TW201800473A - Resin composition, resin sheet, multilayer printed wiring board, and semiconductor device - Google Patents

Abstract

The present invention provides a resin composition and a resin sheet with a support body that exhibit excellent coating property and heat resistance and that are also excellent in plating adhesion and developing characteristics, when used in a multilayer printed wiring board, and a multilayer printed wiring board and a semiconductor device that use the resin composition and the resin sheet. The resin composition comprises a biphenyl aralkyl type epoxy resin (A) represented by the following formula (1), a photocuring initiator (B), a compound (C) represented by the following formula (2), and a compound (D) having an ethylenically unsaturated group other than the component (C).

Description

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

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

Because of the miniaturization and high density of multilayer printed circuit boards, there have been active discussions to reduce the thickness of multilayer boards used in multilayer printed circuit boards. Along with the reduction in thickness, the insulation layer is also required to be reduced in thickness, and a resin sheet containing no glass cloth is required. The resin composition used as the material of the insulating layer is mainly made of a thermosetting resin, and is generally an opening for conducting between the insulating layers by laser processing. In addition, a resin sheet using a thermosetting resin generally uses a method of forming a conductor circuit by copper plating as a method of forming a conductor circuit on an insulating layer.

On the other hand, when using laser processing to make holes, there is a problem that the higher the density of a high-density substrate, the longer the processing time. Therefore, in recent years, a resin sheet that can be subjected to a single hole-opening process in a developing step by using a resin composition that is hardened by light or the like and dissolved by development has been sought. Furthermore, since the conductor circuit is formed by copper plating on the insulating layer, it is desirable that the conductor circuit does not peel off and has high adhesion to the copper plating of the insulating layer.

Among the resin compositions used in such laminates and resin sheets, the alkali development type is the mainstream, and in order to enable development, an acrylate containing an acid anhydride group and a carboxyl group is used. In addition, because of copper plating adhesion, epoxy resin is used. For example, Patent Document 1 discloses a photosensitive thermosetting resin composition including a carboxyl-modified epoxy (meth) acrylic acid obtained by reacting a bisphenol epoxy resin with (meth) acrylic acid and then reacting an acid anhydride. Ester resin; biphenyl epoxy resin; photopolymerization initiator; and diluent. In addition, Patent Document 2 discloses an epoxy resin composition containing an epoxy resin, a hardening agent, and silicon dioxide particles, and a silicon dioxide component surface-treated with a silane coupling agent. It does not contain a hardening accelerator or a component of the ring. The total content of the oxygen resin and the hardener is 3.5 parts by weight or less. The hardening accelerator is contained. The average particle diameter of the silicon dioxide particles is 1 μm or less. In the silicon dioxide component, each 1 g of the silicon dioxide particles The surface treatment amount B (g) of the aforementioned silane coupling agent is relative to the formula (X) (C (g) / silicon dioxide particles 1g = [specific surface area of silicon dioxide particles (m ² / g) / silane The minimum coating area of the coupling agent (m ² / g)] ...... Formula (X)) Calculated 値 C (g) per 1 g of the silica particles is in the range of 10 to 80%. [Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Application Laid-Open No. 2005-62450 Patent Document 2: Japanese Patent Application Laid-Open No. 2011-174082

[Problems to be Solved by the Invention] However, hardened products using conventional epoxy resins cannot obtain sufficient physical properties, and there are limits to the formation of a protective film with high developability and high copper plating adhesion and an interlayer insulating layer.

In addition, the hardened material obtained from the resin composition described in Patent Document 1 is limited in its use for etching photoresist and solder resist for printed circuit boards. Although it has excellent flexibility and heat resistance, it is used for copper for interlayer insulation. The plating adhesion is not satisfactory.

The hardened material obtained from the resin composition described in Patent Document 2 is excellent in copper plating adhesion, but the opening is limited to laser processing, and it is impossible to make a single opening by the development step.

In view of the above problems, the present invention provides a resin composition having excellent coating properties and heat resistance, excellent developability and copper plating adhesion when used in a multilayer printed circuit board, a resin sheet with a support, and the use of these resins. Multilayer printed circuit boards, semiconductor devices. [Methods for solving problems]

The inventors of the present case found that by using a compound (C) represented by the following formula (2) containing a biphenylaralkyl-based epoxy resin (A) represented by the following formula (1), a photohardening initiator (B), and The resin composition of the compound (D) having an ethylenically unsaturated group other than the component (C) can solve the above-mentioned problems and has completed the present invention.

[Chemized 1]

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

［Chemical 2］

In formula (2), most of R ₁ each independently represent a hydrogen atom or a methyl group, and most of R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent, and most of R ₃ Each independently represents a substituent represented by the following formula (3), a substituent represented by the following formula (4), or a hydroxyl group;

［Chemical 3］

［Chemical 4］

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

That is, the present invention includes the following. [1] A resin composition comprising: a biphenylaralkyl-based epoxy resin (A) represented by the aforementioned formula (1), a photocuring initiator (B), and a compound (C) represented by the aforementioned formula (2) And a compound (D) having an ethylenically unsaturated group other than the compound (C) represented by the aforementioned formula (2). [2] The resin composition according to [1] further contains a maleimide compound (E). [3] The resin composition such as [1] or [2] further contains a filler (F). [4] The resin composition according to any one of [1] to [3], further containing a compound (G) selected from the group consisting of a cyanate compound, a phenol resin, and an oxetane. Resin, benzo The compound and the biphenylaralkyl-type epoxy resin (A) represented by the above (1) are any one or more selected from the group consisting of different epoxy resins.

[5] The resin composition according to any one of [1] to [4], wherein the acid value of the compound (C) represented by the formula (2) is 30 mgKOH / g or more and 120 mgKOH / g or less. [6] The resin composition according to any one of [1] to [5], wherein the content of the component (A) is 3 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition. . [7] The resin composition according to any one of [1] to [6], wherein the compound (D) having an ethylenically unsaturated group is a compound having a (meth) acrylfluorenyl group and / or having ethylene Of the compound. [8] The resin composition according to [3], wherein the filler (F) is selected from the group consisting of silica, boehmite, barium sulfate, polysiloxane powder, fluororesin-based filler, and ethyl carbamate. Any one or more of the group consisting of an ester resin-based filler, an acrylic resin-based filler, a polyethylene-based filler, a styrene-butadiene rubber, and a silicone rubber.

[9] The resin composition according to any one of [1] to [8], further containing a heat curing accelerator (H). [10] The resin composition according to any one of [1] to [9], further containing a naphthalene-type epoxy resin represented by the following formula (5);

［Chemical 5］

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

［Chemical 6］

In Formula (6), R ₅ to R ₁₀ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁₁ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. [12] A resin sheet having a support and a resin composition such as any one of [1] to [11] arranged on a surface of the support. [13] A multilayer printed circuit board having the resin composition according to any one of [1] to [11]. [14] A semiconductor device including the resin composition according to any one of [1] to [11]. [Effect of Invention]

According to the present invention, it is possible to provide a resin composition hardened by active energy rays, which has excellent plating adhesion, coating properties, heat resistance, and developability, and has physical properties suitable for a multilayer printed circuit board, a resin sheet with a support, and use. These resin sheets are multilayer printed circuit boards and semiconductor devices.

Hereinafter, this embodiment (hereinafter referred to as "this embodiment") will be described in detail. The following embodiment is an example for explaining the present invention, and the present invention is not limited to the following. The present invention can be appropriately modified and implemented within the scope of the gist thereof.

In this specification, "(meth) acrylfluorenyl" means both "acrylfluorenyl" and its corresponding "methacrylfluorenyl", and "(meth) acrylate" means "acrylate" and As for the corresponding "methacrylate", "(meth) acrylic acid" means both "acrylic acid" and its corresponding "methacrylic acid". In this embodiment, "resin solid content" or "resin solid content in resin composition" means components other than the solvent and filler in the resin composition unless otherwise specified, and "resin solid content 100" "Part by mass" means that the total amount of components other than the solvent and filler in the resin composition is 100 parts by mass.

The resin composition of this embodiment contains a biphenylaralkyl-type epoxy resin (A) represented by the aforementioned formula (1), a photocuring initiator (B), a compound (C) represented by the aforementioned formula (2), and (C) An ethylenically unsaturated compound (D) other than the component. Each component is explained below.

<Biphenylaralkyl-type epoxy resin (A) represented by Formula (1)> The biphenylaralkyl-type epoxy resin (A) (also referred to as component (A)) used in this embodiment has the foregoing A compound having a biphenylaralkyl skeleton having a structure of formula (1). The hardened | cured material obtained by containing this resin (A) has high copper-plating adhesiveness, and can form the protective film excellent in developability, and an interlayer insulation layer.

In formula (1), n represents an integer of 0-15. Considering the developmental viewpoint, it should be an integer from 0 to 5.

In the resin composition of this embodiment, the content of the component (A) is not particularly limited. Considering the viewpoint of improving the adhesion of copper plating, the content of the component (A), the component (C), and the component (D) is 100 with respect to the total. It is preferably 3 parts by mass or more, more preferably 4 parts by mass or more, and more preferably 5 parts by mass or more. From the viewpoint of sufficiently hardening and improving heat resistance, it is preferably 90 parts by mass or less, more preferably 89 parts by mass or less, and more preferably 88 parts by mass or less.

In the resin composition of this embodiment, the content of the component (A) is not particularly limited. From the viewpoint of copper plating adhesion and improvement of developability, it is 3 masses with respect to 100 mass parts of the resin solid content in the resin composition. It is more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and more preferably 15 parts by mass or more. From the viewpoint of sufficiently hardening and improving heat resistance, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and 30 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 content is less than mass.

As the resin (A), a commercially available product can also be used, and examples thereof include NC3000FH (n = 8 to 10 in formula (1)), NC3000H (n = 2 to 5 in formula (1)), and NC3000L (formula (1) ) (N = 1 to 3), NC3000 (n = 1 to 3 in formula (1)), CER3000L (n = 0 to 2 in formula (1)) (the above are the trade names of Nippon Kayakusho (stock) ) System) and so on. One of them can be used alone or two or more can be appropriately mixed.

<Photocuring Initiator (B)> The photocuring initiator (B) (also referred to as component (B)) used in this embodiment is not particularly limited, and it can be used in the field generally used for photocurable resin compositions. Knowers.

For example: benzoin, benzoin methyl ether, benzoin ether, benzoin propyl ether, benzoin isobutyl ether, benzoin peroxide, benzoin peroxide, laurel peroxide, acetamidine peroxide , Exemplified organic peroxides such as benzamidine p-chloroperoxide, di-tert-butyl diperoxyphthalate, fluorenylphosphine oxides, acetophenone, 2,2-diethoxy-2- Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1-one, Diethoxyacetophenone, 1-hydroxycyclohexyl phenone, 2-methyl-1- [4- (methylthio) phenyl] -2-olino-propane-1-one, 2-benzyl Acetophenones such as 2-dimethylamino-1- (4-phosphonophenyl) -butan-1-one, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthracene Anthraquinones such as quinone, 2-pentylanthraquinone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone and other thioxanthone, acetophenone dimethyl Acetals, ketals such as benzyl dimethyl ketal, benzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 4,4'-bismethylaminobenzophenone Isobenzophenones, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, bis (2, Phosphine oxides such as 4,6-trimethylbenzyl) -phenylphosphine oxide, 1,2-octanedione, 1- [4- (phenylsulfanyl)-, 2- (O-benzoyl醯 oxime)] and other oxime esters and other radical photocuring initiators, fluorophosphonic acid p-methoxyphenyldiazonium salt, hexafluorophosphonic acid N, N-diethylaminophenyldiazonium salt Diazonium salts of Lewis acid, diphenylphosphonium hexafluorophosphonate, diphenylphosphonium hexafluoroantimonate, etc., phosphonium salts of Lewis acid, triphenylphosphonium hexafluorophosphonate, triphenyl hexafluoroantimonate Pyrene salts such as rhenium acid, phosphonium salts such as hexafluoroantimonate, other halides, tertiary initiators, borate initiators, and other photoacid generators Isocationic photopolymerization initiator.

Examples of the fluorenylphosphine oxides include phosphine oxide compounds represented by the following formula (6) such as bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide, and 2,4,6-trimethylbenzene Formamyl-diphenyl-phosphine oxide and the like. In particular, the phosphine oxide compound represented by the following formula (6) has a high UV absorption rate at a long wavelength, and is excellent in allowing UV light to reach the inside of the resin. Therefore, it can ideally react with the biphenylaralkyl-type epoxy resin (A), the compound (C), and the compound (D) in this embodiment, and it is possible to produce a resin sheet and a multilayer printed circuit board with better heat resistance.

［Hua 7］

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

C1-C4 alkyl groups, for example: methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, second butyl, third butyl, etc. alkyl.

C1-C20 alkyl group, for example: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, second butyl, third butyl, Neopentyl, 1,1-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, Linear or branched alkyl groups such as 1,1-dimethylbutyl and 1,1,3-trimethylbutyl.

Examples of the aryl group having 6 to 20 carbon atoms include non-substituted aryl groups such as phenyl, naphthyl, biphenyl, bitriphenyl, phenanthryl, and anthracenyl; tolyl, dimethylphenyl, isopropylphenyl, Alkyl-substituted aryl groups such as third butylphenyl and di-third butylphenyl.

Among them, considering the reactivity suitable for multilayer printed circuit board applications, and the viewpoint of high reliability of metal conductors, fluorenylphosphine oxides, 2-benzyl-2-dimethylamino-1- (4-phosphonobenzene A radical-type photohardening initiator such as acetophenone such as butan-1-one is preferable. As described above, considering the viewpoint of obtaining better heat resistance, the phosphine oxide compound represented by the formula (6) is more preferable. Of these, bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide is more desirable.

These photohardening initiators (B) may be used singly or in combination of two or more kinds as appropriate, and two types of initiators of a radical type and a cationic type may be used in combination.

In addition, 2-benzyl-2-dimethylamino-1- (4-phosphonophenyl) -butanone-1, bis (2,4,6-trimethylbenzyl) -phenyl oxide Phosphine and 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide can also be used commercially. Irgacure (registered trademark) 369 (manufactured by BASF Japan) and Irgacure (registered Trademark) 819 (made by BASF Japan) and Irgacure (registered trademark) TPO (made by BASF Japan).

In the resin composition of the present embodiment, the content of the photocuring initiator (B) is not particularly limited. In consideration of the viewpoint that the resin composition is sufficiently hardened by active energy rays to improve heat resistance, the content of the resin composition ( A) The total content of component (C) and component (D) is 100 parts by mass, preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, and more preferably 0.3 part by mass or more. From the viewpoint of hindering thermal curing after photo-hardening and lowering heat resistance, 30 parts by mass or less is preferable, 25 parts by mass or less is more preferable, and 20 parts by mass or less is more preferable.

The content of the photocuring initiator (B) in the resin composition of this embodiment is not particularly limited, but it is preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more, based on 100 parts by mass of the resin solid content in the resin composition. Good, 0.3 mass parts or more is more preferable, 1 mass part or more is more preferable, and 1.8 mass parts or more is more preferable. In addition, considering the viewpoint of hindering thermal curing after light curing and reducing heat resistance, it is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and 20 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition. Still more preferred is 10 parts by mass or less.

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

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

A 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 may be a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms, preferably 1 to 14, more preferably 1 to 10 carbon atoms; 3 to 22 carbon atoms, preferably 3 to 14, More preferably, it is an alicyclic hydrocarbon group of 3 to 10; 6 to 22 carbon atoms, preferably 6 to 14, and more preferably 6 to 10 aromatic hydrocarbon group. Aliphatic hydrocarbon groups, such as: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, second butyl, third butyl, neopentyl, 1 1,1-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, 1,1-bis Linear or branched alkyl groups such as methylbutyl, 1,1,3-trimethylbutyl; linear or branched alkenyl groups such as vinyl, allyl, isopropenyl; ethynyl , Propargyl and other linear or branched alkynyl. Cycloaliphatic hydrocarbon groups, for example: cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-methyl-1-cyclohexyl, adamantyl; cyclopentadienyl, indenyl, Cyclic unsaturated hydrocarbon groups such as fluorenyl. Aromatic hydrocarbon groups, such as: unsubstituted aryl groups such as phenyl, naphthyl, biphenyl, bitriphenyl, phenanthryl, and anthracenyl; tolyl, dimethylphenyl, isopropylphenyl, and third butyl Alkyl-substituted aryl groups such as phenyl, di-tert-butylphenyl; and other aryl groups. These hydrocarbon groups may be substituted with at least one hydrogen atom into another hydrocarbon group. At least one hydrogen atom is substituted with a hydrocarbyl group of another hydrocarbyl group, for example: an aryl-substituted alkyl group such as benzyl, cumyl, or a cyclic saturated hydrocarbon-substituted alkyl group such as cyclohexylmethyl.

It may also have a hydrocarbon group having 1 to 22 carbon atoms with a substituent, preferably a linear or branched alkyl group. Considering the viewpoint of improving the heat resistance of the hardened material for a plurality of R ₂ , it is preferable to include a methyl group, and it is more preferable that R ₂ is a methyl group. The plurality of R ₃ each independently represent a substituent represented by the aforementioned formula (3), a substituent represented by the aforementioned formula (4), or a hydroxyl group. Among them, considering the viewpoint of improving heat resistance, it is preferable to include a hydroxyl group. In addition, in this embodiment, it is also preferable to use a plurality of compounds (C) in which R ₃ contains a substituent represented by the formula (3) from the viewpoint of improving developability. In this embodiment, a plurality of compounds (C) containing a substituent represented by the aforementioned formula (4) in R ₃ are used, and the viewpoint of improving heat resistance is also desirable. In the formula (4), R ₄ represents a hydrogen atom or a methyl group. Among them, from the viewpoint of improving the reactivity of the photo-hardening reaction, a hydrogen atom is preferred.

Considering the viewpoint of improving the developability of a plurality of R ₃ , it is preferable that the ratio of the substituents represented by the above formula (3) among all the substituents of R ₃ is in a range of 20% to 98%, and the above formula (4) The ratio of the substituents is preferably in the range of 5% to 98%, and the ratio of the hydroxyl groups is in the range of 10% to 98% (the sum of the ratios of these substituents is 100%). Among these, from the viewpoint of improving the developability, it is particularly preferable that at least one of R ₃ is a substituent represented by the aforementioned formula (3).

If the compound (C) contains any one or more of the following compounds (C1) to (C5), it is preferable to improve the reactivity of the photocuring reaction, the heat resistance and developability of the cured product, and therefore it is desirable to contain at least the compound (C1 ) Is more preferable, and it is more preferable to contain any two or more of (C1) to (C5), and it is more preferable to contain any one or more of compound (C1) and (C2) to (C5). It is also preferable that the compound (C) contains at least the compounds (C2) and (C3).

［Chem 8］

［Hua 9］

［Chem10］

［Chem 11］

［Hua 12］

Such compounds can also be used commercially, 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 (the above are trade names, manufactured by Nippon Kayaku Co., Ltd.), etc.

In the resin composition of the present embodiment, the acid value of the compound (C) is preferably 30 mgKOH / g or more from the viewpoint of improving developability, and from the viewpoint of improving the developability, it is more preferably 50 mgKOH / g or more. In addition, considering the viewpoint of preventing the solution from being dissolved by the developer after being hardened by the active energy ray, the acid value of the compound (C) should preferably be 120 mgKOH / g or less, and the viewpoint of preventing dissolution more preferably, it is more preferably 110 mgKOH / g or less. . In addition, the "acid value" in this embodiment represents the osmium measured according to the method of JISK0070: 1992.

In the resin composition of this embodiment, the content of the compound (C) is not particularly limited. Considering that the resin composition is hardened by active energy rays, the content of the compound (C) is relative to the component (A), the component (C), and the component in the resin composition. (D) The total content of 100 parts by mass is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and more preferably 3 parts by mass or more. Moreover, considering the viewpoint of sufficiently hardening by active energy rays to improve heat resistance, 99 parts by mass or less is more preferable, 98 parts by mass or less is more preferable, and 97 parts by mass or less is more preferable.

In the resin composition of this embodiment, the content of the compound (C) is not particularly limited. Considering that the resin composition is hardened by active energy rays, it is 1 part by mass or more relative to 100 parts by mass of the resin solid content in the resin composition. Preferably, 2 parts by mass or more is preferable, 3 parts by mass or more is more preferable, 10 parts by mass or more is more preferable, 25 parts by mass or more is more preferable, and 30 parts by mass or more is most preferable. In addition, considering the viewpoint of sufficiently hardening by using active energy rays to improve heat resistance, it is preferably 99 parts by mass or less, more preferably 98 parts by mass or less, and 97 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. More preferably, 90 parts by mass or less is more preferable, 75 parts by mass or less is more preferable, and 72 parts by mass or less is most preferable.

<Ethylene unsaturated compound (D) other than (C) component> The resin composition of this embodiment contains (C) in order to improve reactivity to active energy rays (for example, ultraviolet rays) and heat resistance. Compound (D) having an ethylenically unsaturated group other than the component (also referred to as component (D)). The compound (D) having an ethylenically unsaturated group used in this embodiment is a compound other than the compound (C) represented by the aforementioned formula (2) and has one or more ethylenically unsaturated groups in one molecule. The compound may be, but is not particularly limited to, for example, a compound having a (meth) acrylfluorenyl group, a vinyl group, or the like. One of them may be used alone or two or more of them may be appropriately mixed.

Examples of the compound having a (meth) acrylfluorenyl group include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, and polyethylene glycol (Meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether, phenylethyl (meth) acrylate, isoamyl (meth) acrylate, cyclohexyl (meth) acrylate, ( Benzyl (meth) acrylate, tetrahydrofuran methyl (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Nonanediol di (meth) acrylate, glycol glycol di (meth) acrylate, diethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, ginseng (meth) acrylic acid Oxyethyl 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 hydroxytrimethylacetic acid neopentyl glycol di (meth) acrylate, ε-caprolactone Modified six (A ) Dineopentaerythryl Acrylate, ε-caprolactone modified poly (nepentaerythritol), poly (meth) acrylate Dinepentaerythritol, trimethylolpropane tris (methyl Group) acrylate, trihydroxyethylpropane tri (meth) acrylate, and its ethylene oxide adduct, neopentyl tetrakis (meth) acrylate, and its ethylene oxide adduct, Neopentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and ethylene oxide adducts thereof.

In addition, urethane (meth) acrylates having both a (meth) acryl group and a urethane bond in the same molecule, and also having a (meth) acryl group and Responsive oligoesters which are ester-bonded polyester (meth) acrylates, epoxy (meth) acrylates derived from epoxy resins and which also have a (meth) acrylfluorenyl group, and these bonds are used in combination Polymer and so on.

The aforementioned urethane (meth) acrylates are reactants of hydroxyl-containing (meth) acrylates, polyisocyanates, and other alcohols used as needed. For example, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glyceryl mono (meth) acrylate, Glyceryl (meth) acrylates such as glyceryl (meth) acrylate, neopentaerythritol di (meth) acrylate, neopentaerythritol tri (meth) acrylate, dineopentapenta (meth) acrylate Sugar alcohols (meth) acrylates such as tetraol esters, dipentaerythritol hexa (meth) acrylate, and toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, iso Furone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexanemethylene diisocyanate, and polyisocyanates such as their isocyanurates and biuret reactants Wait for a reaction to become urethane (meth) acrylates.

The polyester (meth) acrylates are, for example, caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide, and / or propylene oxide-modified phthalic acid (meth) acrylic acid Monofunctional (poly) esters (meth) acrylates such as esters, ethylene oxide-modified succinic acid (meth) acrylates, caprolactone-modified tetrahydrofuran methyl (meth) acrylates; hydroxytrimethyl Acetate neopentyl glycol di (meth) acrylate, caprolactone modified hydroxytrimethyl acetate neopentyl glycol di (meth) acrylate, epichlorohydrin modified phthalic acid di ( Di (poly) esters (meth) acrylates such as (meth) acrylates; 1 mol of trimethylolpropane or glycerol added to ε-caprolactone, γ-butyrolactone, δ -Mono, di or tri (meth) acrylates of trihydric alcohols obtained from cyclic lactone compounds such as valerolactone.

In addition, cyclic internals such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone such as neomolerol or bis (trimethylol) propane with 1 mol addition or more can be cited. Mono-, di-, tri-, or tetra- (meth) acrylates of triols obtained from ester compounds, ε-caprolactone, γ-butyrolactone, and 1 mol added to dipentaerythritol Monohydric alcohols derived from cyclic lactone compounds such as esters, δ-valerolactones, or polyhydric alcohols such as poly (meth) acrylates, tetrahydric alcohols, pentahydric alcohols, or hexahydric alcohols Mono (meth) acrylate or poly (meth) acrylate.

Furthermore, (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butanediol, 3-methyl-1,5-pentanediol, and hexanediethylene glycol) Glycol components such as alcohol and maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, decyl Polyacids such as diacids, azelaic acid, sodium 5-sulfoisophthalate, and the reactants of these anhydrides are (meth) acrylates of polyester polyols; Polyfunctional (poly) esters such as (meth) acrylates of cyclic lactone-modified polyester diols composed of such anhydrides and ε-caprolactone, γ-butyrolactone, δ-valerolactone ( (Meth) acrylates and the like, but are not limited thereto.

The epoxy (meth) acrylates are epoxy compounds and carboxylate compounds of (meth) acrylic acid. For example: phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, p-hydroxyphenylmethane epoxy (meth) acrylate, dicyclopentadiene phenol Type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, biphenol type epoxy (meth) acrylate, bisphenol A novolac epoxy (meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate, glyoxal epoxy (meth) acrylate, heterocyclic epoxy (meth) acrylate Etc., and these anhydride-modified epoxy acrylates.

Examples of the compound having a vinyl group include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of the styrenes include styrene, methylstyrene, ethylstyrene, and divinylbenzene. Examples of other vinyl compounds include triallyl isocyanurate, trimethylallyl isocyanurate, diallyl nadicarium imine, and the like.

Among these, the viewpoint of considering heat resistance is selected from the group consisting of neopentyl tetrakis (meth) acrylate, dipentaerythritol hexa (meth) acrylate, cresol novolac epoxy (methyl ) Acrylic ester, bisphenol A epoxy (meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate, and bisallyl nadic acid imine Considering the viewpoint of improving heat resistance, dineopentaerythritol (meth) acrylate is more preferable. By containing such a compound having an ethylenically unsaturated group, the heat resistance of the obtained cured product tends to be further improved.

In the resin composition of the present embodiment, the content of the compound (D) having an ethylenically unsaturated group other than the component (C) is not particularly limited. Considering that the developability is good, the content of the component in the resin composition ( A) The total content of component (C) and component (D) is 100 parts by mass, preferably 0.5 part by mass or more, more preferably 1.0 part by mass or more, and more preferably 1.5 part by mass or more. From the viewpoint of making the heat resistance of the cured product good, 90 parts by mass or less is preferred, 70 parts by mass or less is more preferred, and 50 parts by mass or less is more preferred.

In the resin composition of this embodiment, the content of the compound (D) is not particularly limited, and considering the viewpoint of making the developability good, it is preferably 0.5 parts by mass or more relative to 100 parts by mass of the resin solid content in the resin composition, and 1.0 is preferably 1.0 More than mass parts is more preferable, more than 1.5 mass parts is more preferable, more than 5.0 mass parts is more preferable, and more than 10 mass parts is most preferable. Moreover, considering the viewpoint of making the heat resistance of the cured product good, it is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, and more preferably 50 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. 25 mass parts or less is more preferable, and 20 mass parts or less is most preferable.

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

The maleimide imine compound (E) used in this embodiment is not particularly limited as long as it is a compound having one or more maleimide imine groups in the molecule. Specific examples thereof include, for example, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidephenyl) methane, 2,2-bisamidine4- ( 4-maleimide phenoxy) -phenylammonium propane, 4,4-diphenylmethane bismaleimide, bis (3,5-dimethyl-4-maleimide) benzene Methyl), methane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, bis (3,5-diethyl-4-maleimidephenyl) methane, Phenylmethanemaleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene bismaleimide Imine, m-phenylene bis-citramene imine, p-phenylene bis-citramene imine, 2,2-bis (4- (4-maleimide phenoxy) -phenyl) propane , 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide , 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenylpyridine Lyme imine, 1,3-bis (3-maleimide phenoxy) benzene, 1,3-bis (4-maleimide phenoxy) benzene, 4,4-diphenyl Methane Shuangkangang Imine, 2,2-bis [4- (4-citraconiminophenoxy) phenyl] propane, bis (3,5-dimethyl-4-citraconimidophenyl) methane, Bis (3-ethyl-5-methyl-4-citraconiminophenyl) methane, bis (3,5-diethyl-4-citraconiminophenyl) methane, polyphenylmethane Maleimide, novolak-type maleimide compound, biphenylaralkyl-type maleimide compound, maleimide compound represented by the following formula (7), and formula (8) Maleimide compounds, prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds, and the like.

Among them, novolac-type maleimide compounds and biphenylaralkyl-type maleimide compounds are particularly preferred. From the viewpoint of obtaining good coating properties and excellent heat resistance, a maleimide compound represented by the following formula (7) and a maleimide compound represented by the following formula (8) are preferable, and the following formula (7 The maleimide compound represented by) is more preferable. A commercially available product such as BMI-2300 (manufactured by Yamato Chemical Industry Co., Ltd.) may be used as the maleimide compound represented by the following formula (7). As the maleimide compound represented by the following formula (8), a commercially available product such as MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.) can also be used. These maleimide compounds (E) can be used individually by 1 type or in mixture of 2 or more types as appropriate.

［Chemical 13］

In the 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 an integer of 1 to 10, more preferably an integer of 1 to 5.

［Chem 14］

In the formula (8), a plurality of R ₆ each independently represent a hydrogen atom or a methyl group. n ₂ represents an integer of 1 or more, and preferably an integer of 1 to 5. These maleimide compounds (E) can be used individually by 1 type or in mixture of 2 or more types as appropriate.

In the resin composition of this embodiment, the content of the maleimide compound (E) is not particularly limited. Considering the viewpoint of sufficiently curing the resin composition and improving the heat resistance, the content of the resin composition (A), The total content of the component (C) and the component (D) is 100 parts by mass, preferably 0.01 part by mass or more, more preferably 0.02 part by mass or more, and more preferably 0.03 part by mass or more. From the viewpoint of making the developability good, 50 parts by mass or less is preferable, 45 parts by mass or less is more preferable, and 40 parts by mass or less is more preferable.

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

<Filling Material (F)> In the resin composition of this embodiment, in order to improve various properties such as coating film properties and heat resistance, a filler (F) (also referred to as a component (F)) may be used in combination. The filler (F) used in this embodiment is not particularly limited as long as it has insulation properties. For example, silicon dioxide (such as natural silicon dioxide, fused silicon dioxide, amorphous silicon dioxide, and hollow silicon dioxide) Silicon oxide, etc.), aluminum compounds (such as boehmite, aluminum hydroxide, aluminum oxide, etc.), magnesium compounds (such as magnesium oxide, magnesium hydroxide, etc.), calcium compounds (such as calcium carbonate, etc.), molybdenum compounds (such as molybdenum oxide) , Zinc molybdate, etc.), barium compounds (e.g. barium sulfate, barium silicate, etc.), talc (e.g. natural talc, calcined talc, etc.), mica (mica), glass (e.g. short fibrous glass, spherical glass, fine powder) Glass (e.g. E glass, T glass, D glass, etc.), polysiloxane powder, fluororesin-based filler, urethane resin-based filler, acrylic resin-based filler, polyethylene-based filler, styrene・ Butadiene rubber and silicone rubber. Among them, it is selected from the group consisting of silicon dioxide, boehmite, barium sulfate, polysiloxane powder, fluororesin-based filler, urethane resin-based filler, acrylic resin-based filler, polyethylene-based filler, and benzene. One or more of the group consisting of ethylene butadiene rubber and silicone rubber is preferred. 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 good coating properties, silicon dioxide is preferable, and fused silicon dioxide is particularly preferable. Specific examples of the silicon dioxide include SFP-130MC made by Denka Co., Ltd., SC2050-MB made by Admatechs Co., Ltd., SC1050-MLE, YA010C-MFN, and YA050C-MJA. These fillers (F) can be used individually by 1 type or in mixture of 2 or more types suitably.

In the resin composition of this embodiment, the content of the filler (F) is not particularly limited. From the viewpoint of improving the heat resistance of the cured product, it is 5 parts by mass or more relative to 100 parts by mass of the resin solid content in the resin composition. Good, more preferably 10 parts by mass or more, and more preferably 20 parts by mass or more. Furthermore, considering the viewpoint of making the developability of the resin composition good, it is preferably 400 parts by mass or less, more preferably 350 parts by mass or less, and even more preferably 300 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. , 200 mass parts or less is more desirable, and 100 mass parts or less is most desirable.

<Silane coupling agent and wetting and dispersing agent> In the resin composition of this embodiment, in order to improve the dispersibility of the filler and the adhesion strength between the polymer and / or the resin and the filler, a silane coupling agent and / or Wetting dispersant. These silane coupling agents are not particularly limited as long as they are silane coupling agents generally used for the surface treatment of inorganic substances. Specific examples, for example: amine silane based on γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane; γ-glycidyloxy Silyl epoxy systems such as propyltrimethoxysilane; acrylate silane systems such as γ-propenyloxypropyltrimethoxysilane; N-β- (N-vinylbenzylaminoethyl) -γ-amine Cationic silanes such as propyltrimethoxysilane hydrochloride; silane coupling agents of phenylsilane. These silane coupling agents can be used individually by 1 type or in combination of 2 or more types as appropriate.

The content of the silane coupling agent in the resin composition of this embodiment is not particularly limited, but is usually 0.1 to 10 parts by mass based on 100 parts by mass of the resin composition. Wetting and dispersing agents are not particularly limited as long as they are dispersing stabilizers used in coating applications. Specific examples include, for example, wetting and dispersing agents such as DISPERBYK (registered trademark) -110, 111, 118, 180, 161, BYK (registered trademark) -W996, W9010, and W903 manufactured by BYK Chemie Japan. These wetting and dispersing agents may be used singly or in combination of two or more kinds as appropriate. The content of the wetting and dispersing agent in the resin composition of this embodiment is not particularly limited, but is usually 0.1 to 10 parts by mass based on 100 parts by mass of the resin composition.

<Choose from cyanate ester compound, phenol resin, oxetane resin, benzo Compound and any one or more compounds (G) in the group consisting of an epoxy resin different from the biphenylaralkyl-type epoxy resin (A) represented by the above (1)> Compound (G) used in this embodiment (Also referred to as component (G)), in addition to the copper plating adhesion obtained by using component (A), the flame retardance, heat resistance, hardness Various properties are used for characteristics such as thermal expansion characteristics. For example, when heat resistance is required, cyanate compounds, benzo Compounds and the like may be used in addition to phenol resins and oxetane resins. When a biphenylaralkyl-type epoxy resin (A), a light curing initiator (B), a compound (C) and a compound (D), and a cyanate compound are used together, heat resistance (glass transition temperature) can be obtained Resin composition with excellent low thermal expansion and plating adhesion. Furthermore, it is preferable to use a cyanate ester compound and a maleimide compound together to obtain a resin composition having more excellent plating adhesion. If the biphenylaralkyl-type epoxy resin (A) represented by the above (1) and an epoxy resin different from the epoxy resin (A) are used together, a resin having particularly excellent developability and plating adhesion can be obtained.组合 物。 Composition.

One of them may be used alone or two or more thereof may be appropriately mixed. Details of these compounds and / or resins (G) are described below.

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

For example, it is represented by general formula (9).

[Chemized 15]

In the formula (9), Ar ₁ represents a benzene ring, a naphthalene ring, or two benzene rings obtained by a single bond. When there are many, they may be the same or different. Ra independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 6 carbon atoms, and 6 to 12 carbon atoms The aryl group is obtained by bonding. Ra in the aromatic ring may have a substituent, Ar _1, and R _a group in the optionally substituted at any position. p represents the number of cyanooxy groups bonded to Ar ₁ and each independently represents an integer of 1 to 3. q represents the number of Ra bonded to Ar _1; when Ar ₁ is a benzene ring, it represents 4-p, when it is a naphthalene ring, it represents 6-p, and when two benzene rings are bonded by a single bond, it is 8-p. t represents the average number of repeats and is an integer from 0 to 50. The cyanate ester compound may also be a mixture of compounds having different t. When there are a plurality of X, each independently represents a single bond, a divalent organic group having 1 to 50 carbon atoms (a hydrogen atom may be substituted with a hetero atom.), And a divalent organic group having 1 to 10 nitrogen atoms (for example, -NRN- (Here R represents an organic group.)), A carbonyl group (-CO-), a carboxyl group (-C (= O) O-), a carbonyl dioxide (-OC (= O) O-), and a sulfonyl group (-SO _2- ), a divalent sulfur atom, or a divalent oxygen atom.

The alkyl group of Ra in the general formula (9) may have any of a linear or branched chain structure and a cyclic structure (such as a cycloalkyl group). The hydrogen atom in the alkyl group in the general formula (9) and the aryl group in Ra may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, or a cyano group. Wait. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a third butyl group, an n-pentyl group, a 1-ethylpropyl group, and a 2,2-dimethyl group. Propyl, cyclopentyl, hexyl, cyclohexyl, and trifluoromethyl. Specific examples of the aryl group include phenyl, xylyl, mesityl, naphthyl, phenoxyphenyl, ethylphenyl, ortho, m- or p-fluorophenyl, dichlorophenyl, and dicyano Phenyl, trifluorophenyl, methoxyphenyl, ortho, m- or p-tolyl, etc. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a third butoxy group.

Specific examples of the divalent organic group having 1 to 50 carbon atoms of X in the general formula (9) include methylene, ethylene, trimethylene, cyclopentyl, cyclohexyl, and trimethyl ring. Hexyl, biphenylmethylene, dimethylmethylene-phenylene-dimethylmethylene, fluorene diyl, and phthalone diyl. The hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, an alkoxy 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 of X in the general formula (9) include an imine group and a polyfluoreneimide group.

The organic group of X in the general formula (9) is, for example, a structure represented by the following general formula (10) or the following general formula (11).

［Hua 16］

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

［Hua 17］

In formula (11), Ar ₃ represents a benzenetetrayl group, a naphthalenetetrayl group, or a biphenyltetrayl group, and when v is 2 or more, they may be the same as or different from each other. Ri and Rj 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 alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a trifluoromethyl group, or Aryl substituted with at least 1 cyanooxy group. v represents an integer from 0 to 5, but may be a mixture of compounds having different v values.

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

［Hua 18］

Here, z represents an integer of 4-7. Rk each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Specific examples of Ar ₂ of general formula (10) and Ar ₃ of general formula (11) include two carbon atoms represented by general formula (10), or two oxygen atoms represented by general formula (11). Phenyltetrayl at position 1, 4 or 1, 3, the above 2 carbon atoms or 2 oxygen atoms are bonded at 4, 4 'position, 2, 4' position, 2, 2 'position, 2, 3' Biphenyl tetrayl at the 3, 3 ', or 3, 4' position, and the above 2 carbon atoms or 2 oxygen atoms are bonded to the 2, 6, 1, 5, 1, 6, and 1 Naphthalene tetrayl at the 8-, 1, 3-, 1, 4-, or 2, 7-position. Rb, Rc, Rd, Re, Rf, and Rg in the general formula (10), and alkyl and aryl groups of Ri and Rj in the general formula (11) are the same as defined in the general formula (9).

Specific examples of the cyanooxy-substituted aromatic compound represented by the general formula (9) include cyanobenzene, 1-cyano-2-, 1-cyano-3-, and 1-cyano- 4-methylbenzene, 1-cyanooxy-2-, 1-cyanooxy-3-, or 1-cyanooxy-4-methoxybenzene, 1-cyanooxy-2,3-, 1 -Cyanooxy-2,4-, 1-cyanooxy-2,5-, 1-cyanooxy-2,6-, 1-cyanooxy-3,4- or 1-cyanooxy-3 , 5-Dimethylbenzene, cyanoethylbenzene, cyanobutylbenzene, cyanooctylbenzene, cyanononylbenzene, 2- (4-cyanophenyl) -2- Phenylpropane (cyanoester of 4-α-cumylphenol), 1-cyanooxy-4-cyclohexylbenzene, 1-cyanooxy-4-vinylbenzene, 1-cyanooxy-2 -Or 1-cyanooxy-3-chlorobenzene, 1-cyanooxy-2,6-dichlorobenzene, 1-cyanooxy-2-methyl-3-chlorobenzene, cyanooxynitrobenzene, 1-cyanooxy-4-nitro-2-ethylbenzene, 1-cyanooxy-2-methoxy-4-allylbenzene (cyanate of eugenol), methyl ( 4-cyanooxyphenyl) sulfide, 1-cyanooxy-3-trifluoromethylbenzene, 4-cyanooxybiphenyl, 1-cyanooxy-2- or 1-cyano-4- Ethyl benzene, 4-cyanooxybenzaldehyde, methyl 4-cyanooxybenzoate, 4-cyanooxybenzoic acid Ester, 1-cyanooxy-4-acetamidobenzene, 4-cyanobenzophenone, 1-cyanooxy-2,6-di-third-butylbenzene, 1,2-dicyanoxy Benzene, 1,3-dicyanooxybenzene, 1,4-dicyanooxybenzene, 1,4-dicyanooxy-2-third butylbenzene, 1,4-dicyanooxy-2 , 4-dimethylbenzene, 1,4-dicyanooxy-2,3,4-dimethylbenzene, 1,3-dicyanooxy-2,4,6-trimethylbenzene, 1, 3-dicyanooxy-5-methylbenzene, 1-cyanooxy or 2-cyanonaphthalene, 1-cyanooxy4-methoxynaphthalene, 2-cyano-6-methylnaphthalene, 2-cyano-7-methoxynaphthalene, 2,2'-dicyanooxy-1,1'-binaphthalene, 1,3-, 1,4-, 1,5-, 1,6- , 1,7-, 2,3-, 2,6- or 2,7-dicyanooxynaphthalene, 2,2'- or 4,4'-dicyanooxybiphenyl, 4,4'-di Cyanoxy octafluorobiphenyl, 2,4'- or 4,4'-dicyanooxydiphenylmethane, bis (4-cyanooxy-3,5-dimethylphenyl) methane, 1, 1-bis (4-cyanooxyphenyl) ethane, 1,1-bis (4-cyanoxyphenyl) propane, 2,2-bis (4-cyanoxyphenyl) propane, 2,2 -Bis (4-cyanooxy-3-methylphenyl) propane, 2,2-bis (2-cyanoxy-5-biphenyl) propane, 2,2-bis (4-cyanoxybenzene Hexafluoropropane, 2,2-bis (4-cyanooxy-3,5-dimethylbenzene) ) Propane, 1,1-bis (4-cyanooxyphenyl) butane, 1,1-bis (4-cyanoxyphenyl) isobutane, 1,1-bis (4-cyanoxybenzene) ) Pentane, 1,1-bis (4-cyanooxyphenyl) -3-methylbutane, 1,1-bis (4-cyanoxyphenyl) -2-methylbutane, 1 , 1-bis (4-cyanooxyphenyl) -2,2-dimethylpropane, 2,2-bis (4-cyanooxyphenyl) butane, 2,2-bis (4-cyanooxy Phenyl) pentane, 2,2-bis (4-cyanooxyphenyl) hexane, 2,2-bis (4-cyanoxyphenyl) -3-methylbutane, 2,2- Bis (4-cyanooxyphenyl) -4-methylpentane, 2,2-bis (4-cyanooxyphenyl) -3,3-dimethylbutane, 3,3-bis (4 -Cyanooxyphenyl) hexane, 3,3-bis (4-cyanoxyphenyl) heptane, 3,3-bis (4-cyanoxyphenyl) octane, 3,3-bis ( 4-cyanoxyphenyl) -2-methylpentane, 3,3-bis (4-cyanoxyphenyl) -2-methylhexane, 3,3-bis (4-cyanoxybenzene) Yl) -2,2-dimethylpentane, 4,4-bis (4-cyanoxyphenyl) -3-methylheptane, 3,3-bis (4-cyanoxyphenyl)- 2-methylheptane, 3,3-bis (4-cyanoxyphenyl) -2,2-dimethylhexane, 3,3-bis (4-cyanoxyphenyl) -2,4 -Dimethylhexane, 3,3-bis (4-cyanooxyphenyl) -2,2,4-trimethylpentane, 2,2-bis (4-cyanooxybenzene) ) -1,1,1,3,3,3-hexafluoropropane, bis (4-cyanooxyphenyl) phenylmethane, 1,1-bis (4-cyanoxyphenyl) -1- Phenylethane, bis (4-cyanooxyphenyl) biphenylmethane, 1,1-bis (4-cyanooxyphenyl) cyclopentane, 1,1-bis (4-cyanoxyphenyl) ) Cyclohexane, 2,2-bis (4-cyanooxy-3-isopropylphenyl) propane, 1,1-bis (3-cyclohexyl-4-cyanoxyphenyl) cyclohexane, Bis (4-cyanooxyphenyl) diphenylmethane, bis (4-cyanooxyphenyl) -2,2-dichloroethylene, 1,3-bis [2- (4-cyanoxyphenyl) ) -2-propyl] benzene, 1,4-bis [2- (4-cyanoxyphenyl) -2-propyl] benzene, 1,1-bis (4-cyanoxyphenyl) -3 , 3,5-trimethylcyclohexane, 4- [bis (4-cyanoxyphenyl) methyl] biphenyl, 4,4-dicyanobenzophenone, 1,3-bis (4 -Cyanooxyphenyl) -2-propen-1-one, bis (4-cyanooxyphenyl) ether, bis (4-cyanooxyphenyl) sulfide, bis (4-cyanoxyphenyl) ) 碸, 4-cyanooxybenzoic acid-4-cyanooxyphenyl ester (4-cyanooxyphenyl-4-cyanooxybenzoate), bis- (4-cyanooxyphenyl) carbonic acid Ester, 1,3-bis (4-cyanooxyphenyl) adamantane, 1,3-bis (4-cyanooxyphenyl) -5,7-dimethyladamantane, 3,3-bis ( 4-cyanooxyphenyl) isobenzofuran- 1 (3H) -one (cyanoester of phenolphenolphthalein), 3,3-bis (4-cyanooxy-3-methylphenyl) isobenzofuran-1 (3H) -one (o-cresolphenolphthalein Cyanate ester), 9,9'-bis (4-cyanooxyphenyl) fluorene, 9,9-bis (4-cyanoxy-3-methylphenyl) fluorene, 9,9-bis ( 2-cyanooxy-5-biphenyl) pyrene, ginseng (4-cyanooxyphenyl) methane, 1,1,1-ginseng (4-cyanoxyphenyl) ethane, 1,1,3 -Ginseng (4-cyanooxyphenyl) propane, α, α, α'-Ginseng (4-cyanooxyphenyl) -1-ethyl-4-isopropylbenzene, 1,1,2,2 -4- (4-cyanooxyphenyl) ethane, 4- (4-cyanooxyphenyl) methane, 2,4,6-ginseng (N-methyl-4-cyanooxyaniline) -1, 3,5-tri, 2,4-bis (N-methyl-4-cyanoanilide) -6- (N-methylaniline) -1,3,5-tri, bis (N-4 -Cyanooxy-2-methylphenyl) -4,4'-oxydiphthalimide, bis (N-3-cyanooxy-4-methylphenyl) -4,4 '-Oxydiphthalimide, bis (N-4-cyanoxyphenyl) -4,4'-oxydiphthalimide, bis (N-4-cyanooxy Methyl-2-methylphenyl) -4,4 '-(hexafluoroisopropylidene) diphthalimidine, ginseng (3,5-dimethyl-4-cyanooxybenzyl) Isocyanurate, 2-phenyl-3,3-bis (4-cyanooxyphenyl) benzyl Lactamamine, 2- (4-methylphenyl) -3,3-bis (4-cyanooxyphenyl) benzylmethamamine, 2-phenyl-3,3-bis (4-cyanooxy Methyl-3-methylphenyl) benzamidine, 1-methyl-3,3-bis (4-cyanooxyphenyl) indololin-2-one, and 2-phenyl-3, 3-bis (4-cyanooxyphenyl) indololin-2-one.

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

Moreover, as another specific example of the cyanate compound represented by the said General formula (9), a phenol novolak resin and a cresol novolak resin (Phenol, an alkyl-substituted phenol, or a halogen-substituted phenol and a formalin may be substituted according to a well-known method. Formaldehyde compounds such as forest and paraformaldehyde are obtained by reaction in an acidic solution), phenol novolac resin (made by reacting hydroxybenzaldehyde and phenol in the presence of an acidic catalyst), novolac resin (made by using a fluorenone compound with 9,9-bis (hydroxyaryl) fluorenes obtained by reaction in the presence of acid catalysts), phenolaralkyl resins, cresol aralkyl resins, naphthol aralkyl resins and biphenylaralkyl resins ( According to a known method, Ar _4- (CH ₂ Y) ₂ (Ar ₄ represents a phenyl group, and Y represents a halogen atom. The same applies to the following paragraphs.) The dihalomethyl compound and phenol compound represented by acid contact Obtained by reaction with or without catalyst, by reacting a bis (alkoxymethyl) compound represented by Ar _4- (CH ₂ OR) ₂ with a phenol compound in the presence of an acidic catalyst, or by making Ar _4- (CH ₂ OH) ₂ represented by the bis (hydroxymethyl) compound and a phenol compound in an acidic catalyst It is obtained by the following reaction, or obtained by polycondensing an aromatic aldehyde compound, an aralkyl compound, and a phenol compound), and a phenol-modified xylene formaldehyde resin (according to a known method, the xylene formaldehyde resin and the phenol compound are reacted in an acidic catalyst. Obtained by reacting in the presence of), modified naphthalene formaldehyde resin (obtained by reacting naphthalene formaldehyde resin with a hydroxy-substituted aromatic compound in the presence of an acidic catalyst in accordance with a known method), phenol-modified dicyclopentadiene resin, Phenol resins with a poly (naphthalene ether) structure (obtained by dehydration condensation of a polyvalent hydroxynaphthalene compound having two or more phenolic hydroxyl groups in one molecule in the presence of a basic catalyst according to a known method) And obtained by performing cyanation with the same method as above, and the prepolymers and the like. They are not particularly limited. These cyanate ester compounds can be used individually by 1 type or in mixture of 2 or more types.

Among them, phenol novolac type cyanate compound, naphthol aralkyl type cyanate compound, biphenylaralkyl type cyanate compound, naphthyl ether type cyanate compound, xylene resin type cyanate compound 2. An adamantane skeleton type cyanate compound is preferable, and a naphthol aralkyl type cyanate compound is particularly preferable in terms of maintaining excellent heat resistance and obtaining excellent plating adhesion.

The manufacturing method of these cyanate ester compounds is not specifically limited, A well-known method can be used. Examples of this production method include a method of obtaining or synthesizing a hydroxyl-containing compound having a desired skeleton, and modifying the hydroxyl group by a known method to form a cyanate. A method for cyanating a hydroxy group, for example, a method described in Ian Hamerton, "Chemistry and Technology of Cyanate Ester Resins," Blackie Academic & Professional.

The hardened resin using these cyanate compounds has excellent characteristics such as glass transition temperature, low thermal expansion, and plating adhesion.

The content of the cyanate ester compound in the resin composition of this embodiment is not particularly limited, and considering the viewpoint of obtaining better plating adhesion and heat resistance, it is preferably 0.01 parts by mass relative to 100 parts by mass of the resin solid content. ~ 50 parts by mass, more preferably 0.05 parts by mass to 40 parts by mass, still more preferably 0.1 parts by mass to 20 parts by mass, and even more preferably 0.2 parts by mass to 5 parts by mass.

<Phenol resin> A phenol resin may be a phenol resin having two or more hydroxyl groups in one molecule, and generally known ones can be used. 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 phenol resin, propylene oxide phenol Resin, aralkyl novolac phenol resin, biphenylaralkyl phenol resin, cresol novolac phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, anthracene Phenol resin, naphthalene skeleton modified novolac phenol resin, phenol aralkyl phenol resin, naphthol aralkyl phenol resin, dicyclopentadiene phenol resin, biphenyl phenol resin, alicyclic phenol There are no particular restrictions on resins, polyol-type phenol resins, phosphorus-containing phenol resins, phenol resins containing polymerizable unsaturated hydrocarbon groups, and hydroxyl-containing silicone resins. Among these phenol resins, biphenylaralkyl-type phenol resin, naphthol-aralkyl-type phenol resin, phosphorus-containing phenol resin, and hydroxyl-containing silicone resin are preferable from the viewpoint of flame retardancy. These phenol resins can be used individually by 1 type or in mixture of 2 or more types as appropriate.

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

<Oxetane resin> As the oxetane resin, generally known ones can be used. For example: oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane Alkyloxetane such as cyclobutane, 3-methyl-3-methoxymethyloxetane, 3,3-bis (trifluoromethyl) perfluorooxetane, 2 -Chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl-type oxetane, OXT-101 (manufactured by East Asia Synthetic, trade name), OXT-121 (East Asia Synthetic System, trade name), etc., without special restrictions. One of them may be used or two or more of them may be appropriately mixed.

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

<Benzo Compounds> Benzo As long as the compound is two or more dihydrobenzo in one molecule A ring compound is sufficient, and generally known ones can be used. Example: Bisphenol A benzo BA-BXZ (manufactured by Konishi Chemical Co., Ltd.) bisphenol F type benzo BF-BXZ (manufactured by Konishi Chemical, trade name), bisphenol S benzo BS-BXZ (manufactured by Konishi Chemical, trade name), phenol-phenolphthalein type benzo Etc., but without special restrictions. One of them may be used alone or two or more of them may be appropriately mixed.

Benzo The content of the 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. Benzo When the content of the compound is within the above range, the heat resistance tends to be further improved.

<Epoxy resin> In the resin composition of this embodiment, in order to improve the heat resistance of a hardened | cured material, you may use together the epoxy resin different from the biphenyl aralkyl type epoxy resin (A) shown by said (1). Such an epoxy resin is different from the aforementioned epoxy resin (A), and is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. Specific examples thereof include, for example, bisphenol A 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, xylenol novolac epoxy resin, polyfunctional phenol epoxy resin, naphthalene epoxy resin, naphthalene skeleton modified phenolic Varnish-type epoxy resin, naphthyl ether-type epoxy resin, phenol aralkyl-type epoxy resin, anthracene-type epoxy resin, trifunctional phenol-type epoxy resin, 4-functional phenol-type epoxy resin, triglycidyl Isocyanurate, propylene oxide epoxy resin, alicyclic epoxy resin, dicyclopentadiene novolac epoxy resin, biphenol novolac epoxy resin, phenol aralkyl novolac epoxy resin Epoxy resin, naphthol aralkyl novolac epoxy resin, aralkyl novolac epoxy resin, naphthol aralkyl epoxy resin, dicyclopentadiene epoxy resin, polyol ring Oxygen resins, phosphorus-containing epoxy resins, propylene oxide amines, and double bonds such as butadiene Compounds obtained by oxidation, compounds obtained by the reaction of hydroxyl-containing silicone resins with epichlorohydrin, and halides of these.

Among them, one or more selected from the group consisting of a naphthalene-type epoxy resin, a polyfunctional phenol-type epoxy resin, and a naphthalene-type epoxy resin is preferred, and a naphthalene-type epoxy resin is more preferred. By containing such a type of epoxy resin, developability and plating adhesion tend to be further improved. If a naphthalene-type epoxy resin uses a resin represented by the following formula (5), the developability and plating adhesion are further improved, which is preferable. A commercially available product can be used for this epoxy resin, and HP-4710 (trade name) manufactured by DIC Corporation is mentioned. Since the naphthalene-type epoxy resin represented by the following formula (5) is low-molecular and multifunctional, it has excellent solubility in a developing solution. Therefore, it is considered that a resin composition excellent in developability can be obtained by using it in combination with a biphenylaralkyl-type epoxy resin (A).

［Hua 19］

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

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

<Thermal hardening accelerator (H)> In the resin composition of this embodiment, a thermal hardening accelerator (H) (also referred to as a component (H)) may be used within a range that does not impair the characteristics of this embodiment. The heat curing accelerator (H) used in this embodiment is not particularly limited, and examples thereof include benzamidine peroxide, laurel peroxide, acetamidine peroxide, p-chloropermanium peroxide, and diperoxyphthalate. Examples of organic peroxides such as tert-butyl esters; azo compounds such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine , 2-N-ethylaniline ethanol, tri-n-butylamine, pyridine, quinoline, N-methylline, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine, etc. Tertiary amines; phenols such as phenol, xylenol, cresol, resorcinol, catechol, etc .; lead naphthenate, lead stearate, zinc naphthenate, zinc caprylate, tin oleate, malic acid Organometallic salts such as dibutyltin, manganese naphthenate, cobalt naphthenate, iron acetoacetate; those organic metal salts dissolved in hydroxy-containing compounds such as phenol and bisphenol; tin chloride, chloride Inorganic metal salts such as zinc and aluminum chloride; dioctyltin oxide, other alkyltin, alkyltin oxide and other organic tin compounds; 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole 1-benzyl Imidazole compounds such as 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 preferable in terms of heat resistance. , 2-ethyl-4-methylimidazole has high reactivity with biphenylaralkyl-type epoxy resin (A), compound (C), and compound (D), and it is more desirable to obtain better heat resistance. ideal.

These thermosetting accelerators can be used individually by 1 type or in mixture of 2 or more types suitably. The content of the thermosetting accelerator (H) in the resin composition of this embodiment is not particularly limited, but is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass based on 100 parts by mass of the resin solid content in the resin composition. Serving.

<Organic solvent> The resin composition of this embodiment may contain a solvent as needed. For example, if an organic solvent is used, the viscosity of the resin composition can be adjusted. The type of the solvent is not particularly limited as long as it dissolves part or all of the resin in the resin composition. Specific examples thereof are not particularly limited, for example: ketones such as acetone, methyl ethyl ketone, methylcythreon; aromatic hydrocarbons such as toluene and xylene; fluorenamines such as dimethylformamide; propylene glycol monomethyl ether and its ethyl Acid ester. These organic solvents may be used singly or in combination of two or more kinds as appropriate.

<Other components> In the resin composition of this embodiment, various properties such as thermosetting resins, thermoplastic resins and oligomers, elastomers, etc., which have not been listed so far, can be used in a range that does not impair the characteristics of this embodiment. Molecular compounds; flame retardant compounds not listed so far; additives, etc. They are not limited as long as they are general users. Examples of flame retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine, Ring compounds, phosphoric acid ester compounds of phosphorus compounds, aromatic condensed phosphates, halogen-containing condensed phosphates, and the like. Examples of the additives include ultraviolet absorbers, antioxidants, fluorescent brighteners, light sensitizers, dyes, pigments, tackifiers, lubricants, defoamers, surface modifiers, gloss agents, and polymerization inhibitors. These components can be used individually by 1 type or in mixture of 2 or more types suitably. The content of the other components in the resin composition of this embodiment is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.

<The manufacturing method of a resin composition> The resin composition of this embodiment is a biphenyl aralkyl-type epoxy resin (A) represented by the said Formula (1), a light hardening initiator (B), the said Compounds (D) with ethylenically unsaturated groups other than the compounds (C) and (C) components represented by formula (2), and optionally maleimide compounds (E), fillers (F), compounds (G) and other ingredients are appropriately mixed to prepare. The resin composition of this embodiment is suitably used as a varnish when manufacturing the resin sheet of the present invention described later.

The manufacturing method of the resin composition of this embodiment is not specifically limited, For example, the method of mixing each said component with a solvent in order and fully stirring.

When manufacturing a resin composition, if necessary, a well-known process (stirring, mixing, kneading process, etc.) is performed for dissolving or dispersing each component uniformly. Specifically, the dispersibility of the inorganic filler (G) with respect to the resin composition can be improved by using a stirring tank equipped with a stirrer having an appropriate stirring ability and performing a stirring dispersion treatment. For the above stirring, mixing, and kneading processes, for example, a stirring device such as an ultrasonic homogenizer for dispersing purpose, a three-roller, a ball mill, a bead mill, or a sand mill may be used for mixing purpose, or a revolution or self-transformation A known device such as a mixing device is appropriately used. Moreover, when preparing the resin composition of this embodiment, an organic solvent can be used as needed. The type of the organic solvent is not particularly limited as long as it dissolves the resin in the resin composition, and specific examples thereof are as described above.

<Applications> The resin composition of this embodiment can be used for applications requiring an insulating resin composition, and is not particularly limited. It can be used for insulating films such as photosensitive films, photosensitive films with a support, and prepregs, Circuit board (laminate board application, multilayer printed circuit board application, etc.), solder resist, underfill material, die-bonding material, semiconductor sealing material, hole landfill resin, parts landfill resin, etc. Among them, a resin composition and a solder resist for an insulating layer of a multilayer printed circuit board are suitably used.

<Resin sheet> The resin sheet of this embodiment includes a support and a resin composition layer formed on the surface of the support and containing the resin composition of this embodiment. The resin composition is coated on the support. Resin sheet with support on one or both sides. The resin sheet can be produced by coating a resin composition on a support and drying it.

The support used for the resin sheet of this embodiment is not particularly limited, and a known product can be used, and a resin film is preferred. Resin film, such as: polyimide film, polyimide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polyethylene naphthalate film, polyvinyl alcohol film, resin film such as triethylacetate film. Among them, PET film is preferred.

In order that the said resin film may peel easily from a resin composition layer, it is suitable to use the surface coated with the release agent. The thickness of the resin film is preferably in a range of 5 μm to 100 μm, and more preferably in a range of 10 μm to 50 μm. If the thickness is less than 5 μm, peeling of the support before development tends to tend to break the support, and if the thickness exceeds 100 μm, the resolution when exposed from the support tends to decrease.

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

Furthermore, the resin composition layer of the resin sheet in this embodiment may be protected by a protective film. The resin composition layer side is protected by a protective film to prevent dirt or the like from adhering to the surface of the resin composition layer, or to prevent scratches. As the protective film, a film made of the same material as the resin film can be used. The thickness of the protective film is not particularly limited, and a range of 1 μm to 50 μm is preferable, and a range of 5 μm to 40 μm is more preferable. When the thickness is less than 1 μm, the handleability of the protective film tends to decrease, and when it exceeds 50 μm, the inexpensiveness tends to be poor. In addition, the protective film is preferably relative to the adhesive force between the resin composition layer and the support, and the adhesive force between the resin composition layer and the protective film is preferably smaller.

The manufacturing method of the resin sheet of this embodiment is not particularly limited, for example, a method of manufacturing a resin sheet by applying the resin composition of this embodiment to a support such as a PET film and removing the organic solvent by drying. The coating can be performed using, for example, a roll coater, a comma coater, a gravure coater, a die coater, a rod coater, a lip coater, a knife coater, A known method such as a squeeze coater is used. The drying can be performed by, for example, 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 considered to be 5 mass% or less relative to the total mass of the resin composition layer in consideration of preventing the diffusion of the organic solvent in a subsequent step. Considering the thickness of the resin composition layer with respect to the support, from the viewpoint of improving the operability, the thickness of the resin composition layer of the resin sheet is preferably 1.0 μm or more. In addition, considering the viewpoint of improving transmittance and improving developability, 300 μm or less is preferable.

The resin sheet of this embodiment can be used as an interlayer insulation layer of a multilayer printed circuit board.

<Multilayer printed wiring board> The multilayer printed wiring board of this embodiment is provided with the interlayer insulation layer containing the resin composition of this embodiment, For example, the said resin sheet can be superimposed and hardened. Specifically, it can be manufactured by the following method.

(Laminating step) The resin composition layer side of the resin sheet of this embodiment is laminated on one or both sides of a circuit board using a vacuum laminator. Circuit substrates include, for example, glass epoxy substrates, metal substrates, ceramic substrates, silicon substrates, semiconductor sealing resin substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. Here, the circuit board refers to a board in which a patterned conductive layer (circuit) is formed on one or both sides of the substrate as described above. In addition, in a multilayer printed circuit board in which a conductor layer and an insulating layer are alternately laminated, a substrate of a conductor layer (circuit) on one side or both sides of which is the outermost layer of the printed circuit board and subjected to pattern processing is also included herein. 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 the resin sheet and the circuit board are preheated if necessary, and the resin composition layer is pressed and heated to the circuit board while being pressed. In the resin sheet of this embodiment, it is preferable to use a method of laminating on a circuit board under reduced pressure by using a vacuum layer method.

The conditions of the lamination step are not particularly limited. For example, the crimping temperature (laminating temperature) is preferably 50 ° C to 140 ° C, the crimping pressure is preferably 1kgf / cm ² to 15kgf / cm ² , and the crimping time is preferably It is preferable to perform lamination under a reduced pressure of 5 seconds to 300 seconds and an air pressure of 20 mmHg or less. The lamination step may be a batch method or a continuous method using a roller. The vacuum layer method can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators, such as Nikko-Materials (shares) two-stage additional laminators.

(Exposure Step) After the resin sheet is provided on the circuit board in the lamination step, a predetermined portion of the resin composition layer is irradiated with active energy rays, and an exposure step is performed to harden the resin composition layer in the irradiation portion. Active energy rays can be irradiated through a mask pattern, or a direct drawing method that directly irradiates active energy rays can be used.

Active energy rays, such as ultraviolet rays, visible rays, electron beams, X-rays, etc., especially ultraviolet rays are preferred. The amount of ultraviolet radiation is approximately 10 mJ / cm ² to 1000 mJ / cm ² . Exposure methods using a mask pattern include a contact exposure method in which a mask pattern is closely adhered to a multilayer printed circuit board, and a non-contact exposure method in which the light is not closely adhered and exposed using parallel light rays. When a support is present on the resin composition layer, the support may be exposed from the support, or the support may be peeled and exposed.

(Developing step) When a support is present on the resin composition layer after the exposure step, the support is removed by wet development to remove uncured portions (unexposed portions) and developed to form a pattern of an insulating layer.

In the case of the above-mentioned wet development, the developing solution is not particularly limited as long as it can selectively dissolve the unexposed portion, and a developing solution such as an alkaline aqueous solution, an aqueous developing solution, or an organic solvent can be used. In this embodiment, it is particularly preferable to perform the development step using an alkaline aqueous solution. These developers can be used alone or in combination of two or more. The development method can be performed by a known method such as spray coating, shaking dipping, brushing, and scraping.

The alkaline aqueous 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 4-borate, ammonia, amines, and the like.

The concentration of the alkaline aqueous solution is preferably 0.1% by mass to 60% by mass relative to the entire amount of the developing solution. The temperature of the alkaline aqueous solution can be adjusted in accordance with the developability. In addition, these alkaline aqueous solutions can be used individually or in combination of 2 or more types.

In the pattern formation of this embodiment, if necessary, two or more of the above-mentioned development methods may be used in combination. The development methods include immersion method, immersion method, spray method, high-pressure spray method, brushing, scraping, etc. The high-pressure spray method is ideal because it can improve the resolution. The spraying pressure when the spraying method is adopted should preferably be 0.02MPa ~ 0.5MPa.

(Post-baking step) A post-baking step is performed after the development step described above to form an insulating layer (hardened material). The post-baking step may include an ultraviolet irradiation step using a high-pressure mercury lamp, a heating step using a clean oven, or the like, and they may be used in combination. When irradiating ultraviolet rays, the irradiation amount can be adjusted as needed. For example, irradiation can be performed with an irradiation amount of about 0.05 J / cm ² to 10 J / cm ² . The heating conditions can be appropriately selected according to the type and content of the resin component in the resin composition, and it is preferably performed at 150 ° C to 220 ° C for 20 minutes to 180 minutes, and more preferably at 160 ° C to 200 ° C. Select from 30 minutes to 150 minutes.

(Plating Step) Then, a conductive layer is formed on the surface of the insulating layer by dry plating or wet plating. For the dry plating, a known method such as a vapor deposition method, a sputtering method, or an ion plating method can be used. In the vapor deposition method (vacuum vapor deposition method), for example, a support can be placed in a vacuum container, and the metal can be heated and evaporated to form a metal film on the insulating layer. In the sputtering method, for example, a support can be placed in a vacuum container, a passive gas such as argon can be introduced, a DC voltage can be applied, and the free passive gas can collide with the target metal, and the punched metal can be used on the insulating layer. A metal film is formed.

In the case of wet plating, the surface of the formed insulating layer is sequentially subjected to a swelling treatment using a swelling liquid, a roughening treatment using an oxidizing agent, and a neutralizing treatment using a neutralizing solution to sequentially surface the insulating layer. Roughening. The swelling treatment using the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 ° C to 80 ° C for 1 minute to 20 minutes. Examples of the swelling solution include an alkaline solution, and examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Commercially available swelling liquids include, for example, Appdes (registered trademark) MDS-37 manufactured by Uemura Industries Co., Ltd. and the like.

The roughening treatment by the oxidant is performed by immersing the insulating layer in the oxidant solution at 60 ° C to 80 ° C for 5 minutes to 30 minutes. Oxidizing agents, such as alkaline permanganate solution obtained by dissolving potassium permanganate, sodium permanganate in aqueous sodium hydroxide solution, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, etc. The concentration of permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by mass. Commercially available oxidants include, for example, alkaline permanganic acid solutions such as Appdes (registered trademark) MDE-40, Appdes (registered trademark) manufactured by Uemura Industries, Ltd. The neutralization treatment using the neutralization solution is performed by immersing in the neutralization solution at 30 ° C to 50 ° C for 1 minute to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution. Commercial products include Appdes (registered trademark) MDN-62 manufactured by Uemura Industries.

Next, electroless plating and electrolytic plating are combined to form a conductor layer. In addition, the conductive layer may form a plating resist in a reverse pattern, and the conductive layer may be formed only by electroless plating. For the subsequent pattern formation method, for example, a subtractive method and a semi-additive method can be used.

<Semiconductor Device> The semiconductor device of this embodiment includes an interlayer insulating layer containing the resin composition of this embodiment, and can be specifically manufactured by the following method. A semiconductor device can be manufactured by mounting a semiconductor wafer at a conducting position of the multilayer printed circuit board of this embodiment. Here, the conducting point is where the electric signal is transmitted in the multilayer printed circuit board, and its position can be on the surface or in the landfill. The semiconductor wafer is not particularly limited as long as it is an electric circuit element using a semiconductor as a material.

The method for mounting a semiconductor wafer when manufacturing the semiconductor device of this embodiment is not particularly limited as long as the semiconductor wafer will function effectively. Specific examples include wire bonding methods, flip-chip mounting methods, and bumpless additions. Mounting method using a layer (BBUL), mounting method using an anisotropic conductive film (ACF), mounting method using a non-conductive film (NCF), and the like.

Moreover, a semiconductor device can also be manufactured by laminating the resin sheet of this embodiment on a semiconductor wafer. After lamination, it can be manufactured by the same method as the aforementioned multilayer printed wiring board. [Example]

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

[Synthesis Example 1] (Synthesis of cyanate ester compound) 300 g (1.28 mol based on OH group) and 194.6 g (1.92 of triethylamine) of 1-naphthol aralkyl resin (produced by Nippon Steel & Sumikin Chemical Co., Ltd.) mol) (1.5 mol with respect to 1 mol of hydroxyl group) was dissolved in 1800 g of methylene chloride, and was designated as solution 1. 125.9 g (2.05 mol) of cyanogen chloride (1.6 mol relative to 1 mol of hydroxyl group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol relative to 1 mol of hydroxyl group), and 1205.9 water g Keep the liquid temperature at -2 ~ -0.5 ℃ under stirring, and take solution 1 for 30 minutes. After the solution 1 was added, the solution was stirred at the same temperature for 30 minutes, and the solution was obtained by dissolving 65 g (0.64 mol) of triethylamine (0.5 mol relative to 1 mol of hydroxyl group) in 65 g of dichloromethane over 10 minutes. 2). After the solution 2 was added, it was stirred at the same temperature for 30 minutes to complete the reaction. After that, the reaction solution was left to stand and separated into an organic phase and an aqueous phase. The obtained organic phase was washed 5 times with 1300 g of water. The conductivity of the 5th water washing wastewater was 5 μS / cm. It was confirmed that the ionic compounds to be removed were sufficiently removed by washing with water. The washed organic phase was concentrated under reduced pressure, and finally concentrated and dried at 90 ° C for 1 hour to obtain 331 g of the desired naphthol aralkyl cyanate compound (SNCN) (orange sticky substance). The mass average molecular weight Mw of the obtained SNCN was 600. The IR spectrum of SNCN shows an absorption of 2250 cm ^-1 (cyanate ester group), and does not show an absorption of a hydroxyl group.

[Example 1] (Production of resin composition and resin sheet) A biphenylaralkyl type epoxy resin (A) represented by the formula (1) was used as a biphenylaralkyl type epoxy resin (formula (1) N in the formula is 1 to 3. 22.4 parts by mass of NC3000L (trade name), manufactured by Nippon Kayaku Co., Ltd., and 2-benzyl-2-dimethylamino-1- as a light curing initiator (B) 6.5 parts by mass of (4-phosphonophenyl) -butanone-1 (Irgacure (registered trademark) 369, manufactured by BASF Japan (stock)), a propylene glycol monomethyl ester of TrisP-PA epoxy acrylate compound as compound (C) Ether acetate (hereinafter sometimes referred to as PGMEA) solution (KAYARAD (registered trademark) ZCR-6007H, 65% by mass of non-volatile content, acid value: 70mgKOH / g, manufactured by Nippon Kayaku Co., Ltd.) Volatile component conversion: 50.4 parts by mass), and dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Nippon Kayakusho (stock)) as the ethylenically unsaturated compound (D) other than (C) component )) 17.4 parts by mass, 3.3 parts by mass as a maleimide compound (BMI-2300 (trade name), manufactured by Daiwa Chemical Industry Co., Ltd.) as a maleimide compound (E), as a filler (F ) Siloxane-treated silica (Hereinafter sometimes referred to as MEK) slurry (SC2050MB (trade name), average particle size 0.5 μm, non-volatile content 70% by mass, manufactured by Admatechs (stock)) 71.4 parts by mass (in terms of non-volatile content, 50 parts by mass) Blend and stir with an ultrasonic homogenizer to obtain a varnish (solution of resin composition). These varnishes were coated on a PET film (Unipeel (registered trademark) TR1-38, Unitika (trade name), trade name)) with a thickness of 38 μm using an automatic coating device (PI-1210, manufactured by Tester Sangyo). It heat-dried at 80 degreeC for 7 minutes, and obtained the resin sheet which used PET film as a support and the thickness of the resin composition layer was 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).

(Production of the inner layer circuit board) The glass cloth substrate BT resin on which the inner layer circuit has been formed is a copper-clad laminated board (copper foil thickness 18 μm, thickness 0.2 mm, CCL (registered trademark) made by Mitsubishi Gas Chemical Co., Ltd.)- Both sides of HL832NS) were roughened with a copper surface made of Mec (strand) CZ8100 to obtain an inner-layer circuit board.

(Production of laminated body for evaluation) The resin surface of the resin sheet was placed on an inner-layer circuit board, and vacuum was applied for 30 seconds (5.0 MPa or less) using a vacuum laminator (manufactured by Nikko Materials), and then the pressure was applied. 10 kgf / cm ² was laminated for 30 seconds at a temperature of 70 ° C. Then, lamination was performed at a pressure of 10 kgf / cm ² and a temperature of 70 ° C. for 60 seconds to obtain a laminate obtained by laminating an inner circuit board, a resin composition layer, and a support. An exposure step of irradiating the obtained laminate with 200 mJ / cm ² of ultraviolet rays was performed, the support was peeled off, developed with a 1% by mass sodium carbonate aqueous solution, and then an exposure step of irradiating with 1000 mJ / cm ² of ultraviolet rays was performed. After the 120-minute heat treatment, after the baking step, it was used as an evaluation laminate.

(Production of hardened material for evaluation) The resin sheet was irradiated with 200 mJ / cm ² of ultraviolet rays, and then exposed to 1000 mJ / cm ² of ultraviolet rays. The heating step was performed at 180 ° C for 120 minutes, and the support was peeled off. Body as a hardened body for evaluation.

[Example 2] As a component (A), 21.9 parts by mass of a biphenylaralkyl-type epoxy resin (NC3000L (trade name), manufactured by Nippon Kayaku Co., Ltd.) was used as a photocuring initiator (B). 6.5 parts by mass of 2-benzyl-2-dimethylamino-1- (4-phosphonophenyl) -butanone-1 (Irgacure (registered trademark) 369, manufactured by BASF Japan (stock)) as a compound (C ) TrisP-PA epoxy acrylate compound PGMEA solution (KAYARAD (registered trademark) ZCR-6007H, non-volatile content 65% by mass, acid value: 70mgKOH / g, manufactured by Nippon Kayaku Co., Ltd.) 77.5 parts by mass (according to 50.4 parts by mass in terms of non-volatile content), and dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Nippon Kadaku (Japanese Chemicals) (Manufactured by the company) 17.4 parts by mass, 3.3 parts by mass of the maleimide compound (BMI-2300 (trade name), manufactured by Daiwa Chemical Industry Co., Ltd.) as the maleimide compound (E), as a filler ( F) 71.4 parts by mass of MEK slurry (SC2050MB (trade name), average particle size 0.5 μm, non-volatile content 70% by mass, manufactured by Admatechs (stock)) of silicon dioxide treated with silicon dioxide (equivalent to non-volatile content) 50 quality ), As Synthesis Example Compound (G) of an isocyanate compound to obtain the SNCN0.5 parts by mass was blended, stirred with ultrasonic homogenizer, to obtain a varnish (resin solution of the composition). These varnishes were coated on a PET film (Unipeel (registered trademark) TR1-38, Unitika (trade name), trade name)) with a thickness of 38 μm using an automatic coating device (PI-1210, manufactured by Tester Sangyo). Heat drying was performed at 80 ° C. for 7 minutes to obtain a resin sheet having a PET film as a support and a resin composition layer having a thickness of 30 μm. Using this resin sheet, it carried out similarly to Example 1, and obtained the laminated body for evaluation, and the hardened | cured material for evaluation.

[Example 3] As a component (A), 21.9 parts by mass of a biphenylaralkyl-type epoxy resin (NC3000L (trade name), manufactured by Nippon Kayaku Co., Ltd.) was used as a photocuring initiator (B). 6.5 parts by mass of bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide (Irgacure (registered trademark) 819, manufactured by BASF Japan (stock)) as a TrisP-PA ring of compound (C) 77.5 parts by mass of a PGMEA solution of an oxyacrylate compound (KAYARAD (registered trademark) ZCR-6007H, 65% by mass of nonvolatile matter, acid value: 70mgKOH / g, manufactured by Nippon Kayaku Co., Ltd.) 50.4 parts by mass), and dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayakusho Co., Ltd.) as an ethylenically unsaturated compound (D) other than (C) component 17.4 mass Parts, 3.3 parts by mass of a maleimide compound (BMI-2300 (trade name), manufactured by Daiwa Chemical Industry Co., Ltd.) as a maleimide compound (E), and a silane oxide as a filler (F) 71.4 parts by mass of MEK slurry (SC2050MB (trade name) with silicon dioxide, average particle diameter of 0.5 μm, non-volatile content of 70% by mass, manufactured by Admatechs (stock), 50 parts by mass of non-volatile content), 0.5 part by mass of the cyanate compound SNCN obtained as Synthesis Example 1 of the compound (G) was blended and stirred with an ultrasonic homogenizer to obtain a varnish (a solution of a resin composition). These varnishes were coated on a PET film (Unipeel (registered trademark) TR1-38, Unitika (trade name), trade name)) with a thickness of 38 μm using an automatic coating device (PI-1210, manufactured by Tester Sangyo). Heat drying was performed at 80 ° C. for 7 minutes to obtain a resin sheet having a PET film as a support and a resin composition layer having a thickness of 30 μm. Using this resin sheet, it carried out similarly to Example 1, and obtained the laminated body for evaluation, and the hardened | cured material for evaluation.

[Example 4] Naphthalene-type epoxy resin (HP-4710 (trade name), manufactured by DIC (Korea) Co., Ltd.) was used as a component (A) of 15.8 parts by mass of Nippon Kayaku Co., Ltd. 6.1 parts by mass of 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide (Irgacure (registered trademark) 819, manufactured by BASF Japan) as a light curing initiator (B) 6.5 parts by mass of a PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H, 65% by mass of non-volatile content, acid value: 70 mgKOH / g, compound (C)) )) 77.5 parts by mass (50.4 parts by mass in terms of non-volatile content), as a compound other than (C), having ethylenically unsaturated compounds (D), dineopentaerythritol hexaacrylate (KAYARAD (registered (Trademark) DPHA, Nippon Kayaku Co., Ltd.) 17.4 parts by mass of a maleimide compound (BMI-2300 (trade name), Yamato Chemical Industry Co., Ltd.) as the maleimide compound (E) 3.3 parts by mass of MEK slurry (SC2050MB (trade name), silicon dioxide-treated silica) as filler (F), average particle diameter of 0.5 μm, 70% by mass of non-volatile content, manufactured by Admatechs (stock), 71.4 parts by mass (Press no 50 parts by mass in terms of hair ingredient conversion), 0.5 parts by mass of the cyanate compound SNCN obtained in Synthesis Example 1 of compound (G) was blended and stirred with an ultrasonic homogenizer to obtain a varnish (solution of resin composition) ). These varnishes were coated on a PET film (Unipeel (registered trademark) TR1-38, Unitika (trade name), trade name)) with a thickness of 38 μm using an automatic coating device (PI-1210, manufactured by Tester Sangyo). Heat drying was performed at 80 ° C. for 7 minutes to obtain a resin sheet having a PET film as a support and a resin composition layer having a thickness of 30 μm. Using this resin sheet, it carried out similarly to Example 1, and obtained the laminated body for evaluation, and the hardened | cured material for evaluation.

[Example 5] As a component (A), 15.8 parts by mass of a biphenylaralkyl-type epoxy resin (NC3000L (trade name), manufactured by Nippon Kayaku Co., Ltd.), and a naphthalene-type epoxy as a component (G) 6.1 parts by mass of a resin (HP-4710 (trade name), manufactured by DIC Corporation), 2,4,6-trimethylbenzyl-diphenyl-oxidation as a light curing initiator (B) 6.5 parts by mass of phosphine (Irgacure (registered trademark) 819, manufactured by BASF Japan (stock)), a PGMEA solution of a TrisP-PA epoxy acrylate compound (CYARAD (registered trademark) ZCR-6007H, non-volatile content) as a compound (C) 65% by mass, acid value: 70mgKOH / g, manufactured by Nippon Kayaku Co., Ltd. 77.5 parts by mass (50.4 parts by mass in terms of non-volatile content), as a compound having an ethylenically unsaturated group other than the component (C) (D) 17.4 parts by mass of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) as a maleimide compound (E) as a maleimide compound (E) 3.3 parts by mass of BMI-2300 (trade name), manufactured by Yamato Chemical Industry Co., Ltd., MEK slurry (SC2050MB (trade name)) of siloxane-treated silica as a filler (F), average particle diameter of 0.5 μm, Non-volatile 70% by mass, manufactured by Admatechs (stock) 71.4 parts by mass (50 parts by mass in terms of nonvolatile content), 0.5 parts by mass of the cyanate compound SNCN obtained as Synthesis Example 1 of the compound (G), 0.2 parts by mass of 2-ethyl-4-methylimidazole (2E4MZ (trade name), manufactured by Shikoku Chemical Co., Ltd.) of the hardening accelerator (H) was blended, and the mixture was stirred with an ultrasonic homogenizer to obtain a varnish ( Resin composition solution). These varnishes were coated on a PET film (Unipeel (registered trademark) TR1-38, Unitika (trade name), trade name)) with a thickness of 38 μm using an automatic coating device (PI-1210, manufactured by Tester Sangyo). Heat drying was performed at 80 ° C. for 7 minutes to obtain a resin sheet having a PET film as a support and a resin composition layer having a thickness of 30 μm. Using this resin sheet, it carried out similarly to Example 1, and obtained the laminated body for evaluation, and the hardened | cured material for evaluation.

[Comparative Example 1] Compound (C) was replaced with bisphenol F-type epoxy acrylate (KAYARAD (registered trademark) ZFR-1553H, 68% by mass of non-volatile content, acid value: 70 mgKOH / g, Nippon Kayaku Co., Ltd. Manufacture) 74.1 parts by mass (50.4 parts by mass in terms of non-volatile content), except that the same procedure as in Example 1 was performed to prepare a varnish, and obtain a resin sheet, a laminate for evaluation, and a cured product for evaluation.

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

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

[Comparative Example 3] A varnish was prepared in the same manner as in Example 1 except that the component (A) was replaced with 22.4 parts by mass of a polyfunctional epoxy resin (1031S (trade name), manufactured by Mitsubishi Chemical Corporation). A resin 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).

［Hua 20］

[Physical property evaluation] The resin sheet, the laminate for evaluation, and the hardened material for evaluation were measured and evaluated by the following methods. The results are shown in Table 1.

<Paintability> The resin surface end of each resin sheet with a support of A4 size was gently pressed with a finger, and the degree of adhesion to the finger was evaluated according to the following criteria. ○: Hardly adhered to fingers. The end of the resin sheet with a support is adhered to a finger, but peels off from the finger when the height is less than 30 mm. ×: Adhesion to fingers. The end of the resin sheet with a support is adhered to a finger, and the floating height is 30 mm or more.

<Heat resistance (glass transition temperature)> A DMA device (Dynamic Viscoelasticity Measurement Device DMAQ800 (trade name) manufactured by TA Instruments Co., Ltd.) was used to heat the evaluation hardened material at 10 ° C / min, and the position of the peak of Loss Modulus was defined as glass transition. Temperature (Tg, ° C).

<Developability> After the development surface of the laminated body for measurement and evaluation is counted from the start of the development step until no residue is visually observed, it is observed with a SEM (scanning electron microscope) (1000 times magnification), and it is evaluated whether There are residues. ：: The time until visually observing the developing residue is 50 sec or less, and there is no developing residue within 30 mm square after SEM observation, and the developability is very excellent. ○: The time until the development residue was not visually observed was more than 50 sec. However, after the SEM observation, there was no development residue within a range of 30 mm square, and the developability was excellent. ×: Development residues exist within a 30 mm square, and the developability is not good.

Wet roughening treatment of conductive hardened material for evaluation and conductor layer plating: The multilayered printed circuit boards obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were electroless copper plating treatments (manufactured by chemical name) : MCD-PL, MDP-2, MAT-SP, MAB-4-C, MEL-3-APEAver. 2) Electroless copper plating of about 0.8 μm is performed, and drying is performed at 130 ° C. for 1 hour. Then, electrolytic copper plating was performed so that the thickness of the plated copper was 18 μm, and drying was performed at 180 ° C. for 1 hour. In this way, a sample having a conductor layer (plated copper) having a thickness of 18 μm formed on the insulating layer was prepared for the following evaluations.

<Plating adhesion (kN / m)> Using the sample prepared according to the above procedure, the adhesion of plated copper was measured three times in accordance with JISC6481, and the average 値 was calculated. The samples that were raised due to the drying after electrolytic copper plating were evaluated using the non-raised portions.

【Table 1】

As can be seen from Table 1, Examples 1 to 5 are excellent in plating adhesion and heat resistance. Among them, Examples 2 to 5 have good heat resistance and plating adhesion, and Examples 3 to 5 are particularly excellent in heat resistance and plating adhesion. The developability of Examples 4 and 5 was also excellent. In contrast, Comparative Examples 1 to 3 had insufficient plating adhesion. Therefore, according to the present invention, a resin composition having excellent plating adhesion, excellent heat resistance and developability, a resin sheet using the composition, a multilayer printed circuit board, and a semiconductor device can be obtained.

no

Claims (14)

A resin composition comprising a biphenylaralkyl-type epoxy resin (A) represented by the following formula (1), a photohardening initiator (B), a compound (C) represented by the following formula (2), and the following Compound (D) having an ethylenically unsaturated group other than compound (C) represented by formula (2); In formula (1), n represents an integer from 0 to 15; ［化 2］ In formula (2), most of R ₁ each independently represent a hydrogen atom or a methyl group, and most of R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent, and most of R ₃ Each independently represents a substituent represented by the following formula (3), a substituent represented by the following formula (4), or a hydroxyl group; ［Chemical 4］ In the formula (4), R ₄ represents a hydrogen atom or a methyl group. For example, the resin composition of the scope of application for a patent further contains a maleimide compound (E). For example, the resin composition in the scope of patent application 1 further contains a filler (F). For example, the resin composition in the first patent application range further contains a compound (G) selected from the group consisting of a cyanate compound, a phenol resin, an oxetane resin, and a benzo The compound and the biphenylaralkyl-type epoxy resin (A) represented by the above (1) are any one or more selected from the group consisting of different epoxy resins. For example, the resin composition of the scope of application for patent No. 1 wherein the acid value of the compound (C) represented by the formula (2) is 30 mgKOH / g or more and 120 mgKOH / g or less. For example, the resin composition of the first patent application range, 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. For example, the resin composition according to item 1 of the application, wherein the compound (D) having an ethylenically unsaturated group is a compound having a (meth) acrylfluorenyl group and / or a compound having a vinyl group. For example, the resin composition of claim 3, wherein the filler (F) is selected from the group consisting of silicon dioxide, boehmite, barium sulfate, polysiloxane powder, fluororesin-based filler, and ethyl carbamate. Any one or more of the group consisting of an ester resin-based filler, an acrylic resin-based filler, a polyethylene-based filler, a styrene-butadiene rubber, and a silicone rubber. For example, the resin composition of the scope of application for a patent further contains a thermosetting accelerator (H). For example, the resin composition of the first patent application scope further contains a naphthalene-type epoxy resin represented by the following formula (5); . For example, the resin composition of the scope of application for a patent, wherein the photohardening initiator (B) contains a phosphine oxide compound represented by the 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 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. A resin sheet has a support and a resin composition as set forth in the scope of patent application No. 1 on the surface of the support. A multilayer printed circuit board having a resin composition as described in the first patent application. A semiconductor device having the resin composition as described in the first patent application.