adamantane, 1,3-bis (4-cyanatophenyl) -5,7-dimethyladamantane, 3,3-bis (4-cyanatophenyl) isobenzofuran-1 (3H) -one (for phenolphthalein) Cyanate), 3,3-bis (4-cyanato-3-methylphenyl) isobenzofuran-1 (3H) -one (o-cresol phthalate) Rain's cyanate), 9,9'-bis (4-cyanatophenyl) fluorene, 9,9-bis (4-cyanato-3-methylphenyl) fluorene, 9,9-bis (2-cyanato-5-biphenyl) Yl) fluorene, 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-tetrakis (4-cyanatophenyl) 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-methylaniline) ) -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'-(hexafluoroisopropylidene ) Diphthalimide, tris (3,5-dimethyl-4-cyanatobenzyl) isocyanurate, 2-phenyl-3,3-bis (4-cyanatophenyl) phthalimidine, 2- (4-methylphenyl) -3, 3-bis (4-cyanatophenyl) phthalimidine, 2-phenyl-3,3-bis (4-cyanato-3-methylphenyl) phthalimidine, 1-methyl-3,3 Bis (4-cyanatophenyl) indolin-2-one, and 2-phenyl-3,3-bis (4-cyanatophenyl) include indolin-2-one.

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

Further, other specific examples of the cyanate ester compound represented by the general formula (9) include phenol novolac resins and cresol novolac resins (phenol, alkyl-substituted phenol or halogen-substituted phenol, formalin, A product obtained by reacting a formaldehyde compound such as paraformaldehyde in an acidic solution), a trisphenol novolak resin (a product obtained by reacting hydroxybenzaldehyde and phenol in the presence of an acidic catalyst), a fluorene novolac resin (9 , 9-bis (hydroxyaryl) fluorenes in the presence of an acidic catalyst), phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin and biphenyl aralkyl resin (known methods) _{_{More, Ar 4 - (CH 2 Y}} ) 2 (. Ar 4 represents a phenyl group, Y represents a halogen atom and the same in this paragraph.) And bishalogenomethyl compounds represented by the phenol compound An acid catalyst or non-catalyzed reaction, a bis (alkoxymethyl) compound represented by Ar ₄ — (CH ₂ OR) ₂ and a phenol compound in the presence of an acidic catalyst, or A product obtained by reacting a bis (hydroxymethyl) compound represented by Ar ₄ — (CH ₂ OH) ₂ and a phenol compound in the presence of an acidic catalyst, or an aromatic aldehyde compound, an aralkyl compound and a phenol compound. Polycondensed), phenol-modified xylene formaldehyde resin (by known methods, xylene formaldehyde resin and phenol compound) In the presence of an acidic catalyst), modified naphthalene formaldehyde resin (reacted naphthalene formaldehyde resin and hydroxy-substituted aromatic compound in the presence of an acidic catalyst by a known method), phenol-modified dicyclo Pentadiene resin, phenol resin having polynaphthylene ether structure (by polyhydric hydroxynaphthalene compound having two or more phenolic hydroxy groups in one molecule by dehydration condensation in the presence of a basic catalyst And the like, and those prepolymers obtained by cyanating a phenol resin such as) by the same method as described above. These are not particularly limited. These cyanate ester compounds can be used alone or in combination of two or more.

Among them, 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, adamantane skeleton type cyanate ester A compound is preferable, and a naphthol aralkyl-type cyanate ester compound is particularly preferable because excellent plating adhesion can be obtained while maintaining excellent heat resistance.

The method for producing these cyanate ester compounds is not particularly limited, and a known method can be used. Examples of such production methods include a method of obtaining or synthesizing a hydroxy group-containing compound having a desired skeleton, and modifying the hydroxy group by a known method to form 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 using these cyanate ester compounds has excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion.

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

<Phenolic resin>
As the phenol resin, a generally known resin can be used as long as it is a phenol resin having 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 phenolic resin, cresol novolac type phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified novolak type phenolic resin, phenolaralkyl type phenolic resin, naphthol aralkyl type Phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin Alicyclic phenolic resins, polyol-type phenolic resin, a phosphorus-containing phenol resin, a polymerizable unsaturated hydrocarbon of the group containing phenolic resin and hydroxyl-containing silicone resins and the like, but is not particularly limited. Among these phenol resins, biphenyl aralkyl type phenol resins, naphthol aralkyl type phenol resins, phosphorus-containing phenol resins, and hydroxyl group-containing silicone resins 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 phenolic resin is not particularly limited, and is preferably 0.1 to 50 parts by mass, more preferably 0.2 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 oxetane resins can be used. For example, oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, alkyloxetane such as 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 (product name), OXT-121 (product name) And the like are not particularly limited. These can be used alone or in combination of two or more.

The content of the oxetane resin is not particularly limited, and is preferably 0.1 to 50 parts by mass, more preferably 0.2 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, generally known compounds can be used as long as they have two or more dihydrobenzoxazine rings in one molecule. For example, bisphenol A type benzoxazine BA-BXZ (trade name, manufactured by Konishi Chemical) bisphenol F type benzoxazine BF-BXZ (trade name, manufactured by Konishi Chemical), bisphenol S type benzoxazine BS-BXZ (trade name, manufactured by Konishi Chemical) ), Phenolphthalein type benzoxazine and the like, but not particularly limited. These can be used alone or in combination of two or more.

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

<Epoxy resin>
In the resin composition of this embodiment, in order to improve the heat resistance of the cured product, an epoxy resin different from the biphenyl aralkyl type epoxy resin (A) represented by (1) can be used in combination.
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, for example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, Cresol novolak type epoxy resin, xylene novolak type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, naphthylene ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, Trifunctional phenolic epoxy resin, tetrafunctional phenolic epoxy resin, triglycidyl isocyanurate, glycidyl ester epoxy resin, alicyclic Poxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, phenol aralkyl novolak type epoxy resin, naphthol aralkyl novolak type epoxy resin, aralkyl novolak type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, Examples thereof include compounds obtained by epoxidizing double bonds such as polyol-type epoxy resins, phosphorus-containing epoxy resins, glycidylamine, and butadiene, compounds obtained by the reaction of hydroxyl group-containing silicone resins and epichlorohydrin, and halides thereof.

Among these, it is preferable that it is 1 or more types selected from the group which consists 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 kind of epoxy resin, the developability and 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 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 is exemplified. The naphthalene type epoxy resin represented by the following formula (5) has a low molecular weight and is multifunctional, and therefore has excellent solubility in a developer. Therefore, it is thought that the resin composition which is excellent also in developability can be obtained by using together with a biphenyl aralkyl type epoxy resin (A).

These epoxy resins can be used singly or in appropriate combination of two or more.

The content of the epoxy resin is not particularly limited, but from the viewpoint of further improving developability, the epoxy resin (A), the epoxy resin (A), and the epoxy resin (A) with respect to 100 parts by mass of the resin solid content in the resin composition The total amount with different epoxy resins is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more. preferable. Moreover, from the viewpoint of further improving the copper plating adhesion, with respect to 100 parts by mass of the resin solid content in the resin composition, the total of the epoxy resin (A) and the epoxy resin different from the epoxy resin (A), 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 from the viewpoint of plating adhesion, and 2 to 4: 1. ~ 2 is more preferred.

<Thermosetting accelerator (H)>
In the resin composition of the present embodiment, a thermosetting accelerator (H) (also referred to as component (H)) can be used as long as the characteristics of the present embodiment are not impaired. The thermosetting accelerator (H) used in the present embodiment is not particularly limited. For example, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate Organic peroxides 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 Class: Naphthenes Organometallic salts such as lead, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate and acetylacetone iron; these organometallic salts contain hydroxyl groups such as phenol and bisphenol Inorganic compounds such as tin chloride, zinc chloride and aluminum chloride; Dioctyl tin oxide, other organic tin compounds such as alkyl tin and alkyl tin oxide; 2-ethyl-4-methylimidazole, 1 , 2-dimethylimidazole, 1-benzyl-2-phenylimidazole, imidazole compounds such as triphenylimidazole (TPIZ), and the like. Of these, 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. -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 singly or in appropriate combination of two or more.
In the resin composition of the present embodiment, the content of the thermosetting accelerator (H) is not particularly limited, but is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. And preferably 0.05 to 5 parts by mass.

<Organic solvent>
The resin composition of the present embodiment may contain a solvent as necessary. For example, when an organic solvent is used, the viscosity at the time of preparing the resin composition can be adjusted. The kind of solvent will not be specifically limited if it can melt | dissolve part or all of resin in a resin composition. Specific examples thereof include, but are not particularly limited to, for example, ketones such as acetone, methyl ethyl ketone, and methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol monomethyl ether and acetate thereof Is mentioned.
These organic solvents can be used alone or in combination of two or more.

<Other ingredients>
In the resin composition of the present embodiment, various polymer compounds such as thermosetting resins, thermoplastic resins and oligomers thereof, elastomers, etc., which have not been mentioned so far, as long as the characteristics of the present embodiment are not impaired. Flame retardant compound not mentioned so far; combined use of additives and the like is also possible. These are not particularly limited as long as they are generally used. Examples of flame retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, phosphate compounds of phosphorus compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters. Additives include UV absorbers, antioxidants, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, antifoaming agents, surface conditioners, brighteners, polymerization inhibitors, etc. It is done. These components can be used alone or in appropriate combination 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.

<Method for producing resin composition>
The resin composition of this 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 ( C) Prepared by appropriately mixing the compound (D) having an ethylenically unsaturated group other than the component and, if necessary, the maleimide compound (E), the filler (F), the compound (G) and other components. Is done. The resin composition of this embodiment can be used suitably as a varnish at the time of producing the resin sheet of this invention mentioned later.

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

In the production of the resin composition, a known process (such as stirring, mixing, and kneading process) for uniformly dissolving or dispersing each component can be performed as 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 provided with a stirrer having an appropriate stirring ability. The stirring, mixing, and kneading processes described above are, for example, a stirring device for dispersion such as an ultrasonic homogenizer, a device for mixing such as a three-roll, ball mill, bead mill, and sand mill, or a revolving or rotating type. It can carry out suitably using well-known apparatuses, such as a mixing apparatus. Moreover, when preparing the resin composition of this embodiment, an organic solvent can be used as needed. 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.

<Application>
The resin composition of the present embodiment can be used for applications where an insulating resin composition is required, and is not particularly limited, but includes an insulating resin sheet such as a photosensitive film, a photosensitive film with a support, and a prepreg. It can be used for applications such as circuit boards (for laminated boards, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-filling resins, and the like. Especially, it can be conveniently used as a resin composition for insulating layers of a multilayer printed wiring board or a solder resist.

<Resin sheet>
The resin sheet of the present embodiment includes a support and a resin composition layer formed on the surface of the support and including the resin composition of the present embodiment. It is the resin sheet with a support body apply | coated to. The resin sheet can be produced by applying the resin composition on a support and drying it.

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

The resin film having a release agent coated on the surface thereof can be suitably 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 broken when the support is peeled off before development, and if the thickness exceeds 100 μm, the resolution when exposed from the support tends to decrease. is there.

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

Furthermore, in the resin sheet in the present embodiment, the resin composition layer may be protected with a protective film.
By protecting the resin composition layer side with a protective film, it is possible to prevent adhesion or scratches of dust or the like to the surface of the resin composition layer. 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. When the thickness is less than 1 μm, the handleability of the protective film tends to be lowered, and when it exceeds 50 μm, the inexpensiveness 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.

Although the manufacturing method of the resin sheet of this embodiment is not specifically limited, For example, a resin sheet is manufactured by apply | coating the resin composition of this embodiment to support bodies, such as PET film, and removing an organic solvent by drying. The method of doing is mentioned.
The coating can be performed by a known method using, for example, a roll coater, comma coater, gravure coater, die coater, bar coater, lip coater, knife coater, squeeze coater, or the like. The drying can be performed, for example, by a method of heating in a dryer at 60 to 200 ° C. for 1 to 60 minutes.
The amount of the remaining 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 diffusion of the organic solvent in the subsequent step. The thickness of the resin composition layer with respect to the support is preferably 1.0 μm or more in terms of the resin composition layer thickness of the resin sheet from the viewpoint of improving the 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 this 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, for example, by stacking and curing one or more of the above-described resin sheets. Specifically, it can be produced by the following method.

(Lamination process)
The resin composition layer side of the resin sheet of this embodiment is laminated on one side or both sides of a circuit board using a vacuum laminator. Examples of the circuit board include a glass epoxy board, a metal board, a ceramic board, a silicon board, a semiconductor sealing resin board, a polyester board, a polyimide board, a BT resin board, and a thermosetting polyphenylene ether board. Here, the circuit board refers to a board on which a conductor layer (circuit) patterned on one or both sides of the board is formed. Further, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, a substrate having a conductor layer (circuit) in which one or both surfaces of the outermost layer of the printed wiring board are patterned is also here. It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like. In the laminating step, when the resin sheet has a protective film, the protective film is peeled and removed, and then the resin sheet and the circuit board are preheated as necessary, while the resin composition layer is pressed and heated. Crimp to 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 suitably used.

The conditions for the laminating step are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 50 ° C. to 140 ° C., the pressure bonding pressure is preferably 1 kgf / cm ² to 15 kgf / cm ² , and the pressure bonding time. Is preferably 5 seconds to 300 seconds, and lamination is performed under reduced pressure so that the air pressure is 20 mmHg or less. 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. As a commercially available vacuum laminator, for example, a 2-stage build-up laminator manufactured by Nikko Materials Co., Ltd. can be exemplified.

(Exposure process)
After the resin sheet is provided on the circuit board by the laminating process, an exposure process 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. The active energy ray may be irradiated through a mask pattern or a direct drawing method in which an active energy ray is directly irradiated.

Examples of active energy rays include ultraviolet rays, visible rays, electron beams, X-rays and the like, and ultraviolet rays are particularly preferable. The irradiation amount of ultraviolet rays is about 10 mJ / cm ² to 1000 mJ / cm ² . There are two types of exposure methods that pass through the mask pattern: a contact exposure method in which the mask pattern is brought into close contact with the multilayer printed wiring board, and a non-contact exposure method in which exposure is carried out using parallel light rays without being brought into close contact. It doesn't matter. Moreover, when the support body exists on a resin composition layer, you may expose from a support body and may expose after a support body peels.

(Development process)
After the exposure step, if a support is present on the resin composition layer, the support is removed, and then development is performed by removing the uncured portion (unexposed portion) by wet development. Thus, the pattern of the insulating layer can be formed.

In the case of the above-described wet development, the developer is not particularly limited as long as it selectively elutes an unexposed portion, but a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent is used. . In the present embodiment, a development step using an alkaline aqueous solution is particularly preferable. These developers can be used alone or in combination of two or more. Moreover, as a developing method, it can carry out by well-known methods, such as spraying, rocking immersion, brushing, and scraping, for example.

The alkaline aqueous solution used as the developer is not particularly limited. For example, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, 4-sodium borate, ammonia And amines.

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 developer. Moreover, the temperature of aqueous alkali solution can be adjusted according to developability. Furthermore, these aqueous alkali solutions can be used alone or in combination of two or more.

In the pattern formation of this embodiment, two or more kinds of development methods described above may be used in combination as necessary. Development methods include a dip method, a paddle method, a spray method, a high-pressure spray method, brushing, and slapping, and the high-pressure spray method is suitable for improving the resolution. The spray pressure when the spray method is employed is preferably 0.02 MPa to 0.5 MPa.

(Post bake process)
After the development step, a post-bake step is performed to form an insulating layer (cured product). Examples of the post-bake process include an ultraviolet irradiation process using a high-pressure mercury lamp and a heating process using a clean oven, and these can be used in combination. Case of ultraviolet irradiation can adjust its dose optionally, the irradiation can be carried out, for example ^{0.05J / cm 2 ~ 10J / cm} 2 of about dose. The heating conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, 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 vapor deposition, sputtering, and ion plating can be used. In the vapor deposition method (vacuum vapor deposition method), for example, a metal film can be formed on the insulating layer by placing the support in a vacuum vessel and evaporating the metal by heating. In the sputtering method, for example, the support is placed in a vacuum vessel, an inert gas such as argon is introduced, a direct current voltage is applied, the ionized inert gas is made to collide with the target metal, and the struck metal is used. A metal film can be formed on the insulating layer.

In the case of wet plating, the surface of the insulating layer is roughened by performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order. . The swelling treatment with the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 to 80 ° C. for 1 to 20 minutes. Examples of the swelling liquid 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 an oxidizing agent solution at 60 to 80 ° C. for 5 to 30 minutes. Examples of the oxidizing agent include 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. it 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 the neutralizing solution is performed by immersing in the neutralizing solution at 30 to 50 ° C. for 1 to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution, and a commercially available product is Updes (registered trademark) MDN-62 manufactured by Uemura Kogyo Co., Ltd.

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

<Semiconductor device>
The semiconductor device of this embodiment includes an interlayer insulating layer containing the resin composition of this embodiment, and can be specifically manufactured by the following method. A semiconductor device can be manufactured by mounting a semiconductor chip in a conductive portion of the multilayer printed wiring board of the present embodiment. Here, the conduction location is a location for transmitting an electrical signal in the multilayer printed wiring board, and the location may be the surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The semiconductor chip mounting method for manufacturing the semiconductor device of the present embodiment is not particularly limited as long as the semiconductor chip functions effectively. Specifically, the wire bonding mounting method, the flip chip mounting method, and the bump are used. Examples include a mounting method using a none buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

Also, a semiconductor device can be manufactured by laminating the resin sheet of this embodiment on a semiconductor chip. After lamination, it can be produced by using the same method as the above multilayer printed wiring board.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[Synthesis Example 1]
(Synthesis of cyanate ester compound)
300 g of 1-naphthol aralkyl resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) (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.
125.9 g (2.05 mol) of cyanogen chloride (1.6 mol with respect to 1 mol of hydroxy group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol with respect to 1 mol of hydroxy group) ), 1205.9 g of water was poured over 30 minutes with stirring while maintaining the liquid temperature at -2 to -0.5 ° C. After the completion of the pouring of solution 1, after stirring at the same temperature for 30 minutes, 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. Over time. After the end of pouring the solution 2, the reaction was completed by stirring at the same temperature for 30 minutes.
Thereafter, the reaction solution was allowed to stand to separate an organic phase and an aqueous phase. The organic phase obtained was washed 5 times with 1300 g of water. The electric conductivity of the waste water in 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 desired naphthol aralkyl-type cyanate ester compound (SNCN) (orange viscous product). The obtained SNCN had a mass average molecular weight Mw of 600. Further, the IR spectrum of SNCN showed absorption of 2250 cm ⁻¹ (cyanate group) and did not show absorption of a hydroxy group.

[Example 1]
(Production of resin composition and resin sheet)
As the biphenyl aralkyl type epoxy resin (A) represented by the formula (1), a 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 (Irgacure (registered trademark) 369, BASF Japan Co., Ltd.) 6.5 parts by mass, as compound (C), propylene glycol monomethyl ether acetate (hereinafter sometimes abbreviated as PGMEA) solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H, Nonvolatile content 65% by mass, acid value: 70 mg KOH / g, Nippon Kayaku Co., Ltd.) 77.5 parts by mass (nonvolatile content) As a compound (D) having an ethylenically unsaturated group other than the component (C) (50.4 parts by mass), dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 17 .4 parts by mass, as maleimide compound (E), maleimide compound (BMI-2300 (trade name), manufactured by Daiwa Kasei Kogyo Co., Ltd.) 3.3 parts by mass, and as filler (F), methyl ethyl ketone of epoxysilane-treated silica (Hereinafter sometimes abbreviated as MEK) Slurry (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 (non-volatile equivalent 50 mass) Part) was mixed and stirred with an ultrasonic homogenizer to obtain a varnish (resin composition solution). Using these varnishes on a 38 μm thick PET film (Unipeel® TR1-38, manufactured by Unitika Ltd., trade name) using an automatic coating apparatus (PI-1210, manufactured by Tester Sangyo Co., Ltd.) This 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 at least one of the compound (C1) and the compounds (C2) to (C5).

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

(Preparation of evaluation laminate)
The resin surface of the resin sheet was placed on the inner layer circuit board, vacuumed for 30 seconds (5.0 MPa or less) using a vacuum laminator (Nikko Materials Co., Ltd.), and then pressure 10 kgf / cm. ^2. Laminate molding was performed at a temperature of 70 ° C. for 30 seconds. Furthermore, the laminated body by which the inner-layer circuit board, the resin composition layer, and the support body were laminated | stacked by performing lamination molding for 60 second at a pressure of 10 kgf / cm < ² > and temperature of 70 degreeC was obtained. The obtained laminate is subjected to an exposure step of irradiating with 200 mJ / cm ² of ultraviolet light, peeled off the support, developed with a 1% by mass sodium carbonate aqueous solution, and further irradiated with 1000 mJ / cm ² of ultraviolet light. Then, a post-baking process in which heat treatment was performed at 180 ° C. for 120 minutes was performed, and then a laminate for evaluation was obtained.

(Production of cured product for evaluation)
The resin sheet is irradiated with 200 mJ / cm ² of ultraviolet light, further subjected to an exposure process of irradiating 1000 mJ / cm ² of ultraviolet light, subjected to a post-baking process of heating at 180 ° C. for 120 minutes, and then the support is peeled off. The cured product was evaluated.

[Example 2]
As component (A), 21.9 parts by mass of biphenyl aralkyl type epoxy resin (NC3000L (trade name), manufactured by Nippon Kayaku Co., Ltd.) and as photocuring initiator (B), 2-benzyl-2-dimethylamino- 6.5 parts by mass of 1- (4-morpholinophenyl) -butanone-1 (Irgacure (registered trademark) 369, manufactured by BASF Japan Ltd.), as a compound (C), a PGMEA solution of a TrisP-PA epoxy acrylate compound ( KAYARAD (registered trademark) ZCR-6007H, nonvolatile 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 nonvolatile content), (C) As a compound (D) having an ethylenically unsaturated group other than the components, dipentaerythritol hexaacrylate (KAYARAD (registered trademark)) 17.4 parts by mass of PHA (Nippon Kayaku Co., Ltd.), maleimide compound (E) as maleimide compound (BMI-2300 (trade name), Daiwa Kasei Kogyo Co., Ltd.) 3.3 parts by mass, filler As (F), 71.4 parts by mass of MEK slurry of epoxysilane-treated silica (SC2050MB (trade name), average particle size 0.5 μm, nonvolatile content 70% by mass, manufactured by Admatechs Co., Ltd.) As a compound (G), 0.5 part by mass of the cyanate ester compound SNCN obtained in Synthesis Example 1 was blended and stirred with an ultrasonic homogenizer to obtain a varnish (resin composition solution). Using these varnishes on a 38 μm thick PET film (Unipeel® TR1-38, manufactured by Unitika Ltd., trade name) using an automatic coating apparatus (PI-1210, manufactured by Tester Sangyo Co., Ltd.) It 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, in the same manner as in Example 1, an evaluation laminate and an evaluation cured product were obtained.

Example 3
As component (A), 21.9 parts by mass of biphenyl aralkyl type epoxy resin (NC3000L (trade name), manufactured by Nippon Kayaku Co., Ltd.) and 2,4,6-trimethylbenzoyl- as photocuring initiator (B) 6.5 parts by mass of diphenyl-phosphine oxide (Irgacure (registered trademark) 819, manufactured by BASF Japan KK), as a compound (C), PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H) , 65% by mass of non-volatile content, acid value: 70 mg KOH / 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, Japan) As a maleimide compound (E), maleimide compound (BMI-2300 (trade name), manufactured by Daiwa Kasei Kogyo Co., Ltd.) 3.3 parts by weight, and as a filler (F) , MEK slurry of epoxysilane-treated silica (SC2050MB (trade name), average particle size 0.5 μm, nonvolatile content 70% by mass, manufactured by Admatechs) 71.4 parts by mass (50 parts by mass in terms of nonvolatile content), As the compound (G), 0.5 part by mass of the cyanate ester compound SNCN obtained in Synthesis Example 1 was blended and stirred with an ultrasonic homogenizer to obtain a varnish (solution of resin composition). Using these varnishes on a 38 μm thick PET film (Unipeel® TR1-38, manufactured by Unitika Ltd., trade name) using an automatic coating apparatus (PI-1210, manufactured by Tester Sangyo Co., Ltd.) It 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, in the same manner as in Example 1, an evaluation laminate and an evaluation cured product were obtained.

Example 4
As component (A), biphenylaralkyl type epoxy resin (NC3000L (trade name), manufactured by Nippon Kayaku Co., Ltd.) 15.8 parts by mass, as component (G), naphthalene type epoxy resin (HP-4710 (trade name)) (Manufactured by DIC Corporation) 6.1 parts by mass, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Irgacure (registered trademark) 819, BASF Japan Ltd.) as a photocuring initiator (B) (Product) 6.5 parts by mass, as a compound (C), PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H, nonvolatile content 65% by mass, acid value: 70 mgKOH / g, Nippon Kayaku ( Co., Ltd.) 77.5 parts by mass (50.4 parts by mass in terms of nonvolatile content), having an ethylenically unsaturated group other than component (C) As compound (D), dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 17.4 parts by mass, as maleimide compound (E), maleimide compound (BMI-2300 (trade name) ), 3.3 parts by mass of Daiwa Kasei Kogyo Co., Ltd., as filler (F), MEK slurry of epoxysilane-treated silica (SC2050MB (trade name), average particle size 0.5 μm, nonvolatile content 70% by mass, 71.4 parts by mass (manufactured by Admatechs Co., Ltd.) (50 parts by mass in terms of nonvolatile content), compound (G) is blended with 0.5 parts by mass of the cyanate ester compound SNCN obtained in Synthesis Example 1, and ultrasonic waves The mixture was stirred with a homogenizer to obtain a varnish (resin composition solution). Using these varnishes on a 38 μm thick PET film (Unipeel® TR1-38, manufactured by Unitika Ltd., trade name) using an automatic coating apparatus (PI-1210, manufactured by Tester Sangyo Co., Ltd.) It 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, in the same manner as in Example 1, an evaluation laminate and an evaluation cured product were obtained.

Example 5
As component (A), biphenylaralkyl type epoxy resin (NC3000L (trade name), manufactured by Nippon Kayaku Co., Ltd.) 15.8 parts by mass, as component (G), naphthalene type epoxy resin (HP-4710 (trade name)) (Manufactured by DIC Corporation) 6.1 parts by mass, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Irgacure (registered trademark) 819, BASF Japan Ltd.) as a photocuring initiator (B) (Product) 6.5 parts by mass, as a compound (C), PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H, nonvolatile content 65% by mass, acid value: 70 mgKOH / g, Nippon Kayaku ( Co., Ltd.) 77.5 parts by mass (50.4 parts by mass in terms of nonvolatile content), having an ethylenically unsaturated group other than component (C) As compound (D), dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 17.4 parts by mass, as maleimide compound (E), maleimide compound (BMI-2300 (trade name) ), 3.3 parts by mass of Daiwa Kasei Kogyo Co., Ltd., as filler (F), MEK slurry of epoxysilane-treated silica (SC2050MB (trade name), average particle size 0.5 μm, nonvolatile content 70% by mass, (Made by Admatechs) 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 as a compound (G), a thermosetting accelerator ( H), 0.2 parts by mass of 2-ethyl-4-methylimidazole (2E4MZ (trade name), manufactured by Shikoku Kasei Co., Ltd.) is blended, and an ultrasonic homogenizer is used. Stirring gave a varnish (resin composition solution). Using these varnishes on a 38 μm thick PET film (Unipeel® TR1-38, manufactured by Unitika Ltd., trade name) using an automatic coating apparatus (PI-1210, manufactured by Tester Sangyo Co., Ltd.) It 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, in the same manner as in Example 1, an evaluation laminate and an evaluation cured product were obtained.

[Comparative Example 1]
Instead of the compound (C), 74.1 parts by mass of 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.) 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 the structure represented by the above formula (2).

[Comparative Example 2]
A varnish was prepared in the same manner as in Example 1 except that 22.4 parts by mass of a naphthalene type epoxy resin (HP-4710 (trade name), manufactured by DIC Corporation) was used instead of the component (A). 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 A sheet, a laminate for evaluation, and a cured product for evaluation were obtained.

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

(Measurement 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 properties>
A finger was lightly pressed against the resin surface edge of each A4-sized resin sheet with a support, and the degree of sticking to the finger was evaluated according to the following criteria.
○: Sticking to the finger is hardly recognized. Although the edge part of the resin sheet with a support body sticks to a finger | toe, it peels off from a finger | toe and falls by less than 30 mm in height.
X: Sticking to the finger is recognized. The edge part of the resin sheet with a support body sticks to a finger | toe, and 30 mm or more in height rises.

<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 measured at the glass transition temperature (Tg, ° C. ).

<Developability>
The development surface of the evaluation laminate was visually measured for the time from the start of the development process until the residue disappeared, and then observed with a scanning electron microscope (SEM) (magnification 1000 times). Evaluated by criteria.
(Double-circle): The time until the visual development residue disappears is 50 sec or less, and there is no development residue in the range of 30 mm square even after SEM observation, and the developability is very excellent.
◯: Although the time until the visual development residue disappears exceeds 50 sec, there is no development residue in the 30 mm square area 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 and conductor layer plating of cured product for evaluation:
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 Uemura Kogyo (names of chemicals used: MCD-PL, MDP-2, MAT-SP, MAB-4). -C, MEL-3-APEA
ver. In 2), about 0.8 μm of electroless copper plating was applied, and drying was performed at 130 ° C. for 1 hour. Subsequently, electrolytic copper plating was performed 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 subjected to the following evaluation.

<Plating adhesion (kN / m)>
Using the sample prepared by the above procedure, the adhesive strength of plated copper was measured according to JIS.
Measurement was performed three times according to C6481, and an average value was obtained. About the sample swollen by the drying after electrolytic copper plating, it evaluated using the part which is not swollen.

As is apparent 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 Examples 3 to 5 are particularly excellent in heat resistance and plating adhesion. Furthermore, Examples 4 and 5 are 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 excellent in plating adhesion, heat resistance and developability, a resin sheet using the resin composition, a multilayer printed wiring board, and a semiconductor device can be obtained.

Claims

Biphenyl aralkyl type epoxy resin (A) represented by the following formula (1), photocuring initiator (B), compound (C) represented by the following formula (2) and compound represented by the following formula (2) A resin composition containing a compound (D) having an ethylenically unsaturated group other than (C).

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

(In Formula (2), a plurality of R 1 s each independently represent a hydrogen atom or a methyl group, and a plurality of R 2 s each independently have a hydrogen atom or a substituent having 1 carbon atom) And a plurality of R 3 each independently represents a substituent represented by the following formula (3), a substituent represented by the following formula (4), or a hydroxy group.

(In formula (4), R 4 represents a hydrogen atom or a methyl group).
The resin composition according to claim 1, further comprising a maleimide compound (E).
The resin composition according to claim 1 or 2, further comprising a filler (F).
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 biphenylaralkyl type epoxy resin (A) represented by (1) above (G The resin composition according to any one of claims 1 to 3, further comprising:
The resin composition according to any one of claims 1 to 4, wherein an acid value of the compound (C) represented by the formula (2) is 30 mgKOH / g or more and 120 mgKOH / g or less.
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. object.
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 filler, urethane resin filler, acrylic resin filler, polyethylene filler, styrene / butadiene rubber and silicone rubber. The resin composition according to claim 3, which is at least one selected from the group.
The resin composition according to any one of claims 1 to 8, further comprising a thermosetting accelerator (H).
The resin composition according to any one of claims 1 to 9, further comprising a naphthalene type epoxy resin represented by the following formula (5).
The resin composition according to any one of claims 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 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 11 represents an alkyl group having 1 to 20 carbon atoms or 6 to 20 carbon atoms. An aryl group of
A resin sheet comprising the support and the resin composition according to any one of claims 1 to 11 disposed on the surface of the support.
A multilayer printed wiring board comprising the resin composition according to any one of claims 1 to 11.
A semiconductor device comprising the resin composition according to any one of claims 1 to 11.