KR102324899B1 - Resin composition, resin sheet, multilayer printed wiring board and semiconductor device - Google Patents

Abstract

When used for a multilayer printed wiring board, it is excellent in coating-film property and heat resistance, and is excellent in plating adhesiveness and developability, the resin sheet with a support body, the multilayer printed wiring board using them, and a semiconductor device are provided. A compound having an ethylenically unsaturated group other than the dicyclopentadiene type epoxy resin (A) represented by the following formula (1), the photocuring initiator (B), the compound (C) represented by the following formula (2), and the component (C) A resin composition containing (D).

Description

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

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

Investigation of reducing the thickness of the laminated board used for a multilayer printed wiring board by size reduction and density increase of a multilayer printed wiring board is performed actively. With thickness reduction, thickness reduction is calculated|required also about an insulating layer, and the resin sheet which does not contain a glass cloth is calculated|required. As for the resin composition used as the material of an insulating layer, a thermosetting resin is mainstream, and the drilling for obtaining conduction|electrical_connection between insulating layers is generally performed by laser processing. Moreover, in the resin sheet using a thermosetting resin, as a method of forming a conductor circuit on an insulating layer, the method of forming a conductor circuit by copper plating is common.

On the other hand, the hole drilling by laser processing has a problem that processing time becomes longer, so that a high-density board|substrate with a large number of holes becomes. Therefore, in recent years, by using the resin composition which hardens|cures with a light beam etc. and melt|dissolves by image development, the resin sheet which becomes possible for a collective hole processing in a developing process is calculated|required. Moreover, in order to form a conductor circuit by copper plating on an insulating layer, it is calculated|required that copper plating adhesiveness is high with respect to an insulating layer so that a conductor circuit may not peel.

In the resin composition used for such a laminated board or a resin sheet, an alkali developing type is mainstream, and in order to enable image development, the acrylate containing an acid anhydride group or a carboxyl group is used. In addition, an epoxy resin is used for copper plating adhesion. For example, Patent Document 1 describes a curable resin composition comprising a carboxyl group-containing resin comprising a carboxyl group-containing resin having a novolak skeleton, an inorganic filler, a thermosetting component comprising a maleimide compound, and a compound having a urethane bond. has been Further, Patent Document 2 contains an epoxy resin, a curing agent, and a silica component in which silica particles are surface-treated with a silane coupling agent, and does not contain a curing accelerator, or 100 weight in total of the epoxy resin and the curing agent. The curing accelerator is contained in an amount of 3.5 parts by weight or less per part, the average particle diameter of the silica particles is 1 µm or less, and the surface treatment amount B of the silane coupling agent per 1 g of the silica particles in the silica component (g ) A, formula (X) (C (g) / silica particles 1 g = [specific surface area of silica particles (m / g) / minimum coverage area of silane coupling agent (m / g)] ... formula (X) The epoxy resin composition which exists in 10-80% of range with respect to the value C (g) per 1 g of silica particle calculated by ) is disclosed.

Japanese Patent Laid-Open No. 2016-8267 Japanese Patent Laid-Open No. 2011-174082

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

Moreover, the use of the hardened|cured material obtained from the resin composition of patent document 1 is limited to the etching resist for printed wiring boards, and a soldering resist, and although it is excellent in gold plating tolerance, copper plating adhesiveness is sufficient for using as an interlayer insulating layer. Did not do it.

In the hardened|cured material obtained from the resin composition of patent document 2, although it is excellent in copper-plating adhesiveness, since hole drilling is limited to laser processing, it becomes impossible to make a hole collectively by a developing process.

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

The present inventors have ethylenic properties other than the dicyclopentadiene type epoxy resin (A) represented by the following formula (1), the photocuring initiator (B), the compound (C) represented by the following formula (2), and its (C) component By using the resin composition containing the compound (D) which has an unsaturated group, it discovered that the said subject was solvable, and came to complete this invention.

[Formula 1]

(in Formula (1), n represents the integer of 0-15.).

[Formula 2]

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

[Formula 3]

[Formula 4]

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

That is, the present invention includes the following contents.

[1] A dicyclopentadiene type epoxy resin (A) represented by the formula (1), a photocuring initiator (B), a compound (C) represented by the formula (2), and a compound (C) represented by the formula (2) ), the resin composition containing the compound (D) which has an ethylenically unsaturated group other than.

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

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

[4] 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 dicyclopentadiene type epoxy resin (A) represented by (1) above 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 compound (C) represented by the formula (2) has an acid value of 30 mgKOH/g or more and 120 mgKOH/g or less.

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

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

[8] The filler (F) is selected from the group consisting of silica, boehmite, barium sulfate, silicone powder, fluororesin filler, urethane resin filler, acrylic resin filler, polyethylene filler, styrene butadiene rubber, and silicone rubber Any one or more types, The resin composition according to [3].

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

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

[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).

[Formula 6]

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

[12] A resin sheet comprising a 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].

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in plating adhesiveness, coating-film property, heat resistance and developability, and it is a resin composition hardened|cured with active energy ray which has physical properties suitable for a multilayer printed wiring board, a resin sheet with a support body, a multilayer printed wiring board using them, and a semiconductor device can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated in detail. The following present embodiment is an illustration for demonstrating this invention, and is not the meaning which limits this invention to the following content. The present invention can be implemented with appropriate modifications within the scope of the gist.

In addition, "(meth)acryloyl group" in this specification means both an "acryloyl group" and a "methacryloyl group" corresponding thereto, and "(meth)acrylate" means "acrylate" and "methacrylate" corresponding thereto, and "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid" corresponding thereto. In addition, in this embodiment, "resin solid content" or "resin solid content in the resin composition" refers to a component in the resin composition excluding a solvent and a filler, unless otherwise specified, and "resin solid content 100 parts by mass" Let it say that the sum total of the components in a resin composition except a solvent and a filler is 100 mass parts.

The resin composition of this embodiment other than the dicyclopentadiene type epoxy resin (A) represented by the said Formula (1), a photocuring initiator (B), and the compound (C) and (C) components represented by the said Formula (2) The compound (D) which has an ethylenically unsaturated group of Hereinafter, each component is demonstrated.

<Dicyclopentadiene type epoxy resin (A) represented by Formula (1)>

The dicyclopentadiene-type epoxy resin (A) (it is also called a component (A)) used for this embodiment is a compound which has a structure of the said Formula (1), and has dicyclopentadiene skeleton. The hardened|cured material obtained including this resin (A) can form preferably a protective film with high copper-plating adhesiveness, and an interlayer insulating layer, having high developability.

In Formula (1), n represents the integer of 0-15. Preferably, it is an integer of 0-5 from a developable point.

The resin composition of this embodiment WHEREIN: Although content of a component (A) is not specifically limited, From a viewpoint of improving copper plating adhesiveness, 100 mass parts of total content of a component (A), a component (C), and a component (D) It is preferable to set it as 3 mass parts or more with respect to it, It is more preferable to set it as 4 mass parts or more, It is still more preferable to set it as 5 mass parts or more. Moreover, from a viewpoint of fully hardening and improving heat resistance, it is preferable to set it as 90 mass parts or less, It is more preferable to set it as 89 mass parts or less, 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 3 mass parts or more with respect to 100 mass parts of resin solid content in a resin composition. It is preferable to set it as 5 mass parts or more, It is more preferable to set it as 5 mass parts or more, It is still more preferable to set it as 10 mass parts or more, It is still more preferable to set it as 15 mass parts or more. Further, from the viewpoint of sufficiently curing and improving heat resistance, with respect to 100 parts by mass of the resin solid content in the resin composition, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and 30 parts by mass or less. It is more preferable to use it, and it is still more preferable to set it as 28 mass parts or less.

A commercial item can also be used for resin (A), For example, XD-1000 (n=1-3 in Formula (1)) (trade name, Nippon Kayaku Co., Ltd. product), HP-7200L (Formula (1)) n = 1 to 3) (trade name, manufactured by DIC Co., Ltd.) and the like.

These can also be used individually by 1 type or in mixture of 2 or more types suitably.

<Photocuring Initiator (B)>

Although the photocuring initiator (B) (it is also called a component (B)) used for this embodiment is not specifically limited, Generally, a well-known thing can be used in the field|area used for a photocurable resin composition.

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, Organic peroxides exemplified by di-tert-butyl-di-perphthalate, acylphosphine oxides, acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylaceto Phenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- ( Acetophenones such as methylthio)phenyl]-2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2- Anthraquinones such as ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chloro Thioxanthone such as thioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bismethylaminobenzophenone, etc. Phosphine oxides such as benzophenones, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione, 1- Radical photocuring initiators such as oxime esters such as [4-(phenylthio)-, 2-(O-benzoyloxime)], p-methoxyphenyldiazonium fluorophosphonate, N,N-di Diazonium salts of Lewis acids, such as ethylaminophenyldiazonium hexafluorophosphonate, iodonium salts of Lewis acids, such as diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate, tri Sulfonium salts of Lewis acids such as phenylsulfonium hexafluorophosphonate and triphenylsulfonium hexafluoroantimonate, phosphonium salts of Lewis acids such as triphenylphosphonium hexafluoroantimonate, and other halogens and cationic photopolymerization initiators such as cargoes, triazine-based initiators, borate-based initiators, and other photoacid generators.

As acylphosphine oxides, phosphine oxide compounds represented by the following formula (6) such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine Fin oxide etc. are mentioned. In particular, the phosphine oxide compound represented by the following formula (6) has a high UV absorptivity of a long wavelength, and is excellent in allowing UV light to reach the inside of the resin. Therefore, the dicyclopentadiene type epoxy resin (A), compound (C), compound (D), etc. which concern on this embodiment can be made to react suitably, and manufacture of the resin sheet and multilayer printed wiring board which are more excellent in heat resistance becomes possible

[Formula 7]

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

Examples of the alkyl group having 1 to 4 carbon atoms include linear or and a branched alkyl group.

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

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

Among them, acylphosphine oxides, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-buta, from the viewpoint of having reactivity suitable for multilayer printed wiring board applications and high reliability to metal conductors. A radical type photocuring initiator of acetophenones, such as non-1, is preferable, and as mentioned above, the phosphine oxide compound represented by the said Formula (6) is more preferable at the point from which heat resistance is obtained more, and bis(2) ,4,6-trimethylbenzoyl)-phenylphosphine oxide is more preferable.

These photocuring initiators (B) can also be used individually by 1 type or in mixture of 2 or more types, and may use both the initiator of a radical type and a cationic type together.

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, Irgacure (registered trademark) 369 (manufactured by BASF Japan Co., Ltd.), Irgacure (registered trademark) 819 (manufactured by BASF Japan Co., Ltd.) and Irgacure (registered), respectively. Trademark) TPO (manufactured by BASF Japan Co., Ltd.) is preferably used.

Although content of the photocuring initiator (B) in the resin composition of this embodiment is not specifically limited, From a viewpoint of fully hardening a resin composition with an active energy ray and improving heat resistance, component (A) in a resin composition, It is preferable to set it as 0.1 mass part or more with respect to 100 mass parts of total content of a component (C) and a component (D), It is more preferable to set it as 0.2 mass part or more, It is further more preferable to set it as 0.3 mass part or more. In addition, from the viewpoint of inhibiting thermal curing after photocuring and reducing heat resistance, the amount is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and still more preferably 20 parts by mass or less.

Although content of the photocuring initiator (B) in the resin composition of this embodiment is not specifically limited, It is preferable to set it as 0.1 mass part or more with respect to 100 mass parts of resin solid content in a resin composition, It is 0.2 mass part or more. It is more preferable to set it as 0.3 mass part or more, It is still more preferable to set it as 1 mass part or more, It is still more preferable to set it as 1.8 mass part or more. In addition, from the viewpoint of inhibiting thermal curing after photocuring to reduce heat resistance, with respect to 100 parts by mass of the resin solid content in the resin composition, it is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, 20 It is more preferable to set it as a mass part or less, and it is still more preferable to set it as 10 mass parts 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). A compound (C) may be used individually by 1 type, may contain isomers, such as a structural isomer and a stereoisomer, and may use it combining 2 or more types of compounds from which mutually differ in structure suitably.

In said formula (2), some R<_1> represents a hydrogen atom or a methyl group each independently. Especially, it is preferable to contain a hydrogen atom from a viewpoint of improving the reactivity of a 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.

Examples of the hydrocarbon group include a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms, preferably 1 to 14, more preferably 1 to 10; an alicyclic hydrocarbon group having 3 to 22 carbon atoms, preferably 3 to 14 carbon atoms, more preferably 3 to 10 carbon atoms; C6-C22, Preferably it is 6-14, More preferably, it is a 6-10 aromatic hydrocarbon group.

Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, isobutyl group, sec-butyl group, 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-dimethyl linear or branched alkyl groups such as a butyl group and a 1,1,3-trimethylbutyl group; linear or branched alkenyl groups, such as a vinyl group, an allyl group, and an isopropenyl group; and linear or branched alkynyl groups such as ethynyl group and propargyl 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; Cyclic unsaturated hydrocarbon groups, such as a cyclopentadienyl group, an indenyl group, and a fluorenyl group, are mentioned.

Examples of the aromatic hydrocarbon group include unsubstituted aryl groups such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group and an anthracenyl group; alkyl group-substituted aryl groups such as tolyl group, dimethylphenyl group, isopropylphenyl group, t-butylphenyl group and di-t-butylphenyl group; Aryl groups, such as these are mentioned.

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

As a C1-C22 hydrocarbon group which may have a substituent, a linear or branched alkyl group is preferable.

A plurality of R ₂ is, as is preferred, more preferably containing a methyl group in view of improving the heat resistance of the cured product is a methyl group all of R _2.

A plurality of R ₃ each independently represents a substituent represented by the formula (3), a substituent represented by the formula (4), or a hydroxy group. Especially, it is preferable to include a hydroxyl group 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 the said Formula (3) among some _R<3>. In this embodiment, it is also preferable from a viewpoint of improving heat resistance to use the compound (C) containing the substituent represented by the said Formula (4) among some _R<3>. In the formula (4), R ₄ represents a hydrogen atom or a methyl group. Especially, it is preferable that it is a hydrogen atom from a viewpoint of improving the reactivity of a photocuring reaction.

A plurality of R ₃ is from the viewpoint of improving developability, _{among the substituents of all R 3} , the ratio of the substituents represented by the formula (3) is in the range of 20% or more and 98% or less, the substituents represented by the formula (4) It is preferable that the ratio is in the range of 5% or more and 98% or less, and the ratio of the hydroxyl group is in the range of 10% or more and 98% or less (the sum of the ratios of these substituents is 100%). _{Especially, it is especially preferable that at least 1 of some R<3>} becomes a substituent represented by said Formula (3) from a viewpoint of improving developability.

As the compound (C), it is preferable to include any one or more of the following compounds (C1) to (C5) because the reactivity of the photocuring reaction, heat resistance and developability of the cured product can be improved, and at least the compound ( It is more preferable to include C1), more preferably includes any two or more types of (C1) to (C5), and includes any one or more types of compound (C1) and compounds (C2) to (C5). It is more preferable to do It is also preferable that the compound (C) contains at least the compounds (C2) and (C3).

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

Commercial products may be used for such compounds, 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, brand name, manufactured by Nippon Kayaku Co., Ltd.) etc. are mentioned.

The resin composition of this embodiment WHEREIN: It is preferable that the acid value of compound (C) shall be 30 mgKOH/g or more from a viewpoint of improving developability, and it is that it is 50 mgKOH/g or more from a point which developability improves more. more preferably. Moreover, from a viewpoint of preventing dissolution by a developing solution after hardening with an active energy ray, it is preferable that the acid value of compound (C) shall be 120 mgKOH/g or less, From a point which can prevent more dissolution, 110 mgKOH /g or less is more preferable. In addition, "acid value" in this embodiment shows the value measured by the method according to JISK0070:1992.

The resin composition of this embodiment WHEREIN: Although content of a compound (C) is not specifically limited, From a viewpoint of hardening a resin composition with an active energy ray, component (A), a component (C), and a component (D) in a resin composition ) It is preferable to set it as 1 mass part or more with respect to 100 mass parts of total content, It is more preferable to set it as 2 mass parts or more, It is still more preferable to set it as 3 mass parts or more. Moreover, from a viewpoint of fully hardening with an active energy ray and improving heat resistance, it is preferable to set it as 99 mass parts or less, It is more preferable to set it as 98 mass parts or less, It is further more preferable to set it as 97 mass parts or less.

In the resin composition of this embodiment, content of a compound (C) is although it does not specifically limit, From a viewpoint of hardening a resin composition with an active energy ray, It is 1 mass part or more with respect to 100 mass parts of resin solid content in a resin composition. It is preferable to set it as 2 parts by mass or more, more preferably to be 3 parts by mass or more, still more preferably to 10 parts by mass or more, even more preferably to 25 parts by mass or more, , it is most preferably set to 30 parts by mass or more. Moreover, it is preferable to set it as 99 mass parts or less with respect to 100 mass parts of resin solid content in a resin composition from a viewpoint of fully hardening by an active energy ray and improving heat resistance, It is more preferable to set it as 98 mass parts or less, 97 It is still more preferable to set it as a mass part or less, It is still more preferable to set it as 90 mass parts or less, It is still more preferable to set it as 75 mass parts or less, It is most preferable to set it as 72 mass parts or less.

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

In order for the resin composition of this embodiment to increase the reactivity with respect to an active energy ray (for example, ultraviolet-ray) and to improve heat resistance, the compound (D) (component (D) which has ethylenically unsaturated groups other than (C)component) also called). The compound (D) having an ethylenically unsaturated group used in the present embodiment is not particularly limited as long as it is a compound other than the compound (C) represented by the formula (2) and has one or more ethylenically unsaturated groups in one molecule, For example, the compound which has a (meth)acryloyl group, a vinyl group, etc. is mentioned. These can also be used individually by 1 type or in mixture of 2 or more types suitably.

Examples of the compound having a (meth) acryloyl group include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene Glycol (meth) acrylate monomethyl ether, phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylic Rate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, glycol di (meth) acrylate, diethylene di ( Meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate, 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 hydroxypivalate neopheneglycol di(meth)acrylate, ε-caprolactone Modified dipentaerythritol hexa(meth)acrylate, ε-caprolactone modified dipentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, tri Ethylolpropane 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 its ethylene oxide adduct, etc. are mentioned.

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

The said urethane (meth)acrylates are a reaction product of hydroxyl-containing (meth)acrylate, polyisocyanate, and other alcohols used as needed. For example, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerin mono (meth) acrylate, Glycerin (meth)acrylates such as glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipenta Sugar alcohol (meth)acrylates such as erythritol hexa(meth)acrylate, toluene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogen Polyisocyanates, such as addition xylene diisocyanate, dicyclohexane methylene diisocyanate, their isocyanurate, and a biuret reactant, etc. are made to react, and it becomes urethane (meth)acrylates.

The polyester (meth) acrylates are, for example, caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and/or propylene oxide-modified phthalic acid (meth) acrylate, ethylene oxide-modified succinic acid (meth) ) Monofunctional (poly)ester (meth)acrylates, such as acrylate and caprolactone-modified tetrahydrofurfuryl (meth)acrylate; Di(poly) such as hydroxypivalate ester neopentyl glycol di(meth)acrylate, caprolactone-modified hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, epichlorhydrin-modified phthalate di(meth)acrylate ) ester (meth)acrylates; Mono, di or tri (meth) acrylate of triol obtained by adding 1 mol or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone to 1 mol of trimethylolpropane or glycerin can be heard

Furthermore, mono, di, tri of triols obtained by adding 1 mol or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone to 1 mol of pentaerythritol or ditrimethylolpropane Or tetra (meth) acrylate or dipentaerythritol 1 mole or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone is added to 1 mole of triol mono, or and mono(meth)acrylates or poly(meth)acrylates of polyhydric alcohols such as triol, tetraol, pentaol, or hexaol of poly(meth)acrylate.

And furthermore, a diol component such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, (poly)butylene glycol, 3-methyl-1,5-pentanediol, and hexanediol, and maleic acid Polybasic acids, such as acid, fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, 5-sodium sulfoisophthalic acid, and reactants thereof with anhydrides (meth)acrylate of a phosphorus polyester polyol; Polyfunctional (poly)ester, such as (meth)acrylate, of a cyclic lactone-modified polyesterdiol comprising the above diol component, polybasic acid, anhydride thereof, ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. Although (meth)acrylates etc. are mentioned, It is not limited to these.

The said epoxy (meth)acrylates are the compound which has an epoxy group, and the carboxylate compound of (meth)acrylic acid. For example, phenol novolak type epoxy (meth) acrylate, cresol novolak type epoxy (meth) acrylate, trishydroxyphenylmethane type epoxy (meth) acrylate, dicyclopentadienephenol type epoxy (meth) acrylic rate, 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) ) acrylates, glyoxal-type epoxy (meth)acrylates, heterocyclic epoxy (meth)acrylates, 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. Styrene, methylstyrene, ethylstyrene, divinylbenzene, etc. are mentioned as styrene. As other vinyl compounds, triallyl isocyanurate, trimethallyl isocyanurate, bisallylnadiimide, etc. are mentioned.

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, It is preferable that it is at least 1 type selected from the group which consists of a naphthalene skeleton containing epoxy (meth)acrylate and bisallylnadiimide, It is more preferable that it is dipentaerythritol hexa (meth)acrylate from a point which heat resistance improves more. . There exists a tendency for the heat resistance of the hardened|cured material obtained to improve more by including the compound which has this kind of ethylenically unsaturated group.

In the resin composition of this embodiment, content of the compound (D) which has ethylenically unsaturated groups other than (C) component is although it does not specifically limit, From a viewpoint of making developability favorable, component (A) in a resin composition, It is preferable to set it as 0.5 mass part or more with respect to 100 mass parts of total content of a component (C) and a component (D), It is more preferable to set it as 1.0 mass part or more, It is further more preferable to set it as 1.5 mass parts 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 further more preferable to set it as 50 mass parts or less.

The resin composition of this embodiment WHEREIN: Although content of a compound (D) is not specifically limited, From a viewpoint of making developability favorable, it is preferable to set it as 0.5 mass part or more with respect to 100 mass parts of resin solid content in a resin composition. and more preferably 1.0 parts by mass or more, still more preferably 1.5 parts by mass or more, still more preferably 5.0 parts by mass or more, and most preferably 10 parts by mass or more. In addition, from the viewpoint of improving the heat resistance of the cured product, with respect to 100 parts by mass of the resin solid content in the resin composition, it is preferably set to 90 parts by mass or less, more preferably 70 parts by mass or less, and 50 parts by mass or less. It is still more preferable, and it is still more preferable to set it as 25 mass parts or less, and it is most preferable to set it as 20 mass parts or less.

<Maleimide compound (E)>

In the resin composition of this embodiment, a maleimide compound (E) (it is also called a component (E)) can be used. The maleimide compound (E) is described in detail below.

The maleimide compound (E) used for this embodiment will not be specifically limited if it is a compound which has one or more maleimide groups in a molecule|numerator. Specific examples thereof include, for example, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy) -phenyl}propane, 4,4-diphenylmethanebismaleimide, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, Bis(3,5-diethyl-4-maleimidephenyl)methane, phenylmethanemaleimide, o-phenylenebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, o-phenylene Biscitraconimide, m-phenylenebiscitraconimide, p-phenylenebiscitraconimide, 2,2-bis(4-(4-maleimidephenoxy)-phenyl)propane, 3,3 -Dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide-(2,2,4- Trimethyl)hexane, 4,4-diphenyletherbismaleimide, 4,4-diphenylsulfonebismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimide) Midphenoxy)benzene, 4,4-diphenylmethanebiscitraconimide, 2,2-bis[4-(4-citraconimidephenoxy)phenyl]propane, bis(3,5-dimethyl-4 -Citraconimidephenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidephenyl)methane, bis(3,5-diethyl-4-citraconimidephenyl)methane, polyphenyl Methanemaleimide, a novolak-type maleimide compound, a biphenyl aralkyl-type maleimide compound, a maleimide compound represented by the following formula (7), a maleimide compound represented by the following formula (8), and a free polymer of these maleimide compounds or a free polymer of a maleimide compound and an amine compound.

Among these, a novolak type maleimide compound and a biphenyl aralkyl type maleimide compound are especially preferable. Moreover, from a viewpoint that favorable coating-film property is obtained and it is excellent in heat resistance, the maleimide compound represented by following formula (7) and the maleimide compound represented by following formula (8) are preferable, and the maleimide represented by following formula (7) A compound is more preferable. A commercial item can also be used as a maleimide compound represented by following formula (7), For example, BMI-2300 (made by Daiwa Chemical Industry Co., Ltd.) is mentioned. As a maleimide compound represented by following formula (8), a commercial item can also be used, for example, MIR-3000 (made by Nippon Kayaku Co., Ltd.) is mentioned.

These maleimide compounds (E) can also be used individually by 1 type or in mixture of 2 or more types as appropriate.

[Formula 13]

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

[Formula 14]

(In formula (8), a plurality of R ₆ each 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 also be used individually by 1 type or in mixture of 2 or more types suitably.

Although content of the maleimide compound (E) in the resin composition of this embodiment is not specifically limited, From a viewpoint of fully hardening a resin composition and improving heat resistance, component (A) in a resin composition, component (C) And it is preferable to set it as 0.01 mass part or more with respect to 100 mass parts of total content of a component (D), It is more preferable to set it as 0.02 mass part or more, It is further more preferable to set it as 0.03 mass part or more. 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.

The resin composition of this embodiment WHEREIN: Content in particular of a maleimide compound (E) is not restrict|limited, To 100 mass parts of resin solid content, Preferably it is 0.01 mass part - 50 mass parts, More preferably, it is 0.02 mass They are parts - 45 mass parts, More preferably, they are 0.03 mass parts - 20 mass parts, More preferably, they are 0.1 mass parts - 10 mass parts, Most preferably, they are 1 mass part - 7 mass parts. When content of a maleimide compound exists in the said range, there exists a tendency for the heat resistance of hardened|cured material to improve more.

<Filling material (F)>

In order to improve various characteristics, such as coating-film property and heat resistance, to the resin composition of this embodiment, it is also possible to use together a filler (F) (it is also called a component (F)). The filler (F) used in the present embodiment is not particularly limited as long as it has insulating properties. For example, silica (eg natural silica, fused silica, amorphous silica, hollow silica, etc.), aluminum compound (eg 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 (such as barium sulfate, barium silicate, etc.), talc (such as natural talc, calcined talc, etc.), mica (mica), glass (such as short fiber glass, spherical glass, fine powder glass ( For example, E glass, T glass, D glass, etc.)), silicone powder, a fluororesin filler, a urethane resin filler, an acrylic resin filler, a polyethylene filler, a styrene butadiene rubber, a silicone rubber, etc. are mentioned.

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

These fillers (F) may be surface-treated with the silane coupling agent etc. mentioned later.

In particular, from a viewpoint that the heat resistance of hardened|cured material is improved and favorable coating-film property is acquired, silica is preferable and fused silica is especially preferable. Specific examples of silica include SFP-130MC manufactured by Denka Corporation, and SC2050-MB, SC1050-MLE, YA010C-MFN, and YA050C-MJA manufactured by Admatex Corporation.

These fillers (F) can also be used individually by 1 type or in mixture of 2 or more types suitably.

The resin composition of this embodiment WHEREIN: Although content of the filler (F) is not specifically limited, From a viewpoint of improving the heat resistance of hardened|cured material, it is preferable to set it as 5 mass parts or more with respect to 100 mass parts of resin solid content in a resin composition. and it is more preferable to set it as 10 mass parts or more, and it is still more preferable to set it as 20 mass parts or more. Moreover, from a viewpoint of making the developability of a resin composition favorable, it is preferable to set it as 400 mass parts or less with respect to 100 mass parts of resin solid content in a resin composition, It is more preferable to set it as 350 mass parts or less, 300 mass parts or less More preferably, it is 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 this embodiment, in order to improve the dispersibility of a filler, polymer and/or resin, and adhesive strength of a filler, it is also possible to use together a silane coupling agent and/or a wet dispersing agent.

As these silane coupling agents, if it is a silane coupling agent generally used for the surface treatment of an inorganic substance, it will not specifically limit. As a specific example, For example, Aminosilane systems, such as (gamma)-aminopropyl triethoxysilane and N-(beta)-(aminoethyl)-gamma-aminopropyl trimethoxysilane; Epoxysilane systems, such as (gamma)-glycidoxy propyl trimethoxysilane; Acrylic silane systems, such as (gamma)-acryloxypropyl trimethoxysilane; cationic silanes such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride; and a phenylsilane-based silane coupling agent. It is also possible to use these silane coupling agents individually by 1 type or in combination of 2 or more type.

In the resin composition of this embodiment, content of a silane coupling agent is although it does not specifically limit, Usually, it is 0.1-10 mass parts with respect to 100 mass parts of resin compositions.

The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for paints. Specific examples include, for example, DISPERBYK (registered trademark)-110, 111, 118, 180, 161, BYK (registered trademark)-W996, W9010, W903 manufactured by Big Chemie Japan Co., Ltd. Wetting and dispersing agents can be heard These wetting and dispersing agents can also be used individually by 1 type or in mixture of 2 or more types.

In the resin composition of this embodiment, content of a wet dispersant is although it does not specifically limit, Usually, it is 0.1-10 mass parts with respect to 100 mass parts of resin compositions.

<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 dicyclopentadiene type epoxy resin (A) represented by (1) above ( G)>

The compound (G) (also referred to as component (G)) used in the present embodiment is a cured cured product required in the field in which the resin composition is used in addition to the copper plating adhesion obtained by using the component (A). According to characteristics such as flame retardancy, heat resistance, and thermal expansion characteristics, various types can be used. For example, when heat resistance is calculated|required, a cyanate ester compound, a benzoxazine compound, etc. are mentioned, In addition, a phenol resin, an oxetane resin, etc. can be used. Moreover, when an epoxy resin different from the epoxy resin (A) is used together with the dicyclopentadiene-type epoxy resin (A) represented by the above (1), a resin composition particularly excellent in developability and plating adhesion can be obtained. .

In addition, these can also be used individually by 1 type or in mixture of 2 or more types suitably.

Hereinafter, the detail of these compounds and/or resin (G) is demonstrated.

<Cyanic acid ester compound>

As a cyanate ester compound, if it is resin which has in a molecule|numerator the aromatic moiety by which at least 1 cyanato group (cyanate ester group) was substituted, it will not specifically limit.

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

[Formula 15]

In Formula (9), Ar ₁ represents that a benzene ring, a naphthalene ring, or two benzene rings are bonded together. When there are two or more, they may mutually be same or different. Each Ra independently represents 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, a group in which an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms are bonded. The aromatic ring for Ra may have a substituent, and the substituent in Ar<_1> and Ra can select arbitrary positions. p represents the number of cyanato groups couple|bonded with Ar<_{1>, and is an integer of 1-3 each independently.} a p - 8 when combined be a p, 2 of the benzene ring only - q represents a number of Ra binding to the Ar _1, Ar ₁ is 4 when the benzene ring - p, a naphthalene ring, when one six. t represents an average number of repetitions, is an integer of 0-50, and the mixture of the compound from which t differs may be sufficient as the cyanate ester compound. When there is a plurality of X's, 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), or a divalent organic group having 1 to 10 nitrogen atoms (for example, -NRN - (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 is represented.

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

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, there may be

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a 1-ethylpropyl group, and a 2,2-dimethylpropyl group. , a cyclopentyl group, a hexyl group, a cyclohexyl group, and a trifluoromethyl group.

Specific examples of the aryl group include a phenyl group, a xylyl group, a mesityl group, a naphthyl group, a phenoxyphenyl group, an ethylphenyl group, an o-, m- or p-fluorophenyl group, a dichlorophenyl group, a dicyanophenyl group, a trifluorophenyl group, a methoxyphenyl group, and an 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 of the general formula (9) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, A biphenylylmethylene group, a dimethylmethylene-phenylene-dimethylmethylene group, a fluorenediyl group, a phthaliddiyl group, etc. are mentioned. A hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, or a cyano group.

As a divalent organic group of 1-10 nitrogen numbers in X of General formula (9), an imino group, a polyimide group, etc. are mentioned.

Moreover, as an organic group of X in General formula (9), the thing of a structure represented by the following general formula (10) or the following general formula (11) is mentioned, for example.

[Formula 16]

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 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or an aryl group having at least one phenolic hydroxy group. Rd and Re are each independently selected from 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, or a hydroxyl group. u represents the integer of 0-5.

[Formula 17]

In formula (11), Ar ₃ represents a benzenetetrayl group, a naphthalenetetrayl group, or a biphenyltetrayl group, and when v is 2 or more, they may be the same as 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 cyanato The group represents an aryl group substituted by at least one. Although v represents the integer of 0-5, the mixture of the compound from which v differs may be sufficient.

In addition, as X in General formula (9), the divalent group represented by a following formula is mentioned.

[Formula 18]

Here, in formula, z represents the integer of 4-7. Rk each independently represents a hydrogen atom or a C1-C6 alkyl group.

_{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) are 1, benzenetetrayl group bonded to the 4th position or the 1,3 position, the two carbon atoms or the two oxygen atoms are at the 4,4' position, the 2,4' position, the 2,2' position, the 2,3' position, 3, A biphenyltetrayl group bonded to the 3' position or the 3,4' position, and the two carbon atoms or the two oxygen atoms are at the 2,6 position, the 1,5 position, the 1,6 position, or the 1,8 position. , a naphthalenetetrayl group bonded to the 1,3 position, the 1,4 position, or the 2,7 position.

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

Specific examples of the cyanato-substituted aromatic compound represented by the general formula (9) include 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-cyanatophenyl)-2-phenylpropane (cyanate of 4-α-cumylphenyl), 1-cyanato-4-cyclohexylbenzene, 1- Cyanato-4-vinylbenzene, 1-cyanato-2- or 1-cyanato-3-chlorobenzene, 1-cyanato-2,6-dichlorobenzene, 1-cyanato-2-methyl-3-chloro Benzene, cyanatonitrobenzene, 1-cyanato-4-nitro-2-ethylbenzene, 1-cyanato-2-methoxy-4-allylbenzene (cyanate of eugenol), methyl (4-cyanato Phenyl) 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-tert-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-dicyanatocinaphthalene, 2,2'- or 4,4'-dicyanatobiphenyl, 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-cyanatophenyl)pentane, 1,1-bis(4-cyanatophenyl) -3-Methylbutane, 1,1-bis(4-cyanatophenyl)-2-methylbutane, 1,1-bis(4-cyanatophenyl)-2,2-dimethylpropane, 2,2-bis( 4-cyanatophenyl)butane, 2,2-bis(4-cyanatophenyl)pentane, 2,2-bis(4-cyanatophenyl)hexane, 2,2-bis(4-cyanatophenyl)-3 -Methylbutane, 2,2-bis(4-cyanatophenyl)-4-methylpentane, 2,2-bis(4-cyanatophenyl)-3,3-dimethylbutane, 3,3-bis(4- Cyanatophenyl)hexane, 3,3-bis(4-cyanatophenyl)heptane, 3,3-bis(4-cyanatophenyl)octane, 3,3-bis(4-cyanatophenyl)-2-methyl Pentane, 3,3-bis(4-cyanatophenyl)-2-methylhexane, 3,3-bis(4-cyanatophenyl)-2,2-dimethylpentane, 4,4-bis(4-cyanato) Phenyl)-3-methylheptane, 3,3-bis(4-cyanatophenyl)-2-methylheptane, 3,3-bis(4-cyanatophenyl)-2,2-dimethylhexane, 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-phenylethane, bis(4 -Cyanatophenyl)biphenylmethane, 1,1-bis(4-cyanatophenyl)cyclopentane, 1,1-bis(4-cyanatophenyl)cyclohexane, 2,2-bis(4-cyanato- 3-Isopropylphenyl)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-cyanato) Phenyl)-2-propyl]benzene, 1,1-bis(4-cyanatophenyl)-3,3,5-trimethylcyclohexane, 4-[bis(4-cyanatophenyl)methyl]biphenyl, 4, 4-dicyanatobenzophenone, 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-cyanatophenyl)adamantane, 1,3-bis(4-cyanatophenyl)-5,7-dimethyladamantane, 3,3-bis(4-cyanatophenyl)iso Benzofuran-1(3H)-one (cyanate of phenolphthalein), 3,3-bis(4-cyanato-3-methylphenyl)isobenzofuran-1(3H)-one (cyanate of o-cresolphthalein) ), 9,9'-bis(4-cyanatophenyl)fluorene, 9,9-bis(4-cyanato-3-methylphenyl)fluorene, 9,9-bis(2-cyanato-5-bi Phenylyl) 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-cyanato) Phenyl)methane, 2,4,6-tris(N-methyl-4-cyanatoanilino)-1,3,5-triazine, 2,4-bis(N-methyl-4-cyanatoanilino) -6-(N-methylanilino)-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-cyanato Phenyl) phthalimidine, 2-phenyl-3,3-bis (4-cyanato-3-methylphenyl) phthalimidine, 1-methyl-3,3-bis (4-cyanatophenyl) indoline-2- , and 2-phenyl-3,3-bis(4-cyanatophenyl)indolin-2-one.

These cyanate ester compounds can be used individually by 1 type or in mixture of 2 or more types.

Moreover, as another specific example of the cyanate ester compound represented by the said General formula (9), a phenol novolak resin and a cresol novolak resin (phenol, an alkyl-substituted phenol or a halogen-substituted phenol by a well-known method, formalin, Formaldehyde compound such as paraformaldehyde is reacted in an acidic solution), trisphenol novolak resin (hydroxybenzaldehyde and phenol are reacted in the presence of an acidic catalyst), fluorene novolak resin (fluorenone compound and 9,9-bis(hydroxyaryl)fluorenes reacted in the presence of an acidic catalyst), phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin and biphenyl aralkyl resin (by a known method , Ar ₄ -(CH ₂ Y) ₂ (Ar ₄ represents a phenyl group, Y represents a halogen atom. Hereinafter, the same applies in this paragraph). A bishalogenomethyl compound and a phenol compound are reacted with an acid catalyst or Reacted without a catalyst, reacted with a _{bis(alkoxymethyl) compound as represented by Ar 4} -(CH ₂ OR) ₂ and a phenol compound in the presence of an acidic catalyst, or Ar ₄ —(CH ₂ OH) ₂ A bis(hydroxymethyl) compound and a phenol compound as represented by reacting in the presence of an acidic catalyst, or polycondensation of an aromatic aldehyde compound, an aralkyl compound, and a phenol compound), phenol-modified xyleneformaldehyde resin (by a known method, a xyleneformaldehyde resin and a phenol compound are reacted in the presence of an acidic catalyst), a modified naphthaleneformaldehyde resin (by a known method, a naphthaleneformaldehyde resin and a hydroxy-substituted aromatic compound are acidified reacted in the presence of a catalyst), a phenol-modified dicyclopentadiene resin, a phenol resin having a polynaphthylene ether structure (a polyhydric hydroxynaphthalene compound having two or more phenolic hydroxyl groups in one molecule by a known method phenol resins such as those obtained by dehydration condensation in the presence of a basic catalyst) by cyanating by the same method as described above, of free polymers and the like. These are not particularly limited. These cyanate ester compounds can be used individually by 1 type or in mixture of 2 or more types.

Among these, a phenol novolak type cyanate ester compound, a naphthol aralkyl type cyanate ester compound, a biphenyl aralkyl type cyanate ester compound, a naphthylene ether type cyanate ester compound, a xylene resin type cyanate ester compound, A danthanum skeleton type cyanate ester compound is preferable, and a naphthol aralkyl type cyanate ester compound is especially preferable at the point of plating adhesiveness.

It does not specifically limit as a manufacturing method of these cyanate ester compounds, A well-known method can be used. Examples of such a production method include a method in which a hydroxyl group-containing compound having a desired skeleton is obtained or synthesized, and the hydroxyl group is modified by a known method to cyanate. As a method of cyanating a hydroxyl group, the method described in Ian Hamerton, "Chemistry and Technology of Cyanate Ester Resins," Blackie Academic & Professional is mentioned, for example.

The cured resin using these cyanate ester compounds has excellent properties such as glass transition temperature, low thermal expansibility, and plating adhesion.

In the resin composition of this embodiment, content of the cyanate ester compound is although it does not specifically limit, From a viewpoint of plating adhesiveness and heat resistance, with respect to 100 mass parts of resin solid content, Preferably it is 0.01 mass part - 50 mass parts, More preferably, they are 0.05 mass parts - 40 mass parts, More preferably, they are 0.1 mass parts - 20 mass parts, More preferably, they are 0.2 mass parts - 5 mass parts.

<Phenolic resin>

As a phenol resin, if it is a phenol resin which has two or more hydroxyl groups in 1 molecule, a generally well-known thing can be used. For example, bisphenol A phenol resin, bisphenol E phenol resin, bisphenol F phenol resin, bisphenol S phenol resin, phenol novolak resin, bisphenol A novolac phenol resin, glycidyl ester phenol resin, are Alkyl novolak type phenol resin, biphenyl aralkyl type phenol resin, cresol novolak type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolac Type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, phosphorus-containing phenol resin, polymerizable unsaturated Although hydrocarbon group containing phenol resin, hydroxyl group containing silicone resin, etc. are mentioned, It is not restrict|limited in particular. Among these phenol resins, a biphenyl aralkyl type phenol resin, a naphthol aralkyl type phenol resin, a phosphorus containing phenol resin, and a hydroxyl group containing silicone resin are preferable at a flame retardant point. It is also possible to use these phenol resins individually by 1 type or in mixture of 2 or more types.

Content in particular of a phenol resin is not restrict|limited, To 100 mass parts of resin solid content, Preferably they are 0.1 mass part - 50 mass parts, More preferably, they are 0.2 mass parts - 45 mass parts. When content of a phenol resin exists in the said range, there exists a tendency for heat resistance to improve more.

<oxetane resin>

As an oxetane resin, a generally well-known thing can be used. For example, alkyloxetane, such as oxetane, 2-methyloxetane, 2, 2- dimethyloxetane, 3-methyloxetane, 3, 3- dimethyloxetane, 3-methyl-3- methoxymethyl ox Cetane, 3,3-di(trifluoromethyl)perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl type oxetane, OXT-101 (manufactured by Toa Synthesis, trade name), OXT-121 (manufactured by Toa Synthesis, trade name), and the like, but are not particularly limited. These can also be used 1 type or in mixture of 2 or more types suitably.

Content in particular of an oxetane resin is not restrict|limited, To 100 mass parts of resin solid content, Preferably they are 0.1 mass part - 50 mass parts, More preferably, they are 0.2 mass parts - 45 mass parts. When content of an oxetane resin exists in the said range, there exists a tendency for heat resistance to improve more.

<benzoxazine compound>

As a benzoxazine compound, if it is a compound which has two or more dihydrobenzoxazine rings in 1 molecule, a generally well-known thing can be used. For example, bisphenol A-type benzoxazine BA-BXZ (manufactured by Konishi Chemicals, trade name) bisphenol F-type benzooxazine BF-BXZ (manufactured by Konishi Chemicals, trade name), bisphenol S-type benzoxazine BS-BXZ (manufactured by Konishi Chemicals) , brand name), phenolphthalein-type benzoxazine, and the like, are not particularly limited. These can also be used individually by 1 type or in mixture of 2 or more types suitably.

Content in particular of a benzoxazine compound is not restrict|limited, With respect to 100 mass parts of resin solid content, Preferably they are 0.1 mass part - 50 mass parts, More preferably, they are 0.2 mass parts - 45 mass parts. When content of a benzoxazine compound exists in the said range, there exists a tendency for heat resistance to improve more.

<Epoxy resin>

In the resin composition of this embodiment, in order to improve the heat resistance of hardened|cured material, it is also possible to use together the epoxy resin different from the dicyclopentadiene type epoxy resin (A) represented by said (1).

Unlike the said epoxy resin (A), such an epoxy resin will not be specifically limited if it is a compound which has two or more epoxy groups in 1 molecule. Specific examples thereof include, for example, bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol A novolac epoxy resin, biphenyl epoxy resin, phenolo Volak 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 phenol type epoxy resin, tetrafunctional phenol type epoxy resin, triglycidyl isocyanurate, glycidyl ester type epoxy resin, alicyclic epoxy resin, biphenyl novolac type epoxy Resin, phenol aralkyl novolak type epoxy resin, naphthol aralkyl novolak type epoxy resin, aralkyl novolak type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, polyol type epoxy resin, phosphorus containing A compound obtained by epoxidizing a double bond such as an epoxy resin, glycidylamine, or butadiene, a compound obtained by reaction of a hydroxyl group-containing silicone resin with epichlorhydrin, and halides thereof.

Among them, at least one selected from the group consisting of a biphenyl aralkyl type epoxy resin, a naphthylene ether type epoxy resin, a polyfunctional phenol type epoxy resin, and a naphthalene type epoxy resin is preferable, and a naphthalene type epoxy resin is more preferable . There exists a tendency for developability and plating adhesiveness to improve more by including this kind of epoxy resin.

As a naphthalene type epoxy resin, it is preferable to use resin represented by following formula (5), since developability and plating adhesiveness improve more. As this epoxy resin, a commercial item can be used and DIC Corporation make HP-4710 (brand name) is mentioned. Since the naphthalene type epoxy resin represented by following formula (5) is a low molecular weight and polyfunctionality, it is excellent in the solubility with respect to a developing solution. Therefore, it is thought that the resin composition excellent also in developability can be obtained by combined use with a dicyclopentadiene type epoxy resin (A).

[Formula 19]

It is also possible to use these epoxy resins individually by 1 type or in mixture of 2 or more types.

Although content in particular of an epoxy resin is not restrict|limited, From a viewpoint of improving developability more, with respect to 100 mass parts of resin solid content in a resin composition, the said epoxy resin (A) and an epoxy resin (A) are the sum total of a different epoxy resin. , It is preferable to set it as 3 mass parts or more, It is more preferable to set it as 5 mass parts or more, It is still more preferable to set it as 10 mass parts or more, It is still more preferable to set it as 15 mass parts or more. In addition, from the viewpoint of further improving copper plating adhesion, the total of the epoxy resin (A) and the epoxy resin different from the epoxy resin (A) is 50 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 preferable to set it as 40 mass parts or less, It is still more preferable to set it as 30 mass parts or less, It is further more preferable to set it as 28 mass parts or less.

Moreover, the ratio in particular of the said epoxy resin (A) and the epoxy resin different from an epoxy resin (A) is although it does not restrict|limit, From the point of plating adhesiveness, 1-10:1-3 are preferable, 2-4:1- 2 is more preferable.

<Thermal curing accelerator (H)>

In the resin composition of this embodiment, it is also the range in which the characteristic of this embodiment is not impaired. WHEREIN: It is also possible to use the thermosetting accelerator (H) (it is also called a component (H)). Although it does not specifically limit as a thermosetting accelerator (H) used for this embodiment, For example, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert- butyl- di-peroxide organic peroxides exemplified by phthalates and the like; azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine , tertiary amines such as triethylenediamine, tetramethylbutanediamine, and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcin, and catechol; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, and iron acetylacetone; What is formed by dissolving these organometallic salts in hydroxyl-containing compounds, such as a phenol and a bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; organotin compounds such as dioctyl tin oxide, other alkyl tins and alkyl tin oxides; and imidazole compounds such as 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-phenylimidazole, and triphenylimidazole (TPIZ). Among them, imidazole compounds such as 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-phenylimidazole and triphenylimidazole (TPIZ) are heat resistant. From the point of view, it is preferable, and 2-ethyl-4-methylimidazole is more preferable at the point from which more excellent heat resistance is obtained.

It is also possible to use these thermosetting accelerators individually by 1 type or in mixture of 2 or more types.

In the resin composition of this embodiment, content of a thermosetting accelerator (H) is although it does not specifically limit, Usually, it is 0.01-10 mass parts with respect to 100 mass parts of resin solid content in a resin composition, Preferably it is 0.05- 5 parts by mass.

<Organic solvent>

The resin composition of this embodiment may contain the solvent as needed. For example, if an organic solvent is used, the viscosity at the time of preparation of a resin composition can be adjusted. The kind of solvent will not be specifically limited, if it can melt|dissolve some or all of resin in a resin composition. Although it does not specifically limit as the specific example, For example, Ketones, such as acetone, methyl ethyl ketone, a methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; Propylene glycol monomethyl ether and its acetate are mentioned.

It is also possible to use these organic solvents individually by 1 type or in mixture of 2 or more types.

<Other ingredients>

Various high molecular compounds, such as a thermosetting resin, a thermoplastic resin, its oligomer, and elastomers, which are not illustrated in the range in which the characteristic of this embodiment is not impaired in the resin composition of this embodiment so far; Flame-retardant compound which is not illustrated so far; A combination of additives and the like is also possible. These will not be specifically limited as long as they are generally used. For example, as a flame retardant compound, nitrogen-containing compounds, such as melamine and benzoguanamine, an oxazine ring containing compound, and the phosphate compound of a phosphorus compound, aromatic condensed phosphate ester, halogen-containing condensed phosphate ester, etc. are mentioned. As an additive, a ultraviolet absorber, antioxidant, a fluorescent whitening agent, a photosensitizer, dye, a pigment, a thickener, a lubricant, an antifoamer, a surface conditioning agent, a brightening agent, a polymerization inhibitor, etc. are mentioned. It is also possible to use these components individually by 1 type or in mixture of 2 or more types.

The resin composition of this embodiment WHEREIN: Although content of another component is although it does not specifically limit, Usually, it is 0.1-10 mass parts, respectively with respect to 100 mass parts of resin compositions.

<The manufacturing method of a resin composition>

The resin composition of this embodiment other than the dicyclopentadiene type epoxy resin (A) represented by the said Formula (1), a photocuring initiator (B), and the compound (C) and (C) components represented by the said Formula (2) It is prepared by mixing suitably the compound (D) which has ethylenically unsaturated group of, and a maleimide compound (E), a filler (F), a compound (G), and another component as needed. 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 manufacturing method of the resin composition of this embodiment is not specifically limited, For example, each component mentioned above is mix|blended with a solvent one by one, and the method of fully stirring is mentioned.

At the time of manufacture of a resin composition, a well-known process (stirring, mixing, kneading process, etc.) for dissolving or dispersing each component uniformly can be performed as needed. The dispersibility of the inorganic filler (G) with respect to a resin composition can be improved by performing a stirring dispersion process specifically, using the stirring tank which attached the stirrer which has suitable stirring ability. The above stirring, mixing and kneading treatment is, for example, a stirring device for the purpose of dispersion such as an ultrasonic homogenizer, a device for the purpose of mixing such as three rolls, a ball mill, a bead mill, a sand mill, or , it can be suitably carried out using a known device such as an orbital or autorotation mixing device. In addition, at the time of preparation of the resin composition of this embodiment, an organic solvent can be used as needed. The kind of organic solvent will not be specifically limited if resin in a resin composition can be melt|dissolved, The specific example is as having mentioned above.

<Use>

The resin composition of the present embodiment can be used for applications requiring an insulating resin composition, and is not particularly limited, Insulating resin sheets such as a photosensitive film, a photosensitive film with a support, a prepreg, and a circuit board (for laminated board use, It can be used for uses, such as a multilayer printed wiring board use), a soldering resist, an underfill material, a die-bonding material, a semiconductor sealing material, hole filling resin, component embedding resin. Especially, it can use suitably as a resin composition for insulating layers of a multilayer printed wiring board, and a soldering resist.

<Resin sheet>

The resin sheet of this embodiment is a support body and the support body which apply|coated the above-mentioned resin composition to the single side|surface or both surfaces of a support body provided with the resin composition layer which is formed on the surface of the support body and contains the resin composition of this embodiment. is a resin sheet formed with A resin sheet can be manufactured by apply|coating and drying a resin composition on a support body.

Although the support body used in the resin sheet of this embodiment is not specifically limited, A well-known thing can be used, It is preferable that it is a resin film. Examples of the resin film include a polyimide film, a polyamide film, a polyester film, a polyethylene terephthalate (PET) film, a polybutylene terephthalate (PBT) film, a polypropylene (PP) film, and a polyethylene (PE) film. Resin films, such as a film, a polyethylene naphthalate film, a polyvinyl alcohol film, and a triacetyl acetate film, are mentioned. Especially, PET film is preferable.

As for the said resin film, in order to make peeling from a resin composition layer easy, what apply|coated the release agent to the surface can be used preferably. It is preferable that it is the range of 5 micrometers - 100 micrometers, and, as for the thickness of a resin film, it is more preferable that it is the range of 10 micrometers - 50 micrometers. When this thickness is less than 5 micrometers, there exists a tendency for a support body to become brittle at the time of peeling of the support body performed before image development, and when thickness exceeds 100 micrometers, there exists a tendency for the resolution at the time of exposing from a support body to fall.

Moreover, in order to reduce the scattering of the light at the time of exposure by active energy rays, such as an ultraviolet-ray, it is preferable that the resin film is excellent in transparency.

In addition, the resin sheet in this embodiment WHEREIN: The resin composition layer may be protected by the protective film.

By protecting the resin composition layer side with a protective film, adhesion of dust, etc. to the resin composition layer surface, and a flaw can be prevented. As a protective film, the film comprised by the same material as said resin film can be used. Although the thickness of a protective film is not specifically limited, It is preferable that it is the range of 1 micrometer - 50 micrometers, It is more preferable that it is the range of 5 micrometers - 40 micrometers. When thickness is less than 1 micrometer, there exists a tendency for the handleability of a protective film to fall, and when thickness exceeds 50 micrometers, there exists a tendency for cheapness to be inferior. Moreover, it is preferable that the adhesive force of a resin composition layer and a protective film is small with respect to the adhesive force of a resin composition layer and a support body as for a protective film.

Although the manufacturing method of the resin sheet of this embodiment is not specifically limited, For example, the method of manufacturing a resin sheet by apply|coating the resin composition of this embodiment to supports, such as a PET film, and removing the organic solvent by drying. and the like.

The said application|coating can be performed by the well-known method using, for example, a roll coater, a comma coater, a gravure coater, a die coater, a bar coater, a lip coater, a knife coater, a squeeze coater, etc. The said drying can be performed by the method etc. of heating for 1 to 60 minutes in a 60-200 degreeC drying machine, for example.

It is preferable that the amount of residual organic solvent in a resin composition layer shall be 5 mass % or less with respect to the total mass of a resin composition layer from a viewpoint of preventing the diffusion of the organic solvent in a subsequent process. It is preferable that the thickness of the resin composition layer with respect to a support body sets it as 1.0 micrometer or more in the resin composition layer thickness of a resin sheet from a viewpoint of improving handleability. Moreover, it is preferable to set it as 300 micrometers or less from a viewpoint of improving the transmittance|permeability and making developability favorable.

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 this embodiment is equipped with the interlayer insulating layer containing the resin composition of this embodiment, For example, it can overlap and harden one or more resin sheets mentioned above, and it can also be obtained. Specifically, it can manufacture by the following method.

(Lamination process)

The resin composition layer side of the resin sheet of this embodiment is laminated on the single side|surface or both surfaces of a circuit board using a vacuum laminator. Examples of the circuit board include a glass epoxy substrate, a metal substrate, a ceramic substrate, a silicon substrate, a semiconductor encapsulation resin substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. have. In addition, a circuit board here means the board|substrate in which the pattern-processed conductor layer (circuit) was formed on the single side|surface or both surfaces of the above board|substrate. Further, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, a substrate in which one or both sides of the outermost layer of the printed wiring board is formed of a conductor layer (circuit) subjected to pattern processing is also included in the circuit board herein. do. Moreover, the roughening process may be previously given to the conductor layer surface by blackening process, copper etching, etc. Lamination process WHEREIN: After peeling and removing the protective film when a resin sheet has a protective film, a resin sheet and a circuit board are preheated as needed, and it press-bonds to a circuit board, pressurizing and heating a resin composition layer. In the resin sheet of this embodiment, the method of laminating on a circuit board under reduced pressure by the vacuum lamination method is used preferably.

The conditions of the lamination step are not particularly limited, but for example, the compression pressure (lamination temperature) is preferably 50°C to 140°C, and the compression pressure is preferably 1 kgf/cm2 to 15 kgf/cm2, The compression time is preferably 5 seconds to 300 seconds, and lamination is preferably carried out under reduced pressure at an air pressure of 20 mmHg or less. In addition, a batch type may be sufficient as a lamination process, and the continuous type using a roll may be sufficient as it. The vacuum lamination method can be implemented using a commercially available vacuum laminator. As a commercially available vacuum laminator, the Nikko Materials Co., Ltd. product 2 stage buildup laminator etc. are mentioned, for example.

(exposure process)

After a resin sheet is formed on a circuit board by a lamination process, an active energy ray is irradiated to a predetermined part of a resin composition layer, and the exposure process of hardening the resin composition layer of an irradiation part is performed. Irradiation of an active energy ray may let a mask pattern pass, and the direct drawing method which irradiates an active energy ray directly may be used.

As an active energy ray, an ultraviolet-ray, a visible ray, an electron beam, X-ray etc. are mentioned, for example, Especially an ultraviolet-ray is preferable. The irradiation dose of ultraviolet rays is approximately 10 mJ/cm 2 to 1000 mJ/cm 2 . Although there exist the contact exposure method which adheres a mask pattern to a multilayer printed wiring board, and is implemented by making it adhere|attach and the non-contact exposure method which exposes using parallel light without adhering to the exposure method which allows a mask pattern to pass, you may use either. In addition, when a support body exists on a resin composition layer, you may expose from on a support body, and you may expose a support body after peeling.

(developing process)

After the exposure step, when a support is present on the resin composition layer, the pattern of the insulating layer can be formed by removing the support and then developing the non-photocured portion (unexposed portion) by wet development. have.

In the case of the wet development, the developer is not particularly limited as long as the unexposed portion is selectively eluted, but a developer such as an alkaline aqueous solution, an aqueous developer, and an organic solvent is used. In this embodiment, especially the image development process by alkaline aqueous solution is preferable. These developing solutions can be used individually or in combination of 2 or more types. In addition, as a developing method, it can implement by well-known methods, such as spraying, rocking|fluctuation immersion, brushing, and scraping, for example.

Although the aqueous alkali solution used as a developing solution is not specifically limited, For example, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, sodium 4-borate, ammonia, amines, etc. are mentioned.

It is preferable that the density|concentration of the said aqueous alkali solution is 0.1 mass % - 60 mass % with respect to the developing solution whole quantity. In addition, the temperature of aqueous alkali solution can be adjusted according to developability. In addition, these aqueous alkali solutions can be used individually or in combination of 2 or more types.

In pattern formation of this embodiment, you may use together and use 2 or more types of said image development methods as needed. The development method includes a dip method, a paddle method, a spray method, a high-pressure spray method, brushing, slapping, and the like, and the high-pressure spray method is preferable in order to improve resolution. As a spray pressure in the case of employ|adopting a spray system, 0.02 Mpa - 0.5 Mpa are preferable.

(Post-bake process)

After the said image development process is complete|finished, a post-baking process is implemented and an insulating layer (hardened|cured material) is formed. As a post-baking process, the ultraviolet irradiation process by a high pressure mercury lamp, the heating process using a clean oven, etc. are mentioned, It is also possible to use these together. When irradiating an ultraviolet-ray, the irradiation amount can be adjusted as needed, For example, it can irradiate with the irradiation amount of about 0.05 J/cm<2> - 10 J/cm<2>. The heating conditions may be appropriately selected depending on the type, content, etc. of the resin component in the resin composition, preferably at 150°C to 220°C for 20 minutes to 180 minutes, more preferably at 160°C to 200°C for 30 minutes. It is selected from the range of minutes to 150 minutes.

(Plating process)

Next, a conductor layer is formed on the surface of the insulating layer by dry plating or wet plating. As dry plating, well-known methods, such as a vapor deposition method, a sputtering method, and an ion plating method, can be used. The vapor deposition method (vacuum vapor deposition method) can form a metal film on an insulating layer by putting a support body in a vacuum container, and heat-evaporating a metal, for example. In the sputtering method, for example, a support is placed in a vacuum container, an inert gas such as argon is introduced, a DC voltage is applied, the ionized inert gas collides with a target metal, and the metal on the insulating layer by the bounced metal Film formation can be performed.

In the case of wet plating, the surface of the formed insulating layer is roughened by performing a swelling treatment with a swelling solution, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution in this order. do. The swelling treatment by the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50°C to 80°C for 1 minute to 20 minutes. An alkali solution is mentioned as a swelling liquid, and sodium hydroxide solution, potassium hydroxide solution, etc. are mentioned as this alkali solution. As a commercially available swelling liquid, Updes (trademark) MDS-37 etc. by the Uemura Kogyo Co., Ltd. product are mentioned, for example.

The roughening process by an oxidizing agent is performed by immersing an insulating layer in the oxidizing agent solution for 5 minutes - 30 minutes at 60 degreeC - 80 degreeC. As an oxidizing agent, the alkaline permanganic acid solution which melt|dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid etc. are mentioned, for example. Moreover, it is preferable that the density|concentration of the permanganate in an alkaline permanganic acid solution shall be 5 mass % - 10 mass %. As an oxidizing agent marketed, alkaline permanganic acid solutions, such as Uemura Kogyo Co., Ltd. product Updes (trademark) MDE-40, Updes (trademark) ELC-SH, are mentioned, for example. The neutralization process by a neutralizing liquid is performed by making it immerse in the neutralizing liquid for 1 minute - 10 minutes at 30 degreeC - 50 degreeC. As a neutralization liquid, an acidic aqueous solution is preferable, and Uemura Kogyo Co., Ltd. product Updes (trademark) MDN-62 is mentioned as a commercial item.

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 may be formed, and the conductor layer may be formed only by electroless plating. As a method of subsequent pattern formation, a subtractive method, a semi-additive method, etc. can be used, for example.

<Semiconductor device>

The semiconductor device of this embodiment is equipped with the interlayer insulating layer containing the resin composition of this embodiment, and can be specifically manufactured with the following method. A semiconductor device can be manufactured by mounting a semiconductor chip in the conduction|electrical_connection point of the multilayer printed wiring board of this embodiment. Here, a conduction|electrical_connection point is a point which transmits the electrical signal in a multilayer printed wiring board, The point may be a surface, a buried point may be sufficient, and any may be sufficient as it. In addition, a semiconductor chip will not be specifically limited if it is an electric circuit element which uses a semiconductor as a material.

Although the semiconductor chip mounting method at the time of manufacturing the semiconductor device of this embodiment is not specifically limited as long as the semiconductor chip functions effectively, Specifically, a wire bonding mounting method, a flip chip mounting method, and a bumpless build The mounting method by the up layer (BBUL), the mounting method by the anisotropic conductive film (ACF), the mounting method by the nonelectroconductive film (NCF), etc. are mentioned.

Moreover, a semiconductor device can be manufactured also by laminating the resin sheet of this embodiment to a semiconductor chip. After lamination, it can be manufactured using the same method as the above-mentioned multilayer printed wiring board.

Example

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all to these Examples.

[Synthesis Example 1]

(Synthesis of cyanate ester compound)

300 g of 1-naphthol aralkyl resin (manufactured by Nippon Steel Chemical Co., Ltd.) (in terms of OH groups: 1.28 mol) and 194.6 g (1.92 mol of triethylamine) (1.5 mol with respect to 1 mol of hydroxyl groups) were added to 1800 g of dichloromethane It was dissolved and this was made into solution 1.

125.9 g (2.05 mol) of cyanogen chloride (1.6 mol per 1 mol of hydroxyl group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol per 1 mol of hydroxyl group), 1205.9 g of water , the solution 1 was poured over 30 minutes, maintaining the liquid temperature at -2 to -0.5°C under stirring. After completion of 1 week of solution, 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 per 1 mol of hydroxyl group) was dissolved in 65 g of dichloromethane was added to 10 It went down over the course of a minute. After 2 weeks of completion of the solution, the reaction was completed by stirring at the same temperature for 30 minutes.

After that, the reaction solution was allowed to stand to separate an organic phase and an aqueous phase. The obtained organic phase was washed 5 times with 1300 g of water. The electrical conductivity of the wastewater of the 5th time of water washing was 5 microseconds/cm, and it confirmed that the ionic compound which can be removed by washing|cleaning with water was fully removed.

The organic phase after washing with water was concentrated under reduced pressure and finally concentrated to dryness at 90°C for 1 hour to obtain 331 g of the target naphthol aralkyl-type cyanate ester compound (SNCN) (orange viscous substance). The mass average molecular weight Mw of the obtained SNCN was 600. In addition, the IR spectrum of SNCN showed absorption of 2250 cm ^-1 (cyanic acid ester group), and absorption of a hydroxyl group was not shown.

[Example 1]

(Preparation of resin composition and resin sheet)

As a dicyclopentadiene type epoxy resin (A) represented by Formula (1), it is a dicyclopentadiene type epoxy resin (n in Formula (1) is 1-3. XD-1000 (brand name), Nippon Kayaku Co., Ltd.) ) production) 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 ( Note) 6.5 parts by mass, as compound (C), a propylene glycol monomethyl ether acetate (hereinafter sometimes abbreviated as PGMEA) solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H, 65% by mass of non-volatile content, acid value: 70 mgKOH/g, manufactured by Nippon Kayaku Co., Ltd.) 77.5 parts by mass (50.4 parts by mass in terms of non-volatile content), (C) As a compound (D) having an ethylenically unsaturated group other than component, 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), Daiwa Chemical Industries, Ltd.) ) production) 3.3 parts by mass, as filler (F), methylethylketone (hereinafter, sometimes abbreviated as MEK) slurry of epoxysilane-treated silica (SC2050MB (trade name), average particle size of 0.5 µm, nonvolatile content 70% by mass; 71.4 parts by mass (manufactured by Admatex Co., Ltd.) (50 parts by mass in terms of non-volatile matter) was blended, followed by stirring with an ultrasonic homogenizer to obtain a varnish (solution of the resin composition). These varnishes were applied on a 38 µm-thick PET film (Unipil (registered trademark) TR1-38, manufactured by Unitica Co., Ltd., trade name) using an automatic coating device (PI-1210, manufactured by Tester Industries, Ltd.) and heat-drying at 80 degreeC for 7 minutes, the PET film was used as a support body, and the resin sheet whose thickness of a resin composition layer is 30 micrometers was obtained.

In addition, the said KAYARAD (trademark) ZCR-6007H is a mixture containing the said compound (C1) and any one or more types of the said compound (C2)-(C5).

(Production of inner-layer circuit board)

Both sides of a glass cloth base BT resin double-sided copper-clad laminate (copper foil thickness of 18 µm, thickness of 0.2 mm, CCL (registered trademark)-HL832NS manufactured by Mitsubishi Gas Chemical Co., Ltd.) on which an inner-layer circuit was formed were copper-clad with CZ8100 manufactured by MAC Co., Ltd. The surface roughening process was performed and the inner-layer circuit board was obtained.

(Production of laminate for evaluation)

The resin surface of the said resin sheet is arrange|positioned on the inner-layer circuit board, and after performing evacuation (5.0 MPa or less) for 30 second using a vacuum laminator (manufactured by Nikko Materials Co., Ltd.), pressure 10 kgf/cm<2>, temperature Lamination molding was performed at 70 degreeC for 30 second. Furthermore, the laminated body in 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 the pressure of 10 kgf/cm<2> and the temperature of 70 degreeC was obtained. The obtained laminate is subjected to an exposure step of irradiating an ultraviolet ray of 200 mJ/cm 2 , the support is peeled off, developed with a 1 mass % sodium carbonate aqueous solution, and further subjected to an exposure step of irradiating an ultraviolet ray of 1000 mJ/cm 2 , After performing the post-baking process heat-processed for 180 degreeC and 120 minutes, it was set as the laminated body for evaluation.

(Production of cured product for evaluation)

After irradiating the resin sheet with ultraviolet rays of 200 mJ/cm 2 , and performing an exposure process of irradiating ultraviolet rays of 1000 mJ/cm 2 , and performing a post-baking process of heat treatment at 180° C. for 120 minutes, the support is peeled and evaluated It was set as a hardened|cured material for use.

[Example 2]

21.9 parts by mass of a dicyclopentadiene type epoxy resin (XD-1000 (trade name), manufactured by Nippon Kayaku Co., Ltd.) as the component (A), 2-benzyl-2-dimethylamino-1 as the photocuring initiator (B) -(4-morpholinophenyl)-butanone-1 (Irgacure (registered trademark) 369, manufactured by BASF Japan Co., Ltd.) 6.5 parts by mass, as compound (C), a PGMEA solution of TrisP-PA epoxy acrylate compound ( KAYARAD (registered trademark) ZCR-6007H, non-volatile content 65 mass%, acid value: 70 mgKOH/g, manufactured by Nippon Kayaku Co., Ltd.) 77.5 parts by mass (50.4 parts by mass in terms of non-volatile content), ethylenic properties other than component (C) As the compound (D) having an unsaturated group, 17.4 parts by mass of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.), as the maleimide compound (E), a maleimide compound (BMI-2300) (trade name), manufactured by Daiwa Chemical Industry Co., Ltd.) 3.3 parts by mass, MEK slurry of epoxysilane-treated silica (SC2050MB (trade name)), average particle size 0.5 µm, non-volatile content 70 mass%, as the filler (F), Ard Co., Ltd. 71.4 parts by mass (manufactured by Matex) (50 parts by mass in terms of nonvolatile matter), 0.5 parts by mass of the cyanate ester compound SNCN obtained in Synthesis Example 1 as compound (G), and stirring with an ultrasonic homogenizer to varnish (resin composition) solution) was obtained. These varnishes were applied on a 38 µm-thick PET film (Unipil (registered trademark) TR1-38, manufactured by Unitica Co., Ltd., trade name) using an automatic coating device (PI-1210, manufactured by Tester Industries, Ltd.) and heat-drying at 80 degreeC for 7 minutes, the PET film was used as a support body, and the resin sheet whose thickness of a resin composition layer is 30 micrometers was obtained. Using this, it carried out similarly to Example 1, and obtained the laminated body for evaluation and the hardened|cured material for evaluation.

[Example 3]

As the component (A), 21.9 parts by mass of a dicyclopentadiene type epoxy resin (XD-1000 (trade name), manufactured by Nippon Kayaku Co., Ltd.), as the photocuring initiator (B), bis(2,4,6-trimethylbenzoyl) )-phenylphosphine oxide (Irgacure (registered trademark) 819, manufactured by BASF Japan Co., Ltd.) 6.5 parts by mass, as compound (C), a PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H) , 65% by mass of non-volatile content, acid value: 70 mgKOH/g, manufactured by Nippon Kayaku Co., Ltd.) 77.5 parts by mass (50.4 parts by mass in terms of non-volatile content), (C) As a compound (D) having an ethylenically unsaturated group other than component , 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), Daiwa Chemical Industries, Ltd.) Manufactured by Co.) 3.3 parts by mass, as filler (F), MEK slurry of epoxysilane-treated silica (SC2050MB (trade name), average particle size of 0.5 µm, non-volatile content 70 mass%, manufactured by Admatex Co., Ltd.) 71.4 parts by mass ( 50 parts by mass in terms of non-volatile content), and 0.5 parts by mass of the cyanate ester compound SNCN obtained in Synthesis Example 1 as the compound (G), followed by stirring with an ultrasonic homogenizer to obtain a varnish (solution of the resin composition). These varnishes were applied on a 38 µm-thick PET film (Unipil (registered trademark) TR1-38, manufactured by Unitica Co., Ltd., trade name) using an automatic coating device (PI-1210, manufactured by Tester Industries, Ltd.) and heat-drying at 80 degreeC for 7 minutes, the PET film was used as a support body, and the resin sheet whose thickness of a resin composition layer is 30 micrometers was obtained. Using this, it carried out similarly to Example 1, and obtained the laminated body for evaluation and the hardened|cured material for evaluation.

[Example 4]

19.9 parts by mass of a dicyclopentadiene type epoxy resin (XD-1000 (trade name), manufactured by Nippon Kayaku Co., Ltd.) as the component (A), bis(2,4,6-trimethylbenzoyl) as the photocuring initiator (B) )-phenylphosphine oxide (Irgacure (registered trademark) 819, manufactured by BASF Japan Co., Ltd.) 6.5 parts by mass, as compound (C), a PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H) , 65% by mass of non-volatile content, acid value: 70 mgKOH/g, manufactured by Nippon Kayaku Co., Ltd.) 77.5 parts by mass (50.4 parts by mass in terms of non-volatile content), (C) As a compound (D) having an ethylenically unsaturated group other than component , 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), Daiwa Chemical Industries, Ltd.) Manufactured by Co.) 3.3 parts by mass, as filler (F), MEK slurry of epoxysilane-treated silica (SC2050MB (trade name), average particle size of 0.5 µm, non-volatile content 70 mass%, manufactured by Admatex Co., Ltd.) 71.4 parts by mass ( 50 parts by mass in terms of non-volatile content), as the compound (G), 0.5 parts by mass of the cyanate ester compound SNCN obtained in Synthesis Example 1 and 2 parts by mass of a naphthalene type epoxy resin (HP-4710 (trade name), manufactured by DIC Corporation) It was mix|blended, and it stirred with the ultrasonic homogenizer, and obtained the varnish (solution of a resin composition). These varnishes were applied on a 38 µm-thick PET film (Unipil (registered trademark) TR1-38, manufactured by Unitica Co., Ltd., trade name) using an automatic coating device (PI-1210, manufactured by Tester Industries, Ltd.) and heat-drying at 80 degreeC for 7 minutes, the PET film was used as a support body, and the resin sheet whose thickness of a resin composition layer is 30 micrometers was obtained. Using this, it carried out similarly to Example 1, and obtained the laminated body for evaluation and the hardened|cured material for evaluation.

[Example 5]

As the component (A), 15.8 parts by mass of a dicyclopentadiene type epoxy resin (XD-1000 (trade name), manufactured by Nippon Kayaku Co., Ltd.), as the photocuring initiator (B), bis(2,4,6-trimethylbenzoyl) )-phenylphosphine oxide (Irgacure (registered trademark) 819, manufactured by BASF Japan Co., Ltd.) 6.5 parts by mass, as compound (C), a PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H) , 65% by mass of non-volatile content, acid value: 70 mgKOH/g, manufactured by Nippon Kayaku Co., Ltd.) 77.5 parts by mass (50.4 parts by mass in terms of non-volatile content), (C) As a compound (D) having an ethylenically unsaturated group other than component , 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), Daiwa Chemical Industries, Ltd.) Manufactured by Co.) 3.3 parts by mass, as filler (F), MEK slurry of epoxysilane-treated silica (SC2050MB (trade name), average particle size of 0.5 µm, non-volatile content 70 mass%, manufactured by Admatex Co., Ltd.) 71.4 parts by mass ( 50 parts by mass in terms of non-volatile content), as the compound (G), 0.5 parts by mass of the cyanate ester compound SNCN obtained in Synthesis Example 1, and 6.1 parts by mass of a naphthalene-type epoxy resin (HP-4710 (trade name), manufactured by DIC Corporation) It was mix|blended, and it stirred with the ultrasonic homogenizer, and obtained the varnish (solution of a resin composition). These varnishes were applied on a 38 µm-thick PET film (Unipil (registered trademark) TR1-38, manufactured by Unitica Co., Ltd., trade name) using an automatic coating device (PI-1210, manufactured by Tester Industries, Ltd.) and heat-drying at 80 degreeC for 7 minutes, the PET film was used as a support body, and the resin sheet whose thickness of a resin composition layer is 30 micrometers was obtained. Using this, it carried out similarly to Example 1, and obtained the laminated body for evaluation and the hardened|cured material for evaluation.

[Example 6]

As the component (A), 5.9 parts by mass of a dicyclopentadiene type epoxy resin (XD-1000 (trade name), manufactured by Nippon Kayaku Co., Ltd.), as the photocuring initiator (B), bis(2,4,6-trimethylbenzoyl) )-phenylphosphine oxide (Irgacure (registered trademark) 819, manufactured by BASF Japan Co., Ltd.) 6.5 parts by mass, as compound (C), a PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H) , 65% by mass of non-volatile content, acid value: 70 mgKOH/g, manufactured by Nippon Kayaku Co., Ltd.) 77.5 parts by mass (50.4 parts by mass in terms of non-volatile content), (C) As a compound (D) having an ethylenically unsaturated group other than component , 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), Daiwa Chemical Industries, Ltd.) Manufactured by Co.) 3.3 parts by mass, as filler (F), MEK slurry of epoxysilane-treated silica (SC2050MB (trade name), average particle size of 0.5 µm, non-volatile content 70 mass%, manufactured by Admatex Co., Ltd.) 71.4 parts by mass ( 50 parts by mass in terms of non-volatile content), as the compound (G), 0.5 parts by mass of the cyanate ester compound SNCN obtained in Synthesis Example 1 and 16 parts by mass of a naphthalene-type epoxy resin (HP-4710 (trade name), manufactured by DIC Corporation) It was mix|blended, and it stirred with the ultrasonic homogenizer, and obtained the varnish (solution of a resin composition). These varnishes were applied on a 38 µm-thick PET film (Unipil (registered trademark) TR1-38, manufactured by Unitica Co., Ltd., trade name) using an automatic coating device (PI-1210, manufactured by Tester Industries, Ltd.) and heat-drying at 80 degreeC for 7 minutes, the PET film was used as a support body, and the resin sheet whose thickness of a resin composition layer is 30 micrometers was obtained. Using this, it carried out similarly to Example 1, and obtained the laminated body for evaluation and the hardened|cured material for evaluation.

[Example 7]

As the component (A), 15.8 parts by mass of a dicyclopentadiene type epoxy resin (XD-1000 (trade name), manufactured by Nippon Kayaku Co., Ltd.), as the photocuring initiator (B), bis(2,4,6-trimethylbenzoyl) )-phenylphosphine oxide (Irgacure (registered trademark) 819, manufactured by BASF Japan Co., Ltd.) 6.5 parts by mass, as compound (C), a PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H) , 65% by mass of non-volatile content, acid value: 70 mgKOH/g, manufactured by Nippon Kayaku Co., Ltd.) 77.5 parts by mass (50.4 parts by mass in terms of non-volatile content), (C) As a compound (D) having an ethylenically unsaturated group other than component , 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), Daiwa Chemical Industries, Ltd.) Manufactured by Co.) 3.3 parts by mass, as filler (F), MEK slurry of epoxysilane-treated silica (SC2050MB (trade name), average particle size of 0.5 µm, non-volatile content 70 mass%, manufactured by Admatex Co., Ltd.) 71.4 parts by mass ( 50 parts by mass in terms of non-volatile content), 0.5 parts by mass of the cyanate ester compound SNCN obtained in Synthesis Example 1 as compound (G), and 6.1 parts by mass of a naphthalene type epoxy resin (HP-4710 (trade name), manufactured by DIC Corporation) , as a thermal curing accelerator (H), 0.2 parts by mass of 2-ethyl-4-methylimidazole (2E4MZ (trade name), manufactured by Shikoku Chemical Co., Ltd.) was blended and stirred with an ultrasonic homogenizer to varnish (resin composition solution) was obtained. These varnishes were applied on a 38 µm-thick PET film (Unipil (registered trademark) TR1-38, manufactured by Unitica Co., Ltd., trade name) using an automatic coating device (PI-1210, manufactured by Tester Industries, Ltd.) and heat-drying at 80 degreeC for 7 minutes, the PET film was used as a support body, and the resin sheet whose thickness of a resin composition layer is 30 micrometers was obtained. Using this, it carried out similarly to Example 1, and obtained the laminated body for evaluation and the hardened|cured material for evaluation.

[Comparative Example 1]

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

In addition, KAYARAD (trademark) ZFR-1553H does not have the structure shown by said 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 Co., Ltd.) was used instead of the component (A), and a resin sheet and laminate for evaluation and a cured product for evaluation.

[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 Co., Ltd.) was used instead of the component (A), a resin sheet, a laminate for evaluation, and A cured product for evaluation was obtained.

In addition, the said polyfunctional epoxy resin (1031S (brand name), Mitsubishi Chemical Co., Ltd. product) has the following structural formula (12).

[Formula 20]

[Physical property measurement evaluation]

The resin sheet, the laminated body for evaluation, and the hardened|cured material for evaluation were measured and evaluated by the following method. Their results are shown in Table 1.

<coatability>

A finger was lightly pressed against the resin surface end of the resin sheet on which each A4 size support was formed, and the degree of adhesion to the finger was evaluated according to the following criteria.

○: Adherence to the finger is hardly observed. The end of the resin sheet on which the support is formed is attached to the finger, but it peels off from the finger at a height of less than 30 mm and falls.

x: adhesion to a finger is confirmed. The end of the resin sheet on which the support body was formed is attached to the finger and floats 30 mm or more in height.

<Heat resistance (glass transition temperature)>

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

<developability>

After measuring the time until the residue disappears visually from the start of the developing process on the developing surface of the laminated body for evaluation, it observed with SEM (scanning electron microscope) (1000 times magnification), and the presence or absence of a residue was checked. It was evaluated based on the following criteria.

(double-circle): The time until the development residue disappears visually is 50 sec or less, and there is no development residue in the range of 30 mm even after SEM observation, and it is very excellent in developability.

(circle): Although the time until the development residue disappears visually exceeds 50 sec, there is no development residue in the range of 30 mm even after SEM observation, and it is excellent in developability.

x: There is a developing residue in the range of 30 mm in width and height, and it is inferior to developability.

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

The multilayer printed wiring boards obtained in Examples 1 and 2 and Comparative Examples 1 to 3 were subjected to an electroless copper plating process manufactured by Uemura Kogyo (chemical liquid names: MCD-PL, MDP-2, MAT-SP, MAB-4-C). , MEL-3-APEA ver.2), electroless copper plating of about 0.8 µm was performed, and drying was performed at 130°C for 1 hour. Then, electrolytic copper plating was performed so that the thickness of plating copper might be set to 18 micrometers, and it dried at 180 degreeC for 1 hour. In this way, the sample in which the 18-micrometer-thick conductor layer (plated copper) was formed on the insulating layer was produced, and it used for the following evaluation.

<Plating adhesion (kN/m)>

Using the sample produced by the above procedure, the adhesive force of the plated copper was measured three times according to JIS C 6481, and the average value was obtained. About the sample swollen by drying after electrolytic copper plating, it evaluated using the part which is not swollen.

As is clear from Table 1, Examples 1-7 are excellent in plating adhesiveness and heat resistance. Especially, Example 2 has favorable heat resistance and plating adhesiveness, and Examples 3-7 are more excellent in heat resistance. On the other hand, Comparative Examples 1-3 are insufficient in plating adhesiveness or heat resistance. Therefore, according to this invention, the resin composition excellent in plating adhesiveness and heat resistance, the resin sheet using the same, a multilayer printed wiring board, and a semiconductor device are obtained.

Claims (14)

containing the dicyclopentadiene type epoxy resin (A) represented by the following formula (1), a photocuring initiator (B), a compound (C), and a compound (D) having an ethylenically unsaturated group;
The said photocuring initiator (B) contains the phosphine oxide compound represented by following formula (6),
The compound (C) includes any one or more of a compound represented by the following formula (C2) to a compound represented by the following formula (C5) and a compound represented by the following formula (C1);
The resin composition wherein the compound (D) having an ethylenically unsaturated group is different from any of the compounds represented by the following formula (C1) to the compound represented by the following formula (C5).

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

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

The method of claim 1,
The resin composition which further contains a maleimide compound (E). The method of claim 1,
The resin composition which further contains a filler (F). The method of claim 1,
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 dicyclopentadiene type epoxy resin (A) represented by (1) above (G) ), which further contains a resin composition. The method of claim 1,
The acid value of the said compound (C) is 30 mgKOH/g or more and 120 mgKOH/g or less, The resin composition. The method of claim 1,
The resin composition whose content of a component (A) is 3 mass parts or more and 50 mass parts or less with respect to 100 mass parts of resin solid content in a resin composition. The method of claim 1,
The resin composition in which the compound (D) which has the said ethylenically unsaturated group is a compound which has a (meth)acryloyl group, and/or a compound which has a vinyl group. 4. The method of claim 3,
The filler (F) is any one selected from the group consisting of silica, boehmite, barium sulfate, silicone powder, fluororesin filler, urethane resin filler, acrylic resin filler, polyethylene filler, styrene butadiene rubber and silicone rubber. The above, the resin composition. The method of claim 1,
A resin composition further comprising a thermal curing accelerator (H). The method of claim 1,
The resin composition which further contains the naphthalene type epoxy resin represented by following formula (5).

The resin sheet which has a support body and the resin composition in any one of Claims 1-10 arrange|positioned on the surface of this support body. The multilayer printed wiring board which has the resin composition in any one of Claims 1-10. The semiconductor device which has the resin composition in any one of Claims 1-10. delete