CN116589826A - Resin composition - Google Patents

Resin composition Download PDF

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Publication number
CN116589826A
CN116589826A CN202310095132.6A CN202310095132A CN116589826A CN 116589826 A CN116589826 A CN 116589826A CN 202310095132 A CN202310095132 A CN 202310095132A CN 116589826 A CN116589826 A CN 116589826A
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China
Prior art keywords
resin composition
compound
mass
resin
component
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CN202310095132.6A
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Chinese (zh)
Inventor
川合贤司
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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Publication of CN116589826A publication Critical patent/CN116589826A/en
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    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • B32B15/082—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 vinyl resins; comprising acrylic resins
    • 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
    • B32B15/092—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 epoxy resins
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • 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
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C09D125/00—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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • 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
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C09D179/085—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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

The subject of the invention is to provide: a resin composition which can suppress the dielectric loss tangent to a low value even in a high-temperature environment and which is excellent in crack resistance after a stain-removing treatment. The solution of the present invention is a resin composition comprising (A) a copolymer of a divinyl aromatic compound and styrene, (B) an epoxy resin, and (C) an active ester compound, wherein the component (A) contains a structural unit represented by the following formula (a 1) derived from the divinyl aromatic compound (a), and has a weight average molecular weight of 40000 or more.(wherein R is 1 Represents an aromatic hydrocarbon group having 6 to 30 carbon atoms. ).

Description

Resin composition
Technical Field
The present invention relates to a resin composition comprising an epoxy resin. Further, the present invention relates to a cured product, a sheet-like laminate, a resin sheet, a printed wiring board, and a semiconductor device each obtained using the resin composition.
Background
As a technique for manufacturing a printed wiring board, a stack (build up) method of manufacturing a printed wiring board in which insulating layers and conductor layers are alternately stacked is known. In the manufacturing method based on the stacking method, generally, the insulating layer is formed by curing a resin composition. As an insulating layer of a printed wiring board of a semiconductor device, it is required to exhibit good dielectric characteristics (low dielectric constant, low dielectric loss tangent) in order to suppress transmission loss during operation in a high-frequency environment.
As a resin composition forming a cured product exhibiting good dielectric characteristics, for example, a resin composition containing an active ester compound as a curing agent for an epoxy resin is reported in patent document 1, and a resin composition containing a specific copolymer of divinylbenzene and styrene is reported in patent document 2.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2009-235165
Patent document 2: international publication No. 2018/181842.
Disclosure of Invention
Problems to be solved by the invention
The resin composition containing the active ester compound as a curing agent as described in patent document 1 can form a cured product having excellent dielectric characteristics as compared with the case of using a normal phenol curing agent, but on the other hand, tends to easily generate cracks after the stain removal treatment. In addition, it has been found that, when a semiconductor device is exposed to a high-temperature environment, such as during operation in a high-frequency environment, even if a material exhibiting good dielectric characteristics in a room-temperature environment, the dielectric characteristics (particularly dielectric loss tangent) may be deteriorated in a high-temperature environment, and the desired dielectric characteristics may not be achieved in an actual use environment.
The subject of the invention is to provide: a resin composition which can be obtained as a cured product having a low dielectric loss tangent even in a high-temperature environment and excellent crack resistance after a stain-removing treatment; and a cured product, a sheet-like laminate, a resin sheet, a printed wiring board, and a semiconductor device each obtained using the resin composition.
Means for solving the problems
As a result of intensive studies to achieve the object of the present invention, the inventors have unexpectedly found that a cured product which can suppress the dielectric loss tangent to a low value even in a high-temperature environment and can suppress the occurrence of cracks after the desmear treatment can be obtained by using an epoxy resin and an active ester compound as components of a resin composition and a copolymer containing a divinyl aromatic compound and styrene, and have completed the present invention.
That is, the present invention includes the following;
[1] a resin composition comprising (A) a copolymer of a divinyl aromatic compound and styrene, (B) an epoxy resin, and (C) an active ester compound,
(A) The component (a) contains a structural unit represented by the following formula (a 1) derived from a divinyl aromatic compound (a) and has a weight average molecular weight of 40000 or more,
[ chemical formula 1]
(wherein R is 1 Represents an aromatic hydrocarbon group having 6 to 30 carbon atoms. )
[2] The resin composition according to the above [1], wherein the component (C) has a carbon-carbon double bond;
[3]above [1]]Or [2]]The resin composition is characterized in that the sum of the values obtained by dividing the mass of the nonvolatile component of the component (B) by the epoxy equivalent is denoted as W B And the sum of the mass of the nonvolatile component (C) divided by the equivalent weight of the active ester group is denoted as W C At the time W C /W B Is 1.0 or more;
[4] the resin composition according to any one of the above [1] to [3], further comprising (D) an inorganic filler;
[5] the resin composition according to any one of [1] to [4], further comprising (E) a radical polymerizable compound;
[6] the resin composition according to any one of [1] to [5] above, which is used for forming an interlayer insulating layer of a printed wiring board;
[7] the resin composition according to any one of the above [1] to [6], wherein the component (A) contains a structural unit derived from a monovinylaromatic compound (c) other than styrene in addition to each structural unit derived from the divinylaromatic compound (a) and the styrene (b), respectively;
[8] the resin composition according to any one of the above [1] to [7], wherein when the total of the structural unit derived from the divinylaromatic compound (a), the structural unit derived from the styrene (b) and the structural unit derived from the monovinylaromatic compound (c) other than styrene is 100 mol%,
The structural unit derived from the divinyl aromatic compound (a) is 2 mol% or more and less than 95 mol%;
[9] the resin composition according to any one of the above [1] to [8], wherein the component (A) contains at least any one terminal group represented by the following formula (t 1), (t 2) or (t 3) at the terminal of the copolymer;
[ chemical formula 2]
(wherein R is 2 Represents an aromatic hydrocarbon group having 6 to 30 carbon atoms. Z is Z 1 Represents a vinyl group, a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. * The binding site to the main chain is indicated, and the meaning is the same hereinafter. )
[ chemical formula 3]
(wherein R is 3 R is R 4 Each independently represents an aromatic hydrocarbon group having 6 to 30 carbon atoms. Z is Z 3 Z is as follows 4 Each independently represents a vinyl group, a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. )
[ chemical formula 4]
(wherein R is 5 Represents an aromatic hydrocarbon group having 6 to 30 carbon atoms. Z is Z 5 Represents a vinyl group, a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. ) [10]Above [1]]～[9]The tree of any one ofIn the fat composition, when the total of the structural units derived from the divinylaromatic compound (a), the structural units derived from the styrene (b) and the structural units derived from the monovinylaromatic compound (c) other than styrene is set to 100 mol% in the component (A),
The total of the terminal groups represented by the formula (a 1), the formulas (t 1), (t 2) and (t 3) is in the range of 2 mol% to 80 mol%;
[11] the cured product of the resin composition according to any one of the above [1] to [10 ];
[12] a sheet-like laminate comprising the resin composition according to any one of [1] to [10 ];
[13] a resin sheet having a support and a resin composition layer formed of the resin composition according to any one of [1] to [10] provided on the support;
[14] a printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [10 ]; [15] a semiconductor device comprising the printed wiring board according to [14 ].
ADVANTAGEOUS EFFECTS OF INVENTION
By the present invention, it is possible to provide: a resin composition which can provide a cured product having a low dielectric loss tangent even in a high-temperature environment and excellent crack resistance after a stain-removing treatment; a cured product of the resin composition; a sheet-like laminate and a resin sheet each comprising the resin composition; and a printed wiring board and a semiconductor device comprising a cured product of the resin composition.
Detailed Description
The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and may be arbitrarily modified and implemented within the scope not exceeding the scope of the claims and their equivalents.
In the following description, unless otherwise specified, the amounts of the respective components are the amounts of nonvolatile components. In the following description, unless otherwise specified, the term "nonvolatile components in the resin composition" refers to components other than the inorganic filler (D) among the nonvolatile components contained in the resin composition, unless otherwise specified, and the term "resin components" may be included in the inorganic filler (D).
< resin composition >
The resin composition of the present invention comprises (A) a copolymer of a divinyl aromatic compound and styrene, (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, a cured product having a low dielectric loss tangent and excellent crack resistance after the stain removal treatment can be obtained even in a high-temperature environment such as 90 ℃. In the present invention, a cured product having excellent peel strength between an insulating layer and a plated conductor layer (also referred to simply as "plated peel strength" in this specification) can be obtained, and a cured product having a low dielectric loss tangent at room temperature or normal temperature region such as 23 ℃ and a low relative dielectric constant at any of room temperature or normal temperature region such as 23 ℃ and high temperature environment such as 90 ℃ can be obtained.
The resin composition of the present invention may further contain optional components in addition to the copolymer of (a) a divinylaromatic compound and styrene, (B) an epoxy resin, and (C) an active ester compound. Examples of the optional components include (D) an inorganic filler, (E) a radical polymerizable compound, (F) another curing agent, (G) a curing accelerator, (H) another additive, and (K) an organic solvent. In the present specification, the components (a) to (K) are sometimes referred to as "(a) component", "(B) component", and the like, respectively. The components contained in the resin composition will be described in detail below.
Copolymer of (A) a divinylaromatic compound and styrene
(A) The copolymer of a divinylaromatic compound and styrene contains a structural unit represented by the following formula (a 1) derived from the divinylaromatic compound (a) and has a weight average molecular weight of 40000 or more,
[ chemical formula 5]
(wherein R is 1 Represents an aromatic hydrocarbon group having 6 to 30 carbon atoms).
In the present specification, R is represented by formula (a 1) 1 The aromatic hydrocarbon group of (a) may be a condensed aromatic hydrocarbon group, and for example, may have a structure in which a plurality of aromatic hydrocarbon groups such as biphenyl are linked by a single bond. At R as 1 In the aromatic hydrocarbon group of (a), the main chain relative to the repeating unit shown in the formula (a 1), namely, -CH 2 The substitution position of the vinyl group represented by the formula (a 1) with respect to-CH-is not particularly limited, and may be an ortho-position, a meta-position, a para-position, or at least any of these positional isomers, preferably a meta-position, a para-position, or at least any of these positional isomers. As R 1 The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 12, still more preferably 6 to 10.
The structural unit referred to in this specification includes a repeating unit present in the main chain of the copolymer and a unit or a terminal group present in a terminal or side chain.
(A) The component (c) is preferably a polyfunctional vinyl aromatic copolymer containing not only each structural unit derived from the divinyl aromatic compound (a) and the styrene (b), but also structural units derived from the monovinyl aromatic compound (c) other than styrene.
As the structural unit derived from the monovinylaromatic compound (c) other than styrene, for example, R shown in the above formula (a 1) is preferable 1 Namely an aromatic hydrocarbon group having 6 to 30 carbon atoms, as R 1 R in the formula (a 1) may be suitably used 1 The above matters are described. The structural unit derived from (c) may be a structural unit having, for example, 1 to 2 substituents on the aromatic ring, and examples of the substituent include a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably a saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms.
(A) In the component (a), the total of the structural unit derived from the divinylaromatic compound (a), the structural unit derived from the styrene (b) and the structural unit derived from the monovinylaromatic compound (c) other than styrene is preferably 2 mol% or more and less than 95 mol%, more preferably 10 mol% or more and 75 mol% or less, and still more preferably 15 mol% or more and 70 mol% or less, based on 100 mol%.
In the present specification, the compounds (monomers) of (a) to (c) may be abbreviated as "(a)", "(b)", and "(c)", respectively. The structural unit derived from the divinylaromatic compound (a) may have various structures such as a product obtained by reacting only 1 of the two vinyl groups, a product obtained by reacting 2 of the two vinyl groups, or the like, and, when the total of the structural units derived from (a), (b), and (c) is 100 mol%, it is preferable that the structural unit contains 2 to 80 mol% of the repeating unit (structural unit) obtained by reacting only 1 of the vinyl groups represented by the formula (a 1), more preferably 5 to 70 mol%, still more preferably 10 to 60 mol%, and particularly preferably 15 to 50 mol%.
(A) In the component (a), when the total of the structural unit derived from the divinylaromatic compound (a), the structural unit derived from the styrene (b) and the structural unit derived from the monovinylaromatic compound (c) other than styrene is set to 100 mol%, the total of the structural unit derived from the styrene (b) and the structural unit derived from the monovinylaromatic compound (c) other than styrene is preferably 5 mol% or more and less than 98 mol%, more preferably 25 mol% or more and 90 mol% or less, and still more preferably 30 mol% or more and 85 mol% or less.
(A) When the component (c 1) contains a structural unit (c 1) derived from a monovinylaromatic compound (c) other than styrene, the ratio of the structural unit (b 1) derived from styrene (b) to the structural unit (c 1) derived from the monovinylaromatic compound (c) other than styrene, on a molar basis, is (b 1): (c 1) is preferably 99: 1-20: 80, more preferably 98: 2-30: 70.
in the present specification, the term "total of the structural units derived from the divinylaromatic compound (a), the structural units derived from the styrene (b), and the structural units derived from the monovinylaromatic compound (c) other than styrene" and the term "total of the structural units derived from the divinylaromatic compound (a), the structural units derived from the styrene (b), and the structural units derived from the monovinylaromatic compound (c) other than styrene" when the component (a) does not contain the structural units derived from the monovinylaromatic compound (c) other than styrene (also referred to as "structural unit (c 1)") as an optional monomer means "total of the structural units derived from the divinylaromatic compound (a) and the structural units derived from the styrene (b)", and the term "total of the structural units derived from the divinylaromatic compound (a), the structural units derived from the monovinylaromatic compound (c) other than styrene" when the structural unit (c 1) is contained. In the present specification, "divinyl aromatic compound (a), styrene (b) and optional monovinyl aromatic compound (c) other than styrene" and the descriptions based thereon refer to "divinyl aromatic compound (a) and styrene (b)" when component (a) does not contain an optional structural unit (c 1), and "divinyl aromatic compound (a), styrene (b) and monovinyl aromatic compound (c) other than styrene" when component (a) contains a structural unit (c 1).
In the present specification, "the sum of the structural units derived from the styrene (b) and the structural units derived from the monovinylaromatic compound (c) other than styrene" and the description based thereon are also the same, and refer to "the structural unit derived from the styrene (b)" when the component (a) does not contain the optional structural unit (c 1), and the sum of the structural unit derived from the styrene (b) and the structural unit derived from the monovinylaromatic compound (c) other than styrene "when the component (a) contains the structural unit (c 1). In the present specification, "styrene (b) and an optional monovinylaromatic compound (c) other than styrene" and the description based thereon refer to "styrene (b)" when component (a) does not contain an optional structural unit (c 1) and "styrene (b) and a monovinylaromatic compound (c) other than styrene" when component (a) contains a structural unit (c 1).
(A) The component (c) may contain not only each structural unit derived from the divinylaromatic compound (a) and the styrene (b), and each structural unit derived from the optional monovinylaromatic compound (c) other than styrene, but also structural units derived from the monomer (d) other than these components (a), (b) and (c). (A) When the component (d 1) is contained as the constituent unit derived from the monomer (d), the constituent unit derived from the divinyl aromatic compound (a), the constituent unit derived from the styrene (b), the constituent unit derived from the monovinyl aromatic compound (c) other than styrene, and the constituent unit (d 1) are each preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, still more preferably 80 mol% or more, and particularly preferably 90 mol% or more, based on 100 mol% of the total of the constituent units derived from (a), (b), and optionally (c).
(A) The component (c) preferably contains at least one terminal group represented by the following formula (t 1), (t 2) or (t 3) at the terminal of the copolymer. The divinylaromatic compound (a), the styrene (b) and the optional monovinylaromatic compound (c) other than styrene are polymerized to form not only a repeating unit (structural unit) comprising the (a 1) but also terminal groups represented by the following formulae (t 1), (t 2) and (t 3), respectively,
[ chemical formula 6]
(wherein R is 2 Represents an aromatic hydrocarbon group having 6 to 30 carbon atoms. Z is Z 1 Represents a vinyl group, a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. * The binding site to the main chain is indicated, and the meaning is the same hereinafter. )
[ chemical formula 7]
(wherein R is 3 R is R 4 Each independently represents an aromatic hydrocarbon group having 6 to 30 carbon atoms. Z is Z 3 Z is as follows 4 Each independently represents a vinyl group, a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. )
[ chemical formula 8]
(wherein R is 5 Represents an aromatic hydrocarbon group having 6 to 30 carbon atoms. Z is Z 5 Represents a vinyl group, a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. ).
(A) In the component (a), when the total of the structural unit derived from the divinylaromatic compound (a), the structural unit derived from the styrene (b) and the structural unit derived from the monovinylaromatic compound (c) other than styrene is 100 mol%, the total of the structural unit represented by the formula (a 1) and the terminal groups represented by the formulas (t 1), (t 2) and (t 3) is, for example, in the range of 2 to 80 mol%, preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and particularly preferably 15 to 65 mol%. This represents the vinyl and terminal group content of the multifunctional vinyl aromatic copolymer.
(A) The amount of the terminal group (tv) having a vinyl group introduced into the component is preferably 0.2 or more per 1 molecule. Here, the terminal groups (tv) having vinyl groups are all (t 1), Z in (t 2) 3 And/or Z 4 A group which is vinyl, and Z in (t 3) 5 A group that is vinyl. More preferably 0.5 or more, still more preferably 0.6 or more per 1 molecule.
(A) In the component (c), when the total of the terminal groups of the formulae (t 1), (t 2) and (t 3) is 100 mol%, the terminal group of the formula (t 3) is preferably 70 mol% or less. Here, the terminal group represented by formula (t 3) is a terminal group having a vinylidene bond (bonding). More preferably 60 mol% or less, and still more preferably 50 mol% or less. In addition, in the component (a), when the total of the structural unit represented by the formula (a 1) and the terminal groups of the formulae (t 1), (t 2) and (t 3) is set to 100 mol%, the terminal group of the formula (t 3) is preferably 30 mol% or less, more preferably 20 mol% or less.
(A) The weight average molecular weight (Mw) of the component (B), preferably the polyfunctional vinyl aromatic copolymer, is 40000 or more. By including the polyfunctional vinyl aromatic copolymer having an Mw of 40000 or more, a cured product having a low dielectric loss tangent and excellent crack resistance after stain removal treatment can be obtained even in a high-temperature environment such as 90 ℃. The upper limit of the Mw is preferably 20000 or less, more preferably 15000 or less, and further preferably 10000 or less. (A) The weight average molecular weight of the component (a) is a weight average molecular weight in terms of polystyrene measured by Gel Permeation Chromatography (GPC).
(A) The number average molecular weight (Mn) of the component (A), preferably the polyfunctional vinyl aromatic copolymer, is preferably 300 to 100,000, more preferably 400 to 50,000, and still more preferably 500 to 10,000. (A) The number average molecular weight of the component (a) is a weight average molecular weight in terms of polystyrene measured by Gel Permeation Chromatography (GPC). The value of the molecular weight distribution (Mw/Mn) represented by the ratio of Mw to Mn is, for example, 100 or less, preferably 50 or less, more preferably 1.5 to 30, and most preferably 2.0 to 20.
(A) The component, preferably the polyfunctional vinyl aromatic copolymer, is preferably a soluble polyfunctional vinyl aromatic copolymer soluble in at least any one of toluene, xylene, tetrahydrofuran, dichloroethane or chloroform as a solvent, more preferably soluble in all of the above solvents. The term "soluble in a solvent" as used herein means that the soluble polyfunctional vinyl aromatic copolymer is dissolved in an amount of 5g or more, more preferably 30g or more, particularly preferably 50g or more, based on 100g of the solvent.
Examples of the divinylaromatic compound (a) are not particularly limited as long as they are aromatic compounds having two vinyl groups, and divinylbenzene (including each positional isomer or a mixture thereof), divinylnaphthalene (including each positional isomer or a mixture thereof), and divinylbiphenyl (including each positional isomer or a mixture thereof) are preferably used. In addition, they may be used singly or in combination of two or more. More preferably divinylbenzene (meta, para or mixtures of their positional isomers).
Examples of the monovinylaromatic compound (c) other than styrene are not particularly limited as long as it is an aromatic compound other than styrene having one vinyl group, and examples thereof include vinylaromatic compounds such as vinylnaphthalene and vinylbiphenyl; nuclear alkyl-substituted vinyl aromatic compounds such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinylbenzene and the like; etc. Preferably, ethyl vinyl benzene (including each positional isomer or a mixture thereof), ethyl vinyl biphenyl (including each positional isomer or a mixture thereof), and ethyl vinyl naphthalene (including each positional isomer or a mixture thereof), and more preferably, ethyl vinyl benzene (meta, para, or a mixture of isomers thereof).
As the component (a), a polyfunctional vinyl aromatic copolymer described in patent document 2 can be used.
The content of the component (a) is, for example, 0.1 mass% or more, preferably 0.3 mass% or more, more preferably 0.5 mass% or more, further preferably 1 or 1.0 mass% or more, further more preferably 1.05 mass% or more, and further, for example, 3 mass% or less, preferably 2 mass% or less, more preferably 1.5 mass% or less, further preferably 1.3 mass% or less, further more preferably 1.1 mass% or less, relative to 100 mass% of the nonvolatile component in the resin composition.
The content of the component (a) is, for example, 0.01 mass% or more, preferably 0.1 mass% or more, more preferably 1 mass% or more, still more preferably 2 mass% or more, still more preferably 3 mass% or more, particularly preferably 3.5 mass% or more, and further, for example, 15 mass% or less, preferably 10 mass% or less, more preferably 7 mass% or less, still more preferably 5 mass% or less, and still more preferably 4.5 mass% or less, relative to 100 mass% of the resin component in the resin composition.
Epoxy resin (B)
The resin composition of the present invention contains (B) an epoxy resin. The epoxy resin (B) is a curable resin having an epoxy group.
Examples of the epoxy resin (B) include a bisxylenol (bisbenzoxol) type epoxy resin, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenol type epoxy resin, a naphthol novolac (naphthalene type epoxy resin, a phenol novolac (phenol novolac) type epoxy resin, a tert-butyl-catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidylamine type epoxy resin, a glycidyl ester type epoxy resin, a cresol novolac (cresol novolac) type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, a alicyclic epoxy resin, a heterocyclic epoxy resin, a spiro-containing epoxy resin, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, a tetraphenyl ethane type epoxy resin, a phthalein type epoxy resin, an phthalein type epoxy resin, and an phthalein type epoxy resin. (B) The epoxy resin may be used alone or in combination of 1 or more than 2.
The resin composition preferably contains (B) an epoxy resin having 2 or more epoxy groups in 1 molecule. The proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, based on 100% by mass of the nonvolatile component of the (B) epoxy resin.
The epoxy resin includes an epoxy resin that is liquid at a temperature of 20 ℃ (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20 ℃ (hereinafter sometimes referred to as "solid epoxy resin"). The resin composition of the present invention may contain, as the epoxy resin, only a liquid epoxy resin, or only a solid epoxy resin, or may contain a liquid epoxy resin and a solid epoxy resin in combination. The epoxy resin in the resin composition of the present invention is preferably a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin, more preferably a solid epoxy resin.
As the liquid epoxy resin, a liquid epoxy resin having 2 or more epoxy groups in 1 molecule is preferable.
As the liquid epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, and epoxy resin having a butadiene structure are preferable.
Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC corporation; "828US", "828EL", "jER828EL", "825", "EPIKOTE828EL" manufactured by Mitsubishi chemical corporation (bisphenol A type epoxy resin); "jER807", "1750" manufactured by mitsubishi chemical company (bisphenol F type epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by mitsubishi chemical company; "630", "630LSD", "604" (glycidyl amine type epoxy resin) manufactured by Mitsubishi chemical corporation; "ED-523T" (glycine ring epoxy resin) manufactured by ADEKA company; "EP-3950L", "EP-3980S" (glycidyl amine type epoxy resins) manufactured by ADEKA Co; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA Co., ltd; "ZX1059" manufactured by Nippon iron gold chemical Co., ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., ltd; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daxil corporation; "PB-3600" by Daxillon corporation, and "JP-100" and "JP-200" by Japan, respectively (epoxy resin having butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1, 4-glycidyl cyclohexane type epoxy resin) manufactured by Nippon Ten Kagaku Kogyo Co., ltd. They may be used alone or in combination of 1 or more than 2.
The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.
As the solid epoxy resin, there are preferable a binaphthol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a naphthol novolac-type epoxy resin, a cresol novolac-type epoxy resin, a dicyclopentadiene-type epoxy resin, a triphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthylene-ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol a-type epoxy resin, a bisphenol AF-type epoxy resin, a phenol aralkyl-type epoxy resin, a tetraphenyl ethane-type epoxy resin, a phenol benzopyrrolone-type epoxy resin, a phenolphthalein-type epoxy resin.
Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC corporation; "HP-4700", "HP-4710" manufactured by DIC corporation (naphthalene type tetrafunctional epoxy resin); "N-690" (cresol novolac type epoxy resin) manufactured by DIC Co., ltd; "N-695" manufactured by DIC Co., ltd. (cresol novolak type epoxy resin); "HP-7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type epoxy resin) manufactured by DIC Co; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin) manufactured by DIC Co., ltd; "EPPN-502H" (triphenol type epoxy resin) manufactured by Japanese chemical Co., ltd; "NC7000L" manufactured by Japanese chemical Co., ltd. (naphthol novolac type epoxy resin); "NC3000H", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by japan chemical pharmaceutical company; "ESN475V" (naphthalene type epoxy resin) manufactured by nifmonster chemical & materials co., ltd.; "ESN485" (naphthol type epoxy resin) manufactured by Nissan chemical materials Co., ltd; "ESN375" manufactured by Nissan chemical materials Co., ltd. (dihydroxynaphthalene type epoxy resin); "YX4000H", "YX4000HK", "YL7890" (Bixylenol type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical corporation; "YX8800" (anthracene-type epoxy resin) manufactured by mitsubishi chemical company; "YX7700" manufactured by Mitsubishi chemical corporation (phenol aralkyl type epoxy resin); "PG-100", "CG-500" manufactured by Osaka gas chemical Co., ltd; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER1010" (bisphenol a type epoxy resin) manufactured by mitsubishi chemical company; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by mitsubishi chemical company; "WHR991S" (phenol benzopyrrolidone type epoxy resin) manufactured by Japanese chemical Co., ltd. They may be used alone or in combination of 1 or more than 2.
When the epoxy resin (B) is used in combination of a liquid epoxy resin and a solid epoxy resin, the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin/solid epoxy resin) is not particularly limited, but is preferably 10 or less, more preferably 5 or less, and further preferably 1 or less.
(B) The epoxy group equivalent of the epoxy resin is preferably 50g/eq to 5,000g/eq, more preferably 60g/eq to 2,000g/eq, still more preferably 70g/eq to 1,000g/eq, still more preferably 80g/eq to 500g/eq. The epoxy equivalent is the mass of the resin per 1 equivalent of epoxy. The epoxy equivalent weight can be determined in accordance with JISK 7236.
(B) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured by Gel Permeation Chromatography (GPC) as a value in terms of polystyrene.
The content of the component (B) is, for example, 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, still more preferably 10% by mass or more, and further, for example, 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 13% by mass or less, still more preferably 11% by mass, relative to 100% by mass of the nonvolatile component in the resin composition.
The content of the component (B) is, for example, 10 mass% or more, preferably 15 mass% or more, more preferably 20 mass% or more, still more preferably 25 mass% or more, still more preferably 30 mass% or more, particularly preferably 35 mass% or more, and further, for example, 60 mass% or less, preferably 55 mass% or less, more preferably 50 mass% or less, still more preferably 45 mass% or less, and still more preferably 43 mass% or less, relative to 100 mass% of the resin component in the resin composition.
Active ester compound (C)
The resin composition of the present invention contains (C) an active ester compound. (C) The active ester compound may be used alone or in combination of 1 or 2 or more in any ratio, and the same applies to the (C1) component and the (C2) component described later. (C) The active ester compound may have a function of reacting with (B) the epoxy resin to crosslink the (B) the epoxy resin. The active ester compound (C) may be a compound having a carbon-carbon unsaturated bond, and the unsaturated bond is preferably a carbon-carbon double bond, and may be, for example, a bond similar to a carbon-carbon unsaturated bond of the component (C1) described later.
As the (C) active ester compound, generally, compounds having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, esters of heterocyclic hydroxyl compounds, and the like, can be preferably used. The active ester compound is preferably obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improvement in heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester compound obtained from a carboxylic acid compound and a phenol compound (phenol compound) and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the Phenolic compound (phenol compound) or naphthol compound include hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, dicyclopentadiene type diphenol compound, novolac (Phenolic Novolac) and the like. The "dicyclopentadiene type phenol compound" herein means a phenol compound obtained by condensing 2 molecules of phenol with 1 molecule of dicyclopentadiene.
Specifically, as the (C) active ester compound, a dicyclopentadiene type active ester compound, a naphthalene type active ester compound containing a naphthalene structure, an active ester compound containing an acetyl compound of a novolac resin, an active ester compound containing a benzoyl compound of a novolac resin are preferable, and among them, at least one selected from the dicyclopentadiene type active ester compound and naphthalene type active ester compound is more preferable, and a dicyclopentadiene type active ester compound is further preferable. As the dicyclopentadiene type active ester compound, an active ester compound containing a dicyclopentadiene type diphenol structure is preferable. The "dicyclopentadiene type diphenol structure" means a divalent structural unit formed from phenylene-dicyclopentylene-phenylene.
As the commercial product of the active ester compound (C), examples of the active ester compound containing a dicyclopentadiene type diphenol structure include "EXB9451", "EXB9460S", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000-65T", "HPC-8000H-65TM" (manufactured by DIC); examples of the active ester compound having a naphthalene structure include "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T" (manufactured by DIC Co.); the phosphorus-containing active ester compound may be "EXB9401" (manufactured by DIC corporation), the phenol novolac acetylate active ester compound may be "DC808" (manufactured by Mitsubishi chemical corporation), the phenol novolac benzoyl active ester compound may be "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi chemical corporation), the styrene-and naphthalene-containing active ester compound may be "PC1300-02-65MA" (manufactured by AirWater corporation).
(C) The active ester group equivalent of the active ester compound is preferably 50g/eq to 500g/eq, more preferably 50g/eq to 400g/eq, still more preferably 100g/eq to 300g/eq. The active ester group equivalent is the mass of the active ester compound per 1 equivalent of active ester group.
(C1) Compound containing aromatic ester skeleton and unsaturated bond
As the (C) active ester compound, a compound (C1) containing an aromatic ester skeleton and an unsaturated bond (also referred to as a "(C1) component" in the present specification) can be used.
(C1) The component (A) is preferably a compound represented by the following general formula (AE 1-1);
[ chemical formula 9]
(in the general formula (AE 1-1), ar 11 Each independently represents a monovalent aromatic hydrocarbon group optionally having a substituent, ar 12 Each independently represents an optionally substituted divalent aromatic hydrocarbon group, ar 13 Each independently represents a divalent aromatic hydrocarbon group optionally having a substituent, a divalent aliphatic hydrocarbon group optionally having a substituent, an oxygen atom, a sulfur atom, or a divalent group formed by a combination of these (groups). n represents an integer of 0 to 10. ).
As Ar 11 Examples of the monovalent aromatic hydrocarbon group represented by the formula (i) include a group obtained by removing 1 hydrogen atom from a monocyclic aromatic compound, such as phenyl, furyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, and triazinyl; a group obtained by removing 1 hydrogen atom from a condensed ring aromatic compound such as naphthyl, anthryl, phenalenyl (phenalenyl), phenanthryl, quinolinyl, isoquinolinyl, quinazolinyl, phthalazinyl, pteridinyl, coumarin (coumarinyl), indolyl, benzimidazolyl, benzofuranyl, acridinyl, etc.; etc., and, among other things, Phenyl is preferred.
As Ar 12 Examples of the divalent aromatic hydrocarbon group include arylene groups and aralkylene groups, and arylene groups are preferable. The arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms, and still more preferably an arylene group having 6 to 10 carbon atoms. Examples of such arylene groups include phenylene, naphthylene, anthrylene, and biphenylene. Among them, phenylene is preferable.
As Ar 13 Divalent groups formed from a combination of these (groups) are preferred. As Ar 13 Represented divalent aromatic hydrocarbon group, with Ar 12 The meaning of the divalent aromatic hydrocarbon radicals represented is the same. As Ar 13 The divalent aliphatic hydrocarbon group represented is more preferably a divalent saturated aliphatic hydrocarbon group, preferably an alkylene group or a cycloalkylene group, and more preferably a cycloalkylene group.
The cycloalkylene group is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and still more preferably a cycloalkyl group having 5 to 10 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclopentylene group, a cycloheptylene group, and cycloalkylene groups represented by the following formulas (a) to (d), and cycloalkyl groups represented by the formula (c) are preferable;
[ chemical formula 10]
(in the formulae (a) to (d), "×" indicates a chemical bond).
As Ar 11 Represented by monovalent aromatic hydrocarbon radicals, ar 12 Represented divalent aromatic hydrocarbon group, and Ar 13 Examples of the substituent that the divalent aromatic hydrocarbon group and the divalent aliphatic hydrocarbon group may have include an unsaturated hydrocarbon group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, and the like. The substituents may be contained alone or in combination of 2 or more. Wherein Ar is 11 The substituent of (2) preferably contains an unsaturated bond.
When the compound represented by the general formula (AE 1-1) is an oligomer or a polymer, n represents the average value thereof.
Specific examples of the component (C1) include the following compounds. Specific examples of the component (C1) include compounds described in paragraphs 0068 to 0071 of International publication No. 2018/235424 and in paragraphs 0113 to 0115 of International publication No. 2018/235425. Wherein s represents an integer of 0 or 1 or more, and r represents an integer of 1 to 10;
[ chemical formula 11]
The weight average molecular weight of the component (C1) is preferably 150 or more, more preferably 200 or more, further preferably 250 or more, preferably 3000 or less, more preferably 2000 or less, further preferably 1500 or less, from the viewpoint of remarkably obtaining the effect of the present invention. (C1) The weight average molecular weight of the component (a) is a weight average molecular weight in terms of polystyrene measured by Gel Permeation Chromatography (GPC).
The active ester equivalent (unsaturated bond equivalent) of the component (C1) is preferably 50g/eq or more, more preferably 100g/eq or more, still more preferably 150g/eq or more, preferably 2000g/eq or less, still more preferably 1000g/eq or less, still more preferably 500g/eq or less, from the viewpoint of remarkably obtaining the effect of the present invention. The active ester equivalent (unsaturated bond equivalent) is the mass of the (C1) component containing 1 equivalent of unsaturated bond.
An active ester compound having at least any one of the groups represented by the following formulas (1) to (3) < (C2)
As the (C) active ester compound, (C2) an active ester compound having at least any one of the groups represented by the following formulas (1) to (3) (also referred to as "(C2 component" in the present specification ");
[ chemical formula 12]
In the formula (3), n represents an integer of 1 to 5.
(C2) The component (A) may be a compound having at least one of the groups represented by the formulas (1) to (3) and having an active ester moiety reactive with the component (A). The component (C2) preferably has at least one of the groups represented by the formulas (1) to (3) at the terminal. As the component (C2), the two terminals may be different groups or the two terminals may be the same group.
The methyl group in the group represented by formula (1), the phenyl group in the group represented by formula (2), and the styrene moiety in the group represented by formula (3) are each preferably bonded to any one of the ortho-position, meta-position, and para-position, more preferably to the chemical bond represented by the x.
(C2) The component (A) is preferably a compound represented by the following general formula (AE 2-1);
[ chemical formula 13]
(in the general formula (AE 2-1), ar 11 Ar is independently a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3) 12 Each independently represents an optionally substituted divalent aromatic hydrocarbon group, ar 13 Each independently represents a divalent aromatic hydrocarbon group optionally having a substituent, a divalent aliphatic hydrocarbon group optionally having a substituent, an oxygen atom, a sulfur atom, or a divalent group formed by a combination of these (groups). a represents an integer of 1 to 6, and b represents an integer of 0 to 10. ).
As Ar 11 The group represented by formula (1) and the group represented by formula (2) are preferable.
Ar 12 Ar and Ar 13 Ar in the general formula (AE 1-1) 12 Ar and Ar 13 The meanings are the same as Ar 12 Represented divalent aromatic hydrocarbon group, and Ar 13 Examples of the substituent which the divalent aromatic hydrocarbon group and the divalent aliphatic hydrocarbon group may have include an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen Atoms, and the like. The substituents may be contained alone or in combination of 2 or more.
As Ar 13 The represented divalent group formed by the combination of these groups is preferably a divalent group formed by combining a divalent aromatic hydrocarbon group optionally having a substituent with an oxygen atom, more preferably a divalent group formed by alternately combining 1 or more divalent aromatic hydrocarbon groups optionally having a substituent with 1 or more oxygen atoms, and even more preferably a divalent group formed by alternately combining 1 or more naphthylene groups optionally having a substituent with 1 or more oxygen atoms. Therefore, naphthyloxy group which may be substituted is further preferable.
When the compound represented by the general formula (AE 2-1) is an oligomer or a polymer, a represents the average value thereof. b has the same meaning as n in the formula (AE 1-1), and is preferably 0.
(C2) The component (A) is preferably a compound represented by the general formula (AE 2-2);
[ chemical formula 14]
(in the general formula (AE 2-2), ar 21 Ar is independently a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3) 22 Each independently represents an optionally substituted divalent aromatic hydrocarbon group, ar 23 Each independently represents a divalent aromatic hydrocarbon group optionally having a substituent. a1 represents an integer of 1 to 6, and c1 represents an integer of 1 to 5. ).
Ar 21 Ar and Ar 22 Ar in the general formula (AE 2-1) 11 Ar and Ar 12 The meaning is the same.
Ar 23 Ar in the general formula (AE 2-1) 13 The meaning of the divalent aromatic hydrocarbon group optionally having a substituent is the same. a1 has the same meaning as a in the general formula (AE 2-1).
(C2) The component (A) is preferably a compound represented by the general formula (AE 2-3);
[ chemical formula 15]
(in the general formula (AE 2-3), ar 31 Each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3). a2 represents an integer of 1 to 6, c2 represents an integer of 1 to 5, and d each independently represents an integer of 0 to 6. ).
Ar 31 Ar in the general formula (AE 2-1) 11 The meaning is the same. a2 and c2 have the same meanings as a and c1 in the general formula (AE 2-1), respectively. d preferably represents an integer of 1 to 5, more preferably an integer of 1 to 4.
(C2) The components may be synthesized by known methods, and for example, may be synthesized by the methods described in the examples below. (C2) The synthesis of the components can be performed, for example, by the method described in International publication No. 2018/235424 or International publication No. 2018/235425.
The weight average molecular weight of the component (C2) is preferably 150 or more, more preferably 200 or more, further preferably 250 or more, preferably 4000 or less, more preferably 3000 or less, further preferably 2500 or less, from the viewpoint of remarkably obtaining the effect of the present invention. (C2) The weight average molecular weight of the component (a) is a weight average molecular weight in terms of polystyrene measured by Gel Permeation Chromatography (GPC).
(C2) The active ester equivalent (unsaturated bond equivalent) of the component (C1) is the same as that of the component (C1).
The ratio of the amount of the component (B) to the amount of the component (C) is represented by W, which is obtained by adding all the values obtained by dividing the mass of the nonvolatile component (B) by the epoxy equivalent weight B And the sum of the mass of the nonvolatile component (C) divided by the equivalent weight of the active ester group is denoted as W C At the time W C /W B Preferably 1.0 or more, more preferably 1.01 or more, still more preferably 1.03 or more, still more preferably 1.05 or more, particularly preferably 1.06 or more, and further preferably 2.0 or less, more preferably 1.75 or less, still more preferably 1.5 or less, still more preferably 1.4 or less, particularly preferably 1.3 or less. By making the ratio of the amount of the component (B) to the amount of the component (C) within the above-mentioned range, it is possible to easily obtainThe effect of the invention.
The content of the component (C) is, for example, 3 mass% or more, preferably 5 mass% or more, more preferably 10 mass% or more, further preferably 13 mass% or more, and is, for example, 30 mass% or less, preferably 25 mass% or less, more preferably 20 mass% or less, further preferably 15 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition.
The content of the component (C) is, for example, 30 mass% or more, preferably 40 mass% or more, more preferably 45 mass% or more, further preferably 48 mass% or more, and is, for example, 70 mass% or less, preferably 60 mass% or less, more preferably 55 mass% or less, further preferably 53 mass% or less, based on 100 mass% of the resin component in the resin composition.
Inorganic filler (D)
The resin composition of the present invention may contain (D) an inorganic filler as an optional component. (D) The inorganic filler is contained in the resin composition in a particulate state. (D) The inorganic filler may be used alone or in combination of 1 or more than 2.
As the material of the inorganic filler (D), an inorganic compound is used. Examples of the material of the inorganic filler (D) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate. Among these, silica is particularly preferable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, spherical silica is preferable as silica. (D) The inorganic filler may be used alone in 1 kind, or may be used in combination in an arbitrary ratio of 2 or more kinds.
Examples of the commercial products of the inorganic filler (D) include "SP60-05" and "SP507-05" manufactured by Nissan chemical materials Co., ltd; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "YC100C", "YA050C-MJE", "YA010C" manufactured by Admatechs; "UFP-30", "DAW-03", "FB-105FD", manufactured by DENKA Co., ltd; "Silfil NSS-3N", "SilfilNSS-4N", "SilfilNSS-5N" manufactured by Tokuyama; "CellSpheres" ("MGH-005") manufactured by Taiheiyo-ceramic company; and "eyebox" ("BA-S") manufactured by solar volatile catalyst formation company.
(D) The average particle diameter of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, further preferably 2 μm or less, further more preferably 1 μm or less, and particularly preferably 0.7 μm or less. (D) The lower limit of the average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. (D) The average particle size of the inorganic filler material can be determined using a laser diffraction-scattering method based on Mie scattering theory. Specifically, the measurement can be performed by: the particle size distribution of the inorganic filler was prepared based on volume by using a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size was used as the average particle size. As a measurement sample, a product obtained by weighing 100mg of an inorganic filler, 10g of methyl ethyl ketone into a vial, and dispersing the mixture by ultrasonic waves for 10 minutes was used. For the measurement sample, a laser diffraction type particle size distribution measuring apparatus was used, the wavelength of the light source was set to blue and red, the volume-based particle size distribution of the inorganic filler was measured by a flow cell (flowcell) method, and the average particle size as the median particle size was calculated from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, inc.
(D) The specific surface area of the inorganic filler is not particularly limited,preferably 0.1m 2 Preferably at least 0.5m 2 Preferably 1m or more, and more preferably 1m 2 Preferably 3m or more per gram 2 And/g. (D) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100m 2 Preferably less than or equal to/g, more preferably 70m 2 Preferably 50m or less per gram 2 Preferably less than or equal to/g, particularly preferably 40m 2 And/g or less. The specific surface area of the inorganic filler material can be obtained by: the specific surface area was calculated by the BET multipoint method by adsorbing nitrogen gas on the surface of a sample using a specific surface area measuring apparatus (MacsorbHM-1210, manufactured by Mountech Co.).
(D) The inorganic filler is preferably surface-treated with a suitable surface treatment agent. By performing the surface treatment, the moisture resistance and dispersibility of the inorganic filler (D) can be improved. Examples of the surface treatment agent include vinyl silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy silane coupling agents such as 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-epoxypropoxypropyl methyldimethoxysilane, 3-epoxypropoxypropyl trimethoxysilane, 3-epoxypropoxypropyl methyldiethoxysilane, and 3-epoxypropoxypropyl triethoxysilane; styrene-based silane coupling agents such as p-styryl trimethoxysilane; methacrylic silane coupling agents such as 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyl diethoxy silane, and 3-methacryloxypropyl triethoxy silane; acrylic silane coupling agents such as 3-acryloxypropyl trimethoxysilane; amino silane coupling agents such as N-2- (aminoethyl) -3-aminopropyl methyldimethoxy silane, N-2- (aminoethyl) -3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyl trimethoxy silane, N-phenyl-8-aminooctyl trimethoxy silane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl trimethoxy silane; isocyanurate-based silane coupling agents such as tris (trimethoxysilylpropyl) isocyanurate; 3-ureidopropyl trialkoxysilane and the like ureido silane coupling agents; mercapto silane coupling agents such as 3-mercaptopropyl methyl dimethoxy silane and 3-mercaptopropyl trimethoxy silane; isocyanate silane coupling agents such as 3-isocyanatopropyl triethoxysilane; anhydride-based silane coupling agents such as 3-trimethoxysilylpropyl succinic anhydride; silane coupling agents, etc.; non-silane coupling-alkoxysilane compounds such as methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1, 6-bis (trimethoxysilyl) hexane, trifluoropropyltrimethoxysilane, and the like. The surface treatment agent may be used alone in 1 kind, or may be used in combination in an arbitrary ratio of 2 or more kinds.
Examples of the commercial products of the surface treatment agent include "KBM-1003" and "KBE-1003" (vinyl silane coupling agent) manufactured by Xinyue chemical industries, inc.; "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agent); "KBM-1403" (styrene-based silane coupling agent); "KBM-502", "KBM-503", "KBE-502", "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", "KBM-903", "KBE-9103P", "KBM-573", "KBM-575" (amino-based silane coupling agents); "KBM-9659" (isocyanurate-based silane coupling agent); "KBE-585" (ureido silane coupling agent); "KBM-802", "KBM-803" (mercapto silane coupling agent); "KBE-9007N" (isocyanate-based silane coupling agent); "X-12-967C" (anhydride-based silane coupling agent); "KBM-13", "KBM-22", "KBM-103", "KBE-13", "KBE-22", "KBE-103", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" (non-silane coupling-alkoxysilane compounds) and the like.
From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably controlled to a predetermined range. Specifically, the inorganic filler is preferably surface-treated with 0.2 to 5 mass% of a surface-treating agent, more preferably 0.2 to 3 mass% of a surface-treating agent, and even more preferably 0.3 to 2 mass% of a surface-treating agent, based on 100 mass% of the inorganic filler.
The degree of surface treatment based on the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02mg/m from the viewpoint of improving dispersibility of the inorganic filler 2 The above is more preferably 0.1mg/m 2 The above is more preferably 0.2mg/m 2 The above. On the other hand, from the viewpoint of preventing the rise of the melt viscosity of the resin composition and the melt viscosity in the form of a sheet, it is preferably 1.0mg/m 2 Hereinafter, more preferably 0.8mg/m 2 Hereinafter, it is more preferably 0.5mg/m 2 The following is given.
(D) The carbon amount per unit surface area of the inorganic filler may be measured after the surface-treated inorganic filler is subjected to a washing treatment with a solvent such as Methyl Ethyl Ketone (MEK). Specifically, MEK as a solvent in a sufficient amount may be added to the inorganic filler surface-treated with the surface treating agent, and ultrasonic washing may be performed at 25 ℃ for 5 minutes. The supernatant was removed, and the solid content was dried, and then the carbon content per unit surface area of the inorganic filler was measured using a carbon analyzer. As the carbon analyzer, EMIA-320V manufactured by horiba, inc. can be used.
The content of the inorganic filler (D) in the resin composition is not particularly limited, and may be preferably 95 mass% or less, more preferably 90 mass% or less, and still more preferably 88 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The lower limit of the content of the inorganic filler (D) in the resin composition is not particularly limited, and the non-volatile component in the resin composition may be, for example, 0 mass% or more, 1 mass% or more, 10 mass% or more, 20 mass% or more, 30 mass% or more, etc., and may be preferably 40 mass% or more, more preferably 50 mass% or more, still more preferably 60 mass% or more, still more preferably 65 mass% or more, and particularly preferably 70 mass% or more, assuming that the non-volatile component in the resin composition is 100 mass%.
(E) radical polymerizable Compound
The resin composition of the present invention may contain (E) a radical polymerizable compound as an optional component. (E) The radical polymerizable compound may be used alone or in combination of 1 or more than 2.
The radical polymerizable compound is not particularly limited as long as it has 1 or more (preferably 2 or more) radical polymerizable unsaturated groups in 1 molecule. Examples of the radical polymerizable compound include compounds having 1 or more radical polymerizable unsaturated groups selected from the group consisting of maleimide groups, vinyl groups, allyl groups, styryl groups, vinylphenyl groups, acryl groups, methacryl groups, fumaryl groups, and maleimide groups. Among them, from the viewpoint of easy obtaining of a cured product excellent in dielectric characteristics, it is preferable to contain (E1) a maleimide compound and/or (E2) another radical polymerizable compound. (E2) The other radical polymerizable compound is a compound having not a maleimide group but a radical polymerizable unsaturated group other than a maleimide group, and preferably contains 1 or more kinds selected from (meth) acrylic resins and styrene resins.
The type of the maleimide compound (E1) is not particularly limited as long as it has 1 or more (preferably 2 or more) maleimide groups (2, 5-dihydro-2, 5-dioxo-1H-pyrrol-1-yl) in 1 molecule. Examples of the maleimide compound include maleimide resins containing an aliphatic skeleton having 36 carbon atoms derived from a dimer diamine, such as "BMI-3000J", "BMI-5000", "BMI-1400", "BMI-1500", "BMI-1700" and "BMI-689" (all manufactured by design molecule (Designer Molecules)), and the like; maleimide resins containing an indane skeleton described in Japanese patent application laid-open technical bulletin No. 2020-500211; maleimide resins containing an aromatic ring skeleton directly bonded to the nitrogen atom of a maleimide group, such as "MIR-3000-70MT", "MIR-5000-60T" (all manufactured by Japanese chemical Co., ltd.), "BMI-4000" (manufactured by Dai chemical Co., ltd.), "BMI-80" (manufactured by KI chemical Co., ltd.).
The (meth) acrylic resin is not particularly limited as long as it has 1 or more (meth) acryloyl groups (preferably 2 or more) in 1 molecule. The term "(meth) acryl" is a generic term for acryl and methacryl. Examples of THE methacrylic resin include (meth) acrylic resins such as "A-DOG" (manufactured by Xinzhou chemical industry Co., ltd.), "DCP-A" (manufactured by Kagaku chemical Co., ltd.), "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", "DPHA" (manufactured by Nippon chemical Co., ltd.).
The styrene resin is not particularly limited as long as it has 1 or more (preferably 2 or more) styryl groups or vinylphenyl groups in 1 molecule. Examples of the styrene resin include "OPE-2St", "OPE-2St1200", "OPE-2St2200" (all manufactured by Mitsubishi gas chemical corporation) and the like.
The content of the radical polymerizable compound (E) in the resin composition may be 0 mass% or more, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, particularly preferably 0.5 mass% or more, and for example, 10 mass% or less, preferably 5 mass% or less, more preferably 3 mass% or less, particularly preferably 1.5 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition.
The content of the radical polymerizable compound (E) in the resin composition may be 0 mass% or more, preferably 0.1 mass% or more, more preferably 1 mass% or more, particularly preferably 2 mass% or more, and for example, 20 mass% or less, preferably 10 mass% or less, more preferably 7 mass% or less, particularly preferably 5 mass% or less, based on 100 mass% of the resin component in the resin composition.
(F) other curing Agents
The resin composition of the present invention sometimes contains (F) other curing agents as optional ingredients. The other curing agent (F) does not include those belonging to the above-mentioned components (A) to (C) and (E). (F) The other curing agent may have a function as an epoxy resin curing agent for curing the resin composition by reacting with the (B) epoxy resin, similarly to the above-mentioned (C) active ester compound. (F) The other curing agents may be used alone or in combination of 1 or more than 2.
Examples of the other curing agent (F) include phenol curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanate curing agents, and thiol curing agents. Among them, it is preferable to use 1 or more curing agents selected from phenolic curing agents and carbodiimide curing agents.
As the phenolic curing agent, a curing agent having 1 or more, preferably 2 or more hydroxyl groups bonded to an aromatic ring such as a benzene ring or naphthalene ring in 1 molecule can be used. From the viewpoints of heat resistance and water resistance, a phenol curing agent having a phenol structure (Novolac structure) is preferable. In addition, from the viewpoint of adhesion, a nitrogen-containing phenol-based curing agent is preferable, and a phenol-based curing agent containing a triazine skeleton is more preferable. Among them, a novolac resin (Phenolic Novolac Resin) containing a triazine skeleton is preferable from the viewpoint of highly satisfying heat resistance, water resistance and adhesion. Specific examples of the phenolic curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Ming He Chemicals, and "NHN", "CBN", "GPH" manufactured by Japanese chemical Co., ltd., and "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395", and "LA-7052", "LA-7054", "LA-3018-50P", "LA-1356", "TD2090", "TD-2090-60M" manufactured by DIC.
As the carbodiimide-based curing agent, a curing agent having 1 or more, preferably 2 or more carbodiimide structures in 1 molecule can be used. Specific examples of the carbodiimide-based curing agent include: aliphatic dicarboximides such as tetramethylene-bis (t-butylcarbodiimide), and cyclohexanedis (methylene-t-butylcarbodiimide); aromatic dicarboximides such as phenylene-bis (xylyl carbodiimide); aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylene carbodiimide, poly (methylenedicyclohexyl carbodiimide) and poly (isophorone carbodiimide); and aromatic polycarbodiimides such as poly (phenylene carbodiimides), poly (naphthylene carbodiimides), poly (tolylene carbodiimides), poly (methyldiisopropylphenylene carbodiimides), poly (triethylphenylene carbodiimides), poly (diethylphenylene carbodiimides), poly (triisopropylphenylene carbodiimides), poly (diisopropylphenylene carbodiimides), poly (xylylene carbodiimides), poly (tetramethylxylylene carbodiimides), poly (methylenediphenylene carbodiimides), poly [ methylenebis (methylphenyl) carbodiimides ]. Examples of the commercially available carbodiimide-based curing agents include "CARBODILITEV-02B", "CARBODILITEV-03", "CARBODILITEV-04K", "CARBODILITEV-07" and "CARBODILITEV-09" manufactured by Nigrossedently chemical Co., ltd; "Stabaxol P", "Stabaxol P400", "Hycasyl510", etc. manufactured by Rhein Chemie, inc.
As the acid anhydride-based curing agent, a curing agent having 1 or more acid anhydride groups in 1 molecule, preferably a curing agent having 2 or more acid anhydride groups in 1 molecule, can be used. Specific examples of the acid anhydride-based curing agent include: phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3'-4,4' -diphenyl sulfone tetracarboxylic dianhydride, 1, 3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-C ] furan-1, 3-dione, ethylene glycol bis (dehydrated trimellitate), styrene-maleic anhydride copolymerized from styrene and maleic acid, and the like. Examples of the commercial products of the acid anhydride-based curing agent include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by New Japan physical and chemical Co., ltd; "YH-306", "YH-307" manufactured by Mitsubishi chemical corporation; "HN-2200", "HN-5500" manufactured by Hitachi chemical Co., ltd; gram Lei Weili (CrayValley) company "EF-30", "EF-40", "EF-60", "EF-80", etc.
As the amine-based curing agent, a curing agent having 1 or more, preferably 2 or more amino groups in 1 molecule can be used. Examples of the amine-based curing agent include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, and among these, aromatic amines are preferable. The amine-based curing agent is preferably a primary amine or a secondary amine, more preferably a primary amine. Specific examples of the amine-based curing agent include: 4,4' -methylenebis (2, 6-dimethylaniline), 4' -diaminodiphenylmethane, 4' -diaminodiphenylsulfone, 3' -diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine 4,4' -diaminodiphenyl ether, 3' -dimethyl-4, 4' -diaminobiphenyl, 2' -dimethyl-4, 4' -diaminobiphenyl, 3' -dihydroxybenzidine, 2-bis (3-amino-4-hydroxyphenyl) propane 3, 3-dimethyl-5, 5-diethyl-4, 4-diphenyl methane diamine, 2-bis (4-aminophenoxy) phenyl) propane, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, and the like. Examples of the commercial products of the amine-based curing agent include "SEIKACURE-S" manufactured by SEIKA corporation; "kayabond c-200S", "kayabond c-100", "KAYAHARDA-A", "KAYAHARDA-B", "KAYAHARDA-S" manufactured by japan chemical company; "EPICURE W" manufactured by Mitsubishi chemical corporation; "DTDA" manufactured by Sumitomo refinement Co., ltd.
Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE chemical Co., ltd; "HFB2006M" manufactured by Showa Polymer Co., ltd; "P-d", "F-a", etc. manufactured by the chemical industry Co., ltd.
Examples of the cyanate-based curing agent include: difunctional cyanate resins such as bisphenol a dicyanate, polyphenol cyanate, oligo (3-methylene-1, 5-phenylene cyanate), 4 '-methylenebis (2, 6-dimethylphenyl cyanate), 4' -ethylenediphenyl dicyanate, hexafluorobisphenol a dicyanate, 2-bis (4-cyanate-based) phenylpropane, 1-bis (4-cyanate-based phenylmethane), bis (4-cyanate-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate-phenyl-1- (methylethylene)) benzene, bis (4-cyanate-phenyl) sulfide, and bis (4-cyanate-based phenyl) ether; polyfunctional cyanate resins derived from phenol novolac resins, cresol novolac resins, and the like; prepolymers obtained by triazinizing a part of these cyanate resins, and the like. Specific examples of the cyanate ester curing agent include "PT30" and "PT60" manufactured by lonza japan (both of which are phenol novolac type polyfunctional cyanate ester resins), "BA230" and "BA230S75" (prepolymers obtained by triazining a part or all of bisphenol a dicyanate to form a trimer).
Examples of the thiol curing agent include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), and tris (3-mercaptopropyl) isocyanurate.
(F) The active group equivalent of the other curing agent is preferably 50g/eq to 3000g/eq, more preferably 100g/eq to 1000g/eq, still more preferably 100g/eq to 500g/eq, and particularly preferably 100g/eq to 300g/eq. The active group equivalent means the mass of the curing agent per 1 equivalent of active group.
The ratio of the amount of the epoxy resin to the amount of the curing agent, that is, the ratio of the amount of the component (B) ' to the amount of the component (C) ' to the amount of the component (F) ' is represented by W, which is obtained by adding all the values obtained by dividing the mass of the nonvolatile component (B) by the equivalent amount of the epoxy group B Non-volatile component (C)The sum of the mass of the hair component divided by the equivalent weight of the active ester group is denoted as W C And the sum of the values obtained by dividing the mass of the nonvolatile component of component (F) by the active group equivalent is denoted as W F When (W) C +W F )/W B Preferably 1.0 or more, more preferably 1.01 or more, further preferably 1.1 or 1.10 or more, further more preferably 1.15 or more, particularly preferably 1.2 or more, further preferably 2.0 or less, more preferably 1.75 or less, further preferably 1.5 or less, further more preferably 1.4 or 1.40 or less, particularly preferably 1.35 or less. The effect of the present invention can be easily obtained by setting the amount ratio of the epoxy resin to the curing agent within the above range.
The content of the other curing agent (F) in the resin composition may be 0 mass% or more, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, particularly preferably 1.0 mass% or more, preferably 20 mass% or less, more preferably 10 mass% or less, and particularly preferably 5 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition.
The content of the other curing agent (F) in the resin composition may be 0 mass% or more, preferably 0.1 mass% or more, more preferably 1.0 mass% or more, particularly preferably 5.0 mass% or more, preferably 50 mass% or less, more preferably 20 mass% or less, and particularly preferably 10 mass% or less, based on 100 mass% of the resin component in the resin composition.
(G) curing accelerator
The resin composition of the present invention sometimes contains (G) a curing accelerator as an optional ingredient.
Examples of the curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. (G) The curing accelerator may be used alone or in combination of 1 or more than 2.
Examples of the phosphorus-based curing accelerator include: aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis (tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydrohexahydrophthalate, tetrabutylphosphonium 2, 6-bis [ (2-hydroxy-5-methylphenyl) methyl ] -4-methylphenoxy, and di-t-butylmethylphosphonium tetraphenylborate; aromatic phosphonium salts such as methyltriphenyl phosphonium bromide, ethyltriphenyl phosphonium bromide, propyltriphenyl phosphonium bromide, butyltriphenyl phosphonium bromide, benzyltriphenyl phosphonium chloride, tetraphenyl phosphonium bromide, p-tolyltrimethyl phosphonium tetra-p-tolylborate, tetraphenyl phosphonium tetraphenyl borate, tetraphenyl phosphonium tetra-p-tolylborate, triphenylethyl phosphonium tetraphenyl borate, tris (3-methylphenyl) ethyl phosphonium tetraphenyl borate, tris (2-methoxyphenyl) ethyl phosphonium tetraphenyl borate, (4-methylphenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyltriphenyl phosphonium thiocyanate, and the like; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactant; aliphatic phosphines such as tributylphosphine, tri-t-butylphosphine, trioctylphosphine, di-t-butyl (2-butenyl) phosphine, di-t-butyl (3-methyl-2-butenyl) phosphine, and tricyclohexylphosphine; dibutyl phenyl phosphine, di-tert-butyl phenyl phosphine, methyl diphenyl phosphine, ethyl diphenyl phosphine, butyl diphenyl phosphine, diphenyl cyclohexyl phosphine, triphenyl phosphine, tri-o-tolyl phosphine, tri-m-tolyl phosphine, tri-p-tolyl phosphine, tri (4-ethylphenyl) phosphine, tri (4-propylphenyl) phosphine, tri (4-isopropylphenyl) phosphine, tri (4-butylphenyl) phosphine, tri (4-tert-butylphenyl) phosphine, tri (2, 4-dimethylphenyl) phosphine, tri (2, 5-dimethylphenyl) phosphine, tri (2, 6-dimethylphenyl) phosphine, tri (3, 5-dimethylphenyl) phosphine, tri (2, 4, 6-trimethylphenyl) phosphine, tri (2, 6-dimethyl-4-ethoxyphenyl) phosphine, tri (2-methoxyphenyl) phosphine, tri (4-ethoxyphenyl) phosphine, tri (4-tert-butoxyphenyl) phosphine, diphenyl-2-pyridylphosphine, 1, 2-bis (diphenyl) ethane, 1, 3-bis (diphenyl) propane, bis (2, 2 '-diphenyl) phosphine, bis (2, 2' -diphenyl) phosphine, etc.
Examples of urea-based curing accelerators include: 1, 1-dimethylurea; aliphatic dimethylureas such as 1, 3-trimethylurea, 3-ethyl-1, 1-dimethylurea, 3-cyclohexyl-1, 1-dimethylurea, and 3-cyclooctyl-1, 1-dimethylurea; aromatic ureas such as 3-phenyl-1, 1-dimethylurea, 3- (4-chlorophenyl) -1, 1-dimethylurea, 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea, 3- (3-chloro-4-methylphenyl) -1, 1-dimethylurea, 3- (2-methylphenyl) -1, 1-dimethylurea, 3- (4-methylphenyl) -1, 1-dimethylurea, 3- (3, 4-dimethylphenyl) -1, 1-dimethylurea, 3- (4-isopropylphenyl) -1, 1-dimethylurea, 3- (4-methoxyphenyl) -1, 1-dimethylurea, 3- (4-nitrophenyl) -1, 1-dimethylurea, 3- [4- (4-methoxyphenoxy) phenyl ] -1, 1-dimethylurea, 3- [4- (4-chlorophenoxy) phenyl ] -1, 1-dimethylurea, N- (1, 4-phenylene) bis (N ', N ' -dimethylurea, N- (4-dimethylphenyl) bis (N, N ' -dimethylurea, etc.
Examples of the guanidine curing accelerator include: dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1-dimethylbiguanide, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and the like.
Examples of the imidazole-based curing accelerator include: 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -undecylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate adduct, and process for preparing the same, imidazole compounds such as 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins.
As the imidazole-based curing accelerator, commercially available products may be used, and examples thereof include "1B2PZ", "2MZA-PW", "2PHZ-PW", and "P200-H50" manufactured by Mitsubishi chemical corporation.
Examples of the metal curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include: cobalt (II) acetylacetonate, cobalt (III) acetylacetonate and other organic cobalt complexes, copper (II) acetylacetonate and other organic copper complexes, zinc (II) acetylacetonate and other organic zinc complexes, iron (III) acetylacetonate and other organic iron complexes, nickel (II) acetylacetonate and other organic nickel complexes, manganese (II) acetylacetonate and other organic manganese complexes, and the like. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 1, 8-diazabicyclo (5, 4, 0) -undecene.
As the amine-based curing accelerator, commercially available ones can be used, and examples thereof include "MY-25" manufactured by Ajinomoto Fine chemical Co., inc.
The content of the (G) curing accelerator in the resin composition is not particularly limited, but is preferably 15 mass% or less, more preferably 10 mass% or less, further preferably 5 mass% or less, and particularly preferably 3 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The lower limit of the content of the (G) curing accelerator in the resin composition is not particularly limited, and the content of the nonvolatile component in the resin composition may be, for example, 0 mass% or more, 0.001 mass% or more, 0.01 mass% or more, 0.1 mass% or more, 0.5 mass% or more, or the like, based on 100 mass%.
(H) other additives
The resin composition of the present invention may further contain an optional additive as a nonvolatile component. Examples of such additives include radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; phenolic curing agents (phenol curing agents), naphthol curing agents, acid anhydride curing agents, thiol curing agents, benzoxazine curing agents, cyanate curing agents, carbodiimide curing agents, imidazole curing agents, and other epoxy curing agents other than active ester compounds; thermoplastic resins such as phenoxy resin, polyvinyl acetal resin, polyolefin resin, polysulfone resin, polyether sulfone resin, polyphenylene oxide resin, polycarbonate resin, polyether ether ketone resin, and polyester resin; organic fillers such as rubber particles; organocopper compounds, organozinc compounds, organocobalt compounds, and other organometallic compounds; coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine, etc.; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as Benton and montmorillonite; an antifoaming agent such as an organosilicon antifoaming agent, an acrylic antifoaming agent, a fluorine antifoaming agent, and a vinyl resin antifoaming agent; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; an adhesion improver such as urea silane; adhesion-imparting agents such as triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, and triazine-based adhesion-imparting agents; antioxidants such as hindered phenol antioxidants and hindered amine antioxidants; fluorescent whitening agents such as stilbene derivatives; a surfactant such as a fluorine-based surfactant and an organosilicon-based surfactant; flame retardants such as phosphorus flame retardants (for example, phosphate compounds, phosphazene compounds, phosphinic acid compounds, and red phosphorus), nitrogen flame retardants (for example, melamine sulfate), halogen flame retardants, and inorganic flame retardants (for example, antimony trioxide); a dispersant such as a phosphate dispersant, a polyoxyalkylene dispersant, an alkyne dispersant, a silicone dispersant, an anionic dispersant, and a cationic dispersant; and stabilizers such as borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, and carboxylic anhydride stabilizers. (H) The other additives may be used alone in 1 kind, or may be used in combination in an arbitrary ratio of 2 or more kinds. (H) The content of the other additives can be appropriately set by those skilled in the art.
Organic solvent (K)
The resin composition of the present invention may further contain an optional organic solvent as a volatile component in addition to the above-mentioned nonvolatile components. As the organic solvent (K), a known organic solvent may be suitably used, and the kind thereof is not particularly limited. Examples of the organic solvent (K) include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ -butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1, 4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate (ethyl diglycolacetate), γ -butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane and methylcyclohexane; aromatic solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (K) The organic solvents may be used alone or in combination of 2 or more kinds in any ratio.
In one embodiment, the content of the (K) organic solvent is not particularly limited, and when the total content of the components in the resin composition is set to 100 mass%, for example, 60 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, 15 mass% or less, 10 mass% or less, and the like may be used.
Method for producing resin composition
The resin composition of the present invention can be produced, for example, by: to an arbitrary preparation vessel, (A) a copolymer of a divinyl aromatic compound and styrene, (B) an epoxy resin, and (C) an active ester compound, if necessary, (D) an inorganic filler, if necessary, (E) a radical polymerizable compound, if necessary, (F) other curing agents, if necessary, (G) a curing accelerator, if necessary, (H) other additives, and if necessary, (K) an organic solvent are added in an arbitrary order and/or partially or all at the same time, and mixed. In addition, the temperature may be set appropriately during the process of adding and mixing the components, and heating and/or cooling may be performed temporarily or throughout. In addition, during or after the addition and mixing, the resin composition may be stirred or oscillated to be uniformly dispersed by using a stirring device such as a mixer or an oscillation device, for example. In addition, the defoaming may be performed under low pressure conditions such as vacuum while stirring or shaking.
< Properties of resin composition >
The resin composition of the present invention comprises (A) a copolymer of a divinyl aromatic compound and styrene, (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, a cured product which can be suppressed to a low value in dielectric loss tangent even in a high-temperature environment such as 90 ℃ and which is excellent in crack resistance after the stain removal treatment can be obtained, and preferably a cured product which is excellent in further plating peel strength (copper adhesion) and further low in dielectric loss tangent at room temperature or normal temperature region such as 23 ℃ and low in relative permittivity at any of room temperature or normal temperature region and high-temperature environment can be obtained.
The cured product of the resin composition of the present invention may have a feature that cracking after the stain removal treatment (roughening treatment) is suppressed. Therefore, in one embodiment, after the circuit board is manufactured and the stain removal treatment is performed as in test example 3 below, the number of cracks may be preferably 10 or less (10% or less) when 100 copper pads of the circuit board are observed.
The cured product of the resin composition of the present invention may have a characteristic that the dielectric loss tangent (Df) is low even in a high-temperature environment such as 90 ℃. Therefore, in one embodiment, as in test example 2 described below, the dielectric loss tangent (Df) of the cured product of the resin composition when measured at 5.8GHz and 90 ℃ may be preferably 0.020 or less, more preferably 0.010 or less, still more preferably 0.009 or less, yet more preferably 0.007 or less, 0.006 or less, particularly preferably 0.005 or less, and 0.004 or less.
The cured product of the resin composition of the present invention may have a characteristic that the dielectric loss tangent (Df) is low even at room temperature or normal temperature such as 23 ℃. Therefore, in one embodiment, as in test example 2 below, the dielectric loss tangent (Df) of the cured product of the resin composition when measured at 5.8GHz and 23 ℃ may be preferably 0.020 or less, more preferably 0.010 or less, still more preferably 0.009 or less, 0.008 or less, still more preferably 0.007 or less, 0.006 or less, still more preferably 0.005 or less, 0.004 or less, and particularly preferably 0.003 or less.
The cured product of the resin composition of the present invention may have a characteristic that the relative dielectric constant (Dk) is low even in a high-temperature environment such as 90 ℃. Therefore, in one embodiment, as in test example 2 below, the relative dielectric constant (Dk) of the cured product of the resin composition when measured at 5.8GHz and 90 ℃ may be preferably 5.0 or less, more preferably 4.0 or less, further preferably 3.5 or less, and in the case of containing hollow silica as the inorganic filler (D), it can be further reduced, and may be preferably 5.0 or less, more preferably 4.0 or less, further preferably 3.5 or less, and particularly preferably 3.0 or less.
The cured product of the resin composition of the present invention may have a characteristic that the relative dielectric constant (Dk) is low even at room temperature or normal temperature such as 23 ℃. Therefore, in one embodiment, as in test example 2 below, the relative dielectric constant (Dk) of the cured product of the resin composition when measured at 5.8GHz and 23 ℃ may be preferably 5.0 or less, more preferably 4.0 or less, further preferably 3.5 or less, and in the case of containing hollow silica as the inorganic filler (D), it can be further reduced, and may be preferably 5.0 or less, more preferably 4.0 or less, further preferably 3.5 or less, and particularly preferably 3.0 or less.
The cured product of the resin composition of the present invention may have a characteristic of excellent copper adhesion. Therefore, in one embodiment, as in test example 1 described below, the copper plating peel strength calculated from the load when the copper plating conductor layer is peeled off in the vertical direction can be preferably 0.2kgf/cm or more, more preferably 0.3kgf/cm or more, still more preferably 0.35kgf/cm or more, and particularly preferably 0.4kgf/cm or more, by forming the copper plating conductor layer on the cured product according to JISC 6481. The upper limit is not particularly limited, and may be, for example, 10kgf/cm or less, 5kgf/cm or less, 3kgf/cm or less, 1 or 1.0kgf/cm or less, or the like.
Use of resin composition
The resin composition of the present invention can be suitably used as a resin composition for insulation use, particularly a resin composition for forming an insulating layer. Specifically, the resin composition can be suitably used as a resin composition for forming an insulating layer (resin composition for forming an insulating layer for forming a conductor layer) for forming a conductor layer (including a rewiring layer) formed on the insulating layer. In the printed wiring board described later, the resin composition may be suitably used as a resin composition for forming an insulating layer of the printed wiring board (a resin composition for forming an insulating layer of the printed wiring board). The resin composition of the present invention can be widely used in applications requiring a resin composition, such as a sheet-like laminate material such as a resin sheet or a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a filling resin, and a component embedding resin.
In addition, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as "a resin composition for forming a rewiring layer (a resin composition for forming a rewiring layer) for forming an insulating layer of a rewiring layer" and "a resin composition for sealing a semiconductor chip (a resin composition for sealing a semiconductor chip)". When manufacturing the semiconductor chip package, a rewiring layer may be further formed on the sealing layer;
(1) A step of laminating a temporary fixing film on the base material,
(2) A step of temporarily fixing the semiconductor chip on the temporary fixing film,
(3) A step of forming a sealing layer on the semiconductor chip,
(4) A step of peeling the base material and the temporary fixing film from the semiconductor chip,
(5) A step of forming a rewiring forming layer as an insulating layer on a surface of the semiconductor chip from which the base material and the temporary fixing film are peeled, and
(6) And forming a rewiring layer as a conductor layer on the rewiring layer.
In addition, since the resin composition of the present invention forms an insulating layer having excellent embedding properties for components, it can be suitably used in the case where a printed wiring board is a component-embedded circuit board.
< sheet laminate >)
The resin composition of the present invention can be used by coating in a varnish state, but in industry, it is generally preferable to use the resin composition in the form of a sheet laminate containing the resin composition.
As the sheet-like laminate, a resin sheet and a prepreg shown below are preferable.
In one embodiment, a resin sheet includes a support, and a resin composition layer provided on the support, the resin composition layer being formed from the resin composition of the present invention.
The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoints of thinning of the printed wiring board and providing a cured product excellent in insulation even if the cured product of the resin composition is a film. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be usually 5 μm or more, 10 μm or more, or the like.
Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.
When a film formed of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter, abbreviated as "PET") and polyethylene naphthalate (hereinafter, abbreviated as "PEN"), polycarbonates (hereinafter, abbreviated as "PC"), acrylic polymers such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.
When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil formed of a single metal of copper may be used, or a foil formed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.
The surface of the support to be bonded to the resin composition layer may be subjected to a matting treatment, a corona treatment, or an antistatic treatment.
As the support, a support with a release layer having a release layer on a surface to be bonded to the resin composition layer can be used. The release agent used for the release layer of the support having a release layer includes, for example, 1 or more release agents selected from the group consisting of alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. Examples of the support having a release layer include "SK-1", "AL-5", "AL-7" made by Leideraceae, and "Miller (Lumiror) T60" made by Toli, and "Purex" made by Di, and "Unipel" made by UNITKA, you Niji, which are commercially available products, as a PET film having a release layer containing an alkyd-based release agent as a main component.
The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. In the case of using the support with a release layer, the thickness of the entire support with a release layer is preferably in the above range.
In one embodiment, the resin sheet may further include an optional layer, as required. Examples of the optional layer include a protective film provided on a surface of the resin composition layer that is not bonded to the support (i.e., a surface opposite to the support) and selected for the support. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, dust or the like can be prevented from adhering to the surface of the resin composition layer or from being damaged on the surface of the resin composition layer.
The resin sheet can be manufactured, for example, by: a resin varnish prepared by dissolving a resin composition in an organic solvent is prepared by directly applying a liquid resin composition to a support using a die coater (diecap) or the like, and then applied to the support, followed by drying, thereby forming a resin composition layer.
The organic solvent may be the same as the organic solvent described as a component of the resin composition. The organic solvent may be used alone or in combination of 1 or more than 2.
Drying can be performed by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, and the drying is performed so that the content of the organic solvent in the resin composition layer becomes 10 mass% or less, preferably 5 mass% or less. Although the boiling point of the organic solvent varies depending on the resin composition or the resin varnish, for example, when the resin composition or the resin varnish containing 30 to 60 mass% of the organic solvent is used, the resin composition layer can be formed by drying at 50 to 150 ℃ for 3 to 10 minutes.
The resin sheet may be wound into a roll and stored. When the resin sheet has a protective film, the protective film can be peeled off for use.
In one embodiment, the prepreg is formed by impregnating a sheet-like fibrous base material with the resin composition of the present invention.
The sheet-like fibrous base material used for the prepreg is not particularly limited, and a sheet-like fibrous base material commonly used as a base material for the prepreg, such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-like fibrous base material is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fibrous base material is not particularly limited. Typically 10 μm or more.
The prepreg can be produced by a known method such as a hot melt method or a solvent method.
The thickness of the prepreg may be in the same range as the resin composition layer in the resin sheet described above.
The sheet-like laminate of the present invention can be preferably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and can be more preferably used for forming an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board).
< printed wiring Board >)
The printed wiring board of the present invention comprises an insulating layer formed from a cured product obtained by curing the resin composition of the present invention.
The printed wiring board can be manufactured by a method including the steps (I) and (II) described below, for example, using the resin sheet described above;
(I) A step of laminating the resin sheet on the inner layer substrate in such a manner that the resin composition layer of the resin sheet is bonded to the inner layer substrate,
(II) a step of forming an insulating layer by curing (e.g., thermally curing) the resin composition layer.
The "inner substrate" used in the step (I) is a member to be a substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both surfaces of the substrate is sometimes referred to as an "inner layer circuit substrate". In addition, intermediate products to be further formed into insulating layers and/or conductor layers at the time of manufacturing the printed wiring board are also included in the so-called "inner layer substrate" in the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer board having a component embedded therein may be used.
Lamination of the inner substrate and the resin sheet can be performed by, for example, thermally pressing the resin sheet against the inner substrate from the support side. As a member for heat-press bonding the resin sheet to the inner layer substrate (hereinafter, also referred to as "heat-press bonding member"), for example, a heated metal plate (SUS end plate or the like), a metal roller (SUS roller) or the like can be cited. It is preferable that the heat pressure bonding member is not directly pressed against the resin sheet but is pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.
Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably 60 to 160 ℃, more preferably 80 to 140 ℃, the thermocompression bonding pressure is preferably 0.098 to 1.77MPa, more preferably 0.29 to 1.47MPa, and the thermocompression bonding time is preferably 20 to 400 seconds, more preferably 30 to 300 seconds. The lamination is preferably carried out under reduced pressure of 26.7hPa or less.
Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressurized laminators manufactured by the company name machine, vacuum applicators (vacuum applicator) manufactured by Nikko-Materials, and batch vacuum pressurized laminators.
After lamination, the heat and pressure bonding member is pressed from the support body side at normal pressure (atmospheric pressure), for example, whereby the laminated resin sheets can be smoothed. The pressing conditions for the smoothing treatment may be set to the same conditions as those for the above-described lamination of the heat press-bonding. The smoothing treatment may be performed by a commercially available laminator. The lamination and smoothing treatment may be continuously performed using the commercially available vacuum laminator described above.
The support may be removed between the step (I) and the step (II), or may be removed after the step (II).
In the step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer formed of a cured product of the resin composition. The curing condition of the resin composition layer is not particularly limited, and conditions generally employed in forming an insulating layer of a printed wiring board can be used.
For example, the heat curing condition of the resin composition layer varies depending on the kind of the resin composition, etc., and in one embodiment, the curing temperature is preferably 120 to 240 ℃, more preferably 150 to 220 ℃, still more preferably 170 to 210 ℃. The curing time may be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and still more preferably 15 minutes to 100 minutes.
The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, the resin composition layer is preheated at a temperature of 50 to 120 ℃, preferably 60 to 115 ℃, more preferably 70 to 110 ℃ for 5 minutes or more, preferably 5 to 150 minutes, more preferably 15 to 120 minutes, still more preferably 15 to 100 minutes, before the resin composition layer is thermally cured.
In the case of manufacturing a printed wiring board, (III) a step of forming a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further performed. These steps (III) to (V) can be performed according to various methods known to those skilled in the art that can be used for manufacturing a printed wiring board. When the support is removed after the step (II), the removal of the support may be performed between the step (II) and the step (III), between the step (III) and the step (IV), or between the step (IV) and the step (V). If necessary, the insulating layer and the conductor layer may be formed repeatedly in the steps (II) to (V), thereby forming a multilayer wiring board.
In other embodiments, the printed wiring board of the present invention may be manufactured using the prepreg described above. The production method is basically the same as in the case of using a resin sheet.
The step (III) is a step of forming a hole in the insulating layer, whereby a through hole, a through hole (through hole), or the like can be formed in the insulating layer. The step (III) may be performed using, for example, a drill, a laser, a plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer. The size and shape of the holes can be appropriately determined according to the design of the printed wiring board.
The step (IV) is a step of roughening the insulating layer. In general, in this step (IV), the removal of the contamination is also performed. The step and condition of the roughening treatment are not particularly limited, and known steps and conditions generally used in forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer may be roughened by sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid.
The swelling liquid used in the roughening treatment is not particularly limited, and examples thereof include an alkali solution, a surfactant solution, and the like, preferably an alkali solution, and more preferably a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include "SwellingDipSecuriganthP", "Swelling Dip Securiganth SBU" manufactured by America Japan (ATOTECHJAPAN), inc. The swelling treatment with the swelling liquid is not particularly limited, and for example, the insulating layer may be immersed in the swelling liquid at 30 to 90 ℃ for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to a proper level, it is preferable to impregnate the insulating layer in a swelling liquid at 40 to 80 ℃ for 5 to 15 minutes.
The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 100 ℃ for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10 mass%. Examples of the commercially available oxidizing agent include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Anmeite Japan Co., ltd.
The neutralizing liquid used in the roughening treatment is preferably an acidic aqueous solution, and examples of the commercial product include "Reduction Solution Securiganth P" manufactured by ameter japan.
The neutralization solution-based treatment may be performed by immersing the treated surface, on which the roughening treatment by the oxidizing agent is completed, in the neutralization solution at 30 to 80 ℃ for 5 to 30 minutes. In view of handling properties, it is preferable to dip the object subjected to the roughening treatment by the oxidizing agent in a neutralizing solution at 40 to 70 ℃ for 5 to 20 minutes.
The step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. There is no particular limitation on the conductor material used in the conductor layer.
In a preferred embodiment, the conductor layer comprises one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer include a layer formed of an alloy of two or more metals selected from the group described above (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, from the viewpoints of versatility of conductor layer formation, cost, ease of patterning, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferable, and a single metal layer of copper is further preferable.
The conductor layer may have a single-layer structure, or may have a multilayer structure in which two or more single metal layers or alloy layers each made of a different metal or alloy are stacked. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.
The thickness of the conductor layer is usually 3 μm to 35 μm, preferably 5 μm to 30 μm, depending on the design of the desired printed wiring board.
In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of an insulating layer using a conventionally known technique such as a half-addition method or a full-addition method, and it is preferable to form the conductor layer by a half-addition method from the viewpoint of ease of manufacturing. Hereinafter, an example of forming a conductor layer by a half-additive method is shown.
First, a plating seed layer is formed on the surface of an insulating layer by electroless plating. Next, a mask pattern exposing a part of the plating seed layer is formed on the formed plating seed layer corresponding to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, whereby a conductor layer having a desired wiring pattern can be formed.
In other embodiments, the conductor layer may be formed using a metal foil. When the conductor layer is formed using a metal foil, the step (V) is preferably performed between the step (I) and the step (II). For example, after the step (I), the support is removed, and a metal foil is laminated on the surface of the exposed layer of the resin composition. Lamination of the layer of the resin composition and the metal foil may be performed by a vacuum lamination method. The lamination conditions may be the same as those described for the step (I). Next, step (II) is performed to form an insulating layer. Then, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method or a modified semi-additive method using a metal foil on the insulating layer.
The metal foil can be produced by a known method such as electrolysis or rolling. Examples of the commercial products of the metal foil include HLP foil manufactured by JX Nitshi metal Co., ltd., JXUT-III foil, 3EC-III foil manufactured by Mitsui metal mine Co., ltd., TP-III foil, and the like.
Semiconductor device
The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.
Examples of the semiconductor device include various semiconductor devices that can be used in electric products (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, electric trains, ships, aircraft, and the like).
Examples
The present invention will be specifically described below with reference to examples. The present invention is not limited by these examples. Hereinafter, "part" and "%" representing amounts refer to "part by mass" and "% by mass", respectively, unless otherwise specifically stated. The temperature condition when the temperature is not specified is room temperature (25 ℃).
Synthesis example 1: synthesis of divinylbenzene-styrene copolymer
According to example 1 of patent document 2, 3.0 mol (390.6 g) of divinylbenzene, 1.8 mol (229.4 g) of ethylvinylbenzene, 10.2 mol (1066.3 g) of styrene, and 15.0 mol (1532.0 g) of n-propyl acetate were charged into a 5.0L reactor, and 600 mmol of a diethyl ether complex of boron trifluoride was added at 70℃to carry out a reaction for 4 hours. After stopping the polymerization solution with an aqueous sodium hydrogencarbonate solution, the oil layer was washed 3 times with pure water, and devolatilized under reduced pressure at 60℃to recover the copolymer. The obtained copolymer was weighed, and it was confirmed that 6.7g of copolymer A was obtained. The weight average molecular weight (Mw) of copolymer A was 41300;
Based on NMR measurement, GC analysis, number average molecular weight converted to standard polystyrene, and the like, the structural unit of the copolymer a is calculated as described in patent document 2 as follows;
structural units derived from divinylbenzene (a): 30.4 mol%
Structural units derived from styrene (b): 57.4 mol%
Structural units derived from ethylvinylbenzene (c): 12.2 mol%
Structural units having residual vinyl groups derived from divinylbenzene (a): 23.9 mol%
Introduction amount of vinyl group-containing terminal group (tv): 0.66 (personal/molecular)
A terminal group of formula (t 1): 1.49 mol%
A terminal group of formula (t 2): 1.31 mol%
A terminal group of formula (t 3): 2.21 mole%.
< synthetic example 2: synthesis of active ester Compound A
A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer was charged with 203.0g of isophthaloyl dichloride (mole number of acyl chloride: 2.0 mol) and 1400g of toluene, and the inside of the system was subjected to a nitrogen substitution under reduced pressure to dissolve the isophthaloyl dichloride. Next, 113.9g (0.67 mol) of o-phenylphenol and 240g (molar number of phenolic hydroxyl groups: 1.33 mol) of benzyl-modified naphthalene compound were charged, and the system was dissolved by nitrogen substitution under reduced pressure. Then, 0.70g of tetrabutylammonium bromide was dissolved, and 400g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while the inside of the system was controlled to 60℃or lower under nitrogen purging. Next, stirring was continued under this condition for 1.0 hour. After the reaction, the mixture was allowed to stand for separation, and the aqueous layer was removed. Further, water was poured into the toluene layer in which the reactant was dissolved, and the mixture was stirred and mixed for 15 minutes, and the mixture was left to stand for separation, whereby the water layer was removed. This operation was repeated until the pH of the aqueous layer became 7. Then, the water was removed by decantation (decanter) dehydration to obtain an active ester compound a in the form of a toluene solution containing 62 mass% of nonvolatile components. The active ester equivalent of the active ester compound a obtained was 238g/eq.
< synthesis example 3: synthesis of active ester Compound B
A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer was charged with 165g of an addition polymerization resin (hydroxyl equivalent: 165 g/equivalent (eq), a softening point of 85 ℃ C.), 134g (1.0 mol) of o-allylphenol and 1200g of toluene, and the inside of the system was purged with nitrogen under reduced pressure. Then, 203g (1.0 mol) of isophthaloyl dichloride was charged, and the inside of the system was purged with nitrogen under reduced pressure. 0.6g of tetrabutylammonium bromide was added, the inside of the system was controlled to 60℃or lower while the nitrogen purging was performed, 412g of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours, and after the completion of the dropwise addition, the mixture was stirred for 1.0 hour. After the completion of the reaction, the aqueous layer was removed by standing and separating. To the toluene layer thus obtained, water was further added, and the mixture was stirred for 15 minutes, followed by standing and liquid separation to remove the water layer. This operation was repeated until the pH of the aqueous layer became 7. Then, the nonvolatile content was adjusted to 70 mass% by heat drying, whereby an active ester resin represented by the following chemical formula was obtained;
[ chemical formula 16]
In the above chemical formula, S is each independently an integer of 0 or 1 or more, and the average value of r calculated from the charge ratio is 1. The broken line in the chemical formula is a structure obtained by reacting isophthaloyl dichloride, and an addition polymerization resin of phenol and/or o-allylphenol. The ester group equivalent of the active ester resin calculated from the charge ratio was 214 g/equivalent (eq.).
Example 1
10 parts of naphthalene type epoxy resin (HP-4032-SS, manufactured by DIC Co., ltd., epoxy equivalent of 144 g/eq.), 5 parts of naphthalene aralkyl type epoxy resin (ESN-475V, manufactured by Nitro iron chemical materials Co., ltd., epoxy equivalent of 330 g/eq.), 5 parts of biphenyl aralkyl type epoxy resin (NC-3100, manufactured by Japanese chemical Co., ltd., epoxy equivalent of 258 g/eq.), 43 parts of active ester type curing agent ("HPC-8150-62T", active group equivalent of 229g/eq., nonvolatile component 61.5 mass% toluene solution), 43 parts of other curing agent (phenol type curing agent, 1-methoxy 2-propanol solution, manufactured by DIC Co., ltd., hydroxyl equivalent of 151g/eq., nonvolatile component 50 mass%) 5 parts, and the compound obtained in synthetic example 1 as the component (A)4 parts of a substance (50% by mass of toluene solution), spherical silica (manufactured by Kogyo Co., ltd., "SO-C2", average particle diameter: 0.5 μm, specific surface area: 5.8 m) surface-treated with an inorganic filler (amine-based alkoxysilane compound (manufactured by Kogyo Co., ltd., "KBM 573") 2 135 parts of a curing accelerator (1B 2PZ, manufactured by Sichuang chemical industry Co., ltd.), 0.5 part of MEK10 parts, and 10 parts of cyclohexanone were uniformly dispersed by using a high-speed rotary mixer to obtain a resin varnish.
Example 2
In example 1, 43 parts of an active ester-based curing agent ("HPC-8150-62T", active group equivalent is 223g/eq., toluene solution containing no volatile component 61.5% by mass) was changed to 40 parts of an active ester-based curing agent (HPC-8000-65T ", manufactured by DIC Co., ltd., active group equivalent is 223g/eq., toluene solution containing no volatile component 65% by mass). A resin varnish was obtained in the same manner as in example 1, except for the above matters.
Example 3
In example 1, 43 parts of an active ester-based curing agent ("HPC-8150-62T", active group equivalent is 223g/eq., nonvolatile matter 61.5 mass% toluene solution) was changed to 43 parts of an active ester A (active group equivalent is 238g/eq., nonvolatile matter 61.5 mass% toluene solution) obtained in Synthesis example 2. A resin varnish was obtained in the same manner as in example 1, except for the above matters.
Example 4
In example 1, 43 parts of an active ester-based curing agent ("HPC-8150-62T", active group equivalent is 223g/eq., nonvolatile matter 61.5 mass% toluene solution) was changed to 37 parts of the active ester B (active group equivalent is 214g/eq., nonvolatile matter 70 mass% toluene solution) obtained in Synthesis example 3. A resin varnish was obtained in the same manner as in example 1, except for the above matters.
Example 5
In example 1, 43 parts of an active ester-based curing agent ("HPC-8150-62T", active group equivalent is 223g/eq., nonvolatile matter 61.5 mass% toluene solution) was changed to 37 parts of an active ester-based curing agent (AirWater company "PC1300-02-65MA", active group equivalent is 199g/eq., nonvolatile matter 65 mass% methyl amyl ketone solution). A resin varnish was obtained in the same manner as in example 1, except for the above matters.
Example 6
In example 1, 2 parts of a MEK solution (nonvolatile matter 62 mass%) of a maleimide compound a (Mw/mn=1.81, t "=1.47 (mainly 1, 2 or 3)) represented by the following formula (M) was further synthesized by the method described in synthesis example 1 of japanese patent application laid-open publication No. 2020-500211. A resin varnish was obtained in the same manner as in example 1 except for the above matters;
[ chemical formula 17]
Example 7
In example 1, 2 parts of another thermosetting resin (maleimide resin (MIR-5000-60T, manufactured by Japanese chemical Co., ltd., nonvolatile matter 60% by mass in toluene) was further used, and a resin varnish was obtained in the same manner as in example 1 except for the above matters.
Example 8
In example 1, 2 parts of another thermosetting resin (maleimide resin (MIR-3000-70 MT, manufactured by Japanese chemical Co., ltd., nonvolatile matter 70% by mass of toluene/MEK mixed solution)) was further used, and a resin varnish was obtained in the same manner as in example 1 except for the above matters.
Example 9
In example 1, 2 parts of another thermosetting resin (maleimide resin (BMI-689, manufactured by Seiko Co., ltd.) was further used, and a resin varnish was obtained in the same manner as in example 1 except for the above matters.
Example 10
In example 1, 2 parts of another thermosetting resin (acrylate resin (A-DOG, new Yoghurt chemical Co., ltd.) was further used, and a resin varnish was obtained in the same manner as in example 1 except for the above matters.
Example 11
In example 1, 2 parts of another thermosetting resin (styrene resin (OPE-2 St-1200, manufactured by Mitsubishi gas chemical corporation, toluene solution having a nonvolatile content of 65% by mass)) was further used, and a resin varnish was obtained in the same manner as in example 1 except for the above matters.
Example 12
In example 1, spherical silica (SO-C2, manufactured by Santa Clara, co., ltd.) having been surface-treated with an inorganic filler (an amine-based alkoxysilane compound (KBM 573, manufactured by Xinyue chemical industry Co., ltd.) had an average particle diameter of 0.5 μm and a specific surface area of 5.8m 2 A resin varnish was obtained in the same manner as in example 1 except that (g)/(g) 135 parts was changed to 100 parts and 35 parts of an inorganic filler having a hollow portion (spherical silica having a hollow portion (BA-S, manufactured by daily-swing catalyst formation corporation) surface-treated with an amine-based alkoxysilane compound (KBM 573, manufactured by singe chemical industry Co.).
Comparative example 1
In example 1, a resin varnish was obtained in the same manner as in example 1, except that 4 parts of the compound (50 mass% toluene solution) obtained in synthesis example 1 was not used as the component (a).
Comparative example 2
In example 10, a resin varnish was obtained in the same manner as in example 10 except that 4 parts of the compound (50 mass% toluene solution) obtained in synthesis example 1 was not used as the component (a).
Comparative example 3
In example 11, a resin varnish was obtained in the same manner as in example 11 except that 4 parts of the compound (50 mass% toluene solution) obtained in synthesis example 1 was not used as the component (a).
Preparation example 1: production of evaluation substrate A comprising insulating layer and conductive layer formed of resin sheet A
(1) Preparation of resin sheet A having a thickness of 40 μm as a layer of the resin composition
As a support, a polyethylene terephthalate film (AL 5, manufactured by Lindeke Co., ltd.) having a thickness of 38 μm was prepared. The resin varnishes obtained in examples and comparative examples were uniformly applied to the release layer of the support so that the thickness of the dried resin composition layer became 40. Mu.m. Then, the resin composition was dried at 80℃to 100℃for 4 minutes (average 90 ℃) to obtain a resin sheet A comprising a support and a resin composition layer.
(2) Preparation of inner substrate
The copper surface of the glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil 18 μm thick, substrate 0.4mm thick, R1515A manufactured by sonification corporation) on which the inner layer circuit was formed was roughened by etching 1 μm on both sides with a microetching agent (CZ 8101 manufactured by MEC corporation).
(3) Lamination of resin sheet A
The resin sheet a was laminated on both sides of the inner substrate using a batch vacuum press laminator (CVP 700, manufactured by Nikko-Materials, level 2 stack laminator) so that the resin composition layer was in contact with the inner substrate. Lamination is carried out by: the pressure was reduced for 30 seconds to adjust the air pressure to 13hPa or less, and then the pressure was applied at 120℃under a pressure of 0.74MPa for 30 seconds. Next, hot pressing was performed at 100℃under a pressure of 0.5MPa for 60 seconds.
(4) Thermosetting of resin composition layer
Then, the inner substrate laminated with the resin sheet a was put into an oven at 130 ℃ for 30 minutes to heat, then transferred into an oven at 170 ℃ for 30 minutes to heat, and the resin composition layer was thermally cured to form an insulating layer. Then, the support was peeled off to obtain a cured substrate a having an insulating layer, an inner substrate, and an insulating layer in this order.
(5) Roughening treatment
The cured substrate a is subjected to a desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was performed.
The cured substrate a was immersed in a swelling solution (an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide, manufactured by ameter japan corporation) at 60 ℃ for 5 minutes, and then immersed in an oxidizing agent solution (an aqueous solution of potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) at 80 ℃ for 20 minutes. Next, the resultant mixture was immersed in a neutralization solution (America Japanese Kogyo "Reduction Solution Securiganth P", sulfuric acid aqueous solution) at 40℃for 5 minutes, and then dried at 80℃for 15 minutes.
(6) Formation of conductor layer
According to the semi-additive method, a conductor layer is formed on the roughened surface of the insulating layer. That is, the substrate after the roughening treatment is subjected to a treatment comprising PdCl 2 After immersing in the electroless plating solution at 40℃for 5 minutes, immersing in the electroless copper plating solution at 25℃for 20 minutes. Next, heating was performed at 150 ℃ for 30 minutes, annealing treatment was performed, and then, a resist layer was formed, and patterning was performed by etching. Then, copper sulfate was electrolytically plated to form a conductor layer having a thickness of 25. Mu.m, and annealing was performed at 190℃for 60 minutes. The obtained substrate was referred to as "evaluation substrate a".
Test example 1: determination of peel strength of plated conductor layer
The peel strength of the insulating layer and the conductor layer was measured in accordance with japanese industrial standards (JIS C6481). Specifically, a notch having a width of 10mm and a length of 100mm was formed in the conductor layer of the evaluation substrate a, one end thereof was peeled off, and the resultant was clamped by a jig, and a load (kgf/cm) at a speed of 50 mm/min at room temperature when peeled off in the vertical direction by 35mm was measured to determine the peel strength. A tensile tester (TSE Co., ltd. "AC-50C-SL") was used for the measurement.
Test example 2: determination of relative permittivity and dielectric loss tangent
The resin sheet a obtained in production example 1 (1) was cured in an oven at 190 ℃ for 90 minutes using the resin varnishes obtained in examples and comparative examples. The support was peeled from the resin sheet a taken out of the oven, whereby a cured product of the resin composition layer was obtained. The cured product was cut into a length of 80mm and a width of 2mm to obtain a cured product for evaluation.
For each cured product for evaluation, the relative dielectric constant (Dk value) and the dielectric loss tangent (Df value) were measured by using Agilent technology (Agilent Technologies) Inc. "HP8362B" using a cavity perturbation method at a measurement frequency of 5.8GHz and at a measurement temperature of 23℃and 90 ℃. The average value of the 2 test pieces was calculated by measuring them.
Preparation example 2: preparation of resin sheet B having a thickness of 25 μm as a layer of the resin composition
As a support, a polyethylene terephthalate film (AL 5, manufactured by Lindeke Co., ltd.) having a thickness of 38 μm was prepared. The resin varnishes obtained in examples and comparative examples were uniformly applied to the release layer of the support so that the thickness of the dried resin composition layer became 25. Mu.m, and the resin composition layer was dried at 70℃to 80℃for 2.5 minutes to obtain a resin sheet B comprising the support and the resin composition layer.
Test example 3: evaluation of crack resistance after stain removal treatment
The resin sheet B having a thickness of 25 μm produced in production example 2 was laminated on both surfaces of the inner layer substrate by bonding the resin composition layer to the inner layer substrate by using an intermittent vacuum pressure laminator (CVP 700 "manufactured by Nikko-Materials corporation, grade 2 stack laminator) on both surfaces of a core material (manufactured by hitachi chemical industry company," E705GR ", having a thickness of 400 μm) having a circular copper pad (copper thickness of 35 μm) having a diameter of 350 μm formed in a lattice shape at 400 μm intervals so that the residual copper ratio became 60%. The lamination is carried out by: the pressure was reduced for 30 seconds to a gas pressure of 13hPa or less, and then pressure bonding was performed for 30 seconds at a temperature of 100℃and a pressure of 0.74 MPa. It was put into an oven at 130℃for 30 minutes and then transferred into an oven at 170℃for 30 minutes. Further, the support was peeled off, and the obtained circuit board was immersed in Swelling Dip Securiganth P of Anmei Japanese Co., ltd., as a swelling liquid, at 60℃for 10 minutes. Next, the mixture was subjected to a roughening treatment in an Anmei Japanese Co., ltd.) of Concentrate Compact P (KMnO 4 :60g/L, naOH:40g/L in water) was immersed in the solution at 80℃for 30 minutes. Finally, in An Meite as a neutralization solutionThe solution was immersed in Reduction Solution Securiganth P of Japanese Kogyo at 40℃for 5 minutes. 100 copper pads of the roughened circuit board were observed to confirm the presence or absence of cracks in the resin composition layer. If the number of cracks is 10 or less, the evaluation is good, and if the number of cracks is more than 10, the evaluation is good.
The amounts (parts by mass) of the components (a) to (G) including the volatile components used in the resin compositions of examples and comparative examples and the measurement results of the test examples are shown in table 1 below. In table 1, the nonvolatile components (mass%) of each component are described in the column "n.v.".
TABLE 1
From the above, it is found that by using a resin composition comprising (a) a copolymer of a divinylaromatic compound and styrene, (B) an epoxy resin, and (C) an active ester compound, a cured product having a low dielectric loss tangent (Df) even in a high temperature environment such as 90 ℃ and excellent crack resistance after stain removal treatment can be obtained. It is also known that the cured product is excellent in further plating peel strength (copper adhesion), and further has a low dielectric loss tangent (Df) at room temperature or in a room temperature region such as 23 ℃ and a low relative dielectric constant (Dk) at room temperature or in any of a room temperature region and a high temperature environment.

Claims (15)

1. A resin composition comprising (A) a copolymer of a divinyl aromatic compound and styrene, (B) an epoxy resin and (C) an active ester compound,
wherein the component (A) contains a structural unit represented by the following formula (a 1) derived from a divinyl aromatic compound (a) and has a weight average molecular weight of 40000 or more,
wherein R is 1 Represents the number of carbon atoms 6Aromatic hydrocarbon groups of about 30.
2. The resin composition according to claim 1, wherein component (C) has a carbon-carbon double bond.
3. The resin composition according to claim 1, wherein W is a value obtained by adding all of the values obtained by dividing the mass of the nonvolatile component of the component (B) by the epoxy equivalent B And the sum of the mass of the nonvolatile component (C) divided by the equivalent weight of the active ester group is denoted as W C At the time W C /W B Is 1.0 or more.
4. The resin composition according to claim 1, further comprising (D) an inorganic filler.
5. The resin composition according to claim 1, further comprising (E) a radical polymerizable compound.
6. The resin composition according to claim 1, which is used for forming an interlayer insulating layer of a printed wiring board.
7. The resin composition according to claim 1, wherein the component (A) contains structural units derived from a monovinylaromatic compound (c) other than styrene in addition to structural units derived from the divinylaromatic compound (a) and styrene (b), respectively.
8. The resin composition according to claim 1, wherein, in the component (A), when the total of the structural unit derived from the divinylaromatic compound (a), the structural unit derived from the styrene (b) and the structural unit derived from the monovinylaromatic compound (c) other than styrene is set to 100 mol%,
the structural unit derived from the divinylaromatic compound (a) is 2 mol% or more and less than 95 mol%.
9. The resin composition according to claim 1, wherein the component (A) contains at least any one of terminal groups represented by the following formulas (t 1), (t 2) or (t 3) at the terminal of the copolymer,
wherein R is 2 Represents an aromatic hydrocarbon group having 6 to 30 carbon atoms,
Z 1 represents a vinyl group, a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms,
* Represents a binding site to the main chain, and the meaning is the same hereinafter;
wherein R is 3 R is R 4 Each independently represents an aromatic hydrocarbon group having 6 to 30 carbon atoms,
Z 3 Z is as follows 4 Each independently represents a vinyl group, a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms;
wherein R is 5 Represents an aromatic hydrocarbon group having 6 to 30 carbon atoms,
Z 5 represents a vinyl group, a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.
10. The resin composition according to claim 1, wherein, in the component (A), when the total of the structural unit derived from the divinylaromatic compound (a), the structural unit derived from the styrene (b) and the structural unit derived from the monovinylaromatic compound (c) other than styrene is set to 100 mol%,
the total of the terminal groups represented by the formula (a 1), the formulas (t 1), (t 2) and (t 3) is in the range of 2 mol% to 80 mol%.
11. A cured product of the resin composition according to any one of claims 1 to 10.
12. A sheet-like laminate comprising the resin composition according to any one of claims 1 to 10.
13. A resin sheet, comprising:
support body
A resin composition layer formed of the resin composition according to any one of claims 1 to 10, provided on the support.
14. A printed wiring board comprising an insulating layer formed from the cured product of the resin composition according to any one of claims 1 to 10.
15. A semiconductor device comprising the printed wiring board of claim 14.
CN202310095132.6A 2022-02-14 2023-02-10 Resin composition Pending CN116589826A (en)

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JP2022020824A JP2023117983A (en) 2022-02-14 2022-02-14 resin composition

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Publication number Priority date Publication date Assignee Title
JP5181769B2 (en) 2008-03-26 2013-04-10 Ｄｉｃ株式会社 Epoxy resin composition and cured product thereof

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