WO2022264985A1 - 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 - Google Patents

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 Download PDF

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WO2022264985A1
WO2022264985A1 PCT/JP2022/023706 JP2022023706W WO2022264985A1 WO 2022264985 A1 WO2022264985 A1 WO 2022264985A1 JP 2022023706 W JP2022023706 W JP 2022023706W WO 2022264985 A1 WO2022264985 A1 WO 2022264985A1
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group
compound
formula
mass
parts
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English (en)
French (fr)
Japanese (ja)
Inventor
優音 熊沢
俊介 片桐
卓也 鈴木
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Priority to JP2023509476A priority Critical patent/JP7302760B2/ja
Priority to KR1020237028144A priority patent/KR102646474B1/ko
Priority to US18/570,322 priority patent/US12221523B2/en
Priority to CN202280043127.4A priority patent/CN117529509B/zh
Priority to EP22824974.4A priority patent/EP4321541B1/en
Publication of WO2022264985A1 publication Critical patent/WO2022264985A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/36—Amides or imides
    • C08F22/40—Imides, e.g. cyclic imides
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08L79/085—Unsaturated polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/085—Photosensitive compositions characterised by adhesion-promoting non-macromolecular additives
    • 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
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits

Definitions

  • the present invention relates to resin compositions, resin sheets, multilayer printed wiring boards, and semiconductor devices.
  • the resin composition used as the material of the insulating layer is mainly a thermosetting resin, and holes for obtaining electrical connection between the insulating layers are generally made by laser processing.
  • drilling holes by laser processing has the problem that the processing time becomes longer as the number of holes in a high-density substrate increases. Therefore, in recent years, by using a resin composition that allows the exposed area to be cured (exposure process) and the unexposed area to be removed (development process) by irradiation with light, etc., it is possible to perform batch drilling in the exposure and development processes. There is a demand for a resin sheet that makes this possible.
  • a method of exposure a method of exposing through a photomask using a mercury lamp as a light source is used, and a material that can be suitably exposed to the light source of this mercury lamp is desired.
  • This exposure method using a mercury lamp as a light source uses ghi crosstalk (g-line wavelength 436 nm, h-line wavelength 405 nm, i-line wavelength 365 nm), etc., and a general-purpose photocuring initiator can be selected.
  • a direct drawing exposure method has also been introduced in which drawing is performed directly on a photosensitive resin composition layer without using a photomask based on digital data of a pattern.
  • This direct writing exposure method has better alignment accuracy than the exposure method that uses a photomask, and can produce highly detailed patterns.
  • the light source uses monochromatic light such as a laser.
  • a DMD (Digital Micromirror Device) type apparatus capable of forming a high-definition resist pattern uses a light source with a wavelength of 405 nm (h-line).
  • i-line wavelength 365 nm
  • Alkaline development is used as the development method because it can obtain high-definition patterns.
  • the conductor layer is directly formed on one or both sides of the insulating layer by sputtering, ion plating, vapor deposition, electroless plating, or the like.
  • Methods of forming thin films have been practiced. However, these methods have a problem that the adhesion between the conductor layer and the insulating layer is remarkably lowered, for example, when exposed to high temperature in a moisture absorption state or a reflow process.
  • Patent Document 1 describes a resin composition containing a bismaleimide compound (curable resin) and a photoradical polymerization initiator (curing agent). .
  • Patent Document 2 describes a resin composition containing a polyvalent carboxy group-containing compound obtained by reacting a bismaleimide with a monoamine and then reacting an acid anhydride, and a curable resin such as an epoxy resin. There is a description. Patent Document 2 describes a polyvalent carboxy group-containing compound capable of obtaining a cured product having alkali developability.
  • Patent Document 1 a bismaleimide compound is used as the curable resin, but since the maleimide compound usually has poor light transparency, when the maleimide compound is included, the light does not sufficiently reach the photocuring initiator, The photocuring initiator hardly generates radicals and its reactivity is very low. Therefore, in Patent Document 1, the maleimide compound is cured by performing additional heating before development. Moreover, even if an adhesive metal such as titanium is inserted between the conductor layer and the insulating layer, the insulating layer after curing cannot obtain sufficient adhesion to the adhesive metal such as titanium. However, when exposed to high temperatures such as in a hygroscopic state or in a reflow process, the adhesion strength is significantly reduced.
  • Patent Document 1 Since the resin composition described in Patent Document 1 does not have sufficient alkali developability in the first place, an unexposed resin composition remains even after development. Therefore, in Patent Document 1, a high-definition pattern cannot be obtained, and cannot be used for manufacturing a high-density printed wiring board.
  • Patent Document 2 there is no specific description regarding adhesion to adhesive metals such as titanium.
  • the polyvalent carboxy group-containing compound needs to be obtained by reacting bismaleimide with monoamine and then reacting with an acid anhydride, so the process is complicated.
  • an aromatic amine compound is used as the monoamine, this polyvalent carboxy group-containing compound contains an amide group having an aromatic ring in its structure. Therefore, since this polyvalent carboxyl group-containing compound has poor light transmittance and inhibits the photocuring reaction, it is actually difficult to use it in a photosensitive resin composition.
  • the present invention has been made in view of such problems of the prior art. It has excellent photocurability with respect to energy rays, can impart excellent alkali developability in the development process, and the resulting insulating layer has excellent adhesion to adhesive metals such as titanium. , a resin composition, a resin sheet, a multilayer printed wiring board, and a semiconductor device.
  • a resin composition and a resin sheet containing a specific bismaleimide compound (A) and a specific imidazole compound (B) are effective in the exposure step in the production of a multilayer printed wiring board.
  • It does not inhibit the photocuring reaction has excellent photocurability with respect to various active energy rays, can provide excellent alkali developability in the development process, and the obtained insulating layer is made of titanium or the like. Since it has excellent adhesion with adhesive metals, it has been found that a high-density printed wiring board having a high-definition pattern and a semiconductor device can be obtained by using these, and the present invention has been completed. .
  • the present invention includes the following contents.
  • R 1 represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms.
  • R 2 is It represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms, and each R 3 independently represents a hydrogen atom or 1 to 1 carbon atoms.
  • each of R 4 to R 7 is independently a hydrogen atom, an aldehyde group, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted good, an aryl group having 6 to 20 carbon atoms, and the total number of carbon atoms of R 4 to R 7 is 8 or more).
  • the imidazole compound (B) is 2-undecylimidazole, 2-heptadecylimidazole, 1-(triphenylmethyl)imidazole, 1-(2,6-diisopropylphenyl)imidazole, 1-(10-hydroxy decyl)imidazole, 1-(2-phenylethyl)-1H-imidazole, 1-(2-cyanoethyl)-2-undecylimidazole, 1-benzyl-2-methylimidazole, 2,4-diphenyl-1H-imidazole, 4,5-diphenylimidazole, 1-tritylimidazole-4-carboxaldehyde, 2,4,5-triphenylimidazole, 2-(4-hydroxyphenyl)-4,5-diphenylimidazole, 2-(4-fluorophenyl )-4,5-diphenylimidazole, 2-(2-chlorophenyl)-4,5-diphos
  • each R 8 independently represents a group represented by the following formula (4) or a hydrogen atom.
  • Each R 9 independently represents a hydrogen atom or a straight group having 1 to 6 carbon atoms. A chain or branched alkyl group, provided that at least one of R 8 is a group represented by the following formula (4).
  • R 10 , R 11 and R 12 are each independently a hydrogen atom or an optionally substituted linear or branched alkyl group having 1 to 8 carbon atoms indicates.
  • R 13 , R 14 and R 15 are each independently a hydrogen atom, a hydroxy group, or an optionally substituted linear or branched C 1-6 is an alkyl group of n 2 is an integer of 1 to 10.
  • each R 16 independently represents a hydrogen atom, a methyl group, or an ethyl group.
  • Each R 17 independently represents a hydrogen atom or a methyl group.
  • each R 18 independently represents a hydrogen atom or a methyl group.
  • n 3 represents an integer of 1 to 10.
  • each R 19 independently represents a hydrogen atom, a methyl group, or an ethyl group.
  • each R 20 independently represents a hydrogen atom or a methyl group, and n 4 represents an integer of 1 to 10).
  • a semiconductor device comprising the resin composition according to any one of [1] to [6].
  • the resin composition and resin sheet of the present invention in the exposure step in the production of a multilayer printed wiring board, it does not inhibit the photocuring reaction and has excellent photocurability with respect to various active energy rays.
  • the development step excellent alkali developability can be imparted, and the resulting insulating layer has excellent adhesion to adhesive metals such as titanium.
  • a dense printed wiring board and a semiconductor device can be provided.
  • FIG. 1 is a 1 H-NMR chart of the photocuring initiator (E1) obtained in Synthesis Example 1.
  • FIG. FIG. 2 is a 1 H-NMR chart of an amic acid compound (MA-TMDA).
  • FIG. 3 is a 1 H-NMR chart of a maleimide compound (TMDM).
  • 4 is a 1 H-NMR chart of the compound (C1) obtained in Synthesis Example 3.
  • FIG. 1 is a 1 H-NMR chart of the photocuring initiator (E1) obtained in Synthesis Example 1.
  • FIG. 2 is a 1 H-NMR chart of an amic acid compound (MA-TMDA).
  • FIG. 3 is a 1 H-NMR chart of a maleimide compound (TMDM).
  • 4 is a 1 H-NMR chart of the compound (C1) obtained in Synthesis Example 3.
  • this embodiment the form for carrying out the present invention (hereinafter referred to as "this 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 and implemented within the scope of the gist thereof.
  • (Meth)acryl in this specification means both “acryl” and “methacryl” corresponding thereto.
  • the term “resin solid content” or “resin solid content in the resin composition” includes imidazole compound (B) and one or more carboxy groups in the resin composition.
  • Compound (C), photocuring initiator (E), additives, solvents, and components excluding fillers, and "100 parts by mass of resin solid content” refers to the imidazole compound (B), It means that the total amount of components excluding the compound (C) containing one or more carboxyl groups, the photo-curing initiator (E), the additive, the solvent, and the filler is 100 parts by mass.
  • Mw indicates mass average molecular weight
  • Mn indicates number average molecular weight
  • Mw/Mn indicates molecular weight distribution.
  • Mw, Mn, and Mw/Mn can be determined by gel permeation chromatography (GPC), in terms of polystyrene standards.
  • the resin composition of the present embodiment comprises a bismaleimide compound (A) (component (A) or a bismaleimide compound (A )) and an imidazole compound (B) (also referred to as component (B) or compound (B)) represented by formula (2).
  • the resin composition of the present embodiment contains compound (A) and compound (B), and is suitably used for producing a multilayer printed wiring board.
  • Adhesive metals such as titanium include, for example, titanium, zirconia, chromium, molybdenum, tin, nickel, magnesium, aluminum, tungsten, and alloys of these metals.
  • the resin composition of the present embodiment contains a bismaleimide compound (A) containing a structural unit represented by formula (1) and maleimide groups at both ends of the molecular chain.
  • R 1 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms.
  • R 2 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms.
  • Each R 3 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms.
  • Each n 1 independently represents an integer of 1-10.
  • the present inventors have found that the inclusion of the bismaleimide compound (A) together with the imidazole compound (B), which will be described later, allows the resin composition to have excellent photocurability with respect to various active energy rays (light rays). We presume that the reason for this is as follows.
  • maleimide compounds have poor light transmittance, so when a resin composition contains a maleimide compound, light does not sufficiently reach the photocuring initiator dispersed in the resin composition, causing the photocuring initiator to generate radicals. unlikely to occur. Therefore, the radical photoreaction of the maleimide compound is generally difficult to proceed, and even if the radical polymerization or dimerization reaction of maleimide alone proceeds, the reactivity is very low.
  • the bismaleimide compound (A) has the constitutional unit represented by the formula (1), ie, the alicyclic skeleton, and therefore has very excellent light transmittance.
  • the imidazole compound (B) does not inhibit the light transmittance, does not participate in the photoradical reaction, and does not react with the bismaleimide compound (A). Therefore, the light sufficiently reaches the photocuring initiator, the photoradical reaction of the maleimide occurs efficiently, and the compound (C) containing one or more carboxyl groups described later (component (C) or compound (C)), a maleimide compound (D) described later (also referred to as component (D) or compound (D)), and a photocuring initiator (E) described later (component (E) or initiator (E ) can be photocured using various active energy rays.
  • a chloroform solution containing 1% by mass of the bismaleimide compound was prepared, and the transmittance of the chloroform solution containing 1% by mass of the bismaleimide compound was measured using an active energy ray having a wavelength of 365 nm (i-line). In some cases, the transmittance is 5% or more, showing very excellent light transmittance.
  • the transmittance of a chloroform solution containing 1% by mass of a bismaleimide compound was measured using an active energy ray having a wavelength of 405 nm (h-line), the transmittance was 5% or more, which was very high. Exhibits excellent light transmission.
  • the transmittance at a wavelength of 365 nm (i-line) is preferably 8% or more, more preferably 10% or more, from the viewpoint of exhibiting more excellent light transmittance.
  • the transmittance at a wavelength of 405 nm (h-line) is preferably 8% or more, and preferably 10% or more, from the viewpoint of producing a printed wiring board having a higher density and finer wiring formation (pattern). more preferred.
  • the upper limit of the transmittance at a wavelength of 365 nm (i-line) and the transmittance at a wavelength of 405 nm (h-line) is, for example, 99.9% or less.
  • photocuring initiators tend to have low absorbance for light in the long wavelength region. For example, when using an active energy ray (ray) containing a wavelength of 405 nm (h-line), since the light of this wavelength is a relatively long wavelength, it is not absorbed by ordinary photocuring initiators, and this light is suitable. Polymerization does not proceed unless a photo-curing initiator capable of absorbing into and generating radicals is used.
  • ray active energy ray
  • the photocuring initiator (E) described later when the absorbance of a chloroform solution containing 0.01% by mass of the photocuring initiator (E) is measured, light with a wavelength of 405 nm (h line)
  • a photo-curing initiator exhibiting an extremely excellent light absorption property such as an absorbance of 0.1 or more.
  • the bismaleimide compound (A) and the imidazole compound (B) are excellent in light transmittance as described above, for example, even when an active energy ray containing a wavelength of 365 nm or an active energy ray containing a wavelength of 405 nm is used, the light is It sufficiently reaches the photocuring initiator, a radical reaction using radicals generated from the photocuring initiator proceeds, and photocuring becomes possible even in a composition containing a large amount of the bismaleimide compound (A).
  • maleimide compounds have extremely low water solubility and do not have reactivity with alkaline components in alkaline developing solutions, making it difficult to obtain alkaline developability.
  • the resin composition contains the bismaleimide compound (A) and the imidazole compound (B), it has excellent photocurability and very good alkali developability. The reason for this is not clear, but the inventors presume as follows.
  • the bismaleimide compound (A) has a relatively long chain and a flexible structure, and does not have a structure that causes interaction with the alkali component in the alkali developer.
  • the imidazole compound (B) does not have a structure that causes an interaction with an alkaline component in an alkaline developer. Therefore, the bismaleimide compound (A) and the imidazole compound (B) can be used in the alkaline developer while maintaining the structure of other components such as the compound (C) that is optionally blended in the alkaline developer. It can be dissolved in an alkaline developer along with the dissolution in .
  • the bismaleimide compound (A) and the imidazole compound (B) do not interact with the alkaline component in the alkaline developer. It is presumed that the resin composition has excellent alkali developability without inhibiting the components shown.
  • an adhesive metal such as titanium is usually inserted between the conductor layer (copper thin film) and the insulation layer in order to increase the adhesion between the conductor layer and the insulation layer.
  • the insulating layer surface does not have enough functional groups that have adhesiveness to metals such as titanium, even if an adhesive metal such as titanium is inserted between the conductor layer and the insulating layer, it will not work after curing. cannot obtain sufficient adhesion to adhesive metals such as titanium. Therefore, when the insulating layer is exposed to high temperature in a moisture-absorbing state or during a reflow process, etc., the adhesion strength between the conductor layer and the insulating layer is remarkably lowered, and there is a risk of peeling.
  • the resin composition contains the maleimide compound (A) and the imidazole compound (B), the resulting insulating layer has excellent adhesion to an adhesive metal such as titanium.
  • an adhesive metal such as titanium.
  • the imidazole compound (B) does not participate in the photoradical reaction and does not react with the bismaleimide compound (A). Therefore, even in a cured product (insulating layer) after photocuring of the bismaleimide compound (A), the imidazole compound (B) can exist while maintaining its structure. Since the imidazole compound (B) is bulky with a total number of carbon atoms of 8 or more contained in the functional group together with the specific functional group, even if the resin composition contains a compound having a carboxy group, the salt will not be formed. It is difficult to form and allows it to remain in its structure until an adhesive metal such as titanium is inserted.
  • the insulating layer can obtain sufficient adhesion to adhesive metals such as titanium, and the insulating layer is exposed to high temperatures during moisture absorption and reflow processes. It is presumed that it is possible to maintain excellent adhesion strength with the conductor layer even if the
  • the resin composition of the present embodiment does not inhibit the photocuring reaction in the exposure step in the production of a multilayer printed wiring board, has excellent photocurability with respect to various active energy rays, and develops.
  • excellent alkali developability can be imparted, and the resulting insulating layer has excellent adhesiveness with adhesive metals such as titanium.
  • the obtained cured product is also excellent in heat resistance, insulation reliability, and thermal stability. Therefore, according to the present embodiment, a protective film and an insulating layer can be suitably formed in a multilayer printed wiring board and a semiconductor device, and a high-density printed wiring board having a high-definition pattern and a semiconductor device can be obtained. can get.
  • the bismaleimide compound (A) is not particularly limited as long as it exhibits the effects of the present invention, but it preferably has a mass average molecular weight of 100 to 5000 in terms of obtaining a suitable viscosity and being able to suppress an increase in the viscosity of the varnish. , 300-4500.
  • R 1 is a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. show.
  • R 1 is preferably a linear or branched alkylene group, more preferably a linear alkylene group, from the viewpoint of obtaining a suitable viscosity and being able to control the viscosity increase of the varnish.
  • the number of carbon atoms in the alkylene group is preferably from 2 to 14, more preferably from 4 to 12, from the viewpoint that a more suitable viscosity can be obtained and the viscosity increase of the varnish can be more suitably controlled.
  • Examples of linear or branched alkylene groups include methylene, ethylene, propylene, 2,2-dimethylpropylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene.
  • the number of carbon atoms in the alkenylene group is preferably from 2 to 14, more preferably from 4 to 12, from the viewpoint that more suitable viscosity can be obtained and the viscosity increase of the varnish can be more suitably controlled.
  • Linear or branched alkenylene groups include, for example, vinylene group, 1-methylvinylene group, arylene group, propenylene group, isopropenylene group, 1-butenylene group, 2-butenylene group, 1-pentenylene group, 2 -pentenylene group, isopentylene group, cyclopentenylene group, cyclohexenylene group, dicyclopentadienylene group, and the like.
  • R 2 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms.
  • R 2 is preferably a straight-chain or branched alkylene group, more preferably a straight-chain alkylene group, from the viewpoint that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be more controlled. preferable.
  • the number of carbon atoms in the alkylene group is preferably from 2 to 14, more preferably from 4 to 12, from the viewpoint that a more suitable viscosity can be obtained and the viscosity increase of the varnish can be more suitably controlled.
  • the above R 1 can be referred to.
  • the number of carbon atoms in the alkenylene group is preferably from 2 to 14, more preferably from 4 to 12, from the viewpoint that more suitable viscosity can be obtained and the viscosity increase of the varnish can be more suitably controlled.
  • the linear or branched alkenylene group the above R 1 can be referred to.
  • R 1 and R 2 may be the same or different, but are preferably the same from the viewpoint of easier synthesis of the bismaleimide compound (A).
  • each R 3 is independently a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. show.
  • Each R 3 is independently a hydrogen atom or a linear or branched alkyl group having 1 to 16 carbon atoms, since a more suitable viscosity can be obtained and the viscosity increase of the varnish can be better controlled. More preferably, among R 3 , 1 to 5 groups (R 3 ) are linear or branched alkyl groups having 1 to 16 carbon atoms, and the remaining groups (R 3 ) are hydrogen atoms.
  • 1 to 3 groups (R 3 ) among R 3 are linear or branched alkyl groups having 1 to 16 carbon atoms, and the remaining groups (R 3 ) are hydrogen atoms.
  • 1 to 3 groups (R 3 ) among R 3 are linear or branched alkyl groups having 1 to 16 carbon atoms, and the remaining groups (R
  • the number of carbon atoms in the alkyl group is preferably from 2 to 14, more preferably from 4 to 12, in order to obtain a more suitable viscosity and to more suitably control the viscosity increase of the varnish.
  • Linear or branched alkyl groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, 1-ethylpropyl group, n-butyl group, 2-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 2-pentyl group, tert-pentyl group, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, n-heptyl, n-octyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylpentan
  • the number of carbon atoms in the alkenyl group is preferably from 2 to 14, more preferably from 4 to 12, in order to obtain a more suitable viscosity and more suitably control the viscosity increase of the varnish.
  • Linear or branched alkenyl groups include, for example, vinyl, allyl, 4-pentenyl, isopropenyl, isopentenyl, 2-heptenyl, 2-octenyl, and 2-nonenyl groups. be done.
  • each n 1 independently represents an integer of 1-10.
  • the bismaleimide compound (A) has maleimide groups at both ends of its molecular chain. Both ends mean both ends in the molecular chain of the bismaleimide compound (A). means that the maleimido group is at the chain end of R 1 or at the chain end at the N atom of the maleimide ring or at both ends.
  • the bismaleimide compound (A) may have maleimide groups other than both ends of the molecular chain.
  • the maleimide group is represented by formula (11), and the N atom is bonded to the molecular chain of the bismaleimide compound (A).
  • the maleimide groups bonded to the bismaleimide compound (A) may all be the same or different, but preferably the maleimide groups at both ends of the molecular chain are the same.
  • each R 21 independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. Both R 21 are preferably hydrogen atoms from the viewpoint of more favorable photocuring.
  • the number of carbon atoms in the alkyl group is preferably 1 to 3, more preferably 1 to 2, from the viewpoint of more favorable photocuring.
  • the linear or branched alkyl group the above R 3 can be referred to.
  • Examples of such a bismaleimide compound (A) include maleimide compounds represented by formula (12). These may be used singly or in admixture of two or more.
  • a represents an integer of 1-10.
  • a is preferably an integer of 1 to 6 from the viewpoint that a more suitable viscosity can be obtained and the viscosity increase of the varnish can be more suitably controlled.
  • a commercially available product can also be used as the bismaleimide compound (A).
  • Examples of commercially available products include MIZ-001 (trade name, containing maleimide compound of formula (12)) manufactured by Nippon Kayaku Co., Ltd.
  • the content of the bismaleimide compound (A) makes it possible to obtain a cured product containing the bismaleimide compound as a main component, can further improve the photocurability, and has excellent heat resistance and From the viewpoint of obtaining thermal stability, it is preferably contained in an amount of 10 to 90 parts by mass, more preferably 30 to 80 parts by mass, with respect to 100 parts by mass of the resin solid content in the resin composition. More preferably 75 parts by mass, even more preferably 50 to 70 parts by mass, even more preferably 55 to 65 parts by mass.
  • the content of the bismaleimide compound (A) is From the viewpoint that it is possible to obtain a cured product as a component, the photocurability can be further improved, and excellent heat resistance and thermal stability can be obtained, the bismaleimide compound (A) and the maleimide compound (D ) with respect to the total 100 parts by mass, preferably 10 to 90 parts by mass, more preferably 30 to 80 parts by mass, even more preferably 40 to 75 parts by mass, 50 to 70 parts by mass It is even more preferably contained, and even more preferably 55 to 65 parts by mass.
  • maleimide compound (D) examples include the compound represented by the formula (5), the compound represented by the formula (6), the compound represented by the formula (7), the compound represented by the formula (8), the compound represented by the formula ( 9) and the compound represented by the formula (10), preferably containing at least one selected from the group consisting of the compound represented by the formula (5), the compound represented by the formula (6) and more preferably at least one selected from the group consisting of compounds represented by the formula (7), the compound represented by the formula (5) and the compound represented by the formula (6) It is further preferable to contain at least one selected from the group consisting of
  • the bismaleimide compound (A) is contained.
  • the amount of bismaleimide compound (A) and compound (B) can impart better alkali developability and exhibit better curability without inhibiting the photocuring initiator in the resin composition.
  • the compound (C), the compound (D), and the total 100 parts by weight of the initiator (E) preferably 10 to 85 parts by weight, more preferably 15 to 80 parts by weight, 30 It is more preferably 70 parts by mass, and even more preferably 40 to 60 parts by mass.
  • the bismaleimide compound (A) can be used singly or in a suitable mixture of two or more.
  • a bismaleimide compound (A) can be produced by a known method.
  • 1,2,4,5-cyclohexanetetracarboxylic dianhydride, a monomer containing a diamine including dimer diamine and the like, and maleic anhydride are generally heated at about 80 to 250°C, preferably about 100 to 200°C.
  • the polyaddition reaction is usually carried out for about 0.5 to 50 hours, preferably about 1 to 20 hours to obtain a polyadduct.
  • the polyadduct is subjected to an imidation reaction at a temperature of usually about 60 to 120° C., preferably about 80 to 100° C., for about 0.1 to 2 hours, preferably about 0.1 to 0.5 hours.
  • the bismaleimide compound (A) can be obtained by a dehydration ring closure reaction.
  • Dimer diamine is obtained, for example, by a reductive amination reaction of dimer acid, and the amination reaction is performed by a known method such as a reduction method using ammonia and a catalyst (for example, JP-A-9-12712). method).
  • a dimer acid is a dibasic acid obtained by dimerizing an unsaturated fatty acid by an intermolecular polymerization reaction or the like. Although it depends on synthesis conditions and purification conditions, it usually contains a small amount of monomer acid, trimer acid, etc. in addition to dimer acid. A double bond remains in the molecule obtained after the reaction.
  • a dimer acid is obtained, for example, by polymerizing an unsaturated fatty acid using a Lewis acid and a Bronsted acid as a catalyst.
  • a dimer acid can be produced by a known method (for example, the method described in JP-A-9-12712).
  • unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-gamma-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, boseopentaenoic acid, osponded acid, sardine acid, tetracosapentaenoic acid, docosahexaenoic acid, and herring acid.
  • the number of carbon atoms in the unsaturated fatty acid is generally 4-24, preferably 14-20.
  • the diamine-containing monomer is previously dissolved or dispersed in an organic solvent in an inert atmosphere such as argon, nitrogen, or the like, to form a diamine-containing monomer solution and preferably.
  • 1,2,4,5-Cyclohexanetetracarboxylic dianhydride can be dissolved in an organic solvent or dispersed in a slurry state, or added in a solid state to the above-mentioned diamine-containing monomer solution. preferable.
  • An arbitrary bismaleimide compound (A) is obtained by preparing the number of moles of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and the total number of moles of the monomer containing diamine and the maleimide compound. be able to.
  • solvents can be used in the polyaddition reaction and imidization reaction.
  • solvents include amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; Esters such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -methyl- ⁇ -butyrolactone, ethyl lactate, methyl acetate, ethyl acetate, and butyl acetate; methanol, ethanol , and aliphatic alcohols having 1 to 10 carbon atoms such as propanol; aromatic group-containing phenols such as phenol and cresol; aromatic group-containing alcohols such as benzyl
  • a catalyst in the imidization reaction for example, tertiary amines and dehydration catalysts can be used.
  • Preferred tertiary amines are heterocyclic tertiary amines such as pyridine, picoline, quinoline, and isoquinoline.
  • Dehydration catalysts include, for example, acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride.
  • the amount of the catalyst to be added is, for example, about 0.5 to 5.0 times the molar equivalent of the imidizing agent with respect to the amide group, and 0.5 to 10.0 times the molar amount of the dehydration catalyst with respect to the amide group. Equivalent weights are preferred.
  • this solution may be used as the bismaleimide compound (A) solution, or a poor solvent may be added to the reaction solvent to turn the bismaleimide compound (A) into a solid.
  • poor solvents include water, methyl alcohol, ethyl alcohol, 2-propyl alcohol, ethylene glycol, triethylene glycol, 2-butyl alcohol, 2-pentyl alcohol, 2-hexyl alcohol, cyclopentyl alcohol, cyclohexyl alcohol, phenol, and t-butyl alcohol.
  • the resin composition of this embodiment contains the imidazole compound (B) represented by formula (2).
  • Compound (B) can be used singly or in combination of two or more.
  • R 4 to R 7 are each independently a hydrogen atom, an aldehyde group, an optionally substituted alkyl group having 1 to 20 carbon atoms, or optionally a substituted group. , represents an aryl group having 6 to 20 carbon atoms, and the total number of carbon atoms of R 4 to R 7 is 8 or more.
  • the compound (B) does not inhibit light transmittance, does not participate in photoradical reactions, and does not react with the bismaleimide compound (A). Therefore, in the exposure step in manufacturing a multilayer printed wiring board, a cured product can be suitably obtained using various active energy rays without inhibiting the photocuring reaction. Moreover, compound (B) does not have a structure that causes an interaction with an alkaline component in an alkaline developer. Therefore, in the development step, a resin composition containing the compound (B) can be obtained together with the bismaleimide compound (A), and after exposure, excellent alkali developability is imparted to the resin composition in the unexposed areas. be able to.
  • the compound (B) has a specific functional group, and the total number of carbon atoms contained in the functional group is 8 or more, so it is bulky, so in the cured product (insulating layer) after photocuring, titanium It can remain in place while retaining its structure until an adhesive metal is inserted.
  • the imidazole compound since the imidazole compound has excellent adhesion to metals, the obtained insulating layer can obtain sufficient adhesion to adhesive metals such as titanium. Therefore, even if the insulating layer is exposed to high temperature in a moisture absorption state or a reflow process, etc., it is possible to maintain excellent adhesion strength with the conductor layer.
  • Compound (B) is contained at 1% by mass by preparing a chloroform or N-methylpyrrolidone solution and using an active energy ray containing a wavelength of 365 nm (i-line) to contain 1% by mass of compound (B).
  • the transmittance is preferably 5% or more.
  • This compound (B) exhibits extremely excellent light transmittance.
  • the transmittance of a chloroform or N-methylpyrrolidone solution containing 1% by mass of the compound (B) is measured using an active energy ray having a wavelength of 405 nm (h-line), the transmittance is It is preferably 5% or more.
  • the transmittance at a wavelength of 405 nm (h-line) is 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more, in that order, since a resin composition with excellent photocurability can be obtained. is a preferable range.
  • the upper limit of the transmittance at a wavelength of 365 nm (i-line) and the transmittance at a wavelength of 405 nm (h-line) is, for example, 99.9% or less.
  • each of R 4 to R 7 is independently a hydrogen atom, an aldehyde group, an optionally substituted alkyl group having 1 to 20 carbon atoms, or a substituent. represents an aryl group having 6 to 20 carbon atoms, which may have
  • the aldehyde group includes, for example, a formyl group or a group represented by *--R 23 --CHO.
  • R 23 include linear or branched hydrocarbon groups having a total of 1 to 20 carbon atoms. Note that * indicates a bond with any one of R 4 to R 7 .
  • the hydrocarbon group may have a substituent.
  • substituents include, but are not limited to, halogen atoms (fluorine, chlorine, bromine, iodine, etc.), hydroxy groups, cyano groups, nitro groups, thiol groups, heterocyclic groups, straight chain aliphatic hydrocarbon group, branched aliphatic hydrocarbon group, cycloaliphatic hydrocarbon group, aryl group, aralkyl group, alkoxy group, alkenyl group, acyl group, alkoxycarbonyl group, alkyloyloxy group, aryloyloxy and alkylsilyl groups.
  • a formyl group is preferable because better compatibility can be obtained.
  • the optionally substituted alkyl group having 1 to 20 carbon atoms includes, for example, an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms.
  • alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, cyclohexyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, p-tert-butylcyclohexyl group, n-decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group,
  • the hydrocarbon group may have a substituent, and the above substituents may be referred to.
  • R 4 to R 7 contain at least an alkyl group having 8 or more carbon atoms, more preferably an alkyl group having 10 to 20 carbon atoms, in order to obtain better light transmittance. is more preferred, and it is even more preferred to contain an alkyl group having 11 to 18 carbon atoms.
  • the substituent when a substituent is included, the substituent preferably includes a halogen atom, a hydroxy group, a cyano group, and an aryl group because it does not participate in the photoradical reaction.
  • a fluorine atom and a chlorine atom are more preferable as the halogen atom in the substituent.
  • the aryl group in the substituent a phenyl group is more preferable.
  • R 4 to R 7 it is preferable for R 4 to R 7 to contain at least a phenylmethyl group and a phenylethyl group, because it is difficult to form a salt with a carboxylic acid and a more bulky structure can be obtained.
  • Examples of the optionally substituted aryl group having 6 to 20 carbon atoms include phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group and anthracenyl group.
  • substituents reference may be made to the foregoing. Among them, it is preferable that at least a phenyl group is included in R 4 to R 7 from the viewpoint of obtaining better light transmittance. Moreover, it is preferable not to contain a substituent, since the structure can be maintained for a longer time even in the cured product without participating in the photoradical reaction.
  • the substituent should include a halogen atom, a hydroxy group, a cyano group, a straight-chain aliphatic hydrocarbon group, and a branched aliphatic hydrocarbon group, since it does not participate in the photoradical reaction. is preferred.
  • a halogen atom a hydroxy group, a cyano group, a straight-chain aliphatic hydrocarbon group, and a branched aliphatic hydrocarbon group, since it does not participate in the photoradical reaction. is preferred.
  • a phenyl group is more preferable.
  • An isopropyl group is more preferable as the branched aliphatic hydrocarbon group in the substituent.
  • R 4 to R 7 include at least an undecyl group, an ethylcyano group, and a phenyl group, since they can provide more excellent light transmittance and can retain the structure even in the cured product for a longer time without participating in photoradical reactions. is preferred. Any group of R 4 to R 7 contains an undecyl group, and any group of R 4 to R 7 contains an ethylcyano group, that is, any group of R 4 to R 7 contains an undecyl group and It preferably contains an ethyl cyano group. It is preferred that each of the three groups selected from R 4 to R 7 has a phenyl group.
  • the total number of carbon atoms of R 4 to R 7 is 8 or more.
  • the carbon atoms contained in these groups are also carbon count in numbers. That is, when R 4 to R 7 contain a formyl group, one carbon atom of the formyl group is counted.
  • a methylcyano group (--CH 2 CN) has two carbon atoms.
  • carbon atoms are included in the substituents of R 4 to R 7 , the number of carbon atoms is also counted.
  • a diisopropylphenyl group has 12 carbon atoms
  • a cyanophenyl group has 7 carbon atoms.
  • the carbon atoms of the imidazole ring are not counted. That is, when R 4 to R 7 contain a hydrogen atom, the number of carbon atoms in the imidazole ring bonded to the hydrogen atom is not counted, and the number of carbon atoms is 0 in this case. That is, in the present specification, imidazole in which all of R 4 to R 7 are hydrogen atoms has a total number of carbon atoms of 0.
  • the total number of carbon atoms of R 4 to R 7 is preferably 10 to 20 from the viewpoint of maintaining a light transmittance that does not hinder photocuring, hardly participating in the reaction, and obtaining a bulky structure. 11-18 is more preferred.
  • imidazole compound (B) 2-undecylimidazole, 2-heptadecylimidazole, 1-(triphenylmethyl)imidazole, 1-(2,6-diisopropylphenyl)imidazole, 1-(10-hydroxydecyl)imidazole, 1-(2-phenylethyl)-1H-imidazole, 1-(2-cyanoethyl)-2-undecylimidazole, 1 -benzyl-2-methylimidazole, 2,4-diphenyl-1H-imidazole, 4,5-diphenylimidazole, 1-tritylimidazole-4-carboxaldehyde, 2,4,5-triphenylimidazole, 2-(4- hydroxyphenyl)-4,5-diphenylimidazole, 2-(4-fluorophenyl)-4,5-diphenylimidazole, 2-(2-chlorophenyl)-4,5-diphen
  • the imidazole compound (B) 2-undecylimidazole and 1-(2-cyanoethyl)-2-undecyl are used because they can further improve adhesion with adhesive metals such as titanium. More preferably, it contains at least one selected from the group consisting of imidazole and 2,4,5-triphenylimidazole.
  • the content of the imidazole compound (B) is such that the insulating layer and the adhesive metal such as titanium have more sufficient adhesion, and the insulating layer is exposed to high temperatures such as in a moisture absorption state and in a reflow process.
  • the resin solid content of 100 parts by mass in the resin composition is 0. .1 to 50 parts by mass, more preferably 0.2 to 30 parts by mass, and even more preferably 0.3 to 10 parts by mass.
  • the resin composition contains the compound (C), the compound (D), and the initiator (E) together with the bismaleimide compound (A) and the imidazole compound (B), the imidazole compound (B)
  • the content is such that the insulating layer and the adhesive metal such as titanium have more sufficient adhesion, and even if the insulating layer is exposed to high temperatures in a moisture absorption state or in a reflow process, it will be more firmly attached to the conductor layer.
  • bismaleimide compound (A), compound (B), compound (C), compound (D), and initiator (E) with respect to a total of 100 parts by mass, preferably 0.1 to 20 parts by mass, more preferably 0.15 to 15 parts by mass, even more preferably 0.2 to 10 parts by mass , 0.3 to 7.0 parts by mass.
  • the resin composition of the present embodiment preferably further contains a compound (C) containing one or more carboxy groups.
  • Compound (C) is not particularly limited as long as it contains one or more carboxy groups.
  • the carboxyl group may be a salt such as a sodium salt or a potassium salt, or when two or more carboxyl groups are contained in the molecule, they may be an acid anhydride formed by linking them together.
  • Compound (C) can be used singly or in combination of two or more.
  • the resin composition containing the curing initiator (E) By using the resin composition containing the curing initiator (E), a cured product can be suitably obtained using various active energy rays without inhibiting the photocuring reaction.
  • the development step along with the bismaleimide compound (A) and the imidazole compound (B), the compound (C) and optionally the maleimide compound (D) and the photo-curing initiator (E) are included.
  • a resin composition can be obtained, and after exposure, excellent alkali developability can be imparted to the resin composition in the unexposed areas. The reason for this is not clear, but the inventors presume as follows.
  • the compound (C) does not have a functional group involved in the photocuring reaction in the exposure step and does not inhibit the photocuring reaction.
  • the bismaleimide compound (A) and the imidazole compound (B) do not have a skeleton that inhibits light transmittance, and have excellent light transmittance. Therefore, photopolymerization proceeds even when the compound (C), and optionally the compound (D) and the initiator (E) are included together with the bismaleimide compound (A) and the imidazole compound (B), A cured product can be preferably obtained.
  • the compound (C) can exist in the resin composition in the unexposed area.
  • the alkaline component in the alkaline developer and the carboxy group in the compound (C) can suitably form a salt, and the water solubility is improved. Therefore, excellent alkali developability can be obtained.
  • N-methylpyrrolidone solution containing 1% by mass of compound (C) is prepared, and an active energy ray containing a wavelength of 365 nm (i-line) is used to extract N-methyl containing 1% by mass of compound (C).
  • the transmittance is preferably 5% or more.
  • Such a compound (C) exhibits very good light transmittance.
  • the transmittance of an N-methylpyrrolidone solution containing 1% by mass of the compound (C) is measured using an active energy ray having a wavelength of 405 nm (h-line), the transmittance is 5% or more. is. Even in this case, it exhibits very good light transmittance.
  • a compound (C) when such a compound (C) is used, for example, when producing a printed wiring board having a high-density and high-definition wiring formation (pattern) using a direct drawing exposure method, an activity including a wavelength of 405 nm (h-line) Even when an energy beam is used, the photoradical reaction of maleimide occurs efficiently.
  • the transmittance at a wavelength of 365 nm (i-line) is 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more, in that order, since a resin composition with excellent photocurability can be obtained. is a preferable range.
  • the transmittance at a wavelength of 405 nm (h-line) is 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more, in that order, since a resin composition with excellent photocurability can be obtained. is a preferable range.
  • the upper limit of the transmittance at a wavelength of 365 nm (i-line) and the transmittance at a wavelength of 405 nm (h-line) is, for example, 99.9% or less.
  • the molecule of compound (C) preferably contains an integer of 2 to 20 carboxy groups in order to obtain better alkali developability.
  • the molecular weight of the compound (C) is preferably 50 to 10,000, more preferably 100 to 8,000, even more preferably 130 to 6,000, further preferably 150 to 5,000, from the viewpoint of further improving developability. It is even more preferred to have
  • the mass average molecular weight of compound (C) is preferably 50 to 10,000, more preferably 100 to 8,000, and even more preferably 150 to 5,000, from the viewpoint of further improving developability.
  • the content of the compound (C) can impart better alkali developability and can express good curability without inhibiting the photocuring reaction in the resin composition. It is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and 1.0 to 15 parts by mass with respect to 100 parts by mass of the resin solid content in the product is more preferable, more preferably 1.5 to 10 parts by mass, even more preferably 2.0 to 10 parts by mass.
  • the content of the compound (C) is more excellent.
  • bismaleimide compound (A), compound (B), compound (C), compound It is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, more preferably 1.0 to 100 parts by mass of (D) and the initiator (E). It is more preferably 10 parts by mass, and even more preferably 1.5 to 5.0 parts by mass.
  • Examples of the compound (C) include formic acid, aliphatic compounds containing one or more carboxy groups, aromatic compounds containing one or more carboxy groups, hetero compounds containing one or more carboxy groups, and anhydrides. . These compounds (C) can be used singly or in admixture of two or more.
  • aliphatic compounds containing one or more carboxyl groups include chain aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, chain aliphatic polycarboxylic acids, and alicyclic polycarboxylic acids. . These compounds have hydrogen atoms and substituents such as alkyl groups, alkoxy groups, aryloxy groups, aryl groups, aminoalkyl groups, hydroxy groups, amino groups, and carboxyalkyl groups in their molecules. good too. In addition, when these compounds have two or more carboxyl groups in the molecule, they may be acid anhydrides formed by linking them together.
  • these compounds When these compounds have a carboxyalkyl group in the molecule, they may be an acid anhydride formed by combining the carboxyalkyl group and the carboxy group. When these compounds have two or more carboxyalkyl groups in the molecule, they may be acid anhydrides formed by linking them together.
  • alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n -heptyl group, and n-octyl group.
  • alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-hexanoxy, and 2-methylpropoxy groups.
  • Aryloxy groups include, for example, a phenoxy group and a p-tolyloxy group.
  • Aryl groups include, for example, phenyl, toluyl, benzyl, methylbenzyl, xylyl, mesityl, naphthyl, and anthryl groups.
  • aminoalkyl groups include aminomethyl, aminoethyl, aminopropyl, aminodimethyl, aminodiethyl, aminodipropyl, aminobutyl, aminohexyl, and aminononyl groups.
  • Carboxyalkyl groups include, for example, carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, carboxyhexyl, and carboxynonyl groups.
  • Chain aliphatic monocarboxylic acids include, for example, acetic acid, propionic acid, isobutyric acid, butyric acid, isovaleric acid, valeric acid, caproic acid, lactic acid, succinic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecane saturated fatty acids such as hexadecanoic acid, heptadecanoic acid and octadecanoic acid; unsaturated fatty acids such as oleic acid, elaidic acid, erucic acid, nervonic acid, linolenic acid, stearidonic acid, eicosapentaenoic acid, linoleic acid and linolenic acid mentioned.
  • alicyclic monocarboxylic acids examples include cyclopropanecarboxylic acid, cyclopropenecarboxylic acid, cyclobutanecarboxylic acid, cyclobutenecarboxylic acid, cyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, cyclohexenecarboxylic acid, and cycloheptanecarboxylic acid.
  • Acids monocyclic carboxylic acids such as cycloheptenecarboxylic acid, cyclooctanecarboxylic acid, and cyclooctenecarboxylic acid, norbornanecarboxylic acid, tricyclodecanecarboxylic acid, tetracyclododecanecarboxylic acid, adamantanecarboxylic acid, methyladamantanecarboxylic acid , ethyladamantanecarboxylic acid, and polycyclic or bridged alicyclic carboxylic acids such as butyladamantanecarboxylic acid.
  • chain aliphatic polycarboxylic acids include carboxylic acids in which one or more carboxy groups are further added to chain aliphatic monocarboxylic acids.
  • Examples include propiondioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, and octadecanedioic acid.
  • alicyclic polycarboxylic acids include carboxylic acids in which one or more carboxy groups are further added to alicyclic monocarboxylic acids.
  • carboxylic acids in which one or more carboxy groups are further added to alicyclic monocarboxylic acids.
  • Examples of the base skeleton of aromatic compounds containing one or more carboxyl groups include benzoic acid, phenyleneacetic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, pentacarboxybenzene, hexacarboxybenzene, naphthalenecarboxylic acid, and naphthalene.
  • Aromatic compounds have, for example, hydrogen atoms and alkyl groups, alkoxy groups, aryloxy groups, aryl groups, aminoalkyl groups, hydroxy groups, amino groups, carboxyalkyl groups, etc. on the aromatic rings of these parent skeletons. It may have a substituent.
  • these compounds when these compounds have two or more carboxyl groups in the molecule, they may be acid anhydrides formed by linking them together.
  • they when these compounds have a carboxyalkyl group in the molecule, they may be an acid anhydride formed by combining the carboxyalkyl group and the carboxy group.
  • these compounds When these compounds have two or more carboxyalkyl groups in the molecule, they may be acid anhydrides formed by linking them together.
  • substituents reference can be made to the above.
  • hetero compound containing one or more carboxy groups examples include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, and quinuclidine. , chromenes, thianthrenes, phenothiazines, phenoxazines, xanthenes, acridines, phenazines, and carbazoles.
  • Hetero compounds have, for example, hydrogen atoms and substituents such as alkyl groups, alkoxy groups, aryloxy groups, aryl groups, aminoalkyl groups, hydroxy groups, amino groups, and carboxyalkyl groups on their parent skeleton. You may have In addition, when these compounds have two or more carboxyl groups in the molecule, they may be acid anhydrides formed by linking them together. When these compounds have a carboxyalkyl group in the molecule, they may be an acid anhydride formed by combining the carboxyalkyl group and the carboxy group. When these compounds have two or more carboxyalkyl groups in the molecule, they may be acid anhydrides formed by linking them together. For these substituents, reference can be made to the above.
  • the compatibility with the bismaleimide compound (A) and the imidazole compound (B) is even more excellent, and the alkali component in the alkali developer can quickly and suitably form a salt. is further improved, it is preferable to contain the compound represented by formula (3).
  • each R 8 independently represents a group represented by formula (4) or a hydrogen atom.
  • Each R 9 independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. However, at least one of R 8 is a group represented by formula (4).
  • -* represents a bond with the oxygen atom (O) directly linked to R 8 in formula (3).
  • R 8 preferably contains two or more groups represented by formula (4), more preferably three or more groups, because R 8 can impart better alkali developability. is more preferably a group represented by formula (4).
  • the group represented by formula (4) when the position of the carbonyl group is the 1-position with respect to the cyclohexane ring, if a carboxy group is bonded at the 2-position with respect to the carbonyl group, another A carboxy group may be attached to any of the 3- to 6-positions on the cyclohexane ring.
  • the structure of the carbonyl group and the two carboxy groups bonded to the cyclohexane ring has a three-dimensional structure. It exists as a isomer and as a mixture of cis and trans isomers. That is, the compound represented by formula (3) may be a single compound or a mixture containing two or more isomers.
  • At least one of R 8 is preferably a group represented by formula (13) because it can impart better alkali developability. That is, in the group represented by formula (13), the steric structure of the carbonyl group bonded to the 1-position of the cyclohexane ring and the carboxy group at the 2-position is preferably cis. The other carboxyl group may have a cis or trans conformation. Since R 8 can impart even better alkali developability, it preferably contains two or more groups represented by formula (13), more preferably three or more groups, and all R 8 are represented by the formula A group represented by (13) is more preferable.
  • R 8 is a group represented by formula (13), better alkali developability can be imparted
  • the present inventors presume as follows. there is That is, when the carbonyl group bonded to the 1-position and the carboxy group bonded to the 2-position are cis-isomers, the carboxy group at the 2-position and the alkaline component in the alkaline developer form a salt in the resin composition. It can take a three-dimensional structure that is easier to form. Therefore, it is presumed that the water solubility is further improved and the inflow of the alkaline developer into the resin composition is further promoted.
  • -* represents a bond with the oxygen atom (O) directly linked to R 8 in formula (3).
  • each R 9 independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.
  • Linear or branched alkyl groups having 1 to 6 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 2-pentyl group, tert-pentyl group, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, and 2-methylpentan-3-yl groups.
  • R 9 is preferably a linear alkyl group having 1 to 6 carbon atoms from the viewpoint of exhibiting better solubility in solvents, such as methyl, ethyl, n-propyl, 2-butyl. More preferred are isobutyl, tert-butyl, and n-pentyl groups, and even more preferred are methyl, ethyl, and n-propyl groups.
  • the compound represented by the formula (3) can impart better alkali developability, and from the viewpoint of exhibiting better solubility in solvents, the compound represented by the formula (14), and the compound represented by the formula (15) ), and more preferably a compound represented by formula (15).
  • the content of the compound represented by formula (3) can impart better alkali developability, and the resin composition exhibits better curability without inhibiting the photocuring reaction. Therefore, it is preferably 10 to 100 parts by mass, more preferably 30 to 99 parts by mass, and 50 to 95 parts by mass with respect to the total 100 parts by mass of the compound (C). More preferably, it is contained in an amount of 60 to 93 parts by mass, and even more preferably in an amount of 80 to 90 parts by mass.
  • the compound represented by formula (3) can be produced by a known method.
  • an alcohol compound represented by formula (16) and an acid anhydride represented by formula (17) (cyclohexane-1, 2,4-tricarboxylic acid-1,2-anhydride).
  • the acid anhydride represented by formula (17) since the structure of two carbonyl groups and one carboxy group bonded to the cyclohexane ring has a three-dimensional structure, the cis form, the trans form, and the cis form and the trans form. Exists as a mixture of bodies. That is, the acid anhydride represented by formula (17) may be of one type alone, or may be a mixture containing two or more isomers.
  • each R 22 independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.
  • R 9 in the above formula (3) can be referred to, including preferred embodiments thereof.
  • Examples of alcohol compounds represented by formula (17) include ditrimethylolethane, ditrimethylolpropane, ditrimethylolbutane, ditrimethylolpentane, 2,2′-(oxybis(methylene))bis(propane-1,3- diol), 2,2′-(oxybis(methylene))bis(2-methylpropane-1,3-diol), and 2-((2,2-bis(hydroxymethyl)butoxy)methyl)-2-methyl propane-1,3-diol and the like.
  • the acid anhydride represented by the formula (17) when a cured product is produced using the compound represented by the formula (3), it is possible to impart better alkali developability, so in the formula (18) It preferably contains the represented acid anhydride (cis,cis-cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride). That is, in the acid anhydride represented by formula (18), when the positions of the carbonyl group are 1-position and 2-position with respect to the cyclohexane ring, the carbonyl group and , and two carbonyl groups are preferably cis-forms.
  • the esterification reaction can be carried out with or without a solvent.
  • the solvent is not particularly limited as long as it does not react with the alcohol compound and the acid anhydride.
  • solvents include halogen solvents such as dichloromethane, chloroform, dichloroethane, and chlorobenzene; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, dioxane, and acetonitrile; Ketone solvents such as isobutyl ketone, cyclopentanone, and cyclohexanone; Cellosolve solvents such as 2-ethoxyethanol and propylene glycol monomethyl ether; Aliphatic alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; aromatic group-containing phenol solvents such as; ethyl lactate, methyl acetate, ethyl acetate, butyl
  • halogen solvents aprotic polar solvents, ketone solvents, and ester solvents are preferable because they can sufficiently dissolve alcohol compounds and acid anhydrides.
  • Dichloromethane is preferred as the halogen solvent.
  • Dimethylacetamide is preferred as the aprotic polar solvent.
  • Methyl ethyl ketone is preferred as the ketone solvent.
  • Propylene glycol monomethyl ether is preferred as the cellosolve solvent.
  • Preferred ester solvents are butyl acetate, ⁇ -butyrolactone, and propylene glycol monomethyl ether acetate.
  • the amount used is usually 20 to 2000 parts by mass with respect to a total of 100 parts by mass of the alcohol compound and acid anhydride.
  • the esterification reaction may be carried out without a catalyst or with a catalyst.
  • the catalyst When using a catalyst, the catalyst includes acidic compounds such as hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid; sodium hydroxide, potassium hydroxide, water metal hydroxides such as calcium oxide and magnesium hydroxide; amine compounds such as triethylamine, tripropylamine, diisopropylethylamine, and tributylamine; aniline, N-methylaniline, N,N-dimethylaniline, and benzylamine; Aliphatic amines having an aromatic ring; heterocyclic compounds such as pyridine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, imidazole, triazole, and tetrazole; tetramethyl ammonium hydroxide
  • catalysts can be used singly or in admixture of two or more.
  • amine compounds, aliphatic amines having an aromatic ring, and heterocyclic compounds are preferred, and triethylamine and 4-dimethylaminopyridine are more preferred, from the viewpoint of good reactivity.
  • the amount used is usually 0.0001 to 1000 parts by mass per 1 part by mass of the alcohol compound.
  • the method of adding the catalyst is, for example, a method of adding directly to the alcohol compound and / or acid anhydride, or adding a solution dissolved in a soluble solvent or the like to the alcohol compound, acid anhydride, and / or a solvent containing these addition method.
  • the esterification reaction temperature is not particularly limited depending on the amount of catalyst and the solvent used, but is usually -20 to 150°C.
  • the reaction time is also not particularly limited, but is usually 0.5 to 100 hours. The reaction may be completed in one step or may be carried out in two or more steps.
  • the alcohol compound represented by formula (16) and the acid anhydride represented by formula (17) have relatively high reactivity, they can be esterified even without a catalyst.
  • the acid anhydride represented by the formula (17) preferably contains the acid anhydride represented by the formula (18) because of its higher reactivity with the alcohol compound.
  • no catalyst means that no or only a very small amount of a catalyst that contributes to the esterification reaction is added. Specifically, it means that the amount of the catalyst is 50 ppm or less with respect to 1 part by mass of the alcohol compound represented by formula (16) during the reaction. Moreover, during the reaction, it is preferable that the amount of the catalyst contributing to the esterification reaction is 0 ppm.
  • a halogen solvent, a ketone solvent, a ketone solvent, a halogen solvent, a ketone solvent, a and ester solvents are preferred.
  • Halogen solvents and ester solvents are more preferred from the viewpoints of exhibiting better solubility and suppressing hydrolysis of the acid anhydride.
  • the ester solvent is more preferable because it allows the alcohol compound and the acid anhydride to react satisfactorily, suppresses the hydrolysis of the acid anhydride, and reduces the environmental load.
  • Dichloromethane is preferable as the halogen solvent because it can exhibit better solubility.
  • ketone solvent methyl ethyl ketone is preferable from the viewpoint of exhibiting better solubility.
  • ester solvent butyl acetate, ⁇ -butyrolactone, and propylene glycol monomethyl ether acetate are preferable from the viewpoint of exhibiting better solubility.
  • the amount of the solvent used is usually 20 to 2000 parts by mass with respect to a total of 100 parts by mass of the alcohol compound and the acid anhydride, and is 20 to 1000 parts by mass to further reduce the environmental load. is preferred, and 20 to 500 parts by mass is more preferred.
  • the reaction temperature for esterification can be appropriately set depending on the solvent used, but it is usually -20 to 150°C, and since the esterification proceeds more favorably, it is 0 to 150°C. more preferably 20 to 120°C.
  • the reaction time is usually 0.5 to 100 hours. Side reactions are suppressed and the esterification proceeds more favorably, so the reaction time is preferably 0.5 to 80 hours. More preferably, it is 0.5 to 50 hours.
  • the reaction may be completed in one step or may be performed in two or more steps.
  • the alcohol compound and the acid anhydride can be sufficiently esterified without a catalyst, so the cost of the catalyst can be reduced, the step of removing the catalyst can be omitted, and impurities can be removed.
  • a compound of relatively high purity can be obtained. Therefore, under these production conditions, it is possible to omit the step of isolating the compound represented by the formula (3) from the reaction mixture described below and the purification step.
  • the reaction temperature and reaction time are as described above. The reason for this is not clear, but the inventors presume as follows. That is, the ester solvent can further suppress hydrolysis of the acid anhydride represented by formula (17), and can further suppress side reactions other than the intended esterification reaction. Therefore, it is presumed that impurities are less likely to occur compared to other solvents, and that the target product with higher purity can be obtained.
  • the method for isolating the target compound from the reaction mixture containing the compound represented by formula (3) is that when the target compound precipitates from the reaction solvent, it can be isolated by filtration or centrifugation. can.
  • the solvent is distilled off under reduced pressure, a suitable poor solvent is added to the reaction mixture, or the reaction mixture is discharged into the poor solvent to precipitate, It can be isolated by filtration or centrifugation.
  • poor solvents include hydrocarbons such as hexane, heptane, cyclohexane, toluene, and xylene. These solvents can be used singly or in admixture of two or more.
  • the isolated compound needs to be further purified, it can be purified using known methods.
  • Such methods include, for example, a distillation purification method, a recrystallization method, a column chromatography method, a sludge treatment, and an activated carbon treatment.
  • the obtained compound represented by formula (3) can be identified by a known method such as NMR (nuclear magnetic resonance spectroscopy).
  • the purity of the compound can be analyzed, for example, by GPC, liquid chromatography, IR spectroscopy, and the like.
  • Volatile components such as by-products and residual solvents in the compound can be quantitatively analyzed by, for example, GPC and gas chromatography.
  • Halides remaining in the compound can be identified, for example, by a liquid chromatograph-mass spectrometer, and can also be quantified by ion chromatography after decomposition by potentiometric titration with a silver nitrate solution or combustion method.
  • a fully hydrogenated aromatic polycarboxylic acid and/or a partially hydrogenated aromatic polycarboxylic acid can be used as the compound (C) from the viewpoint of imparting even better alkali developability to the resin composition. More preferably, it contains an acid anhydride of a compound. These compounds are more preferably used together with the compound represented by the formula (3), since they can impart even better alkali developability to the resin composition.
  • Acid anhydrides of fully hydrogenated aromatic polycarboxylic acids and acid anhydrides of partially hydrogenated aromatic polycarboxylic acids include, for example, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, and acid anhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride; 1,2,3-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 3,3′,4,4 '-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 2,3,3',4'-benzophenonetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid acid, 2,2',3,3'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 4,4'-oxyd
  • Acid anhydrides of fully hydrogenated aromatic polycarboxylic acids and acid anhydrides of partially hydrogenated aromatic polycarboxylic acids can impart even better alkali developability, and together with the compound represented by formula (3)
  • monocyclic cycloalkanes such as cyclopentane and cyclohexane
  • monocyclic cycloalkenes such as cyclopropene and cyclohexene
  • bicyclic alkanes such as decalin
  • bicyclic alkenes such as norbornene and norbornadiene
  • monocyclic cycloalkanes or monocyclic cycloalkenes are preferably monocyclic cycloalkanes or monocyclic cycloalkenes.
  • Such preferred acid anhydrides include, for example, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride and 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride. Further excellent alkali developability can be imparted, and when used together with the compound represented by formula (3), the compatibility with the compound represented by formula (3) is further improved. -cyclohexanetricarboxylic acid-1,2-anhydride is more preferred, and cis,cis-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride is more preferred.
  • the total content of the acid anhydride of the fully hydrogenated aromatic polycarboxylic acid and the partially hydrogenated aromatic polycarboxylic acid can impart better alkali developability, and in the resin composition Since it is possible to express better curability without inhibiting the photocuring reaction, it is preferably 0.05 to 40 parts by mass with respect to the total 100 parts by mass of the compound (C), and 0.1 to It is more preferably 35 parts by mass, still more preferably 1.0 to 30 parts by mass, even more preferably 5.0 to 25 parts by mass, and even more preferably 10 to 20 parts by mass. .
  • the resin composition of the present embodiment includes a compound represented by formula (5), a compound represented by formula (6), a compound represented by formula (7), a compound represented by formula (8), a compound represented by formula It is preferable to further include at least one maleimide compound (D) selected from the group consisting of compounds represented by (9) and compounds represented by formula (10).
  • the photoradical reactivity of maleimide compounds is usually very low.
  • the bismaleimide compound (A) is very excellent in light transmittance.
  • the imidazole compound (B) is also excellent in light transmittance. Therefore, even when the resin composition contains the maleimide compound (D), the bismaleimide compound (A) can be used together with the compound (B) and optionally the compound (C) and the initiator (E). Therefore, even if various active energy rays are used, sufficient light reaches the photo-curing initiator, the radical reaction using the radicals generated from the photo-curing initiator proceeds, and the photo-radical reaction of maleimide occurs efficiently. , can be light cured.
  • the resin composition containing the maleimide compound (D) also has excellent photocurability against various active energy rays in the exposure step in the production of a multilayer printed wiring board, and exhibits excellent alkalinity in the development step.
  • Developability can be imparted, and the resulting insulating layer has excellent adhesion to adhesive metals such as titanium.
  • the obtained cured product is also excellent in heat resistance, insulation reliability, and thermal stability. Therefore, according to the present embodiment, a protective film and an insulating layer can be suitably formed in a multilayer printed wiring board and a semiconductor device, and a high-density printed wiring board having a high-definition pattern and a semiconductor device can be obtained. can get.
  • the maleimide compound (D) it is possible to express better curability, more excellent heat resistance and thermal stability, and better solubility in solvents, a low melting point, low water absorption, and other resins.
  • At least selected from the group consisting of the compound represented by the formula (5), the compound represented by the formula (6), and the compound represented by the formula (7) from the viewpoint of expressing better compatibility of It preferably contains one type, and more preferably contains at least one type selected from the group consisting of the compound represented by formula (5) and the compound represented by formula (6).
  • R 10 , R 11 and R 12 each independently represent a hydrogen atom or an optionally substituted linear or branched alkyl group having 1 to 8 carbon atoms. show.
  • Linear or branched alkyl groups having 1 to 8 carbon atoms which may have a substituent include, for example, 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, cyclopentyl group, hexyl group, heptyl group and the like.
  • a hydrogen atom in these alkyl groups may be substituted with a fluorine atom, a halogen atom such as a chlorine atom, a cyano group, or the like.
  • a fluorine atom such as a chlorine atom, a cyano group, or the like.
  • a halogen atom such as a chlorine atom, a cyano group, or the like.
  • it is preferably a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group, more preferably a methyl group, an ethyl group, or an isopropyl group, and still more preferably a methyl group.
  • the compound represented by formula (5) exhibits even better photocurability, heat resistance, thermal stability, solubility in solvents, low melting point, low water absorption, and compatibility with other resins. From the viewpoint of achieving the above, the compound represented by Formula (19) (also referred to as TMDM in the present embodiment) is even more preferable.
  • R 13 , R 14 and R 15 are each independently a hydrogen atom, a hydroxy group, or an optionally substituted linear or branched C 1-6 Indicates an alkyl group.
  • n 2 represents an integer of 1-10.
  • R 3 in the above formula (1) can be referred to.
  • Alkyl groups include methyl, ethyl, n-propyl, and isopropyl from the viewpoint of exhibiting better solubility in solvents, a lower melting point, lower water absorption, and better compatibility with other resins. group is preferred, and methyl group is more preferred.
  • R 13 , R 14 and R 15 are linear or branched alkyl groups having 1 to 6 carbon atoms from the viewpoint of exhibiting better solubility in solvents. and R 14 is preferably a hydrogen atom. Preferable alkyl groups are as described above. n 2 is preferably an integer of 1 to 10, and an integer of 1 to 6, from the viewpoint of better solubility in solvents, more suitable viscosity, and more suitable control of the viscosity increase of the varnish. is more preferable.
  • n 21 is an integer of 1-5.
  • n 22 is an integer of 1-10.
  • each R 16 independently represents a hydrogen atom, a methyl group, or an ethyl group
  • each R 17 independently represents a hydrogen atom or a methyl group.
  • R 16 is preferably a methyl group or an ethyl group from the viewpoint of exhibiting better solubility in solvents, a low melting point, low water absorption, and better compatibility with other resins.
  • R 17 is preferably a hydrogen atom from the viewpoint of exhibiting better solubility in solvents, a low melting point, low water absorption, and better compatibility with other resins.
  • maleimide compound represented by formula (7) a commercially available product may be used, for example, BMI-70 (trade name) represented by formula (22) manufactured by K.I. Kasei Co., Ltd. may be mentioned.
  • each R 18 independently represents a hydrogen atom or a methyl group.
  • n 3 represents an integer of 1-10.
  • the maleimide compound represented by the formula (8) a commercially available product may be used, and examples thereof include MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd. represented by the formula (23).
  • n 31 is an integer of 1-10.
  • each R 19 independently represents a hydrogen atom, a methyl group, or an ethyl group.
  • R 19 is preferably a methyl group or an ethyl group from the viewpoint of exhibiting better solubility in solvents, a low melting point, low water absorption, and better compatibility with other resins.
  • the maleimide compound represented by formula (9) a commercially available product may be used, for example, BMI-80 (trade name) represented by formula (24) manufactured by K.I. Kasei Co., Ltd. may be mentioned.
  • each R 20 independently represents a hydrogen atom or a methyl group.
  • n 4 represents an integer of 1-10.
  • R 20 is preferably a hydrogen atom from the viewpoint of exhibiting better solubility in solvents, a low melting point, low water absorption, and better compatibility with other resins.
  • n 4 is more preferably an integer of 1 to 5 from the viewpoints of better solubility in solvents, more suitable viscosity, and more suitable control of the increase in viscosity of the varnish.
  • maleimide compound represented by formula (10) a commercially available product may be used, for example, BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd. represented by formula (25).
  • n 41 is an integer of 1-5.
  • the total content of the maleimide compound (D) is 10 to 90 parts per 100 parts by mass of the resin solid content in the resin composition, from the viewpoint of obtaining better heat resistance and thermal stability. It is preferably contained in parts by mass, more preferably 20 to 70 parts by mass, even more preferably 25 to 60 parts by mass, even more preferably 30 to 50 parts by mass, and 35 to 45 parts by mass. More preferably included.
  • the total content of the maleimide compound (D) is 100 in total of the bismaleimide compound (A) and the maleimide compound (D) from the viewpoint of obtaining better heat resistance and thermal stability.
  • parts by mass preferably 10 to 90 parts by mass, more preferably 20 to 70 parts by mass, even more preferably 25 to 60 parts by mass, and 30 to 50 parts by mass Even more preferably, it is even more preferable to contain 35 to 45 parts by mass.
  • a total of 100 parts by mass of the bismaleimide compound (A), the compound (B), the compound (C), the compound (D), and the initiator (E) is preferably 10 to 85 parts by mass, more preferably 15 to 80 parts by mass, even more preferably 20 to 45 parts by mass, and even more preferably 25 to 40 parts by mass. preferable.
  • the resin composition of the present embodiment may further contain another maleimide compound different from the bismaleimide compound (A) and the maleimide compound (D).
  • Such other maleimide compounds are not particularly limited as long as they are compounds having one or more maleimide groups in the molecule.
  • maleimide compounds include, for example, N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-anilinophenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl) Maleimide, 6-maleimidohexanoic acid, 4-maleimidobutyric acid, bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 4,4-diphenylmethanebismaleimide, bis (3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethanemaleimide, o-Phenylenebismaleimide
  • maleimide compounds As other maleimide compounds, it is preferable to use compounds with excellent light transmittance.
  • the total content of the other maleimide compounds is usually about 0.01 to 40 parts by mass per 100 parts by mass of the resin solid content in the resin composition. .
  • the resin composition of the present embodiment preferably further contains a photocuring initiator (E).
  • the photocuring initiator (E) is not particularly limited, and those known in the field generally used in photocurable resin compositions can be used.
  • the photocuring initiator (E) can be photocured using various active energy rays.
  • Photocuring initiators (E) include, for example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl Peroxides and organic peroxides exemplified by di-tert-butyl-di-perphthalate; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl) - acylphosphine oxides such as phenylphosphine oxide, benzoyl-diphenyl-phosphine oxide and bisbenzoyl-phenylphosphine oxide; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl
  • the photo-curing initiator (E) can also use a commercial product, for example, IGM Resins B.V. V. Omnirad (registered trademark) 369 (trade name) manufactured by IGM Resins B.I. V. Omnirad (registered trademark) 819 (trade name) manufactured by IGM Resins B.I. V. Company Omnirad (registered trademark) 819DW (trade name), IGM Resins B.I. V. Company Omnirad (registered trademark) 907 (trade name), IGM Resins B.I. V. Company Omnirad (registered trademark) TPO (trade name), IGM Resins B.I. V. Company Omnirad (registered trademark) TPO-G (trade name), IGM Resins B.I.
  • These photo-curing initiators (E) can be used singly or in admixture of two or more.
  • the photo-curing initiator (E) is prepared by preparing a chloroform solution containing 0.01% by mass, and using an active energy ray containing a wavelength of 365 nm (i-line), the photo-curing initiator (E) is 0.01 mass
  • the absorbance is preferably 0.1 or more, and this photocuring initiator (E) exhibits very excellent absorbance.
  • the absorbance of a chloroform solution containing 0.01% by mass of a photocuring initiator (E) is measured using an active energy ray having a wavelength of 405 nm (h-line), the absorbance is 0.1.
  • a photocuring initiator (E) when producing a printed wiring board having a high-density and high-definition wiring formation (pattern) using a direct drawing exposure method, a wavelength of 405 nm (h-line) Photoradical reaction of maleimide occurs efficiently even when an active energy ray containing is used.
  • the absorbance at a wavelength of 365 nm (i-line) is more preferably 0.15 or more because a resin composition having excellent photocurability can be obtained.
  • the absorbance at a wavelength of 405 nm (h-line) is more preferably 0.15 or more because a resin composition with excellent photocurability can be obtained.
  • the upper limit of the absorbance at a wavelength of 365 nm (i-line) and the absorbance at a wavelength of 405 nm (h-line) is, for example, 99.9 or less.
  • the content of the photocuring initiator (E) allows the photocuring to proceed more sufficiently without inhibiting the photocuring reaction in the resin composition, and makes the exposed area more sufficiently insoluble in alkali developability. From this point of view, it is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 30 parts by mass, and 0.3 to 10 parts by mass in 100 parts by mass of the resin solid content in the resin composition. It is more preferably 1.0 to 9.0 parts by mass, and even more preferably 1.0 to 9.0 parts by mass.
  • the photocuring initiator (E ) content of bismaleimide compound (A) It is preferably 0.1 to 20 parts by mass, preferably 0.15 to 15 parts by mass, with respect to a total of 100 parts by mass of the compound (B), the compound (C), the compound (D), and the initiator (E). more preferably, 0.2 to 10 parts by mass, and even more preferably 1.0 to 9.0 parts by mass.
  • oxime esters and acylphosphine oxides are preferable because they have higher sensitivity to various active energy rays.
  • 1,2-octanedione and 1-[4-(phenylthio)-,2-(O-benzoyloxime) are preferred because they have higher sensitivity to various active energy rays and better solubility in solvents.
  • ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), photocuring initiation represented by formula (26) and a photocuring initiator represented by formula (27) are more preferable, and a photocuring initiator represented by formula (26) and a photocuring initiator represented by formula (27) are more preferable.
  • the resin composition can be variously It is presumed that the higher sensitivity to active energy rays and the more excellent photocurability are due to the following reasons. That is, the photocuring initiator (E1) and the photocuring initiator (E2) have excellent compatibility with the bismaleimide compound (A) and the imidazole compound (B). Furthermore, these photocuring initiators have high absorbance for various active energy rays, especially active energy rays including i-line with a wavelength of 365 nm and active energy rays including h-line with a wavelength of 405 nm. , easily generate active radicals.
  • the resin composition does not inhibit the photocuring reaction in the exposure step in the production of a multilayer printed wiring board, and has excellent photocurability against various active energy rays. Excellent alkali developability can be imparted, and the obtained insulating layer has excellent adhesiveness with adhesive metals such as titanium. Moreover, the obtained cured product is also excellent in heat resistance, insulation reliability, and thermal stability. Therefore, according to the present embodiment, a protective film and an insulating layer can be suitably formed in a multilayer printed wiring board and a semiconductor device, and a high-density printed wiring board having a high-definition pattern and a semiconductor device can be obtained. can get.
  • the photocuring initiator (E1) and The total content of the photocuring initiator (E2) can impart better alkali developability and can express good curability without inhibiting the photocuring initiator in the resin composition. It is preferably 0.1 to 20 parts by mass with respect to a total of 100 parts by mass of the bismaleimide compound (A), the compound (B), the compound (C), the compound (D), and the initiator (E), It is more preferably 0.2 to 15 parts by mass, even more preferably 0.3 to 10 parts by mass, and even more preferably 0.5 to 8.0 parts by mass.
  • photocuring initiator (E1) represented by formula (26) The photocuring initiator (E1) represented by formula (26) is the following compound.
  • R25 represents an acetyl group or a benzoyl group. Among them, an acetyl group is preferable because it has higher sensitivity to various active energy rays.
  • R 26 represents a phenyl group or naphthyl group which may have a substituent.
  • groups include, for example, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a tetrafluoropropoxy group, a pentafluoropropoxy group, a hexafluoropropoxy group, a fluorine atom, a chlorine atom, a bromine atom, and a halogen atom such as an iodine atom, a nitro group, a cyano group, a carbamoyl group, a sulfamoyl group, and a phenyl group or naphthyl group having a substituent such as an alkoxy group having 1 to 4 carbon atoms.
  • a tetrafluoropropoxyphenyl group, a pentafluoropropoxyphenyl group, and a hexafluoropropoxyphenyl group are preferable, and a tetrafluoropropoxyphenyl group is more preferable, because they have higher sensitivity to various active energy rays.
  • R 27 represents a hydrogen atom or an optionally substituted linear or branched C 1-16 alkyl group.
  • Linear or branched alkyl groups having 1 to 16 carbon atoms which may have a substituent include, for example, 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, cyclopentyl group, hexyl group, 5-ethylhexyl group, 6-methylheptyl group, octyl group and the like.
  • 5-ethylhexyl group, 6-methylheptyl group, and octyl group are preferred, and 5-ethylhexyl group is preferred because they show better compatibility with the bismaleimide compound (A) and imidazole compound (B). more preferred.
  • Each R 28 independently represents a hydrogen atom or an optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms.
  • R 27 in formula (26) can be referred to.
  • a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable, and a methyl group is more preferable, because they are more excellent in solvent solubility.
  • n 5 independently represents an integer of 1-5.
  • the photo-curing initiator (E1) represented by formula (26) is an initiator in which the N-O bond is the (E) form or the initiator in the (Z) form, It may be a mixture of the (E) initiator and the (Z) initiator.
  • the photocuring initiator (E1) represented by formula (26) has sensitivity to various active energy rays, particularly active energy rays including i-rays with a wavelength of 365 nm and active energy rays including h-rays with a wavelength of 405 nm.
  • the photocuring initiator represented by the formula (28) is more preferable because it has a much higher value and is even more excellent in solvent solubility.
  • the photocuring initiator represented by formula (28) may be an initiator in which the NO bond is the (E) form, or an initiator in which the NO bond is the (Z) form, or (E) It may be a mixture of an initiator that is a isomer and an initiator that is a (Z) isomer.
  • the photo-curing initiator (E1) can be produced by a known method and is not particularly limited, but for example, the method described in JP-A-2014-500852 can be employed.
  • the resulting photocuring initiator (E1) can be identified by known methods such as NMR (nuclear magnetic resonance spectroscopy).
  • the purity of the photocuring initiator (E1) can be analyzed, for example, by GPC, liquid chromatography, IR spectroscopy, and the like.
  • Volatile components such as by-products and residual solvent in the photocuring initiator (E1) can be quantitatively analyzed by, for example, GPC and gas chromatography.
  • the remaining halogen compounds can be identified, for example, by a liquid chromatograph-mass spectrometer, and are decomposed by potentiometric titration using a silver nitrate solution or combustion method. It can also be quantified later by ion chromatography.
  • photocuring initiator (E2) represented by formula (27) The photocuring initiator (E2) represented by formula (27) is the following compound.
  • R 29 represents an optionally substituted C 6-24 aryl group or an optionally substituted C 3-24 heteroaryl group.
  • optionally substituted aryl groups having 6 to 24 carbon atoms include hydrogen atom, alkyl group having 1 to 4 carbon atoms, trifluoromethyl group, tetrafluoropropoxy group, fluorine atom, chlorine atom and bromine.
  • a phenanthryl group, and anthracenyl group having a substituent such as an atom, a halogen atom such as an iodine atom, a nitro group, a cyano group, a carbamoyl group, a sulfamoyl group, and an alkoxy group having 1 to 4 carbon atoms.
  • the optionally substituted heteroaryl group having 3 to 24 carbon atoms includes, for example, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a tetrafluoropropoxy group, a fluorine atom, a chlorine atom, A pyrrolyl group, a furyl group, a benzofuryl group, a thienyl group having a substituent such as a halogen atom such as a bromine atom and an iodine atom, a nitro group, a cyano group, a carbamoyl group, a sulfamoyl group, and an alkoxy group having 1 to 4 carbon atoms.
  • pyrazolyl group imidazolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, triazolyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, quinolyl group, isoquinolyl group, indolyl group, benzofuranyl group, benzothienyl group, A benztriazolyl group, a benzimidazolyl group, and the like are included. Among them, a benzofuryl group and a benzothienyl group are preferable, and a benzofuryl group is more preferable, because of their higher sensitivity to various active energy rays.
  • R 30 represents an acetyl group or a benzoyl group. Among them, an acetyl group is preferable because it has higher sensitivity to various active energy rays.
  • R 31 represents a hydrogen atom or an optionally substituted linear or branched C 1-16 alkyl group.
  • Linear or branched alkyl groups having 1 to 16 carbon atoms which may have a substituent include, for example, 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, cyclopentyl group, isopentyl group, hexyl group, 5-ethylhexyl group, heptyl group and the like.
  • isopentyl group, hexyl group and 5-ethylhexyl group are preferred, and isopentyl group is more preferred, because they exhibit better compatibility with the bismaleimide compound (A) and imidazole compound (B).
  • X represents an oxygen atom or a sulfur atom.
  • a sulfur atom is preferable because it has higher sensitivity to various active energy rays.
  • the photo-curing initiator (E2) represented by formula (27) is an initiator in which the NO bond is the (E) form or an initiator in the (Z) form, It may be a mixture of the (E) form of the initiator and the (Z) form of the initiator.
  • the photocuring initiator (E2) represented by formula (27) has sensitivity to various active energy rays, especially active energy rays including i-rays with a wavelength of 365 nm and active energy rays including h-rays with a wavelength of 405 nm.
  • the photocuring initiator represented by the formula (29) is more preferable because it has a higher molecular weight and excellent solvent solubility.
  • the photocuring initiator represented by formula (29) may be an initiator in which the N—O bond is the (E) form, or an initiator in the (Z) form, or (E) It may be a mixture of an initiator that is a isomer and an initiator that is a (Z) isomer.
  • the photocuring initiator (E2) can be produced by a known method and is not particularly limited, but for example, the method described in JP-T-2016-531926 can be employed.
  • the resulting photocuring initiator (E2) can be identified by known methods such as NMR (nuclear magnetic resonance spectroscopy).
  • the purity of the photocuring initiator (E2) can be analyzed, for example, by GPC, liquid chromatography, IR spectroscopy, and the like.
  • Volatile components such as by-products and residual solvent in the photocuring initiator (E2) can be quantitatively analyzed by, for example, GPC and gas chromatography.
  • the remaining halogen compounds can be identified, for example, by a liquid chromatograph-mass spectrometer, and are decomposed by potentiometric titration using a silver nitrate solution or combustion method. It can also be quantified later by ion chromatography.
  • the photocuring initiator (E) includes acylphosphine oxides together with the photocuring initiator (E1) and/or the photocuring initiator (E2).
  • it has even more excellent photocurability to active energy rays including i-lines with a wavelength of 365 nm and active energy rays including h-lines with a wavelength of 405 nm. It is preferable because a high-density printed wiring board having a pattern and a semiconductor device can be obtained.
  • the photo-curing initiator (E1) and the photo-curing initiator (E2) include various active energy rays (light rays), in particular, active energy rays including i-rays with a wavelength of 365 nm and h-rays with a wavelength of 405 nm. It has a relatively high absorbance for active energy rays.
  • the photo-curing initiator (E1) and the photo-curing initiator (E2) are very excellent in surface curability because the radical generation density is less likely to be lost even on surfaces exposed to air.
  • acylphosphine oxides exhibit high absorbance with respect to various active energy rays (light rays), particularly active energy rays including i-lines with a wavelength of 365 nm and active energy rays including h-lines with a wavelength of 405 nm.
  • light rays particularly active energy rays including i-lines with a wavelength of 365 nm and active energy rays including h-lines with a wavelength of 405 nm.
  • the photocuring initiator (E1) and/or the photocuring initiator (E2) it becomes possible to have even better photocurability.
  • the bismaleimide compound (A) and the imidazole compound (B) are excellent in transmittance for various active energy rays.
  • the resin composition can be cured relatively uniformly from the surface exposed to air to the inside (deep portion) not exposed to air.
  • the total content of the photocuring initiator (E1) and the photocuring initiator (E2) can impart better alkali developability, and the photocuring initiation in the resin composition bismaleimide compound (A), compound (B), compound (C), compound (D), photo-curing initiator (E1), photo-curing It is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, more preferably 0.1 to 20 parts by mass, based on a total of 100 parts by mass of the initiator (E2) and acylphosphine oxides.
  • acylphosphine oxides More preferably 3 to 10 parts by mass.
  • the total content of acylphosphine oxides is bismaleimide compound (A), imidazole compound (B), compound (C), compound (D), photocuring initiator (E1), photocuring initiator ( It is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, more preferably 0.3 to 10 parts by mass, based on a total of 100 parts by mass of E2) and acylphosphine oxides. Parts by mass are more preferred.
  • the resin composition contains the bismaleimide compound (A), the imidazole compound (B), the compound (C), the compound (D), and the initiator (E), the total acylphosphine oxides
  • the acylphosphine oxides are preferably compounds represented by formula (30).
  • the compound represented by the formula (30) has a higher absorbance to various active energy rays (light rays), in particular, active energy rays including an i-line with a wavelength of 365 nm and an active energy ray including an h-line with a wavelength of 405 nm. have Moreover, by using together with the photocuring initiator (E1) and/or the photocuring initiator (E2), it becomes possible to have even more excellent photocurability.
  • each R 32 independently represents a substituent represented by formula (31) or a phenyl group. At least one of R 32 is preferably a substituent represented by formula (31).
  • each R 33 independently represents a hydrogen atom or a methyl group.
  • -* represents a bond with the phosphorus atom (P) directly connected to R 32 in formula (30).
  • At least one of R 33 is preferably a methyl group, and more preferably all are methyl groups.
  • a chloroform solution containing 0.01% by mass of this compound was prepared, and the absorbance of this chloroform solution was measured using an active energy ray containing a wavelength of 365 nm (i-line).
  • the absorbance is 0.1 or more, showing very excellent absorbance for light with a wavelength of 365 nm (i-line). Therefore, this compound suitably generates radicals with respect to light with a wavelength of 365 nm (i-line).
  • the absorbance is preferably 0.15 or more.
  • the upper limit is, for example, 99.9 or less.
  • a chloroform solution containing 0.01% by mass of this compound was prepared, and the absorbance of this chloroform solution was measured using an active energy ray containing a wavelength of 405 nm (h-line).
  • the absorbance is 0.1 or more, showing very excellent absorbance for light with a wavelength of 405 nm (h-line).
  • an active agent containing a wavelength of 405 nm (h-line) is used. Even when an energy beam is used, the photoradical reaction of maleimide occurs efficiently.
  • the absorbance at a wavelength of 405 nm (h-line) is more preferably 0.15 or more because a resin composition with excellent photocurability can be obtained.
  • the upper limit is, for example, 99.9 or less.
  • Examples of the compound represented by formula (30) include acylphos such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. fin oxides.
  • the bismaleimide compound (A) and the imidazole compound (B) are more compatible with each other, are more excellent in solvent solubility, have more excellent light transmittance, and have a curing initiator (E1) and / or Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide is preferable because it can have even better photocurability when used together with the photocuring initiator (E2). .
  • These compounds can be used singly or in admixture of two or more.
  • a filler can be used in the resin composition of the present embodiment in order to improve various properties such as coating properties and heat resistance. It is preferable that the filler has insulating properties and does not impair the permeability to various active energy rays used for photocuring.
  • fillers include silica (e.g., natural silica, fused silica, amorphous silica, hollow silica, etc.), aluminum compounds (e.g., boehmite, aluminum hydroxide, alumina, aluminum nitride, etc.), boron compounds (e.g., boron nitride, etc.), magnesium compounds (e.g., magnesium oxide, magnesium hydroxide, etc.), calcium compounds (e.g., calcium carbonate, etc.), molybdenum compounds (e.g., molybdenum oxide, zinc molybdate, etc.), barium compounds (e.g., barium sulfate, barium silicate, etc.), talc (e.g., natural talc, calcined talc, etc.), mica, glass (e.g., short fiber glass, spherical glass, fine powder glass, E glass, T glass, and D glass etc.), silicone powder, fluororesin fillers, a
  • These fillers may be surface-treated with a silane coupling agent or the like, which will be described later.
  • Silica is preferable, and fused silica is more preferable, from the viewpoint of further improving the heat resistance of the cured product and obtaining better coating properties.
  • Specific examples of silica include SFP-130MC (trade name) manufactured by Denka Corporation, SC2050-MB (trade name), SC1050-MLE (trade name) and YA010C-MFN (trade name) manufactured by Admatechs Co., Ltd. ), and YA050C-MJA (trade name).
  • the particle size of the filler is not particularly limited, it is usually 0.005 to 10 ⁇ m, preferably 0.01 to 1.0 ⁇ m, from the viewpoint of obtaining more ultraviolet light transmittance of the resin composition.
  • the content of the filler is usually based on 100 parts by mass of the resin solid content in the resin composition, from the viewpoint of improving the light transmittance of the resin composition and the heat resistance of the cured product. It is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and even more preferably 100 parts by mass or less. In addition, when a filler is contained, the lower limit is usually 1 part by mass.
  • silane coupling agent and wetting and dispersing agent A silane coupling agent and/or a wetting and dispersing agent may be used in combination with the resin composition of the present embodiment in order to further improve the dispersibility of the filler and the adhesive strength between the polymer and/or resin and the filler. can.
  • silane coupling agents are not particularly limited as long as they are silane coupling agents generally used for surface treatment of inorganic substances.
  • Silane N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyldi ethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, [3-(6-aminohexylamino)propyl]trimethoxysilane, and [3-(N , N-dimethylamino)-propyl]trimethoxysilane; ⁇ -glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, Epoxysilanes such as sidoxypropy
  • the content of the silane coupling agent in the resin composition is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • the wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for paints. Specific examples include DISPERBYK (registered trademark)-110 (trade name), 111 (trade name), 118 (trade name), 180 (trade name), and 161 (trade name) manufactured by Big Chemie Japan Co., Ltd. , BYK®-W996 (trade name), W9010 (trade name), and W903 (trade name). These wetting and dispersing agents can be used singly or in combination of two or more.
  • the content of the wetting and dispersing agent is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • these compounds and resins when exposed to various active energy rays, especially active energy rays including i-line with a wavelength of 365 nm and active energy rays including h-line with a wavelength of 405 nm, the resin composition becomes photosensitive. and photocuring is preferred. These compounds and resins can be used singly or in admixture of two or more.
  • the cyanate ester compound is not particularly limited as long as it is a resin having an aromatic moiety substituted with at least one cyanato group (cyanate ester group) in the molecule.
  • Ar 1 represents a benzene ring, a naphthalene ring, or a single bond of two benzene rings. When there are more than one, they may be the same or different.
  • Ra is each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 1 carbon atom A group in which an alkyl group of ⁇ 6 and an aryl group of 6 to 12 carbon atoms are bonded.
  • the aromatic ring in Ra may have a substituent, and the substituents in Ar 1 and Ra can be selected at arbitrary positions.
  • p represents the number of cyanato groups bonded to Ar 1 and each independently represents an integer of 1-3.
  • q represents the number of Ra atoms bonded to Ar 1 , and is 4-p when Ar 1 is a benzene ring, 6-p when it is a naphthalene ring, and 8-p when two benzene rings are single bonded.
  • . t represents the average number of repetitions and is an integer of 0 to 50, and the cyanate ester compound may be a mixture of compounds with different t.
  • a divalent organic group having 1 to 50 carbon atoms (a hydrogen atom may be substituted with a hetero atom), a divalent nitrogen atom having 1 to 10
  • the organic group for example, -N-R-N-, where R represents an organic group
  • the alkyl group for Ra in formula (32) may have either a linear or branched chain structure or a cyclic structure (eg, cycloalkyl group, etc.). Further, the hydrogen atom in the alkyl group in formula (32) and the aryl group in Ra is substituted with a halogen atom such as a fluorine atom and a chlorine atom, an alkoxy group such as a methoxy group and a phenoxy group, or a cyano group. may
  • alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl and 2,2-dimethylpropyl. group, cyclopentyl group, hexyl group, cyclohexyl group, trifluoromethyl group and the like.
  • alkenyl groups include vinyl, (meth)allyl, isopropenyl, 1-propenyl, 2-butenyl, 3-butenyl, 1,3-butandienyl, and 2-methyl-2-propenyl. , 2-pentenyl group, and 2-hexenyl group.
  • aryl groups include phenyl, xylyl, mesityl, naphthyl, phenoxyphenyl, ethylphenyl, o-, m- or p-fluorophenyl, dichlorophenyl, dicyanophenyl and trifluorophenyl. groups, methoxyphenyl groups, o-, m- or p-tolyl groups, and the like.
  • Alkoxy groups include, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy groups.
  • divalent organic group having 1 to 50 carbon atoms for X in formula (32) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, and a biphenylylmethylene group. dimethylmethylene-phenylene-dimethylmethylene group, fluorenediyl group, and phthalidodiyl group.
  • a hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom and a chlorine atom, an alkoxy group such as a methoxy group and a phenoxy group, a cyano group, and the like.
  • a halogen atom such as a fluorine atom and a chlorine atom
  • an alkoxy group such as a methoxy group and a phenoxy group
  • a cyano group and the like.
  • Examples of the divalent organic group having 1 to 10 nitrogen atoms in X of formula (32) include an imino group and a polyimide group.
  • examples of the organic group for X in formula (32) include those having a structure represented by formula (33) and those having a structure represented by formula (34).
  • Ar 2 represents a benzenediyl group, a naphthalenediyl group, or a biphenyldiyl group, and when u is an integer of 2 or more, they may be the same or different.
  • Rb, Rc, Rf, and Rg each independently have 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 represents an aryl 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 hydroxy group.
  • u represents an integer of 0 to 5;
  • Ar 3 represents a benzenediyl group, a naphthalenediyl group, or a biphenyldiyl group, and when v is an integer of 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 alkoxy group having 1 to 4 carbon atoms, a hydroxy group, and a trifluoromethyl group. , or an aryl group substituted with at least one cyanato group.
  • v represents an integer of 0 to 5, it may be a mixture of compounds with different v.
  • X in formula (32) includes a divalent group represented by the following formula.
  • Each Rk independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • Ar 2 in formula (33) and Ar 3 in formula (34) include two carbon atoms represented by formula (33) or two oxygen atoms represented by formula (34), a benzenediyl group bonded to the 1,3-position or 1,3-position; , 3′- or 3,4′-positions, and two carbon atoms or two oxygen atoms attached to the 2,6-positions, 1,5-positions, 1,6-positions, 1, Naphthalenediyl groups bonded to 8-position, 1,3-position, 1,4-position, or 2,7-position can be mentioned.
  • the alkyl group and aryl group for Rb, Rc, Rd, Re, Rf and Rg in formula (33) and Ri and Rj in formula (34) are the same as in formula (32).
  • cyanato-substituted aromatic compound represented by formula (32) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, 1-cyanato-4-methylbenzene, 1-cyanato -2-, 1-cyanato-3-, or 1-cyanato-4-methoxybenzene, 1-cyanato-2,3-, 1-cyanato-2,4-, 1-cyanato-2,5-, 1- cyanato-2,6-, 1-cyanato-3,4- or 1-cyanato-3,5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, cyanatooctylbenzene, cyanatononylbenzene, 2-(4 -cyanatophenyl)-2-phenylpropane (4- ⁇ -cumylphenol cyanate), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-4
  • cyanate ester compounds can be used singly or in an appropriate mixture of two or more.
  • cyanate ester compound represented by formula (32) includes phenol novolak resins and cresol novolac resins (by a known method, phenol, alkyl-substituted phenol or halogen-substituted phenol and formalin, paraformaldehyde, etc.
  • Ar 4 —(CH 2 OR) 2 (R represents an alkyl group) and a phenolic compound reacted in the presence of an acidic catalyst or Ar A bis(hydroxymethyl) compound represented by 4- (CH 2 OH) 2 and a phenol compound are reacted in the presence of an acidic catalyst, or an aromatic aldehyde compound, an aralkyl compound and a phenol compound are polymerized.
  • phenol-modified xylene formaldehyde resin by a known method, a xylene formaldehyde resin and a phenolic compound are reacted in the presence of an acidic catalyst
  • modified naphthalene formaldehyde resin by a known method, a naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound in the presence of an acidic catalyst
  • a phenol-modified dicyclopentadiene resin or a phenol resin having a polynaphthylene ether structure
  • a known method a phenolic hydroxy group in one molecule
  • Polyhydric hydroxy naphthalene compounds having two or more in the presence of a basic catalyst, such as those obtained by dehydration condensation cyanated by the same method as described above, and these prepolymers, etc. mentioned.
  • These cyanate ester compounds can be used singly or in admixture of two or more.
  • the method for producing these cyanate ester compounds is not particularly limited, and known methods can be used.
  • a specific example is a method of obtaining or synthesizing a hydroxy group-containing compound having a desired skeleton, and modifying the hydroxy group by a known technique to form a cyanate.
  • Methods for cyanating a hydroxy group include, for example, the methods described in Ian Hamerton, "Chemistry and Technology of Cyanate Ester Resins," Blackie Academic & Professional.
  • Cured products using these cyanate ester compounds have excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion.
  • the content of the cyanate ester compound is 0.01 to 40 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • phenolic resin generally known phenolic resins having two or more hydroxy groups in one molecule can be used.
  • phenolic resin generally known phenolic resins having two or more hydroxy groups in one molecule can be used.
  • bisphenol A type phenol resin bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolak resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type phenol resin, biphenyl Aralkyl-type phenolic resins, cresol novolac-type phenolic resins, polyfunctional phenolic resins, naphthol resins, naphthol novolak resins, polyfunctional naphthol resins, anthracene-type phenolic resins, naphthalene skeleton-modified novolac-type phenolic resins, phenol aralkyl-type phenolic resins, naphthol aralkyl
  • the content of the phenolic resin in the resin composition is 0.01 to 40 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • oxetane resins can be used.
  • OXT-101 manufactured by Toagosei Co., Ltd.
  • the content of the oxetane resin is 0.01 to 40 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • benzoxazine compound generally known compounds can be used as long as they are compounds having two or more dihydrobenzoxazine rings in one molecule.
  • bisphenol A-type benzoxazine BA-BXZ (trade name, manufactured by Konishi Chemical Industry Co., Ltd.)
  • bisphenol F-type benzoxazine BF-BXZ (trade name, manufactured by Konishi Chemical Industry Co., Ltd.)
  • bisphenol S-type benzoxazine BS -BXZ trade name, manufactured by Konishi Chemical Industry Co., Ltd.
  • Pd-type benzoxazine trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.
  • Fa-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.)
  • phenol phthalate and rhein-type benzoxazines (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.)
  • the content of the benzoxazine compound in the resin composition is 0.01 to 40 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • Epoxy resins are not particularly limited, and generally known ones can be used.
  • epoxy resin a commercially available product can be used. is about 4
  • a naphthalene-type epoxy resin manufactured by DIC Corporation, HP-4710 (trade name) represented by formula (36).
  • epoxy resins can be used singly or in an appropriate mixture of two or more.
  • the content of the epoxy resin in the resin composition is 0.01 to 40 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • ⁇ Other compounds> Other compounds include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether; styrenes such as styrene, methylstyrene, ethylstyrene, and divinylbenzene; triallyl isocyanurate, trimethallyl Examples include isocyanurate and bisallylnadimide. These compounds can be used singly or in admixture of two or more.
  • the content of other compounds is 0.01 to 40 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
  • the resin composition of the present embodiment may contain an organic solvent, if necessary.
  • an organic solvent By using an organic solvent, it is possible to adjust the viscosity during preparation of the resin composition.
  • the type of organic solvent is not particularly limited as long as it can dissolve part or all of the resin in the resin composition.
  • organic solvents include halogen solvents such as dichloromethane, chloroform, dichloroethane, and chlorobenzene; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, dioxane, and acetonitrile; acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • ketone solvents such as , cyclopentanone, and cyclohexanone
  • cellosolve solvents such as 2-ethoxyethanol and propylene glycol monomethyl ether
  • aliphatic alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol
  • aromatic group-containing phenol solvents ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, methyl methoxypropionate, methyl hydroxyisobutyrate, ⁇ -butyrolactone, and propylene glycol monomethyl ether acetate
  • Aromatic hydrocarbon solvents such as xylene and the like are included.
  • a bismaleimide compound (A) and an imidazole compound (B), a compound (C), a compound (D), and a photocuring initiator (E) that are blended as necessary, and further, other resins and compounds, aprotic polar solvents, ketone solvents, cellosolve solvents, and ester solvents are preferable from the viewpoint of exhibiting better solubility, and aprotic solvents from the viewpoint of exhibiting further excellent solubility Polar solvents, ketone solvents, and ester solvents are more preferred.
  • Dimethylacetamide is preferred as the aprotic polar solvent.
  • Methyl ethyl ketone is preferred as the ketone solvent.
  • Propylene glycol monomethyl ether is preferred as the cellosolve solvent.
  • Preferred ester solvents are butyl acetate, ⁇ -butyrolactone, and propylene glycol monomethyl ether acetate. These organic solvents can be used singly or in admixture of two or more.
  • the resin composition of the present embodiment includes various high-performance resins such as thermosetting resins, thermoplastic resins, oligomers thereof, and elastomers that have not been mentioned so far, as long as the properties of the present embodiment are not impaired.
  • Molecular compounds; flame-retardant compounds not mentioned heretofore; additives and the like can also be used in combination. These are not particularly limited as long as they are commonly used.
  • flame-retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine; oxazine ring-containing compounds; phosphorus compounds such as phosphate compounds of phosphorus compounds, aromatic condensed phosphates, and halogen-containing condensed phosphates. mentioned.
  • Additives include UV absorbers, antioxidants, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, surface conditioners, brighteners, polymerization inhibitors, and heat A hardening accelerator etc. are mentioned. These components can be used singly or in admixture of two or more. The content of the other components in the resin composition is usually 0.1 to 10 parts by weight per 100 parts by weight of the resin solid content in the resin composition.
  • the resin composition of the present embodiment comprises a bismaleimide compound (A) and an imidazole compound (B), and optionally a compound (C), a maleimide compound (D), other maleimide compounds, a photocuring initiator (E ), fillers, other resins, other compounds, additives and the like can be appropriately mixed.
  • the method for producing the resin composition includes, for example, a method in which each component described above is sequentially added to a solvent and thoroughly stirred.
  • each component such as the bismaleimide compound (A) and the imidazole compound (B) in the resin composition is dispersed by stirring and dispersing using a stirring tank equipped with a stirrer having an appropriate stirring capacity. Dispersibility can be improved.
  • Stirring, mixing, and kneading processes include, for example, a stirring device for dispersion such as an ultrasonic homogenizer, a device for mixing such as three rolls, a ball mill, a bead mill, and a sand mill, or a revolving or rotating type It can be appropriately carried out using a known device such as a mixing device.
  • an organic solvent can be used as necessary during the preparation of the resin composition.
  • the type of 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 can be suitably used as a varnish when producing the resin sheet of this embodiment, which will be described later.
  • a varnish can be obtained by a well-known method.
  • the varnish is prepared by adding 10 to 900 parts by mass, preferably 30 to 500 parts by mass of an organic solvent to 100 parts by mass of the components excluding the organic solvent in the resin composition, and performing the known treatment (stirring, mixing , and kneading treatment, etc.).
  • the organic solvent used for preparing the varnish is not particularly limited, and specific examples thereof are as described above.
  • the resin composition of the present embodiment can be suitably used for producing a multilayer printed wiring board, and can be preferably used for applications requiring an insulating resin composition.
  • Examples include photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit boards (laminated board applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, and hole filling. It can be used for resins, part embedding resins, and the like.
  • the resin composition is excellent in photocurability and alkali developability, and therefore can be suitably used as a solder resist for multilayer printed wiring boards.
  • the resin composition has excellent photocurability and alkali developability, and has excellent adhesion to adhesive metals such as titanium, so that it can be more preferably used as an insulating layer for multilayer printed wiring boards. can.
  • a cured product is obtained by curing the resin composition.
  • the cured product can be obtained, for example, by melting or dissolving the resin composition in a solvent, pouring it into a mold, and curing it under normal conditions using light.
  • the wavelength region of light is preferably in the range of 100 to 500 nm where curing proceeds efficiently with a photopolymerization initiator or the like.
  • the resin sheet of the present embodiment is a support-attached resin sheet having a support and a resin layer disposed on one or both sides of the support, wherein the resin layer contains the resin composition of the present embodiment.
  • a resin sheet can be produced by coating a resin composition on a support and drying the resin composition.
  • the resin layer in the resin sheet has excellent photocurability and alkali developability.
  • the insulating layer obtained using the resin sheet has excellent adhesiveness with adhesive metals such as titanium.
  • a known support can be used, and is not particularly limited, but is preferably a resin film.
  • resin films 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. film, triacetyl acetate film, and the like. Among them, PET film is preferred.
  • a release agent is preferably applied to the surface of the resin film so that it can be easily separated from the resin layer.
  • the thickness of the resin film is preferably in the range of 5-100 ⁇ m, more preferably in the range of 10-50 ⁇ m. When the thickness is less than 5 ⁇ m, the support tends to be torn when the support is peeled off before alkali development. There is As used herein, the thickness can be measured using, for example, a micrometer.
  • the resin film preferably has excellent transparency in order to reduce scattering of light during exposure.
  • the resin layer may be protected with a protective film.
  • a protective film By protecting the resin layer side with a protective film, it is possible to prevent dust from adhering to the surface of the resin layer and scratches on the surface of the resin layer.
  • the protective film a film made of the same material as the resin film can be used.
  • the thickness of the protective film is preferably in the range of 1-50 ⁇ m, more preferably in the range of 5-40 ⁇ m. If the thickness is less than 1 ⁇ m, the protective film tends to be difficult to handle, and if it exceeds 50 ⁇ m, it tends to be inexpensive.
  • the protective film preferably has a lower adhesive strength between the resin layer and the protective film than the adhesive strength between the resin layer and the support.
  • Examples of the method for producing a resin sheet include a method for producing a resin sheet by applying a resin composition to a support such as a PET film and drying it to remove the organic solvent. 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, and the like. Drying can be carried out, for example, by heating in a dryer at 60 to 200° C. for 1 to 60 minutes.
  • the amount of the organic solvent remaining in the resin layer is preferably 5% by mass or less with respect to the total mass of the resin layer from the viewpoint of further preventing diffusion of the organic solvent in subsequent steps.
  • the thickness of the resin layer is preferably 1 to 50 ⁇ m from the viewpoint of improving handleability.
  • a resin sheet can be preferably used for manufacturing an insulating layer of a multilayer printed wiring board from the viewpoint of being superior in handleability.
  • the multilayer printed wiring board of the present embodiment has an insulating layer and conductor layers formed on one or both sides of the insulating layer, and the insulating layer contains the resin composition of the present embodiment.
  • the insulating layer can also be obtained, for example, by stacking one or more resin sheets and curing them.
  • the number of laminations of each of the insulating layer and the conductor layer can be appropriately set according to the intended use. Also, the order of the insulating layer and the conductor layer is not particularly limited.
  • the conductor layer may be a metal foil used for various printed wiring board materials, and examples thereof include metal foils of copper, aluminum, and the like. Copper metal foils include copper foils such as rolled copper foils and electrolytic copper foils.
  • the thickness of the conductor layer is usually 1-100 ⁇ m. Specifically, it can be produced by the following method.
  • the resin layer side of the resin sheet is laminated on one side or both sides of the circuit board using a vacuum laminator.
  • circuit substrates include 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.
  • the circuit board means a board having a patterned conductor layer (circuit) formed on one side or both sides of the board as described above.
  • a board in which one or both sides of the outermost layer of the multilayer printed wiring board is a patterned conductor layer (circuit) is also a circuit board.
  • the insulating layer laminated on the multilayer printed wiring board may be an insulating layer obtained by stacking one or more resin sheets of the present embodiment and curing.
  • the insulating layer may be obtained by stacking one or more of the resin sheet of the embodiment and a known resin sheet different from each other.
  • the method of stacking the resin sheet of the present embodiment and a known resin sheet different from the resin sheet of the present embodiment is not particularly limited.
  • the surface of the conductor layer may be roughened in advance by blackening and/or copper etching.
  • the resin sheet and the circuit board are preheated as necessary to pressurize and heat the resin layer of the resin sheet. while crimping it onto the circuit board.
  • a method of laminating a resin layer of a resin sheet on a circuit board under reduced pressure by a vacuum lamination method is preferably used.
  • the conditions of the lamination process are, for example, a pressure bonding temperature (laminating temperature) of 50 to 140° C., a pressure of 1 to 15 kgf/cm 2 , a pressure bonding time of 5 to 300 seconds, and an air pressure of 20 mmHg or less under reduced pressure. Lamination is preferred. Moreover, the lamination process may be of a batch type or a continuous type using rolls. A vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a two-stage build-up laminator manufactured by Nikko Materials Co., Ltd., and the like.
  • a predetermined portion of the resin layer is irradiated with various active energy rays as a light source to cure the resin layer in the irradiated portion.
  • Compound (C) which is blended as necessary, does not inhibit the photocuring reaction in the exposure step.
  • the irradiation may be performed through a mask pattern, or a direct writing method for direct irradiation may be used.
  • Active energy rays include, for example, ultraviolet rays, visible rays, electron beams, and X-rays.
  • the wavelength of the active energy ray is, for example, in the range of 200-600 nm.
  • the irradiation dose is about 5 to 1000 mJ/cm 2 .
  • the active energy ray for example, has a wavelength of 365 nm (i-line).
  • the dose is approximately 5 to 10,000 mJ/cm 2 .
  • an active energy ray containing, for example, a wavelength of 405 nm (h-line) is used as the active energy ray.
  • the dose is approximately 10 to 10,000 mJ/cm 2 .
  • Exposure through a mask pattern includes a contact exposure method in which the mask pattern is brought into close contact with the multilayer printed wiring board, and a non-contact exposure method in which a lens or mirror is used to expose the mask pattern. You can use it. Further, when a support exists on the resin layer, exposure may be performed from above the support, or exposure may be performed after peeling off the support.
  • the unexposed resin layer containing the resin composition of the present embodiment has excellent alkali developability and can quickly remove the unexposed resin composition. Therefore, a printed wiring board having a high-definition pattern can be obtained.
  • the developer is not particularly limited as long as it selectively elutes the unexposed portions, but tetramethylammonium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution, sodium hydroxide aqueous solution, and An alkaline developer such as an aqueous potassium hydroxide solution is used. In this embodiment, it is more preferable to use a tetramethylammonium hydroxide aqueous solution.
  • alkaline developers can be used singly or in combination of two or more.
  • alkali developing method known methods such as dipping, puddle, spraying, rocking immersion, brushing, and scraping can be used. In pattern formation, these developing methods may be used in combination, if necessary.
  • a developing method it is preferable to use a high-pressure spray because the resolution is further improved. A spray pressure of 0.02 to 0.5 MPa is preferable when a spray method is employed.
  • a post-baking process is performed to form an insulating layer (hardened material).
  • the post-baking process include an ultraviolet irradiation process using a high-pressure mercury lamp, a heating process using a clean oven, and the like, and these processes can be used in combination.
  • the irradiation dose can be adjusted as necessary, for example, irradiation can be performed at a dose of approximately 0.05 to 10 J/cm 2 .
  • the heating conditions can be appropriately selected as necessary, preferably in the range of 150 to 220° C. for 20 to 180 minutes, more preferably in the range of 160 to 200° C. and 30 to 150 minutes.
  • Conductor layer forming step After forming the insulating layer (hardened material), a conductor layer is formed on the surface of the insulating layer by dry plating.
  • the surface of the insulating layer may be subjected to surface modification treatment before dry plating.
  • known methods such as plasma etching treatment, reverse sputtering treatment, and corona treatment can be used.
  • dry plating vapor deposition methods such as PVD (physical vapor deposition) and CVD (chemical vapor deposition), sputtering methods, and known metal vapor deposition methods such as ion plating methods can be used.
  • the surface of the insulating layer is generally cleaned and activated by a method such as plasma treatment with oxygen gas or argon gas, and then a metal layer is formed by depositing a base metal.
  • secondary vapor deposition is performed on the surface of to form a secondary vapor deposition layer.
  • the thickness of the metal layer is typically 0.001-0.1 ⁇ m.
  • the thickness of the secondary vapor deposition layer is usually 0.01-0.4 ⁇ m.
  • the total thickness of the metal layer and the secondary deposition layer is preferably 0.5 ⁇ m or less.
  • Titanium, zirconia, chromium, molybdenum, tin, nickel, magnesium, aluminum, tungsten, and alloys of these metals are usually used as the underlying metal.
  • Metals used for secondary deposition typically include copper and nickel. When a highly active metal such as titanium is used as the underlayer, nickel or the like may be appropriately used as the barrier layer.
  • the imidazole compound (B) has a specific functional group and the total number of carbon atoms contained in the functional group is 8 or more. , is thought to exist in the insulating layer while retaining its structure. Therefore, the insulating layer obtains good adhesion with adhesive metals such as titanium, especially titanium, such as titanium, zirconia, chromium, molybdenum, tin, nickel, magnesium, aluminum, tungsten and alloys of these metals. be able to.
  • the insulating layer can maintain excellent adhesion strength with the conductor layer even when exposed to high temperatures such as in a moisture absorption state or during a reflow process.
  • the multilayer printed wiring board is placed in a vacuum container, and the metal is heated and evaporated to form the base and the secondary vapor deposition layer on the insulating layer.
  • a multilayer printed wiring board is placed in a vacuum chamber, an inert gas such as argon is introduced, a direct current voltage is applied, and the ionized inert gas collides with the target metal, and is ejected.
  • the metal can form an underlayer and a secondary deposition layer on the insulating layer.
  • a conductor layer is formed on the surface of the secondary deposition layer by electroless plating, electrolytic plating, or the like.
  • the thickness of the conductor layer is usually 0.1-20 ⁇ m.
  • a method for subsequent pattern formation for example, a subtractive method, a semi-additive method, or the like can be used.
  • the semiconductor device of this embodiment includes the resin composition of this embodiment. Specifically, it can be produced by the following method.
  • a semiconductor device can be manufactured by mounting a semiconductor chip on a conductive portion of a multilayer printed wiring board.
  • the conductive portion means a portion of the multilayer printed wiring board that transmits an electric signal, and the portion may be a surface or an embedded portion.
  • the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.
  • the method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Specifically, a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). etc.
  • a semiconductor device can also be manufactured by forming an insulating layer containing a resin composition on a semiconductor chip or a substrate on which a semiconductor chip is mounted.
  • the shape of the substrate on which the semiconductor chips are mounted may be wafer-like or panel-like. After forming, it can be manufactured using the same method as the multilayer printed wiring board described above.
  • the mixture was liquid-separated, and the aqueous layer was extracted with 50 mL of ethyl acetate three times. All the organic layers were combined and washed once with 100 mL of water, once with 10 mL of saturated brine, and twice with 5 mL of saturated brine. After drying with magnesium sulfate and separating the solid content by filtration, the solvent was distilled off at 40° C. to obtain a yellow solid. The obtained yellow solid was dissolved in 6.5 mL of acetone, and the acetone solution was poured into 300 mL of water.
  • the content of the compound (C1) contained in the reaction solution obtained above was measured by the following method.
  • a sample solution was prepared by adding 50 mg of the reaction solution to 4500 mg of THF (tetrahydrofuran), and the solution was subjected to GPC measurement under the following conditions. From the obtained elution curve, the peak area was calculated, and the GPC area fraction (content rate) of each component contained in the reaction solution was calculated. The peak area was calculated from the area between the elution curve and the baseline, and peaks that were not completely separated were calculated by vertical division.
  • phenylphosphine oxide (OMnirad (registered trademark) 819 (trade name) manufactured by IGM Resins B.V.) and a compound represented by formula (28) as a photocuring initiator (E)
  • E1 Mix 6.38 parts by mass and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), add 227.0 parts by mass of methyl ethyl ketone (MEK), A varnish (resin composition) was obtained by heating on a hot plate heated to 90°C.
  • This varnish is dropped onto a PET film having a thickness of 25 ⁇ m (Unipeel (registered trademark) TR1-25 (trade name) manufactured by Unitika Ltd.) and spin-coated (500 rpm for 10 seconds, then 1000 rpm for 30 seconds) to form a coating film. formed.
  • the obtained coating film was dried at 90° C. for 5 minutes to obtain a resin sheet having a PET film as a support and a resin layer having a thickness of 5 ⁇ m.
  • the resulting resin sheet was placed on a silicon wafer (manufactured by Advantech Co., Ltd., thickness: 525 ⁇ m, with oxide film (thickness: 1 ⁇ m)) so that the resin surface of the resin sheet faced the oxide film side, and was placed in a vacuum laminator. (manufactured by Nikko Materials Co., Ltd.), vacuuming (5.0 hPa or less) was performed for 30 seconds. Thereafter, lamination molding was performed at a pressure of 10 kgf/cm 2 and a temperature of 100° C. for 30 seconds. Furthermore, lamination molding was carried out at a pressure of 7 kgf/cm 2 and a temperature of 100° C. for 60 seconds to obtain a laminate for evaluation in which a silicon wafer, a resin layer and a support were laminated.
  • Example 2 As the bismaleimide compound (A), Nippon Kayaku Co., Ltd. MIZ-001 (trade name, mass average molecular weight (Mw): 3000, compound represented by formula (12)) 60 parts by mass, and an imidazole compound (B ) as 2-undecylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R 4 to R 7 : 11) 4.0 parts by mass, and as compound (C), the formula 5.25 parts of the compound (C1) represented by (15) and, as the compound (C), cis,cis-cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (Mitsubishi Gas Chemical Co., Ltd.) ) and 1.08 parts by mass of H-TMAn-S (trade name) manufactured by Gun Ei Chemical Industry Co., Ltd., and a compound represented by the formula (20) as the maleimide compound (D) (BCPH01 (trade name, mass
  • phenylphosphine oxide (OMnirad (registered trademark) 819 (trade name) manufactured by IGM Resins B.V.) and a compound represented by formula (28) as a photocuring initiator (E)
  • E1 Mix 6.38 parts by mass and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), add 224.4 parts by mass of methyl ethyl ketone (MEK), A varnish (resin composition) was obtained by heating on a hot plate heated to 90°C.
  • a resin sheet and a laminate for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.
  • Example 3 As the bismaleimide compound (A), Nippon Kayaku Co., Ltd. MIZ-001 (trade name, mass average molecular weight (Mw): 3000, compound represented by formula (12)) 60 parts by mass, and an imidazole compound (B ) as 2-undecylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R 4 to R 7 : 11) 3.0 parts by mass, and as compound (C), the formula 5.25 parts of the compound (C1) represented by (15) and, as the compound (C), cis,cis-cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (Mitsubishi Gas Chemical Co., Ltd.) ) and 1.08 parts by mass of H-TMAn-S (trade name) manufactured by Gun Ei Chemical Industry Co., Ltd., and a compound represented by the formula (20) as the maleimide compound (D) (BCPH01 (trade name, mass
  • phenylphosphine oxide (OMnirad (registered trademark) 819 (trade name) manufactured by IGM Resins B.V.) and a compound represented by formula (28) as a photocuring initiator (E)
  • E1 Mix 6.38 parts by mass and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), add 222.5 parts by mass of methyl ethyl ketone (MEK), A varnish (resin composition) was obtained by heating on a hot plate heated to 90°C.
  • a resin sheet and a laminate for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.
  • phenylphosphine oxide (OMnirad (registered trademark) 819 (trade name) manufactured by IGM Resins B.V.) and a compound represented by formula (28) as a photocuring initiator (E)
  • E1 Mix 6.38 parts by mass and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), add 220.7 parts by mass of methyl ethyl ketone (MEK), A varnish (resin composition) was obtained by heating on a hot plate heated to 90°C.
  • a resin sheet and a laminate for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.
  • Example 5 As the bismaleimide compound (A), Nippon Kayaku Co., Ltd. MIZ-001 (trade name, mass average molecular weight (Mw): 3000, compound represented by formula (12)) 60 parts by mass, and an imidazole compound (B ) as 2-undecylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R 4 to R 7 : 11) 1.0 parts by mass, and as compound (C), the formula 5.25 parts of the compound (C1) represented by (15) and, as the compound (C), cis,cis-cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (Mitsubishi Gas Chemical Co., Ltd.) ) and 1.08 parts by mass of H-TMAn-S (trade name) manufactured by Gun Ei Chemical Industry Co., Ltd., and a compound represented by the formula (20) as the maleimide compound (D) (BCPH01 (trade name, mass
  • phenylphosphine oxide (OMnirad (registered trademark) 819 (trade name) manufactured by IGM Resins B.V.) and a compound represented by formula (28) as a photocuring initiator (E)
  • E1 Mix 6.38 parts by mass and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), add 218.8 parts by mass of methyl ethyl ketone (MEK), A varnish (resin composition) was obtained by heating on a hot plate heated to 90°C.
  • a resin sheet and a laminate for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.
  • Example 6 As the bismaleimide compound (A), Nippon Kayaku Co., Ltd. MIZ-001 (trade name, mass average molecular weight (Mw): 3000, compound represented by formula (12)) 60 parts by mass, and an imidazole compound (B ) as 2-undecylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R 4 to R 7 : 11) 0.5 parts by mass, and as compound (C), the formula 5.25 parts of the compound (C1) represented by (15) and, as the compound (C), cis,cis-cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (Mitsubishi Gas Chemical Co., Ltd.) ) and 1.08 parts by mass of H-TMAn-S (trade name) manufactured by Gun Ei Chemical Industry Co., Ltd., and a compound represented by the formula (20) as the maleimide compound (D) (BCPH01 (trade name, mass
  • phenylphosphine oxide (OMnirad (registered trademark) 819 (trade name) manufactured by IGM Resins B.V.) and a compound represented by formula (28) as a photocuring initiator (E)
  • E1 Mix 6.38 parts by mass and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), add 217.9 parts by mass of methyl ethyl ketone (MEK), A varnish (resin composition) was obtained by heating on a hot plate heated to 90°C.
  • a resin sheet and a laminate for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.
  • Example 7 As the bismaleimide compound (A), Nippon Kayaku Co., Ltd. MIZ-001 (trade name, mass average molecular weight (Mw): 3000, compound represented by formula (12)) 60 parts by mass, and an imidazole compound (B ), 1-(2-cyanoethyl)-2-undecylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R 4 to R 7 : 14) 4.95 parts by mass , as the compound (C), 5.25 parts of the compound (C1) represented by the formula (15), and as the compound (C), cis,cis-cyclohexane-1,2,4-tricarboxylic acid-1,2- 1.08 parts by mass of an anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.) and a compound represented by the formula (20) as a maleimide compound (D) (Gun Ei Chemical Industry Co., Ltd. MIZ
  • BCPH01 (trade name) 25 parts by mass, 15 parts by mass of the compound (TMDM) represented by the formula (19) as the maleimide compound (D), and bis(2, 1.12 parts by mass of 4,6-trimethylbenzoyl)-phenylphosphine oxide (OMnirad (registered trademark) 819 (trade name) manufactured by IGM Resins B.V.) and a photocuring initiator (E) of the formula ( 28) and 6.38 parts by mass of the compound (E1) represented by the formula and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed to obtain methyl ethyl ketone (MEK) 226. 2 parts by mass were added and heated on a hot plate heated to 90° C. to obtain a varnish (resin composition). A resin sheet and a laminate for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.
  • TMDM 4,6-
  • Example 8 As the bismaleimide compound (A), Nippon Kayaku Co., Ltd. MIZ-001 (trade name, mass average molecular weight (Mw): 3000, compound represented by formula (12)) 60 parts by mass, and an imidazole compound (B ), 1-(2-cyanoethyl)-2-undecylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R 4 to R 7 : 14) 1.25 parts by mass , as the compound (C), 5.25 parts of the compound (C1) represented by the formula (15), and as the compound (C), cis,cis-cyclohexane-1,2,4-tricarboxylic acid-1,2- 1.08 parts by mass of an anhydride (H-TMAn-S (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.) and a compound represented by the formula (20) as a maleimide compound (D) (Gun Ei Chemical Industry Co., Ltd. MIZ
  • BCPH01 (trade name) 25 parts by mass, 15 parts by mass of the compound (TMDM) represented by the formula (19) as the maleimide compound (D), and bis(2, 1.12 parts by mass of 4,6-trimethylbenzoyl)-phenylphosphine oxide (OMnirad (registered trademark) 819 (trade name) manufactured by IGM Resins B.V.) and a photocuring initiator (E) of the formula ( 28) and 6.38 parts by mass of the compound (E1) represented by the formula and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed to obtain methyl ethyl ketone (MEK) 219. .3 parts by mass was added and heated on a hot plate heated to 90° C. to obtain a varnish (resin composition). A resin sheet and a laminate for evaluation were obtained in the same manner as in Example 1 using the obtained varnish.
  • TMDM 4,6
  • Example 9 As the bismaleimide compound (A), Nippon Kayaku Co., Ltd. MIZ-001 (trade name, mass average molecular weight (Mw): 3000, compound represented by formula (12)) 60 parts by mass, and an imidazole compound (B ), 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R 4 to R 7 : 18) 5.33 parts by mass, and the compound (C ) as 5.25 parts of the compound (C1) represented by the formula (15), and as the compound (C), cis,cis-cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (Mitsubishi 1.08 parts by mass of H-TMAn-S (trade name) manufactured by Gas Kagaku Co., Ltd., and a compound represented by the formula (20) as the maleimide compound (D) (BCPH01 (manufactured by Gun Ei Chemical Industry Co
  • Example 10 As the bismaleimide compound (A), Nippon Kayaku Co., Ltd. MIZ-001 (trade name, mass average molecular weight (Mw): 3000, compound represented by formula (12)) 60 parts by mass, and an imidazole compound (B ), 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R 4 to R 7 : 18) 1.0 parts by mass, and the compound (C ) as 5.25 parts of the compound (C1) represented by the formula (15), and as the compound (C), cis,cis-cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (Mitsubishi 1.08 parts by mass of H-TMAn-S (trade name) manufactured by Gas Kagaku Co., Ltd., and a compound represented by the formula (20) as the maleimide compound (D) (BCPH01 (manufactured by Gun Ei Chemical Industry Co
  • Example 11 As the bismaleimide compound (A), Nippon Kayaku Co., Ltd. MIZ-001 (trade name, mass average molecular weight (Mw): 3000, compound represented by formula (12)) 60 parts by mass, and an imidazole compound (B ), 0.5 parts by mass of 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., in formula (2), the total number of carbon atoms of R 4 to R 7 : 18), and the compound (C ) as 5.25 parts of the compound (C1) represented by the formula (15), and as the compound (C), cis,cis-cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (Mitsubishi 1.08 parts by mass of H-TMAn-S (trade name) manufactured by Gas Kagaku Co., Ltd., and a compound represented by the formula (20) as the maleimide compound (D) (BCPH01 (manufactured by Gun Ei Chemical Industry Co
  • phenylphosphine oxide (OMnirad (registered trademark) 819 (trade name) manufactured by IGM Resins B.V.) and a compound represented by formula (28) as a photocuring initiator (E)
  • E1 Mix 6.38 parts by mass and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), add 221.9 parts by mass of methyl ethyl ketone (MEK), A varnish (resin composition) was obtained by heating on a hot plate heated to 90°C. Precipitation of the resin content occurred in the obtained varnish, and a resin sheet and a laminate for evaluation could not be produced.
  • MEK methyl ethyl ketone
  • phenylphosphine oxide (OMnirad (registered trademark) 819 (trade name) manufactured by IGM Resins B.V.) and a compound represented by formula (28) as a photocuring initiator (E)
  • E1 Mix 6.38 parts by mass and 3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), add 222.3 parts by mass of methyl ethyl ketone (MEK), A varnish (resin composition) was obtained by heating on a hot plate heated to 90°C. Precipitation of the resin content occurred in the obtained varnish, and a resin sheet and a laminate for evaluation could not be produced.
  • MEK methyl ethyl ketone
  • N-phenyl-3-aminopropyltrimethoxysilane manufactured by Tokyo Chemical Industry Co., Ltd.
  • MEK methyl ethyl ketone
  • Omnirad registered trademark 819 (trade name) 1.12 parts by mass
  • N-phenyl -3-aminopropyltrimethoxysilane manufactured by Tokyo Chemical Industry Co., Ltd.
  • MEK methyl ethyl ketone
  • Photo DSC (TA Instruments Japan Co., Ltd.) attached with a light source (Omnicure (registered trademark) S2000 (trade name) manufactured by Uvix Co., Ltd.) capable of irradiating active energy rays including wavelengths of 200 to 600 nm DSC-2500 (trade name) manufactured by the company), the obtained resin sheet is irradiated with an active energy ray containing a wavelength of 200 to 600 nm at an illuminance of 30 mW for an exposure time of 3.5 minutes, and the horizontal axis is time (sec). , with the vertical axis representing heat flow (mW).
  • the enthalpy (J/g) was defined as the peak area when a horizontal line was drawn from the end point of the graph. Curability was evaluated according to the following criteria. "AA”: The enthalpy was 1 (J/g) or more. “CC”: Enthalpy was less than 1 (J/g). “Measurable”: The resin sheet could not be obtained and could not be measured. An enthalpy of 1 (J/g) or more means that curing of the resin proceeds sufficiently by exposure at a predetermined wavelength.
  • ⁇ Peel strength> Using a light source (MA-20 (trade name) manufactured by Mikasa Co., Ltd.) capable of irradiating an active energy ray containing a wavelength of 200 to 600 nm to the obtained laminate for evaluation, a wavelength of 200 to 200 nm is applied from above the support. An active energy ray containing 600 nm was applied at an illumination intensity of 18 mW and an irradiation dose of 200 mJ/cm 2 . After that, using a hot plate heated to 90° C., the surface of the silicon wafer was heated at 90° C. for 60 seconds. After that, it was cooled to room temperature.
  • a light source MA-20 (trade name) manufactured by Mikasa Co., Ltd.
  • the support PET film
  • TMAH tetramethylammonium hydroxide
  • developer manufactured by Tokuyama Corp.
  • HMW-201GX trade name
  • active energy rays containing wavelengths of 200 to 600 nm are applied at an irradiation dose of 1000 mJ / Illuminated at cm 2 . After that, heating was performed at 180° C.
  • electrolytic copper plating is applied to the surface of the copper layer so that the thickness of the plated copper is 18 ⁇ m, and drying is performed at 180 ° C. for 1 hour to form a titanium layer (thickness: 50 nm) on the cured product.
  • a copper layer (thickness: 300 nm) as a secondary deposition layer and a plated copper layer (thickness: 18 ⁇ m) as a conductor layer were formed to prepare a wiring board for evaluation.
  • the peel strength of the conductor layer was measured three times in accordance with JIS C6481 "Testing Method for Copper-Clad Laminates for Printed Wiring Boards", and the average value (kN/m) was calculated. asked.
  • the laminate for evaluation could not be obtained and the wiring board for evaluation could not be produced.
  • the present embodiment good photosensitivity and photocuring are possible when exposed to any active energy ray having a wavelength of 200 to 600 nm. According to this embodiment, a cured product having excellent alkali developability can be obtained. According to this embodiment, the obtained cured product (insulating layer) has excellent adhesiveness with adhesive metals such as titanium.
  • the resin composition of the present embodiment can be suitably used for producing a multilayer printed wiring board, and can be preferably used for applications requiring an insulating resin composition.
  • Examples include photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit boards (laminated board applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, and hole filling. It can be used for resins, part embedding resins, and the like.

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  • Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
PCT/JP2022/023706 2021-06-15 2022-06-14 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 Ceased WO2022264985A1 (ja)

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KR1020237028144A KR102646474B1 (ko) 2021-06-15 2022-06-14 수지 조성물, 수지 시트, 다층 프린트 배선판, 및 반도체 장치
US18/570,322 US12221523B2 (en) 2021-06-15 2022-06-14 Resin composition, resin sheet, multilayer printed wiring board, and semiconductor device
CN202280043127.4A CN117529509B (zh) 2021-06-15 2022-06-14 树脂组合物、树脂片、多层印刷电路板、及半导体装置
EP22824974.4A EP4321541B1 (en) 2021-06-15 2022-06-14 Resin composition, resin sheet, multilayer printed wiring board and semiconductor device

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