WO2020262577A1 - 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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- WO2020262577A1 WO2020262577A1 PCT/JP2020/025139 JP2020025139W WO2020262577A1 WO 2020262577 A1 WO2020262577 A1 WO 2020262577A1 JP 2020025139 W JP2020025139 W JP 2020025139W WO 2020262577 A1 WO2020262577 A1 WO 2020262577A1
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- 0 C*C1(C)CC*(C)CC(*N(C(C(CC2C(N3C)=O)C4CC2C3=O)=O)C4=O)CC1 Chemical compound C*C1(C)CC*(C)CC(*N(C(C(CC2C(N3C)=O)C4CC2C3=O)=O)C4=O)CC1 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N O=C(C=CC1=O)N1c1ccccc1 Chemical compound O=C(C=CC1=O)N1c1ccccc1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N OCC(c1ccccc1)=O Chemical compound OCC(c1ccccc1)=O ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 description 1
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- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1025—Preparatory processes from tetracarboxylic acids or derivatives and diamines polymerised by radiations
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- 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
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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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- 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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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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- 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
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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
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/12—Mountings, e.g. non-detachable insulating substrates
- H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
- H01L23/145—Organic substrates, e.g. plastic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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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
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
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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
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/036—Multilayers with layers of different types
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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
- H05K3/0011—Working of insulating substrates or insulating layers
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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
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0017—Etching of the substrate by chemical or physical means
- H05K3/0023—Etching of the substrate by chemical or physical means by exposure and development of a photosensitive insulating layer
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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
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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
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
Definitions
- the present invention relates to a resin composition, a resin sheet, a multilayer printed wiring board, and a semiconductor device.
- the insulating layer is also required to be thinned, and a resin sheet containing no glass cloth is required.
- Thermosetting resin is the mainstream of the resin composition used as the material of the insulating layer, and drilling for obtaining continuity between the insulating layers is generally performed by laser processing.
- an exposure method a method of exposing through a photomask using a mercury lamp as a light source is used, and a material that can be suitably exposed by the light source of this mercury lamp is required.
- a ghi mixed line g-line wavelength 436 nm, h-line wavelength 405 nm, i-line wavelength 365 nm
- a general-purpose photocuring initiator can be selected. ..
- a direct drawing exposure method for directly drawing on a photosensitive resin composition layer based on digital data of a pattern without using a photomask has been introduced.
- This direct drawing exposure method has better alignment accuracy than the exposure method using a photomask and can obtain a high-definition pattern. Therefore, it is particularly introduced in a substrate that requires high-density wiring formation. I'm out.
- the light source uses monochromatic light such as a laser, and among them, 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
- Alkaline development is used as the development method because a high-definition pattern can be obtained.
- Patent Document 1 describes 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, and the like.
- a photosensitive thermosetting resin composition containing a photocuring initiator and a diluent is described.
- Patent Document 2 describes a photocurable binder polymer, a photopolymerization compound having an ethylenically unsaturated bond, a photopolymerization (curing) initiator, a sensitizer, and a thermosetting agent, bisallyl nagic.
- 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) as a photosensitive resin composition used for a laminated board or a resin sheet. ing.
- Patent Document 4 describes a resin composition containing a polyvalent carboxy group-containing compound obtained by reacting bismaleimide with monoamine and then reacting with an acid anhydride, and a curable resin such as an epoxy resin. is there. And Patent Document 4 describes a polyvalent carboxy group-containing compound capable of obtaining a cured product having alkali developability.
- Patent Document 2 describes that a bismaleimide compound is used, but it is described as a thermosetting compound, and (meth) acrylate is used as a photopolymerizable compound. Therefore, even in the cured product obtained from this resin composition, the alkali developability is not sufficient, a high-definition resist pattern cannot be obtained, and there is a problem in using a high-density printed wiring board.
- Patent Document 3 a bismaleimide compound is used as a curable resin.
- the maleimide compound usually has poor light transmittance, if the maleimide compound is contained, the light does not sufficiently reach the photocuring initiator and the photocuring is performed. The initiator is less likely to generate radicals and its reactivity is very low. Therefore, in Patent Document 3, the maleimide compound is cured by performing additional heating before development, but since it is accompanied by heating, a high-definition resist pattern cannot be obtained. Further, since this resin composition does not have sufficient alkali developability in the first place, an unexposed resin composition remains even after development. Therefore, also from this point, in Patent Document 3, a high-definition resist pattern cannot be obtained, and this resin composition cannot be used for manufacturing a high-density printed wiring board.
- the polyvalent carboxy group-containing compound described in Patent Document 4 needs to be obtained by reacting bismaleimide with a monoamine and then reacting with an acid anhydride, so that the process is complicated. Further, since an aromatic amine compound is used as the monoamine, this polyvalent carboxy group-containing compound contains an amide group having an aromatic ring in its structure. Therefore, this multivalent carboxy group-containing compound has poor light transmittance and inhibits the photocuring reaction, so that it is difficult to actually use it in a photosensitive resin composition.
- the present invention has been made in view of the above problems, and when used in the production of a printed wiring board, it does not inhibit the photocuring reaction in the exposure process and has excellent photocurability.
- the present inventors have described the above problems by using a resin composition containing a specific bismaleimide compound (A), a compound (B) containing one or more carboxy groups, and a photocuring initiator (C). We have found that we can solve the problem, and have completed the present invention.
- R 1 represents a linear or branched alkylene group having 1 to 16 carbon atoms
- R 2 represents a linear or branched alkenylene group having 2 to 16 carbon atoms. It represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms.
- R 3 is an independent hydrogen atom and 1 to 16 carbon atoms, respectively. It represents a linear or branched alkyl group of 16 or a linear or branched alkenyl group having 2 to 16 carbon atoms.
- N represents an integer of 1 to 10 independently.
- the compound (B) containing one or more carboxy groups is a compound represented by the following formula (2), a compound represented by the following formula (3), a compound represented by the following formula (4), and the like.
- R 4 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, an amino group, or an aminomethyl group.
- K represents an integer of 1 to 5 independently.
- it when it has two or more carboxy groups, it may be an acid anhydride formed by connecting them to each other).
- R 5 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, a carboxymethyl group, an amino group, or an aminomethyl group.
- L is an integer of 1 to 9 independently.
- two or more carboxy groups when they are present, they may be acid anhydrides formed by connecting them to each other.
- R 6 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, a carboxymethyl group, an amino group, or an aminomethyl group.
- M is an integer of 1 to 9 independently.
- carboxy groups when two or more carboxy groups are present, they may be acid anhydrides formed by connecting them to each other.
- R 7 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, a carboxymethyl group, an amino group, or an aminomethyl group.
- O is an integer of 1 to 5 independently.
- carboxy when it has one or more groups, it may be an acid anhydride formed by connecting the carboxymethyl group and the carboxy group to each other.
- carboxy when it has two or more groups, it may be an acid anhydride formed by connecting them to each other.
- the formula (5) when it has two or more carboxymethyl groups, they are connected to each other. It may be an acid anhydride formed in the above.
- R 8 independently represents a substituent or a phenyl group represented by the following formula (7)).
- ⁇ * indicates a bond
- R 9 independently represents a hydrogen atom or a methyl group
- the support has a support and a resin layer arranged on one side or both sides of the support, and the resin layer contains the resin composition according to any one of [1] to [3].
- Resin sheet [5] The resin sheet according to [4], wherein the resin layer has a thickness of 1 to 50 ⁇ m.
- It has an insulating layer and a conductor layer formed on one side or both sides of the insulating layer, and the insulating layer contains the resin composition according to any one of [1] to [3].
- Multi-layer printed wiring board. [7] A semiconductor device comprising the resin composition according to any one of [1] to [3].
- the present invention when used in the production of a multilayer printed wiring board, it does not inhibit the photocuring reaction in the exposure process, has excellent photocurability, and has excellent alkali developability in the developing process. It is possible to provide a resin composition capable of imparting the above, a resin sheet using the same, a multilayer printed wiring board, and a semiconductor device.
- the present embodiment a mode for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail.
- the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents.
- the present invention can be appropriately modified and carried out within the scope of the gist thereof.
- (meth) acrylic means both “acryloxy” and its corresponding "methacrylicoxy
- (meth) acrylate means both “acrylate” and its corresponding “methacrylate”.
- (meth) acrylic means both “acrylic” and the corresponding "methacryl”.
- the resin composition of the present embodiment contains a specific bismaleimide compound (A), a compound (B) containing one or more carboxy groups, and a photocuring initiator (C).
- A specific bismaleimide compound
- B compound containing one or more carboxy groups
- C photocuring initiator
- the resin composition of the present embodiment contains a bismaleimide compound (A) (also referred to as a component (A)).
- the bismaleimide compound (A) contains a structural unit represented by the formula (1) and maleimide groups at both ends of the molecular chain.
- R 1 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms.
- R 2 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms.
- R 3 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms.
- n represents an integer of 1 to 10 independently of each other.
- the maleimide compound has poor light transmittance, so if the resin composition contains the maleimide compound, the light does not sufficiently reach the photocuring initiator dispersed in the resin composition, and the photocuring initiator radicalizes. Hard to occur. Therefore, in general, the photoradical reaction of the maleimide compound is difficult to proceed, and even if the radical polymerization or dimerization reaction of the maleimide alone proceeds, the reactivity is very low. However, since the bismaleimide compound (A) contains a structural unit represented by the formula (1), it is extremely excellent in light transmission.
- the photocuring initiator the photoradical reaction of maleimide occurs efficiently, and the bismaleimide compound (A) is the compound (B) containing one or more carboxy groups, which will be described later, and the photocuring initiation. Together with the agent (C), it can be photocured using various active energy rays.
- a chloroform solution containing 1% by mass of the bismaleimide compound (A) is prepared, and 1% by mass of the bismaleimide compound (A) is added using an active energy ray containing a wavelength of 365 nm (i line).
- the transmittance of the chloroform solution contained in is measured, the transmittance is 5% or more, which is extremely excellent light transmittance.
- the transmittance of a chloroform solution containing 1% by mass of the bismaleimide compound (A) is measured using an active energy ray (light ray) containing a wavelength of 405 nm (h ray), the transmittance is 5 It shows very excellent light transmittance of% or more.
- the transmittance at a wavelength of 365 nm (i-line) is preferably 8% or more, and more preferably 10% or more, from the viewpoint of exhibiting more excellent light transmittance.
- the transmittance at a wavelength of 405 nm (h line) is preferably 8% or more, preferably 10% or more, from the viewpoint of producing a printed wiring board having a higher density and high-definition wiring formation (pattern). More preferred.
- the upper limits of the transmittance at a wavelength of 365 nm (i-line) and the transmittance at a wavelength of 405 nm (h-line) are, for example, 99.9% or less.
- the photocuring initiator tends to have a low absorbance when a long wavelength light beam is used.
- an active energy ray containing a wavelength of 405 nm (h line) since the light having a wavelength of this wavelength is a relatively long wavelength, it is not absorbed by a normal photocuring initiator, and this light is suitably absorbed. If a photocuring initiator capable of generating radicals is not used, the polymerization will not proceed. Therefore, as the photocuring initiator (C) described later, when the absorbance of the chloroform solution containing the photocuring initiator (C) in an amount of 0.01% by mass is measured, the light has a wavelength of 405 nm (h line). On the other hand, it is preferable to use a photocuring initiator having an absorbance of 0.1 or more, which is extremely excellent in absorbency.
- the bismaleimide compound (A) is excellent in light transmission as described above, for example, even when an active energy ray containing a wavelength of 365 nm or an active energy ray containing 405 nm is used, the light is sufficient to the photoinitiator.
- the radical reaction using the radicals generated from the photo-curing initiator proceeds, and photo-curing is possible even in a composition containing a large amount of the bismaleimide compound (A).
- the resin composition of the present embodiment has excellent photocurability by containing the photocurable initiator (C) together with the bismaleimide compound (A) and the compound (B) containing one or more carboxy groups described later. It is also very excellent in alkali developability. The reason for this is not clear, but the present inventors presume as follows. That is, the bismaleimide compound (A) has a relatively long chain and a flexible structure, and does not have a structure that causes an interaction with an alkaline component in an alkaline developer.
- the bismaleimide compound (A) is alkaline as the compound (B) is dissolved in the alkaline developer while maintaining the structure of the compound (B) containing one or more carboxy groups in the alkaline developer. It can be dissolved in a developing solution. Then, in the developing step, when the alkaline developer flows into the unexposed portion (resin composition), the alkaline component in the alkaline developer and the carboxy group in the compound (B) are not inhibited by the bismaleimide compound (A). However, the salt can be formed quickly and preferably, and the water solubility is improved. Therefore, it is presumed that the resin composition of the present embodiment has excellent alkali developability.
- the cured product obtained from the resin composition of the present embodiment is excellent in heat resistance, insulation reliability, and thermal stability, and according to the present embodiment, a protective film and a protective film in a multilayer printed wiring board and a semiconductor device.
- the insulating layer can be preferably formed.
- the bismaleimide compound (A) preferably has a mass average molecular weight of 100 to 5000, more preferably 300 to 4500, from the viewpoint that a suitable viscosity can be obtained and an increase in the viscosity of the varnish can be suppressed.
- the "mass average molecular weight” means the polystyrene standard equivalent mass average molecular weight by the gel permeation chromatography (GPC) method.
- R 1 has a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms. Shown. R 1 is preferably a linear or branched alkylene group, and more preferably a linear alkylene group, from the viewpoint that a suitable viscosity can be obtained and an increase in the viscosity of the varnish can be controlled.
- the number of carbon atoms of the alkylene group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be further controlled.
- Examples of the linear or branched alkylene group include methylene group, ethylene group, propylene group, 2,2-dimethylpropylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group and decylene.
- the number of carbon atoms of the alkenylene group is preferably 2 to 14 and more preferably 4 to 12 from the viewpoint that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be further controlled.
- the linear or branched alkenylene group include a vinylene group, a 1-methylvinylene group, an arylene group, a propenylene group, an isopropenylene group, a 1-butenylene group, a 2-butenylene group, a 1-pentenylene group, and 2 -Pentenylene group, isopentenylene group, cyclopentenylene group, cyclohexenylene group, dicyclopentadienylene group and the like can be mentioned.
- R 2 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms.
- R 2 is preferably a linear or branched alkylene group, and more preferably a linear alkylene group, from the viewpoint that a suitable viscosity can be obtained and an increase in the viscosity of the varnish can be controlled.
- the number of carbon atoms of the alkylene group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be further controlled.
- R 1 can be referred to as a linear or branched alkylene group.
- the number of carbon atoms of the alkenylene group is preferably 2 to 14 and more preferably 4 to 12 from the viewpoint that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be further controlled.
- R 1 can be referred to as a linear or branched alkenylene group.
- R 1 and R 2 may be the same or different, but are preferably the same because the bismaleimide compound (A) can be more easily synthesized.
- R 3 independently comprises a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms.
- R 3 is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 16 carbon atoms independently from the viewpoint that a suitable viscosity can be obtained and an increase in the viscosity of the varnish can be controlled.
- the group (R 3 ) of 1 to 5 is a linear or branched alkyl group having 1 to 16 carbon atoms, and the remaining group (R 3 ) is a hydrogen atom.
- 1 ⁇ 3 group (R 3) is a straight-chain or branched alkyl group having 1 to 16 carbon atoms, more preferably remaining groups (R 3) is a hydrogen atom.
- the number of carbon atoms of the alkyl group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be more controlled.
- Examples of linear or branched alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, 1-ethylpropyl group, n-butyl group, 2-butyl group, isobutyl group and tert-butyl.
- n-pentyl group 2-pentyl group, tert-pentyl group, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, Examples thereof include n-heptyl group, n-octyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 2-methylpentane-3-yl group, and n-nonyl group.
- the number of carbon atoms of the alkenyl group is preferably 2 to 14, more preferably 4 to 12, from the viewpoint that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be more controlled.
- Examples of the linear or branched alkenyl group include a vinyl group, an allyl group, a 4-pentenyl group, an isopropenyl group, an isopentenyl group, a 2-heptenyl group, a 2-octenyl group, and a 2-nonenyl group. Be done.
- n independently represents an integer of 1 to 10.
- the bismaleimide compound (A) has maleimide groups at both ends of the molecular chain.
- both ends mean both ends in the molecular chain of the bismaleimide compound (A), and for example, the structural unit represented by the formula (1) is the molecular chain of the bismaleimide compound (A).
- the maleimide group is at the end of the molecular chain of R 1 , at the end of the molecular chain at the N atom of the maleimide ring, or at both ends.
- the bismaleimide compound (A) may have a maleimide group in addition to both ends of the molecular chain.
- the maleimide group is represented by the formula (8), and the N atom is bonded to the molecular chain of the bismaleimide compound (A).
- the maleimide groups bonded to the bismaleimide compound (A) may be all the same or different, but it is preferable that the maleimide groups at both ends of the molecular chain are the same.
- R 10 independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. Both of R 10 are preferably hydrogen atoms from the viewpoint of being preferably photocured.
- the number of carbon atoms of the alkyl group is preferably 1 to 3 and more preferably 1 to 2 from the viewpoint of preferably photocuring.
- R 3 can be referred to as a linear or branched alkyl group.
- Examples of such a bismaleimide compound (A) include a bismaleimide compound represented by the formula (9). These can be used alone or in admixture of two or more.
- a represents an integer from 1 to 10.
- a is preferably an integer of 1 to 6 from the viewpoint that a more suitable viscosity can be obtained and the increase in the viscosity of the varnish can be more controlled.
- the bismaleimide compound (A) a commercially available product can also be used.
- examples of commercially available products include MIZ-001 manufactured by Nippon Kayaku Co., Ltd. (including a maleimide compound having a trade name of formula (9)).
- the content of the bismaleimide compound (A) makes it possible to obtain a cured product containing the bismaleimide compound as a main component, and from the viewpoint of improving the photocurability, the bismaleimide compound It is preferably 40 to 99 parts by mass, preferably 50 to 97 parts by mass, based on 100 parts by mass in total of (A), the compound (B) containing one or more carboxy groups described later, and the photocuring initiator (C) described later. It is more preferably parts by mass, and even more preferably 60 to 96 parts by mass.
- the bismaleimide compound (A) can be used alone or in admixture of two or more.
- the bismaleimide compound (A) can be produced by a known method.
- 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, a monomer containing diamine containing dimerdiamine and the like, and a maleic anhydride compound are usually about 80 to 250 ° C., preferably 100 to 200 ° C.
- a heavy adduct reaction is carried out to obtain a heavy adduct, and then usually about 60 to 120 ° C., preferably about 80 to 100 ° C.
- the bismaleimide compound (A) is obtained by subjecting the heavy adduct to an imidization reaction, that is, a dehydration ring closure reaction at a temperature of usually about 0.1 to 2 hours, preferably about 0.1 to 0.5 hours. Can be done.
- Dimer diamine is obtained, for example, by a reductive amination reaction of dimer acid, and the amineization reaction is described in a known method such as a reduction method using ammonia and a catalyst (for example, JP-A-9-12712). It can be done by the method of).
- Dimer acid is a dibasic acid obtained by dimerizing unsaturated fatty acids by an intermolecular polymerization reaction or the like. Although it depends on the synthesis conditions and purification conditions, it usually contains a small amount of monomeric acid, trimer acid and the like in addition to dimer acid.
- the double bond remains in the obtained molecule, but in the present embodiment, the double bond existing in the molecule is reduced to become a saturated dibasic acid by the hydrogenation reaction, which is also a dimer acid.
- Dimer acid is obtained, for example, by polymerizing unsaturated fatty acids using Lewis acid and Bronsted acid as catalysts.
- the dimer acid can be produced by a known method (for example, the method described in JP-A-9-12712).
- unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, baxenoic acid, gadrain acid, eicosaenoic acid, erucic acid, nervonic acid, linoleic acid, pinolenic acid, and eleostearic acid.
- the unsaturated fatty acid usually has 4 to 24 carbon atoms, preferably 14 to 20 carbon atoms.
- the diamine-containing monomer is previously dissolved in an organic solvent or dispersed in a slurry in an inert atmosphere such as argon or nitrogen to form a diamine-containing monomer solution. It is preferable to do so. Then, 1,2,4,5-cyclohexanetetracarboxylic dianhydride can be added to the monomer solution containing the diamine after being dissolved in an organic solvent or dispersed in a slurry, or in a solid state. preferable.
- An arbitrary bismaleimide compound (A) can be obtained by preparing the number of moles of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and the total number of moles of the diamine-containing monomer and the maleimide compound. be able to.
- Solvents include, for example, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; Esters such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -methyl- ⁇ -butyrolactone, ethyl lactate, methyl acetate, ethyl acetate, and butyl acetate; methanol, ethanol , And aliphatic alcohols having 1 to 10 carbon atoms such as propanol; phenols and aromatic group-containing phenols such as cresol; aromatic group-containing alcohols such as
- glycols with methanol, ethanol, butanol, hexanol, octanol, benzyl alcohol, phenol, cresol, etc., or glycol ethers such as esters of these monoethers; dioxane, and Examples include ethers such as tetrahydrofuran; cyclic carbonates such as ethylene carbonate and propylene carbonate; aromatic hydrocarbons such as aliphatic and toluene, and xylene; aprotonic polar solvents such as dimethyl sulfoxide. These solvents may be used alone or in combination of two or more, if necessary.
- a catalyst for example, a tertiary amine and a dehydration catalyst can be used.
- a tertiary amine a heterocyclic tertiary amine is preferable, and examples thereof include pyridine, picoline, quinoline, and isoquinoline.
- the dehydration catalyst include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic acid anhydride, trifluoroacetic anhydride and the like.
- the amount of the catalyst added is, for example, about 0.5 to 5.0 times the molar equivalent of the imidizing agent with respect to the amide group, and 0.5 to 10.0 times the molar equivalent of the dehydration catalyst with respect to the amide group.
- the equivalent amount is preferable.
- this solution may be used as a bismaleimide compound (A) solution, or a poor solvent may be added to the reaction solvent to make the bismaleimide compound (A) a solid substance.
- the poor solvent include water, methyl alcohol, ethyl alcohol, 2-propyl alcohol, ethylene glycol, triethylene glycol, 2-butyl alcohol, 2-pentyl alcohol, 2-hexyl alcohol, cyclopentyl alcohol, cyclohexyl alcohol, and phenol. Examples thereof include t-butyl alcohol.
- the resin composition of the present embodiment contains a compound (B) containing one or more carboxy groups (also referred to as a component (B) or a compound (B)).
- the compound (B) is not particularly limited as long as it contains one or more carboxy groups in the compound.
- the carboxy group may be a salt such as a sodium salt and a potassium salt, and when two or more carboxy groups are contained in the molecule, it may be an acid anhydride formed by connecting them to each other.
- Compound (B) can be used alone or in admixture of two or more.
- the compound (B) can be photocured with the bismaleimide compound (A) according to the present embodiment and the photocuring initiator (C) described later by using various active energy rays to obtain a cured product. Further, according to the present embodiment, a resin composition containing the compound (B) can be obtained in the unexposed portion.
- compound (B) prepare an N-methylpyrrolidone solution containing 1% by mass, and use active energy rays containing a wavelength of 365 nm (i-line) to contain N-methyl containing 1% by mass of compound (B). When the transmittance of the pyrrolidone solution is measured, the transmittance is preferably 5% or more. Such compound (B) exhibits very good light transmission.
- the transmittance of the N-methylpyrrolidone solution containing 1% by mass of the compound (B) is measured using an active energy ray containing a wavelength of 405 nm (h line), the transmittance is 5% or more. Is preferable, and even in this case, very excellent light transmittance is exhibited.
- a compound (B) for example, when a printed wiring board having a high-density and high-definition wiring formation (pattern) is produced by using a direct drawing exposure method, an activity containing a wavelength of 405 nm (h line) is included. Even when energy rays are used, the photoradical reaction of maleimide occurs efficiently.
- the transmittance at a wavelength of 365 nm (i-line) is 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more in this order because a resin composition having better photocurability can be obtained. Is a preferable range.
- the transmittance at a wavelength of 405 nm (h line) is 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more in this order because a resin composition having better photocurability can be obtained. Is a preferable range.
- the upper limits of the transmittance at the wavelength of 365 nm (i-line) and the transmittance at the wavelength of 405 nm (h-line) are, for example, 99.9% or less, and may be 100% or less.
- the molecule of compound (B) contains a carboxy group as an integer of 2 to 4 from the viewpoint of obtaining more excellent alkali developability.
- the molecular weight of compound (B) is preferably 50 to 1000, and more preferably 100 to 800, from the viewpoint of further improving developability.
- Examples of the compound (B) include formic acid, an aliphatic compound containing one or more carboxy groups, an aromatic compound containing one or more carboxy groups, and a hetero compound containing one or more carboxy groups. These compounds (B) can be used alone or in admixture of two or more.
- aliphatic compound containing one or more carboxy groups examples include a chain aliphatic monocarboxylic acid, an alicyclic monocarboxylic acid, a chain aliphatic polyvalent carboxylic acid, and an alicyclic polyvalent carboxylic acid. .. These compounds have a hydrogen atom and a substituent such as an alkyl group, an alkoxy group, an aryloxy group, an aryl group, an aminoalkyl group, a hydroxyl group, an amino group, and a carboxyalkyl group in the molecule. May be good.
- these compounds when they have two or more carboxy groups in the molecule, they may be acid anhydrides formed by connecting them to each other.
- they when these compounds have a carboxyalkyl group in the molecule, they may be an acid anhydride formed by connecting the carboxyalkyl group and the carboxy group to each other.
- they When these compounds have two or more carboxyalkyl groups in the molecule, they may be acid anhydrides formed by linking them to each other.
- alkyl group examples include methyl group, ethyl group, n-propyl group, i-propyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group and n. -Heptyl group and n-octyl group can be mentioned.
- alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, an n-hexanoxy group, a 2-methylpropoxy group and the like.
- Examples of the aryloxy group include a phenoxy group and a p-tolyloxy group.
- Examples of the aryl group include a phenyl group, a toluyl group, a benzyl group, a methylbenzyl group, a xsilyl group, a mesityl group, a naphthyl group, and an anthryl group.
- Examples of the aminoalkyl group include an aminomethyl group, an aminoethyl group, an aminopropyl group, an aminodimethyl group, an aminodiethyl group, an aminodipropyl group, an aminobutyl group, an aminohexyl group, an aminononyl group and the like.
- Examples of the carboxyalkyl group include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a carboxybutyl group, a carboxyhexyl group, a carboxynonyl group and the like.
- chain aliphatic monocarboxylic acid examples include acetic acid, propionic acid, isobutyric acid, butyric acid, isovaleric acid, valeric acid, caproic acid, lactic acid, succinic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid and tetradecane.
- Saturated fatty acids such as acids, hexadecanoic acid, heptadecanoic acid, and octadecanoic acid
- unsaturated fatty acids such as oleic acid, elladic acid, erucic acid, nervonic acid, linolenic acid, stearidonic acid, eicosapentaenoic acid, linoleic acid, and linolenic acid
- unsaturated fatty acids such as oleic acid, elladic acid, erucic acid, nervonic acid, linolenic acid, stearidonic acid, eicosapentaenoic acid, linoleic acid, and linolenic acid
- Examples of the alicyclic monocarboxylic acid include cyclopropanecarboxylic acid, cyclopropenecarboxylic acid, cyclobutanecarboxylic acid, cyclobutenecarboxylic acid, cyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, cyclohexenecarboxylic acid, and cycloheptanecarboxylic acid.
- Monocyclic carboxylic acids such as acids, cycloheptenecarboxylic acids, cyclooctanecarboxylic acids, and cyclooctenecarboxylic acids, norbornancarboxylic acids, tricyclodecanecarboxylic acids, tetracyclododecanecarboxylic acids, adamantancarboxylic acids, methyladamantancarboxylic acids , Ethyladamantancarboxylic acid, polycyclic or abridged alicyclic carboxylic acid such as butyladamantancarboxylic acid, and the like.
- Examples of the chain aliphatic polyvalent carboxylic acid include a carboxylic acid in which one or more carboxy groups are further added to the chain aliphatic monocarboxylic acid.
- a carboxylic acid in which one or more carboxy groups are further added to the chain aliphatic monocarboxylic acid.
- propiondioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid and the like can be mentioned.
- Examples of the alicyclic polyvalent carboxylic acid include a carboxylic acid in which one or more carboxy groups are further added to the alicyclic monocarboxylic acid.
- a carboxylic acid in which one or more carboxy groups are further added to the alicyclic monocarboxylic acid.
- Aromatic compound containing one or more carboxy groups examples include benzoic acid, phenylene acetic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, pentacarboxybenzene, hexacarboxybenzene, naphthalenecarboxylic acid, and naphthalene.
- Aromatic compounds include, for example, hydrogen atoms and alkyl groups, alkoxy groups, aryloxy groups, aryl groups, aminoalkyl groups, hydroxyl groups, amino groups, carboxyalkyl groups and the like on the aromatic rings of these parent skeletons. It may have a substituent.
- these compounds when they have two or more carboxy groups in the molecule, they may be acid anhydrides formed by connecting them to each other.
- they when these compounds have a carboxyalkyl group in the molecule, they may be an acid anhydride formed by connecting the carboxyalkyl group and the carboxy group to each other.
- these compounds When these compounds have two or more carboxyalkyl groups in the molecule, they may be acid anhydrides formed by linking them to each other. The above can be referred to for these substituents.
- heterocompound containing one or more carboxy groups examples include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indol, purine, quinoline, isoquinoline, and quinuclysine. , Chromen, thiantorene, phenothiazine, phenoxazine, xanthene, aclysine, phenazine, and carbazole and the like, and examples thereof include compounds containing one or more carboxy groups in the heterocycle.
- the hetero compound has, for example, a hydrogen atom and a substituent such as an alkyl group, an alkoxy group, an aryloxy group, an aryl group, an aminoalkyl group, a hydroxyl group, an amino group, and a carboxyalkyl group on these parent skeletons. You may be doing it. Further, when these compounds have two or more carboxy groups in the molecule, they may be acid anhydrides formed by connecting them to each other. When these compounds have a carboxyalkyl group in the molecule, they may be an acid anhydride formed by connecting the carboxyalkyl group and the carboxy group to each other. When these compounds have two or more carboxyalkyl groups in the molecule, they may be acid anhydrides formed by linking them to each other. The above can be referred to for these substituents.
- a substituent such as an alkyl group, an alkoxy group, an aryloxy group, an aryl group, an aminoalkyl group, a hydroxyl group
- the compound (B) is represented by a compound represented by the formula (2), a compound represented by the formula (3), and a compound represented by the formula (4) from the viewpoint that excellent alkali developability can be imparted to the resin composition. It is preferably a compound and a compound represented by the formula (5).
- the compound represented by the formula (2) is as follows.
- R 4 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, an amino group, or an aminomethyl group. Further, when the compound represented by the formula (2) has two or more carboxy groups, it may be an acid anhydride formed by connecting them to each other. In the formula (2), the upper limit of the number of carboxy groups is 6. R 4 is preferably a hydrogen atom, a hydroxyl group, a carboxy group, or an amino group independently from the viewpoint of alkali developability, and contains a carboxy group from the viewpoint of obtaining more excellent alkali developability. Is more preferable. In addition, benzoic acid tends to be inferior in alkali developability as compared with the compound (B) containing one or more other carboxy groups. Further, k independently represents an integer of 1 to 5.
- the compound represented by the formula (2) is preferably a compound represented by the formula (10) from the viewpoint of obtaining more excellent alkali developability.
- R 4 independently represents a hydrogen atom, a hydroxyl group, an amino group, or an aminomethyl group.
- R 4 is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom, from the viewpoint of exhibiting more excellent alkali developability.
- k independently represents an integer of 0 to 4.
- the carboxy cardinal number p represents an integer of 5-k.
- the carboxy group number p is preferably an integer of 1 to 3 from the viewpoint of exhibiting more excellent alkali developability.
- the number k of R 4 is an integer of 5-p and an integer of 2 to 4.
- the compound represented by the formula (10) may be an acid anhydride containing two or more carboxy groups and formed by connecting them to each other.
- Examples of the compound represented by the formula (2) include 4-aminobenzoic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, 4-aminomethylbenzoic acid, and anhydrides thereof.
- Examples of these anhydrides include phthalic acid anhydride, trimellitic acid anhydride, and pyromellitic acid anhydride.
- the compound represented by the formula (2) is preferably phthalic acid, trimellitic acid, pyromellitic acid, and anhydrides thereof from the viewpoint of obtaining more excellent alkali developability.
- the compound represented by the formula (3) is as follows.
- R 5 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, a carboxymethyl group, an amino group, or an aminomethyl group. Further, when the compound represented by the formula (3) has two or more carboxy groups, it may be an acid anhydride formed by connecting them to each other. In formula (3), the upper limit of the number of carboxy groups is 10. When the compound represented by the formula (3) has a carboxymethyl group, it may be an acid anhydride formed by connecting the carboxymethyl group and the carboxy group to each other.
- R 5 preferably contains a hydrogen atom, a hydroxyl group, a carboxy group, or an amino group independently from the viewpoint of alkali developability, and contains a carboxy group from the viewpoint of obtaining more excellent alkali developability. Is more preferable. Further, l independently represents an integer of 1 to 9. The piperidine carboxylic acid tends to be inferior in alkali developability as compared with the compound (B) containing one or more other carboxy groups.
- R 5 contains a carboxy group
- the number of carboxy groups l is preferably 1 to 3 from the viewpoint of alkali developability.
- the R 5 other than the carboxy group is preferably a hydrogen atom or a hydroxyl group independently, and more preferably a hydrogen atom.
- the compound represented by the formula (3) contains a carboxy group of 1 to 3, the number of R 5 other than the carboxy group is 7 to 9.
- Examples of the compound represented by the formula (3) include piperidinecarboxylic acid, 1,2-piperidindicarboxylic acid, and piperidinedicarboxylic acid anhydride.
- the compound represented by the formula (4) is as follows.
- R 6 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, a carboxymethyl group, an amino group, or an aminomethyl group. Further, when the compound represented by the formula (4) has two or more carboxy groups, it may be an acid anhydride formed by connecting them to each other. In formula (4), the upper limit of the number of carboxy groups is 10. When the compound represented by the formula (4) has a carboxymethyl group, it may be an acid anhydride formed by connecting the carboxymethyl group and the carboxy group to each other.
- R 6 is preferably a hydrogen atom, a hydroxyl group, a carboxy group, or an amino group independently from the viewpoint of alkali developability, and contains a carboxy group from the viewpoint of obtaining more excellent alkali developability. Is more preferable. Further, m independently represents an integer of 1 to 9.
- the compound represented by the formula (4) is preferably the compound represented by the formula (11) from the viewpoint of obtaining more excellent alkali developability.
- R 6 independently represents a hydrogen atom, a hydroxyl group, a carboxymethyl group, an amino group, or an aminomethyl group.
- R 6 is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom, from the viewpoint of exhibiting more excellent alkali developability.
- m represents an integer of 0 to 8 independently.
- the carboxy cardinal number q represents an integer of 9-m.
- the number of carboxy groups q is preferably an integer of 1 to 3 from the viewpoint of exhibiting more excellent alkali developability.
- the number m of R 6 is an integer of 9-q and an integer of 6 to 8.
- the compound represented by the formula (11) may be an acid anhydride containing two or more carboxy groups and formed by connecting them to each other.
- the carboxymethyl group and the carboxy group may be an acid anhydride formed by connecting them to each other.
- Examples of the compound represented by the formula (4) include 3-cyclohexene-1-carboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and cis-4-cyclohexene-1,2-dicarboxylic acid anhydride. Things can be mentioned.
- cis-4-cyclohexene-1,2-dicarboxylic acid and cis-4-cyclohexene-1,2-dicarboxylic acid are obtained from the viewpoint of obtaining more excellent alkali developability. It is preferably an anhydride.
- the compound represented by the formula (5) is as follows.
- R 7 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, a carboxymethyl group, an amino group, or an aminomethyl group.
- the compound represented by the formula (5) may be an acid anhydride formed by linking a carboxymethyl group and a carboxy group to each other.
- the formula (5) when two or more carboxy groups are present, they may be acid anhydrides formed by connecting them to each other.
- the upper limit of the number of carboxy groups is 5.
- the upper limit of the number of carboxymethyl groups is 6.
- R 7 is preferably a hydrogen atom, a hydroxyl group, a carboxy group, or an amino group independently from the viewpoint of alkali developability, and contains a carboxy group from the viewpoint of obtaining more excellent alkali developability. Is more preferable. Further, o independently represents an integer of 1 to 5.
- the compound represented by the formula (5) is preferably the compound represented by the formula (12) from the viewpoint of obtaining more excellent alkali developability.
- R 7 independently represents a hydrogen atom, a hydroxyl group, a carboxymethyl group, an amino group, or an aminomethyl group.
- R 7 is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom, from the viewpoint of exhibiting more excellent alkali developability.
- o independently represents an integer of 0 to 4.
- the carboxy cardinal number r represents an integer of 5-o.
- the number of carboxy groups r is preferably an integer of 1 to 3 from the viewpoint of exhibiting more excellent alkali developability.
- the number o of R 7 is an integer of 5-r and an integer of 2 to 4.
- the carboxymethyl group and the carboxy group may be acid anhydrides formed by connecting them to each other.
- the compound represented by the formula (12) When the compound represented by the formula (12) has two or more carboxy groups, it may be an acid anhydride formed by connecting them to each other. In formula (12), the upper limit of the number of carboxy groups is 5. When the compound represented by the formula (12) has two or more carboxymethyl groups, it may be an acid anhydride formed by connecting them to each other. In formula (12), the upper limit of the number of carboxymethyl groups is 6.
- Examples of the compound represented by the formula (5) include phenylene acetic acid, 1,2-phenylene diacetic acid, 1,3-phenylene diacetic acid, 1,4-phenylene diacetic acid, and anhydrides thereof.
- Examples of these anhydrides include 1,2-phenylene diacetate anhydride.
- the compound represented by the formula (5) is preferably 1,2-phenylene diacetic acid from the viewpoint of obtaining more excellent alkali developability.
- the compound (B) containing one or more of these carboxy groups can be used alone or in admixture of two or more.
- the content of the compound (B) containing one or more carboxy groups can impart more excellent alkali developability to the resin composition, and therefore the bismaleimide compound (A) and the carboxy group are 1
- the amount is preferably 0.01 to 35 parts by mass, more preferably 1 to 30 parts by mass, based on 100 parts by mass of the total of the compound (B) containing one or more and the photocuring initiator (C) described later. It is more preferably 2 to 25 parts by mass.
- the resin composition of the present embodiment contains a photocuring initiator (C) (also referred to as component (C)).
- the photocurable initiator (C) is not particularly limited, and those known in the field generally used in the photocurable resin composition can be used.
- the photo-curing initiator (C) is used together with the bismaleimide compound (A) and the compound (B) containing one or more carboxyl groups for photo-curing using various active energy rays.
- Examples of the photocuring initiator (C) include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, and parachlorobenzoyl.
- Radical photocuring initiators and Diazonium salts of Lewis acids such as p-methoxyphenyldiazonium fluorophosphonate and N, N-diethylaminophenyldiazonium hexafluorophosphonate; iodonium salts of Lewis acids such as diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate; triphenyl Sulfonium salts of Lewis acids such as sulfonium hexafluorophosphonate and triphenylsulfonium hexafluoroantimonate; phosphonium salts of Lewis acids such as triphenylphosphonium hexafluoroantimonate; other halides; triazine initiators; borate initiators ; Other cationic photocuring initiators such as photoacid generators can be mentioned.
- a commercially available product can also be used as the photocuring initiator (C).
- Commercially available products include, for example, IGM Resins B.I. V. Omnirad® 369 (trade name), IGM Resins B. et al. V. Omnirad® 819 (trade name), IGM Resins B. et al. V. Omnirad® 819DW (trade name), IGM Resins B. et al. V. Omnirad® 907 (trade name), IGM Resins B. et al. V. Omnirad® TPO (trade name), IGM Resins B.I. V. Omnirad® TPO-G (trade name), IGM Resins B.I. V.
- Omnirad registered trademark 784 (trademark), Irgacure (registered trademark) OXE01 (trademark) manufactured by BASF Japan Co., Ltd., Irgacure (registered trademark) OXE02 (trademark) manufactured by BASF Japan Co., Ltd. Examples thereof include (registered trademark) OXE03 (trademark) and Irgacure (registered trademark) OXE04 (trademark) manufactured by BASF Japan Co., Ltd.
- the photocuring initiator (C) it is also possible to use one type alone or a mixture of two or more types as appropriate.
- the photocuring initiator (C) is prepared by preparing a chloroform solution contained in an amount of 0.01% by mass, and using an active energy ray containing a wavelength of 365 nm (i-ray), the photocuring initiator (C) is used.
- the absorbance of the chloroform solution containing 0.01% by mass is measured, the absorbance is preferably 0.1 or more, and this photoinitiator (C) exhibits extremely excellent absorbance. ..
- the absorbance of the chloroform solution containing 0.01% by mass of the photoinitiator (C) is measured using an active energy ray containing a wavelength of 405 nm (h line), the absorbance is 0.1.
- the above is preferable, and even in this case, very excellent absorbance is exhibited.
- a photocuring initiator (C) for example, when a printed wiring board having a high-density and high-definition wiring formation (pattern) is manufactured by using a direct drawing exposure method, a wavelength of 405 nm (h line) is used. Even when an active energy ray containing the above is used, the photoradical reaction of maleimide occurs efficiently.
- the absorbance at a wavelength of 365 nm (i-line) is more preferably 0.15 or more because a resin composition having better photocurability can be obtained.
- the absorbance at a wavelength of 405 nm (h line) is more preferably 0.15 or more because a resin composition having better photocurability can be obtained.
- the upper limits of the absorbance at the wavelength of 365 (i-line) and the absorbance at the wavelength of 405 nm (h-line) are, for example, 99.9 or less.
- a compound represented by the formula (6) is preferable.
- R 8 independently represents a substituent or phenyl group represented by formula (7).
- R 9 independently represents a hydrogen atom or a methyl group.
- ⁇ * indicates a bond with the phosphorus atom (P) in formula (6).
- a chloroform solution containing 0.01% by mass of this compound was prepared, and the absorbance of this chloroform solution was measured using an active energy ray containing a wavelength of 365 nm (i-ray).
- the absorbance is 0.1 or more, and it exhibits extremely excellent absorbency for light having a wavelength of 365 nm (i-line). Therefore, this compound preferably generates radicals for light having a wavelength of 365 nm (i-line).
- the absorbance is preferably 0.15 or more.
- the upper limit is, for example, 10.0 or less, 5.0 or less, or 2.0 or less.
- a chloroform solution containing 0.01% by mass of this compound is prepared, and the absorbance of this chloroform solution is measured using an active energy ray containing a wavelength of 405 nm (h line). When measured, it exhibits an absorbance of 0.1 or more and very excellent absorbency for light having a wavelength of 405 nm (h line). Therefore, this compound preferably generates radicals for light having a wavelength of 405 nm (h line).
- the absorbance is preferably 0.15 or more.
- the upper limit is, for example, 10.0 or less, 5.0 or less, or 2.0 or less.
- R 8 independently represents a substituent or phenyl group represented by formula (7). It is preferable that one or more of R 8 are substituents represented by the formula (7).
- R 9 independently represents a hydrogen atom or a methyl group. Of R 9 , one or more is preferably a methyl group, and more preferably all are methyl groups.
- Examples of the compound represented by the formula (6) include acylphos such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
- Examples include fin oxides.
- bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is preferable because it has excellent light transmittance. These compounds may be used alone or in admixture of two or more.
- Acylphosphine oxides show extremely excellent absorption to active energy rays containing a wavelength of 405 nm (h line), for example, a bismaleimide compound having a transmittance of 5% or more at a wavelength of 405 nm (h line).
- (A) can be suitably radically polymerized. Therefore, particularly when used in the production of a multilayer printed wiring board, it does not inhibit the photocuring reaction in the exposure process, has excellent photocurability, and can impart excellent alkali developability in the developing process. It becomes possible to suitably manufacture a resin composition, a resin sheet using the resin composition, a multilayer printed wiring board, and a semiconductor device.
- the content of the photocuring initiator (C) is a bismaleimide compound from the viewpoint of sufficiently promoting the photocuring of the maleimide compound and sufficiently insolubilizing the exposed portion in terms of alkali developability. It is preferably 0.99 to 25 parts by mass with respect to 100 parts by mass of the total of (A), the compound (B) containing one or more carboxy groups, and the photocuring initiator (C), and 2 to 20 parts by mass. It is more preferable that the amount is 2 to 15 parts by mass.
- the resin composition of the present embodiment may contain a maleimide compound (D) (also referred to as a component (D)) other than the bismaleimide compound (A) according to the present embodiment as long as the effects of the present invention are exhibited. Since the bismaleimide compound (A) is extremely excellent in light transmission, even if the maleimide compound (D) is used, sufficient light reaches the photocuring initiator, and the photoradical reaction of the maleimide occurs efficiently. It can be photocured using the active energy rays of.
- the light sufficiently reaches the photocuring initiator, and the radical reaction using the radical generated from the photocuring initiator proceeds.
- photocuring is also possible in the composition containing the maleimide compound (D).
- the maleimide compound (D) will be described below.
- the maleimide compound (D) is other than the maleimide compound (A), and is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule.
- Specific examples thereof include N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-anilinophenylmaleimide, N-carboxyphenylmaleimide, N- (4-carboxy-3-hydroxyphenyl) maleimide, 6 -Maleimidehexanoic acid, 4-maleimidebutyric acid, bis (4-maleimidephenyl) methane, 2,2-bis ⁇ 4- (4-maleimidephenoxy) -phenyl ⁇ propane, 4,4-diphenylmethanebismaleimide, bis (3, 5-Dimethyl-4-maleimidephenyl) methane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, bis (3,5-diethyl-4
- maleimide compound represented by the formula (13) a commercially available product can also be used, and examples thereof include BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd.
- maleimide compound represented by the formula (14) a commercially available product can also be used, and examples thereof include MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd.
- R 10 independently represents a hydrogen atom or a methyl group.
- n 1 represents an integer of 1 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5.
- R 11 independently represents a hydrogen atom or a methyl group.
- n 2 represents an integer of 1 or more, preferably an integer of 1 to 5.
- a chloroform solution containing the maleimide compound (D) in an amount of 1% by mass is prepared and contains a wavelength of 365 nm (i-line).
- the transmittance of this chloroform solution is measured using active energy rays, it is preferable that the transmittance shows a light transmittance of 5% or more. In this case, the transmittance is more preferably 8% or more, and further preferably 10% or more.
- a chloroform solution containing the maleimide compound (D) in an amount of 1% by mass is prepared, and the wavelength is 405 nm (h line).
- the transmittance of this chloroform solution is measured using an active energy ray containing
- a maleimide compound (D) for example, when a printed wiring board having a high-density and high-definition wiring formation (pattern) is manufactured by using a direct drawing exposure method, a wavelength of 405 nm (h line) can be obtained. Even when the active energy rays containing it are used, the photoradical reaction of maleimide occurs efficiently.
- the light transmittance is more preferably 8% or more, further preferably 10% or more, because a resin composition having better photocurability can be obtained.
- Examples of such a maleimide compound (D) include a maleimide compound represented by the formula (15), a maleimide compound represented by the formula (16), and a maleimide compound represented by the formula (23) (17). ), The maleimide compound represented by the formula (18), the maleimide compound represented by the formula (19), the maleimide compound represented by the formula (20), 1,6-bismaleimide- (2). , 2,4-trimethyl) hexane (maleimide compound represented by the formula (21)), maleimide compound represented by the formula (22), and fluorescein-5-maleimide.
- n 3 (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.
- R a is preferably a linear or branched alkyl group, and more preferably a linear alkyl group because it exhibits excellent photocurability.
- the alkyl group preferably has 4 to 12 carbon atoms because it exhibits excellent photocurability.
- the alkenyl group preferably has 4 to 12 carbon atoms because it exhibits excellent photocurability.
- R 3 in the bismaleimide compound (A) can be referred to.
- an n-heptyl group, an n-octyl group, and an n-nonyl group are preferable, and an n-octyl group is more preferable, because they exhibit excellent photocurability.
- an n-heptyl group, an n-octyl group, and an n-nonyl group are preferable, and an n-octyl group is more preferable, because they exhibit excellent photocurability.
- an n-heptyl group, an n-octyl group, and an n-nonyl group are preferable, and an n-octyl group is more preferable, because they exhibit excellent photocurability.
- 2-heptenyl group, 2-octenyl group and 2-nonenyl group are preferable, and 2-octenyl group is more preferable, because they show excellent photocurability.
- 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 linear or branched alkyl group, and more preferably a linear alkyl group because it exhibits excellent photocurability.
- the alkyl group preferably has 4 to 12 carbon atoms because it exhibits excellent photocurability.
- the alkenyl group preferably has 4 to 12 carbon atoms because it exhibits excellent photocurability.
- the alkyl group in Ra can be referred to.
- an n-heptyl group, an n-octyl group, and an n-nonyl group are preferable, and an n-octyl group is more preferable, because they exhibit excellent photocurability.
- the alkenyl group in Ra 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, because they exhibit excellent photocurability.
- the number of n a is 1 or more, preferably 2 to 16, and more preferably 3 to 14 from the viewpoint of exhibiting excellent photocurability.
- n b is 1 or more, preferably 2 to 16, and more preferably 3 to 14 from the viewpoint of exhibiting excellent photocurability.
- n a and n b may be the same or different.
- n 4 (average) is 0.5 or more, preferably 0.8 to 10, and more preferably 1 to 8 from the viewpoint of exhibiting excellent photocurability.
- n 5 represents an integer of 1 or more, preferably an integer of 1 to 10.
- n 6 represents an integer of 1 or more, preferably an integer of 1 to 10.
- R 12 independently represents a hydrogen atom, a methyl group or an ethyl group
- R 13 independently represents a hydrogen atom or a methyl group.
- maleimide compound (D) a commercially available product can also be used.
- Examples of the maleimide compound represented by the formula (17) include Designer Molecules Inc. BMI-689 (trade name, formula (23), functional group equivalent: 346 g / eq.) And the like.
- BMI-3000J (trade name) manufactured by (DMI), Designer Moleculars Inc. BMI-5000 (trade name) manufactured by (DMI), Designer Moleculars Inc. BMI-9000 (trade name) manufactured by (DMI)
- the maleimide compound represented by the formula (21) a commercially available product can also be used, and examples thereof include BMI-TMH manufactured by Daiwa Kasei Kogyo Co., Ltd.
- the maleimide compound represented by the formula (22) a commercially available product can also be used, and examples thereof include BMI-70 (trade name) manufactured by KAI Kasei Co., Ltd.
- These maleimide compounds (D) can be used alone or in admixture of two or more.
- the content of the maleimide compound (D) makes it possible to obtain a cured product containing the maleimide compound as a main component, and from the viewpoint of further improving the photocurability, the bismaleimide compound ( It is preferably 1 to 70 parts by mass, more preferably 3 to 60 parts by mass, and 5 to 50 parts by mass with respect to a total of 100 parts by mass of A), the compound (B) and the photocuring initiator (C). It is more preferably parts by mass.
- the compounding ratio ((A): (D)) of the bismaleimide compound (A) and the maleimide compound (D) makes it possible to obtain a cured product containing the maleimide compound as a main component.
- it is preferably 1 to 99: 99 to 1 on a mass basis, more preferably 5 to 95: 95 to 5, and 10 to 90: 90 to 10. Is more preferable.
- the total content of the bismaleimide compound (A) and the maleimide compound (D) makes it possible to obtain a cured product containing the maleimide compound as a main component, further improving the photocurability.
- the amount is preferably 40 to 99 parts by mass. It is more preferably 50 to 97 parts by mass, and even more preferably 60 to 96 parts by mass.
- the resin composition of the present embodiment may contain a filler (E) (also referred to as a component (E)) in order to improve various properties such as coating film property and heat resistance.
- the filler (E) preferably has insulating properties and does not hinder the permeability to various active energy rays used for photocuring, and has a wavelength of 365 nm (i-line) and / or a wavelength of 405 nm (h). It is more preferable that it does not inhibit the permeability to active energy rays including rays).
- Examples of the filler (E) include silica (for example, natural silica, molten silica, amorphous silica, and hollow silica), aluminum compounds (for example, boehmite, aluminum hydroxide, alumina, and aluminum nitride), and boron compounds (for example, aluminum nitride).
- silica for example, natural silica, molten silica, amorphous silica, and hollow silica
- aluminum compounds for example, boehmite, aluminum hydroxide, alumina, and aluminum nitride
- boron compounds for example, aluminum nitride
- magnesium compounds eg magnesium oxide and magnesium hydroxide
- calcium compounds eg calcium carbonate
- molybdenum compounds eg molybdenum oxide and zinc molybdate
- barium compounds eg barium sulfate, etc.
- barium silicate talc (eg, natural talc, and fired talc), mica, glass (eg, short fibrous glass, spherical glass, fine powder glass, E glass, T glass, and D glass), silicone powder
- fluororesin-based fillers urethane resin-based fillers, (meth) acrylic resin-based fillers, polyethylene-based fillers, styrene / butadiene rubbers, and silicone rubbers.
- These fillers (E) can be used alone or in admixture of two or more.
- These fillers (E) may be surface-treated with a silane coupling agent or the like described later.
- Silica is preferable, and fused silica is more preferable, from the viewpoint of improving the heat resistance of the cured product and obtaining good coating film properties.
- Specific examples of silica include SFP-130MC (trade name) manufactured by Denka Co., Ltd., SC2050-MB (trade name) manufactured by Admatex Co., Ltd., SC1050-MLE (trade name), and YA010C-MFN (trade name). ), YA050C-MJA, etc. (trade name).
- the particle size of the filler (E) is usually 0.005 to 10 ⁇ m, preferably 0.01 to 1.0 ⁇ m, from the viewpoint of ultraviolet light transmission of the resin composition.
- the content of the filler (E) includes the bismaleimide compound (A) and the compound (A) from the viewpoint of improving the light transmittance of the resin composition and the heat resistance of the cured product. It is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and further preferably 100 parts by mass or less with respect to 100 parts by mass of the total of B) and the photocuring initiator (C). ..
- the upper limit value may be 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less.
- the lower limit values are the bismaleimide compound (A), the compound (B) and the photocuring from the viewpoint of obtaining the effect of improving various properties such as coating film property and heat resistance.
- it is 1 part by mass with respect to 100 parts by mass of the total amount of the initiator (C).
- silane coupling agent and wet dispersant In the resin composition of the present embodiment, a silane coupling agent and / or a wet dispersant may be used in combination in order to improve the dispersibility of the filler and the adhesive strength between the polymer and / or the resin and the filler. it can.
- the silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of inorganic substances.
- Specific examples include 3-aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, and N- ⁇ - (aminoethyl) - ⁇ -amino.
- methacrylsilanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyldiethoxymethylsilane, ⁇ -acryloxypropyltri
- Acrylic silanes such as methoxysilane and 3-acryloxypropyltriethoxysilane; isocyanatesilanes such as 3-isocyanpropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane; tris- (trimethoxysilylpropyl) isocyanurate
- Isocyanurate silanes such as 3-mercaptopropyltrimethoxysilane, and mercaptosilanes such as 3-mercaptopropyldimethoxymethylsilane
- ure such as 3-ureidopropyltriethoxysilane.
- Idosilane type Styrylsilane type such as p-styryltrimethoxysilane; Cationic silane type such as N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane hydrochloride; [3- (Trimethoxy) Cyril) propyl] Acid anhydrides such as succinic acid anhydride; phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, and p-tolyltrimethoxysilane; trimethoxy; Examples thereof include arylsilane systems such as (1-naphthyl) silane. These silane coupling agents may be used alone or in admixture of two or more.
- the content of the silane coupling agent is usually 0, based on 100 parts by mass of the total of the bismaleimide compound (A), the compound (B) and the photocuring initiator (C). It is 1 to 10 parts by mass.
- the wet dispersant is not particularly limited as long as it is a dispersion stabilizer used for paints. Specific examples include DISPERBYK (registered trademark) -110 (trademark), 111 (product name), 118 (product name), 180 (product name), 161 (product name), BYK manufactured by Big Chemie Japan Co., Ltd.
- wetting dispersants such as (registered trademark) -W996 (trade name), W9010 (trade name), W903 (trade name) and the like can be mentioned. These wet dispersants can be used alone or in admixture of two or more.
- the content of the wet dispersant is usually 0.1 with respect to a total of 100 parts by mass of the bismaleimide compound (A), the compound (B) and the photocuring initiator (C). ⁇ 10 parts by mass.
- the resin composition of the present embodiment relates to the present embodiment according to the characteristics such as flame retardancy, heat resistance and thermal expansion characteristics of the cured product.
- Bismaleimide compound (A) compound containing one or more carboxy groups (B), photocuring initiator (C), and cyanate ester compound, phenol resin, oxetane resin, benzoxazine other than maleimide compound (D).
- Various types of compounds and resins can be included, such as compounds, epoxy resins, and other compounds.
- these compounds and resins are exposed to the resin composition of the present embodiment when exposed to an active energy ray containing a wavelength of 365 nm (i line) and / or an active energy ray containing 405 nm (h line). It is preferable to photo-cure.
- active energy ray containing a wavelength of 365 nm (i line) and / or an active energy ray containing 405 nm (h line). It is preferable to photo-cure.
- These compounds and resins can be used alone or in admixture of two or more.
- the cyanate ester compound is not particularly limited as long as it is a resin having an aromatic moiety in the molecule in which at least one cyanato group (cyanic acid ester group) is substituted.
- Ar 1 represents a benzene ring, a naphthalene ring, or a single bond of two benzene rings. When there are a plurality of them, they may be the same or different from each other.
- Ra independently has 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 1 to 6 carbon atoms. Indicates a group in which an alkyl group and an aryl group having 6 to 12 carbon atoms are bonded.
- the aromatic ring in Ra may have a substituent, and the substituent in Ar 1 and Ra can be selected at any position.
- p indicates the number of cyanato groups attached to Ar 1 , and each is an integer of 1 to 3 independently.
- q represents the number of Ra to bind to Ar 1, the 4-p when Ar 1 is a benzene ring, when the naphthalene ring when those 6-p, 2 one benzene ring is a single bond is 8-p .
- t indicates the average number of repetitions and is an integer of 0 to 50, and the cyanate ester compound may be a mixture of compounds having different t.
- each of them has a single bond, a divalent organic group having 1 to 50 carbon atoms (the hydrogen atom may be replaced with a hetero atom), and a divalent group having 1 to 10 nitrogen atoms.
- Organic group for example, -N-RN- (where R indicates an organic group)
- the alkyl group in Ra of the formula (24) may have either a linear or branched chain structure or a cyclic structure (for example, a cycloalkyl group). Further, even if the hydrogen atom in the alkyl group in the formula (24) and the aryl group in Ra is substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, or a cyano group. Good.
- alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group and 2,2-dimethylpropyl group.
- alkyl group examples include a group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a trifluoromethyl group and the like.
- alkenyl group examples include vinyl group, (meth) allyl group, isopropenyl group, 1-propenyl group, 2-butenyl group, 3-butenyl group, 1,3-butandienyl group, 2-methyl-2-propenyl. , 2-Pentenyl group, 2-hexenyl group and the like.
- aryl group include phenyl group, xylyl group, mesityl group, naphthyl group, phenoxyphenyl group, ethylphenyl group, o-, m- or p-fluorophenyl group, dichlorophenyl group, dicyanophenyl group and trifluorophenyl.
- alkoxyl group examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group and the like.
- divalent organic group having 1 to 50 carbon atoms in X of the formula (24) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group and a biphenylylmethylene.
- examples thereof include a group, a dimethylmethylene-phenylene-dimethylmethylene group, a fluorinatedyl group, and a phthalidodiyl group.
- the hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, a cyano group or the like.
- a halogen atom such as a fluorine atom or a chlorine atom
- an alkoxyl group such as a methoxy group or a phenoxy group
- a cyano group or the like examples of the divalent organic group having a nitrogen number of 1 to 10 in X of the formula (24) include an imino group and a polyimide group.
- examples of the organic group of X in the formula (24) include those having a structure represented by the formula (25) or the formula (26).
- Ar 2 represents a benzenediyl group, a naphthalenediyl group or a biphenyldiyl group, and when u is an integer of 2 or more, they may be the same or different from each other.
- Rb, Rc, Rf, and Rg each independently have 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. Indicates a group.
- Rd and Re are independently selected from 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, or a hydroxy group. .. u represents an integer from 0 to 5.
- Ar 3 represents a benzenediyl group, a naphthalenediyl group or a biphenyldiyl group, and when v is an integer of 2 or more, they may be the same or different from each other.
- Ri and Rj are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 12 carbon atoms, benzyl groups, alkoxyl groups having 1 to 4 carbon atoms, hydroxy groups, trifluoromethyl groups, respectively. Alternatively, it indicates an aryl group in which at least one cyanato group is substituted.
- v represents an integer of 0 to 5, it may be a mixture of compounds in which v is different.
- z represents an integer of 4 to 7.
- Rk independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- Ar 2 of the formula (25) and Ar 3 of the formula (26) two carbon atoms represented by the formula (25) or two oxygen atoms represented by the formula (26) are 1,4.
- Benzene diyl group bonded to the position or 1,3 position, two carbon atoms or two oxygen atoms at the 4,4'position, 2,4'position, 2,2'position, 2,3'position, 3 , 3'-position, or 3,4'-position bonded biphenyldiyl group, and two carbon atoms or two oxygen atoms at the 2,6, 1,5, 1,6, 1, Examples thereof include a naphthalenediyl group bonded to the 8-position, 1,3-position, 1,4-position, or 2,7-position.
- the alkyl and aryl groups in Rb, Rc, Rd, Re, Rf and Rg of formula (25) and Ri and Rj of formula (26) are synonymous with those in formula (24).
- cyanato-substituted aromatic compound represented by the formula (24) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1-cyanato. -2-, 1-Cyanato-3-, or 1-Cyanato-4-methoxybenzene, 1-Cyanato-2,3-,1-Cyanato-2,4-,1-Cyanato-2,5-,1- Cianato-2,6-,1-Cyanato-3,4- or 1-Cyanato-3,5-dimethylbenzene, Cyanatoethylbenzene, Cyanatobutylbenzene, Cyanatooctylbenzene, Cyanatononylbenzene, 2- (4) -Cyanafel) -2-phenylpropane (cyanate of 4- ⁇ -cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, 1-
- cyanate ester compounds can be used alone or in admixture of two or more.
- phenol novolac resin and cresol novolac resin by a known method, phenol, alkyl-substituted phenol or halogen-substituted phenol, formalin, paraformaldehyde and the like, etc.
- Formaldehyde compound reacted in an acidic solution trisphenol novolac resin (hydroxybenzaldehyde and phenol reacted in the presence of an acidic catalyst), fluorennovolac resin (fluorenone compound and 9,9-bis) (hydroxyaryl) that the fluorenes were reacted in the presence of an acid catalyst), phenol aralkyl resins, cresol aralkyl resin, (by known methods, Ar 4 - (CH 2 Y) naphthol aralkyl resins and biphenyl aralkyl resin 2 (Ar 4 indicates a phenyl group and Y indicates a halogen atom.
- Phenolic-modified xyleneformaldehyde resin (a reaction of xyleneformaldehyde resin and phenol compound in the presence of an acidic catalyst by a known method), modified naphthaleneformaldehyde resin (by a known method, naphthaleneformaldehyde resin) A hydroxy-substituted aromatic compound reacted in the presence of an acidic catalyst), a phenol-modified dicyclopentadiene resin, and a phenolic resin having a polynaphthylene ether structure (by a known method, 2 phenolic hydroxy groups are contained in one molecule).
- Examples thereof include a phenolic resin obtained by dehydrating and condensing a polyvalent hydroxynaphthalene compound having one or more of them in the presence of a basic catalyst), which is cyanated by the same method as described above, and prepolymers thereof. .. These cyanate ester compounds may be used alone or in admixture of two or more.
- the method for producing these cyanate ester compounds is not particularly limited, and known methods can be used.
- An example of such a production method is a method in which a hydroxy group-containing compound having a desired skeleton is obtained or synthesized, and the hydroxy group is modified by a known method to cyanate.
- Examples of the method for cyanating a hydroxy group include the methods described in Ian Hamerton, Chemistry and Technology of Cyanate Ester Resins, Blackie Academic & Professional.
- the cured product using these cyanate ester compounds has excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion.
- the content of the cyanate ester compound is usually 0, based on 100 parts by mass of the total of the bismaleimide compound (A), the compound (B) and the photocuring initiator (C). It is 01 to 40 parts by mass.
- phenol resin As the phenol resin, generally known phenol resins can be used as long as they have two or more hydroxyl groups in one molecule.
- phenol resin generally known phenol resins can be used as long as they have two or more hydroxyl groups in one molecule.
- bisphenol A type phenol resin bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type phenol resin, biphenyl Aralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolak type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type Phenolic resin, dicyclopen
- the content of the phenol resin is usually 0.01 to 100 parts by mass with respect to a total of 100 parts by mass of the bismaleimide compound (A), the compound (B) and the photocuring initiator (C). It is 40 parts by mass.
- oxetane resin As the oxetane resin, generally known ones can be used. For example, alkyl oxetane such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3-di (trifluoro).
- These oxetane resins can be used alone or in admixture of two or more.
- the content of the oxetane resin is usually 0.01 to 100 parts by mass with respect to a total of 100 parts by mass of the bismaleimide compound (A), the compound (B) and the photocuring initiator (C). It is 40 parts by mass.
- benzoxazine compound As the benzoxazine compound, a generally known compound can be used as long as it is a compound having 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 Industry Co., Ltd., trade name
- phenolphthaline type benzoxazine and the like can be mentioned.
- benzoxazine compounds may be used alone or in admixture of two or more.
- the content of the benzoxazine compound is usually 0.01 with respect to a total of 100 parts by mass of the bismaleimide compound (A), the compound (B) and the photocuring initiator (C). ⁇ 40 parts by mass.
- Epoxy resin The epoxy resin is not particularly limited, and generally known epoxy resins can be used.
- epoxy resin a commercially available product can also be used.
- examples of commercially available products include an epoxy resin represented by the formula (27) (NC-3000FH (trade name) manufactured by Nippon Kayaku Co., Ltd., n 7 in the formula (27) is about 4), and a formula.
- examples thereof include a naphthalene type epoxy resin represented by (28) (HP-4710 (trade name) manufactured by DIC Corporation).
- epoxy resins can be used alone or in admixture of two or more.
- the content of the epoxy resin is usually 0.01 to 100 parts by mass with respect to a total of 100 parts by mass of the bismaleimide compound (A), the compound (B) and the photocuring initiator (C). It is 40 parts by mass.
- Other compounds include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether and ethylene glycol divinyl ether, styrenes such as styrene, methylstyrene, ethylstyrene and divinylbenzene, triallyl isocyanurate and trimetaallyl isocyanurate. , And bisallyl nadiimide and the like. These compounds may be used alone or in admixture of two or more. In the resin composition of the present embodiment, the content of other compounds is usually 0.01 with respect to a total of 100 parts by mass of the bismaleimide compound (A), the compound (B) and the photocuring initiator (C). ⁇ 40 parts by mass.
- the resin composition of the present embodiment may contain an organic solvent, if necessary.
- an organic solvent When an organic solvent is used, the viscosity of the resin composition at the time of preparation can be adjusted.
- the type of the organic solvent is not particularly limited as long as it can dissolve a part or all of the resin in the resin composition.
- the organic solvent include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alicyclic ketones such as cyclopentanone and cyclohexanone; cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.
- Ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, and ⁇ -butyrolactone; amides such as dimethylacetamide and dimethylformamide.
- Polar solvents Non-polar solvents such as toluene and aromatic hydrocarbons such as xylene. These organic solvents may be used alone or in admixture of two or more.
- the resin composition of the present embodiment contains various high molecular weight resins such as thermosetting resins, thermoplastic resins, and oligomers thereof, which have not been mentioned so far, as long as the characteristics of the present embodiment are not impaired.
- Molecular compounds; flame-retardant compounds not listed so far; additives and the like can be used in combination. These are not particularly limited as long as they are generally used.
- flame-retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, phosphate compounds of phosphorus compounds, aromatic condensed phosphoric acid esters, halogen-containing condensed phosphoric acid esters, and the like.
- Additives include UV absorbers, antioxidants, optical brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, surface conditioners, brighteners, polymerization inhibitors, heat cures.
- accelerators include accelerators. These components may be used alone or in admixture of two or more. In the resin composition of the present embodiment, the content of the other components is usually 0, respectively, with respect to 100 parts by mass of the total of the bismaleimide compound (A), the compound (B) and the photocuring initiator (C). It is 1 to 10 parts by mass.
- the resin composition of the present embodiment is filled with a bismaleimide compound (A), a compound (B), a photocuring initiator (C), and if necessary, a maleimide compound (D) other than the bismaleimide compound (A). It is prepared by appropriately mixing the material (E), other resins, other compounds, additives and the like.
- the resin composition can be suitably used as a varnish for producing the resin sheet of the present embodiment described later.
- the organic solvent used for preparing the varnish is not particularly limited, and specific examples thereof are as described above.
- Examples of the method for producing the resin composition include a method in which each of the above-mentioned components is sequentially mixed with a solvent and sufficiently stirred.
- the resin composition has excellent photocurability, good solubility in organic solvents, and excellent alkali developability.
- a known treatment for uniformly dissolving or dispersing each component can be performed.
- the dispersibility of each component in the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank equipped with a stirring machine having an appropriate stirring ability.
- a stirring device for dispersing an ultrasonic homogenizer for example, a stirring device for dispersing an ultrasonic homogenizer, a device for mixing three rolls, a ball mill, a bead mill, a sand mill, etc., and a revolving or rotating type mixing device. It can be carried out as appropriate using a known device such as.
- an organic solvent can be used if 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 can be suitably used as a varnish when producing the resin sheet of the present embodiment described later.
- the varnish can be obtained by a known method. For example, in the varnish, 10 to 900 parts by mass of an organic solvent is added to 100 parts by mass of the component excluding the organic solvent in the resin composition of the present embodiment, and the above-mentioned known mixing treatment (stirring, kneading treatment, etc.) is performed. Can be obtained by doing.
- the resin composition can be preferably used in applications where an insulating resin composition is required.
- Applications include, for example, photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit boards (laminated board applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor seals. It can be used as a stop material, a hole filling resin, a component filling resin, and the like.
- the resin composition does not inhibit the photocuring reaction in the exposure process, has excellent photocurability, and can impart excellent alkali developability in the developing process. Therefore, the multilayer printed wiring board It can be suitably used for the insulating layer of the above, or for the solder resist.
- the cured product is obtained by curing the resin composition of the present embodiment.
- the cured product can be obtained, for example, by melting or dissolving the resin composition in a solvent, pouring it into a mold, and curing it under normal conditions using light.
- the wavelength region of light is preferably cured in the range of 100 to 500 nm, which is efficiently cured by a photopolymerization initiator or the like.
- the resin sheet of the present embodiment is a resin sheet with a support having a support and resin layers arranged on one side or both sides of the support, and the resin layer contains the resin composition of the present embodiment. is there.
- the resin sheet can be produced by applying the resin composition on the support and drying it.
- the resin layer in the resin sheet has excellent photocurability and alkali developability.
- a known support can be used, but a resin film is preferable.
- the resin film include polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polyethylene naphthalate film, and polyvinyl alcohol.
- PET film is preferable.
- the resin film is preferably coated with a release agent on the surface in order to facilitate peeling from the resin layer.
- the thickness of the resin film is preferably in the range of 5 to 100 ⁇ m, and more preferably in the range of 10 to 50 ⁇ m. If the thickness is less than 5 ⁇ m, the support tends to be torn easily when the support is peeled off before alkaline development, and if the thickness exceeds 100 ⁇ m, the resolution when exposed from above the support tends to decrease. There is.
- 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 scratches.
- the protective film a film made of the same material as the resin film can be used.
- the thickness of the protective film is preferably in the range of 1 to 50 ⁇ m, 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 inferior.
- the protective film preferably has a smaller adhesive force between the resin layer and the protective film than the adhesive force between the resin layer and the support.
- the method for producing a resin sheet of the present embodiment is, for example, a method of producing a resin sheet by applying the resin composition of the present embodiment to a support such as a PET film and drying it to remove an organic solvent. And so on.
- 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. 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 with respect to 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 handleability.
- the resin sheet can be preferably used for manufacturing an insulating layer of a multilayer printed wiring board.
- the multilayer printed wiring board of the present embodiment has an insulating layer and a conductor layer formed on one side or both sides of the insulating layer, and the insulating layer contains the resin composition of the present embodiment.
- the insulating layer can also be obtained, for example, by stacking one or more resin sheets and curing them.
- the number of layers of the insulating layer and the conductor layer is not particularly limited, and the number of layers can be appropriately set according to the intended use. Further, the order of the insulating layer and the conductor layer is not particularly limited.
- the conductor layer may be a metal foil used for various printed wiring board materials, and examples thereof include metal foils such as copper and aluminum. Examples of the copper metal foil include rolled copper foil and copper foil such as electrolytic copper foil.
- the thickness of the conductor layer is usually 1 to 100 ⁇ m. Specifically, it can be produced by the following method.
- the resin layer side of the resin sheet is laminated on one side or both sides of the circuit board using a vacuum laminator.
- the circuit board include a glass epoxy board, a metal substrate, a ceramic substrate, a silicon substrate, a semiconductor encapsulating 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 side or both sides of the board as described above.
- a circuit board is also a circuit board in which one or both sides of the outermost layer of the multi-layer printed wiring board is a patterned conductor layer (circuit).
- the insulating layer laminated on the multilayer printed wiring board may be an insulating layer obtained by stacking one or more resin sheets of the present embodiment and curing the resin sheet of the present embodiment.
- the insulating layer may be obtained by stacking one or more of the resin sheet of the present embodiment and a known resin sheet different from the resin sheet of the present embodiment.
- the method of stacking the resin sheet of the present embodiment and a known resin sheet different from the resin sheet of the present embodiment is not particularly limited.
- the surface of the conductor layer may be roughened in advance by blackening treatment and / or copper etching or the like.
- the protective film is peeled off and removed, and then the resin sheet and the circuit board are preheated as necessary, and the resin layer of the resin sheet is pressurized 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 laminating method is preferably used.
- the conditions of the laminating process are, for example, a crimping temperature (lamination temperature) of 50 to 140 ° C., a crimping pressure of 1 to 15 kgf / cm 2 , a crimping time of 5 to 300 seconds, and an air pressure of 20 mmHg or less under reduced pressure. It is preferable to laminate. Further, the laminating step may be a batch type or a continuous type using a roll.
- the vacuum laminating method can be performed using a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a 2-stage build-up laminator (trade name) manufactured by Nikko Materials Co., Ltd.
- a predetermined portion of the resin layer is irradiated with active energy rays as a light source to cure the resin layer of the irradiated portion.
- Irradiation may be performed through a mask pattern, or a direct drawing method of direct irradiation may be used.
- the active energy ray include ultraviolet rays, visible rays, electron beams, X-rays and the like.
- the wavelength of the active energy ray is, for example, in the range of 200 to 600 nm. When ultraviolet rays are used, the irradiation amount is about 10 to 1000 mJ / cm 2 .
- an active energy ray having a wavelength of 365 nm (i-line) is used as the active energy ray.
- the irradiation amount thereof is approximately 10 to 10,000 mJ / cm 2 .
- an active energy ray containing a wavelength of 405 nm (h line) is used as the active energy ray.
- the exposure method through which the mask pattern is passed includes a contact exposure method in which the mask pattern is brought into close contact with a multilayer printed wiring board and a non-contact exposure method in which the mask pattern is exposed using parallel light rays without being brought into close contact with each other. It doesn't matter.
- the support is present on the resin layer, it may be exposed from above the support, or the support may be exposed after peeling.
- Alkaline development process When the support is not present on the resin layer, after the exposure step, the non-photocured portion (unexposed portion) is directly removed by alkaline development and developed to form an insulating layer pattern. can do.
- the support is removed, and then the non-photocured portion (unexposed portion) is removed by alkaline development and developed. Thereby, the pattern of the insulating layer can be formed. Since the unexposed resin layer containing the resin composition of the present embodiment has excellent alkali developability, a printed wiring board having a high-definition pattern can be obtained.
- the developer is not particularly limited as long as it selectively elutes the unexposed portion, but is an aqueous solution of tetramethylammonium hydroxide, an aqueous solution of sodium carbonate, an aqueous solution of potassium carbonate, an aqueous solution of sodium hydroxide, and the like.
- An alkaline developer such as an aqueous potassium hydroxide solution is used. In this embodiment, it is particularly preferable to use an aqueous solution of tetramethylammonium hydroxide.
- These alkaline developers can be used alone or in admixture of two or more.
- the alkaline development method for example, a known method such as dip, paddle, spray, rocking immersion, brushing, scraping, etc. can be performed. In the pattern formation of the present embodiment, these developing methods may be used in combination, if necessary. Further, as a developing method, it is preferable to use a high-pressure spray because the resolution is further improved. When the spray method is adopted, the spray pressure is preferably 0.02 to 0.5 MPa.
- a post-baking 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 and a heating step using a clean oven, and these can be used in combination.
- the irradiation amount can be adjusted as needed, and for example, irradiation can be performed at an irradiation amount of about 50 to 10,000 mJ / cm 2 .
- the heating conditions can be appropriately selected as needed, but are preferably selected in the range of 150 to 220 ° C. for 20 to 180 minutes, and more preferably in 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.
- dry plating known methods such as a thin film 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.
- a multilayer printed wiring board is placed in a vacuum vessel, an inert gas such as argon is introduced, a DC voltage is applied, and the ionized inert gas collides with the target metal and is beaten out.
- a metal film can be formed on the insulating layer by the metal.
- a conductor layer is formed by electroless plating or electrolytic plating.
- a subsequent pattern forming method for example, a subtractive method, a semi-additive method, or the like can be used.
- the semiconductor device of this embodiment includes the resin composition of this embodiment. Specifically, it can be produced by the following method.
- a semiconductor device can be manufactured by mounting a semiconductor chip on a conductive portion of a multilayer printed wiring board.
- the conductive portion is a portion of the multilayer printed wiring board that transmits an electric signal, and the location 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 mounting method of the semiconductor chip when manufacturing the semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Specifically, a wire bonding mounting method, a flip chip mounting method, a bumpless build-up layer (BBUL) mounting method, an anisotropic conductive film (ACF) mounting method, and a non-conductive film (NCF) mounting method. And so on.
- a semiconductor device can also be manufactured by forming an insulating layer containing a resin composition on a semiconductor chip or a substrate on which 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 the formation, it can be manufactured by the same method as that of the multilayer printed wiring board.
- maleimide compounds BMI-70 manufactured by KAI Kasei Co., Ltd. (trade name, mass average molecular weight (Mw): 443) and BMI-80 manufactured by KAI Kasei Co., Ltd. (trade name, mass average molecular weight).
- Mw 570, 2,2-bis (4- (4-maleimidephenoxy) -phenyl) propane
- MIR-3000 manufactured by Nippon Kayaku Co., Ltd. (trade name, mass average molecular weight (Mw): 1300) was used to measure the respective transmission rates at the wavelengths of 365 nm and 405 nm.
- This cis-4-cyclohexene is used as the compound (B) containing one or more carboxy groups using cis-4-cyclohexene-1,2-dicarboxylic acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight: 152).
- cis-4-cyclohexene-1,2-dicarboxylic acid anhydride manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight: 152
- Prepare an N-methylpyrrolidone solution containing 1% by mass of -1,2-dicarboxylic acid anhydride and use a UV-vis measuring device (Hitachi spectrophotometer U-4100 (trade name) manufactured by Hitachi High Technologies Co., Ltd.).
- Hitachi spectrophotometer U-4100 (trade name) manufactured by Hitachi High Technologies Co., Ltd.
- the compound (B) containing one or more carboxy groups 4-aminobenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 137), salicylic acid (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 138), Piperidinecarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 129), phthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 166), trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 210), Pyromellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 254), cis-4-cyclohexene-1,2-dicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 170), and 1,2- Using phenylene diacetic acid (manufactured by
- photo-curing initiator (C) bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Omnirad (registered trademark) 819 (trade name) manufactured by IGM Resins BV) is used.
- Example 1 Preparation of resin composition and resin sheet
- the resin surface of the obtained resin sheet is placed on the copper surface (one side) of the inner layer circuit board, and evacuated for 30 seconds (5.0 hPa or less) using a vacuum laminator (manufactured by Nikko Materials Co., Ltd.). ), Then laminating molding was performed at a pressure of 10 kgf / cm 2 and a temperature of 70 ° C. for 30 seconds. Further, laminating molding was performed at a pressure of 10 kgf / cm 2 and a temperature of 70 ° C. for 60 seconds to obtain an evaluation laminate in which the inner layer circuit board, the resin layer, and the support were laminated.
- a vacuum laminator manufactured by Nikko Materials Co., Ltd.
- Example 2 Examples except that 9 parts by mass of 4-aminobenzoic acid was used as the compound (B) containing one or more carboxy groups instead of 9 parts by mass of cis-4-cyclohexene-1,2-dicarboxylic acid anhydride. A resin sheet was obtained in the same manner as in 1. Using this, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 3 As the compound (B) containing one or more carboxy groups, the same procedure as in Example 1 was used except that 9 parts by mass of salicylic acid was used instead of 9 parts by mass of cis-4-cyclohexene-1,2-dicarboxylic acid anhydride. , A resin sheet was obtained. Using this, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 4 Same as Example 1 except that 9 parts by mass of piperidinecarboxylic acid was used as the compound (B) containing one or more carboxy groups instead of 9 parts by mass of cis-4-cyclohexene-1,2-dicarboxylic acid anhydride. A resin sheet was obtained. Using this, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 5 The same as in Example 1 except that 9 parts by mass of phthalic acid was used instead of 9 parts by mass of cis-4-cyclohexene-1,2-dicarboxylic acid anhydride as the compound (B) containing one or more carboxy groups. A resin sheet was obtained. Using this, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 6 Same as in Example 1 except that 9 parts by mass of trimellitic acid was used as the compound (B) containing one or more carboxy groups instead of 9 parts by mass of cis-4-cyclohexene-1,2-dicarboxylic acid anhydride. A resin sheet was obtained. Using this, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 7 Example 1 and Example 1 except that cis-4-cyclohexene-1,2-dicarboxylic acid anhydride (9 parts by mass of pyromellitic acid was used instead of 9 parts by mass) as the compound (B) containing one or more carboxy groups. In the same manner, a resin sheet was obtained. Using this, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 8 For compound (B) containing one or more carboxy groups, for 9 parts by mass of cis-4-cyclohexene-1,2-dicarboxylic acid instead of 9 parts by mass of cis-4-cyclohexene-1,2-dicarboxylic acid anhydride. A resin sheet was obtained in the same manner as in Example 1 except that the resin sheet was obtained. Using this, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 9 This was carried out except that as the compound (B) containing one or more carboxy groups, 9 parts by mass of 1,2-phenylene diacetic acid was used instead of 9 parts by mass of cis-4-cyclohexene-1,2-dicarboxylic acid anhydride. A resin sheet was obtained in the same manner as in Example 1. Using this, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 10 As the photoinitiator (C), 2-benzyl-2-instead of 5 parts by mass of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Omnirad (registered trademark) 819 (trade name)) A resin sheet was obtained in the same manner as in Example 1 except that 5 parts by mass of dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Omnirad (registered trademark) 369 (trade name)) was used. Using this, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Example 11 As the photoinitiator (C), 2-methyl-1- instead of 5 parts by mass of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Omnirad (registered trademark) 819 (trade name)) A resin sheet was obtained in the same manner as in Example 1 except that 5 parts by mass of [4- (methylthio) phenyl] -2-morpholinopropane-1-one (Omnirad (registered trademark) 907 (trade name)) was used. It was. Using this, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- an initiator (C) 5 parts by mass of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Omnirad (registered trademark) 819) is mixed with 5 parts by mass, and 150 mass of methyl ethyl ketone (manufactured by Idemitsu Kosan Co., Ltd.) After diluting in parts, the mixture was stirred with an ultrasonic homogenizer to obtain a varnish (solution of the resin composition). This varnish is applied to a 38 ⁇ m-thick PET film (Unitika Ltd. Unipeel (registered trademark) TR1-38 (trade name)) with an automatic coating device (Tester Sangyo Co., Ltd. PI-1210 (trade name)).
- Example 2 It was applied using and dried by heating at 90 ° C. for 5 minutes to obtain a resin sheet having a PET film as a support and a resin layer having a thickness of 30 ⁇ m. Using this, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Comparative Example 5 A resin sheet was obtained in the same manner as in Comparative Example 3 except that 86 parts by mass of MIR-3000 (trade name) was used instead of 86 parts by mass of BMI-70 (trade name) as the maleimide compound. Using this, an evaluation resin and an evaluation laminate were obtained in the same manner as in Example 1.
- Photo DSC (TA Instruments Japan Co., Ltd.) equipped with a light source capable of irradiating active energy rays with a wavelength of 200 to 600 nm (Omnicure (registered trademark) S2000 (trade name) manufactured by Uvix Co., Ltd.)
- the obtained evaluation resin is irradiated with an active energy ray containing a wavelength of 200 to 600 nm using DSC-2500 (trade name) manufactured by DSC-2500 (manufactured by) with an illuminance of 30 mW and an exposure time of 3.5 minutes, and the horizontal axis is time (sec). ),
- the vertical axis is the heat flow (mW) graph.
- a wavelength 365 nm (i-line) filter or a wavelength 405 nm (h-line) filter is used to generate an active energy ray containing a wavelength of 365 nm (i-line) or an active energy ray containing a wavelength of 405 nm (h-line).
- graphs of time (sec) on the horizontal axis and heat flow (mW) on the vertical axis were obtained except that they were used.
- the peak area when a horizontal line was drawn from the end point of the graph was defined as enthalpy (J / g). Curability was evaluated according to the following criteria.
- AA The enthalpy was 50 (J / g) or more.
- BB The enthalpy was 1 (J / g) or more and less than 50 (J / g).
- CC Enthalpy was less than 1 (J / g).
- An enthalpy of 1 (J / g) or more means that the resin is cured by exposure at a predetermined wavelength, and an enthalpy of 50 (J / g) or more means that the resin is cured by exposure at a predetermined wavelength. , Means that the curing of the resin proceeds sufficiently.
- the obtained evaluation laminate is irradiated from above the support using a light source (MA-20 (trade name) manufactured by Mikasa Co., Ltd.) capable of irradiating an active energy ray containing a wavelength of 405 nm (h line). Irradiation was performed at an amount of 200 mJ / cm 2 , half of the resin sheet was exposed, and the rest was unexposed. Then, the support (PET film) was peeled off and shaken in a 2.38% TMAH (tetramethylammonium hydroxide) aqueous solution (developing solution, manufactured by Tokuyama Corporation) for 60 seconds.
- TMAH tetramethylammonium hydroxide
- FIG. 1 shows photographs after alkaline development performed using the respective evaluation laminates obtained in Example 1 and Comparative Example 1.
- i line an active energy ray containing a wavelength of 365 nm
- h line an active energy ray containing a 405 nm
- 200 to 600 nm When exposed to any of the above light rays, it is well exposed to light and can be photocured. Further, according to the present embodiment, as shown in Tables 2, 3 and FIG. 1, a cured product having excellent alkali developability can be obtained.
- the resin composition of the present embodiment is industrially useful because it has excellent photocurability and alkali developability.
- Applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, component embedding resins, etc. can be used.
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Abstract
Description
例えば、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]下記式(1)で表される構成単位と、分子鎖の両末端にマレイミド基と、を含む、ビスマレイミド化合物(A)と、
カルボキシ基を1つ以上含む化合物(B)と、
光硬化開始剤(C)と、を含む、樹脂組成物。
[5]前記樹脂層の厚さが1~50μmである、[4]に記載の樹脂シート。
[6]絶縁層と、前記絶縁層の片面又は両面に形成された導体層と、を有し、前記絶縁層が、[1]~[3]のいずれかに記載の樹脂組成物を含む、多層プリント配線板。
[7][1]~[3]のいずれかに記載の樹脂組成物を含む、半導体装置。
本実施形態の樹脂組成物は、特定のビスマレイミド化合物(A)と、カルボキシ基を1つ以上含む化合物(B)と、光硬化開始剤(C)とを含む。以下、各成分について説明する。
本実施形態の樹脂組成物は、ビスマレイミド化合物(A)(成分(A)とも称す)を含む。ビスマレイミド化合物(A)は、式(1)で表される構成単位と、分子鎖の両末端にマレイミド基と、を含む。
ビスマレイミド化合物(A)の式(1)中、R1は、炭素数1~16の直鎖状若しくは分岐状のアルキレン基、又は炭素数2~16の直鎖状若しくは分岐状のアルケニレン基を示す。R1としては、好適な粘度が得られ、ワニスの粘度上昇が制御できる点から、直鎖状若しくは分岐状のアルキレン基であることが好ましく、直鎖状のアルキレン基であることがより好ましい。
直鎖状若しくは分岐状のアルキレン基としては、例えば、メチレン基、エチレン基、プロピレン基、2,2-ジメチルプロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基、ノニレン基、デシレン基、ドデシレン基、ウンデシレン基、トリデシレン基、テトラデシレン基、ペンタデシレン基、ヘキサデシレン基、ネオペンチレン基、ジメチルブチレン基、メチルヘキシレン基、エチルヘキシレン基、ジメチルヘキシレン基、トリメチルヘキシレン基、メチルヘプチレン基、ジメチルヘプチレン基、トリメチルヘプチレン基、テトラメチルヘプチレン基、エチルヘプチレン基、メチルオクチレン基、メチルノニレン基、メチルデシレン基、メチルドデシレン基、メチルウンデシレン基、メチルトリデシレン基、メチルテトラデシレン基、及びメチルペンタデシレン基が挙げられる。
直鎖状若しくは分岐状のアルケニレン基としては、例えば、ビニレン基、1-メチルビニレン基、アリレン基、プロペニレン基、イソプロペニレン基、1-ブテニレン基、2-ブテニレン基、1-ペンテニレン基、2-ペンテニレン基、イソペンテニレン基、シクロペンテニレン基、シクロヘキセニレン基、及びジシクロペンタジエニレン基等が挙げられる。
直鎖状若しくは分岐状のアルキレン基としては、R1が参照できる。
直鎖状若しくは分岐状のアルケニレン基としては、R1が参照できる。
直鎖状若しくは分岐状のアルキル基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、1-エチルプロピル基、n-ブチル基、2-ブチル基、イソブチル基、tert-ブチル基、n-ペンチル基、2-ペンチル基、tert-ペンチル基、2-メチルブチル基、3-メチルブチル基、2,2-ジメチルプロピル基、n-ヘキシル基、2-ヘキシル基、3-ヘキシル基、n-へプチル基、n-オクチル基、2-メチルペンチル基、3-メチルペンチル基、4-メチルペンチル基、2-メチルペンタン-3-イル基、及びn-ノニル基が挙げられる。
直鎖状若しくは分岐状のアルケニル基としては、例えば、ビニル基、アリル基、4-ペンテニル基、イソプロペニル基、イソペンテニル基、2-ヘプテニル基、2-オクテニル基、及び2-ノネニル基が挙げられる。
本実施形態において、マレイミド基は、式(8)で表され、N原子がビスマレイミド化合物(A)の分子鎖に結合している。また、ビスマレイミド化合物(A)に結合されるマレイミド基は、全て同一であっても異なっていてもよいが、分子鎖の両末端のマレイミド基は同一であることが好ましい。
直鎖状若しくは分岐状のアルキル基としては、R3が参照できる。
ビスマレイミド化合物(A)は、公知の方法により製造することができる。例えば、1,2,4,5-シクロヘキサンテトラカルボン酸二無水物と、ダイマージアミン等を含むジアミンを含むモノマーと、無水マレイン酸化合物とを、通常80~250℃程度、好ましくは100~200℃程度の温度において、通常0.5~50時間程度、好ましくは1~20時間程度、重付加反応させて重付加物を得る、その後、通常60~120℃程度、好ましくは80~100℃程度の温度において、通常0.1~2時間程度、好ましくは0.1~0.5時間程度、重付加物をイミド化反応、すなわち、脱水閉環反応させることで、ビスマレイミド化合物(A)を得ることができる。
1,2,4,5-シクロヘキサンテトラカルボン酸二無水物のモル数と、ジアミンを含むモノマー及びマレイミド化合物との全量のモル数とを調製することで、任意のビスマレイミド化合物(A)を得ることができる。
触媒の添加量は、例えば、イミド化剤を、アミド基に対して、0.5~5.0倍モル当量程度、脱水触媒を、アミド基に対して、0.5~10.0倍モル当量とすることが好ましい。
本実施形態の樹脂組成物は、カルボキシ基を1つ以上含む化合物(B)(成分(B)又は化合物(B)とも称す)を含む。化合物(B)は、化合物中に、カルボキシ基を1つ以上含めば、特に限定されない。カルボキシ基は、ナトリウム塩、及びカリウム塩などの塩であってもよく、分子内にカルボキシ基を2以上含む場合には、それらが互いに連結して形成された酸無水物であってもよい。化合物(B)は、1種単独又は2種以上を適宜混合して使用することも可能である。
化合物(B)は、1質量%で含まれるN-メチルピロリドン溶液を調製し、波長365nm(i線)を含む活性エネルギー線を用いて、化合物(B)が1質量%で含まれるN-メチルピロリドン溶液の透過率を測定した場合においては、その透過率は5%以上であることが好ましい。このような化合物(B)は非常に優れた光透過性を示す。また、波長405nm(h線)を含む活性エネルギー線を用いて、化合物(B)が1質量%で含まれるN-メチルピロリドン溶液の透過率を測定した場合においては、その透過率が5%以上であることが好ましく、この場合においても非常に優れた光透過性を示す。このような化合物(B)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365nm(i線)における透過率は、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、8%以上、10%以上、20%以上、30%以上、及び40%以上と、この順で好ましい範囲となる。波長405nm(h線)における透過率は、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、8%以上、10%以上、20%以上、30%以上、及び40%以上と、この順で好ましい範囲となる。なお、波長365nm(i線)における透過率、及び波長405nm(h線)における透過率において、それぞれの上限は、例えば、99.9%以下であり、100%以下であってもよい。
カルボキシ基を1つ以上含む脂肪族化合物としては、例えば、鎖状脂肪族モノカルボン酸、脂環式モノカルボン酸、鎖状脂肪族多価カルボン酸、及び脂環式多価カルボン酸が挙げられる。これらの化合物には、分子内に、水素原子、並びにアルキル基、アルコキシ基、アリールオキシ基、アリール基、アミノアルキル基、ヒドロキシル基、アミノ基、及びカルボキシアルキル基等の置換基を有していてもよい。また、これらの化合物は、分子内に、カルボキシ基を2つ以上有する場合には、それらが互いに連結して形成された酸無水物であってもよい。これらの化合物は、分子内に、カルボキシアルキル基を有する場合には、カルボキシアルキル基とカルボキシ基が互いに連結して形成された酸無水物であってもよい。これらの化合物は、分子内に、カルボキシアルキル基を2つ以上有する場合には、それらが互いに連結して形成された酸無水物であってもよい。
アルコキシ基としては、例えば、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、tert-ブトキシ基、n-ヘキサノキシ基、及び2-メチルプロポキシ基等が挙げられる。
アリールオキシ基としては、例えば、フェノキシ基、及びp-トリルオキシ基が挙げられる。
アリール基としては、例えば、フェニル基、トルイル基、ベンジル基、メチルベンジル基、キシリル基、メシチル基、ナフチル基、及びアントリル基が挙げられる。
アミノアルキル基としては、例えば、アミノメチル基、アミノエチル基、アミノプロピル基、アミノジメチル基、アミノジエチル基、アミノジプロピル基、アミノブチル基、アミノヘキシル基、及びアミノノニル基等が挙げられる。
カルボキシアルキル基としては、例えば、カルボキシメチル基、カルボキシエチル基、カルボキシプロピル基、カルボキシブチル基、カルボキシヘキシル基、及びカルボキシノニル基等が挙げられる。
カルボキシ基を1つ以上含む芳香族化合物の母体骨格としては、例えば、安息香酸、フェニレン酢酸、サリチル酸、フタル酸、トリメリット酸、ピロメリット酸、ペンタカルボキシベンゼン、ヘキサカルボキシベンゼン、ナフタレンカルボン酸、ナフタレンジカルボン酸、ナフタレントリカルボン酸、ナフタレンテトラカルボン酸、アントラセンカルボン酸、アントラセンジカルボン酸、アントラセントリカルボン酸、アントラセンテトラカルボン酸、アントラセンペンタカルボン酸等が挙げられる。芳香族化合物は、これらの母体骨格の芳香環上に、例えば、水素原子、並びにアルキル基、アルコキシ基、アリールオキシ基、アリール基、アミノアルキル基、ヒドロキシル基、アミノ基、及びカルボキシアルキル基等の置換基を有していてもよい。また、これらの化合物は、分子内に、カルボキシ基を2つ以上有する場合には、それらが互いに連結して形成された酸無水物であってもよい。これらの化合物は、分子内に、カルボキシアルキル基を有する場合には、カルボキシアルキル基とカルボキシ基が互いに連結して形成された酸無水物であってもよい。これらの化合物は、分子内に、カルボキシアルキル基を2つ以上有する場合には、それらが互いに連結して形成された酸無水物であってもよい。これらの置換基については、前記を参照できる。
カルボキシ基を1つ以上含むヘテロ化合物の母体骨格としては、例えば、フラン、チオフェン、ピロール、イミダゾール、ピラン、ピリジン、ピリミジン、ピラジン、ピロリジン、ピペリジン、ピペラジン、モルホリン、インドール、プリン、キノリン、イソキノリン、キヌクリジン、クロメン、チアントレン、フェノチアジン、フェノキサジン、キサンテン、アクリジン、フェナジン、及びカルバゾール等のヘテロ環に、1つ以上のカルボキシ基を含む化合物が挙げられる。ヘテロ化合物は、これらの母体骨格上に、例えば、水素原子、並びにアルキル基、アルコキシ基、アリールオキシ基、アリール基、アミノアルキル基、ヒドロキシル基、アミノ基、及びカルボキシアルキル基等の置換基を有していてもよい。また、これらの化合物は、分子内に、カルボキシ基を2つ以上有する場合には、それらが互いに連結して形成された酸無水物であってもよい。これらの化合物は、分子内に、カルボキシアルキル基を有する場合には、カルボキシアルキル基とカルボキシ基が互いに連結して形成された酸無水物であってもよい。これらの化合物は、分子内に、カルボキシアルキル基を2つ以上有する場合には、それらが互いに連結して形成された酸無水物であってもよい。これらの置換基については、前記を参照できる。
R4は、アルカリ現像性の点から、各々独立に、水素原子、ヒドロキシル基、カルボキシ基、又はアミノ基であることが好ましく、より優れたアルカリ現像性が得られる点から、カルボキシ基を含むことがより好ましい。
なお、安息香酸は、他のカルボキシ基を1つ以上含む化合物(B)に比べて、アルカリ現像性に劣る傾向にある。
また、kは、各々独立に、1~5の整数を示す。
また、kは、各々独立に、0~4の整数を示す。
カルボキシ基数pは、5-kの整数を示す。カルボキシ基数pは、より優れたアルカリ現像性を示す点から、1~3の整数であることが好ましい。この場合、R4の数kは、5-pの整数で2~4の整数である。
式(10)で表される化合物は、カルボキシ基を2つ以上含み、それらが互いに連結して形成された酸無水物であってもよい。
R5は、アルカリ現像性の点から、各々独立に、水素原子、ヒドロキシル基、カルボキシ基、又はアミノ基であることが好ましく、より優れたアルカリ現像性が得られる点から、カルボキシ基を含むことがより好ましい。
また、lは、各々独立に、1~9の整数を示す。
なお、ピペリジンカルボン酸は、他のカルボキシ基を1つ以上含む化合物(B)に比べて、アルカリ現像性に劣る傾向にある。
R6は、アルカリ現像性の点から、各々独立に、水素原子、ヒドロキシル基、カルボキシ基、又はアミノ基であることが好ましく、より優れたアルカリ現像性が得られる点から、カルボキシ基を含むことがより好ましい。
また、mは、各々独立に、1~9の整数を示す。
また、mは、各々独立に、0~8の整数を示す。
カルボキシ基数qは、9-mの整数を示す。カルボキシ基数qは、より優れたアルカリ現像性を示す点から、1~3の整数であることが好ましい。この場合、R6の数mは、9-qの整数で6~8の整数である。
式(11)で表される化合物は、カルボキシ基を2つ以上含み、それらが互いに連結して形成された酸無水物であってもよい。また、式(11)で表される化合物は、カルボキシメチル基を有する場合には、カルボキシメチル基とカルボキシ基は、それらが互いに連結して形成された酸無水物であってもよい。
R7は、アルカリ現像性の点から、各々独立に、水素原子、ヒドロキシル基、カルボキシ基、又はアミノ基であることが好ましく、より優れたアルカリ現像性が得られる点から、カルボキシ基を含むことがより好ましい。
また、oは、各々独立に、1~5の整数を示す。
また、oは、各々独立に、0~4の整数を示す。
カルボキシ基数rは、5-oの整数を示す。カルボキシ基数rは、より優れたアルカリ現像性を示す点から、1~3の整数であることが好ましい。この場合、R7の数oは、5-rの整数で2~4の整数である。
式(12)において、カルボキシメチル基とカルボキシ基は、それらが互いに連結して形成された酸無水物であってもよい。式(12)で表される化合物は、カルボキシ基を2つ以上有する場合、それらが互いに連結して形成された酸無水物であってもよい。式(12)中、カルボキシ基数の上限は、5である。式(12)で表される化合物は、カルボキシメチル基を2つ以上有する場合、それらが互いに連結して形成された酸無水物であってもよい。式(12)中、カルボキシメチル基数の上限は、6である。
これらのカルボキシ基を1つ以上含む化合物(B)は、1種単独又は2種以上を適宜混合して使用することも可能である。
本実施形態の樹脂組成物は、光硬化開始剤(C)(成分(C)とも称す)を含む。光硬化開始剤(C)は、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、ビスマレイミド化合物(A)及びカルボキシル基を1つ以上含む化合物(B)と共に、種々の活性エネルギー線を用いて光硬化させるために用いられる。
p-メトキシフェニルジアゾニウムフロロホスホネート、及びN,N-ジエチルアミノフェニルジアゾニウムヘキサフロロホスホネート等のルイス酸のジアゾニウム塩;ジフェニルヨードニウムヘキサフロロホスホネート、及びジフェニルヨードニウムヘキサフロロアンチモネート等のルイス酸のヨードニウム塩;トリフェニルスルホニウムヘキサフロロホスホネート、及びトリフェニルスルホニウムヘキサフロロアンチモネート等のルイス酸のスルホニウム塩;トリフェニルホスホニウムヘキサフロロアンチモネート等のルイス酸のホスホニウム塩;その他のハロゲン化物;トリアジン系開始剤;ボーレート系開始剤;その他の光酸発生剤等のカチオン系光硬化開始剤が挙げられる。
光硬化開始剤(C)は、1種単独又は2種以上を適宜混合して使用することも可能である。
式(7)中、R9は、各々独立に、水素原子又はメチル基を表す。R9のうち、1つ以上がメチル基であることが好ましく、全てメチル基であることがより好ましい。
本実施形態の樹脂組成物には、本発明の効果を奏する限り、本実施形態に係るビスマレイミド化合物(A)以外のマレイミド化合物(D)(成分(D)とも称す)を含むことができる。ビスマレイミド化合物(A)は、光透過性に非常に優れるため、マレイミド化合物(D)を用いても、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、種々の活性エネルギー線を用いて光硬化させることができる。そのため、例えば、波長365nmを含む活性エネルギー線、又は405nmを含む活性エネルギー線を用いても、光が光硬化開始剤まで十分に届き、光硬化開始剤から発生したラジカルを用いたラジカル反応が進行し、マレイミド化合物(D)が配合されている組成物においても光硬化が可能となる。以下にマレイミド化合物(D)について述べる。
また、本実施形態においては、ビスマレイミド化合物(A)の光ラジカル反応を効率的に起こさせるために、マレイミド化合物(D)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)を含む活性エネルギー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5%以上の光透過性を示すことが好ましい。このようなマレイミド化合物(D)を用いることで、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。光透過率は、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、8%以上であることがより好ましく、10%以上であることが更に好ましい。
式(16)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が好ましい。
直鎖状若しくは分岐状のアルケニル基としては、ビスマレイミド化合物(A)におけるR3が参照できる。これらの中でも、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、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。
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が好ましい。
アルケニル基の具体例としては、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、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(15)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(15)中のn3=13.6(平均))、ケイ・アイ化成(株)社製BMI-650P(商品名、式(15)中のn3=8.8(平均))、ケイ・アイ化成(株)社製BMI-250P(商品名、式(15)中のn3=3~8(平均))、ケイ・アイ化成(株)社製CUA-4(商品名、式(15)中のn3=1)等が挙げられる。
式(16)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(16)中のx=18、y=18)等が挙げられる。
式(17)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、式(23)、官能基当量:346g/eq.)等が挙げられる。
式(19)で表されるマレイミド化合物としては、市販品を利用することもでき、例えば、Designer Molecules Inc.(DMI)製BMI-1700(商品名)が挙げられる。
式(20)で表されるマレイミド化合物としては、市販品を利用することもでき、例えば、Designer Molecules Inc.(DMI)製BMI-3000(商品名)、Designer Molecules Inc.(DMI)製BMI-3000J(商品名)、Designer Molecules Inc.(DMI)製BMI-5000(商品名)、Designer Molecules Inc.(DMI)製BMI-9000(商品名)が挙げられる。
式(21)で表されるマレイミド化合物としては、市販品を利用することもでき、例えば、大和化成工業株式会社製BMI-TMHが挙げられる。
式(22)で表されるマレイミド化合物としては、市販品を利用することもでき、例えば、ケイ・アイ化成(株)製BMI-70(商品名)が挙げられる。
これらのマレイミド化合物(D)は、1種単独又は2種以上を適宜混合して使用することも可能である。
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(E)(成分(E)とも称す)を含むことができる。充填材(E)としては、絶縁性を有し、光硬化に用いる種々の活性エネルギー線に対する透過性を阻害しないものであることが好ましく、波長365nm(i線)、及び/又は波長405nm(h線)を含む活性エネルギー線に対する透過性を阻害しないものであることがより好ましい。
これらの充填材(E)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。
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、充填材との接着強度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ができる。
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、3-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、3-アミノプロピルジメトキシメチルシラン、3-アミノプロピルジエトキシメチルシラン、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、N-(2-アミノエチル)-3-アミノプロピルトリエトキシシラン、N-(2-アミノエチル)-3-アミノプロピルジメトキシメチルシラン、N-(2-アミノエチル)-3-アミノプロピルジエトキシメチルシラン、 N-フェニル-3-アミノプロピルトリメトキシシラン、N-フェニル-3-アミノプロピルトリエトキシシラン、[3-(6-アミノヘキシルアミノ)プロピル]トリメトキシシラン、及び[3-(N,N-ジメチルアミノ)-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、3-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルジメトキシメチルシラン、3-グリシドキシプロピルジエトキシメチルシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、及び[8-(グリシジルオキシ)-n-オクチル]トリメトキシシラン等のエポキシシラン系;ビニルトリス(2-メトキシエトキシ)シラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ジメトキシメチルビニルシラン、ジエトキシメチルビニルシラン、トリメトキシ(7-オクテン-1-イル)シラン、及びトリメトキシ(4-ビニルフェニル)シランなどのビニルシラン系;3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-メタクリロキシプロピルジメトキシメチルシラン、3-メタクリロキシプロピルジエトキシメチルシランなどのメタクリルシラン系、γ-アクリロキシプロピルトリメトキシシラン、及び3-アクリロキシプロピルトリエトキシシラン等のアクリルシラン系;3-イソシアネートプロピルトリメトキシシラン、及び3-イソシアネートプロピルトリエトキシシランなどのイソシアネートシラン系;トリス-(トリメトキシシリルプロピル)イソシアヌレートなどのイソシアヌレートシラン系;3-メルカプトプロピルトリメトキシシラン、及び3-メルカプトプロピルジメトキシメチルシランなどのメルカプトシラン系;3-ウレイドプロピルトリエトキシシランなどのウレイドシラン系;p-スチリルトリメトキシシランなどのスチリルシラン系;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;[3-(トリメトキシシリル)プロピル]コハク酸無水物などの酸無水物系;フェニルトリメトキシシラン、フェニルトリエトキシシラン、ジメトキシメチルフェニルシラン、ジエトキシメチルフェニルシラン、及びp-トリルトリメトキシシラン等のフェニルシラン系;トリメトキシ(1-ナフチル)シランなどのアリールシラン系が挙げられる。これらのシランカップリング剤は、1種単独又は2種以上を適宜混合して使用することも可能である。
湿潤分散剤としては、塗料用に使用されている分散安定剤であれば、特に限定されない。具体例としては、ビッグケミー・ジャパン(株)製のDISPERBYK(登録商標)-110(商品名)、111(商品名)、118(商品名)、180(商品名)、161(商品名)、BYK(登録商標)-W996(商品名)、W9010(商品名)、W903(商品名)等の湿潤分散剤が挙げられる。これらの湿潤分散剤は、1種単独又は2種以上を適宜混合して使用することも可能である。
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、通常、ビスマレイミド化合物(A)、化合物(B)及び光硬化開始剤(C)の合計100質量部に対して、0.1~10質量部である。
本実施形態では、本発明の効果を奏する限り、硬化した硬化物の難燃性、耐熱性及び熱膨張特性等の特性に応じて、本実施形態の樹脂組成物には、本実施形態に係る、ビスマレイミド化合物(A)、カルボキシ基を1つ以上含む化合物(B)、光硬化開始剤(C)、及びマレイミド化合物(D)以外の、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含むことができる。また、これらの化合物及び樹脂は、波長365nm(i線)を含む活性エネルギー線、及び/又は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、光硬化することが好ましい。
これらの化合物及び樹脂は、1種単独又は2種以上を適宜混合し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(24)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。更にアルコキシル基としては、例えば、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(24)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(25)のAr2及び式(26)のAr3の具体例としては、式(25)に示す2個の炭素原子、又は式(26)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、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、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(25)のRb、Rc、Rd、Re、Rf及びRg、並びに式(26)のRi、Rjにおけるアルキル基及びアリール基は、式(24)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。これらのフェノール樹脂は、1種単独又は2種以上を適宜混合し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)、及びOXT-221(東亞合成(株)製、商品名)等が挙げられる。これらのオキセタン樹脂は、1種単独又は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。これらのベンゾオキサジン化合物は、1種単独又は2種以上を適宜混合して使用することも可能である。
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。これらのエポキシ樹脂は、1種単独又は2種以上を適宜混合して使用することも可能である。
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、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。これらの化合物は、1種単独又は2種以上を適宜混合して使用することも可能である。
本実施形態の樹脂組成物において、その他の化合物の含有量は、通常、ビスマレイミド化合物(A)、化合物(B)及び光硬化開始剤(C)の合計100質量部に対して、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、有機溶剤を含んでもよい。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。有機溶剤の種類は、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。有機溶剤としては、例えば、アセトン、メチルエチルケトン、及びメチルイソブチルケトン等のケトン類;シクロペンタノン、及びシクロヘキサノン等の脂環式ケトン類;プロピレングリコールモノメチルエーテル、及びプロピレングリコールモノメチルエーテルアセテート等のセロソルブ系溶媒;乳酸エチル、酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソアミル、乳酸エチル、メトキシプロピオン酸メチル、ヒドロキシイソ酪酸メチル、及びγ―ブチロラクトン等のエステル系溶媒;ジメチルアセトアミド、及びジメチルホルムアミド等のアミド類などの極性溶剤類;トルエン、及びキシレン等の芳香族炭化水素等の無極性溶剤が挙げられる。
これらの有機溶剤は、1種単独又は2種以上を適宜混合して使用することも可能である。
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、並びに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、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、重合禁止剤、熱硬化促進剤等が挙げられる。これらの成分は、1種単独又は2種以上を適宜混合し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、通常、ビスマレイミド化合物(A)、化合物(B)及び光硬化開始剤(C)の合計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、ビスマレイミド化合物(A)、化合物(B)、光硬化開始剤(C)と、必要に応じて、ビスマレイミド化合物(A)以外のマレイミド化合物(D)、充填材(E)、及びその他の樹脂、その他の化合物、添加剤等を適宜混合することにより調製される。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。なお、ワニスの調製に使用する有機溶媒は、特に限定されず、その具体例は、前記したとおりである。
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好ましく使用することができる。用途としては、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、樹脂組成物は、露光工程においては、光硬化反応を阻害せず、優れた光硬化性を有し、現像工程においては、優れたアルカリ現像性を付与できるため、多層プリント配線板の絶縁層用として、又は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。
硬化物は、本実施形態の樹脂組成物を硬化させてなる。硬化物は、例えば、樹脂組成物を溶融又は溶媒に溶解させた後、型内に流し込み、光を用いて通常の条件で硬化させることにより得ることができる。光の波長領域は、光重合開始剤等により効率的に硬化が進む100~500nmの範囲で硬化させることが好ましい。
本実施形態の樹脂シートは、支持体と、支持体の片面又は両面に配された樹脂層と、を有し、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。樹脂シートにおける樹脂層は、優れた光硬化性及びアルカリ現像性を有する。
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、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、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にあり、50μmを超えると廉価性に劣る傾向にある。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。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、絶縁層と、絶縁層の片面又は両面に形成された導体層とを有し、絶縁層が、本実施形態の樹脂組成物を含む。絶縁層は、例えば、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。絶縁層と導体層のそれぞれの積層数は、特に限定されず、目的とする用途に応じて適宜積層数を設定することができる。また、絶縁層と導体層の順番も特に限定されない。導体層としては、各種プリント配線板材料に用いられる金属箔であってもよく、例えば、銅、及びアルミニウム等の金属箔が挙げられる。銅の金属箔としては、圧延銅箔、及び電解銅箔等の銅箔が挙げられる。導体層の厚みは、通常、1~100μmである。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、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、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、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、多層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。なお、この多層プリント配線板に積層されている絶縁層は、本実施形態の樹脂シートを1枚以上重ねて硬化して得られた絶縁層であってもよく、本実施形態の樹脂シートと、本実施形態の樹脂シートと異なる公知の樹脂シートとをそれぞれ1枚以上重ねて得られた絶縁層であってもよい。なお、本実施形態の樹脂シートと、本実施形態の樹脂シートと異なる公知の樹脂シートとの重ね方は、特に限定されない。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、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。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、例えば、200~600nmの範囲である。紫外線を用いる場合、その照射量はおおむね10~1000mJ/cm2である。また、ステッパー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ては、活性エネルギー線として、例えば、波長365nm(i線)を含む活性エネルギー線を用いることが好ましい。波長365nm(i線)を含む活性エネルギー線を用いた場合、その照射量は、おおむね10~10,000mJ/cm2である。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ては、活性エネルギー線として、例えば、波長405nm(h線)を含む活性エネルギー線を用いることが好ましい。波長405nm(h線)を含む活性エネルギー線を用いた場合、その照射量は、おおむね10~10,000mJ/cm2である。
マスクパターンを通す露光方法には、マスクパターンを多層プリント配線板に密着させて行う接触露光法と、密着させずに平行光線を使用して露光する非接触露光法とがあるが、どちらを用いてもかまわない。また、樹脂層上に支持体が存在している場合は、支持体上から露光してもよいし、支持体を剥離後に露光してもよい。
樹脂層上に支持体が存在していない場合には、露光工程後、直接アルカリ現像にて光硬化されていない部分(未露光部)を除去し、現像することにより、絶縁層のパターンを形成することができる。
また、樹脂層上に支持体が存在している場合には、露光工程後、その支持体を除去した後に、アルカリ現像にて光硬化されていない部分(未露光部)を除去し、現像することにより、絶縁層のパターンを形成することができる。
本実施形態の樹脂組成物を含む未露光の樹脂層は、優れたアルカリ現像性を有するため、高精細なパターンを有するプリント配線板を得ることができる。
本実施形態では、アルカリ現像工程終了後、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、50~10,000mJ/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を形成することができる。
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。具体的には、以下の方法により製造することができる。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。
[原料の評価]
〔透過率、及び吸光度〕
ビスマレイミド化合物(A)として、日本化薬(株)製MIZ-001(商品名、質量平均分子量(Mw):3000)を用いて、このMIZ-001(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日立分光光度計 U-4100(商品名))を用いて、波長365nm、及び405nmにおけるそれぞれの透過率の測定を行った。
同様に、マレイミド化合物として、ケイ・アイ化成(株)製BMI-70(商品名、質量平均分子量(Mw):443)、ケイ・アイ化成(株)製BMI-80(商品名、質量平均分子量(Mw):570、2,2-ビス(4-(4-マレイミドフェノキシ)-フェニル)プロパン)、日本化薬(株)社製MIR-3000(商品名、質量平均分子量(Mw):1300)を用いて、波長365nm、及び405nmにおけるそれぞれの透過率の測定を行った。
同様に、カルボキシ基を1つ以上含む化合物(B)として、4-アミノ安息香酸(東京化成工業(株)製、分子量:137)、サリチル酸(東京化成工業(株)製、分子量:138)、ピペリジンカルボン酸(東京化成工業(株)製、分子量:129)、フタル酸(東京化成工業(株)製、分子量:166)、トリメリット酸(東京化成工業(株)製、分子量:210)、ピロメリット酸(東京化成工業(株)製、分子量:254)、cis-4-シクロへキセン-1,2-ジカルボン酸(東京化成工業(株)製、分子量:170)、及び1,2-フェニレン二酢酸(東京化成工業(株)製、分子量:194)を用いて、波長365nm、及び405nmにおけるそれぞれの透過率の測定を行った。
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 B.V.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 B.V.社製Omnirad(登録商標)907(商品名))を用いて、波長365nm、及び405nmにおけるそれぞれの吸光度の測定を行った。
結果を表1に示す。
(樹脂組成物及び樹脂シートの作製)
ビスマレイミド化合物(A)としてMIZ-001(商品名)を86質量部と、カルボキシ基を1つ以上含む化合物(B)としてcis-4-シクロヘキセン-1,2-ジカルボン酸無水物を9質量部と、光硬化開始剤(C)として、ビス(2,4,6-トリメチルベンゾイル)-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5質量部とを混合し、メチルエチルケトン(出光興産(株)製)150質量部で希釈した後、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(ユニチカ(株)製ユニピール(登録商標)TR1-38(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、90℃で5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。
得られた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(5.0hPa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。
内層回路を形成したガラス布基材BT(ビスマレイミド・トリアジン)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。
得られた樹脂シートの樹脂面を、前記内層回路基板の銅表面(片面)上に配置し、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(5.0hPa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10kgf/cm2、温度70℃で60秒間の積層成形を行うことで内層回路基板と樹脂層と支持体とが積層された評価用積層体を得た。
カルボキシ基を1つ以上含む化合物(B)として、cis-4-シクロヘキセン-1,2-ジカルボン酸無水物9質量部の代わりに、4-アミノ安息香酸9質量部を用いた以外は、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、評価用樹脂及び評価用積層体を得た。
カルボキシ基を1つ以上含む化合物(B)として、cis-4-シクロヘキセン-1,2-ジカルボン酸無水物9質量部の代わりに、サリチル酸9質量部用いた以外は、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、評価用樹脂及び評価用積層体を得た。
カルボキシ基を1つ以上含む化合物(B)として、cis-4-シクロヘキセン-1,2-ジカルボン酸無水物9質量部の代わりに、ピペリジンカルボン酸9質量部用いた以外は、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、評価用樹脂及び評価用積層体を得た。
カルボキシ基を1つ以上含む化合物(B)として、cis-4-シクロヘキセン-1,2-ジカルボン酸無水物9質量部の代わりに、フタル酸9質量部用いた以外は、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、評価用樹脂及び評価用積層体を得た。
カルボキシ基を1つ以上含む化合物(B)として、cis-4-シクロヘキセン-1,2-ジカルボン酸無水物9質量部の代わりに、トリメリット酸9質量部用いた以外は、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、評価用樹脂及び評価用積層体を得た。
カルボキシ基を1つ以上含む化合物(B)として、cis-4-シクロヘキセン-1,2-ジカルボン酸無水物(9質量部の代わりに、ピロメリット酸9質量部用いた以外は、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、評価用樹脂及び評価用積層体を得た。
カルボキシ基を1つ以上含む化合物(B)として、cis-4-シクロヘキセン-1,2-ジカルボン酸無水物9質量部の代わりに、cis-4-シクロヘキセン-1,2-ジカルボン酸9質量部用いた以外は、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、評価用樹脂及び評価用積層体を得た。
カルボキシ基を1つ以上含む化合物(B)として、cis-4-シクロヘキセン-1,2-ジカルボン酸無水物9質量部の代わりに、1,2-フェニレン二酢酸9質量部用いた以外は、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、評価用樹脂及び評価用積層体を得た。
光硬化開始剤(C)として、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(Omnirad(登録商標)819(商品名))5質量部の代わりに、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(Omnirad(登録商標)369(商品名))5質量部用いた以外は、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、評価用樹脂及び評価用積層体を得た。
光硬化開始剤(C)として、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(Omnirad(登録商標)819(商品名))5質量部の代わりに、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(Omnirad(登録商標)907(商品名))5質量部用いた以外は、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、評価用樹脂及び評価用積層体を得た。
ビスマレイミド化合物(A)としてMIZ-001(商品名)を86質量部と、光硬化開始剤(C)としてビス(2,4,6-トリメチルベンゾイル)-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5質量部とを混合し、メチルエチルケトン(出光興産(株)製)150質量部で希釈した後、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(ユニチカ(株)製ユニピール(登録商標)TR1-38(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、90℃で5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。
これを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
ビスマレイミド化合物(A)としてMIZ-001(商品名)を86質量部と、カルボキシ基を1つ以上含む化合物(B)としてcis-4-シクロヘキセン-1,2-ジカルボン酸無水物9質量部とを混合し、メチルエチルケトン(出光興産(株)製)150質量部で希釈した後、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(ユニチカ(株)製ユニピール(登録商標)TR1-38(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、90℃で5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。
これを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
マレイミド化合物としてBMI-70(商品名)を86質量部と、カルボキシ基を1つ以上含む化合物(B)としてcis-4-シクロヘキセン-1,2-ジカルボン酸無水物を9質量部と、光硬化開始剤(C)としてビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(Omnirad(登録商標)819)を5質量部とを混合し、メチルエチルケトン(出光興産(株)製)150質量部で希釈した後、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(ユニチカ(株)製ユニピール(登録商標)TR1-38(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、90℃で5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。
これを用いて、実施例1と同様にして、評価用樹脂及び評価用積層体を得た。
マレイミド化合物として、BMI-70(商品名)86質量部の代わりに、BMI-80(商品名)86質量部用いた以外は、比較例3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、評価用樹脂及び評価用積層体を得た。
マレイミド化合物として、BMI-70(商品名)86質量部の代わりに、MIR-3000(商品名)86質量部用いた以外は、比較例3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、評価用樹脂及び評価用積層体を得た。
実施例及び比較例で得られた評価用樹脂及び評価用積層体を、以下の方法により測定し、評価した。それらの結果を表2、3及び図1に示す。
波長200~600nm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、波長200~600nmを含む活性エネルギー線を、照度30mW、露光時間3.5分間照射して、横軸が時間(sec)、縦軸がヒートフロー(mW)のグラフを得た。
また、光源として、波長365nm(i線)フィルター、又は波長405nm(h線)フィルターを用いて、波長365nm(i線)を含む活性エネルギー線、又は波長405nm(h線)を含む活性エネルギー線を用いたこと以外は、前記と同様の条件により、横軸が時間(sec)、縦軸がヒートフロー(mW)のグラフをそれぞれ得た。
それぞれのグラフにおいて、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、以下の基準で評価した。
AA:エンタルピーが50(J/g)以上であった。
BB:エンタルピーが1(J/g)以上、50(J/g)未満であった。
CC:エンタルピーが1(J/g)未満であった。
なお、エンタルピーが1(J/g)以上とは、所定の波長における露光により、樹脂の硬化が進行することを意味し、エンタルピーが50(J/g)以上とは、所定の波長における露光により、樹脂の硬化が十分に進行することを意味する。
得られた評価用積層体に、波長405nm(h線)を含む活性エネルギー線を照射可能な光源(ミカサ(株)製MA-20(商品名))を用いて、支持体の上から、照射量200mJ/cm2にて照射し、樹脂シートの半分を露光し、残りを未露光とした。その後、支持体(PETフィルム)を剥離し、2.38%TMAH(水酸化テトラメチルアンモニウム)水溶液(現像液、(株)トクヤマ社製)中で60秒間振とうした。60秒間振とう後に得られた積層体について、以下の基準に従って、アルカリ現像性を目視にて評価した。
「AA」:露光部は不溶であるが、未露光部は60秒間の振とうで溶解する。
「CC」:露光部及び未露光部共に不溶である。
また、実施例1及び比較例1で得られたそれぞれの評価用積層体を用いて行ったアルカリ現像後の写真を図1に示した。
比較例3では、405nm(h線)を含む活性エネルギー線、及び波長200~600nmを含む活性エネルギー線に対して感光したが、露光部及び未露光部共に不溶であり、優れたアルカリ現像性は得られなかった。この理由については、マレイミド化合物が比較的低分子量であるため、マレイミド化合物が化合物(B)のアルカリ現像液への溶解に伴って、アルカリ現像液に溶解することができず、そのため、主としてマレイミド化合物が溶け残り、アルカリ現像液に不溶であったと推定された。
Claims (7)
- 下記式(1)で表される構成単位と、分子鎖の両末端にマレイミド基と、を含む、ビスマレイミド化合物(A)と、
カルボキシ基を1つ以上含む化合物(B)と、
光硬化開始剤(C)と、を含む、樹脂組成物。
(式(1)中、R1は、炭素数1~16の直鎖状若しくは分岐状のアルキレン基、又は炭素数2~16の直鎖状若しくは分岐状のアルケニレン基を示す。R2は、炭素数1~16の直鎖状若しくは分岐状のアルキレン基、又は炭素数2~16の直鎖状若しくは分岐状のアルケニレン基を示す。R3は、各々独立に、水素原子、炭素数1~16の直鎖状若しくは分岐状のアルキル基、又は炭素数2~16の直鎖状若しくは分岐状のアルケニル基を示す。nは、各々独立に、1~10の整数を示す。)。 - 前記カルボキシ基を1つ以上含む化合物(B)が、下記式(2)で表される化合物、下記式(3)で表される化合物、下記式(4)で表される化合物、及び下記式(5)で表される化合物からなる群より選択される少なくとも1種以上の化合物である、請求項1に記載の樹脂組成物。
(式(2)中、R4は、各々独立に、水素原子、ヒドロキシル基、カルボキシ基、アミノ基、又はアミノメチル基を示す。kは、各々独立に、1~5の整数を示す。式(2)中、カルボキシ基を2つ以上有する場合には、それらが互いに連結して形成された酸無水物であってもよい。)。
(式(3)中、R5は、各々独立に、水素原子、ヒドロキシル基、カルボキシ基、カルボキシメチル基、アミノ基、又はアミノメチル基を示す。lは、各々独立に、1~9の整数を示す。式(3)中、カルボキシ基を2つ以上有する場合には、それらが互いに連結して形成された酸無水物であってもよい。式(3)中、カルボキシメチル基を有する場合には、カルボキシメチル基とカルボキシ基が互いに連結して形成された酸無水物であってもよい。)。
(式(4)中、R6は、各々独立に、水素原子、ヒドロキシル基、カルボキシ基、カルボキシメチル基、アミノ基、又はアミノメチル基を示す。mは、各々独立に、1~9の整数を示す。式(4)中、カルボキシ基を2つ以上有する場合には、それらが互いに連結して形成された酸無水物であってもよい。式(4)中、カルボキシメチル基を有する場合には、カルボキシメチル基とカルボキシ基が互いに連結して形成された酸無水物であってもよい。)。
(式(5)中、R7は、各々独立に、水素原子、ヒドロキシル基、カルボキシ基、カルボキシメチル基、アミノ基、又はアミノメチル基を示す。oは、各々独立に、1~5の整数を示す。式(5)中、カルボキシ基を1つ以上有する場合には、カルボキシメチル基とカルボキシ基が互いに連結して形成された酸無水物であってもよい。式(5)中、カルボキシ基を2つ以上有する場合には、それらが互いに連結して形成された酸無水物であってもよい。式(5)中、カルボキシメチル基を2つ以上有する場合には、それらが互いに連結して形成された酸無水物であってもよい。)。 - 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1~3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4に記載の樹脂シート。
- 絶縁層と、
前記絶縁層の片面又は両面に形成された導体層と、
を有し、
前記絶縁層が、請求項1~3のいずれか一項に記載の樹脂組成物を含む、多層プリント配線板。 - 請求項1~3のいずれか一項に記載の樹脂組成物を含む、半導体装置。
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| EP20831096.1A EP3916025B1 (en) | 2019-06-28 | 2020-06-26 | Resin composition, resin sheet, multilayer printed wiring board, and semiconductor device |
| CN202210752641.7A CN115032863A (zh) | 2019-06-28 | 2020-06-26 | 树脂组合物、树脂片、多层印刷电路板和半导体装置 |
| US17/621,926 US11466123B2 (en) | 2019-06-28 | 2020-06-26 | Resin composition, resin sheet, multilayer printed wiring board, and semiconductor device |
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| KR (1) | KR102430118B1 (ja) |
| CN (2) | CN113242996B (ja) |
| TW (1) | TWI856124B (ja) |
| WO (1) | WO2020262577A1 (ja) |
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| JPWO2022201621A1 (ja) * | 2021-03-25 | 2022-09-29 | ||
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| WO2023176766A1 (ja) | 2022-03-14 | 2023-09-21 | 三菱瓦斯化学株式会社 | 樹脂、樹脂組成物、硬化物、プリプレグ、金属箔張積層板、樹脂複合シート、プリント配線板、および、半導体装置 |
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| WO2024195764A1 (ja) * | 2023-03-23 | 2024-09-26 | 日本化薬株式会社 | 熱硬化性マレイミド樹脂組成物並びにこれを用いたシート状又はフィルム状組成物、接着剤組成物、プライマー組成物、基板用組成物、コーティング材組成物及び半導体装置 |
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| EP3915784A4 (en) * | 2019-01-22 | 2022-02-23 | Mitsubishi Gas Chemical Company, Inc. | RESIN COMPOSITION, RESIN FILM, MULTILAYER CIRCUIT BOARD AND SEMICONDUCTOR DEVICE |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN115032863A (zh) | 2022-09-09 |
| US20220204695A1 (en) | 2022-06-30 |
| CN113242996A (zh) | 2021-08-10 |
| KR102430118B1 (ko) | 2022-08-05 |
| US11466123B2 (en) | 2022-10-11 |
| JP6850447B1 (ja) | 2021-03-31 |
| TWI856124B (zh) | 2024-09-21 |
| EP3916025B1 (en) | 2023-08-09 |
| CN113242996B (zh) | 2022-07-12 |
| EP3916025A4 (en) | 2022-06-01 |
| KR20210064383A (ko) | 2021-06-02 |
| EP3916025A1 (en) | 2021-12-01 |
| TW202108665A (zh) | 2021-03-01 |
| JPWO2020262577A1 (ja) | 2021-09-13 |
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