WO2018003313A1 - Composition de résine, feuille de résine, carte de circuit imprimé multicouche et dispositif semi-conducteur - Google Patents

Composition de résine, feuille de résine, carte de circuit imprimé multicouche et dispositif semi-conducteur Download PDF

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Publication number
WO2018003313A1
WO2018003313A1 PCT/JP2017/018032 JP2017018032W WO2018003313A1 WO 2018003313 A1 WO2018003313 A1 WO 2018003313A1 JP 2017018032 W JP2017018032 W JP 2017018032W WO 2018003313 A1 WO2018003313 A1 WO 2018003313A1
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Prior art keywords
group
resin
resin composition
mass
compound
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PCT/JP2017/018032
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English (en)
Japanese (ja)
Inventor
慎也 喜多村
鈴木　卓也
誠司 四家
Original Assignee
三菱瓦斯化学株式会社
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Application filed by 三菱瓦斯化学株式会社 filed Critical 三菱瓦斯化学株式会社
Priority to CN201780040121.0A priority Critical patent/CN109415489B/zh
Priority to KR1020187035663A priority patent/KR102324899B1/ko
Priority to JP2018524942A priority patent/JP6939784B2/ja
Publication of WO2018003313A1 publication Critical patent/WO2018003313A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
    • C08G59/4261—Macromolecular compounds obtained by reactions involving only unsaturated carbon-to-carbon bindings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/688—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0296—Conductive pattern lay-out details not covered by sub groups H05K1/02 - H05K1/0295
    • H05K1/0298—Multilayer circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers

Definitions

  • the present invention relates to a resin composition, a resin sheet using the resin composition, a multilayer printed wiring board, and a semiconductor device.
  • Thinning of a laminated board used for a multilayer printed wiring board has been actively conducted by downsizing and increasing the density of the multilayer printed wiring board.
  • the insulating layer is also required to be reduced in thickness, and a resin sheet that does not include glass cloth is required.
  • a thermosetting resin is mainly used as a resin composition as a material for the insulating layer, and a hole for obtaining conduction between insulating layers is generally performed by laser processing.
  • the method of forming a conductor circuit by copper plating is common as a method of forming a conductor circuit on an insulating layer.
  • the drilling by laser processing has a problem that the processing time becomes longer as the number of holes becomes higher. Therefore, in recent years, there has been a demand for a resin sheet that can be collectively punched in a development process by using a resin composition that is cured by light or the like and dissolved by development. Furthermore, since the conductor circuit is formed on the insulating layer by copper plating, it is required that the copper plating adherence to the insulating layer is high so that the conductor circuit is not peeled off.
  • Patent Document 1 describes a curable resin composition including a carboxyl group-containing resin including a carboxyl group-containing resin having a novolak skeleton, an inorganic filler, a thermosetting component including a maleimide compound, and a compound having a urethane bond. ing.
  • Patent Document 2 contains an epoxy resin, a curing agent, and a silica component whose silica particles are surface-treated with a silane coupling agent, and does not contain a curing accelerator, or the epoxy resin and the above
  • the curing accelerator is contained in a content of 3.5 parts by weight or less with respect to a total of 100 parts by weight of the curing agent, the average particle diameter of the silica particles is 1 ⁇ m or less, and the silica component per 1 g of the silica particles.
  • An epoxy resin composition in the range of 10 to 80% with respect to the value C (g) per gram of silica particles calculated by the formula (X)) is disclosed. Yes.
  • a cured product using a conventional epoxy resin does not provide sufficient physical properties, and there is a limit to the formation of a protective film and an interlayer insulating layer having high developability and high copper plating adhesion.
  • the cured product obtained from the resin composition described in Patent Document 1 is limited in use to etching resists and solder resists for printed wiring boards, and is excellent in gold plating resistance, but can be used as an interlayer insulating layer. Copper plating adhesion was not sufficient.
  • the present invention has been made in view of the above problems, and when used in a multilayer printed wiring board, a resin composition having excellent coating properties and heat resistance, and excellent developability and copper plating adhesion, It is an object to provide a resin sheet with a support, a multilayer printed wiring board using them, and a semiconductor device.
  • the inventors have prepared a dicyclopentadiene type epoxy resin (A) represented by the following formula (1), a photocuring initiator (B), a compound (C) represented by the following formula (2), and the (C )
  • A dicyclopentadiene type epoxy resin
  • B photocuring initiator
  • C compound represented by the following formula (2)
  • C the resin composition containing a compound (D) having an ethylenically unsaturated group other than the component
  • n represents an integer of 0 to 15).
  • a plurality of R 1 s each independently represent a hydrogen atom or a methyl group, and a plurality of R 2 s each independently have a hydrogen atom or a substituent having 1 carbon atom
  • a plurality of R 3 each independently represents a substituent represented by the following formula (3), a substituent represented by the following formula (4), or a hydroxy group.
  • R 4 represents a hydrogen atom or a methyl group
  • the present invention includes the following contents.
  • [1] In the dicyclopentadiene type epoxy resin (A) represented by the formula (1), the photocuring initiator (B), the compound (C) represented by the formula (2), and the formula (2)
  • the resin composition containing the compound (D) which has ethylenically unsaturated groups other than the compound (C) represented.
  • [2] The resin composition according to [1], further containing a maleimide compound (E).
  • E a maleimide compound
  • [3] The resin composition according to [1] or [2], further including a filler (F).
  • the filler (F) is silica, boehmite, barium sulfate, silicone powder, fluororesin filler, urethane resin filler, acrylic resin filler, polyethylene filler, styrene / butadiene rubber and silicone.
  • R 5 to R 10 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 11 represents an alkyl group having 1 to 20 carbon atoms or 6 to 20 carbon atoms.
  • An aryl group of [12] A resin sheet comprising the support and the resin composition according to any one of [1] to [11] disposed on the surface of the support.
  • a multilayer printed wiring board comprising the resin composition according to any one of [1] to [11].
  • a semiconductor device comprising the resin composition according to any one of [1] to [11].
  • a resin composition that is excellent in plating adhesion, coating properties, heat resistance and developability, and is cured with active energy rays having physical properties suitable for a multilayer printed wiring board, a resin sheet with a support, and The multilayer printed wiring board and semiconductor device used can be provided.
  • the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
  • the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents.
  • the present invention can be appropriately modified within the scope of the gist.
  • (meth) acryloyl group means both “acryloyl group” and the corresponding “methacryloyl group”
  • “(meth) acrylate” means “acrylate” and the corresponding “methacrylate”.
  • (Meth) acrylic acid means both “acrylic acid” and the corresponding "methacrylic acid”.
  • resin solid content or “resin solid content in the resin composition” means a component in the resin composition excluding the solvent and the filler, unless otherwise specified.
  • the term “solid content of 100 parts by mass” means that the total of the components excluding the solvent and filler in the resin composition is 100 parts by mass.
  • the resin composition of this embodiment includes a dicyclopentadiene type epoxy resin (A) represented by the formula (1), a photocuring initiator (B), a compound (C) represented by the formula (2), and (C)
  • A dicyclopentadiene type epoxy resin
  • B photocuring initiator
  • C compound represented by the formula (2)
  • D The compound (D) which has ethylenically unsaturated groups other than a component is contained.
  • the dicyclopentadiene type epoxy resin (A) (also referred to as component (A)) used in the present embodiment is a compound having a dicyclopentadiene skeleton having the structure of the above formula (1).
  • the cured product obtained by including the resin (A) can suitably form a protective film and an interlayer insulating layer having high copper plating adhesion while having high developability.
  • n represents an integer of 0 to 15.
  • it is an integer of 0 to 5 from the viewpoint of developability.
  • the content of the component (A) is not particularly limited, but from the viewpoint of improving copper plating adhesion, the total content of the component (A), the component (C) and the component (D).
  • the amount is preferably 3 parts by mass or more, more preferably 4 parts by mass or more, and still more preferably 5 parts by mass or more with respect to 100 parts by mass.
  • cure and improving heat resistance it is more preferable to set it as 89 mass parts or less, and it is still more preferable to set it as 88 mass parts or less.
  • content of the component (A) in the resin composition of this embodiment is not specifically limited, From a viewpoint of improving copper plating adhesiveness and developability, it is with respect to 100 mass parts of resin solid content in a resin composition. It is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more. Further, from the viewpoint of sufficiently curing and improving heat resistance, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. Preferably, it is more preferably 30 parts by mass or less, and still more preferably 28 parts by mass or less.
  • the resin (A) a commercially available product can be used.
  • the photocuring initiator (B) (also referred to as component (B)) used in the present embodiment is not particularly limited, and those generally known in the field used in photocurable resin compositions can be used.
  • benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di- Organic peroxides exemplified by perphthalate, acylphosphine oxides, acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2 -Hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyn cyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl Acetophenones such as -2-morpholino-propan-1-one,
  • Acylphosphine oxides include phosphine oxide compounds represented by the following formula (6) such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phos Examples include fin oxide.
  • the phosphine oxide compound represented by the following formula (6) has a high long wavelength UV absorption and is excellent in allowing UV light to reach the inside of the resin. For this reason, the dicyclopentadiene type epoxy resin (A), the compound (C), the compound (D) and the like according to this embodiment can be suitably reacted, and a resin sheet and a multilayer printed wiring board that are superior in heat resistance are manufactured. Is possible.
  • R 5 to R 10 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 11 represents an alkyl group having 1 to 20 carbon atoms or a carbon atom having 6 to 20 carbon atoms.
  • An aryl group is shown.
  • alkyl group having 1 to 4 carbon atoms examples include a straight chain such as methyl group, ethyl group, n-propyl group, n-butyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, etc.
  • a branched alkyl group is exemplified.
  • alkyl group having 1 to 20 carbon atoms examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, sec-butyl, t-butyl group, neopentyl group, 1,1-dimethylpropyl group, 1,1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, 1,1 -Linear or branched alkyl groups such as dimethylbutyl group and 1,1,3-trimethylbutyl group.
  • aryl groups having 6 to 20 carbon atoms include unsubstituted aryl groups such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl groups; tolyl, dimethylphenyl, isopropylphenyl, and t-butyl.
  • alkyl group-substituted aryl groups such as a phenyl group and a di-t-butylphenyl group.
  • acylphosphine oxides 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) are suitable from the viewpoint of reactivity suitable for multilayer printed wiring board applications and high reliability for metal conductors.
  • -Butanone-1 and other radical type photocuring initiators of acetophenones are preferable, and as described above, more heat resistance can be obtained. Therefore, the phosphine oxide compound represented by the formula (6) is more preferable, and bis ( More preferred is 2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
  • photocuring initiators (B) can be used alone or in combination of two or more, and both radical and cationic initiators may be used in combination.
  • 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6-trimethylbenzoyl -Diphenyl-phosphine oxide may be a commercially available product, and Irgacure (registered trademark) 369 (manufactured by BASF Japan Ltd.), Irgacure (registered trademark) 819 (manufactured by BASF Japan Ltd.) and Irgacure (registered) (Trademark) TPO (manufactured by BASF Japan Ltd.) is preferably used.
  • the content of the photocuring initiator (B) in the resin composition of the present embodiment is not particularly limited. From the viewpoint of sufficiently curing the resin composition with active energy rays and improving heat resistance, the resin composition.
  • the total content of component (A), component (C) and component (D) in the content is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, relative to 100 parts by mass. More preferably, the content is 0.3 parts by mass or more. Further, from the viewpoint of inhibiting heat curing after photocuring and reducing heat resistance, it is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and further preferably 20 parts by mass or less. preferable.
  • content of the photocuring initiator (B) in the resin composition of this embodiment is not specifically limited, It shall be 0.1 mass part or more with respect to 100 mass parts of resin solid content in a resin composition.
  • it is more preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, still more preferably 1 part by mass or more, and more preferably 1.8 parts by mass or more. Even more preferred.
  • it is preferably 30 parts by mass or less, and 25 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. More preferably, it is more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less.
  • Compound (C) used in the present embodiment is a compound represented by the formula (2).
  • Compound (C) may be used alone, may contain isomers such as structural isomers and stereoisomers, and may be used in combination of two or more compounds having different structures.
  • R ⁇ 1 > represents a hydrogen atom or a methyl group each independently.
  • a hydrogen atom is contained from a viewpoint of improving the reactivity of photocuring reaction, More preferably, all of R ⁇ 1 > is a hydrogen atom.
  • a plurality of R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent.
  • hydrocarbon group a linear or branched aliphatic hydrocarbon group having 1 to 22, preferably 1 to 14, and more preferably 1 to 10 carbon atoms; 3 to 22 carbon atoms, preferably 3 to 14 and more preferably an alicyclic hydrocarbon group having 3 to 10 carbon atoms; an aromatic hydrocarbon group having 6 to 22 carbon atoms, preferably 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms.
  • Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.
  • neopentyl group 1,1-dimethylpropyl group, 1,1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, 1,1-dimethylbutyl
  • Linear, branched alkyl group such as 1,1,3-trimethylbutyl group
  • linear or branched alkenyl group such as vinyl group, allyl group, isopropenyl group
  • ethynyl group, propargyl group etc.
  • a linear or branched alkynyl group a linear or branched alkynyl group.
  • alicyclic hydrocarbon group examples include cyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 1-methyl-1-cyclohexyl group and adamantyl group; cyclopentadienyl group, indenyl And cyclic unsaturated hydrocarbon groups such as a fluorenyl group.
  • aromatic hydrocarbon groups examples include unsubstituted aryl groups such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl groups; tolyl, dimethylphenyl, isopropylphenyl, and t-butylphenyl.
  • aryl groups such as alkyl group-substituted aryl groups such as di-t-butylphenyl group;
  • At least one hydrogen atom may be substituted with another hydrocarbon group.
  • the hydrocarbon group in which at least one hydrogen atom is substituted with another hydrocarbon group include aryl group-substituted alkyl groups such as benzyl group and cumyl group, and cyclic saturated hydrocarbon group-substituted alkyl groups such as cyclohexylmethyl group. Can be mentioned.
  • the hydrocarbon group having 1 to 22 carbon atoms which may have a substituent is preferably a linear or branched alkyl group.
  • the plurality of R 2 preferably contain a methyl group from the viewpoint of improving the heat resistance of the cured product, and more preferably all of R 2 are methyl groups.
  • R ⁇ 3 > represents the substituent represented by the said Formula (3), the substituent represented by the said Formula (4), or a hydroxy group each independently. Among these, it is preferable that a hydroxyl group is included from a viewpoint of improving heat resistance. Moreover, in this embodiment, it is also preferable from a viewpoint of improving developability to use the compound (C) containing the substituent represented by said Formula (3) among several R ⁇ 3 >. In this embodiment, it is also preferable to use the compound (C) containing a substituent represented by the formula (4) among the plurality of R 3 from the viewpoint of improving heat resistance.
  • R 4 represents a hydrogen atom or a methyl group. Among these, a hydrogen atom is preferable from the viewpoint of improving the reactivity of the photocuring reaction.
  • the plurality of R 3 s are in the range where the ratio of the substituent represented by the formula (3) is 20% or more and 98% or less among all the substituents of R 3 ,
  • the ratio of the substituent represented by 4) is in the range of 5% to 98% and the ratio of the hydroxy group is in the range of 10% to 98% (the sum of the ratios of these substituents is 100%).
  • at least one of the plurality of R 3 is particularly preferably a substituent represented by the above formula (3).
  • the compound (C) preferably contains any one or more of the following compounds (C1) to (C5) because the reactivity of the photocuring reaction, the heat resistance of the cured product and the developability can be improved. More preferably, it contains at least compound (C1), more preferably any two or more of (C1) to (C5), and any one of compound (C1) and compounds (C2) to (C5). More preferably, it contains more than one species. As the compound (C), it is also preferable that at least the compounds (C2) and (C3) are included.
  • Such compounds may be commercially available, for example, KAYARAD (registered trademark) ZCR-6001H, KAYARAD (registered trademark) ZCR-6002H, KAYARAD (registered trademark) ZCR-6006H, KAYARAD (registered trademark) ZCR- 6007H, KAYARAD (registered trademark) ZCR-601H (above, trade name, manufactured by Nippon Kayaku Co., Ltd.), and the like.
  • the acid value of the compound (C) is preferably 30 mgKOH / g or more from the viewpoint of improving developability, and more preferably 50 mgKOH / g or more because developability is further improved. More preferably.
  • the acid value of the compound (C) is preferably 120 mgKOH / g or less, and more preferably 110 mgKOH / g or less because dissolution can be further prevented. More preferably.
  • the “acid value” in the present embodiment indicates a value measured by a method according to JISK 0070: 1992.
  • the content of the compound (C) is not particularly limited, but from the viewpoint of curing the resin composition with active energy rays, the component (A) and component (C) in the resin composition ) And the total content of component (D) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably 3 parts by mass or more. Further, from the viewpoint of sufficiently curing with active energy rays and improving heat resistance, it is preferably 99 parts by mass or less, more preferably 98 parts by mass or less, and further preferably 97 parts by mass or less. preferable.
  • the content of the compound (C) is not particularly limited, but from the viewpoint of curing the resin composition with active energy rays, the resin solid content in the resin composition is 100 parts by mass. 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, still more preferably 10 parts by mass or more, even more preferably 25 parts by mass or more. It is still more preferable, and it is most preferable to set it as 30 mass parts or more. Further, from the viewpoint of sufficiently curing with active energy rays and improving heat resistance, it is preferably 99 parts by mass or less, and 98 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. More preferably, it is more preferably 97 parts by mass or less, still more preferably 90 parts by mass or less, still more preferably 75 parts by mass or less, and most preferably 72 parts by mass or less. preferable.
  • the resin composition of the present embodiment is a compound (D) (component (component) having an ethylenically unsaturated group other than the component (C) in order to increase the reactivity to active energy rays (for example, ultraviolet rays) and improve heat resistance.
  • the compound (D) having an ethylenically unsaturated group used in the present embodiment is other than the compound (C) represented by the formula (2), and has one or more ethylenically unsaturated groups in one molecule.
  • it will not specifically limit if it is a compound For example, the compound which has a (meth) acryloyl group, a vinyl group, etc. is mentioned. These can be used alone or in combination of two or more.
  • a compound having a (meth) acryloyl group methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether , Phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, glycol di (meth) acrylate, diethylenedi (meth) a Relate,
  • urethane (meth) acrylates that have (meth) acryloyl groups and urethane bonds in the same molecule
  • polyester (meth) acrylates that have (meth) acryloyl groups and ester bonds in the same molecule
  • epoxy resins Epoxy (meth) acrylates derived from the above and having a (meth) acryloyl group, and reactive oligomers in which these bonds are used in combination.
  • the urethane (meth) acrylate is a reaction product of a hydroxyl group-containing (meth) acrylate, a polyisocyanate, and other alcohols used as necessary.
  • hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerin (meta) such as glycerin mono (meth) acrylate, glycerin di (meth) acrylate, etc.
  • Sugars (meth) acrylates such as acrylates, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and toluene diisocyanate , Hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, Down diisocyanate, hydrogenated xylene diisocyanate, dicyclohexane diisocyanate, and their isocyanurate, by reacting polyisocyanates such as buret reactants, the urethane (meth) acrylates.
  • polyisocyanates such as buret reactants, the urethane (meth) acrylates.
  • polyester (meth) acrylates examples include caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide-modified phthalic acid (meth) acrylate, ethylene oxide-modified succinic acid (meth) acrylate, and caprolactone-modified.
  • Monofunctional (poly) ester (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate; hydroxypivalate ester neopentyl glycol di (meth) acrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol di (meth) acrylate, epichlorohydrin Di (poly) ester (meth) acrylates such as modified phthalic acid di (meth) acrylate; 1 mole of trimethylolpropane or glycerin Mol of ⁇ - caprolactone, .gamma.-butyrolactone, a triol obtained by adding a cyclic lactone compound such as ⁇ - valerolactone mono- include di- or tri (meth) acrylate.
  • triol mono, di, tri or tetra (meta) obtained by adding 1 mol or more of a cyclic lactone compound such as ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone to 1 mol of pentaerythritol or ditrimethylolpropane.
  • a cyclic lactone compound such as ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone
  • Triol mono or poly (meth) acrylate obtained by adding 1 mol or more of cyclic lactone compound such as ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone to 1 mol of acrylate and dipentaerythritol
  • cyclic lactone compound such as ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone
  • examples thereof include mono (meth) acrylate or poly (meth) acrylate of polyhydric alcohol such as all, pentaol or hexaol.
  • diol components such as (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, 3-methyl-1,5-pentanediol, hexanediol and maleic acid , Fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, polybasic acids such as 5-sodium sulfoisophthalic acid, and anhydrides thereof (Meth) acrylate of a polyester polyol which is a reaction product with a product of a cyclic lactone-modified polyester diol composed of the diol component and a polybasic acid and their anhydrides and ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone,
  • the above epoxy (meth) acrylates are carboxylate compounds of a compound having an epoxy group and (meth) acrylic acid.
  • phenol novolac type epoxy (meth) acrylate cresol novolac type epoxy (meth) acrylate, trishydroxyphenylmethane type epoxy (meth) acrylate, dicyclopentadienephenol type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate Bisphenol F type epoxy (meth) acrylate, biphenol type epoxy (meth) acrylate, bisphenol A novolak type epoxy (meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate, glyoxal type epoxy (meth) acrylate, heterocyclic epoxy ( And (meth) acrylates and the like, and acid anhydride-modified epoxy acrylates thereof.
  • Examples of the compound having a vinyl group include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether.
  • Examples of styrenes include styrene, methyl styrene, ethyl styrene, divinyl benzene and the like.
  • Other vinyl compounds include triallyl isocyanurate, trimethallyl isocyanurate, bisallyl nadiimide and the like.
  • the heat resistance of the resulting cured product tends to be further improved.
  • the content of the compound (D) having an ethylenically unsaturated group other than the component (C) is not particularly limited, but from the viewpoint of improving developability in the resin composition.
  • the total content of 100 parts by mass of component (A), component (C) and component (D) is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, More preferably, it is 1.5 parts by mass or more.
  • the content of the compound (D) is not particularly limited. However, from the viewpoint of improving the developability, the content of the compound (D) is 0.1% with respect to 100 mass parts of the resin solid content in the resin composition. It is preferably 5 parts by mass or more, more preferably 1.0 part by mass or more, still more preferably 1.5 parts by mass or more, still more preferably 5.0 parts by mass or more, Most preferably, it is 10 parts by mass or more. Further, from the viewpoint of improving the heat resistance of the cured product, it is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. 50 parts by mass or less, more preferably 25 parts by mass or less, and most preferably 20 parts by mass or less.
  • a maleimide compound (E) (also referred to as component (E)) can be used.
  • the maleimide compound (E) is described in detail below.
  • the maleimide compound (E) used in the present embodiment is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule.
  • Specific examples thereof include, for example, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2,2-bis ⁇ 4- (4-maleimidophenoxy) -phenyl ⁇ propane, 4,4 -Diphenylmethane bismaleimide, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) Methane, phenylmethanemaleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene biscitraconimide, m-phen
  • novolac maleimide compounds and biphenylaralkyl maleimide compounds are particularly preferred.
  • a maleimide compound represented by the following formula (7) and a maleimide compound represented by the following formula (8) are preferred, and the following formula (7)
  • the maleimide compound represented by these is more preferable.
  • a commercially available product can be used as the maleimide compound represented by the following formula (7), and examples thereof include BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd.).
  • maleimide compound represented by the following formula (8) examples thereof include MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.). These maleimide compounds (E) can be used singly or in appropriate combination of two or more.
  • each of R 5 independently represents a hydrogen atom or a methyl group.
  • N 1 represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably 1) Represents an integer of ⁇ 5).
  • each of R 6 independently represents a hydrogen atom or a methyl group.
  • N 2 represents an integer of 1 or more, preferably an integer of 1 to 5).
  • the content of the maleimide compound (E) in the resin composition of the present embodiment is not particularly limited, but from the viewpoint of sufficiently curing the resin composition and improving heat resistance, the component (A) in the resin composition.
  • the total content of component (C) and component (D) is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and 0.03 parts by mass with respect to 100 parts by mass. More preferably, the above is used.
  • the content of the maleimide compound (E) is not particularly limited, and is preferably 0.01 parts by mass to 50 parts by mass with respect to 100 parts by mass of the resin solid content, and more preferably Is 0.02 parts by mass to 45 parts by mass, more preferably 0.03 parts by mass to 20 parts by mass, still more preferably 0.1 parts by mass to 10 parts by mass, and most preferably 1 part by mass. ⁇ 7 parts by mass.
  • the content of the maleimide compound is within the above range, the heat resistance of the cured product tends to be further improved.
  • a filler (F) (also referred to as component (F)) can be used in combination in order to improve various properties such as coating properties and heat resistance.
  • the filler (F) used in the present embodiment is not particularly limited as long as it has insulating properties.
  • silica for example, natural silica, fused silica, amorphous silica, hollow silica, etc.
  • an aluminum compound for example, boehmite
  • silica silica, boehmite, barium sulfate, silicone powder, fluorine resin filler, urethane resin filler, acrylic resin filler, polyethylene filler, styrene / butadiene rubber and silicone rubber.
  • fluorine resin filler fluorine resin filler
  • urethane resin filler acrylic resin filler
  • polyethylene filler polyethylene filler
  • styrene / butadiene rubber silicone rubber
  • These fillers (F) may be surface-treated with a silane coupling agent described later.
  • silica is preferable and fused silica is particularly preferable from the viewpoint of improving the heat resistance of the cured product and obtaining good coating properties.
  • Specific examples of silica include SFP-130MC manufactured by Denka Corporation, SC2050-MB, SC1050-MLE, YA010C-MFN, YA050C-MJA manufactured by Admatechs Corporation.
  • These fillers (F) can be used singly or in appropriate combination of two or more.
  • the content of the filler (F) is not particularly limited, but from the viewpoint of improving the heat resistance of the cured product, the resin solid content in the resin composition is 100 parts by mass. It is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more. Further, from the viewpoint of improving the developability of the resin composition, it is preferably 400 parts by mass or less, more preferably 350 parts by mass or less, with respect to 100 parts by mass of the resin solid content in the resin composition. Preferably, it is more preferably 300 parts by mass or less, still more preferably 200 parts by mass or less, and most preferably 100 parts by mass or less.
  • silane coupling agent and wetting and dispersing agent In the resin composition of the present embodiment, a silane coupling agent and / or a wet dispersant may be used in combination in order to improve the dispersibility of the filler, the polymer and / or resin, and the adhesive strength between the filler. Is possible.
  • These silane coupling agents are not particularly limited as long as they are silane coupling agents generally used for inorganic surface treatment.
  • aminosilanes such as ⁇ -aminopropyltriethoxysilane and N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane
  • epoxysilanes such as ⁇ -glycidoxypropyltrimethoxysilane
  • Acrylic silanes such as ⁇ -acryloxypropyltrimethoxysilane
  • cationic silanes such as N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane hydrochloride
  • phenylsilane silane cups A ring agent is mentioned.
  • the content of the silane coupling agent is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.
  • the wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for coatings. Specific examples include wet dispersing agents such as DISPERBYK (registered trademark) -110, 111, 118, 180, 161, BYK (registered trademark) -W996, W9010, and W903 manufactured by Big Chemie Japan Co., Ltd. . These wetting and dispersing agents can be used singly or in appropriate combination of two or more. In the resin composition of the present embodiment, the content of the wetting and dispersing agent is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.
  • the compound (G) (also referred to as component (G)) used in the present embodiment is cured, which is required in the field where the resin composition is used, in addition to the copper plating adhesion obtained by using the component (A).
  • Various kinds of materials can be used according to the properties of the cured product such as flame retardancy, heat resistance, and thermal expansion properties.
  • a cyanate ester compound, a benzoxazine compound, and the like can be used, and a phenol resin, an oxetane resin, and the like can also be used.
  • the epoxy resin different from this epoxy resin (A) is used with the dicyclopentadiene type epoxy resin (A) represented by said (1), the resin composition which is excellent in especially developability and plating adhesiveness is obtained. be able to.
  • the cyanate ester compound is not particularly limited as long as it is a resin having in its molecule an aromatic moiety substituted with at least one cyanate group (cyanate ester group).
  • cyanate ester group a resin having in its molecule an aromatic moiety substituted with at least one cyanate group (cyanate ester group).
  • cyanate ester group a resin having in its molecule an aromatic moiety substituted with at least one cyanate group (cyanate ester group).
  • cyanate ester group cyanate ester group
  • Ar 1 represents a single bond of a benzene ring, a naphthalene ring or two benzene rings. When there are a plurality, they may be the same or different.
  • Each Ra is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 6 carbon atoms and an alkyl group having 6 to 12 carbon atoms.
  • a group to which an aryl group is bonded is shown.
  • the aromatic ring in Ra may have a substituent, and the substituent in Ar 1 and Ra can be selected at any position.
  • p represents the number of cyanato groups bonded to Ar 1 , and each independently represents an integer of 1 to 3.
  • q represents the number of Ra bonded to Ar 1, and is 4-p when Ar 1 is a benzene ring, 6-p when Ar 1 is a naphthalene ring, and 8-p when two benzene rings are a single bond.
  • . t represents an average number of repetitions and is an integer of 0 to 50, and the cyanate ester compound may be a mixture of compounds having different t.
  • a divalent organic group having 1 to 50 carbon atoms (a hydrogen atom may be substituted with a hetero atom), a divalent group having 1 to 10 nitrogen atoms.
  • An organic group eg, —N—R—N— (where R represents an organic group)
  • a carbonyl group (—CO—), a carboxy group (—C ( ⁇ O) O—), a carbonyl dioxide group ( —OC ( ⁇ O) O—), a sulfonyl group (—SO 2 —), a divalent sulfur atom or a divalent oxygen atom.
  • the alkyl group in Ra in the general formula (9) may have any of a linear or branched chain structure and a cyclic structure (for example, a cycloalkyl group).
  • the hydrogen atom in the alkyl group in the general formula (9) and the aryl group in Ra is substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, or a cyano group. Also good.
  • alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group, 2,2-dimethylpropyl group.
  • aryl group examples include phenyl group, xylyl group, mesityl group, naphthyl group, phenoxyphenyl group, ethylphenyl group, o-, m- or p-fluorophenyl group, dichlorophenyl group, dicyanophenyl group, trifluorophenyl. Group, methoxyphenyl group, and o-, m- or p-tolyl group.
  • alkoxyl group examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group.
  • divalent organic group having 1 to 50 carbon atoms in X in the general formula (9) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, and biphenylyl.
  • examples include a methylene group, a dimethylmethylene-phenylene-dimethylmethylene group, a fluorenediyl group, and a phthalidodiyl group.
  • the hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, a cyano group, or the like.
  • a halogen atom such as a fluorine atom or a chlorine atom
  • an alkoxyl group such as a methoxy group or a phenoxy group, a cyano group, or the like.
  • Examples of the divalent organic group having 1 to 10 nitrogen atoms in X of the general formula (9) include an imino group and a polyimide group.
  • examples of the organic group of X in the general formula (9) include those having a structure represented by the following general formula (10) or the following general formula (11).
  • Ar 2 represents a benzenetetrayl group, a naphthalenetetrayl group or a biphenyltetrayl group, and when u is 2 or more, they may be the same as or different from each other.
  • Rb, Rc, Rf, and Rg are each independently an aryl having at least one hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or a phenolic hydroxy group. Indicates a group.
  • Rd and Re are each independently selected from any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, and a hydroxy group.
  • . u represents an integer of 0 to 5.
  • Ar 3 represents a benzenetetrayl group, a naphthalenetetrayl group or a biphenyltetrayl group, and when v is 2 or more, they may be the same or different.
  • Ri and Rj are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxyl group having 1 to 4 carbon atoms, a hydroxy group, a trifluoromethyl group, Or an aryl group substituted with at least one cyanato group.
  • v represents an integer of 0 to 5, but may be a mixture of compounds having different v.
  • examples of X in the general formula (9) include a divalent group represented by the following formula.
  • z represents an integer of 4 to 7.
  • Rk independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • Specific examples of Ar 2 in the general formula (10) and Ar 3 in the general formula (11) include two carbon atoms represented by the general formula (10) or two oxygen atoms represented by the general formula (11).
  • a benzenetetrayl group bonded to the 1,4-position or the 1,3-position, the two carbon atoms or the two oxygen atoms are in the 4,4′-position, 2,4′-position, 2,2′-position, 2 , 3′-position, 3,3′-position, or 3,4′-position, and the above two carbon atoms or two oxygen atoms are in the 2,6-position, 1,5-position , 1,6-position, 1,8-position, 1,3-position, 1,4-position, or 2,7-position.
  • Rb, Rc, Rd, Re, Rf and Rg in the general formula (10) and the alkyl group and aryl group in Ri and Rj in the general formula (11) have the same meanings as those in the general formula (9).
  • cyanato-substituted aromatic compound represented by the general formula (9) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1 -Cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methoxybenzene, 1-cyanato-2,3-, 1-cyanato-2,4-, 1-cyanato-2,5-, 1-cyanato-2,6-, 1-cyanato-3,4- or 1-cyanato-3,5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, cyanatooctylbenzene, cyanatononylbenzene, 2- (4-cyanaphenyl) -2-phenylpropane (cyanate of 4- ⁇ -cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenze 1-cyana
  • phenol novolac resins and cresol novolac resins include phenol novolac resins and cresol novolac resins (phenol, alkyl-substituted phenol or halogen-substituted phenol, formalin, A product obtained by reacting a formaldehyde compound such as paraformaldehyde in an acidic solution), a trisphenol novolak resin (a product obtained by reacting hydroxybenzaldehyde and phenol in the presence of an acidic catalyst), a fluorene novolac resin (9 , 9-bis (hydroxyaryl) fluorenes in the presence of an acidic catalyst), phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin and biphenyl aralkyl resin (known methods) More, Ar 4 - (CH 2 Y ) 2 (.
  • Ar 4 represents a phenyl group
  • Y represents a halogen atom and the same in this paragraph.
  • bishalogenomethyl compounds represented by the phenol compound An acid catalyst or non-catalyzed reaction, a bis (alkoxymethyl) compound represented by Ar 4 — (CH 2 OR) 2 and a phenol compound in the presence of an acidic catalyst, or A product obtained by reacting a bis (hydroxymethyl) compound represented by Ar 4 — (CH 2 OH) 2 and a phenol compound in the presence of an acidic catalyst, or an aromatic aldehyde compound, an aralkyl compound and a phenol compound.
  • phenol novolac type cyanate ester compound naphthol aralkyl type cyanate ester compound, biphenyl aralkyl type cyanate ester compound, naphthylene ether type cyanate ester compound, xylene resin type cyanate ester compound, adamantane skeleton type cyanate ester A compound is preferable, and a naphthol aralkyl cyanate compound is particularly preferable from the viewpoint of plating adhesion.
  • the method for producing these cyanate ester compounds is not particularly limited, and a known method can be used. Examples of such production methods include a method of obtaining or synthesizing a hydroxy group-containing compound having a desired skeleton, and modifying the hydroxy group by a known method to form cyanate. Examples of the method for cyanating a hydroxy group include the methods described in Ian Hamerton, “Chemistry and Technology of Cyanate Ester Resins,” “Blackie Academic & Professional”.
  • the cured resin using these cyanate ester compounds has excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion.
  • the content of the cyanate ester compound is not particularly limited, but is preferably 0.01 parts by mass with respect to 100 parts by mass of the resin solid content from the viewpoint of plating adhesion and heat resistance. To 50 parts by mass, more preferably 0.05 to 40 parts by mass, still more preferably 0.1 to 20 parts by mass, and even more preferably 0.2 to 5 parts by mass. It is.
  • phenol resin a generally known resin can be used as long as it is a phenol resin having two or more hydroxyl groups in one molecule.
  • phenol resin a generally known resin can be used as long as it is a phenol resin having two or more hydroxyl groups in one molecule.
  • bisphenol A type phenol resin bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type phenol resin, biphenyl Aralkyl type phenolic resin, cresol novolac type phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified novolak type phenolic resin, phenolaralkyl type phenolic resin, naphthol aralkyl type
  • phenol resins biphenyl aralkyl type phenol resins, naphthol aralkyl type phenol resins, phosphorus-containing phenol resins, and hydroxyl group-containing silicone resins are preferable in terms of flame retardancy. These phenol resins can be used alone or in admixture of two or more.
  • the content of the phenolic resin is not particularly limited, and is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 45 parts by mass with respect to 100 parts by mass of the resin solid content. .
  • the heat resistance tends to be further improved.
  • oxetane resin generally known oxetane resins can be used.
  • the content of the oxetane resin is not particularly limited, and is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 45 parts by mass with respect to 100 parts by mass of the resin solid content. .
  • the heat resistance tends to be further improved.
  • benzoxazine compound generally known compounds can be used as long as they have two or more dihydrobenzoxazine rings in one molecule.
  • bisphenol A type benzoxazine BA-BXZ (trade name, manufactured by Konishi Chemical) bisphenol F type benzoxazine BF-BXZ (trade name, manufactured by Konishi Chemical), bisphenol S type benzoxazine BS-BXZ (trade name, manufactured by Konishi Chemical) ), Phenolphthalein type benzoxazine and the like, but not particularly limited.
  • BA-BXZ trade name, manufactured by Konishi Chemical
  • bisphenol F type benzoxazine BF-BXZ (trade name, manufactured by Konishi Chemical)
  • bisphenol S type benzoxazine BS-BXZ (trade name, manufactured by Konishi Chemical)
  • Phenolphthalein type benzoxazine and the like but not particularly limited. These can be used alone or in combination of two or more.
  • the content of the benzoxazine compound is not particularly limited, and is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 45 parts by mass with respect to 100 parts by mass of the resin solid content. is there.
  • the content of the benzoxazine compound is within the above range, the heat resistance tends to be further improved.
  • an epoxy resin different from the dicyclopentadiene type epoxy resin (A) represented by the above (1) can be used in combination in order to improve the heat resistance of the cured product. .
  • such an epoxy resin is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule.
  • Specific examples thereof include, for example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, Cresol novolak type epoxy resin, xylene novolak type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified novolak type epoxy resin, naphthylene ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, Trifunctional phenolic epoxy resin, tetrafunctional phenolic epoxy resin, triglycidyl isocyanurate, glycidyl ester epoxy resin, alicyclic Poxy resin, biphenyl novolak type epoxy resin, phenol aralkyl novol
  • At least one selected from the group consisting of a biphenyl aralkyl type epoxy resin, a naphthylene ether type epoxy resin, a polyfunctional phenol type epoxy resin, and a naphthalene type epoxy resin is preferable, and a naphthalene type epoxy resin is more preferable.
  • naphthalene type epoxy resin it is preferable to use a resin represented by the following formula (5) because developability and plating adhesion are further improved.
  • this epoxy resin a commercially available product can be used, and HP-4710 (trade name) manufactured by DIC Corporation is exemplified.
  • HP-4710 trade name manufactured by DIC Corporation is exemplified.
  • the naphthalene type epoxy resin represented by the following formula (5) has a low molecular weight and is multifunctional, and therefore has excellent solubility in a developer. Therefore, it is thought that the resin composition which is excellent also in developability can be obtained by using together with a dicyclopentadiene type epoxy resin (A).
  • epoxy resins can be used singly or in appropriate combination of two or more.
  • the content of the epoxy resin is not particularly limited, but from the viewpoint of further improving developability, the epoxy resin (A), the epoxy resin (A), and the epoxy resin (A) with respect to 100 parts by mass of the resin solid content in the resin composition
  • the total amount with different epoxy resins is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more. preferable.
  • the total of the epoxy resin (A) and the epoxy resin different from the epoxy resin (A) is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, further preferably 30 parts by mass or less, and further preferably 28 parts by mass or less.
  • the ratio of the epoxy resin (A) to the epoxy resin different from the epoxy resin (A) is not particularly limited, but is preferably 1 to 10: 1 to 3 from the viewpoint of plating adhesion, and 2 to 4: 1. ⁇ 2 is more preferred.
  • thermosetting accelerator (H) In the resin composition of the present embodiment, a thermosetting accelerator (H) (also referred to as component (H)) can be used as long as the characteristics of the present embodiment are not impaired.
  • the thermosetting accelerator (H) used in the present embodiment is not particularly limited.
  • Organic peroxides such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri -Tertiary amines such as n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcin, catechol Class: Naphthenes Organometallic salts such as lead, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyl
  • imidazole compounds such as 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-phenylimidazole, and triphenylimidazole (TPIZ) are preferable from the viewpoint of heat resistance.
  • TPIZ triphenylimidazole
  • -4-Methylimidazole is more preferable from the viewpoint of obtaining superior heat resistance.
  • thermosetting accelerators can be used singly or in appropriate combination of two or more.
  • the content of the thermosetting accelerator (H) is not particularly limited, but is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. And preferably 0.05 to 5 parts by mass.
  • the resin composition of the present embodiment may contain a solvent as necessary.
  • a solvent for example, when an organic solvent is used, the viscosity at the time of preparing the resin composition can be adjusted.
  • the kind of solvent will not be specifically limited if it can melt
  • These organic solvents can be used alone or in combination of two or more.
  • thermosetting resins thermoplastic resins and oligomers thereof, elastomers, etc.
  • Flame retardant compound not mentioned so far; combined use of additives and the like is also possible. These are not particularly limited as long as they are generally used.
  • flame retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, phosphate compounds of phosphorus compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters.
  • Additives include UV absorbers, antioxidants, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, antifoaming agents, surface conditioners, brighteners, polymerization inhibitors, etc. It is done. These components can be used alone or in appropriate combination of two or more.
  • the content of other components is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.
  • the resin composition of this embodiment includes a dicyclopentadiene type epoxy resin (A) represented by the formula (1), a photocuring initiator (B), a compound (C) represented by the formula (2), and By appropriately mixing the compound (D) having an ethylenically unsaturated group other than the component (C) with the maleimide compound (E), the filler (F), the compound (G) and other components as necessary. Prepared.
  • the resin composition of this embodiment can be used suitably as a varnish at the time of producing the resin sheet of this invention mentioned later.
  • the manufacturing method of the resin composition of this embodiment is not specifically limited, For example, the method of mix
  • a known process for uniformly dissolving or dispersing each component can be performed as necessary.
  • the dispersibility of the inorganic filler (G) in the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank provided with a stirrer having an appropriate stirring ability.
  • the stirring, mixing, and kneading processes described above are, for example, a stirring device for dispersion such as an ultrasonic homogenizer, a device for mixing such as a three-roll, ball mill, bead mill, and sand mill, or a revolving or rotating type.
  • an organic solvent can be used as needed.
  • the type of the organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition, and specific examples thereof are as described above.
  • the resin composition of the present embodiment can be used for applications where an insulating resin composition is required, and is not particularly limited, but includes an insulating resin sheet such as a photosensitive film, a photosensitive film with a support, and a prepreg. It can be used for applications such as circuit boards (for laminated boards, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-filling resins, and the like. Especially, it can be conveniently used as a resin composition for insulating layers of a multilayer printed wiring board or a solder resist.
  • the resin sheet of the present embodiment includes a support and a resin composition layer formed on the surface of the support and including the resin composition of the present embodiment. It is the resin sheet with a support body apply
  • the resin sheet can be produced by applying the resin composition on a support and drying it.
  • the support used in the resin sheet of the present embodiment is not particularly limited, but a known one can be used, and a resin film is preferable.
  • the resin film include polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polyethylene naphthalate film, and polyvinyl alcohol.
  • resin films such as films and triacetyl acetate films. Among these, a PET film is preferable.
  • the resin film having a release agent coated on the surface thereof can be suitably used in order to facilitate peeling from the resin composition layer.
  • the thickness of the resin film is preferably in the range of 5 ⁇ m to 100 ⁇ m, and more preferably in the range of 10 ⁇ m to 50 ⁇ m. If the thickness is less than 5 ⁇ m, the support tends to be broken when the support is peeled off before development, and if the thickness exceeds 100 ⁇ m, the resolution when exposed from the support tends to decrease. is there.
  • the resin film has excellent transparency.
  • the resin composition layer may be protected with a protective film.
  • a protective film By protecting the resin composition layer side with a protective film, it is possible to prevent adhesion or scratches of dust or the like to the surface of the resin composition layer.
  • a protective film a film made of the same material as the above resin film can be used.
  • the thickness of the protective film is not particularly limited, but is preferably in the range of 1 ⁇ m to 50 ⁇ m, and more preferably in the range of 5 ⁇ m to 40 ⁇ m. When the thickness is less than 1 ⁇ m, the handleability of the protective film tends to be lowered, and when it exceeds 50 ⁇ m, the inexpensiveness tends to be inferior.
  • the protective film preferably has a smaller adhesive force between the resin composition layer and the protective film than the adhesive force between the resin composition layer and the support.
  • a resin sheet is manufactured by apply
  • the method of doing is mentioned.
  • the coating can be performed by a known method using, for example, a roll coater, comma coater, gravure coater, die coater, bar coater, lip coater, knife coater, squeeze coater, or the like.
  • the drying can be performed, for example, by a method of heating in a dryer at 60 to 200 ° C. for 1 to 60 minutes.
  • the amount of the remaining organic solvent in the resin composition layer is preferably 5% by mass or less with respect to the total mass of the resin composition layer from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.
  • the thickness of the resin composition layer with respect to the support is preferably 1.0 ⁇ m or more in terms of the resin composition layer thickness of the resin sheet from the viewpoint of improving the handleability. Further, from the viewpoint of improving the transmittance and improving the developability, the thickness is preferably 300 ⁇ m or less.
  • the resin sheet of this embodiment can be used as an interlayer insulating layer of a multilayer printed wiring board.
  • the multilayer printed wiring board of the present embodiment includes an interlayer insulating layer containing the resin composition of the present embodiment, and can be obtained, for example, by stacking and curing one or more of the above-described resin sheets. Specifically, it can be produced by the following method.
  • the resin composition layer side of the resin sheet of this embodiment is laminated on one side or both sides of a circuit board using a vacuum laminator.
  • the circuit board include a glass epoxy board, a metal board, a ceramic board, a silicon board, a semiconductor sealing resin board, a polyester board, a polyimide board, a BT resin board, and a thermosetting polyphenylene ether board.
  • the circuit board refers to a board on which a conductor layer (circuit) patterned on one or both sides of the board is formed.
  • a substrate having a conductor layer (circuit) in which one or both surfaces of the outermost layer of the printed wiring board are patterned is also here. It is included in the circuit board.
  • the surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.
  • the laminating step when the resin sheet has a protective film, the protective film is peeled and removed, and then the resin sheet and the circuit board are preheated as necessary, while the resin composition layer is pressed and heated. Crimp to circuit board.
  • a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used.
  • the conditions for the laminating step are not particularly limited.
  • the pressure bonding temperature (laminating temperature) is preferably 50 ° C. to 140 ° C.
  • the pressure bonding pressure is preferably 1 kgf / cm 2 to 15 kgf / cm 2
  • the pressure bonding time Is preferably 5 seconds to 300 seconds
  • lamination is performed under reduced pressure so that the air pressure is 20 mmHg or less.
  • the laminating step may be a batch type or a continuous type using a roll.
  • the vacuum laminating method can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a 2-stage build-up laminator manufactured by Nikko Materials Co., Ltd. can be exemplified.
  • an exposure process is performed in which a predetermined portion of the resin composition layer is irradiated with active energy rays to cure the resin composition layer of the irradiated portion.
  • the active energy ray may be irradiated through a mask pattern or a direct drawing method in which an active energy ray is directly irradiated.
  • Examples of active energy rays include ultraviolet rays, visible rays, electron beams, X-rays and the like, and ultraviolet rays are particularly preferable.
  • the irradiation amount of ultraviolet rays is about 10 mJ / cm 2 to 1000 mJ / cm 2 .
  • a contact exposure method in which the mask pattern is brought into close contact with the multilayer printed wiring board
  • a non-contact exposure method in which exposure is carried out using parallel light rays without being brought into close contact. It doesn't matter.
  • the support body exists on a resin composition layer, you may expose from a support body and may expose after a support body peels.
  • the developer is not particularly limited as long as it selectively elutes an unexposed portion, but a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent is used. .
  • a development step using an alkaline aqueous solution is particularly preferable.
  • These developers can be used alone or in combination of two or more.
  • a developing method it can carry out by well-known methods, such as spraying, rocking immersion, brushing, and scraping, for example.
  • the alkaline aqueous solution used as the developer is not particularly limited.
  • potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, 4-sodium borate, ammonia And amines are examples of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, 4-sodium borate, ammonia And amines.
  • the concentration of the alkaline aqueous solution is preferably 0.1% by mass to 60% by mass with respect to the total amount of the developer. Moreover, the temperature of aqueous alkali solution can be adjusted according to developability. Furthermore, these aqueous alkali solutions can be used alone or in combination of two or more.
  • development methods include a dip method, a paddle method, a spray method, a high-pressure spray method, brushing, and slapping, and the high-pressure spray method is suitable for improving the resolution.
  • the spray pressure when the spray method is employed is preferably 0.02 MPa to 0.5 MPa.
  • a post-bake step is performed to form an insulating layer (cured product).
  • the post-bake process include an ultraviolet irradiation process using a high-pressure mercury lamp and a heating process using a clean oven, and these can be used in combination. Case of ultraviolet irradiation can adjust its dose optionally, the irradiation can be carried out, for example 0.05J / cm 2 ⁇ 10J / cm 2 of about dose.
  • the heating conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but are preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. It is selected in the range of 30 minutes to 150 minutes at ⁇ 200 ° C.
  • a conductor layer is formed on the surface of the insulating layer by dry plating or wet plating.
  • dry plating known methods such as vapor deposition, sputtering, and ion plating can be used.
  • vapor deposition method vacuum vapor deposition method
  • a metal film can be formed on the insulating layer by placing the support in a vacuum vessel and evaporating the metal by heating.
  • sputtering method for example, the support is placed in a vacuum vessel, an inert gas such as argon is introduced, a direct current voltage is applied, the ionized inert gas is made to collide with the target metal, and the struck metal is used.
  • a metal film can be formed on the insulating layer.
  • the surface of the insulating layer is roughened by performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order.
  • the swelling treatment with the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 to 80 ° C. for 1 to 20 minutes.
  • the swelling liquid include an alkaline solution, and examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution.
  • Examples of commercially available swelling liquids include Updes (registered trademark) MDS-37 manufactured by Uemura Kogyo Co., Ltd.
  • the roughening treatment with an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 to 80 ° C. for 5 to 30 minutes.
  • the oxidizing agent include alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. it can.
  • the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass.
  • Examples of commercially available oxidizing agents include alkaline permanganate solutions such as Updes (registered trademark) MDE-40 and Updes (registered trademark) ELC-SH manufactured by Uemura Kogyo Co., Ltd.
  • the neutralization treatment with the neutralizing solution is performed by immersing in the neutralizing solution at 30 to 50 ° C. for 1 to 10 minutes.
  • the neutralizing solution is preferably an acidic aqueous solution, and a commercially available product is Updes (registered trademark) MDN-62 manufactured by Uemura Kogyo Co., Ltd.
  • a conductor layer is formed by combining electroless plating and electrolytic plating.
  • a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating.
  • a pattern formation method thereafter for example, a subtractive method, a semi-additive method, or the like can be used.
  • the semiconductor device of this embodiment includes an interlayer insulating layer containing the resin composition of this embodiment, and can be specifically manufactured by the following method.
  • a semiconductor device can be manufactured by mounting a semiconductor chip in a conductive portion of the multilayer printed wiring board of the present embodiment.
  • the conduction location is a location for transmitting an electrical signal in the multilayer printed wiring board, and the location may be the surface or an embedded location.
  • the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.
  • the semiconductor chip mounting method for manufacturing the semiconductor device of the present embodiment is not particularly limited as long as the semiconductor chip functions effectively.
  • the wire bonding mounting method, the flip chip mounting method, and the bump are used. Examples include a mounting method using a none buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).
  • BBUL none buildup layer
  • ACF anisotropic conductive film
  • NCF non-conductive film
  • a semiconductor device can be manufactured by laminating the resin sheet of this embodiment on a semiconductor chip. After lamination, it can be produced by using the same method as the above multilayer printed wiring board.
  • the reaction solution was allowed to stand to separate the organic phase and the aqueous phase.
  • the organic phase obtained was washed 5 times with 1300 g of water.
  • the electric conductivity of the waste water in the fifth washing with water was 5 ⁇ S / cm, and it was confirmed that the ionic compounds that could be removed were sufficiently removed by washing with water.
  • the organic phase after washing with water was concentrated under reduced pressure, and finally concentrated to dryness at 90 ° C. for 1 hour to obtain 331 g of the desired naphthol aralkyl-type cyanate ester compound (SNCN) (orange viscous product).
  • SNCN naphthol aralkyl-type cyanate ester compound
  • the obtained SNCN had a mass average molecular weight Mw of 600.
  • the IR spectrum of SNCN showed absorption of 2250 cm ⁇ 1 (cyanate group) and did not show absorption of a hydroxy group.
  • a dicyclopentadiene type epoxy resin (n in the formula (1) is 1 to 3.
  • XD-1000 trade name
  • Japan 22.4 parts by mass of Kayaku Co., Ltd. and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure (registered trademark)) as the photocuring initiator (B) 369, manufactured by BASF Japan Ltd.) 6.5 parts by mass, as compound (C), propylene glycol monomethyl ether acetate (hereinafter sometimes abbreviated as PGMEA) solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark)) ZCR-6007H, 65% by mass of non-volatile content, acid value: 70 mg KOH / g, manufactured by Nippon Kayaku Co., Ltd.) 77.5 parts
  • PGMEA propylene glycol monomethyl ether acetate
  • the KAYARAD (registered trademark) ZCR-6007H is a mixture containing at least one of the compound (C1) and the compounds (C2) to (C5).
  • the obtained laminate is subjected to an exposure step of irradiating with 200 mJ / cm 2 of ultraviolet light, peeled off the support, developed with a 1% by mass sodium carbonate aqueous solution, and further irradiated with 1000 mJ / cm 2 of ultraviolet light. Then, a post-baking process in which heat treatment was performed at 180 ° C. for 120 minutes was performed, and then a laminate for evaluation was obtained.
  • the resin sheet is irradiated with 200 mJ / cm 2 of ultraviolet light, further subjected to an exposure process of irradiating 1000 mJ / cm 2 of ultraviolet light, subjected to a post-baking process of heating at 180 ° C. for 120 minutes, and then the support is peeled off.
  • the cured product was evaluated.
  • Example 2 As component (A), 21.9 parts by mass of dicyclopentadiene type epoxy resin (XD-1000 (trade name), manufactured by Nippon Kayaku Co., Ltd.) and as photocuring initiator (B), 2-benzyl-2- 6.5 parts by mass of dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure (registered trademark) 369, manufactured by BASF Japan Ltd.), and as compound (C), a TrisP-PA epoxy acrylate compound PGMEA solution (KAYARAD (registered trademark) ZCR-6007H, nonvolatile content 65% by mass, acid value: 70 mgKOH / g, manufactured by Nippon Kayaku Co., Ltd.) 77.5 parts by mass (50.4 mass parts in terms of nonvolatile content), As the compound (D) having an ethylenically unsaturated group other than the component (C), dipentaerythritol hexaacrylate (KAYARAD (registered
  • Example 3 As component (A), dicyclopentadiene type epoxy resin (XD-1000 (trade name), manufactured by Nippon Kayaku Co., Ltd.) 21.9 parts by mass, photocuring initiator (B) as bis (2, 4, 4 6.5 parts by mass of 6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure (registered trademark) 819, manufactured by BASF Japan KK), as a compound (C), a PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered)) (Trademark) ZCR-6007H, nonvolatile content 65% by mass, acid value: 70 mg KOH / g, manufactured by Nippon Kayaku Co., Ltd.) 77.5 parts by mass (50.4 parts by mass in terms of nonvolatile content), other than component (C) As a compound (D) having an ethylenically unsaturated group, dipentaerythritol hexaacrylate (KAYARAD (
  • Example 4 As component (A), 19.9 parts by mass of a dicyclopentadiene type epoxy resin (XD-1000 (trade name), manufactured by Nippon Kayaku Co., Ltd.), as a photocuring initiator (B), bis (2,4, 6.5 parts by mass of 6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure (registered trademark) 819, manufactured by BASF Japan KK), as a compound (C), a PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered)) (Trademark) ZCR-6007H, nonvolatile content 65% by mass, acid value: 70 mg KOH / g, manufactured by Nippon Kayaku Co., Ltd.) 77.5 parts by mass (50.4 parts by mass in terms of nonvolatile content), other than component (C) As a compound (D) having an ethylenically unsaturated group, dipentaerythritol hexaacrylate (KA
  • Example 5 As component (A), dicyclopentadiene type epoxy resin (XD-1000 (trade name), manufactured by Nippon Kayaku Co., Ltd.) 15.8 parts by mass, photocuring initiator (B) as bis (2, 4, 4 6.5 parts by mass of 6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure (registered trademark) 819, manufactured by BASF Japan KK), as a compound (C), a PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered)) (Trademark) ZCR-6007H, nonvolatile content 65% by mass, acid value: 70 mg KOH / g, manufactured by Nippon Kayaku Co., Ltd.) 77.5 parts by mass (50.4 parts by mass in terms of nonvolatile content), other than component (C) As a compound (D) having an ethylenically unsaturated group, dipentaerythritol hexaacrylate (KAYARAD (
  • Example 6 As component (A), dicyclopentadiene type epoxy resin (XD-1000 (trade name), manufactured by Nippon Kayaku Co., Ltd.) 5.9 parts by mass, photocuring initiator (B) as bis (2, 4, 4 6.5 parts by mass of 6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure (registered trademark) 819, manufactured by BASF Japan KK), as a compound (C), a PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered)) (Trademark) ZCR-6007H, nonvolatile content 65% by mass, acid value: 70 mg KOH / g, manufactured by Nippon Kayaku Co., Ltd.) 77.5 parts by mass (50.4 parts by mass in terms of nonvolatile content), other than component (C) As compound (D) having an ethylenically unsaturated group, dipentaerythritol hexaacrylate (KAYARAD (registere
  • Example 7 As component (A), dicyclopentadiene type epoxy resin (XD-1000 (trade name), manufactured by Nippon Kayaku Co., Ltd.) 15.8 parts by mass, photocuring initiator (B) as bis (2, 4, 4 6.5 parts by mass of 6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure (registered trademark) 819, manufactured by BASF Japan KK), as a compound (C), a PGMEA solution of TrisP-PA epoxy acrylate compound (KAYARAD (registered)) (Trademark) ZCR-6007H, nonvolatile content 65% by mass, acid value: 70 mg KOH / g, manufactured by Nippon Kayaku Co., Ltd.) 77.5 parts by mass (50.4 parts by mass in terms of nonvolatile content), (C) As a compound (D) having an ethylenically unsaturated group, dipentaerythritol hexaacrylate (KAYARAD (registered
  • KAYARAD registered trademark ZFR-1553H does not have the structure represented by the above formula (2).
  • Example 2 A varnish was prepared in the same manner as in Example 1 except that 22.4 parts by mass of a naphthalene type epoxy resin (HP-4710 (trade name), manufactured by DIC Corporation) was used instead of the component (A). A sheet, a laminate for evaluation, and a cured product for evaluation were obtained.
  • a naphthalene type epoxy resin HP-4710 (trade name), manufactured by DIC Corporation
  • Example 3 A varnish was prepared in the same manner as in Example 1 except that 22.4 parts by mass of a polyfunctional epoxy resin (1031S (trade name), manufactured by Mitsubishi Chemical Corporation) was used instead of the component (A), and the resin A sheet, a laminate for evaluation, and a cured product for evaluation were obtained.
  • a polyfunctional epoxy resin 1031S (trade name), manufactured by Mitsubishi Chemical Corporation
  • the polyfunctional epoxy resin (1031S (trade name), manufactured by Mitsubishi Chemical Corporation) has the following structural formula (12).
  • a finger was lightly pressed against the resin surface edge of each A4-sized resin sheet with a support, and the degree of sticking to the finger was evaluated according to the following criteria.
  • ⁇ Sticking to the finger is hardly recognized. Although the edge part of the resin sheet with a support body sticks to a finger
  • X Sticking to the finger is recognized. The edge part of the resin sheet with a support body sticks to a finger
  • ⁇ Developability> The development surface of the evaluation laminate was visually measured for the time from the start of the development process until the residue disappeared, and then observed with a scanning electron microscope (SEM) (magnification 1000 times). Evaluated by criteria.
  • SEM scanning electron microscope
  • Double-circle The time until the visual development residue disappears is 50 sec or less, and there is no development residue in the range of 30 mm square even after SEM observation, and the developability is very excellent.
  • ⁇ Although the time until the visual development residue disappears exceeds 50 sec, there is no development residue in the 30 mm square area even after SEM observation, and the developability is excellent.
  • X There is a development residue in the range of 30 mm square, and the developability is inferior.
  • Examples 1 to 7 are excellent in plating adhesion and heat resistance. Among them, Example 2 has good heat resistance and plating adhesion, and Examples 3 to 7 are more excellent in heat resistance. On the other hand, Comparative Examples 1 to 3 have insufficient plating adhesion or heat resistance. Therefore, according to this invention, the resin composition excellent in plating adhesiveness and heat resistance, the resin sheet using the same, a multilayer printed wiring board, and a semiconductor device are obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Epoxy Resins (AREA)
  • Materials For Photolithography (AREA)
  • Laminated Bodies (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)

Abstract

L'invention concerne une composition de résine qui, lorsqu'elle est utilisée dans une carte de circuit imprimé multicouche, présente une résistance à la chaleur et un revêtement supérieurs et qui présente une adhérence de placage et une aptitude au développement supérieures. L'invention concerne également une feuille de résine présentant un corps support et une carte de circuit imprimé multicouche et un dispositif semi-conducteur qui utilisent ladite composition de résine et ladite feuille de résine avec présentant un corps support. La composition de résine comprend une résine époxy de type dicyclopentadiène (A) exprimée par la formule (1), un initiateur de photodurcissement (B), un composé (C) exprimé par la formule (2) et un composé (D) qui présente un groupe éthyléniquement insaturé autre que le composant (C).
PCT/JP2017/018032 2016-06-29 2017-05-12 Composition de résine, feuille de résine, carte de circuit imprimé multicouche et dispositif semi-conducteur WO2018003313A1 (fr)

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CN201780040121.0A CN109415489B (zh) 2016-06-29 2017-05-12 树脂组合物、树脂片材、多层印刷布线板及半导体装置
KR1020187035663A KR102324899B1 (ko) 2016-06-29 2017-05-12 수지 조성물, 수지 시트, 다층 프린트 배선판 및 반도체 장치
JP2018524942A JP6939784B2 (ja) 2016-06-29 2017-05-12 樹脂組成物、樹脂シート、多層プリント配線板及び半導体装置

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JP2018062570A (ja) * 2016-10-13 2018-04-19 三菱瓦斯化学株式会社 樹脂組成物、樹脂シート、プリント配線板及び半導体装置
WO2020045489A1 (fr) * 2018-08-30 2020-03-05 三菱瓦斯化学株式会社 Composition de résine, couche de résine, circuit imprimé multicouche et dispositif semi-conducteur
JP2022022261A (ja) * 2018-07-26 2022-02-03 味の素株式会社 樹脂組成物

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WO2021172319A1 (fr) * 2020-02-28 2021-09-02 セントラル硝子株式会社 Résine durcissable, composition de résine durcissable, produit durci, dispositif électronique, matériau de carte stratifiée, agent d'encapsulation de composant électronique et procédé de production de résine durcissable

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