WO2020045489A1 - 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 PDFInfo
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- WO2020045489A1 WO2020045489A1 PCT/JP2019/033681 JP2019033681W WO2020045489A1 WO 2020045489 A1 WO2020045489 A1 WO 2020045489A1 JP 2019033681 W JP2019033681 W JP 2019033681W WO 2020045489 A1 WO2020045489 A1 WO 2020045489A1
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—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
- C08F222/36—Amides or imides
- C08F222/40—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
- 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
- C08G73/124—Unsaturated polyimide precursors the unsaturated precursors containing oxygen in the form of ether bonds in the main chain
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5397—Phosphine oxides
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- 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
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- 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
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- 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
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- 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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0296—Conductive pattern lay-out details not covered by sub groups H05K1/02 - H05K1/0295
- H05K1/0298—Multilayer circuits
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- 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
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- 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
- H05K1/0326—Organic insulating material consisting of one material containing O
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- 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
- H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
- H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
-
- 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
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- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
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- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/05—Patterning and lithography; Masks; Details of resist
- H05K2203/0502—Patterning and lithography
- H05K2203/0514—Photodevelopable thick film, e.g. conductive or insulating paste
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- 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
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer
- H05K3/4676—Single layer compositions
Definitions
- the present invention relates to a resin composition, a resin sheet using the same, a multilayer printed wiring board, and a semiconductor device.
- thermosetting resin is mainly used as a resin composition as a material of an insulating layer, and a hole for obtaining conduction between insulating layers is generally formed by laser processing.
- an exposure method a method of exposing through a photomask using a mercury lamp as a light source is used.
- a direct drawing exposure method for directly drawing a photosensitive resin composition layer based on digital data of a pattern without using a photomask has been introduced as an exposure method.
- This direct writing exposure method has a better alignment accuracy than an exposure method using a photomask and can obtain a high-definition pattern. Therefore, the direct writing exposure method is particularly introduced to a substrate requiring high-density wiring formation. In.
- a monochromatic light such as a laser is used as the light source, and a light source having a wavelength of 405 nm (h-line) is used in a DMD (Digital Micromirror Device) type device capable of forming a high-definition resist pattern.
- DMD Digital Micromirror Device
- a compound having an ethylenically unsaturated group such as (meth) acrylate is used for a photosensitive resin composition used for a laminate and a resin sheet in order to enable quick curing in an exposure step.
- a carboxyl-modified epoxy (meth) acrylate resin obtained by reacting a bisphenol-type epoxy resin with (meth) acrylic acid and then reacting with an acid anhydride, a biphenyl-type epoxy resin, A photosensitive thermosetting resin composition containing a photocuring initiator and a diluent is described.
- Patent Document 2 discloses a photocurable binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, a photopolymerization (curing) initiator, a sensitizer, and bisallylnagic which is a thermosetting agent.
- a resin composition containing an imide compound and a bismaleimide compound is described.
- Patent Document 3 describes a resin composition containing a bismaleimide compound (curable resin) and a photoradical polymerization initiator (curing agent).
- a cured product using a conventional (meth) acrylate resin cannot provide sufficient physical properties, and there is a limit in forming a protective film having high heat resistance and an interlayer insulating layer. Further, this cured product is inferior in insulation reliability such as migration resistance between circuits, and has a problem in use as a high-density printed wiring board.
- the cured product obtained from the resin composition described in Patent Document 1 has excellent flexibility and folding resistance as a solder resist, and is also described as having excellent heat resistance. No specific value is given, and there is a problem that heat resistance and thermal stability are poor when used as an interlayer insulating layer. Also, this cured product is inferior in insulation reliability such as migration resistance between circuits, and has a problem in use as a high-density printed wiring board.
- Patent Document 2 describes using a bismaleimide compound, but describes as a thermosetting agent, and uses (meth) acrylate as a photopolymerizable compound. Therefore, there is a problem that heat resistance and thermal stability are poor when used as an interlayer insulating layer.
- Patent Document 3 a bismaleimide compound is used as a curable resin.
- the maleimide compound has poor light transmittance, if a maleimide compound is included, light does not sufficiently reach the photocuring initiator, and the photocuring initiator is not used. Hardly generates radicals, and its reactivity is very low. Therefore, in Patent Document 3, the maleimide compound is cured by performing additional heating.
- Patent Document 3 does not disclose any use as a light source capable of irradiating active energy rays including a wavelength of 405 nm (h-ray).
- the present invention has been made in view of the above-mentioned problems, and is sensitive to light when exposed to an active energy ray containing a wavelength of 405 nm (h-ray) and can be photocured. It is an object of the present invention to provide a resin composition, a resin sheet, a multilayer printed wiring board, and a semiconductor device having excellent photocurability, heat resistance, thermal stability, and insulation reliability.
- the present inventors contain a specific maleimide compound (A), a specific maleimide compound (B), and a photocuring initiator (C) having an absorbance at a wavelength of 405 nm (h-line) of 0.1 or more. It has been found that the above problem can be solved by using the resin composition described above, and the present invention has been completed.
- the present invention includes the following contents.
- the content of the maleimide compound (A) and the maleimide compound (B) is based on 100 parts by mass of the total of the maleimide compound (A), the maleimide compound (B), and the photocuring initiator (C).
- R 1 each independently represent a substituent or a phenyl group represented by the following formula (2).
- a plurality of R 2 each independently represent a hydrogen atom or a methyl group.
- a support and a resin layer disposed on one or both surfaces of the support, wherein the resin layer contains the resin composition according to any one of [1] to [4].
- Resin sheet [6] The resin sheet according to [5], wherein the thickness of the resin layer is 1 to 50 ⁇ m.
- a multilayer printed wiring board comprising the resin composition according to any one of [1] to [4].
- a semiconductor device comprising the resin composition according to any one of [1] to [4].
- ADVANTAGE OF THE INVENTION when exposed to active energy rays containing a wavelength of 405 nm (h-ray), it is photosensitive and can be photocured. Particularly when used for a multilayer printed wiring board, photocurability, heat resistance, A resin composition, a resin sheet, a multilayer printed wiring board, and a semiconductor device which are excellent in thermal stability and insulation reliability can be provided.
- the present embodiment a mode for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail.
- the following embodiment is an exemplification for describing the present invention, and is not intended to limit the present invention to the following contents.
- the present invention can be appropriately modified and implemented within the scope of the gist.
- (meth) acryloyl group means both “acryloyl group” and the corresponding “methacryloyl group”
- “(meth) acrylate” is “acrylate” and the corresponding “methacrylate”.
- ", And" (meth) acrylic acid means both” acrylic acid “and the corresponding” methacrylic acid ".
- “resin solids” or “resin solids in the resin composition” refers to a photocuring initiator (C), an additive, a solvent, And the components excluding the filler, and the “resin solid content of 100 parts by mass” means that the total of the components excluding the photocuring initiator (C), the additive, the solvent, and the filler in the resin composition is 100 parts. It means that it is parts by mass.
- the resin composition of the present embodiment has a maleimide functional group equivalent of 300 g / eq. And a maleimide compound (A) having a transmittance of 1% or more at a wavelength of 405 nm (h-line) and a maleimide functional group equivalent of 300 g / eq. And a photo-curing initiator (C) having an absorbance of 0.1 or more at a wavelength of 405 nm (h-line).
- A maleimide compound having a transmittance of 1% or more at a wavelength of 405 nm (h-line) and a maleimide functional group equivalent of 300 g / eq.
- a photo-curing initiator (C) having an absorbance of 0.1 or more at a wavelength of 405 nm (h-line).
- the resin composition of the present embodiment contains the maleimide compound (A) (also referred to as component (A)) according to the present embodiment.
- the maleimide compound (A) according to this embodiment has a maleimide functional group equivalent of 300 g / eq.
- the transmittance at a wavelength of 405 nm (h-line) is 1% or more.
- the maleimide compound has poor light transmittance, when the resin composition contains the maleimide compound, light does not sufficiently reach the photocuring initiator dispersed in the resin composition, and the photocuring initiator generates radicals. It is unlikely to occur.
- the photoradical reaction of the maleimide compound generally does not easily proceed, and even if the radical polymerization or dimerization reaction of the maleimide alone proceeds, the reactivity is very low.
- a chloroform solution containing the maleimide compound (A) at 1% by mass is prepared, and the transmittance of the chloroform solution is adjusted using a light beam having a wavelength of 405 nm (h-line). When measured, the transmittance is 1% or more, which indicates very excellent light transmittance. Therefore, light sufficiently reaches the photocuring initiator, and the photoradical reaction of maleimide occurs efficiently.
- the transmittance is preferably 2% or more, and more preferably 4% or more, since a resin composition having more excellent photocurability, heat resistance, and thermal stability can be obtained.
- the upper limit of the transmittance is not particularly limited, but is, for example, 99.9% or less.
- the photopolymerization initiator absorbs light having a wavelength of 405 nm (h-line) and generates radicals.
- the photo-curing initiator (C) described below according to the present embodiment has an absorbance of 0.1 or more at a wavelength of 405 nm (h-line) and an extremely excellent absorbance for light at a wavelength of 405 nm (h-line). Is shown.
- the maleimide compound (A) Since the maleimide compound (A) has excellent light transmittance as described above, an active energy ray including a wavelength of 405 nm (h-ray) sufficiently reaches the photocuring initiator, and a radical generated from the photocuring initiator was used. The radical reaction proceeds efficiently. Therefore, it can be photocured together with the maleimide compound (A) according to the present embodiment, the maleimide compound (B) described later, and the photocuring initiator (C) described later, and a large amount of the maleimide compound (A) is compounded. Photocuring becomes possible also in the composition which is performed.
- an active energy ray containing a wavelength of 405 nm (h-line) is used.
- the maleimide photoradical reaction occurs efficiently.
- the cured product obtained by including the resin composition of the present embodiment is excellent in photocurability, heat resistance, and thermal stability, so that the protective film and the insulating layer can be suitably formed.
- the maleimide compound (A) has a maleimide functional group equivalent of 300 g / eq. Or more, preferably 320 g / eq. Or more, more preferably 340 g / eq. That is all.
- the upper limit is not particularly limited, but is 5,000 g / eq. The following is preferred.
- the maleimide functional group equivalent (g / eq) is calculated from the following formula (1) using the mass average molecular weight and the number of functional groups of the maleimide compound.
- Maleimide functional group equivalent (mass average molecular weight of maleimide compound) / (number of functional groups of maleimide compound) (1)
- the maleimide compound (A) when the maleimide compound (A) is photo-cured together with the later-described maleimide compound (B) and the later-described photo-curing initiator (C) using an active energy ray containing a wavelength of 405 nm (h-ray), it is favorable. A resin composition having excellent insulation reliability in addition to heat resistance and thermal stability can be obtained.
- the present inventors presume as follows. That is, when the maleimide functional group equivalent is 300 g / eq. Since the maleimide compound (A) described above has relatively low water absorption, it is presumed that a cured product having excellent insulation reliability can be obtained by using the maleimide compound (A).
- the maleimide functional group equivalent is 300 g / eq.
- the maleimide compound (B) which has a lower molecular weight, has many reaction points. Therefore, when the transmittance of this chloroform solution is measured using a light beam having a wavelength of 405 nm (h-line), even if the transmittance is low, it is quickly photocured. , A low molecular weight cured product is produced.
- the cured product formed by the maleimide compound (B) becomes a so-called nucleus, and the maleimide compound (A) having a high functional group equivalent is suitably cross-linked to the nucleus, and has good heat resistance and thermal stability. It is estimated that a cured product can be obtained.
- the maleimide compound (A) is not particularly limited as long as the effects of the present invention are exerted. Examples thereof include a maleimide compound represented by the following formula (3), a maleimide compound represented by the following formula (4), and a maleimide compound represented by the following formula (5) ), A maleimide compound represented by the following formula (6), a maleimide compound represented by the following formula (7), a maleimide compound represented by the following formula (8), and fluorescein-5-maleimide Is mentioned.
- n 1 (average) is 1 or more, preferably 1 to 21, and more preferably 1 to 16 from the viewpoint of exhibiting excellent photocurability.
- the number of x is 10 to 35.
- the number of y is 10 to 35.
- Ra represents 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.
- the R a preferably a linear or branched alkyl group, since it shows excellent photo-curable, and more preferably a linear alkyl group.
- the number of carbon atoms of the alkyl group is more preferably 4 to 12 because of excellent photocurability.
- the number of carbon atoms of the alkenyl group is more preferably from 4 to 12, since excellent photocurability is exhibited.
- the alkyl group is not particularly limited as long as the effects of the present embodiment are exerted.
- Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a 2,2-dimethylpropyl group, an n-butyl group, an isobutyl group, sec-butyl, t-butyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylbutyl, n-pentyl, neopentyl, t-pentyl, 2,2-dimethylpentyl, n -Hexyl group, 2-hexyl group, 3-hexyl group, texyl group, n-heptyl group, 2-heptyl group, 3-heptyl group, n-octyl group, 2-octyl group, 3-octyl group, n- Examples include an ethylhexyl group, an
- the alkenyl group is not particularly limited as long as the effects of the present embodiment are exhibited, and examples thereof include a vinyl group, a (meth) allyl group, an isopropenyl group, a 1-propenyl group, a 2-butenyl group, a 3-butenyl group, 3-butanedienyl group, 2-methyl-2-propenyl, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 2- Heptenyl group, 3-heptenyl group, 4-heptenyl group, 5-heptenyl group, 6-heptenyl group, 2-octenyl group, 3-octenyl group, 4-octenyl group, 5-octenyl group, 6-octenyl group, 7- Octenyl, 2-nonenyl group, 3-nonenyl group,
- R b represents 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.
- R b is preferably a straight-chain or branched alkyl group, and more preferably a straight-chain alkyl group because it exhibits excellent photocurability.
- the number of carbon atoms of the alkyl group is more preferably 4 to 12 because of excellent photocurability.
- the number of carbon atoms of the alkenyl group is more preferably from 4 to 12, since excellent photocurability is exhibited.
- the alkyl group the above-mentioned alkyl group for Ra can be referred to.
- an n-heptyl group, an n-octyl group, and an n-nonyl group are preferred, and an n-octyl group is more preferred, since they exhibit excellent photocurability.
- the alkenyl group the alkenyl group for Ra described above can be referred to.
- a 2-heptenyl group, a 2-octenyl group, and a 2-nonenyl group are preferable, and a 2-octenyl group is more preferable, since they exhibit excellent photocurability.
- the number of n a is 1 or more, preferably from 2 to 16, more preferably, from the viewpoint of showing excellent photocuring is 3-14.
- n b is 1 or greater, preferably from 2 to 16, more preferably, from the viewpoint of showing excellent photocuring is 3-14.
- n a and n b can be the same or be different.
- n 2 (average) represents an integer of 1 or more, and is preferably an integer of 1 to 10, and more preferably an integer of 1 to 8 from the viewpoint of excellent photocurability.
- n 3 represents an integer of 1 or more, and is preferably an integer of 1 to 10 from the viewpoint of excellent photocurability.
- n 4 represents an integer of 1 or more, from the viewpoint of showing excellent photocurable an integer from 1 to 10 are preferred.
- maleimide compound (A) a commercially available product can also be used.
- Examples of the maleimide compound represented by the formula (5) include, for example, Designer Molecules Inc. BMI-689 (trade name, the following formula (9), functional group equivalent: 346 g / eq.).
- Examples of the maleimide compound represented by the formula (7) include, for example, Designer Molecular Inc. Ltd. BMI-1700 (trade name, wherein (7), n 3 is a mixture of 1 to 10) are exemplified.
- Examples of the maleimide compound represented by the formula (8) include, for example, Designer Molecular Inc. Ltd. BMI-3000 (trade name, in the formula (8), n 4 is 3.1 (average value)), Designer Molecules Inc. Ltd.
- the blending ratio ((A) :( B)) of the maleimide compound (A) and the later-described maleimide compound (B) is not particularly limited, but is a cured product mainly containing the maleimide compound. From the viewpoint of improving photocurability, heat resistance, thermal stability, and insulation reliability, the ratio is preferably from 1 to 99:99 to 1, and more preferably from 5 to 95: It is more preferably from 95 to 5, and further preferably from 10 to 90: 90 to 10.
- the total content of the maleimide compound (A) and the later-described maleimide compound (B) is not particularly limited, but a cured product containing the maleimide compound as a main component can be obtained.
- the total amount of the maleimide compound (A), the maleimide compound (B), and the photocuring initiator (C) is 100 parts by mass. It is preferably from 50 to 99.9 parts by mass, more preferably from 70 to 99.8 parts by mass, even more preferably from 90 to 99.7 parts by mass.
- the resin composition of the present embodiment contains the maleimide compound (B) (also referred to as component (B)) according to the present embodiment.
- the maleimide compound (B) according to the present embodiment is other than the maleimide compound (A) and has a maleimide functional group equivalent of 300 g / eq. Is less than.
- the maleimide compound (B) has a maleimide functional group equivalent of 300 g / eq. 290 g / eq. And from the viewpoint of reactivity, more preferably 280 g / eq. It is as follows. The lower limit is not particularly limited, but is 110 g / eq. That is all.
- the maleimide functional group equivalent is calculated from the above formula (1) using the mass average molecular weight and the number of functional groups of the maleimide compound.
- the maleimide compound (B) used in the present embodiment is not limited to the maleimide compound (A), and is not particularly limited as long as it has one or more maleimide groups in the molecule.
- Specific examples thereof include N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, 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-maleimidoph
- maleimide compounds (B) a maleimide compound represented by the following formula (10) such as polyphenylmethane maleimide and 1,6-bismaleimide- (2,2,4-trimethyl) hexane are more excellent. It is preferable since a cured product having excellent heat resistance can be obtained.
- n 5 represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1-5.
- a plurality of R 4 each independently represent a hydrogen atom or a methyl group.
- n 6 represents an integer of 1 or more, preferably an integer of 1 to 5.
- R 5 each independently represents a hydrogen atom, a methyl group or an ethyl group
- R 6 each independently represents a hydrogen atom or a methyl group
- the maleimide compound represented by the formula (10) can also be commercially available products, for example, Daiwa Kasei Kogyo Co., Ltd. BMI-2300 (trade name, wherein (10), R 3 are all is a hydrogen atom, n 5 is a mixture of 1-5) can be mentioned.
- the maleimide compound represented by the formula (11) can also be commercially available products, for example, Nippon Kayaku Co., Ltd. MIR-3000 (trade name, in equation (11), R 4 are all A hydrogen atom, and n 6 is a mixture of 1 to 10).
- Examples of the maleimide compound represented by the following formula (12) include BMI-TMH (1,6-bismaleimide- (2,2,4-trimethyl) hexane) manufactured by Daiwa Chemical Industry Co., Ltd.
- BMI-TMH (1,6-bismaleimide- (2,2,4-trimethyl) hexane
- the maleimide compound (B) represented by the formula (10) is prepared by preparing a chloroform solution containing the maleimide compound at 1% by mass and using a light beam having a wavelength of 405 nm (h-line) to adjust the light transmittance of the chloroform solution. When measured, the transmittance is 0%, it is almost not transmitted, and does not polymerize alone. However, when the maleimide compound (A) according to this embodiment and the photocuring initiator (C) described below are photocured, better heat resistance and thermal stability can be obtained.
- the maleimide compound (B) represented by the formula (10) is mixed with the maleimide compound (A) having a high transmittance at a wavelength of 405 nm (h-line), so that a wavelength of 405 nm (h-line) is obtained in the resin composition. ) Is well transmitted. Therefore, it is presumed that the photo-curing initiator (C) favorably absorbs light having a wavelength of 405 nm (h-line) to generate radicals, and the polymerization of the maleimide compound (B) and the maleimide compound (A) proceeds. I have.
- maleimide compounds (B) can be used alone or in combination of two or more.
- the resin composition of the present embodiment contains the photocuring initiator (C) (also referred to as component (C)) in the present embodiment.
- the photo-curing initiator (C) used in the present embodiment is not particularly limited as long as the absorbance at a wavelength of 405 nm (h-line) is 0.1 or more, and is generally known in the field used for a photo-curable resin composition. Can be used.
- the photocuring initiator (C) can be used alone or in combination of two or more.
- the absorbance at a wavelength of 405 nm (h-line) is 0.1 or more means that a chloroform solution containing 1% by mass of the component (C) is prepared, and a light-wavelength of 405 nm (h-line) is used.
- the absorbance of the chloroform solution was measured, it means that the absorbance was 0.1 or more.
- a photo-curing initiator (C) for example, when a printed wiring board having a high-density and high-definition wiring formation (pattern) is manufactured using a direct drawing exposure method, a wavelength of 405 nm (h-line) is used. Even when an active energy ray containing is used, the photoradical reaction of maleimide occurs efficiently.
- the absorbance at a wavelength of 405 nm (h-line) is more preferably 0.2 or more because a resin composition having more excellent photocurability can be obtained.
- the upper limit of the absorbance is not particularly limited, but is, for example, 99.9 or less.
- photocuring initiator (C) a compound represented by the following formula (1) is preferable.
- a plurality of R 1 each independently represent a substituent or a phenyl group represented by the following formula (2). It is preferable that at least one of a plurality of R 1 is a substituent represented by the following formula (2).
- a plurality of R 2 each independently represent a hydrogen atom or a methyl group.
- one or more of a plurality of R 2 is a methyl group, and more preferably, all of them are methyl groups.
- the absorbance of the chloroform solution is measured using a light beam having a wavelength of 405 nm (h-line)
- the absorbance becomes When it is 0.1 or more, it shows very excellent absorption for light having a wavelength of 405 nm (h-line). Therefore, this compound suitably generates a radical with respect to light having a wavelength of 405 nm (h-line).
- the compound represented by the formula (1) preferably has an absorbance of 0.2 or more.
- the upper limit is not particularly limited, but is, for example, 2.0 or less.
- the compound represented by the formula (1) is not particularly limited, but includes, for example, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide And acylphosphine oxides such as ethoxyphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide. These can be used alone or in appropriate combination of two or more kinds.
- Acylphosphine oxides exhibit extremely excellent absorption for active energy rays including a wavelength of 405 nm (h-line), and are preferably a maleimide compound having a transmittance of 1% or more at a wavelength of 405 nm (h-line). Radical polymerization can be performed. Therefore, according to the present embodiment, especially when used for a multilayer printed wiring board, a resin composition excellent in photocurability, heat resistance, heat stability, and insulation reliability, a resin sheet, a multilayer printed wiring board, and A semiconductor device can be suitably manufactured.
- the content of the photocuring initiator (C) is not particularly limited, but the maleimide compound is sufficiently cured by using an active energy ray having a wavelength of 405 nm (h ray), and heat resistance is improved.
- the amount is preferably 0.1 to 50 parts by mass based on 100 parts by mass of the total of the maleimide compound (A), the maleimide compound (B), and the photocuring initiator (C).
- the amount is more preferably from 2 to 30 parts by mass, and even more preferably from 0.3 to 10 parts by mass.
- photopolymerization initiator (C) commercially available products can also be used.
- Omnirad (registered trademark) 819 (trade name) manufactured by IGM Resins
- Omnirad (registered trademark) TPO (trade name) manufactured by IGM Resins
- IGM Resins Inc Omnirad (registered trademark) TPO L G (trade name).
- a filler (D) (also referred to as component (D)) can be used in combination in order to improve various properties such as coating properties and heat resistance.
- the filler (D) used in the present embodiment is not particularly limited as long as it has an insulating property and does not impair the transmittance at a wavelength of 405 nm (h-line).
- Examples of the filler (D) include silica (for example, natural silica, fused silica, amorphous silica, and hollow silica), aluminum compound (for example, boehmite, aluminum hydroxide, and alumina), and magnesium compound (for example, Magnesium compounds such as magnesium oxide and magnesium hydroxide), calcium compounds (such as calcium carbonate), molybdenum compounds (such as molybdenum oxide and zinc molybdate), barium compounds (such as barium sulfate and barium silicate).
- silica for example, natural silica, fused silica, amorphous silica, and hollow silica
- aluminum compound for example, boehmite, aluminum hydroxide, and alumina
- magnesium compound for example, Magnesium compounds such as magnesium oxide and magnesium hydroxide
- calcium compounds such as calcium carbonate
- molybdenum compounds such as molybdenum oxide and zinc molybdate
- barium compounds such as barium sulf
- Talc for example, natural talc and calcined talc
- mica for example, short fiber glass, spherical glass, fine powder glass, E glass, T glass, D glass, etc.
- silicone powder for example, fluororesin-based filler
- Urethane resin-based filler Urethane resin-based filler
- acrylic tree System filler polyethylene fillers
- styrene-butadiene silicone rubber
- filler (D) is composed of silica, boehmite, barium sulfate, silicone powder, fluororesin filler, urethane resin filler, (meth) acrylic resin filler, polyethylene filler, styrene / butadiene rubber, and silicone rubber. It is preferable that at least one member is selected from the group.
- These fillers (D) may be surface-treated with a silane coupling agent described below or the like.
- silica is preferred, and fused silica is more preferred, from the viewpoint of improving the heat resistance of the cured product and obtaining good 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. Name), and YA050C-MJA (trade name).
- These fillers (D) can be used alone or in an appropriate combination of two or more.
- the particle size of the filler is not particularly limited, but is usually from 0.005 to 10 ⁇ m, preferably from 0.01 to 1.0 ⁇ m, from the viewpoint of the ultraviolet transmittance of the resin composition.
- the content of the filler (D) is not particularly limited. From the viewpoint of improving the ultraviolet light transmittance of the resin composition and the heat resistance of the cured product, the content of the filler (D) is preferably 100 parts by mass of the resin solid content in the resin composition. On the other hand, the amount is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less.
- the lower limit value is not particularly limited, but from the viewpoint of obtaining the effect of improving various properties such as coating properties and heat resistance, the resin solid content in the resin composition is 100%. It is usually 1 part by mass with respect to parts by mass.
- a silane coupling agent and / or a wet dispersant may be used in combination in order to improve the dispersibility of the filler, the compatibility between the polymer and / or the resin, and the filler. It is possible.
- the silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of an inorganic substance.
- aminosilanes such as ⁇ -aminopropyltriethoxysilane and N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane
- epoxysilanes such as ⁇ -glycidoxypropyltrimethoxysilane (Meth) acrylsilanes such as ⁇ - (meth) acryloxypropyltrimethoxysilane
- cationic silanes such as N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane hydrochloride
- a phenylsilane-based silane coupling agent such as N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane hydrochloride
- silane coupling agents can be used alone or in an appropriate combination of two or more.
- the content of the silane coupling agent is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.
- the wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for paints.
- DISPERBYK registered trademark
- -110 trade name
- 111 trade name
- 118 trade name
- 180 trade name
- 161 trade name
- BYK registered trademark
- W9010 trade name
- W903 trade name
- these wetting and dispersing agents can be used alone or in an appropriate combination of two or more.
- the content of the wetting and dispersing agent is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.
- a cyanate ester compound when heat resistance is required, a cyanate ester compound, a benzoxazine compound, or the like can be used.
- a phenol resin, an oxetane resin, or the like can be used. These compounds and resins can be used alone or in appropriate combination of two or more kinds.
- the cyanate ester compound is not particularly limited as long as it is a resin having in its molecule an aromatic moiety in which at least one cyanato group (cyanate ester group) is substituted.
- Ar 1 represents a single bond of a benzene ring, a naphthalene ring or two benzene rings. When there are a plurality, they may be the same or different.
- 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 alkoxyl group having 1 to 4 carbon atoms, And a group in which an alkyl group having 6 and an aryl group having 6 to 12 carbon atoms are bonded to each other.
- the aromatic ring in Ra may have a substituent, and the substituent in Ar 1 and Ra can be selected at any position.
- p represents the number of cyanato groups bonded to Ar 1 and is each independently an integer of 1 to 3.
- q represents the number of Ra bonded to Ar 1 , 4-p when Ar 1 is a benzene ring, 6-p when Ar 1 is a naphthalene ring, and 8-p when Ar 1 is a single bond of two benzene rings.
- . t indicates the average number of repetitions, and is an integer of 0 to 50.
- the cyanate ester compound may be a mixture of compounds having different t.
- X is a single bond, a divalent organic group having 1 to 50 carbon atoms (a hydrogen atom may be substituted with a hetero atom) or a divalent organic group having 1 to 10 nitrogen atoms, when there are a plurality of Xs.
- An organic group eg, —N—R—N— (where R represents an organic group)
- a carbonyl group —CO—
- SO 2 sulfonyl group
- the alkyl group for Ra in Formula (14) may have any of a linear or branched chain structure and a cyclic structure (for example, a cycloalkyl group or the like). Further, the hydrogen atom in the alkyl group in Formula (14) and the aryl group in Ra may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, or a cyano group. Good.
- alkyl group examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, and 2,2-dimethylpropyl.
- alkenyl group examples include vinyl, (meth) allyl, isopropenyl, 1-propenyl, 2-butenyl, 3-butenyl, 1,3-butanedienyl, 2-methyl-2-propenyl , A 2-pentenyl group, and a 2-hexenyl group.
- aryl group examples include phenyl, xylyl, mesityl, naphthyl, phenoxyphenyl, ethylphenyl, o-, m- or p-fluorophenyl, dichlorophenyl, dicyanophenyl, trifluorophenyl Group, a methoxyphenyl group, and an o-, m- or p-tolyl group.
- alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group.
- divalent organic group having 1 to 50 carbon atoms in X of the formula (14) include methylene, ethylene, trimethylene, cyclopentylene, cyclohexylene, trimethylcyclohexylene, biphenylylmethylene.
- 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 alkoxyl 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 in the formula (14) include an imino group and a polyimide group.
- examples of the organic group of X in the formula (14) include those having a structure represented by the following formula (15) or the following formula (16).
- Ar 2 represents a benzenediyl group, a naphthalenediyl group or a biphenyldiyl group, and when u is 2 or more, they may be the same or different.
- Rb, Rc, Rf, and Rg each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or an aryl having at least one phenolic hydroxy group. Represents a group.
- Rd and Re are each independently selected from any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, and a hydroxy group.
- . u represents an integer of 0 to 5.
- Ar 3 represents a benzenediyl group, a naphthalenediyl group or a biphenyldiyl group, and when v is 2 or more, they may be the same or different.
- Ri and Rj each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxyl group having 1 to 4 carbon atoms, a hydroxy group, a trifluoromethyl group, Or an aryl group in which at least one cyanato group is substituted.
- v represents an integer of 0 to 5, but may be a mixture of compounds having different v.
- X in the formula (14) includes a divalent group represented by the following formula.
- Rk each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- Rk each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- two carbon atoms represented by the formula (15) or two oxygen atoms represented by the formula (16) are 1,4 Or a benzenediyl group bonded to the 1,3-position, the two carbon atoms or the two oxygen atoms are 4,4′-position, 2,4′-position, 2,2′-position, 2,3′-position, The biphenyldiyl group bonded to the 3,3′-position or the 3,4′-position, and the two carbon atoms or the two oxygen atoms are 2,6-position, 1,5-position, 1,6-position, Examples include a naphthalenediyl group bonded to the 1,8, 1,3, 1,4, or 2,7 position.
- cyanato-substituted aromatic compound represented by the formula (14) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, Cyanato-2-, 1-cyanato-3- or 1-cyanato-4-methoxybenzene, 1-cyanato-2,3-, 1-cyanato-2,4-, 1-cyanato-2,5-, 1 -Cyanato-2,6-, 1-cyanato-3,4- or 1-cyanato-3,5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, cyanatooctylbenzene, cyanatononylbenzene, 2- ( 4-cyanaphenyl) -2-phenylpropane (cyanate of 4- ⁇ -cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenze , 1-cyanato
- cyanate compounds can be used alone or in combination of two or more.
- cyanate ester compound represented by the formula (14) is a phenol novolak resin and a cresol novolak resin (a phenol, an alkyl-substituted phenol or a halogen-substituted phenol, a formalin or para- A formaldehyde compound such as formaldehyde reacted in an acidic solution), a trisphenol novolak resin (a reaction of hydroxybenzaldehyde and phenol in the presence of an acidic catalyst), and a fluoren novolak resin (a fluorenone compound and 9, 9-bis (hydroxyaryl) fluorenes reacted in the presence of an acidic catalyst), phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, and biphenyl aralkyl resin (by a known method).
- phenol novolak resin and a cresol novolak resin a phenol, an alkyl-substituted phenol or a
- Ar 4 - (CH 2 Y ) 2 (.
- Ar 4 represents a phenyl group, Y represents a halogen atom and the same in this paragraph.) Acidified with bis as represented by halogenoalkyl methyl compound and a phenol compound A bis (alkoxymethyl) compound represented by Ar 4 — (CH 2 OR) 2 (R represents an alkyl group) and a phenol compound reacted with or without a catalyst in the presence of an acidic catalyst Or a bis (hydroxymethyl) compound represented by Ar 4 — (CH 2 OH) 2 and a phenol compound reacted in the presence of an acidic catalyst, or an aromatic aldehyde compound And a phenol-modified xylene formaldehyde resin (by a known method, xylene formaldehyde).
- a resin and a phenolic compound reacted in the presence of an acidic catalyst a modified naphthalene formaldehyde resin (a naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound reacted by a known method in the presence of an acidic catalyst), Phenol-modified dicyclopentadiene resin, phenol resin having a polynaphthylene ether structure (a polyhydric hydroxynaphthalene compound having two or more phenolic hydroxy groups in one molecule is dehydrated in the presence of a basic catalyst by a known method) Phenolic resins such as those obtained by condensation) and cyanates thereof by the same method as described above, and prepolymers thereof. These are not particularly limited. These cyanate compounds may be used alone or in combination of two or more.
- the method for producing these cyanate compounds is not particularly limited, and a known method can be used.
- a method of obtaining or synthesizing a hydroxy group-containing compound having a desired skeleton and modifying the hydroxy group by a known method to form a cyanate can be mentioned.
- Examples of the method of cyanating a hydroxy group include the method described in Ian Hamerton, “Chemistry and Technology of the Cyanate Ester Resins,” Blackie Academic & Professional.
- the cured resin using these cyanate compounds has excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion.
- the content of the cyanate ester compound is not particularly limited, but is preferably 0.01 to 40 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.
- phenol resin a generally known phenol resin having two or more hydroxyl groups in one molecule can be used.
- phenol resin a generally known phenol resin having two or more hydroxyl groups in one molecule can be used.
- the content of the phenol resin is not particularly limited, and is preferably 0.01 to 40 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.
- oxetane resin As the oxetane resin, generally known ones can be used. For example, alkyl oxetanes such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3-di (trifluoro Methyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (trade name, manufactured by Toagosei Co., Ltd.), OXT-121 (toagosei Co., Ltd. ), Product name) and the like, and are not particularly limited. These can be used alone or in combination of two or more.
- the content of the oxetane resin is not particularly limited, but is preferably 0.01 to 40 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.
- benzoxazine compound As the benzoxazine compound, generally known compounds can be used as long as they have two or more dihydrobenzoxazine rings in one molecule.
- bisphenol A-type benzoxazine BA-BXZ manufactured by Konishi Chemical Industry Co., Ltd., trade name
- bisphenol F-type benzoxazine BF-BXZ manufactured by Konishi Chemical Industry Co., Ltd., trade name
- bisphenol S-type benzoxazine BS- BXZ manufactured by Konishi Chemical Co., Ltd., trade name
- phenolphthalein-type benzoxazine, etc. are not particularly limited. These can be used alone or in appropriate combination of two or more kinds.
- the content of the benzoxazine compound is not particularly limited, and is preferably 0.01 to 40 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.
- the epoxy resin is not particularly limited, and a generally known epoxy resin can be used.
- a generally known epoxy resin can be used.
- epoxy resin commercially available products can be used.
- a naphthalene type epoxy resin HP-4710 (trade name) manufactured by DIC Corporation
- a compound represented by the following formula (18) in represented by epoxy resin manufactured by Nippon Kayaku Co., Ltd. NC-3000FH (trade name), wherein (18), n 7 is about 4) and the like.
- epoxy resins can be used alone or in combination of two or more.
- the content of the epoxy resin is not particularly limited, but is preferably 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, ethylene glycol divinyl ether, styrenes such as styrene, methyl styrene, ethyl styrene, and divinyl benzene, triallyl isocyanurate, and trialmethallyl isocyanate. Nurate and bisallylnadiimide are exemplified. These can be used alone or in appropriate combination of two or more kinds.
- the content of the other compound is not particularly limited, but is preferably 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 a curing accelerator, if necessary, in order to appropriately adjust the curing speed.
- the curing accelerator is not particularly limited, and those generally used as a curing accelerator such as a cyanate ester compound can be used.
- the curing accelerator include organic metal salts such as zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetone, nickel octylate, and manganese octylate; phenol, xylenol, cresol, resorcinol, and catechol.
- Phenol compounds such as octylphenol and nonylphenol; alcohols such as 1-butanol and 2-ethylhexanol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and 1-cyanoethyl-2-phenyl Imidazoles such as imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole Derivatives such as azoles and adducts of carboxylic acids of these imidazoles or acid anhydrides thereof; amines such as dicyandiamide, benzyldimethylamine and 4-methyl-N, N-dimethylbenzylamine; phosphine compounds, phosphonium Phosphorus compounds such as salt compounds and diphosphine compounds; epoxy-imidazole adduct compounds;
- the resin composition of the present embodiment may contain a solvent as necessary.
- a solvent for example, when an organic solvent is used, the viscosity at the time of preparing the resin composition can be adjusted.
- the type of the solvent is not particularly limited as long as it can dissolve a part or all of the resin in the resin composition. Specific examples thereof include, but are not limited to, ketones such as acetone, methyl ethyl ketone, and methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol monomethyl ether; And its acetate.
- These organic solvents can be used alone or in an appropriate combination of two or more.
- various polymer compounds such as thermosetting resins, thermoplastic resins and oligomers thereof, elastomers, etc., which have not been mentioned above, as long as the properties of the present embodiment are not impaired.
- a flame-retardant compound that has not been mentioned before; an additive may be used in combination. These are not particularly limited as long as they are generally used.
- the flame-retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, phosphate compounds of phosphorus-based compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters.
- Additives include ultraviolet absorbers, antioxidants, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, surface conditioners, brighteners, and polymerization inhibitors. No. These components may be used alone or in combination of two or more. In the resin composition of the present embodiment, the content of other components is not particularly limited, but is usually 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.
- the resin composition of the present embodiment includes the maleimide compound (A), the maleimide compound (B), the photocuring initiator (C), and, if necessary, the filler (D) and other components according to the present embodiment. It is prepared by appropriately mixing resins, other compounds, curing accelerators, additives and the like. Moreover, you may mix an organic solvent as needed.
- the resin composition of the present embodiment can be suitably used as a varnish when producing a resin sheet of the present embodiment described later.
- the method for producing the resin composition of the present embodiment is not particularly limited, and includes, for example, a method in which the above-described components are sequentially mixed with a solvent and sufficiently stirred.
- the dispersibility of the filler in the resin composition can be improved by performing the stirring and dispersion treatment using a stirring tank provided with a stirrer having an appropriate stirring ability.
- the stirring, mixing, and kneading treatment are, for example, a stirrer for dispersion such as an ultrasonic homogenizer, an apparatus for mixing such as a three-roll, ball mill, bead mill, and sand mill, or revolving or rotating. It can be appropriately performed using a known device such as a mold mixing device.
- an organic solvent can be used as necessary.
- the type of the organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition, and specific examples thereof are as described above.
- the resin composition of the present embodiment can be used for applications requiring an insulating resin composition, and is not particularly limited. Applications include, for example, photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit boards (laminate boards, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials, semiconductors It can be used as a sealing material, a resin for filling holes, a resin for filling parts, and the like. Among them, the resin composition of the present embodiment is excellent in photocurability, heat resistance, heat stability, and insulation reliability, and thus is suitably used as an insulating layer of a multilayer printed wiring board and as a solder resist. can do.
- the resin sheet of the present embodiment has a support, a resin layer disposed on one or both surfaces of the support, and the resin layer includes a resin composition of the present embodiment, It is a sheet.
- the resin sheet can be produced by applying a resin composition on a support and drying the resin composition.
- the resin layer in the resin sheet of the present embodiment has excellent heat resistance, thermal stability, and insulation reliability.
- a known support can be used, and is not particularly limited, but is preferably a resin film.
- the resin film include a polyimide film, a polyamide film, a polyester film, a polyethylene terephthalate (PET) film, a polybutylene terephthalate (PBT) film, a polypropylene (PP) film, a polyethylene (PE) film, a polyethylene naphthalate film, and a polyvinyl alcohol.
- PET films are preferred.
- a resin film coated with a release agent on its surface can be suitably used to facilitate release from the resin layer.
- the thickness of the resin film is preferably in the range of 5 to 100 ⁇ m, more preferably in the range of 10 to 50 ⁇ m. When the thickness is less than 5 ⁇ m, the support tends to be broken when the support is peeled off, and when the thickness exceeds 100 ⁇ m, the resolution at the time of exposure from above the support tends to decrease.
- the resin film has excellent transparency.
- the resin layer may be protected by a protective film.
- a protective film By protecting the resin layer side with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin layer and to prevent scratches.
- the protective film a film made of the same material as the above resin film can be used.
- the thickness of the protective film is not particularly limited, but is preferably in the range of 1 to 50 ⁇ m, and more preferably in the range of 5 to 40 ⁇ m. If the thickness is less than 1 ⁇ m, the handleability of the protective film tends to decrease, and if it exceeds 50 ⁇ m, the cost tends to be poor.
- the protective film preferably has a smaller adhesive force between the resin layer and the protective film than an adhesive force between the resin layer and the support.
- the method for producing the resin sheet of the present embodiment is not particularly limited, for example, by applying the resin composition of the present embodiment to a support such as a PET film and drying to remove the organic solvent, the resin sheet Manufacturing method and the like can be mentioned.
- the coating method can be performed by a known method using, for example, a roll coater, a comma coater, a gravure coater, a die coater, a bar coater, a lip coater, a knife coater, a squeeze coater, or the like.
- the drying can be performed, for example, by 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 based on the total mass of the resin layer from the viewpoint of preventing the diffusion of the organic solvent in a later step.
- the thickness of the resin layer is preferably 1 to 50 ⁇ m from the viewpoint of improving the handleability.
- the resin sheet of the present embodiment can be used as an insulating layer of a multilayer printed wiring board.
- the multilayer printed wiring board of the present embodiment includes an insulating layer containing the resin composition of the present embodiment.
- the insulating layer can also be obtained, for example, by curing one or more of the resin sheets described above. Specifically, it can be manufactured by the following method.
- the resin layer side of the resin sheet of the present embodiment is laminated on one or both sides of the circuit board using a vacuum laminator.
- the circuit substrate include a glass epoxy substrate, a metal substrate, a ceramic substrate, a silicon substrate, a semiconductor sealing resin substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate.
- the circuit board refers to a board on which a patterned conductor layer (circuit) is formed on one or both sides of the board.
- one or both outermost layers of the printed wiring board are patterned conductor layers (circuits).
- the board is also included in the circuit board.
- the surface of the conductive layer may be previously subjected to a roughening treatment by a blackening treatment and / or a copper etching or the like.
- the resin sheet and the circuit board are preheated as necessary, and the resin layer of the resin sheet is pressed and heated. While crimping to 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 laminating step are not particularly limited.
- the pressing temperature is 50 to 140 ° C.
- the pressing pressure is 1 to 15 kgf / cm 2
- the pressing time is 5 to 300 seconds
- the air pressure is Is preferably reduced under a reduced pressure of not more than 20 mmHg.
- the laminating step may be a batch type or a continuous type using a roll.
- the vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of a commercially available vacuum laminator include a two-stage build-up laminator manufactured by Nikko Materials Co., Ltd.
- exposing step After a resin layer is provided on the circuit board by a laminating step, a predetermined portion of the resin layer is irradiated with an active energy ray containing a wavelength of 405 nm (h-line) as a light source, and the resin layer in the irradiated part is irradiated. Let it cure. Irradiation may be performed through a mask pattern, or a direct drawing method of directly irradiating may be used. When the direct drawing exposure method is used, a printed wiring board having high-density and high-definition wiring formation (pattern) can be manufactured.
- the active energy ray include an ultraviolet ray, a visible ray, an electron beam, and an X-ray.
- the wavelength of the active energy ray is not particularly limited, but is, for example, in the range of 200 to 600 nm.
- the irradiation amount of the active energy ray containing a wavelength of 405 nm (h ray) is generally 10 to 10,000 mJ / cm 2 .
- the exposure may be performed from above the support or may be performed after the support is peeled off.
- a heat treatment (post-bake) step is performed to form an insulating layer (cured product).
- the post-baking step include an ultraviolet irradiation step using a high-pressure mercury lamp, a heating step using a clean oven, and the like, and these can be used in combination.
- the irradiation amount can be adjusted as necessary, and for example, irradiation can be performed at an irradiation amount of about 0.05 to 10 J / cm 2 .
- the heating conditions can be appropriately selected as needed, but are preferably selected within the range of 150 to 220 ° C. for 20 to 180 minutes, more preferably within the range of 160 to 200 ° C. for 30 to 150 minutes.
- a conductor layer is formed on the surface of the insulating layer by dry plating.
- a known method such as a vapor deposition method, a sputtering method, and an ion plating method can be used.
- a metal film can be formed on an insulating layer by placing a multilayer printed wiring board in a vacuum vessel and heating and evaporating the metal.
- Sputtering method for example, put a multilayer printed wiring board in a vacuum vessel, introduce an inert gas such as argon, apply a DC voltage, hit the ionized inert gas against the target metal, was beaten out
- a metal film can be formed over an insulating layer using a metal.
- a conductor layer is formed by electroless plating, electrolytic plating, or the like.
- a method of forming a pattern thereafter for example, a subtractive method, a semi-additive method, or the like can be used.
- the semiconductor device of the present embodiment includes an insulating layer containing the resin composition of the present embodiment. Specifically, it can be manufactured by the following method.
- a semiconductor device can be manufactured by mounting a semiconductor chip on a conductive portion of the multilayer printed wiring board according to the present embodiment.
- the conductive portion refers to a portion for transmitting an electric signal in the multilayer printed wiring board, and 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 the semiconductor chip when manufacturing the semiconductor device of the present embodiment 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 build-up layer without bumps (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF) And the like.
- a semiconductor device can be manufactured by forming an insulating layer containing the resin composition of the present embodiment on a semiconductor chip or a substrate on which the semiconductor chip is mounted.
- the shape of the substrate on which the semiconductor chip is mounted may be a wafer shape or a panel shape. After formation, it can be manufactured using the same method as that for the above-mentioned multilayer printed wiring board.
- BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd.
- BMI-TMH trade name, formula (12) manufactured by Daiwa Kasei Kogyo Co., Ltd., weight average molecular weight (Mw) ) was used to measure the transmittance at a wavelength of 405 nm using 318 and the number of functional groups was 2).
- Omnirad (registered trademark) 819 was prepared by using 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Omnirad (registered trademark) 819 (trade name) manufactured by IGM Resins). A chloroform solution containing 1% by mass of (trade name) was prepared, and the absorbance at a wavelength of 405 nm was measured using a UV-vis measuring device (U-4100 (trade name)).
- Example 1 Preparation of resin composition and resin sheet
- BMI-1000P (trade name) as the maleimide compound (A)
- BMI-2300 (trade name) as the maleimide compound (B)
- C a photo-curing initiator
- 4.8 parts by mass of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Omnirad (registered trademark) 819 (trade name)) was mixed, and the mixture was stirred with an ultrasonic homogenizer to form a varnish (resin).
- a solution of the composition) was obtained.
- This varnish was coated on a 38 ⁇ m-thick PET film (Unipeel (registered trademark) TR1-38, manufactured by Unitika Ltd., trade name) by an automatic coating apparatus (PI-1210 (trade name, manufactured by Tester Sangyo Co., Ltd.)). It was then dried by heating at 80 ° C. for 7 minutes to obtain a resin sheet having a PET layer as a support and a resin layer thickness of 30 ⁇ m.
- PI-1210 trade name, manufactured by Tester Sangyo Co., Ltd.
- the resin layer was irradiated with an active energy ray containing a wavelength of 405 nm (h-ray) at a dose of 1,000 mJ / cm 2 using a manual double-sided exposure apparatus (manufactured by Oak Manufacturing Co., Ltd.). After exposing and curing the layer, the support was released. Thereafter, using a clean oven (manufactured by Espec Corporation), heat treatment (post bake) was performed at 180 ° C. for 60 minutes to obtain a cured product for evaluation 2 having a reliability evaluation substrate.
- an active energy ray containing a wavelength of 405 nm (h-ray) at a dose of 1,000 mJ / cm 2
- a manual double-sided exposure apparatus manufactured by Oak Manufacturing Co., Ltd.
- Example 2 45.5 parts by mass of BMI-6100 (trade name) as the maleimide compound (A), 45.5 parts by mass of BMI-TMH (trade name) as the maleimide compound (B), and a photo-curing initiator (C) ), 9 parts by mass of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Omnirad (registered trademark) 819 (trade name)) were mixed, and the mixture was stirred with an ultrasonic homogenizer to form a varnish (resin composition).
- a resin sheet was obtained in the same manner as in Example 1.
- a resin for evaluation and cured products 1 and 2 for evaluation were obtained in the same manner as in Example 1.
- Example 3 A resin sheet was obtained in the same manner as in Example 2 except that 45.5 parts by mass of BMI-689 (trade name) was used instead of BMI-6100 (trade name) as the maleimide compound (A). Using this, a resin for evaluation and cured products 1 and 2 for evaluation were obtained in the same manner as in Example 1.
- Example 4 A resin sheet was obtained in the same manner as in Example 1, except that 47.6 parts by mass of BMI-650P (trade name) was used as the maleimide compound (A) instead of BMI-1000P (trade name). Using this, a resin for evaluation and cured products 1 and 2 for evaluation were obtained in the same manner as in Example 1.
- Example 5 A resin sheet was obtained in the same manner as in Example 1, except that 47.6 parts by mass of BMI-250P (trade name) was used as the maleimide compound (A) instead of BMI-1000P (trade name). Using this, a resin for evaluation and cured products 1 and 2 for evaluation were obtained in the same manner as in Example 1.
- Comparative Example 2 A resin sheet was obtained in the same manner as in Comparative Example 1, except that 90 parts by mass of BMI-2300 (trade name) was used instead of BMI-1000P (trade name) as a maleimide compound. Using this, a resin for evaluation and cured products 1 and 2 for evaluation were obtained in the same manner as in Example 1.
- Example 3 A resin was obtained in the same manner as in Example 1 except that 4.8 parts by mass of Omnirad (registered trademark) 369 (trade name) was used instead of Omnirad (registered trademark) 819 (trade name) as a photocuring initiator. I got a sheet. Using this, a resin for evaluation and cured products 1 and 2 for evaluation were obtained in the same manner as in Example 1.
- Example 4 A resin sheet was obtained in the same manner as in Example 1, except that 4.8 parts by mass of Omnirad (registered trademark) 907 (trade name) was used instead of Omnirad (registered trademark) 819 as a photocuring initiator. Using this, a resin for evaluation and cured products 1 and 2 for evaluation were obtained in the same manner as in Example 1.
- Omnirad registered trademark
- cured products 1 and 2 for evaluation were obtained in the same manner as in Example 1.
- Example 1 Using this varnish, a resin sheet was obtained in the same manner as in Example 1. Using this, a resin for evaluation and cured products 1 and 2 for evaluation were obtained in the same manner as in Example 1.
- Photo DSC TIA Instruments Japan
- a light source capable of irradiating an active energy ray including a wavelength of 405 nm (h-ray) (Omnicure (registered trademark) S2000 (trade name) manufactured by Uvics Co., Ltd.)
- the obtained resin for evaluation was irradiated with an active energy ray having a wavelength of 405 nm (h-line) at an illuminance of 30 mW and an exposure time of 3.5 minutes using DSC-2500 (trade name, manufactured by Co., Ltd.). Is a time (sec), and the vertical axis is a heat flow (mW).
- the peak area when a horizontal line was drawn from the end point of this graph was defined as enthalpy (J / g).
- the curability was evaluated by enthalpy, and "1" (J / g) or more was rated “AA", and less than 1 (J / g) was rated "CC".
- the enthalpy is 1 (J / g) or more means that the curing of the resin sufficiently proceeds by exposure using an active energy ray including a wavelength of 405 nm (h-line).
- thermogravimetric measurement device TG-DTA6200 (trade name)
- the measurement was performed under the measurement conditions of the measurement start temperature (20 ° C), the temperature rising rate (10 ° C / min), and the target temperature (500 ° C).
- the cured product for evaluation 1 was measured, and as a result, the temperature at which the weight reduction rate of the cured product for evaluation 1 became 5% was defined as thermal stability (° C.).
- thermal stability ° C.
- "wrinkles" occurred in post-baking. In the measurement of thermal stability, a smooth sample was required, and thus these samples could not be measured.
- ⁇ Insulation reliability test> The obtained cured product for evaluation 2 was subjected to a moisture absorption treatment at 85 ° C. and 60% RH for 168 hours, and then subjected to a reflow treatment at 260 ° C. three times.
- the resistance value of the cured product for evaluation after the reflow treatment was measured for 400 hours under HAST conditions (130 ° C., 85% RH, and 5.0 V), and the final resistance value at that time was calculated.
- the insulation reliability was evaluated by the following evaluation items together with the visual judgment during the measurement. "AA": There is no short circuit during the measurement, and the final resistance value is 1.0 ⁇ 10 7 ( ⁇ ) or more.
- the resin composition of the present embodiment is photosensitive when exposed to an active energy ray containing a wavelength of 405 nm (h-ray), and can be photocured.
- h-ray active energy ray containing a wavelength of 405 nm
- the resin composition of the present invention is photosensitive when exposed to an active energy ray containing a wavelength of 405 nm (h-ray) and can be photocured.
- an active energy ray containing a wavelength of 405 nm (h-ray) when used for a multilayer printed wiring board, it has photocurability and heat resistance. Because of its excellent properties, thermal stability and insulation reliability, it is suitable for applications requiring an insulating resin composition.
- Such applications include, for example, photosensitive films, photosensitive films with supports, insulating resin sheets such as prepregs, circuit boards (laminate boards and multilayer printed wiring boards, etc.), solder resists, underfill materials, Examples include a die bonding material, a semiconductor sealing material, a filling resin, and a component filling resin.
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Abstract
Description
たとえば、特許文献1には、ビスフェノール型エポキシ樹脂と(メタ)アクリル酸とを反応させた後、酸無水物を反応させて得られるカルボキシル変性エポキシ(メタ)アクリレート樹脂と、ビフェニル型エポキシ樹脂と、光硬化開始剤と、希釈剤とを含む感光性熱硬化型樹脂組成物が記載されている。
[1]マレイミド官能基当量が300g/eq.以上であり、かつ、波長405nm(h線)の透過率が1%以上であるマレイミド化合物(A)と、マレイミド官能基当量が300g/eq.未満であるマレイミド化合物(B)と、波長405nm(h線)の吸光度が0.1以上である光硬化開始剤(C)と、を含有する樹脂組成物。
[4]前記光重合開始剤(C)が、下記式(1)で表される化合物である、[1]~[3]のいずれかに記載の樹脂組成物。
[6]前記樹脂層の厚さが1~50μmである、[5]に記載の樹脂シート。
[7][1]~[4]のいずれかに記載の樹脂組成物を有する、多層プリント配線板。
[8][1]~[4]のいずれかに記載の樹脂組成物を有する、半導体装置。
本実施形態の樹脂組成物には、本実施形態に係るマレイミド化合物(A)(成分(A)とも称す)を含む。本実施形態に係るマレイミド化合物(A)は、マレイミド官能基当量が300g/eq.以上であり、かつ、波長405nm(h線)の透過率が1%以上である。
通常、マレイミド化合物は光透過性が悪いため、樹脂組成物がマレイミド化合物を含むと、樹脂組成物中に分散している光硬化開始剤まで十分に光が届かず、光硬化開始剤がラジカルを発生し難い。そのため、一般的にマレイミド化合物の光ラジカル反応は進行し難く、仮にマレイミド単体のラジカル重合や二量化反応が進行しても、その反応性は非常に低い。しかし、本実施形態に係るマレイミド化合物(A)は、マレイミド化合物(A)が1質量%で含まれるクロロホルム溶液を調製し、波長405nm(h線)の光線を用いてこのクロロホルム溶液の透過率を測定した場合に、透過率が1%以上と、非常に優れた光透過性を示す。そのため、光硬化開始剤まで十分に光が届き、マレイミドの光ラジカル反応が効率的に起きる。透過率は、光硬化性、耐熱性、及び熱安定性により優れる樹脂組成物を得ることができることから、2%以上であることが好ましく、4%以上であることがより好ましい。なお、透過率の上限は、特に限定されないが、例えば、99.9%以下である。
そして、本実施形態の樹脂組成物を含んで得られる硬化物は、光硬化性、耐熱性、及び熱安定性に優れるため、保護膜、及び絶縁層を好適に形成することができる。
式(4)中、yの数は、10~35である。
アルキル基の炭素数としては、優れた光硬化性を示すことから、4~12がより好ましい。
アルケニル基の炭素数としては、優れた光硬化性を示すことから、4~12がより好ましい。
アルキル基の炭素数としては、優れた光硬化性を示すことから、4~12がより好ましい。
アルケニル基の炭素数としては、優れた光硬化性を示すことから、4~12がより好ましい。
アルケニル基の具体例としては、前記のRaにおけるアルケニル基を参照できる。この中でも、優れた光硬化性を示すことから、2-ヘプテニル基、2-オクテニル基、及び2-ノネニル基が好ましく、2-オクテニル基がより好ましい。
式(3)で表されるマレイミド化合物としては、例えば、ケイ・アイ化成(株)製BMI-1000P(商品名、式(3)中のn1=13.6(平均))、ケイ・アイ化成(株)社製BMI-650P(商品名、式(3)中のn1=8.8(平均))、ケイ・アイ化成(株)社製BMI-250P(商品名、式(3)中のn1=3~8(平均))、ケイ・アイ化成(株)社製CUA-4(商品名、式(3)中のn1=1)等が挙げられる。
式(4)で表されるマレイミド化合物としては、例えば、Designer Molecules Inc.製BMI-6100(商品名、式(4)中のx=18、y=18)等が挙げられる。
式(5)で表されるマレイミド化合物としては、例えば、Designer Molecules Inc.製BMI-689(商品名、下記の式(9)、官能基当量:346g/eq.)等が挙げられる。
式(7)で表されるマレイミド化合物としては、例えば、Designer Molecules Inc.製BMI-1700(商品名、式(7)中、n3は1~10の混合物である)が挙げられる。
式(8)で表されるマレイミド化合物としては、例えば、Designer Molecules Inc.製BMI-3000(商品名、式(8)中、n4は3.1(平均値)である)、Designer Molecules Inc.製BMI-5000(商品名、式(8)中、n4は1~10の混合物である)、Designer Molecules Inc.製BMI-9000(商品名)が挙げられる。
これらのマレイミド化合物(A)は、1種単独又は2種以上を適宜組み合わせて使用することも可能である。
本実施形態の樹脂組成物には、本実施形態に係るマレイミド化合物(B)(成分(B)とも称す)を含む。本実施形態に係るマレイミド化合物(B)は、マレイミド化合物(A)以外であり、マレイミド官能基当量が300g/eq.未満である。
本実施形態の樹脂組成物には、本実施形態に係光硬化開始剤(C)(成分(C)とも称す)を含む。本実施形態に用いる光硬化開始剤(C)は、波長405nm(h線)の吸光度が0.1以上であれば特に限定されず、一般に光硬化性樹脂組成物で用いられる分野で公知のものを使用することができる。光硬化開始剤(C)は、1種単独又は2種以上を適宜組み合わせて使用することも可能である。
ここで、波長405nm(h線)の吸光度が0.1以上であるとは、成分(C)が1質量%で含まれるクロロホルム溶液を調製し、波長405nm(h線)の光線を用いてこのクロロホルム溶液の吸光度を測定した場合に、吸光度が0.1以上であることを意味する。このような光硬化開始剤(C)を用いると、例えば、直接描画露光法を用いて高密度で高精細な配線形成(パターン)を有するプリント配線板を製造するに際し、波長405nm(h線)を含む活性エネルギー線を用いた場合でも、マレイミドの光ラジカル反応が効率的に起こる。波長405nm(h線)における吸光度は、光硬化性により優れる樹脂組成物を得ることができることから、0.2以上であることがより好ましい。なお、吸光度の上限は、特に限定されないが、例えば、99.9以下である。
本実施形態の樹脂組成物には、塗膜性や耐熱性等の諸特性を向上させるために、充填材(D)(成分(D)とも称す)を併用することも可能である。本実施形態に用いる充填材(D)は、絶縁性を有し、波長405nm(h線)に対する透過性を阻害しないものであれば、特に限定されない。充填材(D)としては、例えば、シリカ(例えば、天然シリカ、溶融シリカ、アモルファスシリカ、及び中空シリカ等)、アルミニウム化合物(例えば、ベーマイト、水酸化アルミニウム、及びアルミナ等)、マグネシウム化合物(例えば、酸化マグネシウム、及び水酸化マグネシウム等)、カルシウム化合物(例えば、炭酸カルシウム等)、モリブデン化合物(例えば、酸化モリブデン、及びモリブデン酸亜鉛等)、バリウム化合物(例えば、硫酸バリウム、及びケイ酸バリウム等)、タルク(例えば、天然タルク、及び焼成タルク等)、マイカ、ガラス(例えば、短繊維状ガラス、球状ガラス、微粉末ガラス、Eガラス、Tガラス、Dガラス等)、シリコーンパウダー、フッ素樹脂系充填材、ウレタン樹脂系充填材、(メタ)アクリル樹脂系充填材、ポリエチレン系充填材、スチレン・ブタジエンゴム、及びシリコーンゴム等が挙げられる。
これらの充填材(D)は、後述のシランカップリング剤等で表面処理されていてもよい。
これらの充填材(D)は、1種単独又は2種以上を適宜組み合わせて使用することも可能である。
本実施形態の樹脂組成物には、充填材の分散性、ポリマー及び/又は樹脂と、充填材との相溶性を向上させるために、シランカップリング剤及び/又は湿潤分散剤を併用することも可能である。
これらのシランカップリング剤としては、一般に無機物の表面処理に使用されているシランカップリング剤であれば、特に限定されない。具体例としては、例えば、γ-アミノプロピルトリエトキシシラン、及びN-β-(アミノエチル)-γ-アミノプロピルトリメトキシシラン等のアミノシラン系;γ-グリシドキシプロピルトリメトキシシラン等のエポキシシラン系;γ-(メタ)アクリロキシプロピルトリメトキシシラン等の(メタ)アクリルシラン系;N-β-(N-ビニルベンジルアミノエチル)-γ-アミノプロピルトリメトキシシラン塩酸塩等のカチオニックシラン系;フェニルシラン系のシランカップリング剤が挙げられる。これらのシランカップリング剤は、1種単独又は2種以上を適宜組み合わせて使用することも可能である。
本実施形態の樹脂組成物において、シランカップリング剤の含有量は、特に限定されないが、通常、樹脂組成物100質量部に対して、0.1~10質量部である。
本実施形態の樹脂組成物において、湿潤分散剤の含有量は、特に限定されないが、通常、樹脂組成物100質量部に対して、0.1~10質量部である。
本実施形態では、波長405nm(h線)を含む活性エネルギー線で露光した場合に、本実施形態の樹脂組成物が感光して、光硬化する限り、硬化した硬化物の難燃性、耐熱性、及び熱膨張特性等、必要とする特性に応じて、シアン酸エステル化合物、フェノール樹脂、オキセタン樹脂、ベンゾオキサジン化合物、エポキシ樹脂、及びその他の化合物等、様々な種類の化合物及び樹脂を用いることができる。例えば、耐熱性を求められる場合には、シアン酸エステル化合物、及びベンゾオキサジン化合物等が挙げられ、他にフェノール樹脂、及びオキセタン樹脂等も用いることができる。
これらの化合物及び樹脂は、1種単独又は2種以上を適宜組み合わせて使用することも可能である。
シアン酸エステル化合物としては、シアナト基(シアン酸エステル基)が少なくとも1個置換された芳香族部分を分子内に有する樹脂であれば特に限定されない。
また、式(14)におけるアルキル基及びRaにおけるアリール基中の水素原子は、フッ素原子、塩素原子等のハロゲン原子、メトキシ基、フェノキシ基等のアルコキシル基、又はシアノ基等で置換されていてもよい。
アルケニル基の具体例としては、ビニル基、(メタ)アリル基、イソプロペニル基、1-プロペニル基、2-ブテニル基、3-ブテニル基、1,3-ブタンジエニル基、2-メチル-2-プロペニル、2-ペンテニル基、及び2-ヘキセニル基等が挙げられる。
アリール基の具体例としては、フェニル基、キシリル基、メシチル基、ナフチル基、フェノキシフェニル基、エチルフェニル基、o-,m-又はp-フルオロフェニル基、ジクロロフェニル基、ジシアノフェニル基、トリフルオロフェニル基、メトキシフェニル基、及びo-,m-又はp-トリル基等が挙げられる。
アルコキシル基の具体例としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、n-ブトキシ基、イソブトキシ基、及びtert-ブトキシ基等が挙げられる。
式(14)のXにおける窒素数1~10の2価の有機基としては、イミノ基、ポリイミド基等が挙げられる。
式(15)のAr2及び式(16)のAr3の具体例としては、式(15)に示す2個の炭素原子、又は式(16)に示す2個の酸素原子が、1,4位又は1,3位に結合するベンゼンジイル基、前記2個の炭素原子又は2個の酸素原子が4,4’位、2,4’位、2,2’位、2,3’位、3,3’位、又は3,4’位に結合するビフェニルジイル基、及び、前記2個の炭素原子又は2個の酸素原子が、2,6位、1,5位、1,6位、1,8位、1,3位、1,4位、又は2,7位に結合するナフタレンジイル基が挙げられる。
式(15)のRb、Rc、Rd、Re、Rf及びRg、並びに式(16)のRi、Rjにおけるアルキル基及びアリール基は、前記式(14)におけるものと同義である。
フェノール樹脂としては、1分子中に2個以上のヒドロキシル基を有するフェノール樹脂であれば、一般に公知のものを使用できる。例えば、ビスフェノールA型フェノール樹脂、ビスフェノールE型フェノール樹脂、ビスフェノールF型フェノール樹脂、ビスフェノールS型フェノール樹脂、フェノールノボラック樹脂、ビスフェノールAノボラック型フェノール樹脂、グリシジルエステル型フェノール樹脂、アラルキルノボラック型フェノール樹脂、ビフェニルアラルキル型フェノール樹脂、クレゾールノボラック型フェノール樹脂、多官能フェノール樹脂、ナフトール樹脂、ナフトールノボラック樹脂、多官能ナフトール樹脂、アントラセン型フェノール樹脂、ナフタレン骨格変性ノボラック型フェノール樹脂、フェノールアラルキル型フェノール樹脂、ナフトールアラルキル型フェノール樹脂、ジシクロペンタジエン型フェノール樹脂、ビフェニル型フェノール樹脂、脂環式フェノール樹脂、ポリオール型フェノール樹脂、リン含有フェノール樹脂、重合性不飽和炭化水素基含有フェノール樹脂及び水酸基含有シリコーン樹脂類等が挙げられるが、特に制限されるものではない。これらのフェノール樹脂は、1種単独又は2種以上を適宜組み合わせて使用することも可能である。
オキセタン樹脂としては、一般に公知のものを使用できる。例えば、オキセタン、2-メチルオキセタン、2,2-ジメチルオキセタン、3-メチルオキセタン、3,3-ジメチルオキセタン等のアルキルオキセタン、3-メチル-3-メトキシメチルオキセタン、3,3-ジ(トリフルオロメチル)パーフルオキセタン、2-クロロメチルオキセタン、3,3-ビス(クロロメチル)オキセタン、ビフェニル型オキセタン、OXT-101(東亞合成(株)製、商品名)、OXT-121(東亞合成(株)製、商品名)等が挙げられる、特に制限されるものではない。これらは、1種又は2種以上を適宜混合して使用することも可能である。
ベンゾオキサジン化合物としては、1分子中に2個以上のジヒドロベンゾオキサジン環を有する化合物であれば、一般に公知のものを用いることができる。例えば、ビスフェノールA型ベンゾオキサジンBA-BXZ(小西化学工業(株)製、商品名)ビスフェノールF型ベンゾオキサジンBF-BXZ(小西化学工業(株)製、商品名)、ビスフェノールS型ベンゾオキサジンBS-BXZ(小西化学工業(株)製、商品名)、フェノールフタレイン型ベンゾオキサジン等が挙げられるが、特に制限されるものではない。これらは、1種単独又は2種以上を適宜組み合わせて使用することも可能である。
エポキシ樹脂としては、特に限定されず、一般に公知のものを使用できる。例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールE型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、ビスフェノールAノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、キシレンノボラック型エポキシ樹脂、多官能フェノール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ナフタレン骨格変性ノボラック型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、アントラセン型エポキシ樹脂、3官能フェノール型エポキシ樹脂、4官能フェノール型エポキシ樹脂、トリグリシジルイソシアヌレート、グリシジルエステル型エポキシ樹脂、脂環式エポキシ樹脂、ジシクロペンタジエンノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、フェノールアラルキルノボラック型エポキシ樹脂、ナフトールアラルキルノボラック型エポキシ樹脂、アラルキルノボラック型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ポリオール型エポキシ樹脂、リン含有エポキシ樹脂、グリシジルアミン、ブタジエン等の二重結合をエポキシ化した化合物、水酸基含有シリコーン樹脂類とエピクロルヒドリンとの反応により得られる化合物、及びこれらのハロゲン化物が挙げられる。
その他の化合物としては、エチルビニルエーテル、プロピルビニルエーテル、ヒドロキシエチルビニルエーテル、エチレングリコールジビニルエーテル等のビニルエーテル類、スチレン、メチルスチレン、エチルスチレン、及びジビニルベンゼン等のスチレン類、トリアリルイソシアヌレート、トリメタアリルイソシアヌレート、及びビスアリルナジイミド等が挙げられる。これらは、1種単独又は2種以上を適宜組み合わせて使用することも可能である。
その他の化合物の含有量は、特に限定されないが、樹脂組成物中の樹脂固形分100質量部に対して、好ましくは0.01~40質量部である。
本実施形態の樹脂組成物には、必要に応じて、硬化速度を適宜調節するために、硬化促進剤を含むことができる。硬化促進剤としては、特に限定されず、シアン酸エステル化合物等の硬化促進剤として一般に使用されているものを用いることができる。硬化促進剤としては、例えば、オクチル酸亜鉛、ナフテン酸亜鉛、ナフテン酸コバルト、ナフテン酸銅、アセチルアセトン鉄、オクチル酸ニッケル、及びオクチル酸マンガン等の有機金属塩類;フェノール、キシレノール、クレゾール、レゾルシン、カテコール、オクチルフェノール、及びノニルフェノール等のフェノール化合物;1-ブタノール、及び2-エチルヘキサノール等のアルコール類;2-メチルイミダゾール、2-エチル-4-メチルイミダゾール、2-フェニルイミダゾール、1-シアノエチル-2-フェニルイミダゾール、1-シアノエチル-2-エチル-4-メチルイミダゾール、2-フェニル-4,5-ジヒドロキシメチルイミダゾール、及び2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾール等のイミダゾール類及びこれらのイミダゾール類のカルボン酸もしくはその酸無水類の付加体等の誘導体;ジシアンジアミド、ベンジルジメチルアミン、及び4-メチル-N,N-ジメチルベンジルアミン等のアミン類;ホスフィン系化合物、ホスホニウム塩系化合物、及びダイホスフィン系化合物等のリン化合物;エポキシ-イミダゾールアダクト系化合物;ベンゾイルパーオキサイド、p-クロロベンゾイルパーオキサイド、ジ-t-ブチルパーオキサイド、ジイソプロピルパーオキシカーボネート、及びジ-2-エチルヘキシルパーオキシカーボネート等の過酸化物;2,2’-アゾビスイソブチロニトリル等のアゾ化合物が挙げられる。これらの硬化促進剤は、1種単独又は2種以上を適宜組み合わせて使用することも可能である。
本実施形態の樹脂組成物において、硬化促進剤の含有量は、特に限定されないが、通常、樹脂組成物100質量部に対して、0.1~20質量部である。
本実施形態の樹脂組成物には、必要に応じて溶剤を含有していてもよい。例えば、有機溶剤を用いると、樹脂組成物の調製時における粘度を調整することができる。溶剤の種類は、樹脂組成物中の樹脂の一部又は全部を溶解可能なものであれば、特に限定されない。その具体例としては、特に限定されないが、例えば、アセトン、メチルエチルケトン、及びメチルセルソルブ等のケトン類;トルエン、及びキシレン等の芳香族炭化水素類;ジメチルホルムアミド等のアミド類;プロピレングリコールモノメチルエーテル、及びそのアセテートが挙げられる。
これら有機溶剤は、1種単独又は2種以上を適宜組み合わせて使用することも可能である。
本実施形態の樹脂組成物には、本実施形態の特性が損なわれない範囲において、これまでに挙げられていない熱硬化性樹脂、熱可塑性樹脂及びそのオリゴマー、エラストマー類等の種々の高分子化合物;これまでに挙げられていない難燃性の化合物;添加剤等の併用も可能である。これらは一般に使用されているものであれば、特に限定されるものではない。例えば、難燃性の化合物では、メラミンやベンゾグアナミン等の窒素含有化合物、オキサジン環含有化合物、及びリン系化合物のホスフェート化合物、芳香族縮合リン酸エステル、及び含ハロゲン縮合リン酸エステル等が挙げられる。添加剤としては、紫外線吸収剤、酸化防止剤、蛍光増白剤、光増感剤、染料、顔料、増粘剤、滑剤、消泡剤、表面調整剤、光沢剤、及び重合禁止剤等が挙げられる。これらの成分は、1種単独又は2種以上を適宜組み合わせて使用することも可能である。
本実施形態の樹脂組成物において、その他の成分の含有量は、特に限定されないが、通常、樹脂組成物100質量部に対して、それぞれ0.1~10質量部である。
本実施形態の樹脂組成物は、本実施形態に係る、マレイミド化合物(A)、マレイミド化合物(B)、光硬化開始剤(C)と、必要に応じて、充填材(D)、及びその他の樹脂、その他の化合物、硬化促進剤、並びに添加剤等を適宜混合することにより調製される。また、必要に応じて、有機溶剤を混合してもよい。本実施形態の樹脂組成物は、後述する本実施形態の樹脂シートを作製する際のワニスとして、好適に使用することができる。
本実施形態の樹脂組成物は、絶縁性の樹脂組成物が必要とされる用途に使用することができ、特に限定されない。用途しては、例えば、感光性フィルム、支持体付き感光性フィルム、プリプレグ、樹脂シート、回路基板(積層板用途、多層プリント配線板用途等)、ソルダーレジスト、アンダーフィル材、ダイボンディング材、半導体封止材、穴埋め樹脂、及び部品埋め込み樹脂等に使用することができる。それらの中でも、本実施形態の樹脂組成物は、光硬化性、耐熱性、熱安定性、及び絶縁信頼性に優れるため、多層プリント配線板の絶縁層用として、及びソルダーレジスト用として好適に使用することができる。
本実施形態の樹脂シートは、支持体と、前記支持体の片面又は両面に配された樹脂層と、を有し、前記樹脂層が、本実施形態の樹脂組成物を含む、支持体付き樹脂シートである。樹脂シートは、樹脂組成物を支持体上に塗布、及び乾燥して製造することができる。本実施形態の樹脂シートにおける樹脂層は、優れた耐熱性、熱安定性、及び絶縁信頼性を有する。
樹脂層側を保護フィルムで保護することにより、樹脂層表面へのゴミ等の付着やキズを防止することができる。保護フィルムとしては前記の樹脂フィルムと同様の材料により構成されたフィルムを用いることができる。保護フィルムの厚さは、特に限定されないが、1~50μmの範囲であることが好ましく、5~40μmの範囲であることがより好ましい。厚さが1μm未満では、保護フィルムの取り扱い性が低下する傾向があり、50μmを超えると廉価性に劣る傾向がある。なお、保護フィルムは、樹脂層と支持体との接着力に対して、樹脂層と保護フィルムとの接着力の方が小さいものが好ましい。
塗布方法は、例えば、ロールコーター、コンマコーター、グラビアコーター、ダイコーター、バーコーター、リップコーター、ナイフコーター、及びスクイズコーター等を用いた公知の方法で行うことができる。前記乾燥は、例えば、60~200℃の乾燥機中で、1~60分加熱させる方法等により行うことができる。
本実施形態の多層プリント配線板は、本実施形態の樹脂組成物を含む絶縁層を備える。絶縁層は、例えば、前記の樹脂シートを1枚以上重ねて硬化して得ることもできる。具体的には、以下の方法により製造することができる。
ラミネート工程では、本実施形態の樹脂シートの樹脂層側を、真空ラミネーターを用いて回路基板の片面又は両面にラミネートする。回路基板としては、例えば、ガラスエポキシ基板、金属基板、セラミック基板、シリコン基板、半導体封止樹脂基板、ポリエステル基板、ポリイミド基板、BTレジン基板、及び熱硬化型ポリフェニレンエーテル基板等が挙げられる。なお、本実施形態において、回路基板とは、前記のような基板の片面又は両面にパターン加工された導体層(回路)が形成された基板をいう。また、本実施形態において、導体層と絶縁層とを交互に積層してなる多層プリント配線板において、プリント配線板の最外層の片面又は両面がパターン加工された導体層(回路)となっている基板も回路基板に含まれる。導体層表面には、黒化処理、及び/又は銅エッチング等により予め粗化処理が施されていてもよい。ラミネート工程において、樹脂シートが保護フィルムを有している場合には、保護フィルムを剥離除去した後、必要に応じて樹脂シート及び回路基板をプレヒートし、樹脂シートの樹脂層を加圧及び加熱しながら回路基板に圧着する。本実施形態においては、真空ラミネート法により減圧下で回路基板に樹脂シートの樹脂層をラミネートする方法が好適に用いられる。
露光工程では、ラミネート工程により、回路基板上に樹脂層が設けられた後、樹脂層の所定部分に、光源として波長405nm(h線)を含む活性エネルギー線を照射し、照射部の樹脂層を硬化させる。照射は、マスクパターンを通してもよいし、直接照射する直接描画法を用いてもよい。直接描画露光法を用いた場合、高密度で高精細な配線形成(パターン)を有するプリント配線板を製造することができる。活性エネルギー線としては、例えば、紫外線、可視光線、電子線、及びX線等が挙げられる。活性エネルギー線の波長としては、特に限定されないが、例えば、200~600nmの範囲である。
本実施形態では、露光工程の後に、加熱処理(ポストベーク)工程を行い、絶縁層(硬化物)を形成する。ポストベーク工程としては、高圧水銀ランプによる紫外線照射工程やクリーンオーブンを用いた加熱工程等が挙げられ、これらを併用することも可能である。紫外線を照射する場合は、必要に応じてその照射量を調整することができ、例えば、0.05~10J/cm2程度の照射量で照射を行うことができる。また加熱の条件は、必要に応じて適宜選択できるが、好ましくは150~220℃で20~180分間の範囲、より好ましくは160~200℃で30~150分間の範囲で選択される。
絶縁層(硬化物)を形成後、乾式めっきにより絶縁層表面に導体層を形成する。乾式めっきとしては、蒸着法、スパッタリング法、及びイオンプレーティング法等の公知の方法を使用することができる。蒸着法(真空蒸着法)は、例えば、多層プリント配線板を真空容器内に入れ、金属を加熱蒸発させることにより、絶縁層上に金属膜を形成することができる。スパッタリング法も、例えば、多層プリント配線板を真空容器内に入れ、アルゴン等の不活性ガスを導入し、直流電圧を印加して、イオン化した不活性ガスをターゲット金属に衝突させ、叩き出された金属により絶縁層上に金属膜形成を行うことができる。
本実施形態の半導体装置は、本実施形態の樹脂組成物を含む絶縁層を備える。具体的には、以下の方法により製造することができる。本実施形態の多層プリント配線板の導通箇所に、半導体チップを実装することにより半導体装置を製造することができる。ここで、導通箇所とは、多層プリント配線板における電気信号を伝える箇所のことであって、その場所は表面であっても、埋め込まれた箇所であってもよい。また、半導体チップは、半導体を材料とする電気回路素子であれば特に限定されない。
マレイミド化合物(A)として、ケイ・アイ化成(株)製BMI-1000P(商品名、式(3)中のn1は13.6(平均値)、質量平均分子量(Mw)は1,338、官能基数は2)を用いて、このBMI-1000P(商品名)が1質量%で含まれるクロロホルム溶液を調製し、UV-vis測定装置((株)日立ハイテクノロジーズ製分光光度計 U-4100(商品名))を用いて、波長405nmにおける透過率の測定を行った。また、マレイミド官能基当量(「官能基当量」とも称す)は、前記の式(1)から算出した。
同様に、光硬化開始剤として、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1(IGM Resins社製Omnirad(登録商標)369(商品名))、及び2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノプロパン-1-オン(IGM Resins社製Omnirad(登録商標)907(商品名))を用いて、波長405nmにおける吸光度の測定を行った。
それらの結果を表1に示した。
(樹脂組成物及び樹脂シートの作製)
マレイミド化合物(A)として、BMI-1000P(商品名)を47.6質量部と、マレイミド化合物(B)として、BMI-2300(商品名)を47.6質量部と、光硬化開始剤(C)として、2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド(Omnirad(登録商標)819(商品名))を4.8質量部とを混合し、超音波ホモジナイザーで攪拌してワニス(樹脂組成物の溶液)を得た。このワニスを厚さ38μmのPETフィルム(ユニピール(登録商標)TR1-38、ユニチカ(株)製、商品名)上に自動塗工装置(テスター産業(株)製PI-1210(商品名))を用いて塗布し、80℃で7分間加熱乾燥して、PETフィルムを支持体とし樹脂層の厚さが30μmである樹脂シートを得た。
内層回路を形成したガラス布基材BT樹脂両面銅張積層板(銅箔厚さ18μm、厚み0.2mm、三菱ガス化学(株)製CCL(登録商標)-HL832NS(商品名))の両面をメック(株)製CZ8100(商品名)にて銅表面の粗化処理を行い、内層回路基板を得た。
前記樹脂シートの樹脂面を張り合わせ、真空ラミネーター(ニッコー・マテリアルズ(株)製)を用いて、30秒間真空引き(5.0MPa以下)を行った後、圧力10kgf/cm2、温度70℃で30秒間の積層成形を行った。さらに圧力7kgf/cm2、温度70℃で60秒間の積層成形を行うことで、両面に支持体を有する評価用樹脂を得た。
手動両面露光装置((株)オーク製作所製)を用いて、1,000mJ/cm2の照射量で波長405nm(h線)を含む活性エネルギー線を前記評価用樹脂に照射して、前記評価用樹脂を露光し、硬化した後、支持体を剥離した。その後、クリーンオーブン(エスペック(株)製)を用いて、180℃及び120分間にて加熱処理(ポストベーク)を施し、評価用硬化物1を得た。
L(パターン幅)/S(パターン間の間隙)=40/40(μm)の信頼性評価基板上に、前記樹脂シートの樹脂面を配置し、真空ラミネーター(ニッコー・マテリアルズ(株)製)を用いて、30秒間真空引き(5.0MPa以下)を行った後、圧力10kgf/cm2、温度70℃で30秒間の積層成形を行った。さらに圧力7kgf/cm2、温度70℃で60秒間の積層成形を行うことで、信頼性評価基板と樹脂層と支持体がこの順で積層された積層体を得た。
その後、手動両面露光装置((株)オーク製作所製)を用いて、1,000mJ/cm2の照射量で波長405nm(h線)を含む活性エネルギー線を前記樹脂層に照射して、前記樹脂層を露光し、硬化した後、支持体を剥離した。その後、クリーンオーブン(エスペック(株)製)を用いて、180℃及び60分間にて加熱処理(ポストベーク)を施し、信頼性評価基板を有する評価用硬化物2を得た。
マレイミド化合物(A)として、BMI-6100(商品名)を45.5質量部と、マレイミド化合物(B)として、BMI-TMH(商品名)を45.5質量部と、光硬化開始剤(C)として、2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド(Omnirad(登録商標)819(商品名))を9質量部とを混合し、超音波ホモジナイザーで攪拌してワニス(樹脂組成物の溶液)を得た。このワニスを用いて、実施例1と同様にして、樹脂シート得た。これを用いて、実施例1と同様にして、評価用樹脂、並びに評価用硬化物1及び2を得た。
マレイミド化合物(A)として、BMI-6100(商品名)の代わりに、BMI-689(商品名)を45.5質量部用いた以外は、実施例2と同様にして、樹脂シート得た。これを用いて、実施例1と同様にして、評価用樹脂、並びに評価用硬化物1及び2を得た。
マレイミド化合物(A)として、BMI-1000P(商品名)の代わりに、BMI-650P(商品名)を47.6質量部用いた以外は、実施例1と同様にして、樹脂シート得た。これを用いて、実施例1と同様にして、評価用樹脂、並びに評価用硬化物1及び2を得た。
マレイミド化合物(A)として、BMI-1000P(商品名)の代わりに、BMI-250P(商品名)を47.6質量部用いた以外は、実施例1と同様にして、樹脂シート得た。これを用いて、実施例1と同様にして、評価用樹脂、並びに評価用硬化物1及び2を得た。
マレイミド化合物として、BMI-1000P(商品名)を90質量部と、光硬化開始剤として2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド(Omnirad(登録商標)819(商品名))を10質量部とを混合し、超音波ホモジナイザーで攪拌してワニス(樹脂組成物の溶液)を得た。このワニスを用いて、実施例1と同様にして、樹脂シート得た。これを用いて、実施例1と同様にして、評価用樹脂、並びに評価用硬化物1及び2を得た。
マレイミド化合物として、BMI-1000P(商品名)の代わりに、BMI-2300(商品名)を90質量部用いた以外は、比較例1と同様にして、樹脂シート得た。これを用いて、実施例1と同様にして、評価用樹脂、並びに評価用硬化物1及び2を得た。
光硬化開始剤として、Omnirad(登録商標)819(商品名)の代わりに、Omnirad(登録商標)369(商品名)を4.8質量部用いた以外は、実施例1と同様にして、樹脂シート得た。これを用いて、実施例1と同様にして、評価用樹脂、並びに評価用硬化物1及び2を得た。
光硬化開始剤として、Omnirad(登録商標)819の代わりに、Omnirad(登録商標)907(商品名)を4.8質量部用いた以外は、実施例1と同様にして、樹脂シート得た。これを用いて、実施例1と同様にして、評価用樹脂、並びに評価用硬化物1及び2を得た。
TrisP-PA(エポキシアクリレート化合物のプロピレングリコールモノメチルエーテルアセテート)溶液(日本化薬(株)製KAYARAD(登録商標)ZCR-6007H、不揮発分65質量%、酸価:70mgKOH/g)を116.9質量部(不揮発分換算で76質量部)と、ジペンタエリスリトールヘキサアクリレート(日本化薬(株)製KAYARAD(登録商標)DPHA)16質量部と、光硬化開始剤としてOmnirad(登録商標)819(商品名)を8質量部とを混合し、超音波ホモジナイザーで攪拌してワニス(樹脂組成物の溶液)を得た。このワニスを用いて、実施例1と同様にして、樹脂シートを得た。これを用いて、実施例1と同様にして、評価用樹脂、並びに評価用硬化物1及び2を得た。
ビスフェノールF型エポキシアクリレート(日本化薬(株)社製KAYARAD(登録商標)ZFR-1553H、不揮発分68質量%、酸価:70mgKOH/g)を105.9質量部(不揮発分換算で72質量部)と、ジペンタエリスリトールヘキサアクリレート(日本化薬(株)社製KAYARAD(登録商標)DPHA)19質量部と、光硬化開始剤としてOmnirad(登録商標)819(商品名)を9質量部とを混合し、超音波ホモジナイザーで攪拌してワニス(樹脂組成物の溶液)を得た。このワニスを用いて、実施例1と同様にして、樹脂シートを得た。これを用いて、実施例1と同様にして、評価用樹脂、並びに評価用硬化物1及び2を得た。
評価用樹脂、並びに評価用硬化物1及び2を、以下の方法により測定し、評価した。それらの結果を表2に示した。
波長405nm(h線)を含む活性エネルギー線を照射可能な光源(ユーヴィックス(株)製Omnicure(登録商標) S2000(商品名))を付属したフォトDSC(ティー・エイ・インスツルメント・ジャパン(株)製DSC-2500(商標名))を用い、得られた評価用樹脂に照度30mW、露光時間3.5分間にて波長405nm(h線)を含む活性エネルギー線を照射して、横軸が時間(sec)、縦軸がヒートフロー(mW)のグラフを得た。このグラフの終点から、水平に線を引いた際のピーク面積をエンタルピー(J/g)とした。硬化性は、エンタルピーで評価し、1(J/g)以上を「AA」、1(J/g)未満を「CC」とした。なお、エンタルピーが1(J/g)以上とは、波長405nm(h線)を含む活性エネルギー線を用いた露光により、樹脂の硬化が十分に進行することを意味した。
得られた評価用硬化物1をDMA装置(TAインスツルメント社製動的粘弾性測定装置DMAQ800(商品名))を用いて10℃/分で昇温し、LossModulusのピーク位置をガラス転移温度(Tg、℃)とした。
なお、比較例1~4にて得られた評価用硬化物1においては、ポストベークにおいて「シワ」が発生した。耐熱性の測定においては、平滑な試料が必要となるため、これらの試料については、測定できなかった。
示差熱重量同時測定装置(TG-DTA6200(商品名))にて、測定開始温度(20℃)、昇温速度(10℃/min)、目標温度(500℃)の測定条件にて、得られた評価用硬化物1を測定し、その結果、評価用硬化物1の重量減少率が5%となった温度を熱安定性(℃)とした。
なお、比較例1~4にて得られた評価用硬化物1においては、ポストベークにおいて「シワ」が発生した。熱安定性の測定においては、平滑な試料が必要となるため、これらの試料については、測定できなかった。
得られた評価用硬化物2を、85℃及び60%RHの条件下で168時間吸湿処理してから、260℃で3回リフロー処理を行った。リフロー処理後の評価用硬化物を、HAST条件(130℃、85%RH、及び5.0V)で400時間抵抗値を測定し、その際の最終抵抗値を算出した。測定中の目視による判断と共に以下で評価項目にて、絶縁信頼性を評価した。
「AA」:測定中に短絡がなく、最終抵抗値が1.0×107(Ω)以上である。
「BB」:測定中に短絡がなく、最終抵抗値が1.0×107(Ω)未満である。
「CC」:測定中に短絡がある。
なお、比較例1~4にて得られた評価用硬化物2においては、ポストベークにおいて「シワ」が発生した。熱安定性の測定においては、平滑な試料が必要となるため、これらの試料については、測定できなかった。
Claims (8)
- マレイミド官能基当量が300g/eq.以上であり、かつ、波長405nm(h線)の透過率が1%以上であるマレイミド化合物(A)と、
マレイミド官能基当量が300g/eq.未満であるマレイミド化合物(B)と、
波長405nm(h線)の吸光度が0.1以上である光硬化開始剤(C)と、
を含有する樹脂組成物。 - 前記マレイミド化合物(A)と前記マレイミド化合物(B)の配合比((A):(B))が、質量基準で、1~99:99~1である、請求項1に記載の樹脂組成物。
- 前記マレイミド化合物(A)及び前記マレイミド化合物(B)の含有量が、前記マレイミド化合物(A)、前記マレイミド化合物(B)及び前記光硬化開始剤(C)の合計100質量部に対して、50~99.9質量部である、請求項1又は2に記載の樹脂組成物。
- 支持体と、
前記支持体の片面又は両面に配された樹脂層と、を有し、
前記樹脂層が、請求項1~4のいずれか一項に記載の樹脂組成物を含む、
樹脂シート。 - 前記樹脂層の厚さが1~50μmである、請求項5に記載の樹脂シート。
- 請求項1~4のいずれか一項に記載の樹脂組成物を有する、多層プリント配線板。
- 請求項1~4のいずれか一項に記載の樹脂組成物を有する、半導体装置。
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201980048733.3A CN112533968B (zh) | 2018-08-30 | 2019-08-28 | 树脂组合物、树脂片、多层印刷电路板、及半导体装置 |
| KR1020207030151A KR102192274B1 (ko) | 2018-08-30 | 2019-08-28 | 수지 조성물, 수지 시트, 다층 프린트 배선판, 및 반도체 장치 |
| EP19855117.8A EP3845575B1 (en) | 2018-08-30 | 2019-08-28 | Resin composition, resin sheet, multilayer printed wiring board, and semiconductor device |
| US17/271,745 US11370857B2 (en) | 2018-08-30 | 2019-08-28 | Resin composition, resin sheet, multilayer printed wiring board, and semiconductor device |
| JP2020503065A JP6746106B2 (ja) | 2018-08-30 | 2019-08-28 | 樹脂組成物、樹脂シート、多層プリント配線板、及び半導体装置 |
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| JP2018161792 | 2018-08-30 | ||
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| US (1) | US11370857B2 (ja) |
| EP (1) | EP3845575B1 (ja) |
| JP (1) | JP6746106B2 (ja) |
| KR (1) | KR102192274B1 (ja) |
| CN (1) | CN112533968B (ja) |
| TW (1) | TWI714240B (ja) |
| WO (1) | WO2020045489A1 (ja) |
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| JP2020033472A (ja) * | 2018-08-30 | 2020-03-05 | 三菱瓦斯化学株式会社 | 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 |
| WO2021117762A1 (ja) * | 2019-12-11 | 2021-06-17 | 三菱瓦斯化学株式会社 | 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 |
| KR20210141405A (ko) | 2020-05-14 | 2021-11-23 | 아지노모토 가부시키가이샤 | 수지 조성물 |
| KR20210146230A (ko) | 2020-05-26 | 2021-12-03 | 아지노모토 가부시키가이샤 | 수지 조성물 |
| CN114656788A (zh) * | 2020-12-23 | 2022-06-24 | 信越化学工业株式会社 | 环状酰亚胺树脂组合物、预浸料、覆铜箔层压板和印刷电路板 |
| JP2025013583A (ja) * | 2020-12-18 | 2025-01-24 | 信越化学工業株式会社 | 熱硬化性マレイミド樹脂組成物 |
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| CN114656788A (zh) * | 2020-12-23 | 2022-06-24 | 信越化学工业株式会社 | 环状酰亚胺树脂组合物、预浸料、覆铜箔层压板和印刷电路板 |
| JP7417345B2 (ja) | 2020-12-23 | 2024-01-18 | 信越化学工業株式会社 | 環状イミド樹脂組成物、プリプレグ、銅張積層板およびプリント配線板 |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20200125746A (ko) | 2020-11-04 |
| KR102192274B1 (ko) | 2020-12-17 |
| EP3845575B1 (en) | 2025-12-10 |
| TWI714240B (zh) | 2020-12-21 |
| US20210206892A1 (en) | 2021-07-08 |
| TW202020049A (zh) | 2020-06-01 |
| JP6746106B2 (ja) | 2020-08-26 |
| CN112533968A (zh) | 2021-03-19 |
| US11370857B2 (en) | 2022-06-28 |
| JPWO2020045489A1 (ja) | 2020-09-10 |
| EP3845575A1 (en) | 2021-07-07 |
| CN112533968B (zh) | 2021-06-18 |
| EP3845575A4 (en) | 2021-10-27 |
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