Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
• • 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
• • 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
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
• • 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
• • 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
  • C09D133/00—Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
• • 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
  • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D153/02—Vinyl aromatic monomers and conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/002—Priming paints
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/032—Organic insulating material consisting of one material
  • H05K1/0346—Organic insulating material consisting of one material containing N
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
  • H05K1/036—Multilayers with layers of different types
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
  • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/22—Secondary treatment of printed circuits
  • H05K3/28—Applying non-metallic protective coatings
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W70/00—Package substrates; Interposers; Redistribution layers [RDL]
  • H10W70/60—Insulating or insulated package substrates; Interposers; Redistribution layers
  • H10W70/67—Insulating or insulated package substrates; Interposers; Redistribution layers characterised by their insulating layers or insulating parts
  • H10W70/69—Insulating materials thereof
  • H10W70/695—Organic materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2379/08—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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2435/00—Characterised by the use 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; Derivatives of such polymers
  • C08J2435/02—Characterised by the use of homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
  • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2479/00—Characterised by the use 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 C08J2461/00 - C08J2477/00
  • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
  • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
  • H05K2201/0203—Fillers and particles
  • H05K2201/0206—Materials
  • H05K2201/0209—Inorganic, non-metallic particles

Definitions

• This embodiment relates to a resin film, a printed wiring board, and a semiconductor package.
• Patent Document 1 which aims to provide a thermosetting resin composition that has a low dielectric tangent, low thermal expansion, and excellent wiring embedding properties and flatness, discloses a technology in which a polybutadiene-based elastomer modified with an acid anhydride is blended in a thermosetting resin composition that contains an inorganic filler and a polyimide compound having a structural unit derived from a maleimide resin having at least two N-substituted maleimide groups and a structural unit derived from a diamine compound.
• a numerical range indicated using “to” indicates a range including the numerical values before and after “to” as the minimum and maximum values, respectively.
• a numerical range of "X to Y" (X and Y are real numbers) means a numerical range of not less than X and not more than Y.
• the expression “not less than X” means X and a numerical value exceeding X.
• the expression “not more than Y” means Y and a numerical value less than Y.
• Each lower limit and upper limit of a numerical range described herein may be arbitrarily combined with the lower limit or upper limit of any other numerical range. In the numerical ranges described in this specification, the lower or upper limit of the numerical range may be replaced with values shown in the examples.
• each component may be abbreviated as component (A), component (B), etc., and other components may be abbreviated in the same manner.
• component (B) a compound that is liquid at 25° C., has a reactive group, and has a molecular weight of 1,000 or less may be referred to as “(B) a reactive liquid compound”.
• the reason why the resin film of the present embodiment can form a cured product having excellent plating properties and excellent flexibility while suppressing the generation of volatile components during heat curing is presumed to be as follows.
• the first resin composition contained in the resin layer for forming an insulating member of the resin film of this embodiment contains, as a component for improving the flexibility of the first resin composition, (B) a compound that is liquid at 25° C. and has a molecular weight of 1,000 or less.
• the (B) reactive liquid compound is a liquid component with a relatively low molecular weight, and therefore can penetrate well between the molecules of the resin component, and it is believed that the flexibility of the resin film can be improved by effectively weakening the intermolecular interaction of the resin component.
• the (B) reactive liquid compound since the (B) reactive liquid compound has a reactive group, the (B) reactive liquid compound may react with itself or with other components during the heat curing of the (A) thermosetting resin. That is, the (B) reactive liquid compound contributes to improving flexibility while suppressing volatilization by the curing reaction. Therefore, it is considered that the resin film of the present embodiment can improve flexibility while suppressing the generation of volatile components compared to the case of using an organic solvent or the like as a component for improving flexibility.
• the first resin composition contains (A) a thermosetting resin.
• the thermosetting resin (A) may be used alone or in combination of two or more kinds.
• thermosetting resins examples include epoxy resins, phenolic resins, maleimide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and melamine resins.
• the (A) thermosetting resin is preferably a maleimide resin, and more preferably one or more types selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of the maleimide resin.
• maleimide-based resins a maleimide resin having one or more N-substituted maleimide groups
• AX maleimide resin
• AX maleimide resin
• AY maleimide resin derivative
• aromatic bismaleimide resin refers to a compound having two N-substituted maleimide groups directly bonded to an aromatic ring.
• aromatic polymaleimide resin refers to a compound having three or more N-substituted maleimide groups directly bonded to an aromatic ring.
• aliphatic maleimide resin means a compound having an N-substituted maleimide group directly bonded to an aliphatic hydrocarbon.
• the maleimide resin (A1) is preferably an aromatic maleimide resin which contains a condensed ring of an aromatic ring and an aliphatic ring in its molecular structure and has two or more N-substituted maleimide groups. Moreover, the maleimide resin (A1) is more preferably an aromatic bismaleimide resin containing a condensed ring of an aromatic ring and an aliphatic ring in the molecular structure and having two N-substituted maleimide groups.
• n a11 is an integer of 0 to 4, and from the viewpoint of availability, is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
• the multiple R a11 's may be the same or different.
• the divalent group represented by X a12 in the above general formula (A2-3) and represented by general formula (A2-3-1) is as follows.
• n a17 is a number from 0 to 5. * represents a binding site.
• R a16 and R a17 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms; n a18 represents an integer of 1 to 8; * represents a bonding site.
• biphenylene group examples include a 4,2'-biphenylene group, a 4,3'-biphenylene group, a 4,4'-biphenylene group, and a 3,3'-biphenylene group. Of these, a 4,4'-biphenylene group is preferable.
• the maleimide resin derivative (AY) is preferably an aminomaleimide resin having a structural unit derived from the above-mentioned maleimide resin (AX) and a structural unit derived from a diamine compound.
• the aminomaleimide resin has a structural unit derived from a maleimide resin (AX) and a structural unit derived from a diamine compound.
• the aminomaleimide resin can be obtained, for example, by subjecting a maleimide resin (AX) to Michael addition with a diamine compound.
• the diamine compound for example, the same amine compound having at least two primary amino groups in one molecule as described in JP-A-2020-200406 can be used.
• thermosetting resins described above from the viewpoints of dielectric properties, conductor adhesion, and heat resistance, (A) thermosetting resins that contain a condensed ring of an aromatic ring and an aliphatic ring in the molecular structure and have two or more N-substituted maleimide groups are preferred.
• the reactive liquid compound (B) preferably has two or more reactive groups in one molecule, more preferably has two to five reactive groups, even more preferably has two to four reactive groups, and particularly preferably has two or three reactive groups.
• the number of reactive groups is within the above range, there is a tendency that excellent flexibility is easily obtained while volatilization during heat curing is more effectively suppressed.
• the molecular weight of the reactive liquid compound (B) is 1,000 or less, preferably 100 to 800, more preferably 150 to 600, and even more preferably 200 to 400.
• the molecular weight of the reactive liquid compound (B) is equal to or greater than the lower limit, the reactive liquid compound (B) tends to be prevented from volatilizing before the first resin composition is heat-cured.
• the molecular weight of the reactive liquid compound (B) is equal to or less than the upper limit, better flexibility tends to be obtained.
• the viscosity of the reactive liquid compound (B) at 25° C. is preferably 1 to 5,000 mPa ⁇ s, more preferably 2 to 1,000 mPa ⁇ s, and even more preferably 4 to 500 mPa ⁇ s.
• the viscosity of the (B) reactive liquid compound at 25° C. is equal to or higher than the above lower limit, the (B) reactive liquid compound tends to be easily prevented from volatilizing.
• the viscosity of the (B) reactive liquid compound at 25° C. is equal to or lower than the above upper limit, better flexibility tends to be easily obtained.
• the viscosity of the reactive liquid compound (B) at 25° C. can be measured by the above-mentioned measuring method.
• (B) reactive liquid compounds having a (meth)acryloyl group as a reactive group include (meth)acrylic acid esters such as mono(meth)acrylic acid esters, di(meth)acrylic acid esters, and trifunctional or higher (meth)acrylic acid esters.
• Examples of mono(meth)acrylic acid esters include methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, heptyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate, isooctyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate, dodecyl(meth)acrylate, lauryl(meth)acrylate, tridecyl(meth)acrylate, stearyl(meth)acrylate, ethyl ...
• Examples include allyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
• acrylate polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol F di(meth)acrylate, dioxane glycol di(meth)acrylate, and the like.
• the (meth)acrylic acid ester is preferably a di(meth)acrylic acid ester.
• a diacrylic acid ester represented by the following general formula (B-1) or a dimethacrylic acid ester represented by the following general formula (B-2) is preferable, and a dimethacrylic acid ester represented by the following general formula (B-2) is more preferable.
• R b1 is an alkylene group having 1 to 20 carbon atoms.
• alkylene group having 1 to 20 carbon atoms examples include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tetradecylene group, a pentadecylene group, etc.
• the alkylene group may be linear, branched, or cyclic, but is preferably linear.
• the content of the (B) reactive liquid compound is not particularly limited, but is preferably 5 to 60 mass%, more preferably 8 to 40 mass%, even more preferably 10 to 30 mass%, and particularly preferably 15 to 25 mass%, relative to the total amount (100 mass%) of the resin components in the first resin composition.
• the content of the (B) reactive liquid compound is not particularly limited, but is preferably 0.5 to 20 mass%, more preferably 1.0 to 15 mass%, and even more preferably 1.5 to 10 mass%, relative to the total solid content (100 mass%) of the first resin composition.
• the first resin composition tends to easily obtain superior low thermal expansion properties, heat resistance, and flame retardancy.
• the resin film of this embodiment has excellent flexibility, it is possible to increase the content of the inorganic filler (C) and further improve the low thermal expansion property.
• the inorganic filler (C) may be used alone or in combination of two or more kinds.
• Examples of the inorganic filler (C) include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, silicon carbide, etc.
• silica, alumina, mica, and talc are preferred, and silica and alumina are more preferred.
• silica examples include precipitated silica produced by a wet method and having a high water content, and dry method silica produced by a dry method and containing almost no bound water, etc. Dry method silica further includes crushed silica, fumed silica, fused silica, etc., depending on the production method.
• the inorganic filler (C) may be surface-treated with a surface treatment agent such as a silane coupling agent.
• the average particle size of the inorganic filler (C) is not particularly limited, but from the viewpoints of dispersibility and fine wiring property of the inorganic filler (C), it is preferably 0.01 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m, even more preferably 0.2 to 1 ⁇ m, and particularly preferably 0.3 to 0.8 ⁇ m.
• the average particle size refers to the particle size at a point corresponding to 50% volume when a cumulative frequency distribution curve of particle sizes is calculated with the total volume of the particles being 100%.
• the average particle size can be measured, for example, by a particle size distribution measuring device using a laser diffraction scattering method.
• the shape of the (C) inorganic filler may be, for example, spherical or crushed, with spherical being preferred.
• the content of the inorganic filler (C) is not particularly limited, but is preferably 20 to 95 mass%, more preferably 40 to 90 mass%, and even more preferably 60 to 80 mass%, relative to the total solid content (100 mass%) of the first resin composition.
• the content of the inorganic filler (C) is equal to or greater than the lower limit, the low thermal expansion, heat resistance, and flame retardancy tend to be improved.
• the content of the inorganic filler (C) is equal to or less than the upper limit, the moldability and conductor adhesion tend to be improved.
• conjugated diene polymer (D1)) means a polymer of a conjugated diene compound. By containing the conjugated diene polymer (D1), the first resin composition tends to have better dielectric properties.
• the conjugated diene polymer (D1) may be used alone or in combination of two or more kinds.
• conjugated diene polymer (D1) a conjugated diene polymer having a plurality of vinyl groups in the side chain is preferred from the viewpoints of compatibility with other resins and dielectric properties.
• the number of vinyl groups that the conjugated diene polymer (D1) has in one molecule is not particularly limited, but from the viewpoints of compatibility with other resins and dielectric properties, it is preferably 3 or more, more preferably 5 or more, and even more preferably 10 or more.
• the upper limit of the number of vinyl groups that the conjugated diene polymer (D1) has in one molecule is not particularly limited, and may be 100 or less, 80 or less, or 60 or less.
• Examples of the conjugated diene polymer (D1) include polybutadiene having a 1,2-vinyl group, butadiene-styrene copolymer having a 1,2-vinyl group, polyisoprene having a 1,2-vinyl group, etc.
• polybutadiene having a 1,2-vinyl group and butadiene-styrene copolymer having a 1,2-vinyl group are preferred, and polybutadiene having a 1,2-vinyl group is more preferred.
• a polybutadiene homopolymer having a 1,2-vinyl group is preferred.
• the 1,2-vinyl group derived from butadiene contained in the conjugated diene polymer (D1) is a vinyl group contained in a structural unit derived from butadiene represented by the following formula (D1-1).
• the content of the structural unit having a 1,2-vinyl group with respect to all structural units derived from butadiene constituting the polybutadiene [hereinafter, may be referred to as the "vinyl group content"] is not particularly limited, but from the viewpoints of compatibility with other resins, dielectric properties and heat resistance, it is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 85 mol% or more.
• the upper limit of the vinyl group content there is no particular limit to the upper limit of the vinyl group content, and it may be 100 mol% or less, 95 mol% or less, or 90 mol% or less.
• the structural unit having a 1,2-vinyl group a structural unit derived from butadiene represented by the above formula (D1-1) is preferable.
• the polybutadiene having a 1,2-vinyl group is preferably a 1,2-polybutadiene homopolymer.
• the modified conjugated diene polymer (D2) is a polymer obtained by modifying a conjugated diene polymer.
• the first resin composition tends to have good heat resistance and low thermal expansion properties, while also being more easily able to obtain excellent dielectric properties.
• the modified conjugated diene polymer (D2) may be used alone or in combination of two or more kinds.
• conjugated diene polymer (d1) for example, the conjugated diene polymer having a vinyl group in the side chain explained above as the conjugated diene polymer (D1) can be used, and the same applies to the preferred embodiments.
• the conjugated diene polymer (d1) may be used alone or in combination of two or more kinds.
• X d1 is a divalent group obtained by removing two N-substituted maleimide groups from the maleimide resin (d2), * d1 is a bond site to a carbon atom derived from a vinyl group that the conjugated diene polymer (d1) has in a side chain, and * d2 is a bond site to another atom.
• the number average molecular weight of the modified conjugated diene polymer (D2) is not particularly limited, but from the viewpoints of compatibility with other resins, dielectric properties, low thermal expansion, and heat resistance, it is preferably 1,100 to 6,000, more preferably 1,300 to 4,000, and even more preferably 1,500 to 2,000.
• the reaction temperature of the above reaction is preferably 70 to 120°C, more preferably 80 to 110°C, and even more preferably 85 to 105°C, from the viewpoints of workability and suppression of gelation of the product during the reaction.
• the reaction time of the above reaction is preferably 0.5 to 15 hours, more preferably 1 to 10 hours, and even more preferably 3 to 7 hours, from the viewpoints of productivity and allowing the reaction to proceed sufficiently.
• these reaction conditions can be appropriately adjusted depending on the types of raw materials used, and are not particularly limited.
• R d1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
• R d2 is an alkyl group having 1 to 5 carbon atoms
• n d1 is an integer of 0 to 5.
• Examples of the styrene-based elastomer (D3) include hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene-styrene block copolymers, and styrene-maleic anhydride copolymers.
• Examples of hydrogenated styrene-butadiene-styrene block copolymers include SEBS obtained by completely hydrogenating the carbon-carbon double bonds in the butadiene block, and SBBS obtained by partially hydrogenating the carbon-carbon double bonds at the 1,2-bond sites in the butadiene block.
• the completely hydrogenated SEBS usually means 90% or more, 95% or more, 99% or more, or 100% of the total carbon-carbon double bonds.
• the partial hydrogenation rate in SBBS is, for example, 60 to 85% of the total carbon-carbon double bonds.
• the hydrogenated styrene-isoprene-styrene block copolymer is obtained as SEPS by hydrogenating the polyisoprene portion.
• SEBS and SEPS are preferred, and SEBS is more preferred.
• the content of structural units derived from styrene-based compounds (hereinafter sometimes referred to as the "styrene content”) is not particularly limited, but is preferably 5 to 60% by mass, more preferably 7 to 40% by mass, and even more preferably 10 to 20% by mass.
• the melt flow rate (MFR) of the styrene-based elastomer (D3) is not particularly limited, but is preferably 0.1 to 20 g/10 min, more preferably 1 to 10 g/10 min, and even more preferably 3 to 7 g/10 min, measured under conditions of 230°C and a load of 2.16 kgf (21.2 N).
• the number average molecular weight of the styrene-based elastomer (D3) is not particularly limited, but is preferably 10,000 to 500,000, more preferably 50,000 to 350,000, and even more preferably 100,000 to 200,000.
• Examples of the (D) elastomer other than the conjugated diene polymer (D1), modified conjugated diene polymer (D2), and styrene-based elastomer (D3) include polyolefin-based resins, polyphenylene ether-based resins, polyester-based resins, polyamide-based resins, polyacrylic-based resins, etc.
• the content of the elastomer (D) is not particularly limited, but is preferably 10 to 80 mass%, more preferably 30 to 70 mass%, and even more preferably 50 to 60 mass%, relative to the total amount (100 mass%) of the resin components in the first resin composition.
• the content of the elastomer (D) is equal to or greater than the lower limit, better dielectric properties tend to be obtained.
• the content of the elastomer (D) is equal to or less than the upper limit, better heat resistance tends to be obtained.
• the total content of one or more selected from the group consisting of conjugated diene polymer (D1), modified conjugated diene polymer (D2) and styrene-based elastomer (D3) is not particularly limited, but from the viewpoint of dielectric properties and conductor adhesion, it is preferably 60 to 100 mass%, more preferably 80 to 100 mass%, and even more preferably 90 to 100 mass% relative to the total amount (100 mass%) of the elastomer (D).
• the (E) curing accelerator contains a radical polymerization initiator.
• the radical polymerization initiator acts as a polymerization initiator for radical polymerization, and decomposes into a compound having an unpaired electron when exposed to energy such as light or heat.
• Examples of the radical polymerization initiator include organic peroxides, inorganic peroxides, azo compounds, etc., which will be described later, and organic peroxides are preferred.
• curing accelerator (E) examples include acid catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, pyridine, tributylamine, and dicyandiamide; imidazole compounds such as methylimidazole, phenylimidazole, and 1-cyanoethyl-2-phenylimidazole; isocyanate mask imidazole compounds such as an addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole; tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; dicumyl peroxide, 2,5-dimethyl-2,5-bis(2,4-dimethylphenyl)-2,5-diisocyanate; Examples of peroxides include organic peroxides such as (t-butylperoxy)hexyne-3, 2,5-dimethyl-2,
• imidazole compounds from the viewpoints of the curing acceleration effect and storage stability, imidazole compounds, isocyanate-masked imidazole compounds, organic peroxides, and carboxylates are preferred, and isocyanate-masked imidazole compounds and organic peroxides are more preferred.
• the content of the curing accelerator (E) is not particularly limited, but is preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 4 to 8 parts by mass relative to the total amount (100 parts by mass) of the thermosetting resin (A) and the reactive liquid compound (B).
• the content of the curing accelerator (E) is equal to or more than the lower limit, a sufficient curing acceleration effect tends to be easily obtained, and when the content of the curing accelerator (E) is equal to or less than the upper limit, storage stability tends to be improved.
• the primer-layer-forming resin layer of the resin film of the present embodiment contains the second resin composition, and is preferably formed in a layer shape from the second resin composition.
• Drilling is a process in which holes are drilled in a circuit board on which an insulating layer and a primer layer have been formed, using a method such as a drill, a laser, plasma, or a combination of these, to form via holes, through holes, etc.
• a method such as a drill, a laser, plasma, or a combination of these, to form via holes, through holes, etc.
• lasers used for drilling include a carbon dioxide laser, a YAG laser, a UV laser, and an excimer laser.
• Comparative Example 1 A resin film with a one-sided PET film (resin film thickness: 100 ⁇ m) in which a resin layer for forming an insulating member was formed on one side of a PET film was produced in the same manner as in Example 1, except that a resin layer for forming a primer layer was not formed in Example 1. Using the resin film with a one-sided PET film, a resin plate with copper foils on both sides and a laminate with cured resin layers on both sides were produced in the same manner as in Example 1.
• the resin plate with copper foil on both sides obtained in each example was immersed in a 10% by mass solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Ltd.), which is a copper etching solution, to remove the copper foil.
• the obtained resin plate was cut into a width of 0.4 mm and a length of 20 mm, and then dried at 105°C for 1 hour to prepare a test piece.
• the test piece was clamped at both ends in the long side direction of the test piece with upper and lower grippers with a gap of 10 mm between the grippers.
• the copper foil was removed by immersing the resin plate with copper foil on both sides obtained in each example in a 10% by mass solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Ltd.), which is a copper etching solution.
• the obtained resin plate was cut into a width of 10 mm and a length of 40 mm, and then dried at 105°C for 1 hour to obtain a test piece.
• the test piece was clamped at both ends in the long side direction of the test piece with upper and lower grippers with a gap of 20 mm between the grippers.
• the plate was treated with a reducing solution (manufactured by Atotech Japan, product name "Reducer Neoganth WA”) at 30°C for 5 minutes. Then, the plate was placed in a chemical copper solution (manufactured by Atotech Japan, product name “Basic Printganth MSK-DK”), and electroless plating was performed until the plating thickness on the resin cured layer reached 0.5 ⁇ m. After electroless plating, the plate was baked at 120°C for 15 minutes to relieve the stress remaining in the plating film and remove the remaining hydrogen gas. Next, electrolytic plating was further performed on the electroless plated surface until the plating thickness on the cured resin layer reached 20 ⁇ m, forming a plated copper layer.
• a reducing solution manufactured by Atotech Japan, product name "Reducer Neoganth WA
• a chemical copper solution manufactured by Atotech Japan, product name "Basic Printganth MSK-DK”
• electroless plating was performed until the plating thickness on the resin cured layer reached
• the resin films of Examples 1 and 2 of this embodiment have excellent flexibility, and the cured products have excellent plating properties. Furthermore, the resin films of Examples 1 and 2 have a mass loss rate of 1.0 mass% or less at 170°C, which indicates that the generation of volatile components during heat curing is suppressed. On the other hand, the resin film of Comparative Example 1 has poor plating properties.

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• 2023
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