WO2022201621A1 - 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5397—Phosphine oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or 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, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
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- H10W74/47—
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
Definitions
- the present invention relates to resin compositions, resin sheets, multilayer printed wiring boards, and semiconductor devices.
- Patent Document 1 discloses a phenol novolak-type cyanate ester resin as a resin having excellent heat resistance and storage stability.
- the cured product using the phenol novolak-type cyanate ester resin described in Patent Document 1 is excellent in thermal expansion resistance, it has a high water absorption rate and may have deteriorated dielectric properties.
- the resin composition used as the material of the insulating layer is mainly a thermosetting resin, and holes for obtaining electrical connection between the insulating layers are generally made by laser processing.
- drilling holes by laser processing has the problem that the processing time becomes longer as the number of holes in a high-density substrate increases. Therefore, in recent years, by using a resin composition that allows the exposed area to be cured (exposure process) and the unexposed area to be removed (development process) by irradiation with light, etc., it is possible to perform batch drilling in the exposure and development processes. There is a demand for a resin sheet that makes this possible.
- a method of exposure a method of exposing through a photomask using a mercury lamp as a light source is used, and a material that can be suitably exposed to the light source of this mercury lamp is desired.
- This exposure method using a mercury lamp as a light source uses ghi crosstalk (g-line wavelength 436 nm, h-line wavelength 405 nm, i-line wavelength 365 nm), etc., and a general-purpose photocuring initiator can be selected.
- a direct drawing exposure method has also been introduced in which drawing is performed directly on a photosensitive resin composition layer without using a photomask based on digital data of a pattern.
- This direct writing exposure method has better alignment accuracy than the exposure method that uses a photomask, and can produce highly detailed patterns.
- the light source uses monochromatic light such as a laser.
- a DMD (Digital Micromirror Device) type apparatus capable of forming a high-definition resist pattern uses a light source with a wavelength of 405 nm (h-line).
- Alkaline development is used as the development method because it can obtain high-definition patterns.
- a compound having an ethylenically unsaturated group such as (meth)acrylate is used in the photosensitive resin composition used for such laminates and resin sheets in order to enable rapid curing in the exposure process.
- a carboxyl-modified epoxy (meth)acrylate resin obtained by reacting a bisphenol-type epoxy resin and (meth)acrylic acid and then reacting an acid anhydride, a biphenyl-type epoxy resin
- a photosensitive thermosetting resin composition is described that includes a photoinitiator and a diluent.
- Patent Document 3 a photocurable binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, a photopolymerization (curing) initiator, a sensitizer, and a heat curing agent bisallyl nagic
- a resin composition includes an imide compound and a bismaleimide compound.
- Patent Document 4 describes a resin composition containing a bismaleimide compound (curable resin) and a photoradical polymerization initiator (curing agent) as a photosensitive resin composition used for laminates and resin sheets. ing.
- Patent Document 5 describes a resin composition containing a polyvalent carboxy group-containing compound obtained by reacting a bismaleimide with a monoamine and then reacting with an acid anhydride, and a curable resin such as an epoxy resin. be. Patent document 5 describes a polyvalent carboxy group-containing compound capable of obtaining a cured product having alkali developability.
- Patent Document 2 describes the use of a bismaleimide compound, it is described as a thermosetting agent, and (meth)acrylate is used as the photopolymerizable compound. Therefore, even the cured product obtained from this resin composition does not have sufficient alkali developability, and a high-definition resist pattern cannot be obtained, which poses a problem for use in high-density printed wiring boards.
- Patent Document 3 a bismaleimide compound is used as a curable resin.
- maleimide compounds generally have poor light transmittance, when a maleimide compound is included, sufficient light does not reach the photocuring initiator, resulting in photocuring. The initiator hardly generates radicals and its reactivity is very low. Therefore, in Patent Document 3, the maleimide compound is cured by performing additional heating before development. Moreover, 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 is obtained by reacting bismaleimide and monoamine, and then reacting an acid anhydride, so the process is complicated. Moreover, 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, since this polyvalent carboxyl group-containing compound has poor light transmittance and inhibits the photocuring reaction, it is actually difficult to use it in a photosensitive resin composition.
- the present invention has been made in view of the above problems, and when used in the manufacture of a printed wiring board, in the exposure process, it does not inhibit the photocuring reaction and has excellent photocurability.
- Another object of the present invention is to provide a resin composition capable of imparting excellent alkali developability in a developing step, a resin sheet using the same, a multilayer printed wiring board, and a semiconductor device.
- the present inventors solved the problem by using a resin composition containing a specific bismaleimide compound (A), a compound (B) containing one or more carboxyl groups, and a photocuring initiator (C). can be solved, and the present invention has been completed.
- the present invention includes the following contents.
- a bismaleimide compound (A) comprising a structural unit represented by the following formula (1) and maleimide groups at both ends of a molecular chain; a compound (B) containing one or more carboxy groups; A resin composition comprising a photocuring initiator (C).
- R 1 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms.
- R 2 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms.
- Each R 3 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms.
- Each n 1 independently represents an integer of 1 to 4.
- Each n2 independently represents an integer of 1 to 4.
- the compound (B) containing one or more carboxyl 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 at least one compound selected from the group consisting of compounds represented by the following formula (5), the resin composition according to [1].
- each R 4 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, an amino group, or an aminomethyl group.
- Each k independently represents an integer of 1 to 5.
- each R 5 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, a carboxymethyl group, an amino group, or an aminomethyl group.
- l each independently represents an integer of 1 to 9.
- it when it has two or more carboxy groups, it may be an acid anhydride formed by linking them together.
- it when it has a carboxymethyl group may be an acid anhydride formed by connecting a carboxymethyl group and a carboxy group to each other.
- each R 6 independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a carboxymethyl group, an amino group, or an aminomethyl group; each m represents an integer of 1 to 9;
- each m represents an integer of 1 to 9;
- when it has a carboxymethyl group may be an acid anhydride formed by connecting a carboxymethyl group and a carboxy group to each other.
- each R 7 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, a carboxymethyl group, an amino group, or an aminomethyl group.
- Each o independently represents an integer of 1 to 5.
- carboxy when it has one or more carboxy groups, it may be an acid anhydride formed by linking a carboxymethyl group and a carboxy group to each other.
- carboxy when it has two or more groups, it may be an acid anhydride formed by linking them together.
- the formula (5) when it has two or more carboxymethyl groups, they are linked together It may be an acid anhydride formed by
- each R 8 independently represents a substituent represented by the following formula (7) or a phenyl group.
- [4] having a support and a resin layer disposed on one or both sides of the support, wherein the resin layer contains the resin composition according to any one of [1] to [3]; resin sheet.
- [6] having an insulating layer and a conductor layer formed on one or both sides of the insulating layer, wherein the insulating layer contains the resin composition according to any one of [1] to [3]; Multilayer printed wiring board.
- a semiconductor device comprising the resin composition according to any one of [1] to [3].
- the present invention when used for manufacturing a multilayer printed wiring board, it does not inhibit the photocuring reaction in the exposure step, has excellent photocurability, and has excellent alkali developability in the development step.
- a resin sheet using the same when used for manufacturing a multilayer printed wiring board, it does not inhibit the photocuring reaction in the exposure step, has excellent photocurability, and has excellent alkali developability in the development step.
- a semiconductor device when used for manufacturing a multilayer printed wiring board, it does not inhibit the photocuring reaction in the exposure step, has excellent photocurability, and has excellent alkali developability in the development step.
- this embodiment the form for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail.
- the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents.
- the present invention can be appropriately modified and implemented within the scope of the gist thereof.
- (meth)acryloxy means both “acryloxy” and corresponding "methacryloxy
- (meth)acrylate means both “acrylate” and corresponding “methacrylate”.
- (meth)acryl means both “acryl” and the corresponding "methacryl”.
- the resin composition of the present embodiment contains a specific bismaleimide compound (A), a compound (B) containing one or more carboxyl groups, and a photocuring initiator (C). Each component will be described below.
- the resin composition of the present embodiment contains a bismaleimide compound (A) (also referred to as component (A)).
- the bismaleimide compound (A) contains a structural unit represented by formula (1) and maleimide groups at both ends of the molecular chain.
- R 1 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms.
- R 2 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms.
- Each R 3 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms.
- Each R 4 is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear or branched alkoxy group having 1 to 6 carbon atoms indicates a group.
- Each n 1 independently represents an integer of 1 to 4.
- Each n2 independently represents an integer of 1 to 4.
- maleimide compounds have poor light transmittance, so when a resin composition contains a maleimide compound, light does not sufficiently reach the photocuring initiator dispersed in the resin composition, causing the photocuring initiator to generate radicals. unlikely to occur. Therefore, the radical photoreaction of the maleimide compound is generally difficult to proceed, and even if the radical polymerization or dimerization reaction of maleimide alone proceeds, the reactivity is very low.
- the bismaleimide compound (A) contains the structural unit represented by the formula (1), it has very excellent light transmittance.
- the light sufficiently reaches the photocuring initiator, the photoradical reaction of maleimide occurs efficiently, and the bismaleimide compound (A) is a compound (B) containing one or more carboxyl groups described later, and 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 an active energy ray containing a wavelength of 365 nm (i-line) is used to extract 1% by mass of the bismaleimide compound (A).
- the transmittance of the chloroform solution contained in is measured, the transmittance is 5% or more, indicating very excellent light transmittance.
- the transmittance of a chloroform solution containing 1% by mass of the bismaleimide compound (A) was measured using an active energy ray (light beam) having a wavelength of 405 nm (h-line), the transmittance was 5%. % or more, showing very excellent light transmittance.
- the transmittance at a wavelength of 365 nm (i-line) is preferably 8% or more, more preferably 10% or more, from the viewpoint of exhibiting more excellent light transmittance.
- the transmittance at a wavelength of 405 nm (h-line) is preferably 8% or more, and preferably 10% or more, from the viewpoint of producing a printed wiring board having a higher density and finer wiring formation (pattern). more preferred.
- the upper 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.
- photocuring initiators tend to have lower absorbance when using long-wavelength light. For example, when an active energy ray containing a wavelength of 405 nm (h-line) is used, since the light of this wavelength is a relatively long wavelength, it is not absorbed by a normal photocuring initiator, and this light is preferably absorbed. Polymerization does not proceed unless a photocuring initiator capable of generating radicals is used.
- the photocuring initiator (C) described later when the absorbance of a chloroform solution containing 0.01% by mass of the photocuring initiator (C) is measured, light with a wavelength of 405 nm (h line)
- a photo-curing initiator exhibiting an extremely excellent absorbency such as an absorbance of 0.1 or more.
- the bismaleimide compound (A) Since the bismaleimide compound (A) has excellent light transmittance as described above, for example, even when an active energy ray containing a wavelength of 365 nm or an active energy ray containing a wavelength of 405 nm is used, the light reaches the photocuring initiator.
- the radical reaction using the radicals generated from the photo-curing initiator proceeds sufficiently to allow photo-curing even in a composition containing a large amount of the bismaleimide compound (A).
- the resin composition of the present embodiment contains a bismaleimide compound (A) and a compound (B) containing one or more carboxyl groups described later (also referred to as compound (B)) and a photocuring initiator (C).
- A bismaleimide compound
- B compound containing one or more carboxyl groups described later
- C photocuring initiator
- the bismaleimide compound (A) has a relatively long chain and a flexible structure, and furthermore does not have a structure that causes an interaction with the alkaline component in the alkaline developer. Therefore, the bismaleimide compound (A) retains the structure of the compound (B) containing one or more carboxyl groups in an alkaline developer, and dissolves in an alkaline developer as the compound (B) dissolves in the alkaline developer. It can be dissolved in the developer. Then, in the development step, when the alkaline developer flows into the unexposed area (resin composition), the alkali component in the alkaline developer and the carboxy group in the compound (B) are combined without being inhibited by the bismaleimide compound (A). can rapidly and favorably form a salt, improving water solubility. 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 has excellent heat resistance, insulation reliability, and thermal stability, and according to the present embodiment, the protective film and the An insulating layer can be suitably formed.
- the bismaleimide compound (A) preferably has a weight-average molecular weight of 100 to 6,000, more preferably 300 to 5,500, in order to obtain a suitable viscosity and suppress an increase in the viscosity of the varnish.
- weight-average molecular weight means the mass average molecular weight of polystyrene standard conversion by gel permeation chromatography (GPC) method.
- R 1 is a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkylene group having 2 to 16 carbon atoms, It represents a branched alkenylene group.
- R 1 is preferably a straight-chain or branched alkylene group, more preferably a straight-chain alkylene group, from the viewpoint that a suitable viscosity can be obtained and the increase in the viscosity of the varnish can be controlled.
- the number of carbon atoms in the alkylene group is preferably from 2 to 14, more preferably from 4 to 12, in order to obtain a more suitable viscosity and control the increase in viscosity of the varnish.
- Linear or branched alkylene groups include, for example, methylene group, ethylene group, propylene group, 2,2-dimethylpropylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group and decylene group.
- the number of carbon atoms in the alkenylene group is preferably from 2 to 14, more preferably from 4 to 12, in order to obtain a more suitable viscosity and control the increase in viscosity of the varnish.
- Linear or branched alkenylene groups include, for example, vinylene group, 1-methylvinylene group, arylene group, propenylene group, isopropenylene group, 1-butenylene group, 2-butenylene group, 1-pentenylene group, 2 -pentenylene group, isopentenylene group, cyclopentenylene group, cyclohexenylene group, dicyclopentadienylene group, and the like.
- R 2 represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms.
- R 2 is preferably a straight-chain or branched alkylene group, more preferably a straight-chain alkylene group, from the viewpoint that a suitable viscosity can be obtained and the increase in the viscosity of the varnish can be controlled.
- the number of carbon atoms in the alkylene group is preferably from 2 to 14, more preferably from 4 to 12, in order to obtain a more suitable viscosity and control the increase in viscosity of the varnish.
- R 1 As a linear or branched alkylene group, reference can be made to R 1 .
- the number of carbon atoms in the alkenylene group is preferably from 2 to 14, more preferably from 4 to 12, in order to obtain a more suitable viscosity and control the increase in viscosity of the varnish.
- R 1 As a linear or branched alkenylene group reference can be made to R 1 .
- R 1 and R 2 may be the same or different, but are preferably the same from the viewpoint of easier synthesis of the bismaleimide compound (A).
- each R 3 is independently a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. indicates Each R 3 is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 16 carbon atoms in order to obtain a suitable viscosity and control the viscosity increase of the varnish.
- R 3 it is more preferable that 1 to 4 groups (R 3 ) are linear or branched alkyl groups having 1 to 16 carbon atoms and the remaining groups (R 3 ) are hydrogen atoms.
- 1 to 3 groups (R 3 ) are linear or branched alkyl groups having 1 to 16 carbon atoms and the remaining groups (R 3 ) are hydrogen atoms.
- the number of carbon atoms in the alkyl group is preferably from 2 to 14, more preferably from 4 to 12, from the viewpoint that more suitable viscosity can be obtained and the increase in viscosity of the varnish can be more controlled.
- Linear or branched alkyl groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, 1-ethylpropyl group, n-butyl group, 2-butyl group, isobutyl group 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, n-heptyl, n-octyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylpentan-3-yl, and n-nonyl groups.
- the number of carbon atoms in the alkenyl group is preferably from 2 to 14, more preferably from 4 to 12, from the viewpoint that a more suitable viscosity can be obtained and the viscosity increase of the varnish can be more controlled.
- Linear or branched alkenyl groups include, for example, vinyl group, allyl group, 4-pentenyl group, isopropenyl group, isopentenyl group, 2-heptenyl group, 2-octenyl group, and 2-nonenyl group. be done.
- each R 4 is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear chain having 1 to 6 carbon atoms. represents a straight or branched alkoxy group. From the viewpoint of dielectric properties, R 4 is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.
- the number of carbon atoms in the alkyl group is preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, from the viewpoint of obtaining more suitable viscosity.
- Linear or branched alkyl groups include, for example, methyl, ethyl, n-propyl and isopropyl groups.
- Halogen atoms include, for example, fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.
- the number of carbon atoms in the alkoxy group is preferably a prime number of 1 to 6, more preferably 1 to 3, from the viewpoint of obtaining a more suitable viscosity.
- Linear or branched alkoxy groups include methoxy, ethoxy, n-propoxy and isopropoxy groups.
- each n 1 independently represents an integer of 1-4.
- n 2 each independently represents an integer of 1 to 4
- the bismaleimide compound (A) has maleimide groups at both ends of its molecular chain.
- both ends mean both ends of the molecular chain of the bismaleimide compound (A).
- the maleimido group is at the chain end of R 1 or at the chain end at the N atom of the maleimide ring or at both ends.
- the bismaleimide compound (A) may have maleimide groups other than both ends of the molecular chain.
- the maleimide group is represented by the following formula (8), and the N atom is bonded to the molecular chain of the above formula (1).
- the maleimide groups bonded to the above formula (1) may all be the same or different, but the maleimide groups at both ends of the molecular chain are preferably the same.
- each R 10 independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. Both R 10 are preferably hydrogen atoms from the viewpoint of suitable photocuring.
- the number of carbon atoms in the alkyl group is preferably from 1 to 3, more preferably from 1 to 2, from the viewpoint of suitable photocuring.
- Examples of such a bismaleimide compound (A) include a bismaleimide compound represented by Formula (9). These may be used singly or in admixture of two or more.
- a represents an integer of 1-10. It is preferable that a is an integer of 1 to 6 from the viewpoint that a more suitable viscosity can be obtained and the increase in viscosity of the varnish can be more controlled.
- the content of the bismaleimide compound (A) is set to (A), with respect to a total of 100 parts by mass of the compound (B) containing one or more carboxyl groups described later and the photocuring initiator (C) described later, it is preferably 40 to 99 parts by mass, and 50 to 97 It is more preferably 60 to 96 parts by mass.
- the bismaleimide compound (A) can be used singly or in a suitable mixture of two or more.
- a bismaleimide compound (A) can be produced by a known method. For example, a monomer containing 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride and a diamine such as dimer diamine, A maleic anhydride compound is subjected to a polyaddition reaction at a temperature of usually about 80 to 250° C., preferably about 100 to 200° C., for about 0.5 to 50 hours, preferably about 1 to 20 hours, to give a polyadduct.
- imidating the polyadduct A bismaleimide compound (A) can be obtained by a reaction, that is, a dehydration ring-closure reaction.
- Dimer diamine is obtained, for example, by a reductive amination reaction of dimer acid, and the amination reaction is performed by a known method such as a reduction method using ammonia and a catalyst (for example, JP-A-9-12712). method).
- a dimer acid is a dibasic acid obtained by dimerizing an unsaturated fatty acid by an intermolecular polymerization reaction or the like. Although it depends on synthesis conditions and purification conditions, it usually contains a small amount of monomer acid, trimer acid, etc. in addition to dimer acid. A double bond remains in the molecule obtained after the reaction.
- a dimer acid is obtained, for example, by polymerizing an unsaturated fatty acid using a Lewis acid and a Bronsted acid as a catalyst.
- a dimer acid can be produced by a known method (for example, the method described in JP-A-9-12712).
- unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-gamma-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, boseopentaenoic acid, ospondic acid, sardine acid, tetracosapentaenoic acid, docosahexaenoic acid, and herring acid.
- the number of carbon atoms in the unsaturated fatty acid is generally 4-24, preferably 14-20.
- the diamine-containing monomer is previously dissolved or dispersed in an organic solvent in an inert atmosphere such as argon, nitrogen, or the like, to form a diamine-containing monomer solution and preferably.
- 4-(2,5-Dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride is dissolved in an organic solvent or dispersed in slurry form. It is preferably added later, or in a solid state, to the monomer solution containing the diamine.
- solvents can be used in the polyaddition reaction and imidization reaction.
- solvents include amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; Esters such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -methyl- ⁇ -butyrolactone, ethyl lactate, methyl acetate, ethyl acetate, and butyl acetate; methanol, ethanol , and aliphatic alcohols having 1 to 10 carbon atoms such as propanol; aromatic group-containing phenols such as phenol and cresol; aromatic group-containing alcohols such as benzyl
- a catalyst in the imidization reaction it is preferable to use a catalyst in the imidization reaction.
- catalysts for example, tertiary amines and dehydration catalysts can be used.
- Preferred tertiary amines are heterocyclic tertiary amines such as pyridine, picoline, quinoline, and isoquinoline.
- Dehydration catalysts include, for example, acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride.
- the amount of the catalyst to be added is, for example, about 0.5 to 5.0 times the molar equivalent of the imidizing agent with respect to the amide group, and 0.5 to 10.0 times the molar amount of the dehydration catalyst with respect to the amide group. Equivalent weights are preferred.
- this solution may be used as the bismaleimide compound (A) solution, or a poor solvent may be added to the reaction solvent to turn the bismaleimide compound (A) into a solid.
- poor solvents include water, methyl alcohol, ethyl alcohol, 2-propyl alcohol, ethylene glycol, triethylene glycol, 2-butyl alcohol, 2-pentyl alcohol, 2-hexyl alcohol, cyclopentyl alcohol, cyclohexyl alcohol, phenol, and t-butyl alcohol.
- the resin composition of the present embodiment contains compound (B) (also referred to as component (B) or compound (B)) containing one or more carboxy groups.
- Compound (B) is not particularly limited as long as it contains one or more carboxy groups.
- the carboxyl group may be a salt such as a sodium salt or a potassium salt, or when two or more carboxyl groups are contained in the molecule, they may be an acid anhydride formed by linking them together.
- Compound (B) can be used singly or in combination of two or more.
- the compound (B) can be photocured with various active energy rays together with the bismaleimide compound (A) according to the present embodiment and a photocuring initiator (C) described below to obtain a cured product. .
- a resin composition containing the compound (B) can be obtained in the unexposed area.
- An N-methylpyrrolidone solution containing 1% by mass of the compound (B) is prepared, and an N- When the transmittance of the methylpyrrolidone solution is measured, the transmittance is preferably 5% or more.
- Such a compound (B) exhibits very good light transmittance.
- the transmittance of an N-methylpyrrolidone solution containing 1% by mass of the compound (B) is measured using an active energy ray having a wavelength of 405 nm (h-line), the transmittance is 5% or more. is preferable, and in this case also very excellent light transmittance is exhibited.
- an active material containing a wavelength of 405 nm (h-line) is used. Even when an energy beam is used, the photoradical reaction of maleimide occurs efficiently.
- the transmittance at a wavelength of 365 nm (i-line) is 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more, in that order, since a resin composition with excellent photocurability can be obtained. is a preferable range.
- the transmittance at a wavelength of 405 nm (h-line) is 8% or more, 10% or more, 20% or more, 30% or more, and 40% or more, in that order, since a resin composition with excellent photocurability can be obtained. is a preferable range.
- the upper limit of the transmittance at a wavelength of 365 nm (i-line) and the transmittance at a wavelength of 405 nm (h-line) is, for example, 99.9% or less, and may be 100% or less.
- the molecule of compound (B) preferably contains an integer of 2 to 4 carboxy groups in order to obtain better alkali developability.
- the molecular weight of the compound (B) is preferably 50 to 1000, more preferably 100 to 800, from the viewpoint of further improving developability.
- Examples of the compound (B) include formic acid, aliphatic compounds containing one or more carboxy groups, aromatic compounds containing one or more carboxy groups, and hetero compounds containing one or more carboxy groups. These compounds (B) can be used singly or in admixture of two or more.
- aliphatic compounds containing one or more carboxyl groups include chain aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, chain aliphatic polycarboxylic acids, and alicyclic polycarboxylic acids. . These compounds have hydrogen atoms and substituents such as alkyl groups, alkoxy groups, aryloxy groups, aryl groups, aminoalkyl groups, hydroxyl groups, amino groups, and carboxyalkyl groups in their molecules. good too. In addition, when these compounds have two or more carboxyl groups in the molecule, they may be acid anhydrides formed by linking them together.
- these compounds When these compounds have a carboxyalkyl group in the molecule, they may be an acid anhydride formed by combining the carboxyalkyl group and the carboxy group. When these compounds have two or more carboxyalkyl groups in the molecule, they may be acid anhydrides formed by linking them together.
- alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n -heptyl group, and n-octyl group.
- alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-hexanoxy, and 2-methylpropoxy groups.
- Aryloxy groups include, for example, a phenoxy group and a p-tolyloxy group.
- Aryl groups include, for example, phenyl, toluyl, benzyl, methylbenzyl, xylyl, mesityl, naphthyl, and anthryl groups.
- aminoalkyl groups include aminomethyl, aminoethyl, aminopropyl, aminodimethyl, aminodiethyl, aminodipropyl, aminobutyl, aminohexyl, and aminononyl groups.
- Carboxyalkyl groups include, for example, carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, carboxyhexyl, and carboxynonyl groups.
- Chain aliphatic monocarboxylic acids include, for example, acetic acid, propionic acid, isobutyric acid, butyric acid, isovaleric acid, valeric acid, caproic acid, lactic acid, succinic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecane saturated fatty acids such as hexadecanoic acid, heptadecanoic acid, and octadecanoic acid; unsaturated fatty acids such as oleic acid, elaidic acid, erucic acid, nervonic acid, linolenic acid, stearidonic acid, eicosapentaenoic acid, and linolenic acid.
- alicyclic monocarboxylic acids examples include cyclopropanecarboxylic acid, cyclopropenecarboxylic acid, cyclobutanecarboxylic acid, cyclobutenecarboxylic acid, cyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, cyclohexenecarboxylic acid, and cycloheptanecarboxylic acid.
- Acids monocyclic carboxylic acids such as cycloheptenecarboxylic acid, cyclooctanecarboxylic acid, and cyclooctenecarboxylic acid, norbornanecarboxylic acid, tricyclodecanecarboxylic acid, tetracyclododecanecarboxylic acid, adamantanecarboxylic acid, methyladamantanecarboxylic acid , ethyladamantanecarboxylic acid, and polycyclic or bridged alicyclic carboxylic acids such as butyladamantanecarboxylic acid.
- chain aliphatic polycarboxylic acids include carboxylic acids in which one or more carboxy groups are further added to chain aliphatic monocarboxylic acids.
- Examples include propanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, and the like.
- alicyclic polycarboxylic acids include carboxylic acids in which one or more carboxy groups are further added to alicyclic monocarboxylic acids.
- carboxylic acids in which one or more carboxy groups are further added to alicyclic monocarboxylic acids.
- Examples of the base skeleton of aromatic compounds containing one or more carboxyl groups include benzoic acid, phenyleneacetic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, pentacarboxybenzene, hexacarboxybenzene, naphthalenecarboxylic acid, and naphthalene.
- Aromatic compounds 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 these compounds have two or more carboxyl groups in the molecule, they may be acid anhydrides formed by linking them together.
- they when these compounds have a carboxyalkyl group in the molecule, they may be an acid anhydride formed by combining the carboxyalkyl group and the carboxy group.
- these compounds When these compounds have two or more carboxyalkyl groups in the molecule, they may be acid anhydrides formed by linking them together.
- substituents reference can be made to the above.
- hetero compound containing one or more carboxy groups examples include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, and quinuclidine. , chromenes, thianthrenes, phenothiazines, phenoxazines, xanthenes, acridines, phenazines, and carbazoles.
- Hetero compounds have, for example, hydrogen atoms and substituents such as alkyl groups, alkoxy groups, aryloxy groups, aryl groups, aminoalkyl groups, hydroxyl groups, amino groups, and carboxyalkyl groups on their parent skeleton. You may have In addition, when these compounds have two or more carboxyl groups in the molecule, they may be acid anhydrides formed by linking them together. When these compounds have a carboxyalkyl group in the molecule, they may be an acid anhydride formed by combining the carboxyalkyl group and the carboxy group. When these compounds have two or more carboxyalkyl groups in the molecule, they may be acid anhydrides formed by linking them together. For these substituents, reference can be made to the above.
- each R 4 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, an amino group, or an aminomethyl group. Moreover, when the compound represented by formula (2) has two or more carboxy groups, it may be an acid anhydride formed by linking them together. In formula (2), the upper limit of the number of carboxy groups is six. From the viewpoint of alkali developability, each R 4 is preferably independently a hydrogen atom, a hydroxyl group, a carboxy group, or an amino group. is more preferred. Benzoic acid tends to be inferior in alkali developability to other compounds (B) containing one or more carboxyl groups. Each 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 better alkali developability.
- each 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, more preferably a hydrogen atom, from the viewpoint of exhibiting better alkali developability.
- each k' independently represents an integer of 0 to 4.
- the number of carboxyl groups p is an integer of 5-k.
- the carboxy group number p is preferably an integer of 1 to 3 from the viewpoint of exhibiting better alkali developability.
- the number k of R 4 is an integer of 5-p and an integer of 2-4.
- the compound represented by the formula (10) may be an acid anhydride formed by linking two or more carboxy groups with each other.
- Examples of the compound represented by formula (2) include 4-aminobenzoic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, 4-aminomethylbenzoic acid, and anhydrides thereof.
- These anhydrides include, for example, phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride.
- phthalic acid, trimellitic acid, pyromellitic acid, and their anhydrides are preferable from the viewpoint of obtaining better alkali developability.
- each R 5 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, a carboxymethyl group, an amino group, or an aminomethyl group. Moreover, when the compound represented by formula (3) has two or more carboxy groups, it may be an acid anhydride formed by linking them together. In formula (3), the upper limit of the number of carboxyl groups is 10. When the compound represented by Formula (3) has a carboxymethyl group, it may be an acid anhydride formed by combining the carboxymethyl group and the carboxy group. From the viewpoint of alkali developability, each R 5 is preferably independently a hydrogen atom, a hydroxyl group, a carboxy group, or an amino group. is more preferred. Each l independently represents an integer of 1 to 9. In addition, piperidinecarboxylic acid tends to be inferior in alkali developability to other compounds (B) containing one or more carboxyl groups.
- R 5 contains a carboxy group
- the number of carboxy groups l is preferably 1 to 3 from the standpoint of alkali developability.
- Each R 5 other than the carboxy group is preferably a hydrogen atom or a hydroxyl group, more preferably a hydrogen atom.
- the number of R 5 other than carboxy groups is 7 to 9.
- Examples of the compound represented by formula (3) include piperidinecarboxylic acid, 1,2-piperidinedicarboxylic acid, and piperidinedicarboxylic anhydride.
- each R 6 independently represents a hydrogen atom, a hydroxyl group, a carboxy group, a carboxymethyl group, an amino group, or an aminomethyl group. Moreover, when the compound represented by formula (4) has two or more carboxy groups, it may be an acid anhydride formed by linking them together. In formula (4), the upper limit of the number of carboxyl groups is 10. When the compound represented by formula (4) has a carboxymethyl group, it may be an acid anhydride formed by combining the carboxymethyl group and the carboxy group. From the viewpoint of alkali developability, each R 6 is preferably independently a hydrogen atom, a hydroxyl group, a carboxy group, or an amino group. is more preferred. Each m independently represents an integer of 1 to 9.
- the compound represented by the formula (4) is preferably a compound represented by the following formula (11) from the viewpoint of obtaining better alkali developability.
- each 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, more preferably a hydrogen atom, from the viewpoint of exhibiting better alkali developability.
- Each m' independently represents an integer of 0 to 8.
- the number of carboxyl groups q is an integer of 9-m.
- the number of carboxyl groups q is preferably an integer of 1 to 3 from the viewpoint of exhibiting better alkali developability.
- the number m of R 6 is an integer of 9-q and an integer of 6-8.
- the compound represented by the formula (11) may be an acid anhydride formed by linking two or more carboxy groups with each other. Further, when the compound represented by formula (11) has a carboxymethyl group, the carboxymethyl group and the carboxy group may be an acid anhydride formed by linking them together.
- Examples of compounds represented by formula (4) include 3-cyclohexene-1-carboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and cis-4-cyclohexene-1,2-dicarboxylic acid.
- Anhydrides are mentioned.
- cis-4-cyclohexene-1,2-dicarboxylic acid and cis-4-cyclohexene-1,2-dicarboxylic acid are used from the viewpoint of obtaining better alkali developability. Anhydrides are preferred.
- each R 7 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 formula (5) has one or more carboxy groups, it may be an acid anhydride formed by connecting a carboxymethyl group and a carboxy group to each other. Moreover, when it has two or more carboxy groups in Formula (5), it may be an acid anhydride formed by linking them together. In formula (5), the upper limit of the number of carboxy groups is five. In formula (5), when it has two or more carboxymethyl groups, it may be an acid anhydride formed by linking them together. In formula (5), the upper limit of the number of carboxymethyl groups is six. From the viewpoint of alkali developability, each R 7 is preferably independently a hydrogen atom, a hydroxyl group, a carboxy group, or an amino group. is more preferred. Each o independently represents an integer of 1 to 5.
- the compound represented by the formula (5) is preferably a compound represented by the following formula (12) from the viewpoint of obtaining better alkali developability.
- each 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, more preferably a hydrogen atom, from the viewpoint of exhibiting better alkali developability.
- Each o' independently represents an integer of 0 to 4.
- the number of carboxyl groups r represents an integer of 5-o'.
- the number of carboxyl groups r is preferably an integer of 1 to 3 from the viewpoint of exhibiting better alkali developability.
- the number o' of R 7 is an integer of 5-r and an integer of 2-4.
- the carboxymethyl group and the carboxy group may be acid anhydrides formed by linking them together.
- the compound represented by formula (12) When the compound represented by formula (12) has two or more carboxy groups, it may be an acid anhydride formed by linking them together. In formula (12), the upper limit of the number of carboxy groups is five. When the compound represented by formula (12) has two or more carboxymethyl groups, it may be an acid anhydride formed by linking them together. In formula (12), the upper limit of the number of carboxymethyl groups is six.
- 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. . These anhydrides include, for example, 1,2-phenylene diacetic anhydride.
- 1,2-phenylenediacetic acid is preferable from the viewpoint of obtaining better alkali developability.
- the compounds (B) containing one or more of these carboxyl groups can be used singly or in admixture of two or more.
- the content of the compound (B) containing one or more carboxy groups can impart excellent alkali developability to the resin composition. It is preferably 0.01 to 35 parts by mass, more preferably 1 to 30 parts by mass, with respect to a total of 100 parts by mass of the compound (B) containing one or more and the photocuring initiator (C) described later. , 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 photocuring initiator (C) is not particularly limited, and those known in the field generally used in photocurable resin compositions can be used.
- the photocuring initiator (C) is used together with the bismaleimide compound (A) and the compound (B) containing one or more carboxyl groups for photocuring using various active energy rays.
- Examples of the photocuring initiator (C) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachloro Organic peroxides exemplified by benzoyl peroxide and di-tert-butyl-di-peroxyphthalate; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethyl Phosphine oxides such as benzoyl)-phenylphosphine oxide, benzoyl-diphenyl-phosphine oxide, and bisbenzoyl-phenylphosphine oxide; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy- 2-phenylacetophenone, 1,1-dichloroace
- a commercially available product can also be used as the photo-curing initiator (C).
- Commercially available products include, for example, IGM Resins B.I. V. Omnirad (registered trademark) 369 (trade name) manufactured by IGM Resins B.V. V. Omnirad (registered trademark) 819 (trade name) manufactured by IGM Resins B.V. V. Omnirad (registered trademark) 819DW (trade name) manufactured by IGM Resins B.V. V. Omnirad (registered trademark) 907 (trade name) manufactured by IGM Resins B.V. V. Omnirad (registered trademark) TPO (trade name) manufactured by IGM Resins B.V. V.
- the photocuring initiator (C) can be used singly or in combination of two or more.
- the photocuring initiator (C) is prepared by preparing a chloroform solution containing 0.01% by mass, and using an active energy ray containing a wavelength of 365 nm (i-line), the photocuring initiator (C) When measuring the absorbance of a chloroform solution containing 0.01% by mass, the absorbance is preferably 0.1 or more, and this photocuring initiator (C) exhibits very good absorbance. . In addition, when the absorbance of a chloroform solution containing 0.01% by mass of a photocuring initiator (C) is measured using an active energy ray having a wavelength of 405 nm (h-line), the absorbance is 0.1.
- a photocuring initiator (C) for example, when producing a printed wiring board having a high-density and high-definition wiring formation (pattern) using a direct drawing exposure method, a wavelength of 405 nm (h-line) Photoradical reaction of maleimide occurs efficiently even when an active energy ray containing is used.
- the absorbance at a wavelength of 365 nm (i-line) is more preferably 0.15 or more because a resin composition having excellent photocurability can be obtained.
- the absorbance at a wavelength of 405 nm (h-line) is more preferably 0.15 or more because a resin composition with excellent photocurability can be obtained.
- the upper limit of the absorbance at a wavelength of 365 nm (i-line) and the absorbance at a wavelength of 405 nm (h-line) is, for example, 99.9 or less.
- a compound represented by the following formula (6) is preferable as such a photocuring initiator (C).
- each R 8 independently represents a substituent represented by formula (7) below or a phenyl group.
- each R 9 independently represents a hydrogen atom or a methyl group.
- -* represents a bond with the phosphorus atom (P) in formula (6).
- the compound represented by the formula (6) For the compound represented by the formula (6), prepare a chloroform solution containing 0.01% by mass of this compound, and measure the absorbance of this chloroform solution using an active energy ray containing a wavelength of 365 nm (i-line).
- the absorbance is 0.1 or more, showing very excellent absorption of light with a wavelength of 365 nm (i-line). Therefore, this compound suitably generates radicals with respect to light with a wavelength of 365 nm (i-line).
- the absorbance is preferably 0.15 or more.
- the upper limit is, for example, 10.0 or less, and may be 5.0 or less, or 2.0 or less.
- the compound represented by formula (6) prepare a chloroform solution containing 0.01% by mass of this compound, and measure the absorbance of this chloroform solution using an active energy ray containing a wavelength of 405 nm (h-line).
- the absorbance is 0.1 or more, showing very excellent absorbency for light with a wavelength of 405 nm (h-line). Therefore, this compound suitably generates radicals with respect to light with 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, and may be 5.0 or less, or 2.0 or less.
- each R 8 independently represents a substituent represented by formula (7) or a phenyl group. At least one of R 8 is preferably a substituent represented by formula (7).
- each R 9 independently represents a hydrogen atom or a methyl group. At least one of R 9 is preferably a methyl group, and more preferably all are methyl groups.
- Examples of the compound represented by the formula (6) include acyl compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.
- acyl compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.
- phosphine oxides include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide is preferred because it has excellent light transmittance.
- These compounds can be used singly or in admixture of two or more.
- Acylphosphine oxides exhibit very excellent absorption of active energy rays including 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 preferably radically polymerized. Therefore, when used in the production of multilayer printed wiring boards in particular, it does not inhibit the photocuring reaction in the exposure step, has excellent photocurability, and can impart excellent alkali developability in the development step. It becomes possible to suitably manufacture a resin composition, a resin sheet using the same, a multilayer printed wiring board, and a semiconductor device.
- the content of the photocuring initiator (C) is the bismaleimide compound ( A), with respect to a total of 100 parts by mass of the compound (B) containing one or more carboxyl groups and the photocuring initiator (C), it is preferably 0.99 to 25 parts by mass, and 2 to 20 parts by mass. more preferably 2 to 15 parts by mass.
- the compound (B) containing one or more carboxy groups is 0.01 to 35 parts by mass, and the photocuring initiator (C) is 0.99 to 25 parts by mass.
- the compound (B) containing one or more carboxy groups is 1 to 30 parts by mass, and the photocuring initiator (C) is 2 to 20 parts by mass. More preferably, when the bismaleimide compound (A) is 60 to 96 parts by mass, the compound (B) containing one or more carboxy groups is 2 to 25 parts by mass, and the photocuring initiator (C) is 2 to 15 parts by mass. Parts by mass are more preferred.
- the resin composition of the present embodiment can contain a maleimide compound (D) (also referred to as component (D)) other than the bismaleimide compound (A) of the present embodiment, as long as the effects of the present invention are achieved. Since the bismaleimide compound (A) is extremely excellent in light transmittance, even when the maleimide compound (D) is used, the light sufficiently reaches the photocuring initiator, and the photoradical reaction of the maleimide occurs efficiently. can be photocured using an active energy ray.
- the light sufficiently reaches the photocuring initiator, and a radical reaction using radicals generated from the photocuring initiator occurs. It progresses and photocuring becomes possible also in the composition in which the maleimide compound (D) is blended.
- the maleimide compound (D) is described below.
- the maleimide compound (D) is not particularly limited as long as it is a compound other than the maleimide compound (A) and has one or more maleimide groups in the molecule.
- Specific examples include N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-anilinophenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, 6 -maleimidohexanoic acid, 4-maleimidobutyric acid, bis(4-maleimidophenyl)methane, 2,2-bis ⁇ 4-(4-maleimidophenoxy)-phenyl ⁇ propane, 4,4-diphenylmethanebismaleimide, bis(3, 5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5
- maleimide compounds represented by formula (14) examples thereof include imide compounds, maleimide compounds represented by formula (14), fluorescein-5-maleimide, prepolymers of these maleimide compounds, and prepolymers of maleimide compounds and amine compounds.
- These maleimide compounds (D) can be used singly or in admixture of two or more.
- maleimide compound represented by the following formula (13) commercially available products can be used, for example, BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd. can be mentioned.
- the maleimide compound represented by formula (14) a commercially available product can be used, and examples include MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd.
- the maleimide compound represented by the following formula (15) a commercially available product can be used, for example, MIR-5000 (trade name) manufactured by Nippon Kayaku Co., Ltd. can be mentioned.
- each R 10 independently represents a hydrogen atom or a methyl group.
- n3 represents an integer of 1 or more, preferably an integer of 1-10, more preferably an integer of 1-5.
- each R 11 independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, each l independently represents an integer of 1 to 3, and n 4 is , represents an integer from 1 to 10.
- alkyl groups having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, and neopentyl groups.
- each R 12 independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group
- each l 2 independently represents an integer of 1 to 3
- n 5 is , represents an integer from 1 to 10.
- alkyl groups having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, and neopentyl groups.
- a chloroform solution containing 1% by mass of the maleimide compound (D) is prepared in order to efficiently cause the photoradical reaction of the bismaleimide compound (A), and includes a wavelength of 365 nm (i line).
- the transmittance of this chloroform solution is measured using an active energy ray, it preferably exhibits a light transmittance of 5% or more. In this case, the transmittance is more preferably 8% or more, more preferably 10% or more.
- a chloroform solution containing 1% by mass of the maleimide compound (D) is prepared in order to efficiently cause the photoradical reaction of the bismaleimide compound (A).
- this chloroform solution When the transmittance of this chloroform solution is measured using an active energy ray containing ), it preferably exhibits a light transmittance of 5% or more.
- a maleimide compound (D) for example, when producing a printed wiring board having a high-density and high-definition wiring formation (pattern) using a direct drawing exposure method, a wavelength of 405 nm (h-line) can be used.
- the photoradical reaction of maleimide occurs efficiently even when the active energy ray containing the maleimide is used.
- the light transmittance is more preferably 8% or more, and even more preferably 10% or more, because a resin composition having excellent photocurability can be obtained.
- Examples of such a maleimide compound (D) include a maleimide compound represented by the following formula (16), a maleimide compound represented by the following formula (17), a maleimide compound represented by the following formula (24), and the like.
- a maleimide compound represented by the following formula (18) a maleimide compound represented by the following formula (19), a maleimide compound represented by the following formula (20), a maleimide compound represented by the following formula (21), 1, 6-bismaleimide-(2,2,4-trimethyl)hexane (a maleimide compound represented by the following formula (22)), a maleimide compound represented by the following formula (23), and fluorescein-5-maleimide. .
- n 6 (average) is 1 or more, preferably 1 to 21, more preferably 1 to 16 from the viewpoint of exhibiting excellent photocurability.
- the number of x is 10-35. In the above formula (17), the number of y is 10-35.
- R a 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 number of carbon atoms in the alkyl group is preferably 4 to 12, since excellent photocurability is exhibited.
- the number of carbon atoms in the alkenyl group is preferably 4 to 12, since excellent photocurability is exhibited.
- 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 preferred, and an n-octyl group is more preferred, since they exhibit excellent photocurability.
- R 3 in the bismaleimide compound (A) can be referred to.
- a 2-heptenyl group, a 2-octenyl group and a 2-nonenyl group are preferred, and a 2-octenyl group is more preferred, since they exhibit 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, more preferably a linear alkyl group because it exhibits excellent photocurability.
- the number of carbon atoms in the alkyl group is preferably 4 to 12, since excellent photocurability is exhibited.
- the number of carbon atoms in the alkenyl group is preferably 4 to 12, since excellent photocurability is exhibited.
- the alkyl group for R a can be referred to.
- an n-heptyl group, an n-octyl group, and an n-nonyl group are preferred, and an n-octyl group is more preferred, since they exhibit excellent photocurability.
- an alkenyl group for R a can be referred to.
- a 2-heptenyl group, a 2-octenyl group and a 2-nonenyl group are preferred, and a 2-octenyl group is more preferred, since 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, more preferably 3 to 14 from the viewpoint of exhibiting excellent photocurability.
- na and nb may be the same or different.
- n 7 (average) is 0.5 or more, preferably 0.8 to 10, more preferably 1 to 8 from the viewpoint of exhibiting excellent photocurability.
- n 8 represents an integer of 1 or more, preferably an integer of 1-10.
- n 9 represents an integer of 1 or more, preferably an integer of 1-10.
- each R 13 independently represents a hydrogen atom, a methyl group or an ethyl group
- R 14 each independently represents a hydrogen atom or a methyl group.
- a commercial item can also be used for the maleimide compound (D).
- maleimide compound represented by the formula (18) for example, Designer Molecules Inc. BMI-689 (trade name, formula (24) above, functional group equivalent: 346 g/eq.), and the like.
- a commercially available product such as Designer Molecules Inc. can be used.
- (DMI) BMI-1700 trade name
- a commercially available product such as Designer Molecules Inc. can be used.
- (DMI) BMI-3000 (trade name), Designer Molecules Inc.
- DMI BMI-3000J (trade name), Designer Molecules Inc.
- DI) BMI-5000 trade name
- maleimide compound represented by the formula (22) a commercially available product can be used, for example, BMI-TMH manufactured by Daiwa Kasei Kogyo Co., Ltd. can be mentioned.
- maleimide compound represented by the formula (23) a commercially available product can be used, for example, BMI-70 (trade name) manufactured by K.I. Kasei Co., Ltd. can be mentioned.
- These maleimide compounds (D) can be used singly 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 the main component, and from the viewpoint of further improving the photocurability, the bismaleimide compound ( A), with respect to a total of 100 parts by mass of the compound (B) and the photocuring initiator (C), it is preferably 1 to 70 parts by mass, more preferably 3 to 60 parts by mass, 5 to 50 parts by mass Parts by mass are more preferred.
- 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 the main component.
- it is preferably 1 to 99: 99 to 1, more preferably 5 to 95: 95 to 5, 10 to 90: 90 to 10 on a mass basis. 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 the main component, thereby further improving photocurability.
- the resin composition of the present embodiment may contain a filler (E) (also referred to as component (E)) in order to improve various properties such as coating properties and heat resistance.
- a filler (E) also referred to as component (E)
- Examples of the filler (E) include silica (e.g., natural silica, fused silica, amorphous silica, and hollow silica), aluminum compounds (e.g., boehmite, aluminum hydroxide, alumina, and aluminum nitride), boron compounds (e.g., , boron nitride), magnesium compounds (e.g. magnesium oxide and magnesium hydroxide), calcium compounds (e.g. calcium carbonate), molybdenum compounds (e.g. molybdenum oxide and zinc molybdate), barium compounds (e.g.
- silica e.g., natural silica, fused silica, amorphous silica, and hollow silica
- aluminum compounds e.g., boehmite, aluminum hydroxide, alumina, and aluminum nitride
- boron compounds e.g., , boron nitride
- magnesium compounds e.g. magnesium oxide and
- talc e.g., natural talc, and calcined talc
- mica e.g., short-fiber glass, spherical glass, fine powder glass, E-glass, T-glass, and D-glass
- silicone powder examples include fluororesin fillers, urethane resin fillers, (meth)acrylic resin fillers, polyethylene fillers, styrene-butadiene rubbers, and silicone rubbers. These fillers (E) can be used singly or in admixture of two or more.
- These fillers (E) may be surface-treated with a silane coupling agent or the like, which will be described later.
- Silica is preferable, and fused silica is more preferable, from the viewpoint of improving the heat resistance of the cured product and obtaining good coating properties.
- Specific examples of silica include SFP-130MC (trade name) manufactured by Denka Corporation, SC2050-MB (trade name), SC1050-MLE (trade name) and YA010C-MFN (trade name) manufactured by Admatechs Co., Ltd. ), and YA050C-MJA (trade name).
- the particle diameter of the filler (E) is usually 0.005 to 10 ⁇ m, preferably 0.01 to 1.0 ⁇ m, from the viewpoint of the ultraviolet light transmittance of the resin composition.
- the content of the filler (E) is, from the viewpoint of improving the light transmittance of the resin composition and the heat resistance of the cured product, the bismaleimide compound (A), the compound ( It is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and even more preferably 100 parts by mass or less with respect to a total of 100 parts by mass of B) and the photocuring initiator (C). .
- the upper limit may be 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less.
- the lower limit is 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 properties and heat resistance. It is usually 1 part by mass with respect to a total of 100 parts by mass of the initiator (C).
- silane coupling agent and wetting and dispersing agent The resin composition of the present embodiment may be used in combination with a silane coupling agent and/or a wetting and dispersing agent in order to improve the dispersibility of the filler and the adhesive strength between the polymer and/or resin and the filler. can.
- silane coupling agents are not particularly limited as long as they are silane coupling agents generally used for surface treatment of inorganic substances.
- Specific examples include 3-aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, N- ⁇ -(aminoethyl)- ⁇ -amino Propyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-3- aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, [3-(6-aminohexylamino)propyl]trimethoxysilane, and [3 Ami
- the content of the silane coupling agent is usually 0.00 parts per 100 parts by mass in total of the bismaleimide compound (A), the compound (B) and the photocuring initiator (C). 1 to 10 parts by mass.
- the wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for paints. Specific examples include DISPERBYK (registered trademark)-110 (trade name), 111 (trade name), 118 (trade name), 180 (trade name), 161 (trade name), and BYK manufactured by Big Chemie Japan Co., Ltd. (registered trademark)-W996 (trade name), W9010 (trade name), W903 (trade name) and other wetting and dispersing agents.
- wetting and dispersing agents can be used singly or in combination of two or more.
- the content of the wetting and dispersing agent is usually 0.1 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 includes the , a bismaleimide compound (A), a compound (B) containing one or more carboxyl groups, a photocuring initiator (C), and a cyanate ester compound other than the maleimide compound (D), a phenolic resin, an oxetane resin, a benzoxazine
- a bismaleimide compound (A) a compound (B) containing one or more carboxyl groups
- C photocuring initiator
- D a cyanate ester compound other than the maleimide compound
- phenolic resin an oxetane resin
- benzoxazine a benzoxazine
- Various types of compounds and resins can be included, such as compounds, epoxies, and other compounds.
- the resin composition of the present embodiment is photosensitized. and photocuring is preferred.
- These compounds and resins can be used singly or in admixture of two or more.
- the cyanate ester compound is not particularly limited as long as it is a resin having an aromatic moiety substituted with at least one cyanato group (cyanate ester group) in the molecule.
- Ar 1 represents a benzene ring, a naphthalene ring, or a single bond of two benzene rings. When there are more than one, they may be the same or different.
- Each Ra is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, or an alkoxyl group having 1 to 4 carbon atoms.
- the aromatic ring in Ra may have a substituent, and the substituents in Ar 1 and Ra can be selected at arbitrary positions.
- p represents the number of cyanato groups bonded to Ar 1 and each independently represents an integer of 1-3.
- q represents the number of Ra atoms bonded to Ar 1 , and is 4-p when Ar 1 is a benzene ring, 6-p when it is a naphthalene ring, and 8-p when two benzene rings are single bonded.
- . t represents the average number of repetitions and is an integer of 0 to 50, and the cyanate ester compound may be a mixture of compounds with different t.
- -NRN- where R represents an organic group
- the alkyl group for Ra in formula (25) may have either a linear or branched chain structure or a cyclic structure (for example, a cycloalkyl group, etc.). Further, the hydrogen atom in the alkyl group in the formula (25) 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 too.
- 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.
- alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl and 2,2-dimethylpropyl. group, cyclopentyl group, hexyl group, cyclohexyl group, trifluoromethyl group and the like.
- alkenyl groups include vinyl, (meth)allyl, isopropenyl, 1-propenyl, 2-butenyl, 3-butenyl, 1,3-butandienyl, and 2-methyl-2-propenyl. , 2-pentenyl group, and 2-hexenyl group.
- aryl groups include phenyl, xylyl, mesityl, naphthyl, phenoxyphenyl, ethylphenyl, o-, m- or p-fluorophenyl, dichlorophenyl, dicyanophenyl and trifluorophenyl. groups, methoxyphenyl groups, o-, m- or p-tolyl groups, and the like.
- alkoxyl groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy groups.
- divalent organic group having 1 to 50 carbon atoms in X of the formula (25) include methylene group, ethylene group, trimethylene group, cyclopentylene group, cyclohexylene group, trimethylcyclohexylene group, biphenylyl methylene group, dimethylmethylene-phenylene-dimethylmethylene group, fluorenediyl group, phthalidodiyl group and the like.
- a 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.
- divalent organic group having 1 to 10 nitrogen atoms in X of formula (25) include an imino group and a polyimide group.
- examples of the organic group of X in formula (25) include those having structures represented by the following formula (26) or the following formula (27).
- Ar 2 represents a benzenediyl group, a naphthalenediyl group or a biphenyldiyl group, and when u is an integer of 2 or more, they may be the same or different.
- Rb, Rc, Rf, and Rg are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or an aryl having at least one phenolic hydroxy group indicates a group.
- Rd and Re are each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, or a hydroxy group.
- . u represents an integer of 0 to 5;
- Ar 3 represents a benzenediyl group, a naphthalenediyl group or a biphenyldiyl group, and when v is an integer of 2 or more, they may be the same or different.
- Ri and Rj are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxyl group having 1 to 4 carbon atoms, a hydroxy group, a trifluoromethyl group, or an aryl group substituted with at least one cyanato group.
- v represents an integer of 0 to 5, it may be a mixture of compounds with different v.
- X in formula (25) includes a divalent group represented by the following formula.
- z represents an integer of 4-7.
- Each Rk independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- Specific examples of Ar 2 in formula (26) and Ar 3 in formula (27) include two carbon atoms represented by formula (26) or two oxygen atoms represented by formula (27), A benzenediyl group bonded to the 1,4- or 1,3-positions, two carbon atoms or two oxygen atoms at the 4,4′-positions, 2,4′-positions, 2,2′-positions, and 2,3′-positions 3,3′ or 3,4′, and two carbon atoms or two oxygen atoms are attached to the 2,6, 1,5 and 1,6 positions.
- cyanato-substituted aromatic compound represented by the formula (25) include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1- cyanato-2-,1-cyanato-3-, or 1-cyanato-4-methoxybenzene, 1-cyanato-2,3-,1-cyanato-2,4-,1-cyanato-2,5-,1 -cyanato-2,6-,1-cyanato-3,4- or 1-cyanato-3,5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, cyanatooctylbenzene, cyanatononylbenzene, 2-( 4-cyanaphenyl)-2-phenylpropane (cyanate of 4- ⁇ -cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzen
- cyanate ester compounds can be used singly or in an appropriate mixture of two or more.
- cyanate ester compound represented by the formula (25) examples include phenol novolak resins and cresol novolac resins (by a known method, phenol, alkyl-substituted phenol or halogen-substituted phenol, formalin, paraformaldehyde, etc.) formaldehyde compound in an acidic solution), trisphenol novolac resin (hydroxybenzaldehyde and phenol reacted in the presence of an acidic catalyst), fluorene novolac resin (fluorenone compound and 9,9- bis(hydroxyaryl)fluorenes in the presence of an acidic catalyst), phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins and biphenyl aralkyl resins (Ar 4 —(CH 2 Y) 2 (Ar 4 represents a phenyl group and Y represents a halogen atom.
- Ar 4 —(CH 2 OR) 2 (R represents an alkyl group) and a phenolic compound reacted in the presence of an acidic catalyst or Ar A bis(hydroxymethyl) compound represented by 4- (CH 2 OH) 2 and a phenol compound are reacted in the presence of an acidic catalyst, or an aromatic aldehyde compound, an aralkyl compound and a phenol compound are polymerized.
- phenol-modified xylene formaldehyde resin by a known method, a xylene formaldehyde resin and a phenolic compound are reacted in the presence of an acidic catalyst
- modified naphthalene formaldehyde resin by a known method, a naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound in the presence of an acidic catalyst
- a phenol-modified dicyclopentadiene resin a phenol resin having a polynaphthylene ether structure
- a known method a phenolic hydroxy group in one molecule polyhydric hydroxynaphthalene compounds having two or more polyhydric naphthalene compounds, in the presence of a basic catalyst, dehydration-condensed
- These cyanate ester compounds can be used singly or in admixture of two
- 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 includes obtaining or synthesizing a hydroxy group-containing compound having a desired skeleton, and modifying the hydroxy group by a known technique to form a cyanate.
- Methods for cyanating a hydroxy group include, for example, the methods described in Ian Hamerton, Chemistry and Technology of Cyanate Ester Resins, Blackie Academic & Professional.
- Cured products using these cyanate ester compounds have excellent properties such as glass transition temperature, low thermal expansion, and plating adhesion.
- the content of the cyanate ester compound is usually 0.00 parts per 100 parts by mass in total of the bismaleimide compound (A), the compound (B) and the photo-curing initiator (C). 01 to 40 parts by mass.
- phenolic resin generally known phenolic resins having two or more hydroxyl groups in one molecule can be used.
- phenolic resin generally known phenolic resins having two or more hydroxyl groups in one molecule can be used.
- bisphenol A type phenol resin bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolak resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type phenol resin, biphenyl Aralkyl-type phenolic resins, cresol novolac-type phenolic resins, polyfunctional phenolic resins, naphthol resins, naphthol novolak resins, polyfunctional naphthol resins, anthracene-type phenolic resins, naphthalene skeleton-modified novolac-type phenolic resins, phenol aralkyl-type phenolic resins, naphthol aral
- the content of the phenolic resin is usually from 0.01 to 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.
- oxetane resin Commonly known oxetane resins can be used. For example, oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, alkyloxetane such as 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3-di(trifluoro methyl) perfluoxetane, 2-chloromethyl oxetane, 3,3-bis(chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (manufactured by Toagosei Co., Ltd., trade name), OXT-121 (Toagosei Co., Ltd. ), trade name), and OXT-221 (manufactured by Toagosei Co., Ltd., trade name). These oxetane resin
- the content of the oxetane resin is usually from 0.01 to 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.
- benzoxazine compound As the benzoxazine compound, generally known compounds can be used as long as they are compounds having two or more dihydrobenzoxazine rings in one molecule.
- bisphenol A-type benzoxazine BA-BXZ 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
- phenolphthalein-type benzoxazine and the like can be mentioned.
- These benzoxazine compounds can be used singly 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 resins are not particularly limited, and generally known ones can be used.
- a commercially available product can also be used as the epoxy resin.
- Commercially available products include, for example, an epoxy resin (NC- 3000FH (trade name) manufactured by Nippon Kayaku Co., Ltd.) represented by the following formula (28); 4), and a naphthalene-type epoxy resin represented by the following formula (29) (HP-4710 (trade name) manufactured by DIC Corporation).
- epoxy resins can be used singly or in an appropriate mixture of two or more.
- the content of the epoxy resin is usually from 0.01 to 100 parts by mass in total of the bismaleimide compound (A), the compound (B) and the photocuring initiator (C). 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 trimethallyl isocyanurate. , and bisallyl nadimide. These compounds can be used singly 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), compound (B) and photocuring initiator (C). ⁇ 40 parts by mass.
- the resin composition of the present embodiment may contain an organic solvent, if necessary. By using an organic solvent, it is possible to adjust the viscosity during preparation of the resin composition.
- the type of organic solvent is not particularly limited as long as it can dissolve part or all of the resin in the resin composition.
- organic solvents examples 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, methyl methoxypropionate, methyl hydroxyisobutyrate, and ⁇ -butyrolactone; Polar solvents such as amides such as dimethylacetamide and dimethylformamide and non-polar solvents such as toluene, xylene, and aromatic hydrocarbons such as anisole. These organic solvents can be used singly or in admixture of two or more.
- the resin composition of the present embodiment includes various high-performance resins such as thermosetting resins, thermoplastic resins, oligomers thereof, and elastomers that have not been mentioned so far, as long as the properties of the present embodiment are not impaired.
- Molecular compounds; flame-retardant compounds not mentioned heretofore; additives and the like can also be used in combination. These are not particularly limited as long as they are commonly used.
- flame-retardant compounds include nitrogen-containing compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, phosphate compounds of phosphorus compounds, aromatic condensed phosphates, and halogen-containing condensed phosphates.
- Additives include ultraviolet absorbers, antioxidants, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, lubricants, antifoaming agents, surface modifiers, brighteners, polymerization inhibitors, thermosetting Accelerators and the like. These components can be used singly or in admixture of two or more. In the resin composition of the present embodiment, the content of other components is usually 0.00 parts per 100 parts by mass in total of the bismaleimide compound (A), the compound (B) and the photo-curing initiator (C). 1 to 10 parts by mass.
- the resin composition of the present embodiment comprises a bismaleimide compound (A), a compound (B), a photocuring initiator (C), and optionally a maleimide compound (D) other than the bismaleimide compound (A), a filling It is prepared by appropriately mixing material (E), other resins, other compounds, additives, and the like.
- the resin composition can be suitably used as a varnish for producing a resin sheet of this embodiment, which will be described later.
- the organic solvent used for preparing the varnish is not particularly limited, and specific examples thereof are as described above.
- a method for producing the resin composition includes, for example, a method in which each component described above is sequentially blended in a solvent and thoroughly stirred.
- the resin composition has excellent photocurability, good solubility in organic solvents, and excellent alkali developability.
- 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 stirrer having an appropriate stirring capacity.
- Stirring, mixing, and kneading are performed by, for example, a stirring device for dispersion such as an ultrasonic homogenizer, a device for mixing such as a triple roll, a ball mill, a bead mill, and a sand mill, and a revolution or rotation type mixing device. It can be appropriately carried out using a known device such as.
- an organic solvent can be used as necessary during the preparation of the resin composition.
- the type of organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition, and specific examples thereof are as described above.
- the resin composition can be suitably used as a varnish when producing the resin sheet of this embodiment, which will be described later.
- a varnish can be obtained by a well-known method.
- the varnish is prepared by adding 10 to 900 parts by mass of an organic solvent to 100 parts by mass of the components excluding the organic solvent in the resin composition of the present embodiment, and performing the known mixing treatment (stirring, kneading treatment, etc.). can be obtained by doing
- the resin composition can be preferably used for applications that require an insulating resin composition.
- 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 encapsulation. It can be used as a sealing material, hole-filling resin, part-embedding resin, and the like.
- the resin composition does not inhibit the photocuring reaction in the exposure step, has excellent photocurability, and can impart excellent alkali developability in the development step, so the multilayer printed wiring board It can be suitably used as an object for insulating layers, or as an object for solder resists.
- a 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 in the range of 100 to 500 nm where curing proceeds efficiently with a photopolymerization initiator or the like.
- the resin sheet of the present embodiment is a support-attached resin sheet having a support and a resin layer disposed on one or both sides of the support, wherein the resin layer contains the resin composition of the present embodiment.
- a resin sheet can be produced by coating a resin composition on a support and drying the resin composition.
- the resin layer in the resin sheet has excellent photocurability and alkali developability.
- a known support can be used, but a resin film is preferable.
- resin films include polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polyethylene naphthalate film, and polyvinyl alcohol. film, triacetyl acetate film, and the like. Among them, PET film is preferred.
- a release agent is preferably applied to the surface of the resin film so that it can be easily separated from the resin layer.
- the thickness of the resin film is preferably in the range of 5-100 ⁇ m, more preferably in the range of 10-50 ⁇ m. When the thickness is less than 5 ⁇ m, the support tends to be torn when the support is peeled off before alkali development.
- the resin film preferably has excellent transparency in order to reduce scattering of light during exposure.
- the resin layer may be protected with a protective film.
- a protective film By protecting the resin layer side with a protective film, it is possible to prevent dust from adhering to the surface of the resin layer and scratches on the surface of the resin layer.
- the protective film a film made of the same material as the resin film can be used.
- the thickness of the protective film is preferably in the range of 1-50 ⁇ m, more preferably in the range of 5-40 ⁇ m. If the thickness is less than 1 ⁇ m, the protective film tends to be difficult to handle, and if it exceeds 50 ⁇ m, it tends to be inexpensive.
- the protective film preferably has a lower adhesive strength between the resin layer and the protective film than the adhesive strength between the resin layer and the support.
- the method for producing the 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 the organic solvent. etc.
- Coating can be performed by a known method using, for example, a roll coater, comma coater, gravure coater, die coater, bar coater, lip coater, knife coater, squeeze coater, and the like. Drying can be carried out, for example, by heating in a dryer at 60 to 200° C. for 1 to 60 minutes.
- the amount of the organic solvent remaining in the resin layer is preferably 5% by mass or less with respect to the total mass of the resin layer from the viewpoint of preventing diffusion of the organic solvent in subsequent steps.
- the thickness of the resin layer is preferably 1 to 50 ⁇ m from the viewpoint of improving handleability.
- the resin sheet can be preferably used for manufacturing insulating layers of multilayer printed wiring boards.
- the multilayer printed wiring board of the present embodiment has an insulating layer and conductor layers formed on one or both sides of the insulating layer, and the insulating layer contains the resin composition of the present embodiment.
- the insulating layer can also be obtained, for example, by stacking one or more resin sheets and curing them.
- the number of laminations of each of the insulating layer and the conductor layer is not particularly limited, and the number of laminations can be appropriately set according to the intended use. Also, the order of the insulating layer and the conductor layer is not particularly limited.
- the conductor layer may be a metal foil used for various printed wiring board materials, and examples thereof include metal foils of copper, aluminum, and the like. Copper metal foils include copper foils such as rolled copper foils and electrolytic copper foils.
- the thickness of the conductor layer is usually 1-100 ⁇ m. Specifically, it can be produced by the following method.
- the resin layer side of the resin sheet is laminated on one side or both sides of the circuit board using a vacuum laminator.
- circuit substrates include glass epoxy substrates, metal substrates, ceramic substrates, silicon substrates, semiconductor sealing resin substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates.
- the circuit board means a board having a patterned conductor layer (circuit) formed on one side or both sides of the board as described above.
- a board in which one or both sides of the outermost layer of the multilayer printed wiring board is a patterned conductor layer (circuit) is also a circuit board.
- the insulating layer laminated on the multilayer printed wiring board may be an insulating layer obtained by stacking one or more resin sheets of the present embodiment and curing the resin sheet of the present embodiment,
- the insulating layer may be obtained by stacking one or more known resin sheets 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 and/or copper etching.
- the resin sheet and the circuit board are preheated as necessary to pressurize and heat the resin layer of the resin sheet. while crimping it onto the circuit board.
- a method of laminating a resin layer of a resin sheet on a circuit board under reduced pressure by a vacuum lamination method is preferably used.
- the conditions of the lamination process are, for example, a pressure bonding temperature (laminating temperature) of 50 to 140° C., a pressure of 1 to 15 kgf/cm 2 , a pressure bonding time of 5 to 300 seconds, and an air pressure of 20 mmHg or less under reduced pressure. Lamination is preferred. Moreover, the lamination process may be of a batch type or a continuous type using rolls. A vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include 2-stage build-up laminator (trade name) manufactured by Nikko Materials Co., Ltd., and the like.
- a predetermined portion of the resin layer is irradiated with active energy rays as a light source to cure the resin layer in the irradiated portion.
- the irradiation may be performed through a mask pattern, or a direct writing method for direct irradiation may be used.
- Active energy rays include, for example, ultraviolet rays, visible rays, electron beams, and X-rays.
- the wavelength of the active energy ray is, for example, in the range of 200-600 nm. When ultraviolet rays are used, the irradiation dose is about 10 to 1000 mJ/cm 2 .
- an active energy ray for example, an active energy ray containing a wavelength of 365 nm (i-line) is used. is preferred.
- an active energy ray containing a wavelength of 365 nm (i-line) is used, the dose is approximately 10 to 10,000 mJ/cm 2 .
- an active energy ray containing, for example, a wavelength of 405 nm (h-line) is used as the active energy ray. is preferred.
- the method of exposure through a mask pattern includes a contact exposure method in which the mask pattern is brought into close contact with the multilayer printed wiring board, and a non-contact exposure method in which parallel light beams are used for exposure without close contact. I don't mind. Further, when a support exists on the resin layer, exposure may be performed from above the support, or exposure may be performed after peeling off the support.
- Alkaline development process If there is no support on the resin layer, after the exposure step, the part that is not photocured (unexposed part) is removed by direct alkali development, followed by development to form a pattern of the insulating layer. can do. Further, when a support exists on the resin layer, after removing the support after the exposure step, the portion which is not photocured (unexposed portion) is removed by alkali development, followed by development. 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, it is possible to obtain a printed wiring board having a high-definition pattern.
- the developer is not particularly limited as long as it selectively elutes the unexposed portions, but tetramethylammonium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution, sodium hydroxide aqueous solution, and An alkaline developer such as an aqueous potassium hydroxide solution is used. In this embodiment, it is particularly preferable to use a tetramethylammonium hydroxide aqueous solution.
- alkaline developers can be used singly or in combination of two or more.
- alkali developing method for example, known methods such as dipping, puddle, spraying, rocking immersion, brushing, and scraping can be used. In the pattern formation of this embodiment, these developing methods may be used in combination, if necessary.
- a developing method it is preferable to use a high-pressure spray because the resolution is further improved. A spray pressure of 0.02 to 0.5 MPa is preferable when a spray method is employed.
- a post-baking process is performed to form an insulating layer (hardened material).
- the post-baking process include an ultraviolet irradiation process using a high-pressure mercury lamp, a heating process using a clean oven, and the like, and these processes can be used in combination.
- the irradiation dose can be adjusted as necessary, for example, irradiation can be performed at a dose of approximately 50 to 10,000 mJ/cm 2 .
- the heating conditions can be appropriately selected as necessary, preferably in the range of 150 to 220° C. for 20 to 180 minutes, more preferably in the range of 160 to 200° C. and 30 to 150 minutes.
- Conductor layer forming step After forming the insulating layer (hardened material), a conductor layer is formed on the surface of the insulating layer by dry plating.
- dry plating known methods such as vapor deposition, sputtering, and ion plating can be used.
- a vapor deposition method vacuum vapor deposition method
- a vapor deposition method can form a metal film on an insulating layer, for example, by placing a multilayer printed wiring board in a vacuum vessel and heating and evaporating metal.
- a multilayer printed wiring board is placed in a vacuum chamber, an inert gas such as argon is introduced, a direct current voltage is applied, and the ionized inert gas collides with the target metal, and is ejected.
- a metal film can be formed on the insulating layer from a metal.
- a conductor layer is formed by electroless plating, electrolytic plating, or the like.
- a method for subsequent pattern formation for example, a subtractive method, a semi-additive method, or the like can be used.
- the semiconductor device of this embodiment includes the resin composition of this embodiment. Specifically, it can be produced by the following method.
- a semiconductor device can be manufactured by mounting a semiconductor chip on a conductive portion of a multilayer printed wiring board.
- the conductive portion means a portion of the multilayer printed wiring board that transmits an electric signal, and the portion may be a surface or an embedded portion.
- the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.
- the method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Specifically, a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). etc.
- a semiconductor device can also be manufactured by forming an insulating layer containing a resin composition on a semiconductor chip or a substrate on which a semiconductor chip is mounted.
- the shape of the substrate on which the semiconductor chips are mounted may be wafer-like or panel-like. After formation, it can be manufactured using the same method as the multilayer printed wiring board.
- A-1 a bismaleimide compound containing a structural unit represented by the general formula (1) and maleimide groups at both ends of a molecular chain Bismaleimide compound A-1 of Synthesis Example 1 (the following formula (3) A compound represented by, a high viscosity liquid at 25 ° C.)
- a represents an integer of 1-10. It is preferable that a is an integer of 1 to 6 from the viewpoint that a more suitable viscosity can be obtained and the increase in viscosity of the varnish can be more controlled.
- n 11 represents an integer of 1 or more, preferably an integer of 1-10, more preferably an integer of 1-5.
- n 9 represents an integer of 1 or more, preferably an integer of 1-10.
- n 12 represents an integer of 1 or more, preferably an integer of 1-6.
- Sensitivity was evaluated according to the following criteria, and the evaluation results are shown in Table 1.
- Evaluation criteria ⁇ : 7 stages remaining at an exposure amount of less than 500 mJcm 2 ⁇ : 7 stages remaining at an exposure amount of 500 mJ/cm 2 or more and less than 1000 mJ/cm 2 ⁇ : 7 stages remaining at an exposure amount of 1000 mJ/cm 2 or more and less than 3000 mJ/cm 2 ⁇ : Exposure No hardening even at 3000 mJ/cm 2 or more
- the photosensitive resin composition obtained in each example and comparative example was applied onto an ultra-low roughness electrolytic copper foil (CF-T4X-SV (trade name), manufactured by Fukuda Metal Foil & Powder Co., Ltd.) having a thickness of 12 ⁇ m. After application using an applicator, it was dried at a temperature of 80° C. for 30 minutes to form a film-like photosensitive resin composition on the copper foil. The coating thickness of the photosensitive resin composition was adjusted so that the film thickness of the film-like photosensitive resin composition after drying was 20 ⁇ m.
- CF-T4X-SV ultra-low roughness electrolytic copper foil
- This film-shaped photosensitive resin composition is exposed using a light source capable of irradiating an active energy ray containing a wavelength of 405 nm (h-line) (super-high pressure mercury lamp 500 W multilight (trade name) manufactured by USHIO Co., Ltd.).
- a cured film was obtained by performing exposure at an amount of 3000 mJ/cm 2 , then curing by heating at a temperature of 180° C. for 60 minutes, and then removing the copper foil by etching.
- the obtained cured film was cut into a 6 cm ⁇ 5 mm test piece, and a tensile tester (trade name "RTG-1201" manufactured by A&D Co., Ltd.) was used at 25 ° C. at a speed of 5 mm / min.
- the tensile modulus (MPa) and elongation at break (%) were measured using
- test piece 10 cm ⁇ 5 cm.
- the dielectric constant and dielectric loss tangent at 10 GHz of the obtained test piece were measured with a cavity resonator method dielectric constant measuring device (manufactured by AET Co., Ltd.). After the measurement, the test piece was immersed in water for 24 hours to absorb water, then removed from the water, wiped off the moisture, left to stand in an environment of 25°C and 30% for one day, and then the dielectric constant and dielectric loss tangent at 10 GHz were measured again. .
- the copper foil on both sides of the copper foil laminate was removed by etching, dried at 130° C. for 30 minutes, and then the cured resin film was cut to prepare a test piece of 10 cm ⁇ 5 cm.
- the obtained test piece was immersed in water for 24 hours to absorb water, then removed from the water and wiped off, and the weight increase rate of the test piece was taken as the water absorption rate.
- the reason for this is that since it is an aromatic maleimide, it is colored, has a low transmittance, and is difficult for the active energy ray to reach. In addition, unlike aliphatic maleimides, it does not have a methylene group adjacent to the maleimide group, and does not generate radical species due to hydrogen abstraction. On the other hand, the bismaleimide compound (A), which is an aliphatic maleimide, has a high transmittance and has a methylene group adjacent to the maleimide group, so that it has good photocurability.
- Comparative Example 4 the same aliphatic maleimide was used, but since the maleimide compound has a relatively high molecular weight, the compound (B) containing one or more carboxyl groups was dissolved together with the alkaline developer. It was presumed that the maleimide compound was involved and could not be dissolved in the alkaline developer, and therefore mainly only the maleimide compound remained undissolved and was insoluble in the alkaline developer. In Comparative Example 5, it was confirmed that the water absorption rate was relatively high and the dielectric loss tangent after water absorption also increased. Therefore, the resin compositions of Examples 1 to 11 are excellent in photocurability and alkali developability, and thus have good photopatternability. It was confirmed that there was no change, that the elastic modulus was low, the insulation reliability was high, and the water absorption was low.
- the resin composition of the present embodiment is excellent in photocurability and alkali developability, it is industrially useful. Applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor sealing materials, hole-filling resins, part-embedding resins, fiber-reinforced composite materials, etc.
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Abstract
Description
例えば、特許文献2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、を含む。
ビスマレイミド化合物(A)中の式(1)で表される構成中、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。
直鎖状若しくは分枝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、イソプロピル基が挙げられる。
直鎖状若しくは分枝状のアルコキシ基としては、メトキシ基、エトキシ基、n-プロポキシ基、イソプロポキシ基が挙げられる。
本実施形態において、マレイミド基は、下記式(8)で表され、N原子が前記式(1)の分子鎖に結合している。また、前記式(1)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、4- (2,5-ジオキソテトラヒドロフラン-3-イル)-1,2,3,4-テトラヒドロナフタレン-1,2-ジカルボン酸無水物と、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。
4-(2,5-ジオキソテトラヒドロフラン-3-イル)-1,2,3,4-テトラヒドロナフタレン-1,2-ジカルボン酸無水物のモル数と、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整することで、任意のビスマレイミド化合物(A)を得ることができる。
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。
前記化合物(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。
前記式(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。
前記式(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。
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。
前記式(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、又は波長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。
炭素数1~5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、n-ブチル基、イソブチル基、sec-ブチル基、t-ブチル基、n-ペンチル基、及びネオペンチル基が挙げられる。
炭素数1~5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、n-ブチル基、イソブチル基、sec-ブチル基、t-ブチル基、n-ペンチル基、及びネオペンチル基が挙げられる。
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。
前記式(17)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。
は各々独立に水素原子又はメチル基を示す。)
前記式(16)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、前記式(16)中のn6=13.6(平均))、ケイ・アイ化成(株)社製BMI-650P(商品名、前記式(16)中のn6=8.8(平均))、ケイ・アイ化成(株)社製BMI-250P(商品名、前記式(16)中のn6=3~8(平均))、ケイ・アイ化成(株)社製CUA-4(商品名、前記式(16)中のn6=1)等が挙げられる。
前記式(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-6100(商品名、前記式(17)中のx=18、y=18)等が挙げられる。
前記式(18)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、前記式(24)、官能基当量:346g/eq.)等が挙げられる。
前記式(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-1700(商品名)が挙げられる。
前記式(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、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。
前記式(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、大和化成工業株式会社製BMI-TMHが挙げられる。
前記式(23)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/又は波長405nm(h線)を含む活性エネルギー線で露光した場合に、本実施形態の樹脂組成物が感光して、光硬化することが好ましい。
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、前記式(25)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(25)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。
前記式(26)のAr2及び式(27)のAr3の具体例としては、前記式(26)に示す2個の炭素原子、又は前記式(27)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。
前記式(26)のRb、Rc、Rd、Re、Rf及びRg、並びに前記式(27)のRi、Rjにおけるアルキル基及びアリール基は、前記式(25)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、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、キシレン、及びアニソール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。
分子量の測定条件は以下の通りである。
機種:GPC TOSOH HLC-8220GPC
カラム:Super HZM-N
溶離液:THF(テトラヒドロフラン);0.35ml/分、40℃
検出器:RI(示差屈折計)
分子量標準:ポリスチレン
[合成例1]
フッ素樹脂コーティングされた撹拌バーを装備した500mlの丸底フラスコに、100gのトルエンと33gのN-メチルピロリドンを投入した。次にPRIAMINE 1075(クローダジャパン株式会社製)80.2g(0.16mol)を加え、ついで無水メタンスルホン酸14.4g(0.16mol)をゆっくりと加え、塩を形成した。ほぼ10分間撹拌して混合し、ついで4-(2,5-ジオキソテトラヒドロフラン-3-イル)-1,2,3,4-テトラヒドロナフタレン-1,2-ジカルボン酸無水物(22.5g、0.08mol)を、撹拌された混合物にゆっくり加えた。ディーンスタークトラップとコンデンサーをフラスコに取り付けた。混合物を6時間熱して還流し、アミン末端のジイミドを形成した。この縮合からの生成水の理論量は、この時までに得られた。反応混合物は、室温以下に冷却され、無水マレイン酸の17.6g(0.19mol)がフラスコに加えられた。混合物は、さらに8時間還流され、期待された量の生成水を得た。室温に冷却された後、さらにトルエン200mlがフラスコに加えられた。次に、希釈された有機層を水(100ml×3回)で洗浄し、塩や未反応の原料を除去した。その後、溶剤を真空下で除去し、暗琥珀色液状のビスマレイミド化合物104g(収率93%、Mw=3,700)を得た(A-1)。
フッ素樹脂コーティングされた撹拌バーを装備した500mlの丸底フラスコに、110gのトルエンと36gのN-メチルピロリドンを投入した。次にPRIAMINE 1075(クローダジャパン株式会社製)90.5g(0.17mol)を加え、ついで無水メタンスルホン酸16.3g(0.17mol)をゆっくりと加え、塩を形成した。ほぼ10分間撹拌して混合し、ついで1,2,4,5-シクロヘキサンテトラカルボン酸二無水物(18.9g、0.08mol)を、撹拌された混合物にゆっくり加えた。ディーンスタークトラップとコンデンサーをフラスコに取り付けた。混合物を6時間熱して還流し、アミン末端のジイミドを形成した。この縮合からの生成水の理論量は、この時までに得られた。反応混合物は、室温以下に冷却され、無水マレイン酸19.9g(0.20mol)がフラスコに加えられた。混合物は、さらに8時間還流され、期待された量の生成水を得た。室温に冷却された後、さらにトルエン200mlがフラスコに加えられた。次に、希釈された有機層を水(100ml×3回)で洗浄し、塩や未反応の原料を除去した。その後、溶剤を真空下で除去し、琥珀色ワックス状のビスマレイミド化合物110g(収率92%、Mw=3,000)を得た(A’-3)。
(A-1)一般式(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
合成例1のビスマレイミド化合物A-1(下記式(3)で表される化合物、25℃で高粘度液体)
(A’-1)BMI-2300(ポリフェニルメタンマレイミド、下記式(30)で表される化合物、大和化成(株)製、25℃で固形)
(A’-2)BMI-3000(下記式(12)で表される化合物、DESIGNER MOLECURES Inc.製、25℃で固形)
(A’-3)比較合成例1(下記式(20)で表される化合物、、25℃で液状)
実施例1~11及び比較例1~5の樹脂組成物について、以下に示す評価を行った。その結果を表1にまとめて示した。
実施例1~11及び比較例1~5で得られた感光性樹脂組成物を銅貼積層板(住友ベークライト(株)ELC4762)上にアプリケーターで塗布して、温度80℃において30分間加熱し、膜厚20μmの塗膜を形成した。次いで、波長405nm(h線)を含む活性エネルギー線を照射可能な光源(USHIO(株)製超高圧水銀灯 USH-500BY1(商品名))を用いて、21段ステップタブレットを用いて、現像後の残存段数が7段となる露光量にて投影露光機で露光した。
以下の基準にて感度を評価し、評価結果を表1に示した。
[評価基準]
◎:露光量500mJcm2未満で7段残存
○:露光量500mJ/cm2以上1000mJ/cm2未満で7段残存
△:露光量1000mJ/cm2以上3000mJ/cm2未満で7段残存
×:露光量3000mJ/cm2以上でも硬化せず
得られたBステージ状の感光性樹脂組成物に、波長405nm(h線)を含む活性エネルギー線を照射可能な光源(USHIO(株)製超高圧水銀灯 USH-500BY1(商品名))を用いて、支持体の上から、照射量500mJ/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、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。
[評価基準]
〇: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。
△:露光部は不溶であるが、未露光部は120秒間の振とうで溶解する。
×:露光部及び未露光部共に不溶である。
先ず、厚み12μmの超低粗度電解銅箔(CF-T4X-SV(商品名)、福田金属箔粉工業株式会社製)上に各実施例及び比較例で得られた感光性樹脂組成物をアプリケーターを用いて塗布後、温度80℃において30分間乾燥させ、銅箔上にフィルム状感光性樹脂組成物を形成させた。乾燥後のフィルム状感光性樹脂組成物の膜厚は20μmとなるように感光性樹脂組成物の塗布厚みを調整した。このフィルム状感光性樹脂組成物に対して、波長405nm(h線)を含む活性エネルギー線を照射可能な光源(USHIO(株)製超高圧水銀灯 500Wマルチライト(商品名))を用いて、露光量3000mJ/cm2にて露光を行い、次いで、温度180℃において60分間加熱して硬化させた後、銅箔をエッチングによって除去することにより、硬化膜を得た。
銅箔積層体の銅箔をエッチングにより除去し、130℃で30分乾燥させた後、樹脂フィルムの硬化物を切断して10cm×5cmの試験片を作製した。得られた試験片について、空洞共振器法誘電率測定装置(株式会社エーイーティー製)にて、10GHzでの比誘電率及び誘電正接を測定した。測定後、試験片を24時間水に浸漬して吸水後、水から取り出して水分を拭き取り、25℃30%の環境に一日放置したのち、再び10GHzでの比誘電率及び誘電正接を測定した。
銅箔積層体の両面の銅箔をエッチングにより除去し、130℃で30分乾燥させた後、樹脂フィルムの硬化物を切断して5cm×5mmの試験片を作製した。得られた試験片について、動的粘弾性試験機(DMA:商品名「RSA-G2」、TAInstruments製)により測定し、tanδが最大値のときの温度をガラス転移温度として求めた。
銅箔積層体の両面の銅箔をエッチングにより除去し、130℃で30分乾燥させた後、樹脂フィルムの硬化物を切断して10cm×5cmの試験片を作製した。得られた試験片を24時間水に浸漬して吸水後、水から取り出して水分を拭き取った後、試験片の重量増加率を吸水率とした。
各組成物を、スクリーン印刷法により25μmの厚さになるようにL/S=100μm/100μmのくし型パターンが形成されたエスパネックスMシリーズ(新日鐵化学製:ベースイミド厚25μm Cu厚18μm)上に塗布し、塗膜を80℃の熱風乾燥器で60分乾燥させた。次いで、アフレックス(Grade:25N NT)(AGC株式会社製)を樹脂面に被せ、220℃で2時間加熱することによって、HAST評価用の試験基板を得た。得られた基板の電極部分をはんだによる配線接続を行い、130℃、85%RHの環境下に置き、100Vの電圧をかけ、抵抗値が1×108Ω以下となるまでの時間を測定した。
○‥100時間以上
△‥20~100時間
×‥20時間以下
比較例3では、波長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を照射したが、露光部が硬化せず、硬化物が得られなかった。この理由については、芳香族マレイミドであるため着色しており、透過率が低く、活性エネルギー線が届き難かった。また、脂肪族マレイミドと比較して、マレイミド基隣のメチレン基を有しておらず、水素引き抜きによるラジカル種が発生しないことに起因する。
一方で、脂肪族マレイミドであるビスマレイミド化合物(A)は高い透過率を有しておりマレイミド基隣のメチレン基も有していることから、光硬化性が良好である。
また、比較例4では、同じ脂肪族マレイミドを使用したが、マレイミド化合物が比較的高分子量であるため、カルボキシ基を1つ以上含む化合物(B)のアルカリ現像液への溶解に伴って一緒に巻き込まれて、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のみが溶け残り、アルカリ現像液に不溶であったと推定された。
比較例5では、吸水率が比較的高く、吸水後の誘電正接も上昇することが確認された。
よって、実施例1~11の樹脂組成物は、光硬化性及びアルカリ現像性に優れるため光パターニング性が良好であり、その硬化物の特性としては、低誘電特性かつ吸水後の誘電特性にも変化が無く、低弾性率、絶縁信頼性が高く、低吸水率を有することが確認できた。
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。R4は、各々独立に、水素原子、炭素数1~6の直鎖状若しくは分枝状のアルキル基、ハロゲン原子、ヒドロキシ基、又は炭素数1~6の直鎖状若しくは分枝状のアルコキシ基を示す。n1は、各々独立に、1~4の整数を示す。n2は、各々独立に、1~4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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| KR1020237029191A KR20230159387A (ko) | 2021-03-25 | 2021-11-04 | 수지 조성물, 수지 시트, 다층 프린트 배선판, 및 반도체 장치 |
| JP2022540934A JP7291297B2 (ja) | 2021-03-25 | 2021-11-04 | 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 |
| CN202180095270.3A CN116940617A (zh) | 2021-03-25 | 2021-11-04 | 树脂组合物、树脂片材、多层印刷配线板、及半导体装置 |
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| WO2024079924A1 (ja) * | 2022-10-14 | 2024-04-18 | 日本化薬株式会社 | 樹脂組成物、樹脂シート、多層プリント配線板、及び半導体装置 |
| 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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| KR20230072570A (ko) * | 2021-11-17 | 2023-05-25 | 삼성디스플레이 주식회사 | 감광성 수지 조성물, 이를 이용하여 제조된 표시 패널 및 이의 제조 방법 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010159402A (ja) * | 2008-12-12 | 2010-07-22 | Chisso Corp | インクジェット用インク |
| WO2018056466A1 (ja) * | 2016-09-26 | 2018-03-29 | 日立化成株式会社 | 樹脂組成物、半導体用配線層積層体及び半導体装置 |
| JP2019172782A (ja) * | 2018-03-28 | 2019-10-10 | 日立化成株式会社 | マレイミド樹脂の製造方法 |
| WO2020203834A1 (ja) * | 2019-04-02 | 2020-10-08 | 日本化薬株式会社 | ビスマレイミド化合物、それを用いた感光性樹脂組成物、その硬化物及び半導体素子 |
| WO2020262577A1 (ja) * | 2019-06-28 | 2020-12-30 | 三菱瓦斯化学株式会社 | 樹脂組成物、樹脂シート、多層プリント配線板、及び半導体装置 |
| WO2020262579A1 (ja) * | 2019-06-28 | 2020-12-30 | 三菱瓦斯化学株式会社 | 樹脂組成物、樹脂シート、多層プリント配線板、及び半導体装置 |
| JP2021025050A (ja) * | 2019-08-01 | 2021-02-22 | 積水化学工業株式会社 | 樹脂材料及び多層プリント配線板 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11124433A (ja) | 1997-10-22 | 1999-05-11 | Mitsubishi Gas Chem Co Inc | フェノールノボラック型シアン酸エステルプレポリマー |
| JP2005062450A (ja) | 2003-08-12 | 2005-03-10 | Kyocera Chemical Corp | 感光性熱硬化型樹脂組成物 |
| JP5298956B2 (ja) | 2009-03-02 | 2013-09-25 | 日立化成株式会社 | 感光性樹脂組成物、並びにこれを用いた感光性エレメント、ソルダーレジスト及びプリント配線用基板 |
| JP6379697B2 (ja) | 2014-06-05 | 2018-08-29 | Dic株式会社 | 硬化性樹脂組成物、硬化物および硬化剤 |
| HK1244833B (zh) * | 2015-03-23 | 2019-11-29 | 拓自达电线株式会社 | 树脂浸渗物、复合材料和覆铜层叠体的制造方法 |
-
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010159402A (ja) * | 2008-12-12 | 2010-07-22 | Chisso Corp | インクジェット用インク |
| WO2018056466A1 (ja) * | 2016-09-26 | 2018-03-29 | 日立化成株式会社 | 樹脂組成物、半導体用配線層積層体及び半導体装置 |
| JP2019172782A (ja) * | 2018-03-28 | 2019-10-10 | 日立化成株式会社 | マレイミド樹脂の製造方法 |
| WO2020203834A1 (ja) * | 2019-04-02 | 2020-10-08 | 日本化薬株式会社 | ビスマレイミド化合物、それを用いた感光性樹脂組成物、その硬化物及び半導体素子 |
| WO2020262577A1 (ja) * | 2019-06-28 | 2020-12-30 | 三菱瓦斯化学株式会社 | 樹脂組成物、樹脂シート、多層プリント配線板、及び半導体装置 |
| WO2020262579A1 (ja) * | 2019-06-28 | 2020-12-30 | 三菱瓦斯化学株式会社 | 樹脂組成物、樹脂シート、多層プリント配線板、及び半導体装置 |
| JP2021025050A (ja) * | 2019-08-01 | 2021-02-22 | 積水化学工業株式会社 | 樹脂材料及び多層プリント配線板 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024079924A1 (ja) * | 2022-10-14 | 2024-04-18 | 日本化薬株式会社 | 樹脂組成物、樹脂シート、多層プリント配線板、及び半導体装置 |
| 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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| KR20230159387A (ko) | 2023-11-21 |
| JP7291297B2 (ja) | 2023-06-14 |
| JPWO2022201621A1 (ja) | 2022-09-29 |
| US20240174809A1 (en) | 2024-05-30 |
| CN116940617A (zh) | 2023-10-24 |
| TW202301027A (zh) | 2023-01-01 |
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