JPWO2018003313A1 - Resin composition, resin sheet, multilayer printed wiring board and semiconductor device - Google Patents

Abstract

Provided is a resin composition which is excellent in coating property and heat resistance and excellent in plating adhesion and developability when used for a multilayer printed wiring board, a resin sheet with a support, a multilayer printed wiring board using them, and a semiconductor device. Do. Dicyclopentadiene type epoxy resin (A) represented by the following formula (1), photocuring initiator (B), compound (C) represented by the following formula (2) and ethylenicity other than the component (C) Resin composition containing the compound (D) which has unsaturated group.
[Chemical formula 1]

[Chemical formula 2]

Description

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

  Due to the miniaturization and densification of multilayer printed wiring boards, studies for thinning the laminates used for multilayer printed wiring boards are actively conducted. With the reduction in thickness, a reduction in thickness is also required for the insulating layer, and a resin sheet not containing glass cloth is also required. The resin composition to be the material of the insulating layer is mainly a thermosetting resin, and drilling for obtaining conduction between the insulating layers is generally performed by laser processing. Moreover, in the resin sheet using thermosetting resin, the method of forming a conductor circuit by copper plating as a method of forming a conductor circuit on an insulating layer is common.

  On the other hand, in the case of drilling by laser processing, there is a problem that the processing time is longer as the density of the substrate is larger than the number of holes. Therefore, in recent years, there is a demand for a resin sheet which can be collectively subjected to a hole-piercing process in a developing step by using a resin composition which is cured by light or the like and dissolved by development. Furthermore, 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 off.

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

JP, 2016-8267, A JP, 2011-174082, A

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

  In addition, the cured product obtained from the resin composition described in Patent Document 1 is limited to etching resists and solder resists for printed wiring boards, and is excellent in gold plating resistance, but for use as an interlayer insulating layer Copper plating adhesion was not sufficient.

  Although the cured product obtained from the resin composition described in Patent Document 2 is excellent in copper plating adhesion, since drilling is limited to laser processing, collective drilling can not be performed in the developing step.

  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 which is excellent in coating property and heat resistance, and excellent in developability and copper plating adhesion, Provided are a resin sheet with a support, a multilayer printed wiring board using them, and a semiconductor device.

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

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

(In formula (2), a plurality of R ₁ 's each independently represent a hydrogen atom or a methyl group, and a plurality of R ₂ ' s each independently have a hydrogen atom or a carbon atom which may have a substituent) And 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).

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

That is, the present invention includes the following contents.
[1] Dicyclopentadiene Type Epoxy Resin (A) Represented by Formula (1), Photo-Curing Initiator (B), Compound (C) Represented by Formula (2), and Formula (2) The resin composition containing the compound (D) which has ethylenic unsaturated groups other than the compound (C) represented.
[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 the above (1) The resin composition according to any one of [1] to [3], further comprising a compound (G) of

[5] The resin composition according to any one of [1] to [4], wherein the acid value of the compound (C) represented by the formula (2) is 30 mg KOH / g to 120 mg KOH / g. .
[6] Any one of [1] to [5], wherein the content of the component (A) is 3 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition The resin composition as described in.
[7] The compound according to any one of [1] to [6], wherein the compound (D) having an ethylenically unsaturated group is a compound having a (meth) acryloyl group and / or a compound having a vinyl group Resin composition.
[8] The filler (F) is silica, boehmite, barium sulfate, silicone powder, fluorocarbon resin filler, urethane resin filler, acrylic resin filler, polyethylene filler, styrene butadiene rubber, silicone The resin composition as described in [3] which is any one or more types selected from the group which consists of rubber | gum.
[9] The resin composition according to any one of [1] to [8], which further contains a heat curing accelerator (H).
[10]
The resin composition as described in any one of [1]-[9] which further contains the naphthalene type epoxy resin represented by following formula (5).

[11]
The resin composition as described in any one of [1]-[10] in which the said photocuring initiator (B) contains the phosphine oxide compound represented by following 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 is an alkyl group having 1 to 20 carbon atoms or 6 to 20 carbon atoms The aryl group of
[12] A resin sheet comprising the support and the resin composition according to any one of [1] to [11] disposed on the surface of the support.
[13] A multilayer printed wiring board comprising the resin composition according to any one of [1] to [11].
The semiconductor device which has a resin composition as described in any one of [14] [1]-[11].

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

  Hereinafter, modes for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail. The following present embodiment is an example for describing the present invention, and is not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the present invention.

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

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

<Dicyclopentadiene Type Epoxy Resin (A) Represented by Formula (1)>
The dicyclopentadiene type epoxy resin (A) (also referred to as component (A)) used in the present embodiment is a compound having a dicyclopentadiene skeleton and having a structure of the formula (1). The cured product obtained by containing the resin (A) can suitably form a protective film with high copper plating adhesion and an interlayer insulating layer while having high developability.
In Formula (1), n shows the integer of 0-15. Preferably, it is an integer of 0 to 5 from the viewpoint of developability.

  Although the content of the component (A) is not particularly limited in the resin composition of the present embodiment, the total content of the component (A), the component (C) and the component (D) is from the viewpoint of improving the copper plating adhesion. The amount is preferably 3 parts by mass or more, more preferably 4 parts by mass or more, and still more preferably 5 parts by mass or more with respect to 100 parts by mass. Further, the amount is preferably 90 parts by mass or less, more preferably 89 parts by mass or less, and still more preferably 88 parts by mass or less from the viewpoint of sufficiently curing and improving heat resistance.

  The content of the component (A) in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of improving copper plating adhesion and developability, relative to 100 parts by mass of resin solid content in the resin composition The amount is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more. Further, from the viewpoint of sufficiently curing and improving the heat resistance, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. Preferably, 30 parts by mass or less is more preferable, and 28 parts by mass or less is still more preferable.

A commercial item can also be utilized for resin (A), For example, XD-1000 (n = 1-3 in Formula (1)) (brand name, Nippon Kayaku Co., Ltd. product), HP-7200L (the product name) N = 1 to 3 in the formula (1) (trade name, manufactured by DIC Corporation) and the like.
These may be used alone or in combination of two or more.

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

  For example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di- Organic peroxides, acyl phosphine oxides, acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc. -Hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxychlorohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] Acetophenones such as 2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, 2 -Anthraquinones such as chloroanthraquinone and 2-amyl anthraquinone, thioxanthones such as 2,4-diethylthioxanthone, 2-isopropyl thioxanthone and 2-chlorothioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone, 4- Benzophenones such as benzoyl-4'-methyl diphenyl sulfide, 4,4'-bismethylamino benzophenone, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis (2,4,6-tol Radical type photocuring of phosphine oxides such as methyl benzoyl) -phenyl phosphine oxide, and oxime esters such as 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] Initiators, diazonium salts of Lewis acids such as p-methoxyphenyl diazonium fluorophosphonates, N, N-diethylaminophenyl diazonium hexafluorophosphonates, etc., iodonium salts of Lewis acids such as diphenyliodonium hexafluorophosphonates, diphenyliodonium hexafluoroantimonates, Sulfonium salts of Lewis acids such as triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroantimonate, etc., triphenylphosphonium hexafluoroantemone Cationic photopolymerization initiators such as phosphonium salts of Lewis acids such as H. et al., Other halides, triazine initiators, baud rate initiators, and other photoacid generators.

  Acyl phosphine oxides include phosphine oxide compounds represented by the following formula (6) such as bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide, 2,4,6-trimethyl benzoyl-diphenyl-phos Fin oxide etc. are mentioned. In particular, the phosphine oxide compound represented by the following formula (6) has a high UV absorptivity at a long wavelength and is excellent in causing the UV light to reach the inside of the resin. Therefore, the dicyclopentadiene type epoxy resin (A), the compound (C), the compound (D) and the like according to this embodiment can be suitably reacted, and a resin sheet and a multilayer printed wiring board which are excellent in heat resistance are produced. Is possible.

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 is an alkyl group having 1 to 20 carbon atoms or 6 to 20 carbon atoms Indicates an aryl group.

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

  As a C1-C20 alkyl group, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, an isobutyl group, sec-butyl group, for example, t-Butyl group, neopentyl group, 1,1-dimethylpropyl group, 1,1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, 1,1 -Linear or branched alkyl groups such as dimethylbutyl group and 1,1,3-trimethylbutyl group can be mentioned.

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

  Among them, acylphosphine oxides, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) from the viewpoint of having reactivity suitable for multilayer printed wiring board applications and high reliability to metal conductors. ) -Butanone-1 and other acetophenone radical type photocuring initiators are preferable, and as described above, phosphine oxide compounds represented by the above-mentioned formula (6) are more preferable because heat resistance is further obtained, and bis (bis (bis) More preferred is 2,4,6-trimethyl benzoyl) -phenyl phosphine oxide.

  These photo-curing initiators (B) can be used singly or in combination of two or more kinds as appropriate. Both radical type and cationic type initiators may be used in combination.

  Also, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6-trimethylbenzoyl -A diphenyl- phosphine oxide can also use a commercial item, Irgacure (trademark) 369 (BASF Japan KK made), Irgacure (trademark) 819 (BASF Japan KK) and Irgacure (Registration respectively) Trademark TPO (manufactured by BASF Japan Ltd.) is preferably used.

  The content of the photo-curing initiator (B) in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of sufficiently curing the resin composition with active energy rays and improving the heat resistance, the resin composition The total content of component (A), component (C) and component (D) is preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more. And 0.3 parts by mass or more. In addition, from the viewpoint of inhibiting heat curing after photocuring and reducing heat resistance, it is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and further preferably 20 parts by mass or less. preferable.

  The content of the photo-curing initiator (B) in the resin composition of the present embodiment is not particularly limited, but may be 0.1 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition. Preferably, 0.2 parts by mass or more is more preferable, 0.3 parts by mass or more is further preferable, 1 part by mass or more is further more preferable, and 1.8 parts by mass or more Even more preferred. Further, from the viewpoint of inhibiting heat curing after photo curing and reducing heat resistance, it is preferably 30 parts by mass or less, and 25 parts by mass or less with respect to 100 parts by mass of resin solid content in the resin composition. It is more preferable to do, to be 20 mass parts or less is still more preferable, and it is still more preferable to be 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). The compound (C) may be used alone, may contain isomers such as a structural isomer and a stereoisomer, and two or more kinds of compounds having different structures may be used in combination as appropriate.

In Formula (2), each R ₁ independently represents a hydrogen atom or a methyl group. Among them, it is preferable to contain a hydrogen atom from the viewpoint of improving the reactivity of the light curing reaction, and more preferably, all of R ₁ are hydrogen atoms.
The plurality of R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent.
The hydrocarbon group is a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms, preferably 1 to 14 carbon atoms, more preferably 1 to 10 carbon atoms; 3 to 22 carbon atoms, preferably 3 to 3 carbon atoms 14, more preferably 3 to 10 alicyclic hydrocarbon groups; and aromatic hydrocarbon groups having 6 to 22 carbon atoms, preferably 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms.

  As an aliphatic hydrocarbon group, for example, 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 Group, neopentyl group, 1,1-dimethylpropyl group, 1,1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, 1,1-dimethylbutyl Groups, linear or branched alkyl groups such as 1,1,3-trimethylbutyl group; linear or branched alkenyl groups such as vinyl group, allyl group, isopropenyl group; ethynyl group, propargyl group, etc. And a straight or branched alkynyl group of

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

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

  In these hydrocarbon groups, at least one hydrogen atom may be substituted with another hydrocarbon group. As a hydrocarbon group in which at least one hydrogen atom is substituted by another hydrocarbon group, for example, aryl group-substituted alkyl group such as benzyl group and cumyl group, cyclic saturated hydrocarbon group-substituted alkyl group such as cyclohexylmethyl group It can be mentioned.

As a C1-C22 hydrocarbon group which may have a substituent, a linear or branched alkyl group is preferable.
The plurality of R ₂ preferably contain a methyl group from the viewpoint of improving the heat resistance of the cured product, and more preferably all of R ₂ are methyl groups.

Each R ₃ independently represents a substituent represented by Formula (3), a substituent represented by Formula (4), or a hydroxy group. Among these, from the viewpoint of improving heat resistance, it is preferable to contain a hydroxyl group. Further, in the present embodiment, it is also preferable to use the compound (C) containing a substituent represented by the formula (3) among a plurality of R ₃ from the viewpoint of improving the developability. In the present embodiment, it is also preferable to use the compound (C) containing a substituent represented by the above-mentioned formula (4) among a plurality of R ₃ from the viewpoint of improving the heat resistance. In the formula _(4), R 4 represents a hydrogen atom or a methyl group. Among them, a hydrogen atom is preferable from the viewpoint of improving the reactivity of the light curing reaction.

From the viewpoint of improving developability, the plurality of R ₃ groups have a ratio of a substituent represented by the formula (3) to a range of 20% to 98% among the substituents of all R ₃ ; The ratio of the substituent represented by 4) is in the range of 5% to 98% and the ratio of the hydroxy group is in the range of 10% to 98% (the sum of the ratio of these substituents is 100%) Is preferred. Among them, it is particularly preferable that at least one of the plurality of R ₃ be a substituent represented by the above formula (3) from the viewpoint of improving the developability.
It is preferable that the compound (C) contains any one or more of the following compounds (C1) to (C5) because the reactivity of the photocuring reaction and the heat resistance and the developability of the cured product can be improved. And more preferably at least the compound (C1), and more preferably any two or more of (C1) to (C5), and any one of the compound (C1) and the compounds (C2) to (C5) It is further preferred to include species or more. The compound (C) preferably contains at least the compounds (C2) and (C3).

  Such compounds may be commercially available products, 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 (trade names, manufactured by Nippon Kayaku Co., Ltd.) and the like.

  In the resin composition of the present embodiment, the acid value of the compound (C) is preferably 30 mg KOH / g or more from the viewpoint of improving the developability, and is 50 mg KOH / g or more because the developability is further improved. Is more preferred. In addition, from the viewpoint of preventing dissolution by a developer after curing with active energy rays, the acid value of the compound (C) is preferably 120 mg KOH / g or less, and can be more preferably 110 mg KOH / g or less. It is further preferred that In addition, the "acid value" in this embodiment shows the value measured by the method according to JISK 0070: 1992.

  In the resin composition of the present embodiment, the content of the compound (C) is not particularly limited, but from the viewpoint of curing the resin composition with active energy rays, component (A) in the resin composition, component (C) 1 part by mass or more, preferably 2 parts by mass or more, and more preferably 3 parts by mass or more with respect to 100 parts by mass of the total content of the component (D) and the component (D). Further, from the viewpoint of sufficient curing with active energy rays and improvement of heat resistance, it is preferably 99 parts by mass or less, more preferably 98 parts by mass or less, and further preferably 97 parts by mass or less preferable.

  In the resin composition of the present embodiment, the content of the compound (C) is not particularly limited, but from the viewpoint of curing the resin composition with an active energy ray, 100 parts by mass of resin solid content in the resin composition 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, still more preferably 10 parts by mass or more, 25 parts by mass or more It is further more preferable to use it, and it is most preferable to use 30 parts by mass or more. Further, from the viewpoint of sufficient curing with active energy rays and improvement of heat resistance, it is preferably 99 parts by mass or less, and 98 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferable to use 97 parts by mass or less, still more preferably 90 parts by mass or less, still more preferably 75 parts by mass or less, and most preferably 72 parts by mass or less preferable.

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

  As a compound having a (meth) acryloyl group, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether , Phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, glycol di (meth) acrylate, 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 neopenglycol di (meth) acrylate, ε-caprolactone modified dipentaerythritol hexa (meth) acrylate, ε-caprolactone modified dipentaerythritol poly ( Meta) acrylate, dipentaerythritol poly (meth) acrylate, trimethylolpropane tri (meth) acrylate , Triethylolpropane tri (meth) acrylate, and its ethylene oxide adduct, pentaerythritol tri (meth) acrylate, and its ethylene oxide adduct, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, And ethylene oxide adducts thereof and the like.

  Besides these, urethane (meth) acrylates having a (meth) acryloyl group and a urethane bond in the same molecule, polyester (meth) acrylates having a (meth) acryloyl group and an ester bond in the same molecule, and epoxy resin And epoxy (meth) acrylates having a (meth) acryloyl group in combination, and reactive oligomers in which these bonds are used in combination.

  The above urethane (meth) acrylates are a reaction product of a hydroxyl group-containing (meth) acrylate and a 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 di (meth) acrylate etc ) Sugar alcohols (meth) acrylates such as acrylates, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and toluene diisocyanate Hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, Down diisocyanate, hydrogenated xylene diisocyanate, dicyclohexane diisocyanate, and their isocyanurate, by reacting polyisocyanates such as buret reactants, the urethane (meth) acrylates.

  The above 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) acrylate, caprolactone modified Monofunctional (poly) ester (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate; hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, caprolactone modified hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, epichlorohydrin Di (poly) ester (meth) acrylates such as modified phthalic acid di (meth) acrylate; 1 to 1 mol of trimethylol propane or glycerin Le more ε- caprolactone, .gamma.-butyrolactone, a triol obtained by adding a cyclic lactone compound such as δ- valerolactone mono- include di- or tri (meth) acrylate.

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

  And furthermore, a diol component such as (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, 3-methyl-1,5-pentanediol, hexanediol and maleic acid , Fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, polybasic acids such as 5-sodium sulfoisophthalic acid, and anhydrides thereof (Meth) acrylates of polyester polyols which are the reaction products of products; cyclic lactone-modified polyester diols composed of the above-mentioned diol component, polybasic acid and anhydrides thereof, ε-caprolactone, γ-butyrolactone, δ-valerolactone etc. Polyfunctional such as meta) acrylate May be mentioned poly) ester (meth) acrylates such as, but not limited thereto.

  The epoxy (meth) acrylates are carboxylate compounds of a compound having an epoxy group and (meth) acrylic acid. For example, phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, trishydroxyphenylmethane epoxy (meth) acrylate, dicyclopentadiene phenol epoxy (meth) acrylate, bisphenol A epoxy (meth) acrylate Bisphenol F type epoxy (meth) acrylate, biphenol type epoxy (meth) acrylate, bisphenol A novolac type epoxy (meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate, glyoxal type epoxy (meth) acrylate, heterocyclic epoxy ( Examples thereof include meta) acrylates and the like, and acid anhydride-modified epoxy acrylates and the like 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. Styrenes include styrene, methylstyrene, ethylstyrene, divinylbenzene and the like. Other vinyl compounds include triallyl isocyanurate, trimethallyl isocyanurate, bisallylnadiimide and the like.

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

  In the resin composition of the present embodiment, the content of the compound (D) having an ethylenically unsaturated group other than the component (C) is not particularly limited, but from the viewpoint of making the developability good, in the resin composition The total content of component (A), component (C) and component (D) is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, with respect to 100 parts by mass. More preferably, it is 1.5 parts by mass or more. Further, from the viewpoint of improving the heat resistance of the cured product, it is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, and still more preferably 50 parts by mass or less.

  In the resin composition of the present embodiment, the content of the compound (D) is not particularly limited, but from the viewpoint of improving the developability, the content of the compound (D) relative to 100 parts by mass of the resin solid content in the resin composition is 0. The content is preferably 5 parts by mass or more, more preferably 1.0 parts by mass or more, still more preferably 1.5 parts by mass or more, and still more preferably 5.0 parts by mass or more, Most preferably, it is 10 parts by mass or more. Further, from the viewpoint of improving the heat resistance of the cured product, it is preferably 90 parts by mass or less, and more preferably 70 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. It is more preferable that the amount be 50 parts by mass or less, still more preferably 25 parts by mass or less, and most preferably 20 parts by mass or less.

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

  The maleimide compound (E) used in the present embodiment is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule. Specific examples thereof include, for example, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, 4,4. -Diphenylmethane bismaleimide, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) Methane, phenylmethane maleimide, o-phenylene bismaleimide, m-phenylene bis maleimide, p-phenylene bis maleimide, o-phenylene bis citraconic imide, m-phenylene bis citraconic imide, p-phenylene bis citraconic imide, 2, 2-bis (4- (4-maleimidophov) Noxy) -phenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide- (2,2 , 4-trimethyl) hexane, 4,4-diphenyletherbismaleimide, 4,4-diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, 4,4-Diphenylmethane biscitraconimide, 2,2-bis [4- (4-citraconimidophenoxy) phenyl] propane, bis (3,5-dimethyl-4-citraconimidophenyl) methane, bis (3-ethyl-) 5-Methyl-4-citraconimidophenyl) methane, bis (3,5-die) 4-Cytraconimidophenyl) methane, polyphenylmethane maleimide, novolak maleimide compound, biphenylaralkyl maleimide compound, maleimide compound represented by the following formula (7), maleimide compound represented by the following formula (8), And prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds.

Among these, novolak type maleimide compounds and biphenylaralkyl type maleimide compounds are particularly preferable. Further, from the viewpoint of obtaining good coating properties and excellent heat resistance, maleimide compounds represented by the following formula (7) and maleimide compounds represented by the following formula (8) are preferable, and the following formula (7) The maleimide compound represented by is more preferable. A commercial item can also be utilized as a maleimide compound represented by following formula (7), for example, BMI-2300 (made by Daiwa Kasei Kogyo Co., Ltd.) is mentioned. A commercial item can also be utilized as a maleimide compound represented by following formula (8), for example, MIR-3000 (made by Nippon Kayaku Co., Ltd.) is mentioned.
These maleimide compounds (E) can be used alone or in combination of two or more.

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

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

  The content of the maleimide compound (E) in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of sufficiently curing the resin composition and improving the heat resistance, the component (A) in the resin composition The amount is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and more preferably 0.03 parts by mass with respect to 100 parts by mass of the total content of the components (C) and (D). It is more preferable to set it as the above. Further, from the viewpoint of improving the developability, the amount is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and still more preferably 40 parts by mass or less.

  In the resin composition of the present embodiment, the content of the maleimide compound (E) is not particularly limited, and is preferably 0.01 parts by mass to 50 parts by mass, and more preferably 100 parts by mass of the resin solid content. Is 0.02 to 45 parts by mass, more preferably 0.03 to 20 parts by mass, still more preferably 0.1 to 10 parts by mass, and most preferably 1 part by mass 7 parts by mass. When the content of the maleimide compound is in the above range, the heat resistance of the cured product tends to be further improved.

<Filler (F)>
In the resin composition of the present embodiment, a filler (F) (also referred to as component (F)) can be used in combination to improve various properties such as coating properties and heat resistance. The filler (F) used in the present embodiment is not particularly limited as long as it has an insulating property, and, for example, silica (eg, natural silica, fused silica, amorphous silica, hollow silica, etc.), aluminum compound (eg, boehmite) , Aluminum hydroxide, alumina etc., magnesium compounds (eg magnesium oxide, magnesium hydroxide etc.), calcium compounds (eg calcium carbonate etc.), molybdenum compounds (eg molybdenum oxide, zinc molybdate etc.), barium compounds (eg barium sulfate) , Barium silicate etc., talc (eg natural talc, calcined talc etc.), mica (mica), glass (eg short fiber glass, spherical glass, fine powder glass (eg E glass, T glass, D glass etc) etc. ), Silicone powder, fluorocarbon resin filler, c) Tan resin filler, an acrylic resin-based filler, polyethylene fillers, such as styrene-butadiene rubber and silicone rubber.

  Among them, it is selected from the group consisting of silica, boehmite, barium sulfate, silicone powder, fluorocarbon resin filler, urethane resin filler, acrylic resin filler, polyethylene filler, styrene butadiene rubber and silicone rubber. Preferably, it is one or more.

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

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

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

<Silane coupling agent and wetting and dispersing agent>
In the resin composition of the present embodiment, a silane coupling agent and / or a wetting and dispersing agent may be used in combination to improve filler dispersibility, polymer and / or resin, and adhesive strength between the filler and the filler. It is possible.
It will not specifically limit, if it is a silane coupling agent generally used for the surface treatment of an inorganic substance as these silane coupling agents. Specific examples thereof include aminosilanes such as γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane; and epoxysilanes such as γ-glycidoxypropyltrimethoxysilane Acrylic silanes such as γ-acryloxypropyltrimethoxysilane; Cationic silanes such as N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride; Silane cup of phenylsilanes Ring agents are mentioned. These silane coupling agents may be used alone or in combination of two or more.

  Although content of a silane coupling agent is not specifically limited in the resin composition of this embodiment, 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 thereof include wetting and dispersing agents such as DISPERBYK (registered trademark) -110, 111, 118, 180, 161, BYK (registered trademark) -W996, W9010, W903 and the like manufactured by Big Chemie Japan Co., Ltd. . These wetting and dispersing agents may be used alone or in combination of two or more.
In the resin composition of the present embodiment, the content of the wetting and dispersing agent is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.

  <One or more compounds selected from the group consisting of a cyanate ester compound, a phenol resin, an oxetane resin, a benzoxazine compound, and an epoxy resin different from the dicyclopentadiene type epoxy resin (A) represented by (1) (G)>

  The compound (G) (also referred to as component (G)) used in the present embodiment is required to be cured in the field in which the resin composition is used, in addition to the copper plating adhesion obtained by using the component (A) Various types of materials can be used according to the properties such as the flame retardancy, heat resistance, thermal expansion properties, etc. of the cured product. For example, when heat resistance is required, a cyanate ester compound, a benzoxazine compound, etc. are mentioned, In addition, a phenol resin, an oxetane resin, etc. can also be used. Moreover, when the epoxy resin different from this epoxy resin (A) is used with the dicyclopentadiene type epoxy resin (A) represented by said (1), the resin composition which is excellent in especially developability and plating adhesiveness is obtained. be able to.

Moreover, it is also possible to use these 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.

<Cyanate ester compound>
The cyanate ester compound is not particularly limited as long as it is a resin having an aromatic moiety in which at least one cyanato group (cyanate group) is substituted in the molecule.
For example, what is represented by General formula (9) is mentioned.

In formula (9), Ar ₁ represents a benzene ring, a naphthalene ring or a single bond of two benzene rings. When there are two or more, they may be the same or different. Ra each 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, an alkyl group having 1 to 6 carbon atoms, and 6 to 12 carbon atoms A group to which an aryl group is bonded is shown. The aromatic ring in Ra may have a substituent, and the substituent in Ar ₁ and Ra can be selected at any position. p represents the number of cyanato groups bonded to Ar ₁ and each is independently an integer of 1 to 3. q represents the number of Ra to bind to Ar _1, the 4-p when Ar ₁ is a benzene ring, when the naphthalene ring when those 6-p, 2 one benzene ring is a single bond is 8-p . t represents an average repeat number and is an integer of 0 to 50, and the cyanate ester compound may be a mixture of compounds different in t. In the case where there are a plurality of X's, each independently has 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 nitrogen having 1 to 10 carbons. Organic group (eg, -N-R-N- (wherein R represents an organic group)), carbonyl group (-CO-), carboxy group (-C (= O) O-), carbonyl dioxide group ( -OC (= O) O-), a sulfonyl group (-SO ₂ -), represents any divalent sulfur atom or a divalent oxygen atom.

The alkyl group at Ra in General Formula (9) may have any of a linear or branched chain structure and a cyclic structure (for example, a cycloalkyl group etc.).
The hydrogen atom in the alkyl group in General Formula (9) and the aryl group in Ra is substituted by a halogen atom such as a fluorine atom or chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, or a cyano group It is also good.

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group and 2,2-dimethylpropyl Groups, cyclopentyl group, hexyl group, cyclohexyl group, trifluoromethyl group and the like.
Specific examples of the aryl group include phenyl group, xylyl group, mesityl group, naphthyl group, phenoxyphenyl group, ethylphenyl group, o-, m- or p-fluorophenyl group, dichlorophenyl group, dicyanophenyl group, trifluorophenyl Groups, methoxyphenyl groups, o-, m- or p-tolyl groups and the like. Furthermore, as an alkoxyl group, a methoxy group, an ethoxy group, a propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, a tert- butoxy group etc. are mentioned, for example.

  Specific examples of the divalent organic group having 1 to 50 carbon atoms in X in General Formula (9) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, and a biphenylyl group. A methylene group, dimethyl methylene- phenylene- dimethyl methylene group, fluorenediyl group, and phthalide diyl group etc. are mentioned. The hydrogen atom in the divalent organic group may be substituted by a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, a cyano group or the like.

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

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

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 identical to 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, an aryl having at least one trifluoromethyl group, or a phenolic hydroxy group Indicates a group. Rd and Re are each independently selected from any one kind 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 hydroxy group . u shows the integer of 0-5.

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 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxyl group having 1 to 4 carbon atoms, a hydroxy group, a trifluoromethyl group, Or an aryl group in which at least one cyanato group is substituted. Although v shows the integer of 0-5, it may be a mixture of compounds in which v differs.

  Furthermore, as X in General Formula (9), the bivalent group represented by a following formula is mentioned.

Here, z represents an integer of 4 to 7. Each R k independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Specific examples of Ar _{2 in the} general formula (10) and Ar _{3 in} the general formula (11) include two carbon atoms shown in the general formula (10) or two oxygen atoms shown in the general formula (11) A benzenetetrayl group bonded to the 1,4 or 1,3 position, the above two carbon atoms or the two oxygen atoms are 4,4 ', 2,4', 2,2 ', 2 , A 3 'position, a 3, 3' position, or a biphenyl tetrayl group bonded to the 3, 4 'position, and the above two carbon atoms or two oxygen atoms are 2, 6 or 1, 5 positions And a naphthalene tetrayl group bonded to the 1, 6, 1, 8, 1, 3, 1, 4, or 2, 7 positions.

  Rb, Rc, Rd, Re, Rf and Rg in General Formula (10), and the alkyl group and aryl group in Ri and Rj in General Formula (11) have the same meanings as those in General Formula (9) above.

Specific examples of cyanato-substituted aromatic compounds represented by the above general formula (9) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1 -Cyanato-2-, 1-Cyanato-3-, or 1-Cyanato-4-methoxybenzene, 1-Cyanato-2,3-, 1-Cyanato-2,4-, 1-Cyanato-2,5-, 5 1-Cyanato-2,6-, 1-Cyanato-3,4- or 1-Cyanato-3,5-dimethylbenzene, Cyanatoethylbenzene, Cyanatobutylbenzene, Cyanatooctylbenzene, Cyanatononylbenzene, 2-A (4-Cyanaphenyl) -2-phenylpropane (cyanate of 4-α-cumylphenol), 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-chlorobenzene, Cyanatonitrobenzene, 1-Cyanato-4-nitro -2-ethylbenzene, 1-cyanato-2-methoxy-4-allylbenzene (cyanide of eugenol), methyl (4-cyanatophenyl) sulfide, 1-cyanato-3-trifluoromethylbenzene, 4-cyanatobiphenyl, 1-cyanato-2- or 1-cyanato-4-acetylbenzene, 4-cyanatobenzaldehyde, 4-cyanatobenzoic acid methyl ester, 4-cyanatobenzoic acid phenyl ester, 1-cyanato-4-acetoaminobenzene, 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-disocyanatosocyanate, 2, 2'- or 4, 4'- Jishianat Biphenyl, 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-dimethyl) Phenyl) propane, 1,1-bis (4-cyanatophenyl) butane, 1,1-bis (4-cyanatophenyl) isobutane, 1,1-bis (4-cyanatophenyl) propane Tan, 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, 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-cyanatpheny ) -2-Methylpentane, 3,3-bis (4-cyanatophenyl) -2-methylhexane, 3,3-bis (4-cyanatophenyl) -2,2-dimethylpentane, 4,4-bis (4-cyanatophenyl) -3-methylheptane, 3,3-bis (4-cyanatophenyl) -2-methylheptane, 3,3-bis (4-cyanatophenyl) -2,2-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-cyanat Phenyl) 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-cyanatophenyl) -2-propyl] benzene, 1,1-bis (4-cyanatophenyl) -3,3,5-Trimethylcyclohexane, 4- [bis (4-cyanatophenyl) methyl] biphenyl, 4,4-dicyanatobenzopheno 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) isobenzofuran-1 (3H) -one (cyanphthalate of phenolphthalein) ), 3,3-bis (4-cyanato-3-methylphenyl) isobenzofuran-1 (3H) -one (o-cresolphthalein) 9,9'-bis (4-cyanatophenyl) fluorene, 9,9-bis (4-cyanato-3-methylphenyl) fluorene, 9,9-bis (2-cyanato-5-biphenylyl) Fluorene, tris (4-cyanatophenyl) methane, 1,1,1-tris (4-cyanatophenyl) ethane, 1,1,3-tris (4-cyanatophenyl) propane, α, α, α ' -Tris (4-cyanatophenyl) -1-ethyl-4-isopropylbenzene, 1,1,2,2-tetrakis (4-cyanatophenyl) ethane, tetrakis (4-cyanatophenyl) methane, 2,4 , 6-tris (N-methyl-4-cyanatoanilino) -1,3,5-triazine, 2,4-bis (N-methyl-4-cyanatoanilino) -6- (N-methylanilino) -1,3, -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-cyano) Anatophenyl) phthalimidine, 2-phenyl-3,3-bis (4-cyanato-3-methylphenyl) phthalimidine, 1-methyl-3,3-bis (4-cyanato) Eniru) indolin-2-one, and 2-phenyl-3,3-bis (4-cyanatophenyl) include indolin-2-one.
These cyanate ester compounds can be used singly or in combination of two or more.

Further, as another specific example of the cyanate ester compound represented by the above general formula (9), phenol novolac resin and cresol novolac resin (phenol, alkyl substituted phenol or halogen substituted phenol, formalin or the like by a known method) Reaction of formaldehyde compound such as paraformaldehyde in an acidic solution), trisphenol novolak resin (reaction of hydroxybenzaldehyde and phenol in the presence of an acidic catalyst), fluorene novolac resin (fluorenone compound and 9) , 9-bis (hydroxyaryl) fluorenes in the presence of an acidic catalyst), phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin and biphenyl aralkyl resin (known methods) _{More, Ar 4 - (CH 2 Y} ) 2 (. Ar 4 represents a phenyl group, Y represents a halogen atom and the same in this paragraph.) And bishalogenomethyl compounds represented by the phenol compound obtained by reacting an acidic catalyst or no catalyst, Ar ₄ - (CH ₂ oR) expressed by such bis ₂ (alkoxymethyl) that a compound with a phenol compound is reacted in the presence of an acidic catalyst, or, Ar ₄ - (CH ₂ OH) bis (hydroxymethyl) as represented by _two things compound and a phenol compound is reacted in the presence of an acidic catalyst, or an aromatic aldehyde compound and aralkyl compound with a phenol compound Polycondensed), phenol-modified xylene formaldehyde resin (xylene formaldehyde resin and phenol compound by a known method) (In the presence of an acid catalyst), modified naphthalene formaldehyde resin (a reaction of a naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound in the presence of an acid catalyst by a known method), phenol-modified dicyclo Pentadiene resin, phenolic resin having a polynaphthylene ether structure (in which a multivalent hydroxynaphthalene compound having two or more phenolic hydroxy groups in one molecule is dehydrated and condensed by a known method in the presence of a basic catalyst And the like, and those obtained by cyanating such phenolic resins by the same method as described above, and prepolymers of these. These are not particularly limited. These cyanate ester compounds can be used singly or in combination of two or more.

  Among these, phenol novolac type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds, biphenylaralkyl type cyanate ester compounds, naphthylene ether type cyanate ester compounds, xylene resin type cyanate ester compounds, adamantane skeleton type cyanate ester Compounds are preferred, and naphthol aralkyl type cyanate ester compounds are particularly preferred from the viewpoint of plating adhesion.

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

A resin cured product using these cyanate ester compounds has excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion.
Although the content of the cyanate ester compound is not particularly limited in the resin composition of the present embodiment, it is preferably 0.01 parts by mass with respect to 100 parts by mass of resin solid content from the viewpoint of plating adhesion and heat resistance. 50 parts by mass, more preferably 0.05 parts by mass to 40 parts by mass, further preferably 0.1 parts by mass to 20 parts by mass, still more preferably 0.2 parts by mass to 5 parts by mass It is.

<Phenolic resin>
As the phenolic resin, generally known ones can be used as long as they have two or more hydroxyl groups in one molecule. For example, bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type phenol resin, biphenyl Aralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolac type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type Phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin Alicyclic phenolic resins, polyol-type phenolic resin, a phosphorus-containing phenol resin, a polymerizable unsaturated hydrocarbon of the group containing phenolic resin and hydroxyl-containing silicone resins and the like, but is not particularly limited. Among these phenol resins, biphenylaralkyl type phenol resins, naphtholaralkyl type phenol resins, phosphorus-containing phenol resins, and hydroxyl group-containing silicone resins are preferable in view of flame retardancy. These phenolic resins may be used alone or in combination of two or more.

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

<Oxetane resin>
As the oxetane resin, those generally known can be used. For example, alkyl oxetanes such as oxetane, 2-methyl oxetane, 2,2-dimethyl oxetane, 3-methyl oxetane, 3, 3-dimethyl oxetane, 3-methyl-3-methoxymethyl oxetane, 3, 3-di (trifluoro) Methyl) perfluoxetane, 2-chloromethyl oxetane, 3, 3-bis (chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (made by Toagosei, trade name), OXT-121 (made by Toagosei, trade name) There is no particular limitation, and the like. These may be used alone or in combination of two or more.

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

<Benzoxazine compound>
As the benzoxazine compound, generally known compounds can be used as long as they are compounds having two or more dihydrobenzoxazine rings in one molecule. For example, bisphenol A type benzoxazine BA-BXZ (made by Konishi Chemical, trade name) Bisphenol F type benzoxazine BF-BXZ (made by Konishi Chemical, trade name), bisphenol S type benzoxazine BS-BXZ (made by Konishi Chemical, trade name) And phenolphthalein type benzoxazine etc., but it is not particularly limited. These may be used alone or in combination of two or more.

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

<Epoxy resin>
In the resin composition of the present embodiment, in order to improve the heat resistance of the cured product, it is possible to use an epoxy resin different from the dicyclopentadiene type epoxy resin (A) represented by the above (1) in combination. .

Such an epoxy resin is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule, unlike the epoxy resin (A). Specific examples thereof include, for example, bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol A novolac epoxy resin, biphenyl epoxy resin, phenol novolac epoxy resin, Cresol novolac epoxy resin, xylene novolac epoxy resin, polyfunctional phenol epoxy resin, naphthalene epoxy resin, naphthalene skeleton modified novolak epoxy resin, naphthalene ether epoxy resin, phenol aralkyl epoxy resin, anthracene epoxy resin, Trifunctional phenolic epoxy resin, tetrafunctional phenolic epoxy resin, triglycidyl isocyanurate, glycidyl ester epoxy resin, alicyclic Epoxy resin, biphenyl novolac epoxy resin, phenol aralkyl novolac epoxy resin, naphthol aralkyl novolac epoxy resin, aralkyl novolac epoxy resin, biphenyl aralkyl epoxy resin, naphthol aralkyl epoxy resin, polyol epoxy resin, phosphorus-containing epoxy resin And compounds obtained by epoxidizing a double bond such as glycidyl amine and butadiene, compounds obtained by the reaction of a hydroxyl group-containing silicone resin and epichlorohydrin, and halides of these.
Among them, one or more selected from the group consisting of biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, polyfunctional phenol type epoxy resin, and naphthalene type epoxy resin is preferable, and naphthalene type epoxy resin is more preferable. By including such a type of epoxy resin, developability and plating adhesion tend to be further improved.

  It is preferable to use a resin represented by the following formula (5) as the naphthalene type epoxy resin because the developability and the plating adhesion are further improved. As this epoxy resin, a commercial item can be utilized and DIC Corporation HP-4710 (brand name) is mentioned. The naphthalene type epoxy resin represented by the following formula (5) is low in molecular weight and multifunctional and therefore, is excellent in solubility in a developer. Therefore, it is thought that the resin composition which is excellent also in developability can be obtained by combined use with dicyclopentadiene type epoxy resin (A).

  These epoxy resins may be used alone or in combination of two or more.

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

  Further, the ratio of the epoxy resin (A) to the epoxy resin different from the epoxy resin (A) is not particularly limited, but from the viewpoint of plating adhesion, 1 to 10: 1 to 3 is preferable, and 2 to 4: 1. -2 is more preferable.

<Thermosetting accelerator (H)>
In the resin composition of the present embodiment, it is also possible to use a thermosetting accelerator (H) (also referred to as component (H)) as long as the characteristics of the present embodiment are not impaired. The heat curing accelerator (H) used in the present embodiment is not particularly limited. For example, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate Organic peroxides such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri Tertiary amines such as n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine, etc .; phenols such as phenol, xylenol, cresol, resorcine, catechol, etc. Naften Organometallic salts such as lead, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate; these organic metal salts with hydroxyl groups such as phenol and bisphenol Dissolved in a compound; inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; dioctyl tin oxide, other organic tin compounds such as alkyl tin and alkyl tin oxide; 2-ethyl-4-methylimidazole, 1 And imidazole compounds such as 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 preferred from the viewpoint of heat resistance, 2-ethyl -4-Methylimidazole is more preferable from the viewpoint of obtaining better heat resistance.

These heat curing accelerators can be used alone or in combination of two or more.
In the resin composition of the present embodiment, the content of the thermal curing accelerator (H) is not particularly limited, but generally 0.01 to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. And preferably 0.05 to 5 parts by mass.

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

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

  Although content of another component is not specifically limited in the resin composition of this embodiment, Usually, it is 0.1-10 mass parts, respectively with respect to 100 mass parts of resin compositions.

<Method for Producing Resin Composition>
The resin composition of the present embodiment includes the dicyclopentadiene type epoxy resin (A) represented by the formula (1), the photocuring initiator (B), the compound (C) represented by the formula (2), and By appropriately mixing the compound (D) having an ethylenically unsaturated group other than the component (C) with, if necessary, the maleimide compound (E), the filler (F), the compound (G) and other components Be prepared. The resin composition of this embodiment can be suitably used 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, the method of mix | blending each component mentioned above sequentially with a solvent, and fully stirring is mentioned.

  At the time of production of the resin composition, known processing (stirring, mixing, kneading treatment, etc.) for uniformly dissolving or dispersing each component can be carried out, if necessary. Specifically, the dispersibility of the inorganic filler (G) in the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank provided with a stirrer having an appropriate stirring capacity. The above-mentioned stirring, mixing, and kneading treatment may be, for example, a stirring device for the purpose of dispersing ultrasonic homogenizers, a three-roll mill, a device for the mixing of ball mills, bead mills, sand mills, etc., or revolution or rotation type It can carry out suitably using well-known apparatuses, such as a mixing apparatus. Moreover, at the time of preparation of the resin composition of this embodiment, an organic solvent can be used as needed. The type of the organic solvent is not particularly limited as long as the resin in the resin composition can be dissolved, and specific examples thereof are as described above.

<Use>
The resin composition of the present embodiment can be used for applications where an insulating resin composition is required, and is not particularly limited. However, insulating resin sheets such as photosensitive films, photosensitive films with supports, and prepregs It can be used for applications such as circuit boards (laminated board applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor sealing materials, hole filling resins, component embedding resins and the like. Especially, it can be used conveniently as a resin composition for insulating layers of a multilayer printed wiring board, and a solder resist.

<Resin sheet>
The resin sheet of the present embodiment comprises the support and the resin composition layer formed on the surface of the support and containing the resin composition of the present embodiment, wherein the above-mentioned resin composition is used on one side or both sides of the support. The resin sheet with a support applied to A resin sheet can be manufactured by apply | coating a resin composition on a support body, and drying.

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

  As the above-mentioned resin film, in order to facilitate peeling from the resin composition layer, one having a release agent coated on the surface thereof can be suitably used. The thickness of the resin film is preferably in the range of 5 μm to 100 μm, and more preferably in the range of 10 μm to 50 μm. If the thickness is less than 5 μm, the support tends to be easily broken at the time of peeling of the support before development, and if the thickness exceeds 100 μm, the resolution at the time of exposure from the support tends to decrease. is there.

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

Furthermore, in the resin sheet in this embodiment, the resin composition layer may be protected by a protective film.
By protecting the resin composition layer side with a protective film, it is possible to prevent adhesion of dust and the like to the surface of the resin composition layer and scratches. As a protective film, the film comprised with the material similar to said resin film can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 50 μm, and more preferably in the range of 5 μm to 40 μm. If the thickness is less than 1 μm, the handleability of the protective film tends to decrease, and if it exceeds 50 μm, the price tends to be inferior. The protective film is preferably one in which the adhesive strength between the resin composition layer and the protective film is smaller than the adhesive strength between the resin composition layer and the support.

Although the manufacturing method of the resin sheet of this embodiment is not specifically limited, For example, the resin composition of this embodiment is apply | coated to support bodies, such as a PET film, and a resin sheet is manufactured by removing an organic solvent by drying. And the like.
The application can be performed by a known method using, for example, a roll coater, a comma coater, a gravure coater, a die coater, a bar coater, a lip coater, a knife coater, a squeeze coater or the like. The drying can be performed, for example, by a method of heating in a dryer at 60 to 200 ° C. for 1 to 60 minutes.
The amount of the residual organic solvent in the resin composition layer is preferably 5% by mass or less based on the total mass of the resin composition layer from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step. The thickness of the resin composition layer relative to the support is preferably 1.0 μm or more in terms of the layer thickness of the resin composition of the resin sheet, from the viewpoint of improving the handleability. Moreover, it is preferable to be 300 micrometers or less from a viewpoint of improving a transmittance | permeability and making developability favorable.

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

<Multilayer printed wiring board>
The multilayer printed wiring board of the present embodiment includes an interlayer insulating layer containing the resin composition of the present embodiment, and can be obtained, for example, by overlapping and curing one or more of the above-described resin sheets. Specifically, it can be manufactured by the following method.

(Lamination process)
The resin composition layer side of the resin sheet of the present embodiment is laminated on one side or both sides of the circuit board using a vacuum laminator. Examples of the circuit substrate include a glass epoxy substrate, a metal substrate, a ceramic substrate, a silicon substrate, a semiconductor sealing resin substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means the board | substrate in which the conductor layer (circuit) by which pattern processing was carried out on the single side | surface or both surfaces of the above board | substrates here was formed. In addition, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately stacked, a substrate having a conductor layer (circuit) on which one or both surfaces of the outermost layer of the printed wiring board are patterned is also used here. Included in the circuit board. The surface of the conductor layer may be roughened in advance by blackening treatment, copper etching or the like. In the laminating step, when the resin sheet has a protective film, the protective film is peeled off and removed, and if necessary, the resin sheet and the circuit board are preheated to press and heat the resin composition layer. Crimp on the circuit board. In the resin sheet of the present embodiment, a method of laminating on a circuit board under reduced pressure by vacuum lamination is preferably used.

The conditions of the laminating step are not particularly limited, but, for example, the pressing temperature (laminating temperature) is preferably 50 ° C. to 140 ° C., the pressing pressure is preferably 1 kgf / cm ^{2 to} 15 kgf / cm ² , the pressing time Preferably for 5 seconds to 300 seconds, and laminating under a reduced pressure of 20 mmHg or less. In addition, the laminating process may be a batch system or a continuous system using a roll. The vacuum laminating method can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a 2-stage buildup laminator manufactured by Nikko Materials Co., Ltd. can be mentioned.

(Exposure process)
After the resin sheet is provided on the circuit board in the laminating step, an active energy ray is irradiated to a predetermined portion of the resin composition layer to perform an exposure step of curing the resin composition layer in the irradiated part. The irradiation of active energy rays may be performed through a mask pattern, or a direct writing method of direct irradiation of active energy rays may be used.
As an active energy ray, an ultraviolet-ray, a visible ray, an electron beam, an X ray etc. are mentioned, for example, Especially an ultraviolet-ray is preferable. Dose of ultraviolet light is approximately ^{10mJ / cm 2 ~1000mJ / cm 2} . There are a contact exposure method in which the mask pattern is in close contact with the multilayer printed wiring board, and a noncontact exposure method in which the parallel light beam is used for exposure without intimate contact. I don't care. Moreover, when a support body exists on a resin composition layer, you may expose from on a support body and may expose it after peeling a support body.

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

  In the case of the above wet development, the developer is not particularly limited as long as it selectively dissolves the unexposed area, but a developer such as an aqueous alkaline solution, an aqueous developer, or an organic solvent may be used. . In the present embodiment, in particular, a developing step with an alkaline aqueous solution is preferable. These developers can be used alone or in combination of two or more. Moreover, as a developing method, it can carry out by well-known methods, such as a spray, rocking | fluctuation immersion, brushing, scraping etc., for example.

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

  The concentration of the alkaline aqueous solution is preferably 0.1% by mass to 60% by mass with respect to the total amount of the developer. Further, the temperature of the aqueous alkaline solution can be adjusted in accordance with the developability. Furthermore, these alkaline aqueous solutions can be used individually or in combination of 2 or more types.

  In the pattern formation of the present embodiment, the two or more developing methods described above may be used in combination as needed. The developing 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 suitable for improving the resolution. As a spray pressure in the case of adopting a spray system, 0.02 MPa-0.5 MPa are preferable.

(Post-bake process)
After completion of the development step, a post bake step is performed to form an insulating layer (cured product). 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. Case of ultraviolet irradiation can adjust its dose optionally, the irradiation can be carried out, for example 0.05J / cm ² ~10J / cm ² approximately dose. The heating conditions may be appropriately selected according to the type and content of the resin component in the resin composition, preferably in the range of 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. It is selected in the range of 30 minutes to 150 minutes at -200 ° C.

(Plating process)
Next, a conductor layer is formed on the surface of the insulating layer by dry plating or wet plating. For dry plating, known methods such as vapor deposition, sputtering and ion plating can be used. In the vapor deposition method (vacuum vapor deposition method), for example, the metal film can be formed on the insulating layer by placing the support in a vacuum vessel and heating and evaporating the metal. In the sputtering method, for example, the support is placed in a vacuum vessel, an inert gas such as argon is introduced, a direct current voltage is applied, and the ionized inert gas is caused to collide with the target metal, and the knocked out metal is used. Metal film formation can be performed on the insulating layer.

  In the case of wet plating, the surface of the insulating layer is roughened by sequentially performing a swelling treatment with a swelling solution, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution on the surface of the formed insulating layer. . The swelling treatment with the swelling solution is performed by immersing the insulating layer at 50 ° C. to 80 ° C. for 1 minute to 20 minutes in the swelling solution. As a swelling liquid, an alkaline solution is mentioned, As a alkaline solution, sodium hydroxide solution, potassium hydroxide solution, etc. are mentioned. As a swelling liquid marketed, for example, UPDES® (registered trademark) MDS-37 manufactured by Uemura Kogyo Co., Ltd. can be mentioned.

  The roughening treatment with an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 ° C. to 80 ° C. for 5 minutes to 30 minutes. As the oxidizing agent, for example, alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, etc. may be mentioned. it can. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Uedesu Industrial Co., Ltd. product Updes (registered trademark) MDE-40 and Updes (registered trademark) ELC-SH. The neutralization process with a neutralization liquid is performed by immersing in the neutralization liquid at 30 degreeC-50 degreeC for 1 minute-10 minutes. As a neutralization liquid, an acidic aqueous solution is preferable, and UPDES® (registered trademark) MDN-62 manufactured by Uemura Kogyo Co., Ltd. is mentioned as a commercial item.

  Then, electroless plating and electrolytic plating are combined to form a conductor layer. Alternatively, a plating resist having a pattern reverse to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. As a subsequent pattern formation method, for example, a subtractive method, a semi-additive method or the like can be used.

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

  The method of mounting the semiconductor chip in manufacturing the semiconductor device of the present embodiment is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, bumps A mounting method using a buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a nonconductive film (NCF), and the like can be given.

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

  Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to these examples.

Synthesis Example 1
(Synthesis of cyanate ester compound)
Dissolve 300 g (1.28 mol of OH group conversion) of 1-naphthol aralkyl resin (manufactured by Nippon Steel Sumikin Chemical Co., Ltd.) and 194.6 g (1.92 mol) of triethylamine (1.5 mol with respect to 1 mol of hydroxy group) in dichloromethane. This was solution 1.

  125.9 g (2.05 mol) of cyanogen chloride (1.6 mol to 1 mol of hydroxy group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol to 1 mol of hydroxy group) The solution 1 was poured over 30 minutes, keeping 1205.9 g of water under stirring, at a solution temperature of -2 to -0.5 ° C. After completion of 1 injection of solution, after stirring for 30 minutes at the same temperature, 10 minutes of a solution (solution 2) in which 65 g (0.64 mol) of triethylamine (0.5 mol per 1 hydroxyl group) is dissolved in dichloromethane I poured it over. After completion of solution 2 injection, the reaction was completed by stirring for 30 minutes at the same temperature.

  Thereafter, the reaction solution was allowed to stand to separate the organic phase and the aqueous phase. The resulting organic phase was washed five times with 1300 g of water. The electric conductivity of the fifth washing with water was 5 μS / cm, and it was confirmed that washing with water sufficiently removed the removable ionic compound.

The organic phase after washing with water was concentrated under reduced pressure and finally concentrated to dryness at 90 ° C. for 1 hour to obtain 331 g of the desired naphthol aralkyl type cyanate ester compound (SNCN) (orange viscous material). The mass average molecular weight Mw of the obtained SNCN was 600. In addition, the IR spectrum of SNCN showed an absorption of 2250 cm ^-1 (cyanate group) and no absorption of a hydroxy group.

Example 1
(Preparation of resin composition and resin sheet)
As a dicyclopentadiene type epoxy resin (A) represented by Formula (1), n in a dicyclopentadiene type epoxy resin (Formula (1) is 1 to 3. XD-1000 (trade name), Japan 22.4 parts by mass of Kayaku Co., Ltd. product, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure (registered trademark)) as a photo-curing initiator (B) 369, 6.5 parts by mass of BASF Japan Ltd., as a compound (C), a solution of TrisP-PA epoxy acrylate compound in propylene glycol monomethyl ether acetate (hereinafter sometimes abbreviated as PGMEA) (KAYARAD (registered trademark)) ZCR-6007H, non-volatile matter 65 mass%, acid value: 70 mg KOH / g, Nippon Kayaku Co., Ltd. product 77.5 mass parts (non-volatile matter) Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) as a compound (D) having an ethylenically unsaturated group other than the component (C) 17) .4 parts by mass, maleimide compound (BMI-2300 (trade name), manufactured by Daiwa Kasei Kogyo Co., Ltd.) 3.3 parts by mass as a maleimide compound (E), methyl ethyl ketone of epoxysilane-treated silica as a filler (F) (Hereafter, it may be abbreviated as MEK.) Slurry (SC2050 MB (trade name), average particle diameter 0.5 μm, non volatile matter 70 mass%, manufactured by Admatechs Co., Ltd.) 71.4 parts by mass (in nonvolatile matter conversion 50 mass) Part) was mixed and stirred with an ultrasonic homogenizer to obtain a varnish (a solution of a resin composition). Using an automatic coating apparatus (PI-1210, manufactured by Tester Sangyo Co., Ltd.) on a 38 μm thick PET film (UNIPEL® TR 1-38, manufactured by UNITIKA Co., Ltd., trade name) of these varnishes It apply | coated, and it heat-dried at 80 degreeC for 7 minutes, and used the PET film as a support body, and obtained the resin sheet whose thickness of a resin composition layer is 30 micrometers.

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

(Creating inner layer circuit board)
Glass cloth base material BT resin double-sided copper-clad laminate (copper foil thickness 18 μm, thickness 0.2 mm, CCL (registered trademark)-HL 832 NS manufactured by Mitsubishi Gas Chemical Co., Ltd.) with inner layer circuit formed by Mec Co., Ltd. Roughening treatment of the copper surface was performed with CZ8100 manufactured by Nippon Steel Co., Ltd. to obtain an inner circuit board.

(Preparation of laminate for evaluation)
The resin surface of the resin sheet is placed on the inner layer circuit board, and after vacuuming (5.0 MPa or less) for 30 seconds using a vacuum laminator (manufactured by Nikko Materials Co., Ltd.), the pressure is 10 kgf / cm. ^2. Lamination was performed for 30 seconds at a temperature of 70 ° C. Furthermore, by performing lamination molding at a pressure of 10 kgf / cm ² and a temperature of 70 ° C. for 60 seconds, a laminated body in which the inner layer circuit board, the resin composition layer and the support are laminated is obtained. The resulting laminate was subjected to an exposure step of irradiating 200 mJ / cm ² of ultraviolet light, the support was peeled off, developed with a 1% by mass aqueous solution of sodium carbonate, and further exposed to 1,000 mJ / cm ² of ultraviolet light. And a post-baking step of heat treatment at 180.degree. C. for 120 minutes to obtain a laminate for evaluation.

(Preparation of cured product for evaluation)
The resin sheet is exposed to UV light of 200 mJ / cm ² , exposed to UV light of 1000 mJ / cm ² , and subjected to a post-baking step of heat treatment at 180 ° C. for 120 minutes. To give a cured product for evaluation.

Example 2
21.9 parts by mass of dicyclopentadiene type epoxy resin (XD-1000 (trade name), manufactured by Nippon Kayaku Co., Ltd.) as the component (A), and 2-benzyl -2- as the photocuring initiator (B) 6.5 parts by mass of dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure 369, manufactured by BASF Japan Ltd.), as a compound (C), TrisP-PA epoxy acrylate compound PGMEA solution (KAYARAD (registered trademark) ZCR-6007H, nonvolatile content 65 mass%, acid value: 70 mg KOH / g, Nippon Kayaku Co., Ltd. product) 77.5 mass parts (50.4 mass parts in conversion of nonvolatile content), As the compound (D) having an ethylenically unsaturated group other than the component (C), dipentaerythritol hexaacrylate (KAYARAD (registered trademark) D) 17.4 parts by mass of HA, manufactured by Nippon Kayaku Co., Ltd., 3.3 parts by mass of a maleimide compound (BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd.) as a maleimide compound (E), a filler As (F), MEK slurry of epoxysilane-treated silica (SC2050MB (trade name), average particle diameter 0.5 μm, nonvolatile content 70% by mass, manufactured by Admatechs Co., Ltd.) 71.4 parts by mass (50 converted in nonvolatile content) (Mass part), 0.5 mass parts of cyanate ester compound SNCN obtained by the synthesis example 1 were mix | blended as a compound (G), and it stirred by the ultrasonic homogenizer, and obtained the varnish (solution of resin composition). Using an automatic coating apparatus (PI-1210, manufactured by Tester Sangyo Co., Ltd.) on a 38 μm thick PET film (UNIPEL® TR 1-38, manufactured by UNITIKA Co., Ltd., trade name) of these varnishes It apply | coated, and it heat-dried at 80 degreeC for 7 minutes, and used the PET film as a support body, and obtained the resin sheet whose thickness of a resin composition layer is 30 micrometers. Using this, in the same manner as in Example 1, a laminate for evaluation and a cured product for evaluation were obtained.

[Example 3]
21.9 parts by mass of dicyclopentadiene type epoxy resin (XD-1000 (trade name), manufactured by Nippon Kayaku Co., Ltd.) as the component (A), and bis (2,4, 4) as the photocuring initiator (B) 6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure (registered trademark) 819, 6.5 parts by mass from BASF Japan Ltd.), a PGMEA solution of TrisP-PA epoxy acrylate compound as a compound (C) (KAYARAD (registered trademark) Trademark ZCR-6007H, nonvolatile content 65 mass%, acid value: 70 mg KOH / g, Nippon Kayaku Co., Ltd. product 77.5 parts by mass (50.4 parts by mass converted to nonvolatile content), other than the component (C) As a compound (D) having an ethylenically unsaturated group, dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Japan 17.4 parts by mass of Kayaku Co., Ltd. product, 3.3 parts by mass of maleimide compound (BMI-2300 (trade name), manufactured by Daiwa Kasei Kogyo Co., Ltd.) as maleimide compound (E), filler (F) As MEK slurry of epoxysilane treated silica (SC2050 MB (trade name), average particle diameter 0.5 μm, non volatile matter 70 mass%, manufactured by Admatechs Co., Ltd.) 71.4 parts by mass (50 parts by mass in terms of nonvolatile matter) As a compound (G), 0.5 parts by mass of the cyanate ester compound SNCN obtained in Synthesis Example 1 was blended, and the mixture was stirred by an ultrasonic homogenizer to obtain a varnish (a solution of a resin composition). Using an automatic coating apparatus (PI-1210, manufactured by Tester Sangyo Co., Ltd.) on a 38 μm thick PET film (UNIPEL® TR 1-38, manufactured by UNITIKA Co., Ltd., trade name) of these varnishes It apply | coated, and it heat-dried at 80 degreeC for 7 minutes, and used the PET film as a support body, and obtained the resin sheet whose thickness of a resin composition layer is 30 micrometers. Using this, in the same manner as in Example 1, a laminate for evaluation and a cured product for evaluation were obtained.

Example 4
As component (A), 19.9 parts by mass of dicyclopentadiene type epoxy resin (XD-1000 (trade name), manufactured by Nippon Kayaku Co., Ltd.), and as a photocuring initiator (B), bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure (registered trademark) 819, 6.5 parts by mass from BASF Japan Ltd.), a PGMEA solution of TrisP-PA epoxy acrylate compound as a compound (C) (KAYARAD (registered trademark) Trademark ZCR-6007H, nonvolatile content 65 mass%, acid value: 70 mg KOH / g, Nippon Kayaku Co., Ltd. product 77.5 parts by mass (50.4 parts by mass converted to nonvolatile content), other than the component (C) As a compound (D) having an ethylenically unsaturated group, dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Japan 17.4 parts by mass of Kayaku Co., Ltd. product, 3.3 parts by mass of maleimide compound (BMI-2300 (trade name), manufactured by Daiwa Kasei Kogyo Co., Ltd.) as maleimide compound (E), filler (F) As MEK slurry of epoxysilane treated silica (SC2050 MB (trade name), average particle diameter 0.5 μm, non volatile matter 70 mass%, manufactured by Admatechs Co., Ltd.) 71.4 parts by mass (50 parts by mass in terms of nonvolatile matter) And 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) as Compound (G), The mixture was stirred with an ultrasonic homogenizer to obtain a varnish (a solution of a resin composition). Using an automatic coating apparatus (PI-1210, manufactured by Tester Sangyo Co., Ltd.) on a 38 μm thick PET film (UNIPEL® TR 1-38, manufactured by UNITIKA Co., Ltd., trade name) of these varnishes It apply | coated, and it heat-dried at 80 degreeC for 7 minutes, and used the PET film as a support body, and obtained the resin sheet whose thickness of a resin composition layer is 30 micrometers. Using this, in the same manner as in Example 1, a laminate for evaluation and a cured product for evaluation were obtained.

[Example 5]
15.8 parts by mass of dicyclopentadiene type epoxy resin (XD-1000 (trade name), manufactured by Nippon Kayaku Co., Ltd.) as the component (A), and bis (2,4, 4) as the photo-curing initiator (B) 6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure (registered trademark) 819, 6.5 parts by mass from BASF Japan Ltd.), a PGMEA solution of TrisP-PA epoxy acrylate compound as a compound (C) (KAYARAD (registered trademark) Trademark ZCR-6007H, nonvolatile content 65 mass%, acid value: 70 mg KOH / g, Nippon Kayaku Co., Ltd. product 77.5 parts by mass (50.4 parts by mass converted to nonvolatile content), other than the component (C) As a compound (D) having an ethylenically unsaturated group, dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Japan 17.4 parts by mass of Kayaku Co., Ltd. product, 3.3 parts by mass of maleimide compound (BMI-2300 (trade name), manufactured by Daiwa Kasei Kogyo Co., Ltd.) as maleimide compound (E), filler (F) As MEK slurry of epoxysilane treated silica (SC2050 MB (trade name), average particle diameter 0.5 μm, non volatile matter 70 mass%, manufactured by Admatechs Co., Ltd.) 71.4 parts by mass (50 parts by mass in terms of nonvolatile matter) And 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) as a compound (G) The mixture was stirred with an ultrasonic homogenizer to obtain a varnish (a solution of a resin composition). Using an automatic coating apparatus (PI-1210, manufactured by Tester Sangyo Co., Ltd.) on a 38 μm thick PET film (UNIPEL® TR 1-38, manufactured by UNITIKA Co., Ltd., trade name) of these varnishes It apply | coated, and it heat-dried at 80 degreeC for 7 minutes, and used the PET film as a support body, and obtained the resin sheet whose thickness of a resin composition layer is 30 micrometers. Using this, in the same manner as in Example 1, a laminate for evaluation and a cured product for evaluation were obtained.

[Example 6]
As the component (A), 5.9 parts by mass of dicyclopentadiene type epoxy resin (XD-1000 (trade name), manufactured by Nippon Kayaku Co., Ltd.), and as the photocuring initiator (B), bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure (registered trademark) 819, 6.5 parts by mass from BASF Japan Ltd.), a PGMEA solution of TrisP-PA epoxy acrylate compound as a compound (C) (KAYARAD (registered trademark) Trademark ZCR-6007H, nonvolatile content 65 mass%, acid value: 70 mg KOH / g, Nippon Kayaku Co., Ltd. product 77.5 parts by mass (50.4 parts by mass converted to nonvolatile content), other than the component (C) As a compound (D) having an ethylenically unsaturated group, dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Nipponized 17.4 parts by mass of Medicinal Products Co., Ltd., 3.3 parts by mass of maleimide compound (BMI-2300 (trade name), manufactured by Daiwa Kasei Kogyo Co., Ltd.) as maleimide compound (E), as filler (F) 71.4 parts by mass (50 parts by mass in terms of nonvolatile content) of MEK slurry of epoxysilane-treated silica (SC2050 MB (trade name), average particle diameter 0.5 μm, nonvolatile content 70 mass%, manufactured by Admatex Co., Ltd.) Compound (G) was prepared by blending 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) The mixture was stirred with a sonic homogenizer to obtain a varnish (a solution of a resin composition). Using an automatic coating apparatus (PI-1210, manufactured by Tester Sangyo Co., Ltd.) on a 38 μm thick PET film (UNIPEL® TR 1-38, manufactured by UNITIKA Co., Ltd., trade name) of these varnishes It apply | coated, and it heat-dried at 80 degreeC for 7 minutes, and used the PET film as a support body, and obtained the resin sheet whose thickness of a resin composition layer is 30 micrometers. Using this, in the same manner as in Example 1, a laminate for evaluation and a cured product for evaluation were obtained.

[Example 7]
15.8 parts by mass of dicyclopentadiene type epoxy resin (XD-1000 (trade name), manufactured by Nippon Kayaku Co., Ltd.) as the component (A), and bis (2,4, 4) as the photo-curing initiator (B) 6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure (registered trademark) 819, 6.5 parts by mass from BASF Japan Ltd.), a PGMEA solution of TrisP-PA epoxy acrylate compound as a compound (C) (KAYARAD (registered trademark) Trademark ZCR-6007H, nonvolatile content 65 mass%, acid value: 70 mg KOH / g, Nippon Kayaku Co., Ltd. product 77.5 parts by mass (50.4 parts by mass converted to nonvolatile content), other than the component (C) As a compound (D) having an ethylenically unsaturated group, dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Japan 17.4 parts by mass of Kayaku Co., Ltd. product, 3.3 parts by mass of maleimide compound (BMI-2300 (trade name), manufactured by Daiwa Kasei Kogyo Co., Ltd.) as maleimide compound (E), filler (F) As MEK slurry of epoxysilane treated silica (SC2050 MB (trade name), average particle diameter 0.5 μm, non volatile matter 70 mass%, manufactured by Admatechs Co., Ltd.) 71.4 parts by mass (50 parts by mass in terms of nonvolatile matter) As compound (G), 0.5 parts by mass of cyanate ester compound SNCN obtained in Synthesis Example 1 and 6.1 parts by mass of naphthalene type epoxy resin (HP-4710 (trade name), manufactured by DIC Corporation), As a curing accelerator (H), 0.2 parts by mass of 2-ethyl-4-methylimidazole (2E4MZ (trade name), manufactured by Shikoku Kasei Co., Ltd.) is blended, and the mixture is stirred with an ultrasonic homogenizer to To obtain a solution) of the fat composition. Using an automatic coating apparatus (PI-1210, manufactured by Tester Sangyo Co., Ltd.) on a 38 μm thick PET film (UNIPEL® TR 1-38, manufactured by UNITIKA Co., Ltd., trade name) of these varnishes The coating was applied and dried by heating at 80 ° C. for 7 minutes, and a PET film was used as a support to obtain a resin sheet having a thickness of 30 μm of the resin composition layer. Using this, evaluation was made in the same manner as Example 1 A laminate for evaluation and a cured product for evaluation were obtained.

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

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

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

Comparative Example 3
A varnish is prepared in the same manner as in Example 1 except that 22.4 parts by mass of multifunctional epoxy resin (1031S (trade name), manufactured by Mitsubishi Chemical Corporation) is used instead of the component (A), and a resin is prepared. A sheet, a laminate for evaluation and a cured product for evaluation were obtained.

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

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

<Coating property>
A finger was lightly pressed against the resin surface end of each A4-sized resin sheet with a support, and the degree of sticking to the finger was evaluated based on the following criteria.
○: Almost no sticking to the finger is observed. The end of the resin sheet with support sticks to the finger, but it peels off from the finger and falls at a height of less than 30 mm.
X: Sticking to a finger is recognized. The end of the resin sheet with support is stuck to the finger and floats 30 mm or more in height.

<Heat resistance (glass transition temperature)>
The temperature of the cured product for evaluation was raised at 10 ° C./min using a DMA device (Dynamic Viscoelasticity Measurement Device DMAQ800 (trade name) manufactured by TA Instruments Co., Ltd.), and the peak position of LossModulus was changed to the glass transition temperature (Tg, ° C). ).

<Developability>
After measuring the time from the start of the developing step to the disappearance of the residue by visual observation, the development surface of the laminate for evaluation is observed with a scanning electron microscope (SEM) (magnification: 1000 times) to check the presence or absence of the residue It evaluated by the standard.
◎: The time until the visual development residue disappears is 50 sec or less, there is no development residue in the range of 30 mm square even after SEM observation, and the developability is very excellent.
Good: The time until the visual development residue disappears exceeds 50 sec, but there is no development residue in the range of 30 mm square after SEM observation, and the developability is excellent.
X: There is a development residue in the range of 30 mm square, and the developability is inferior.

Wet roughening treatment and conductor layer plating of cured products for evaluation:
A multilayer printed wiring board obtained in Examples 1 and 2 and Comparative Examples 1 to 3 was subjected to electroless copper plating process (used chemical name: MCD-PL, MDP-2, MAT-SP, MAB-4 manufactured by Uemura Kogyo Co., Ltd.). -C, MEL-3-APEA
ver. In 2), about 0.8 μm of electroless copper plating was applied, and drying was performed at 130 ° C. for 1 hour. Subsequently, electrolytic copper plating was applied such that the thickness of the plated copper became 18 μm, and drying was performed at 180 ° C. for one hour. Thus, a sample in which a conductor layer (plated copper) having a thickness of 18 μm was formed on the insulating layer was produced and subjected to the following evaluation.

<Plating adhesion (kN / m)>
The adhesion of plated copper is measured using the sample prepared by the above procedure.
It measured 3 times according to C6481, and calculated | required the average value. With respect to the dried and swollen sample after electrolytic copper plating, the evaluation was performed using the non-blown part.

As is clear from Table 1, Examples 1 to 7 are excellent in plating adhesion and heat resistance. Among them, Example 2 is good in heat resistance and plating adhesion, and Examples 3 to 7 are more excellent in heat resistance. On the other hand, Comparative Examples 1 to 3 have insufficient plating adhesion or heat resistance. Therefore, according to the present invention, a resin composition excellent in plating adhesion and heat resistance, a resin sheet using the same, a multilayer printed wiring board and a semiconductor device can be obtained.

Claims (14)

Dicyclopentadiene type epoxy resin (A) represented by the following formula (1), photo-curing initiator (B), compound (C) represented by the following formula (2), and represented by the following formula (2) The resin composition containing the compound (D) which has ethylenic unsaturated groups other than a compound (C).
(In formula (1), n shows the integer of 0-15.).
(In formula (2), a plurality of R ₁ 's each independently represent a hydrogen atom or a methyl group, and a plurality of R ₂ ' s each independently have a hydrogen atom or a carbon atom which may have a substituent) And 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).
(In formula (4), R ₄ represents a hydrogen atom or a methyl group.).   The resin composition according to claim 1, further comprising a maleimide compound (E).   The resin composition according to claim 1, further comprising a filler (F).   Any one or more compounds selected from the group consisting of cyanate ester compounds, phenol resins, oxetane resins, benzoxazine compounds and epoxy resins different from the dicyclopentadiene type epoxy resin (A) represented by (1) ((1) The resin composition according to any one of claims 1 to 3, further comprising G).   The resin composition as described in any one of Claims 1-4 whose acid value of the compound (C) represented by said Formula (2) is 30 mgKOH / g or more and 120 mgKOH / g or less.   The resin composition according to any one of claims 1 to 5, wherein the content of the component (A) is 3 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. object.   The resin composition according to any one of claims 1 to 6, wherein the compound (D) having an ethylenically unsaturated group is a compound having a (meth) acryloyl group and / or a compound having a vinyl group.   The filler (F) comprises silica, boehmite, barium sulfate, silicone powder, fluorocarbon resin filler, urethane resin filler, acrylic resin filler, polyethylene filler, styrene butadiene rubber and silicone rubber The resin composition according to claim 3, which is any one or more selected from the group.   The resin composition according to any one of claims 1 to 8, further comprising a heat curing accelerator (H). The resin composition as described in any one of Claims 1-9 which further contains the naphthalene type epoxy resin represented by following formula (5).
The resin composition as described in any one of Claims 1-10 in which the said photocuring initiator (B) contains the phosphine oxide compound represented by following 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 is an alkyl group having 1 to 20 carbon atoms or 6 to 20 carbon atoms The aryl group of   The resin sheet which has the resin composition as described in any one of Claims 1-11 distribute | arranged to the surface of a support body and this support body.   The multilayer printed wiring board which has a resin composition as described in any one of Claims 1-11. The semiconductor device which has a resin composition as described in any one of Claims 1-11.